Chemistry

for Cambridge International AS & A Level

COURSEBOOK
Lawrie Ryan & Roger Norris
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 Contents
How to use this series

How to use this book

Introduction
1 Atomic structure
1.1 Elements and atoms
1.2 Inside the atom
1.3 Numbers of nucleons

2 Electrons in atoms
2.1 Simple electronic structure
2.2 Evidence for electronic structure
2.3 Sub-shells and atomic orbitals
2.4 Electronic configurations
2.5 Periodic patterns of atomic and ionic radii
2.6 Patterns in ionisation energies in the Periodic Table

3 Atoms, molecules and stoichiometry

3.1 Masses of atoms and molecules
3.2 Hydrated and anhydrous compounds
3.3 Accurate relative atomic masses
3.4 Amount of substance
3.5 Mole calculations
3.6 Chemical formulae and chemical equations
3.7 Solutions and concentration
3.8 Calculations involving gas volumes

4 Chemical bonding
4.1 Types of chemical bonding
4.2 Ionic bonding
4.3 Covalent bonding
4.4 Shapes of molecules
4.5 σ bonds and π bonds
4.6 Metallic bonding
4.7 Intermolecular forces
4.8 Hydrogen bonding
4.9 Bonding and physical properties

5 States of matter
5.1 States of matter
5.2 The gaseous state
5.3 The liquid state
5.4 The solid state
5.5 Fullerenes

6 Enthalpy changes
6.1 What are enthalpy changes?
6.2 Standard enthalpy changes
6.3 Measuring enthalpy changes
6.4 Hess’s law
6.5 Bond energies and enthalpy changes
 6.6 Calculating enthalpy changes using bond energies

7 Redox reactions
7.1 What is a redox reaction?
7.2 Oxidation numbers
7.3 Applying the oxidation number rules
7.4 Redox and oxidation number
7.5 Oxidising agents and reducing agents
7.6 Naming compounds
7.7 From name to formula
7.8 Balancing chemical equations using oxidation numbers
7.9 Disproportionation

8 Equilibria
8.1 Reversible reactions and equilibrium
8.2 Changing the position of equilibrium
8.3 Equilibrium expressions and the equilibrium constant, Kc
8.4 Equilibria in gas reactions: the equilibrium constant, Kp
8.5 Equilibria and the chemical industry
8.6 Acid–base equilibria
8.7 Indicators and acid–base titrations

9 Rates of reaction
9.1 Rate of reaction
9.2 The effect of concentration on rate of reaction
9.3 The effect of temperature on rate of reaction
9.4 Catalysis

10 Periodicity
10.1 Structure of the Periodic Table

10.2 Periodicity of physical properties

10.3 Periodicity of chemical properties

10.4 Oxides of Period 3 elements

10.5 Effect of water on oxides and hydroxides of Period 3 elements

10.6 Chlorides of Period 3 elements

10.7 Effect of water on chlorides of Period 3 elements

10.8 Deducing the position of an element in the Periodic Table

11 Group 2
11.1 Physical properties of Group 2 elements

11.2 Reactions of Group 2 elements

11.3 Reactions with oxygen

11.4 Reactions with water

12 Group 17
12.1 Physical properties of Group 17 elements

12.2 Reactions of Group 17 elements

12.3 Reactions of the halide ions

12.4 Disproportionation reactions

13 Nitrogen
13.1 Nitrogen gas

13.2 Ammonia and ammonium compounds

 13.3 Nitrogen oxides in the atmosphere

14 Introduction to organic chemistry

14.1 Representing organic molecules

14.2 Homologous series of organic compounds

14.3 Naming organic compounds

14.4 Bonding in organic molecules

14.5 Structural isomerism

14.6 Stereoisomerism

14.7 Types of organic reaction and reaction mechanisms

14.8 Types of organic reaction

15 Hydrocarbons
15.1 The homologous group of alkanes

15.2 Reactions of alkanes

15.3 The alkenes

15.4 Oxidation of the alkenes

15.5 Addition polymerisation

15.6 Tackling questions on addition polymers

16 Halogenoalkanes
16.1 Making halogenoalkanes

16.2 Nucleophilic substitution reactions

16.3 Mechanism of nucleophilic substitution in halogenoalkanes

16.4 Elimination reactions

17 Alcohols, esters and carboxylic acids

17.1 The homologous series of alcohols

17.2 Reactions to make alcohols

17.3 Reactions of the alcohols

17.4 Carboxylic acids

18 Carbonyl compounds
18.1 The homologous series of aldehydes and ketones

18.2 Preparation of aldehydes and ketones

18.3 Reduction of aldehydes and ketones

18.4 Nucleophilic addition with HCN

18.5 Testing for aldehydes and ketones

18.6 Reactions to form tri-iodomethane

18.7 Infrared spectroscopy

P1 Practical skills 1
P1.1 Introduction

P1.2 Manipulation, measurement and observation

P1.3 Presentation of data and observations

P1.4 Analysis, conclusions and evaluation

19 Lattice energy
19.1 Defining lattice energy

19.2 Enthalpy change of atomisation and electron affinity

 19.3 Born–Haber cycles

19.4 Enthalpy changes in solution

20 Electrochemistry
20.1 Redox reactions revisited

20.2 Electrolysis

20.3 Quantitative electrolysis

20.4 Electrode potentials

20.5 Combining half-cells

20.6 Using E values

20.7 More about electrolysis

21 Further aspects of equilibria

21.1 Conjugate acids and conjugate bases

21.2 pH calculations

21.3 Weak acids: using the acid dissociation constant, Ka

21.4 Buffer solutions

21.5 Equilibrium and solubility

21.6 Partition coefficients

22 Reaction kinetics
22.1 Factors affecting reaction rate

22.2 Rate of reaction

22.3 Rate equations

22.4 Which order of reaction?

22.5 Calculations involving the rate constant, k

22.6 Deducing order of reaction from raw data

22.7 Kinetics and reaction mechanisms

22.8 Catalysis

23 Entropy and Gibbs free energy

23.1 Introducing entropy

23.2 Chance and spontaneous change

23.3 Calculating entropy changes

23.4 Entropy, enthalpy changes and Gibbs free energy

23.5 Gibbs free energy

23.6 Gibbs free energy calculations

24 Transition elements
24.1 What is a transition element?

24.2 Physical and chemical properties of the transition elements

24.3 Ligands and complex formation

25 Benzene and its compounds

25.1 The benzene ring

25.2 Reactions of arenes

25.3 Phenol

25.4 Reactions of phenol

26 Carboxylic acids and their derivatives

 26.1 The acidity of carboxylic acids

26.2 Oxidation of two carboxylic acids

26.3 Acyl chlorides

27 Organic nitrogen compounds

27.1 Amines

27.2 Formation of amines

27.3 Amino acids

27.4 Peptides

27.5 Reactions of the amides

27.6 Electrophoresis

28 Polymerisation
28.1 Condensation polymerisation

28.2 Synthetic polyamides

28.3 Biochemical polyamides

28.4 Degradable polymers

28.5 Polymer deductions

29 Organic synthesis
29.1 Chirality in pharmaceutical synthesis

29.2 Preparing pure enantiomers for use as drugs

29.3 Synthetic routes

30 Analytical chemistry
30.1 General principles of chromatography

30.2 Thin-layer chromatography

30.3 Gas–liquid chromatography

30.4 Proton (1H) nuclear magnetic resonance

30.5 Carbon-13 NMR spectroscopy

P2 Practical skills 2
P2.1 Introduction

P2.2 Planning

P2.3 Analysis, conclusions and evaluation

P2.4 The three remaining skills

Appendices
1 The Periodic Table of the Elements

2 Selected standard electrode potentials

3 Qualitative analysis notes

Acknowledgements
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Stereoisomers are compounds whose molecules have the same atoms bonded to each other, but with
different arrangements of the atoms in space.

There are two types of stereoisomerism:

1 geometrical ( / ) isomerism

2 optical isomerism.

Geometrical ( / ) isomerism
Unlike a C─C single bond, there is about a C═C double bond. This can result in a different
type of isomerism in unsaturated organic compounds. Figure 14.22 gives an example.

Figure 14.22: An example of geometrical ( ) isomerism.

In -1,2-dibromoethene, both the Br atoms remain fixed on the same side of the C═C double bond as
there is no free rotation about this bond because of the presence of a (pi) bond. However, in -1,2-
dibromoethene, the Br atoms are positioned across the C═C double bond. (Remember that the prefix
‘trans-’ means .)

These two stereoisomers have different arrangements of the atoms in space, so they are different
compounds with different physical properties. Stereoisomers can also have some different chemical
properties. For example, they may react at different rates for the same reaction. Whenever we have
unsaturated compounds with the structures shown in Figure 14.23, we can have this geometrical ( / )
type of isomerism.

Figure 14.23: These three arrangements can result in geometrical ( ) isomerism because there is restricted
rotation about the C═C double bond.

There is also geometrical ( ) isomerism possible in . This is because of

the limited rotation about C─C single bonds that make up the rings. We usually show the and
isomers using a combination of skeletal and 3D formulae. For example, 3-methylcyclopentanol and
-3-methylcyclopentanol:
We can also show the two isomers more clearly from a side view:

Another example is a substituted compound of cyclobutane, with two groups substituted into its four-
membered ring. The two geometrical isomers below are called and cyclobutane-1,3-dicarboxylic
acid:

In the isomer, the two carboxylic acid groups are either both pointing above (as shown) or both below
the ring of four carbon atoms. In the -isomer, one carboxylic acid group points above the ring and one
below.

Optical isomerism
If a molecule contains a carbon atom that is bonded to four different atoms or groups of atoms, it can form
two optical isomers. We can describe this carbon atom as an ‘asymmetric’ carbon atom because there is no
plane of symmetry in its molecule. The two different optical isomers, called enantiomers, are mirror
images of each other, and they cannot be superimposed (Figure 14.24). The carbon atom with the four
different groups attached to it is called the chiral centre of the molecule.

Figure 14.24: This pair of molecules are optical isomers, referred to as enantiomers. Trying to superimpose the two
isomers is like trying to superimpose your left hand on top of your right hand, with them both facing downwards: it can’t
be done.

PRACTICAL ACTIVITY 14.1

 Modelling optical isomers
Using a molecular modelling kit, take a black carbon atom and attach four different coloured atoms to
it. Then make another model molecule that is its mirror image using the same colours. Now try
superimposing the two models so all the atoms match up. Can it be done?

Optical isomers differ in their effect on polarised light. Normal light is unpolarised. It can be thought of as
fluctuating electric and magnetic fields, vibrating at right angles to each other in every possible direction.
Passing this unpolarised light through a polariser results in polarised light, which vibrates in only one plane.
A pair of optical isomers will rotate the plane of polarised light by equal amounts but in opposite directions.
One will rotate the plane of polarised light clockwise and the other anticlockwise.
Organic molecules can contain more than one asymmetric carbon atom, i.e. more than one chiral centre. If
there are two asymmetric carbon atoms, then each of its chiral centres will rotate the plane of polarised
light. In this case, there will be four possible optical isomers.

As well as straight and branched chain molecules, can also have chiral centres
in their ring structures. To decide where the chiral centres are, we still have to find any carbon atoms that
are bonded to four different atoms or groups of atoms.

Look at this example of a substituted cyclohexane molecule:

In cyclohexane all the carbon atoms are bonded to two hydrogen atoms so there is no chiral centre. But
when you start substituting other groups or atoms to replace hydrogen atoms, there is a possibility of
asymmetric carbon atoms.

In the cyclic molecule shown we have a hydroxyl (─OH) group and an amine (─NH2) group introduced into
the ring. Let’s consider the carbon atom bonded to the hydroxyl (─OH) group first. This carbon atom is also
bonded to a hydrogen atom (not shown in the skeletal formula). The other two groups bonded to it, making
up its four single bonds, are not the same. Imagine travelling around the ring in a clockwise direction from
this carbon atom, you come to four carbon atoms, each bonded to two hydrogen atoms. Then you come to
the carbon bonded to the ─NH2 group and one hydrogen atom, before arriving back where we started. We
can think of this group as ─(CH2)4CHNH2. After that, travel around the ring in the opposite direction, an
anti-clockwise direction, from same original carbon. This fourth bond from the carbon atom will be attached
to a ─CHNH2(CH2)4 group, so the original carbon atom has four different groups or atoms bonded to it:

an H atom
the ─OH group
the ─(CH2)4CHNH2 group
the ─CHNH2(CH2)4 group.

Now you follow the same process starting from the carbon atom bonded to the ─NH2 group. You will find
that this is also an asymmetric carbon atom. Therefore this cyclic molecule has .

Symmetrical substituted cyclic molecules will not have a chiral centre. Starting from the carbon atom(s)
bonded to the group(s) substituted into the ring, you will find two identical groups ‘going around’ the ring
in both the clockwise and the anticlockwise direction. Therefore, no carbon atom has four different groups
attached to it.

Question
6 a i Draw the displayed formulae and label the / isomers of but-2-ene.

ii Draw the / isomers of 1-bromo-2-chlorocyclobutane.

b The molecule CHBrClF exhibits optical isomerism. Draw the 3D displayed formulae of both optical
isomers.
c i Which one of the following can have optical isomers?

A H2C═CHCH3

B (CH3)2C═CHCHClCH3

C (CH3)3CBr

D CH3CH2CH2CHCl2

ii Draw the displayed formula of your chosen answer and clearly label its chiral centre.

d Consider the two molecules below, methylcyclohexane and 2-methylcyclohexanone:

Compare the number of chiral centres in each molecule and clearly label any chiral centres.

e Look back to the structure of the cholesterol molecule in Figure 14.7.

How many chiral centres are present in a cholesterol molecule?

A 2

B 4

C 6

D 8
14.7 Types of organic reaction and reaction
mechanisms
Chemists find it useful to explain organic reactions by summarising the overall reaction in a series of steps
called a reaction mechanism. Like all chemical reactions, organic reactions involve the breaking and
making of chemical bonds. There are two ways in which covalent bonds can break:

homolytic fission
heterolytic fission.

Homolytic fission
In this type of bond breaking, both the atoms at each end of the bond leave with one electron from the pair
that formed the covalent bond. This is shown in Figure 14.25, using the simple example of a hydrogen
chloride molecule.

Figure 14.25: Homolytic fission of a covalent bond.

The species produced when a bond breaks homolytically are called free radicals. We can show the
formation of free radicals by using an equation:

HCl → H· + Cl·

H· and Cl· are free radicals. All free radicals have an unpaired electron (represented by the dot) and are
very reactive.

You can read more about a free-radical reaction in Section 15.2.

This type of reaction involves the formation of the free radicals in an initiation step. This requires an input
of energy to break a covalent bond, resulting in two free radicals.
The radicals formed can then attack reactant molecules, generating more free radicals. These reactions are
called propagation steps. You can think of these as a chain reaction which only stops when free radicals
react with each other.

Two free radicals reacting together will form a molecule, with no free radicals generated. We call this a
termination step.

The three steps in a free-radical reaction are:

initiation step: the formation of free radicals to start a reaction off

propagation steps: steps in a mechanism that regenerate more free radicals
termination step: the final step in a mechanism, when two free radicals meet and form a product
molecule.

Heterolytic fission
The second type of bond breaking involves the ‘uneven’ breaking of a covalent bond. In heterolytic fission,
the more electronegative atom takes both electrons in the covalent bond. Again, we can use hydrogen
chloride to illustrate this (Figure 14.26).
Figure 14.26: Heterolytic fission of a covalent bond.

We can show this type of bond breaking in an equation. A small curly arrow shows the movement of a pair
of electrons:

The heterolytic fission of a bond can involve a C─X bond, where X is an atom more electronegative than
carbon.
For example:

In this case, as the bond breaks, the Br atom takes both shared electrons, forming a bromide anion (a
negatively charged ion). This leaves the methyl group one electron short, resulting in the formation of a
positively charged ion. This type of alkyl ion is called a carbocation. These positively charged
carbocations often appear in reaction mechanisms (see Section 16.3).

There are three types of carbocations that you need to consider: primary, secondary and tertiary
carbocations (Figure 14.27).

Figure 14.27: Carbocations and their stability relative to each other.

Note that the carbon atom with the positive charge only has three covalent bonds, not the usual four,
making it electron deficient. Any alkyl groups (e.g. ─CH3, ─C2H5, ─C3H7) attached to the positively charged
carbon atom tend to be ‘electron donating’. We say the alkyl groups have a positive inductive effect. The
arrowheads on the bonds in Figure 14.27 are used to show the inductive effect of atoms or groups of
atoms.

The alkyl groups ‘push’ electrons away from themselves, and reduce the charge density of the positive
charge on the carbocation. This has the effect of spreading out the charge around the carbocation, making
it energetically more stable. This means that a tertiary carbocation, with its three ‘electron-donating’ alkyl
groups is the most energetically stable of the three types of carbocation.
 IMPORTANT
The more alkyl groups adjacent to the positively charged carbon atom, the more stable the
carbocation.

As a result of this, tertiary carbocations are more likely to form in reaction mechanisms than secondary
carbocations, and primary carbocations are least favoured. This has effects on the products of some
organic reactions, such as addition reactions to alkenes (see Section 15.3).

Carbocations are an example of a species called an electrophile.

When an electrophile accepts a pair of electrons, this results in the formation of a new covalent bond (see
Section 15.3).

You will also meet nucleophiles when studying organic reactions and their mechanisms. These are
electron-rich species, i.e. they carry a negative (−), or partial negative (δ−), charge.

When a nucleophile donates a pair of electrons, this leads to the formation of a new covalent bond with the
electron-deficient atom under attack (see Section 18.4).

Question
7 a Write an equation to show the homolytic fission of the Cl─Cl bond in a chlorine molecule, Cl2.

b Write an equation to show the heterolytic fission of the C─Cl bond in chloromethane. Include a
curly arrow in your answer.

c Which one of the following species is likely to act as a nucleophile?

A H2

B H+

C OH−

d Explain your answer to part c.

e Which one of the following species is likely to act as an electrophile?

A H2

B H+

C OH−

f Explain your answer to part e.

g Which of these carbocations is most likely to form as an intermediate in an organic reaction?

Justify your answer.
14.8 Types of organic reaction
Addition reactions involve the formation of a single product from two or more reactant molecules. An
example is the addition reaction between an alkene and bromine (see Section 15.3):

C2H4 + Br2 → C2H4Br2

Elimination reactions result in the removal of a small molecule from a larger reactant molecule. An
example is the dehydration of an alcohol by concentrated sulfuric acid (see Section 17.3):

C2H5OH C2H4 + H2O

Condensation reactions involve a first step where addition takes place. This is followed by a second step
where elimination occurs to form the final product. You will meet condensation reactions in Chapter 18
when you study carbonyl compounds.

Substitution reactions involve the replacement of one atom, or a group of atoms, by another. For
example, the free-radical substitution of alkanes by chlorine in sunlight (see Section 15.2):

CH4 + Cl2 CH3Cl + HCl

Here, an H atom in CH4 has been replaced by a Cl atom.

Hydrolysis is the breakdown of a molecule by water. We can speed up this type of reaction by adding acid
or alkali. For example, the hydrolysis of a halogenoalkane by water to give an alcohol (see Section 16.2):

C2H5Br + H2O → C2H5OH + HBr

Hydrolysis with alkali is faster, and gives slightly different products:

C2H5Br + NaOH → C2H5OH + NaBr

Oxidation is defined as the loss of electrons from a species. However, in organic reactions it is often simpler
to think of oxidation reactions in terms of the number of oxygen and / or hydrogen atoms before and
after a reaction.
An example is the partial oxidation of ethanol to ethanal using acidified potassium dichromate(VI) solution
(see Section 17.3):

C2H5OH + [O] → CH3CHO + H2O

before the reaction ethanol contains one O atom and six H atoms
after the reaction ethanal contains one O atom and four H atoms.

In effect, the ethanol loses two H atoms, so we can say that ethanol has been oxidised.

Notice that we use [O] to simplify the chemical equation describing oxidation reactions. This is commonly
used, but the equation must still be balanced: just like a normal equation. For example, in the complete
oxidation of ethanol to ethanoic acid, using the reagents above but under harsher conditions (see Section
17.3):

C2H5OH + 2[O] → CH3COOH + H2O

[O] represents an oxygen atom from the oxidising agent. The 2 in front of the [O] is needed to balance the
equation for oxygen atoms.

For example, in the reduction of a ketone, using sodium tetrahydridoborate, NaBH4 (see Section 18.3):

CH3COCH3 + 2[H] → CH3CH(OH)CH3

Notice that we use [H] to simplify the chemical equation describing reduction reactions. [H] represents a
hydrogen atom from the reducing agent. The 2 in front of the [H] is necessary to balance the equation for
hydrogen atoms.

Question
8 Identify these reactions, choosing from the types of reaction described above:
 a C3H7I + H2O → C3H7OH + HI

b CH3CHO + 2[H] → CH3CH2OH

c C2H5Br → C2H4 + HBr

d C2H4 + H2O → C2H5OH

e C2H6 + Cl2 → C2H5Cl + HCl

REFLECTION

1 The ideas introduced in this chapter will all be revisited in later organic chemistry chapters. It will
be useful for you to create a mind map now of the various ideas introduced. Put ‘Organic
chemistry’ at the centre and label the links branching out to the new concepts. These could
include ‘functional groups’, ‘bonding’, ‘isomers’, ‘mechanisms’, ‘types of reaction’.

Your mind map will be useful to refer back to when studying the other organic chapters and when
revising for exams.

2 Swap your mind map with another learner and discuss similarities and differences. Discuss the
strengths and weaknesses in both mind maps.

Then explain to each other the process you both applied when constructing your mind map.
SUMMARY

We can represent an organic molecule, with increasing detail, by using its:

empirical formula
molecular formula
structural formula
displayed formula
3D displayed formula.

Functional groups give organic compounds their characteristic reactions.

Important functional groups include alkenes, alcohols, halogenoalkanes, aldehydes, ketones, carboxylic acids,
esters, amines and nitriles.

The shapes of organic molecules can be explained by the σ and π bonds between carbon atoms, and the
hybridisation of their atomic orbitals.

There are two types of isomer: structural isomers and stereoisomers.

Structural isomers have the same molecular formula but different structural formulae. We can group these into
position, functional group or chain isomers.

Stereoisomers have the same molecular formula but different arrangement of their atoms in space.
Cis/trans isomers arise because of the restricted rotation around a C═C double bond.
Optical isomers contain a chiral centre (a carbon atom bonded to four different atoms or groups of atoms),
resulting in mirror images of the molecule that cannot be superimposed.
EXAM-STYLE QUESTIONS

1 Which one of the following compounds does not need any numbers in its name? [1]

A CH3CH═CHCH3

B CH3COCH2CH3

C CH3CHBrCH2CH3

D CH3CHClCH2CH2Cl

2 Which one of the molecules below contains a chiral centre? [1]

3 Methylpropane, CH3CH(CH3)CH3, is commonly used in the petrochemical industry.

[1]
a i Name the homologous series that methylpropane belongs to.
[1]
ii Give the molecular formula of methylpropane.
[1]
iii Give the empirical formula of methylpropane.
[1]
iv Draw the displayed formula of methylpropane.
[1]
v Draw the skeletal formula of methylpropane.

b Each carbon atom in methylpropane has hybridised atomic orbitals.

i What type of hybridisation is found in a molecule of methylpropane?

A sp hybridisation

B sp2 hybridisation

C sp3 hybridisation
[1]
D sp4 hybridisation
[1]
ii Give the bond angles found within a molecule of methylpropane.

c When methylpropane is passed over a hot aluminium oxide catalyst, it can be converted
into methylpropene.
[1]
i To which homologous series of organic compounds does methylpropene belong?

ii Methylpropene can be converted back into methylpropane by heating with

hydrogen gas in the presence of a platinum / nickel catalyst:

H2C═C(CH3)CH3 + H2 CH3CH(CH3)CH3
What type of reaction best describes this reaction?

A Oxidation

B Elimination
 C Hydrolysis
[1]
D Addition
[1]
d i Draw the displayed formula of a structural isomer of methylpropene.
[1]
ii Give the empirical formula of both isomers. [Total: 13]
4 A carbon compound P has the percentage composition 85.7% carbon and 14.3% hydrogen. Its
relative molecular mass was found to be 56.
[4]
a i Calculate its empirical formula.
[1]
ii Calculate its molecular formula.

b Write down the names and displayed formulae of all the non-cyclic isomers of compound
P which have the following characteristics:
[6]
i straight chain
[2]
ii branched chain. [Total: 13]
5 A chemist was investigating the best way to produce 1,2-dichloroethane. She devised two
methods, I and II, of doing this.

I She reacted ethane with chlorine in the presence of UV light by the following reaction:
C2H6(g) +2Cl2(g) →C2H4Cl2(l) + 2HCl(g)

After doing this she found that 600 g of ethane gave 148.5 g of C2H4Cl2.
[1]
a i Calculate how many moles of ethane there are in 600 g.

ii Deduce how many moles of 1,2-dichloroethane would have been formed if the yield [1]
had been 100%.
[1]
iii Calculate how many moles of 1,2-dichloroethane there are in 148.5 g.
[1]
iv Calculate the percentage yield of 1,2-dichloroethane.

II She reacted ethene with chlorine in the dark by the following reaction:
C2H4(g) + Cl2(g) → C2H4Cl2(l)

b In this reaction 140 g of ethene gave 396 g of C2H4Cl2.

[3]
Calculate the percentage yield for this reaction. Show your working.

c There are isomers of the compound C2H4Cl2.

[4]
Draw the displayed formulae of the isomers and name them.

d Choose from:

A redox

B substitution

C elimination

D addition

E hydrolysis

to give the type of reaction for:

[1]
i reaction I
[1]
ii reaction II. [Total: 13]
SELF-EVALUATION

After studying this chapter, complete a table like this:

See Needs Almost Ready to

I can section... more work there move on

define the term hydrocarbon and describe what alkanes are 14.1

interpret, name and use the general, structural, displayed and

14.1,
skeletal formulae of all the homologous series introduced in
14.2, 14.3
this chapter

deduce the molecular and/or empirical formula of a

14.1
compound, given its structural, displayed or skeletal formula

explain the following terms:

a functional group
b homolytic and heterolytic fission
c free radical
d initiation
e propagation
f termination
g nucleophile
h electrophile 14.1,
i nucleophilic 14.7, 14.8
j electrophilic
k addition
l substitution
m elimination
n hydrolysis
o condensation
p oxidation
q reduction

describe and explain the shape of, and bond angles of, organic
molecules in terms of their sp, sp2 and sp3 hybridised atomic 14.4
orbitals, and their σ bonds and π bonds

describe and explain the different types of structural

14.5, 14.6
isomerism and stereoisomerism.

explain and identify isomerism, including chiral centres and

14.6
geometrical isomers

deduce possible isomers from a given molecular formula 14.5, 14.6

images

Chapter 15
Hydrocarbons

LEARNING INTENTIONS
In this chapter you will learn how to:

explain the general unreactivity of alkanes, and describe their complete and incomplete combustion
explain the free-radical substitution of alkanes by chlorine and by bromine, as shown by their three-step mechanism

suggest how cracking can be used to obtain more useful alkanes and alkenes of lower relative molecular mass from
larger hydrocarbon molecules

describe the environmental consequences of burning hydrocarbon fuels in vehicles and the removal of pollutants by
catalytic converters
describe the reactions of alkenes as shown by their addition, oxidation and polymerisation
describe the mechanism of electrophilic addition in alkenes, and explain the inductive effects of alkyl groups on the
stability of cations formed
describe the difficulty of disposing of waste poly(alkene)s.

BEFORE YOU START

1 Here are four types of hybridisation of carbon atomic orbitals:

only sp

only sp2

only sp3

sp2 and sp3

Which do you find in the following molecules?

a ethane

b ethene
c propene.

2 a Give the names of:

i CH3CH2CH(CH3)CH3

ii CH3CH2CH2CH═CH2

b Give the structural formulae of:

i 2,3-dimethylhexane

ii pent-2-ene.

3 a Are alkyl groups ‘electron withdrawing’ or ‘electron donating’ to their neighbouring carbon
atom?

b Which type of carbocation is most energetically stable: primary, secondary or tertiary

carbocation?

4 Working with a partner, discuss the difference between an electrophile and a nucleophile, and what
we mean by a ‘reaction mechanism’.

HYDROCARBONS IN USE
Crude oil (Figure 15.1) is our main source of hydrocarbons. Hydrocarbons are compounds containing
carbon and hydrogen only. They provide us with fuels such as petrol, diesel and kerosene.
Hydrocarbons are also the starting compounds used to make many new compounds, such as most of
the plastics we use in everyday life.

Crude oil is a complex mixture of hydrocarbons. It contains alkanes, cycloalkanes and arenes
(compounds containing benzene rings – see Chapter 25).
Cycloalkanes are saturated hydrocarbons in which there is a ‘ring’ consisting of three or more carbon
atoms. Imagine the two carbon atoms at each end of a straight-chain alkane bonding to each other.
These two carbon atoms could then only bond to two hydrogen atoms each, not three as in the
straight-chain alkane. Cyclohexane, C6H12, is an example (Figure 15.2). Note that a cycloalkane does
not follow the general alkane formula, CnH2n+2.
Figure 15.1: Crude oil is extracted from porous seams of rock found beneath an impervious layer of rock within the
Earth’s crust.
Figure 15.2: Hexane (C6H14) and cyclohexane (C6H12).

The crude oil is brought to the surface at oil wells and transported to an oil refinery. The actual
composition of crude oil varies in different oilfields around the world.

At the refinery, the crude oil is processed into useful fuels. The first step is fractional distillation of the
oil. This separates the wide range of different hydrocarbons into fractions. The hydrocarbons in each
fraction will have similar boiling points. This is carried out in tall fractionating columns.

The oil-based compounds that are in high demand are the gasoline fraction (providing petrol) and the
naphtha fraction (providing the starting compounds for making many other chemicals in industry).

Questions for discussion

Discuss with another learner or group of learners:

As you know, the supplies of crude oil are a finite resource and they are rapidly running out. One way
to conserve the oil we have left is to switch from petrol and diesel cars to electric cars. Discuss the
difficulties in making the switch to electric vehicles, as well as the benefits it will bring. Then feedback
your main points to the rest of your group.
15.1 The homologous group of alkanes
The majority of compounds found in the mixture of hydrocarbons we call crude oil are alkanes. We met the
first ten members of this homologous series in Table 14.2. The general formula for the alkanes is CnH2n+2.
For example, the molecular formula of pentane, in which n = 5, is C5H12 (Figure 15.3).

Figure 15.3: Three different ways of representing pentane molecules.

Note that all the carbon–carbon bonds are single covalent bonds. The carbon atoms all display sp3
hybridisation (see Section 4.5). This means that alkanes have the maximum number of hydrogen atoms in
their molecules, and are known as saturated hydrocarbons (Figure 15.4).

Figure 15.4: The 3D displayed formula shows the tetrahedral arrangement of atoms around each carbon atom
(approximate bond angles of 109.5º).

Question
1 a Eicosane is a straight-chain alkane whose molecules contain 20 carbon atoms.

i What is the molecular formula of eicosane?

ii Draw the skeletal formula of eicosane.

b Draw the displayed formula and the skeletal formula of cyclopentane.

c What is the general formula of cycloalkanes?

d Give two differences between a molecule of cyclopentane and a molecule of pentane.

15.2 Reactions of alkanes
The alkanes are generally unreactive compounds. We can explain this by the very small difference in
electronegativity between carbon and hydrogen. Their atoms share the pair of electrons in the single
covalent bonds almost equally. Therefore, alkane molecules are non-polar, so they are not attacked by
nucleophiles or electrophiles (Figure 15.5). They have no partial positive charges (δ+) on any of their
carbon atoms to attract nucleophiles, neither do they have areas of high electron density to attract
electrophiles (see Section 14.7).

However, the alkanes do react with oxygen in combustion reactions and also undergo substitution by
halogens in sunlight. These reactions are covered in the following sections.

Figure 15.5: Non-polar alkanes do not react with polar compounds such as water. The hexane is dyed with iodine to make
it coloured, so it is more clearly visible. The hexane and water in the test-tube are immiscible: they do not mix and they do
not react with each other.

Combustion of alkanes
Alkanes are often used as fuels (Figure 15.6). We burn them for many reasons:

to generate electricity in power stations,

to heat our homes and cook our food
to provide energy needed in industrial processes
to provide fuel for ships, aeroplanes, trains, lorries, buses, cars and motorbikes.
Figure 15.6: Alkanes are useful fuels.

If we burn an alkane in plenty of oxygen, the alkane will undergo complete combustion. All the carbon will
be oxidised fully to form carbon dioxide, and all the hydrogen will be oxidised to form water:

alkane + oxygen carbon dioxide + water

For example, octane is one of the alkanes in petrol that is burned inside the internal combustion engine in
motor vehicles. Some of the octane will undergo complete combustion in a car engine:

2C8H18 + 25O2 → 16CO2 + 18H2O

octane + oxygen → carbon dioxide + water

The equation can also be written as:

C8H18 + 12 O2 → 8CO2 + 9H2O

Pollution from burning hydrocarbon fuels

When the petrol or diesel is mixed with air inside a car engine, there is only a limited supply of oxygen.
Under these conditions, not all the carbon in the hydrocarbon fuel is fully oxidised to carbon dioxide. Some
of the carbon is only partially oxidised to form carbon monoxide (CO) gas. This is called incomplete
combustion.

For example:

2C8H18 + 17O2 16CO + 18H2O

octane + oxygen carbon monoxide + water

or

C8H18 + 8 O2 → 8CO + 9H2O

Carbon monoxide is a toxic gas that bonds with the haemoglobin in your blood. The haemoglobin
molecules can then no longer bond to oxygen and so cannot transport oxygen around your body. Victims of
carbon monoxide poisoning will feel dizzy, then lose consciousness. If not removed from the toxic gas, the
victim will die.

Carbon monoxide is odourless, so this adds to the danger. This is why faulty gas heaters in which
incomplete combustion occurs can kill unsuspecting people in rooms with poor ventilation.

As well as releasing carbon monoxide, road traffic also releases acidic nitrogen oxides, mainly NO and NO2.
These contribute to the problem of acid rain (see Section 13.3). Acid rain can kill trees and aquatic animals
in lakes (Figure 15.7). Acid rain also erodes limestone buildings and statues, as well as corroding metals,
such as iron.

Figure 15.7: These trees have been badly damaged by acid rain.

In normal combustion, nitrogen gas in the air is not oxidised. However, in the very high temperatures in car
engines, oxidation of nitrogen does take place. A variety of nitrogen oxides can be formed and released in
the car’s exhaust fumes (Figure 15.8). For example:

N2(g) + O2(g) ⇌ 2NO(g)

2NO(g) + O2(g) ⇌ 2NO2(g)

Figure 15.8: The vast numbers of cars on the roads pollute our atmosphere. Nitrogen oxides from traffic contribute to
photochemical smog, as well as acid rain.

As well as toxic carbon monoxide and acidic nitrogen oxides, cars also release unburnt hydrocarbons, often
referred to as volatile organic compounds (VOCs), into the air. Some of these are carcinogens (they cause
cancers) and can form PAN, a contributor to photochemical smog (see Section 13.3).

Reducing traffic emissions

Motor vehicles can now be fitted with catalytic converters in their exhaust systems (Figure 15.9). Once
warmed up, a catalytic converter can cause the following reactions to take place:

the oxidation of carbon monoxide to form carbon dioxide

the reduction of nitrogen oxides to form harmless nitrogen gas
the oxidation of unburnt hydrocarbons to form carbon dioxide and water.

Unfortunately, catalytic converters can do nothing to reduce the amount of carbon dioxide (a greenhouse
gas) given off in the exhaust gases of cars and trucks.
Figure 15.9: Catalytic converters reduce the pollutants from car exhausts. Precious metals, such as platinum, are coated
on a honeycomb structure to provide a large surface area on which the reactions can occur.

The following equation describes the reaction between carbon monoxide and nitrogen monoxide. It takes
place on the surface of the precious metal catalyst in a catalytic converter:

2CO + 2NO → 2CO2 + N2

Some of the carbon monoxide gas can also be oxidised inside the hot catalytic converter:

2CO + O2 → 2CO2

Note that more carbon dioxide is released in the process of removing carbon monoxide. Carbon dioxide is
not a toxic gas, but it is still considered a pollutant because of its contribution to enhanced global warming,
resulting in climate change.

Question
2 a Predict what would happen if octane was added to a solution of sodium hydroxide.

b Explain your answer to part a.

c Give the balanced symbol equations for:

i the complete combustion of heptane, C7H16, giving carbon dioxide and water

ii the incomplete combustion of methane, CH4, giving carbon monoxide and water

iii the incomplete combustion of nonane, C9H20, giving carbon monoxide and water.

d i Name two pollutants from a car engine that can be oxidised in a catalytic converter.

ii Name a pollutant that is reduced in a catalytic converter.

iii Which pollutant from a car engine is not reduced by the use of a catalytic converter? What
environmental problem does this pollutant contribute to?

Now swap your answers with another learner and compare your responses. Discuss any differences,
and arrive at an agreed set of answers before looking up the correct answers online.
Substitution reactions of alkanes
The alkanes will undergo substitution reactions with halogens in sunlight.

Consider the reaction between ethane and chlorine in sunlight:

In this reaction, a hydrogen atom in the ethane molecule gets replaced by a chlorine atom. However, this
type of reaction does not take place in darkness (Figure 15.10). So what role does the sunlight play in the
mechanism of this substitution reaction?

Initiation step
The first step in the mechanism is the breaking of the Cl─Cl bond by energy from ultraviolet light in
sunlight. This is called the initiation step in the mechanism:

Figure 15.10: A substitution reaction takes place between alkanes and bromine in sunlight, but there is no reaction in
darkness.

As the Cl─Cl bond breaks, each chlorine atom takes one electron from the pair of electrons in the Cl─Cl
bond. This is an example of homolytic fission of a covalent bond (see Section 14.7). Two Cl atoms are
formed. These Cl atoms, each with an unpaired electron, are called free radicals.

Propagation steps
Free radicals are very reactive. They will attack the normally unreactive alkanes. A chlorine free radical will
attack the ethane molecule:

CH3CH3 + Cl· → ·CH2CH3 + HCl

In this propagation step, a C─H bond in CH3CH3 breaks homolytically. An ethyl free radical, ·CH2CH3, is
produced. This can then attack a chlorine molecule, forming chloroethane and regenerating a chlorine free
radical:

·CH2CH3 + Cl2 → CH3CH2Cl + Cl·

Then the first propagation step can be repeated as the chlorine free radical can attack another ethane
molecule. This forms the ethyl free radical, which regenerates another chlorine free radical, and so on.

The word ‘propagation’ usually refers to growing new plants. In this mechanism the substitution reaction
progresses (grows) in a type of chain reaction.

This reaction is not really suitable for preparing specific halogenoalkanes, because we get a mixture of
substitution products. In the reaction between ethane and chlorine, the products can include many
different chloroalkanes. These can include 1,1-dichloroethane, 1,1,1 trichloroethane, 1,2-dichloroethane,
1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, and so on, as well as chloroethane. If there is enough
chlorine present, we eventually get hexachloroethane (C2Cl6), This variety of chloroalkane products results
from propagation steps in which a chlorine free radical attacks a chloroalkane already formed.

For example:

CH3CH2Cl + Cl· → ·CH2CH2Cl + HCl

This can then be followed by:

The more chlorine gas in the reaction mixture to start with, the greater the proportions of chlorine atoms in
the chloroalkane molecules formed.

Termination steps
Whenever two free radicals meet they will react with each other. A single molecule is the only product. As
no free radicals are made that can carry on the reaction sequence, the chain reaction stops. Examples of
termination steps include:

IMPORTANT

In the initiation step, we start with a molecule and get two free radicals formed.
In each propagation step, we start with a molecule and a free radical and get a different molecule
and a different free radical formed.
In the termination steps, we start with two free radicals and end up with a molecule and no free
radicals.

Overall, the reaction between alkanes and halogens, involving initiation, propagation and termination
steps, is called free-radical substitution.

Question
3 Bromine can react with ethane to form bromoethane.

a What conditions are needed for the reaction between ethane and bromine to take place?

b What do we call this type of reaction?

c Write an equation to show the reaction of ethane and bromine to form bromoethane.

d Why is this reaction not a good way to prepare a pure sample of bromoethane?
 e i Name the three steps in the mechanism of this reaction.

ii Write an equation to show the first step in the mechanism.

iii What type of bond breaking does this first step involve?

REFLECTION
1 At this point, reflect on your work done studying the ‘alkanes’. Make a two-column table to record
‘New things I know about the alkanes’ / ‘New things that I do not really understand yet’.

2 Discuss your table with a fellow learner and explain to each other exactly where your problems lie.
If you can’t sort out any of your difficulties together, ask your teacher to help.
15.3 The alkenes
We have looked at the nature of the double bond found in the hydrocarbons called alkenes in Section 14.4.
Alkenes with one double bond per molecule have the general formula CnH2n. One example is ethene, C2H4.
Whereas alkanes, which contain only single bonds, are described as saturated hydrocarbons, we describe
alkenes as unsaturated hydrocarbons.

Oil refineries provide useful alkenes for the chemical industry. In the introduction to this chapter, we saw
how crude oil is separated into fractions at a refinery. Oil companies find that the demand for each fraction
differs. The lighter fractions, such as the gasoline fraction, are in high demand. So, chemical engineers
convert some of the excess heavier fractions into lighter hydrocarbons. The large, less useful hydrocarbon
molecules are broken down into smaller, more useful molecules. The process is called cracking.

The larger hydrocarbon molecules are fed into a steel chamber that contains no oxygen, so combustion
does not take place. The larger hydrocarbon molecules are heated to a high temperature and are passed
over an aluminium oxide, Al2O3, catalyst (Figure 15.11).
Figure 15.11: a A catalytic cracker occupies the bulk of the central part of this view of an oil refinery. b A computer
graphic showing a catalyst used to crack hydrocarbons.

When large alkane molecules are cracked, they form smaller alkane molecules and alkene molecules. One
possible example of a cracking reaction is:

CH3(CH2)8CH3 CH3(CH2)4CH3 + CH2═CHCH2CH3

C10H22 C6H14 + C4H8

The low-molecular mass alkanes formed (C6H14 in this example) make very useful fuels and are in high
demand. However, the alkenes produced (C4H8 in this example) are also very useful. They are more
reactive than the alkanes because of their double bonds. This makes them useful for the chemical industry
as the starting compounds (feedstock) for making many new products. These include most plastics (see
Section 15.5).

As well as the cracking of alkanes, alkenes can also be made by:

elimination of a hydrogen halide (e.g. HCl) from a halogenoalkane by heating with ethanolic sodium
hydroxide (see Section 16.4)
dehydration of an alcohol by using a heated catalyst (e.g. aluminium oxide, Al2O3) or a concentrated
acid (see Section 17.3).

Dehydration is the elimination of a water molecule from a reactant molecule.

Question
4 a Name the first member of the homologous series of alkenes.

b Give the molecular formula of the alkene containing 18 carbon atoms and one C═C bond.

c Look at the equation for cracking given in the text. Write a word equation for this reaction.

d Write a balanced equation to show the cracking of nonane into heptane and ethene.

e Discuss and suggest why ‘Alkenes are more reactive than alkanes’. Think about whether
electrophiles or nucleophiles would attack alkenes and explain your choice.

Addition reactions of the alkenes

Most reactions of the alkenes are examples of addition reactions. In these reactions one of the two bonds in
the carbon–carbon (C═C) double bond is broken and a new single bond is formed from each of the two
carbon atoms.

The general addition reactions are shown in Figure 15.12.

Figure 15.12: General equations for addition reactions of the alkenes: a with a hydrogen halide, such as hydrogen
bromide, and b with a halogen, such as chlorine.

Addition of hydrogen, H2(g)

When hydrogen gas and an alkene are heated and passed over a finely divided platinum / nickel catalyst,
the addition reaction produces an alkane:

The addition reaction of alkenes with hydrogen is called hydrogenation, and is used in the manufacture of
margarine (Figure 15.13).

Figure 15.13: Unsaturated oils, such as sunflower oil, contain hydrocarbon chains with several carbon–carbon double
bonds. These oils become partially saturated by reacting them with hydrogen, straightening their hydrocarbon chains. This
raises the melting points of the oils, changing them from liquids to soft solids that can be spread easily.

Addition of hydrogen halides, HX(aq)

When an alkene is bubbled through a concentrated solution of a hydrogen halide (either HF, HCl, HBr or HI)
at room temperature, the product is a halogenoalkane. For example:

With longer, asymmetric alkenes there are always two possible products that could be formed.

For example, with propene:

and

IMPORTANT
Where two addition products are possible, the major product is the one that has the halogen atom
bonded to the C═C carbon atom with the highest number of alkyl groups bonded to it.

In the two reactions of propene with HBr shown, the Br bonds to the central C atom to form the major
product. The central C atom has two alkyl (methyl) groups bonded to it compared with the single alkyl
(ethyl) group on the end C atom. Therefore, CH3CHBrCH3 is the major product.

We can explain why this happens by thinking back to the stability of the carbocations discussed in Section
14.7. Remember that each alkyl group tends to donate electrons along its bond to the positively charged
carbon atom in the carbocation. The CH3CHBrCH3 is formed from a secondary carbocation intermediate,
CH3C+HCH3. In Section 14.7 we saw that a secondary carbocation is more stable than a primary
carbocation, in this case CH3CH2C+H2. This is because the positive charge becomes less concentrated by
the inductive effect of two alkyl groups rather than just one alkyl group. Therefore, the secondary
carbocation intermediate is more readily formed in the course of the addition reaction.

The mechanism of electrophilic addition that follows shows how:

a carbocation forms
which is then attacked by a negative ion
to give the final product of the addition reaction.

Figure 15.14: The mechanism for the electrophilic addition of HBr to propene.

Addition of steam, H2O(g)

Scientists in industry use the addition of steam to alkenes to make alcohols. They react steam and the
gaseous alkene at a high temperature and pressure, in the presence of concentrated phosphoric acid,
H3PO4, as the catalyst. When the alkene is ethene, the product is ethanol (Figure 15.15). However, the
ethanol found in alcoholic drinks is always produced by the fermentation of glucose.
Figure 15.15: The addition reaction between ethene and steam.

Addition of halogens, X2(aq)

If we bubble an alkene through a solution of chlorine or bromine at room temperature, we again get an
addition reaction. The colour of the halogen molecules in solution is removed in the course of the reaction
(Figures 15.16 and 15.17).

Figure 15.16: The reaction between ethene and bromine.

The reactant Cl2(aq) is a very pale green solution, called chlorine water. Bromine water, Br2(aq), is orange
or yellow, depending on the concentration of bromine water.

Bromine water is used to test for the presence of the C═C bond in compounds. The compound to be tested
is shaken with bromine water. If it is unsaturated, the bromine water will be decolorised.

Figure 15.17: The addition reaction used to test for an unsaturated compound.

The mechanism of electrophilic addition to alkenes

In Section 14.4 we saw how the double bond in ethene is formed from a σ (sigma) bond and a π (pi) bond.
There are four electrons in total in this double bond. So although ethene is a non-polar molecule, there is
an area of high electron density around the C═C bond. This makes the alkenes open to attack by
electrophiles (see Section 14.7).

Remember that an electrophile is an acceptor of a pair of electrons. HBr is a polar molecule because of the
difference in electronegativity between the H atom and the Br atom. In a molecule of HBr, the H atom
carries a partial positive charge and the Br atom carries a partial negative charge.

In the mechanism of addition, the H atom acts as the electrophile, accepting a pair of electrons from the
C═C bond in the alkene. Look back to Figure 15.14.
But how can a non-polar molecule such as Br2 act as an electrophile? As the bromine molecule and ethene
molecules approach each other, the area of high electron density around the C═C bond repels the pair of
electrons in the Br─Br bond away from the nearer Br atom. This makes the nearer Br atom slightly positive
and the further Br atom slightly negative. Figure 15.18 shows the mechanism of electrophilic addition.
Figure 15.18: The mechanism of the electrophilic addition of bromine to ethene.

As the new bond between the C and Br atom forms, the Br─Br bond breaks heterolytically (see Section
14.7). The Br− ion formed then attacks the highly reactive carbocation intermediate. So, one bromine atom
bonds to each carbon atom, producing 1,2-dibromoethane.

Question
5 a State the general conditions used in the reaction between an alkene and hydrogen.

b Name the product formed when propene reacts with chlorine.

c Ethanol can be used as a solvent.

How is this ethanol made in industry?

d What will be formed when ethene gas is bubbled through a concentrated solution of hydrochloric
acid?

e Define the term electrophile.

f Explain how a chlorine molecule can act as an electrophile in its reaction with an alkene.

g Discuss and then draw the mechanism for the reaction between ethene and chlorine.
15.4 Oxidation of the alkenes
Alkenes can be oxidised by acidified potassium manganate(VII) solution, KMnO4(aq), which is a powerful
oxidising agent. The products formed will depend on the conditions chosen for the reaction. In Figure 15.18,
the R, R1 and R2 are alkyl groups.

PRACTICAL ACTIVITY 15.1

Cold dilute acidified manganate(VII) solution

If an alkene is shaken with a dilute solution of acidified potassium manganate(VII), KMnO4(aq), at room
temperature, the pale purple solution turns colourless. The alkene is converted into a diol, i.e. a
compound with two alcohol (O─H) groups:

This reaction can be used as a test to find out whether a compound is unsaturated. However, the
decolourisation of bromine water is a more commonly used test (see Section 15.3).

Hot concentrated acidified manganate(VII) solution, KMnO4

Under these harsher conditions, the C═C double bond in the alkene is broken completely. The O─H groups
in the diol formed initially are further oxidised to ketones, aldehydes, carboxylic acids or carbon dioxide
gas. The actual products depend on what is bonded to the carbon atoms in the C═C double bond.

Figure 15.19 shows the oxidation products from each type of group bonded to a carbon atom in the C═C
bond.
Figure 15.19: Oxidation of alkenes with hot, concentrated potassium manganate(VII) solution, KMnO4(aq).

To see what is formed when we heat 2-methylprop-1-ene with hot, concentrated acidified KMnO4(aq), look
at equations 1 and 3 in Figure 15.19. The actual oxidation can be represented as:

═ ═

We can use this reaction to determine the position of the double bond in larger alkenes. To do this we
would need to identify the products of the oxidation reaction and work backwards to deduce the original
alkene.

If, for example, carbon dioxide is given off in the oxidation, this tells us that the double bond was between
the end two carbon atoms in the alkene.

We can summarise the oxidations under harsh conditions (using a hot, concentrated solution of potassium
manganate(VII)) in three reactions.

1 If a carbon atom is bonded to two hydrogen atoms, we get oxidation to a CO2 molecule.

H2C═CH2 → CO2 + CO2

2 If a carbon atom is bonded to one hydrogen atom and one alkyl group, we get oxidation to a COOH
(carboxylic acid) group.
 RHC═CHR → RCHO + RCHO → RCOOH + RCOOH

3 If a carbon atom is bonded to two alkyl groups, we get oxidation to a C═O (ketone) group.

R1R2C═CR3R4 → R1R2C═O + R3R4C═O

Question
6 a Draw the displayed formula of the organic product formed when propene is oxidised by a cold
solution of acidified potassium manganate(VII).

Name the compound.

b Draw the displayed formula of the organic product formed when but-2-ene is oxidised by a cold
solution of acidified potassium manganate(VII).

Name the compound.

c Methylbut-2-ene is heated with concentrated acidified potassium manganate(VII) solution.

i Draw the displayed formulae of the products and name them.

ii Write a balanced chemical equation for this reaction, using [O] to show oxygen atoms
involved.

Compare your answers to Question 6 with another learner. Use your combined answers to create a
mark scheme showing where each mark could be awarded.
15.5 Addition polymerisation
Probably the most important addition reaction of the alkenes forms the basis of much of the plastics
industry. Molecules of ethene, as well as other unsaturated compounds, can react with each other under
the right conditions to form polymer molecules.

A polymer is a long-chain molecule made up of many repeating units. The small, reactive molecules that
react together to make the polymer are called monomers. Up to 10 000 ethene monomers can bond
together to form the polymer chains of poly(ethene). Poly(ethene) is commonly used to make carrier bags.

We can show the polymerisation reaction of ethene as:

or by using the displayed formulae:

The section of the polymer shown in the brackets is the repeat unit of the polymer.

The reaction is called addition polymerisation. As in other addition reactions of the alkenes, it involves
the breaking of the π bond in each C═C bond. Then the monomers link together.

Other alkenes and substituted alkenes also polymerise to make polymers with different properties.
Examples of other poly(alkenes) include poly(propene) and poly(chloroethene).
We can show the polymerisation of propene as:

nC3H6 → [ C3H6 ] n

or, using structural formulae:

The polymer chain has methyl (─CH3) groups sticking out from the carbon skeleton of the poly(propene).
We can show this as in Figure 15.20.

Figure 15.20: This shows a regular arrangement of the methyl groups along the poly(propene) polymer chain.

We can also represent the polymer by showing part of its structure using a 3D displayed formula, as shown
in Figure 15.21.
Figure 15.21: A 3D displayed formula of a small section of the poly(propene) molecule.

Question
7 Which one of the following statements is correct?

Discuss all the options with a partner, and explain why each is either correct or incorrect.

A Poly(propene) and poly(ethene) will both decolorise bromine water.

B Poly(ethene) is a saturated hydrocarbon.

C Poly(propene) will melt at a lower temperature than propene.

D The polymerisation of ethene is an example of an electrophilic substitution reaction.

More about addition polymers

We can also use substituted alkenes, such as chloroethene, as monomers:

The [ H2C─CHCl ] section of the polymer chain is the called the repeat unit of poly(chloroethene)
(Figure 15.22).

Figure 15.22: A 3D displayed formula of a small section of the poly(chloroethene) molecule. Its common name is PVC, as
the old name for chloroethene was vinyl chloride.

In poly(alkenes) and substituted poly(alkenes) made of one type of monomer, the repeat unit is the same
as the monomer except that the C═C double bond is changed to a C─C single bond.

Notice that, as in any other addition reaction of the alkenes, addition polymerisation yields only one
product.
 IMPORTANT
Remember that:

the section of the polymer chain shown inside the square brackets by its structural or displayed
formula is called its repeat unit
addition polymerisation is characterised by:

monomers which are unsaturated, e.g. contain a C═C double bond

the polymer being the only product of the reaction.

Disposal of poly(alkene) plastics

Plastics are widely used in many aspects of everyday life. However, the large-scale use of poly(alkene)s
has created a problem when we come to dispose of them. During their life, one of the most useful
properties of poly(alkene)s is their lack of reactivity.

As poly(alkene)s are effectively huge alkane molecules, they are resistant to chemical attack. So they can
take hundreds of years to decompose when dumped in landfill sites, taking up valuable space. They are
non-biodegradable. Therefore, throwing away poly(alkenes) creates rubbish that will pollute the
environment for centuries (Figure 15.23).

Figure 15.23: A beach littered with poly(alkene) plastic waste.

Burning plastic waste

One way to solve this problem would be to burn the poly(alkene)s and use the energy released to generate
electricity. As we have seen in Section 15.2, if hydrocarbons burn in excess oxygen, the products are
carbon dioxide and water. This solution would not help combat global warming, but would help to conserve
our supplies of fossil fuels that currently generate most of our electricity. However, we have also seen that
toxic carbon monoxide is produced from the incomplete combustion of hydrocarbons.

Another problem is the difficulty recycling companies have in separating other plastic waste from the
poly(alkene)s. This happens when objects have just been thrown away and not been sorted according to
their recycling code. Also, if poly(chloroethene) waste is burnt, acidic hydrogen chloride gas will be given
off, as well as toxic compounds called dioxins. Acidic gases should be neutralised before releasing the
waste gases into the atmosphere. Very high temperatures should be used in incinerators to break down
any toxins.
15.6 Tackling questions on addition polymers
In your exam, you might be asked to:

1 deduce the repeat unit of a polymer obtained from a given unsaturated monomer

2 identify the monomer(s) present in a given section of a polymer molecule.

Deducing the repeat unit of an addition polymer for given

monomer(s)
If you are given a monomer with a C═C double bond, simply turn the double bond into a C─C single bond
and show the bonds either side of the two C atoms that would continue the chain:

Identifying the monomer(s) present in a given section of an

addition polymer molecule
First of all, you should split the polymer chain into its repeat units.

With an addition polymer, you then need to put the C═C double bond back into the monomer:

Question
8 Tetrafluoroethene, C2F4, is the monomer for the polymer PTFE, which is used in the non-stick coating
on pans.

a State what PTFE stands for.

 b Give the name of the type of reaction used to form PTFE.

c Write a chemical equation to show the formation of PTFE from C2F4.

d Draw the structure of the repeat unit in PTFE.

e How could poly(alkene) waste be used to conserve fossil fuels?

f Why would your answer to part e add to the problem of enhanced global warming?

g A waste batch of poly(ethene) pellets was burnt in an inefficient industrial incinerator.

h Name a toxic gas that would be released.

i Name the monomer used to make this polymer:

REFLECTION
1 Working as a pair, each write a question and its mark scheme. One of you should devise an
assessment of the free-radical substitution of an alkane, while the other assesses the electrophilic
addition to an alkene. You can use the Exam-style Questions in this coursebook to help with the
style of your question and on-line answers to write a typical mark scheme. However, your question
and answers should be your own work.

Then try to answer each other’s questions, giving your answers back for your partner to mark
using their mark scheme.

2 Use this exercise to give you an idea of your understanding of the key reactions of alkanes and
alkenes. What have you learned from the activity?
SUMMARY

Alkanes are saturated hydrocarbons with the general formula CnH2n+2.

Alkanes are relatively unreactive as they are non-polar. Most reagents are polar and do not usually react with non-
polar molecules.

Alkanes are widely used as fuels. When they burn completely they produce carbon dioxide and water. However,
they produce toxic carbon monoxide gas when they burn in a limited supply of oxygen, e.g. in a car engine.

Cracking of the less useful fractions from the fractional distillation of crude oil produces a range of more useful
alkanes with lower molecular masses, as well as alkenes.

Chlorine atoms or bromine atoms can substitute for hydrogen atoms in alkanes in the presence of ultraviolet light,
producing halogenoalkanes. This is called a free-radical substitution reaction. The Cl─Cl or Br─Br bond undergoes
homolytic fission in ultraviolet light, producing reactive Cl· or Br· free radicals. This initiation step is followed by
propagation steps involving a chain reaction which regenerates the halogen free radicals. Termination steps occur,
when two free radicals combine.

Alkenes are unsaturated hydrocarbons with one carbon–carbon double bond consisting of a σ bond and a π bond.
Their general formula is CnH2n.

Alkenes are more reactive than alkanes because they contain a π bond. The characteristic reaction of the alkenes is
addition, which occurs across the π bond:
ethene produces ethane when heated with hydrogen gas over a platinum / nickel catalyst: this is called
hydrogenation
ethene produces 1,2-dibromoethane when reacted with bromine water at room temperature
ethene produces chloroethane when reacted with hydrogen chloride gas at room temperature
ethene produces ethanol when reacted with steam, in the presence of concentrated H3PO4 catalyst.

The mechanism of the reaction of bromine with ethene is electrophilic addition. Electrophiles accept a pair of
electrons from an electron-rich atom or centre, in this case the π bond. A carbocation intermediate is formed after
the addition of the first bromine atom. This rapidly reacts with a bromide ion to form 1,2-dibromoethane.

Mild oxidation of alkenes by cold, dilute acidified manganate(VII) solution gives a diol. However, a hot, concentrated
acidified manganate(VII) solution will break the C═C bond and give two oxidation products. Identifying the two
products formed will indicate the position of the C═C bond in the original alkene.

Alkenes produce many useful polymers by addition polymerisation. For example, poly(ethene) is made from
CH2═CH2, and poly(chloroethene) is made from CH2═CHCl.

The disposal of poly(alkene) plastic waste is difficult, as much of it is chemically inert and non-biodegradable. When
burnt, waste plastics may produce toxic products, such as hydrogen chloride from PVC, poly(chloroethene).
EXAM-STYLE QUESTIONS

1 2-Methylpentane, 3-ethylpentane and 2,3-dimethylbutane are alkanes.

a For each one give:

[3]
i its molecular formula
[3]
ii its structural formula
[3]
iii its displayed formula
[3]
iv its skeletal formula.
[1]
b Give the general formula that is used to represent alkanes.

c Two of the alkanes in this question are isomers of each other.

[2]
Identify which two and identify the type of isomerism they show.
[2]
d Using terms from part a of this question, define isomers.
[1]
e Name the alkane whose structural formula is CH3CH(CH3)CH2CH(CH3)2
[Total: 18]
[2]
2 a Alkanes are saturated hydrocarbons. Explain the words saturated and hydrocarbons.
[2]
b Alkanes are generally unreactive. Explain why this is so.

c Write balanced symbol equations for the complete combustion of:

[2]
i methane
[2]
ii ethane. [Total: 8]
3 Use the passage below and your own knowledge to answer the questions that follow.
Methane reacts with bromine to give bromomethane and hydrogen bromide. The mechanism for
the reaction is called free-radical substitution and involves homolytic fission of chemical bonds. The
reaction proceeds via initiation, propagation and termination steps.
[1]
a Name the mechanism by which bromine reacts with methane.
[2]
b Write a balanced symbol equation for this reaction.
[1]
c Bonds break in this reaction. What type of bond breaking is involved?
[2]
d Explain the essential conditions that are required for this reaction.

e For this reaction, write down an equation for:

[2]
i an initiation step
[2]
ii a propagation step
[2]
iii a termination step. [Total: 12]
4 In a similar reaction to the one in Question 3, 1.50 g of ethane reacts with chlorine. 1.29 g of
chloroethane is formed. (Ar values: H = 1.0, C = 12.0, Cl = 35.5)
Calculate:
[2]
a the number of moles of ethane that were used
[2]
b the number of moles of chloroethane that were formed
[2]
c the percentage yield

d the number of grams of chloroethane that would have formed if the percentage yield [2]
had been 60.0%. [Total: 8]
5 Propene, cis-pent-2-ene and trans-pent-2-ene are alkenes.
 a For each one give:
[3]
i its molecular formula
[3]
ii its structural formula
[3]
iii its displayed formula
[3]
iv its skeletal formula.
[1]
b Give the general formula that is used to represent alkenes.

c Two of these alkenes are isomers of each other.

[1]
Identify which two.

d Explain why it is not possible to change one of these two isomers into the other at room [2]
temperature.
[8]
e Give displayed formulae and the names of the four alkenes with molecular formula C4H8.

f 3-Methylpent-2-ene has two cis/trans isomers.

[3]
Draw and name the two isomers. [Total: 27]
[1]
6 a Alkenes are unsaturated hydrocarbons. Explain the word unsaturated.
[2]
b Describe the bonding between the two carbon atoms in ethene.
[2]
c Describe and draw the shape of an ethene molecule, labelling all bond angles.

d Explain the meaning of the term functional group. Which functional group is present in [2]
all alkenes?

e Describe a simple chemical test to determine whether an unknown hydrocarbon is

unsaturated.
[2]
Describe the result if the test is positive. [Total: 9]
7 Use the passage below and your own knowledge to answer the questions that follow.
Ethene reacts with bromine to give 1,2-dibromoethane as the only product. The mechanism for the
reaction is electrophilic addition and involves heterolytic fission of chemical bonds. The bromine
molecules behave as electrophiles in this reaction.
[1]
a Name the mechanism by which bromine reacts with ethene.
[2]
b Write a balanced symbol equation for this reaction.
[1]
c Bonds break in this reaction. Give the type of bond breaking involved.
[5]
d Show the mechanism of the reaction as fully as you can, including curly arrows.

e Which substance behaves here as an electrophile? Explain what is meant by the term [2]
electrophile. [Total: 11]
8 In a similar reaction to the reaction described in Question 7, 2.80 g of ethene react with chlorine.
8.91 g of dichloroethane are formed. (Ar values: H = 1.0, C = 12.0, Cl = 35.5)
Calculate:
[2]
a the number of moles of ethene that were used
[2]
b the number of moles of dichloroethane that were formed
[2]
c the percentage yield

d the number of grams of dichloroethane that would have formed if the percentage yield [2]
had been 80.0%. [Total: 8]
9 This question is about the reactions of alkenes with hot, concentrated acidified potassium
manganate(VII) solution.
a i Give two effects that a hot, concentrated solution of acidified potassium [2]
manganate(VII) have on an alkene molecule.
[1]
ii State how this reaction is useful to chemists.

b An alkene is known to be either but-1-ene or but-2-ene. When heated with concentrated

acidified potassium manganate(VII) solution, bubbles of carbon dioxide gas were given
off.
[1]
Name the alkene.

c Pent-2-ene is heated with concentrated acidified potassium manganate(VII) solution.

[3]
i Draw the displayed formulae of the products and name them.

ii Write a balanced chemical equation for this reaction, using [O] to show oxygen [1]
atoms involved. [Total: 8]
SELF-EVALUATION

After studying this chapter, complete a table like this:

Needs
See more Almost Ready to
I can section... work there move on

explain the general unreactivity of alkanes, and describe their

15.1, 15.2
complete and incomplete combustion

explain the free-radical substitution of alkanes by chlorine and

15.2
by bromine, as shown by their mechanism

suggest how cracking can be used to obtain more useful

alkanes, and alkenes, of lower relative molecular mass from 15.3
larger hydrocarbon molecules

describe the environmental consequences of burning

hydrocarbon fuels in vehicles and the removal of pollutants by 15.2
catalytic converters

describe the reactions of alkenes as shown by their addition, 15.3, 15.4,

oxidation and polymerisation 15.5, 15.6

describe the mechanism of electrophilic addition in alkenes,

and explain the inductive effects of alkyl groups on the 15.3
stability of cations formed

describe the difficulty of disposing of waste poly(alkene)s. 15.5

images

Chapter 16
Halogenoalkanes

LEARNING INTENTIONS
In this chapter you will learn how to:

write equations for the main reactions that can produce halogenoalkanes, including the reagents and conditions
used
write equations for the reactions of halogenoalkanes when they undergo:

nucleophilic substitution, such as hydrolysis, formation of nitriles, and the formation of primary amines by
reaction with ammonia
elimination of hydrogen bromide (for example, from 2-bromopropane)
describe and explain the SN1 and SN2 mechanisms of nucleophilic substitution in halogenoalkanes
interpret the different reactivities of halogenoalkanes.

BEFORE YOU START

1 Which statement below describes what happens when a covalent bond breaks heterolytically?
 When the bond breaks …

A one of the atoms takes both the electrons in the bond, and becomes negatively charged

B one of the atoms takes both the electrons in the bond, and becomes positively charged

C both atoms take one electron each from the bond, forming free radicals

D both atoms take one electron each from the bond, with one atom becoming a free radical, and
the other a positive ion.

2 Discuss with a partner how substitution and elimination reactions differ. Write a sentence
explaining the difference. Then look back to Chapter 14 to illustrate your answer with two chemical
equations.

3 Describe the test and result to positively identify a bromide ion.

4 Working with a partner, define nucleophile.

USES OF HALOGENOALKANES

Halogenoalkanes are used in many industrial chemical processes. Halogenoalkanes are formed from
elements such as fluorine and chlorine but, unlike these elements, many halogenoalkanes are
relatively unreactive under normal conditions. This leads to their use as flame retardants and
anaesthetics.

You might have heard of one of the first anaesthetics, chloroform. Its systematic name is
trichloromethane (CHCl3). Nowadays, if you require an anaesthetic, you may receive a gas known as
‘halothane’. Its systematic name is 2-bromo-2-chloro-1,1,1-trifluoroethane.

One of the essential properties of an anaesthetic (Figure 16.1) is chemical inertness (lack of reactivity),
and each halothane molecule contains three very strong C─F bonds that are difficult to break. This
makes halothane inert (very unreactive) and safe to use in the aqueous environment inside the body.

Figure 16.1: An anaesthetist putting a patient to sleep before an operation.

However, under other conditions, such as high in the Earth’s stratosphere, some halogenoalkanes
react in completely different ways.

CFCs are chlorofluorocarbons. Chemists refer to them as chlorofluoroalkanes. When scientists

developed these new compounds in the 1930s, people could see no drawbacks to using the new
‘wonder compounds’. They are all chemically inert. They are not flammable and are not toxic. These
properties made volatile CFCs useful as aerosol propellants, solvents and as the refrigerants inside
fridges. They were also used as blowing agents for polymers such as expanded polystyrene.

However, CFCs have caused a serious environmental issue. They have damaged the ozone layer in the
upper atmosphere. The ozone layer is a thin layer of gas that protects the Earth by absorbing harmful
UV radiation arriving from the Sun.
It turns out that CFCs are unreactive in normal conditions, but high up in the atmosphere they become
totally different. The CFCs can persist in the atmosphere for about a hundred years. The UV light from
the Sun breaks the C─Cl bonds in the CFC molecules. This releases highly reactive chlorine atoms,
called chlorine free radicals. These chlorine free radicals react with ozone molecules. In a sequence of
chain reactions, chemists estimate that each chlorine free radical can destroy a million ozone
molecules.

Governments have been working on the problem, and most industrialised countries have now banned
the use of CFCs (Figure 16.2). Chemists developed new compounds for fridges and aerosols, such as
hydrofluorocarbons (HFCs): for example, CH2FCF3. These non-chlorinated compounds break down
more quickly once released into the air because of the presence of hydrogen in their molecules. This
means that they never rise in the atmosphere as far as the ozone layer. There is now evidence that the
ozone layer is recovering from the effects of CFCs. The hole in the ozone layer is slowly closing up.

Figure 16.2: Banning the use of CFCs has meant that the hole in the ozone layer over Antarctica is now getting
smaller.

Questions for discussion

Discuss with another learner or group of learners:

Discuss how the passage above about the use of halogenoalkanes demonstrates how some
scientific developments can have both good and bad effects on society and the environment.
16.1 Making halogenoalkanes
Very few halogenoalkanes are found in nature. Most are made in chemical reactions between other organic
compounds and a halogen or halide compound.

The main reactions are:

the free-radical substitution of alkanes by chlorine, Cl2, or bromine, Br2, in ultraviolet light:

C2H6 + Cl2 C2H5Cl + HCl

(For more details, see Section 15.2)
the electrophilic addition of an alkene with a halogen, X2, or a hydrogen halide, HX(g), at room
temperature:
C2H4 + Br2 → C2H4Br2
(For more details, see Section 15.3)
substitution of an alcohol. For example, by reactions:

with HX (or with KX and H2SO4 or H3PO4 to make HX),

CH3CH2OH + HCl → CH3CH2Cl + H2O
with PCl3 and heat:

3C2H5OH + PCl3 3C2H5Cl + H3PO3

with PCl5 at room temperature:
C2H5OH + PCl5 → C2H5Cl + HCl + POCl3
or with SOCl2:
C2H5OH + SOCl2 → C2H5Cl + HCl + SO2

The chloroethane made in the reactions above is classified as a primary halogenoalkane, as the chlorine is
bonded to a carbon atom that is bonded to just one alkyl group (a methyl group in this case). We can also
make halogenoalkanes where the carbon atom adjacent to the halogen atom is bonded to two alkyl groups,
called secondary halogenoalkanes. Tertiary halogenoalkanes have three alkyl groups on the adjacent
carbon atom.
16.2 Nucleophilic substitution reactions
We can think of the halogenoalkanes as alkanes that have one or more hydrogen atoms replaced by
halogen atoms.

Remember that the halogens are the elements in Group 17 of the Periodic Table, namely fluorine (F),
chlorine (Cl), bromine (Br) and iodine (I).

The simplest halogenoalkanes, whose molecules contain just one halogen atom, will have the general
formula CnH2n+1X, where X is F, Cl, Br or I. The halogen atom has a huge effect on the reactivity of the
halogenoalkanes compared with that of the alkanes. The halogenoalkanes are more reactive because of
the polar nature of the covalent bond between the carbon and halogen atom unlike the non-polar bonds in
alkane molecules. The carbon bonded to the halogen carries a partial positive charge, and the halogen a
partial negative charge.

Substitution reactions with aqueous alkali, OH−(aq)

When an aqueous solution of sodium hydroxide is heated with a halogenoalkane, a nucleophilic
substitution reaction takes place. The halogen atom in the halogenoalkane is replaced by an ─OH,
hydroxyl group, so the organic product formed is an alcohol:

We can also show this equation as:

CH3CH2Br + OH− → CH3CH2OH + Br−

The aqueous hydroxide ion behaves as a nucleophile here, because it is donating a pair of electrons to the
carbon atom bonded to the halogen in the halogenoalkane. This is why the reaction is called a nucleophilic
substitution.

PRACTICAL ACTIVITY 16.1

Hydrolysis of a halogenoalkane
The reaction is carried out under reflux in the laboratory. This lets us heat the reaction mixture without
evaporating off the volatile organic compounds in the reaction flask. The apparatus is shown in Figure
16.3.

Similar reactions occur with other halogenoalkanes, but the reaction rates differ. We can investigate
the rate of hydrolysis using aqueous silver nitrate solution. The water in the silver nitrate solution acts
as the nucleophile, and again an alcohol is formed. The reaction is called hydrolysis (meaning
‘breakdown by water’):
 Figure 16.3: Reflux apparatus for hydrolysis of a halogenoalkane.

CH3CH2Br + H2O → CH3CH2OH + H+ + Br−

It is a very similar reaction to the reaction that takes place with aqueous alkali.

However, the hydrolysis with water occurs more slowly than with the hydroxide ion, OH−(aq). This is
because the negatively charged hydroxide ion is a more effective nucleophile than a neutral water
molecule. This is due to the fact that, in water, the oxygen atom in H2O only carries partial negative
charge (δ−), whereas in the hydroxide ion, OH−, the oxygen atom carries a full negative charge.

From the equation above, you can see that a halide ion, in this case the bromide ion, Br−, is produced
in the reaction.

In Section 12.3 we used silver nitrate solution to test for halide ions. Remember that:

aqueous chlorides give a white precipitate (silver chloride),

bromides give a cream precipitate (silver bromide)
iodides produce a pale yellow precipitate (silver iodide).

The water in the silver nitrate solution will hydrolyse the halogenoalkane.

Observing this reaction, we can time how long it takes for test-tubes containing the halogenoalkanes and
aqueous silver nitrate solution to become opaque.

Conclusion
We find that:

the fastest nucleophilic substitution reactions take place with the iodoalkanes
 the slowest nucleophilic substitution reactions take place with the fluoroalkanes.

The substitution reaction involves the breaking of the carbon–halogen bond. The bond energies in Table
16.1 help us to explain the rates of reaction:

Bond Bond energy / kJ mol−1

C─F 467 (strongest bond)

C─Cl 346

C─Br 290

C─I 228 (weakest bond)

Table 16.1: Bond energy values of the carbon–halogen bonds.

Notice that the C─I bond is the weakest, so it is broken most easily. When the C─I bond breaks, it forms an I
−
ion during the substitution reaction. The bond breaks heterolytically, with the iodine atom taking both the
electrons in the C─I bond.

This is shown clearly in an ionic equation:

IMPORTANT

The trend in the reactivity of the halogenoalkanes is shown below:

There is more about the mechanism of nucleophilic substitution in Section 16.3.

Substitution with cyanide ions, CN− (in ethanol)

In this reaction the nucleophile is the cyanide, CN−, ion. To carry out the reaction, a solution of potassium
cyanide, KCN, in ethanol (known as an ethanolic solution of potassium cyanide) is made up. This is then
heated under reflux with the halogenoalkane.

An ionic equation for this reaction is:

Notice that the reaction with the cyanide ion adds an extra carbon atom to the original halogenoalkane
carbon chain. In this case, bromoethane is converted to propanenitrile.

Sometimes in industry, chemists need to make a new compound with one more carbon atom than the best
available organic raw material (the starting compound). Therefore, if we can convert the starting
compound to a halogenoalkane, we can then reflux with ethanolic KCN to make a nitrile. We now have an
intermediate nitrile with the correct number of carbon atoms.

We will consider nitriles and their subsequent conversion to carboxylic acids and amines again in Chapter
18.

Substitution with ammonia, NH3 (in ethanol)

If we heat a halogenoalkane with an excess of ammonia dissolved in ethanol under pressure, an amine is
formed.
Here the nucleophile is the ammonia, NH3, molecule. The organic product, ethylamine, is a primary amine,
as the nitrogen atom is attached to only one alkyl group. If the ammonia is not in excess, we get a mixture
of amine products. This is because the primary amine product will act as a nucleophile itself and will attack
halogenoalkane molecules, forming secondary amines, and so on. The secondary amine formed above
would be (CH3CH2)2NH, called diethylamine.

You can read more about amines in Chapter 27.

Question
Work with another learner to discuss and answer these questions:

1 a Name the reactants you would use to produce 1,2-dichloropropane.

b Why does the hydrolysis of a halogenoalkane happen more quickly with OH−(aq) ions than with
water molecules?

c Explain why silver nitrate solution can be used to investigate the rate of hydrolysis of the
halogenoalkanes. Include ionic equations for the formation of the precipitates.

d Why can ammonia and amine molecules act as nucleophiles?

e When ammonia is reacted with an excess of a halogenoalkane, a mixture of amines can be

formed.

If we start with an excess of 1-bromopropane, give the structural formula and name of the tertiary
amine formed.

Compare your answers with those of another pair. Discuss and amend any errors you come across
together.
16.3 Mechanism of nucleophilic substitution in
halogenoalkanes
Many of the reactions of halogenoalkanes are nucleophilic substitutions. In these reactions, the nucleophile
attacks the carbon atom bonded to the halogen. Remember from Chapter 14 that nucleophiles are donors
of an electron pair, and are attracted to electron-deficient atoms.

The carbon–halogen bond is polarised because the halogen is more electronegative than carbon. So the
halogen draws the pair of electrons in the bond away from the carbon atom, nearer to itself. Therefore, the
carbon atom carries a positive charge (shown in Figure 16.4).

Figure 16.4: The carbon–halogen bond is polarised.

The halogen atom is replaced by the nucleophile in the substitution reaction.

There are two possible mechanisms that can operate in the nucleophilic substitution reactions of
halogenoalkanes. The actual mechanism is determined by the structure of the halogenoalkane involved in
the reaction.

Mechanism for primary halogenoalkanes (SN2)

In primary halogenoalkanes containing one halogen atom, the halogen atom is bonded to a carbon atom,
which is itself bonded to one other carbon atom and two hydrogen atoms. This means that the carbon
atom bonded to the halogen is attached to only one alkyl group. For example, 1-chloropropane,
CH3CH2CH2Cl, is a primary halogenoalkane. In this case, the carbon atom bonded to the chlorine atom is
attached to one alkyl group, an ethyl group.

In Section 16.2 we looked at the hydrolysis of bromoethane, another primary halogenoalkane. Figure 16.5
shows the mechanism for that reaction.

Figure 16.5: The mechanism of nucleophilic substitution in a primary halogenoalkane.

The OH− ion donates a pair of electrons to the δ+ carbon atom, forming a new covalent bond. At the same
time, the C─Br bond is breaking. The Br atom takes both the electrons in the bond. This is an example of
heterolytic fission of a covalent bond (see Section 14.7). The Br atom leaves the halogenoalkane as a Br
− ion.
This mechanism is called an SN2 mechanism. The ‘S’ stands for substitution and the ‘N’ stands for
nucleophilic. The ‘2’ tells us that the rate of the reaction, which is determined by the slow step in the
mechanism (see Section 22.1), involves two reacting species. Experiments show us that the rate depends
on both the concentration of the halogenoalkane and the concentration of the hydroxide ions present.

Mechanism for tertiary halogenoalkanes (SN1)

In a tertiary halogenoalkane, the carbon atom bonded to the halogen atom is also bonded to three other
carbon atoms (alkyl groups). For example, 2-bromo-2-methylpropane is a tertiary halogenoalkane. The
carbon atom bonded to the bromine atom is attached to three alkyl groups, all methyl groups. The
structure of this tertiary halogenoalkane is shown in Figure 16.6.

Figure 16.6: A tertiary halogenoalkane, 2-bromo-2-methylpropane.

A tertiary halogenoalkane reacts with a hydroxide ion by a two-step mechanism. The first step in the
mechanism is the breaking of the carbon–halogen bond. This forms a tertiary carbocation (see Section
14.7). Then the tertiary carbocation is attacked immediately by the hydroxide ion (Figure 16.7).

Figure 16.7: The mechanism of nucleophilic substitution in a tertiary halogenoalkane.

This mechanism is known as an SN1 mechanism. The ‘1’ tells us that the rate of the reaction only
depends on one reagent, in this case the concentration of the halogenoalkane, as shown in the first (slow)
step of the mechanism.

Once again, this breaking of the C─Br bond is an example of heterolytic fission.

The Br− ion forms again, as in the SN2 mechanism, but in this mechanism a carbocation ion forms. This
does not happen with primary halogenoalkanes. This is because tertiary carbocations are more stable than
primary carbocations. This is due to the positive inductive effect of the alkyl groups attached to the
carbon atom bonded to the halogen (see Section 14.5). Alkyl groups tend to release electrons to atoms
attached to them. So a tertiary carbocation has three alkyl groups donating electrons towards the
positively charged carbon atom, reducing its charge density. This makes it more stable than a primary
carbocation, which just has one alkyl group releasing electrons (Figure 16.8).
Figure 16.8: The trend in the stability of primary, secondary and tertiary carbocations.

The SN1 mechanism and the SN2 mechanism are both likely to play a part in the nucleophilic substitution of
secondary halogenoalkanes.

Question
2 a Show the mechanism, including appropriate curly arrows, for the hydrolysis of 1-chloropropane,
CH3CH2CH2Cl, by alkali.

Explain what is happening in this mechanism to another learner.

b Draw the structure (displayed formula) of 2-chloro-2-methylbutane.

c Show the mechanism for the hydrolysis of 2-chloro-2-methylbutane by an alkali.

16.4 Elimination reactions
Halogenoalkanes also undergo elimination reactions. An elimination reaction involves the loss of a small
molecule from the original organic molecule. In the case of halogenoalkanes, this small molecule is a
hydrogen halide, such as HCl or HBr.

The reagent used in these elimination reactions is ethanolic sodium hydroxide, heated with the
halogenoalkane:

The original bromoethane molecule has lost an H atom and a Br atom. We can think of it as HBr being
eliminated from the halogenoalkane. The ethanolic OH− ion acts as a base, accepting an H+ ion from the
halogenoalkane to form water.

The C─Br bond breaks heterolytically, forming a Br− ion and leaving an alkene as the organic product.

Notice the importance of the conditions used in organic reactions:

IMPORTANT
If we use NaOH(ethanol), an elimination reaction occurs and an alkene is one of the products.

but

If we use NaOH(aq), a nucleophilic substitution reaction occurs and an alcohol is one of the products.

Question
3 a Write a balanced equation for the reaction of 2-bromopropane with ethanolic sodium hydroxide.

b Name the organic product.

c Discuss with a partner another elimination reaction with a different bromoalkane that would give
the same products as in part a.

Write a balanced equation for this reaction.

REFLECTION

1 Show the mechanism for the hydrolysis of 1-chlorobutane by an aqueous alkali, such as sodium
hydroxide solution, NaOH(aq).

Work as a pair:

listen to your partner explain this mechanism to you

assess each other’s understanding of the SN2 and SN1 mechanisms for the hydrolysis of primary
and tertiary halogenoalkanes.

2 Reflect together on all the knowledge you need to understand and explain the mechanisms of the
hydrolysis of a primary halogenoalkane and a tertiary halogenoalkane by an alkali. Make a list of
the essential knowledge to answer an exam question on SN2 and SN1 mechanisms.
SUMMARY

If one or more of the hydrogen atoms in an alkane molecule are replaced by halogen atoms, the compound is called
a halogenoalkane.

Iodoalkanes are the most reactive halogenoalkanes, whereas fluoroalkanes are the least reactive. We explain this by
the trend in the bond strength of the [Link] bonds. The C─F bond is the strongest bond, and the C─I bond
is the weakest bond. So the C─I bond is most easily broken during its reactions.

Halogenoalkanes are attacked by nucleophiles. This happens because the carbon bonded to the halogen carries a
partial positive charge (δ+), due to the higher electronegativity of the halogen. So halogenoalkanes can undergo
nucleophilic substitution.

Suitable nucleophiles include aqueous alkali, OH−(aq), cyanide, CN−, and ammonia, NH3.

The reaction with OH− ions (or with water) is known as hydrolysis, and an alcohol is formed as the organic product.

Halogenoalkanes will also undergo elimination reactions when heated with ethanolic sodium hydroxide, forming
alkenes as the organic product.
EXAM-STYLE QUESTIONS

1 What type of reaction best describes the heating of chloroethane with ethanolic sodium hydroxide
solution?

A addition

B elimination

C hydrolysis

D substitution [1]

2 Which one of the following is a tertiary halogenoalkane?

A CHBr3

B CH3CH2CH2Br

C (CH3)2CHCHBrCH3

D (CH3)2CBrCH2CH3 [1]

3 Which one of the following will form a carbocation in the mechanism of nucleophilic substitution?

A CH3CH2CH2Cl

B (CH3)2CBrCH3

C CH3CH2Cl

D CH3Br [1]

4 When a solution of potassium cyanide in ethanol is heated under reflux with 1-chloropropane, what
is the organic product of the reaction called?

A butanenitrile

B 1-chloropropanenitrile

C ethanenitrile

D propanenitrile [1]

5 1-Bromobutane will undergo reactions when heated, as shown by reactions A and B.

[2]
a For reactions A and B, give the reagents used in each case.

b Reaction A was repeated using 1-iodobutane instead of 1-bromobutane.

[2]
Explain any difference in the rate of reaction observed.
[1]
c Name the type of organic reaction shown in A.
[3]
d Draw the mechanism for reaction A.

e Reaction A was repeated with 2-bromo-2-methylpropane instead of 1-bromobutane.

[1]
i Name the organic compound formed.

ii The mechanism of the reaction with 2-bromo-2-methylpropane differs from the

mechanism of reaction A.
 Describe how the mechanisms differ. [2]
[1]
f Name the type of reaction shown in B.

g If reaction B was repeated with 2-bromobutane, deduce the other organic products that [2]
can form as well as the product shown above. [Total: 14]
6 Bromochlorodifluoromethane has been used in fire extinguishers. However, its breakdown products
were found to be toxic.
[1]
a Draw the displayed formula of bromochlorodifluoromethane.

b CF3CH2F is being introduced as a replacement for various CFCs in refrigerants and

aerosols.
[1]
Deduce the name of this compound. [Total: 2]
SELF-EVALUATION

After studying this chapter, complete a table like this:

See Needs Almost Ready to

I can section... more work there move on

write equations for the main reactions that can produce

16.1
halogenoalkanes, to include the reagents and conditions used

write equations for the reactions of halogenoalkanes when

they undergo nucleophilic substitution, such as hydrolysis, the
16.2
formation of nitriles, and the formation of primary amines by
their reaction with ammonia

write equations for the reactions of halogenoalkanes when

they undergo elimination of a hydrogen halide by ethanolic 16.4
sodium hydroxide

describe and explain the SN1 and SN2 mechanisms of

16.3
nucleophilic substitution in halogenoalkanes

interpret the different reactivities of halogenoalkanes. 16.2

images

Chapter 17
Alcohols, esters and
carboxylic acids

LEARNING INTENTIONS
In this chapter you will learn how to:

explain the acidity of alcohols compared with water

recall the reactions (reagents and conditions) by which alcohols can be produced

recall the reactions of alcohols in combustion, substitution to give halogenoalkanes, reaction with sodium, oxidation
to carbonyl compounds and carboxylic acids, and dehydration to alkenes

classify hydroxy compounds into primary, secondary and tertiary alcohols

suggest characteristic distinguishing reactions, e.g. mild oxidation
describe the acid and base hydrolysis of esters
describe the formation of carboxylic acids from alcohols, aldehydes and nitriles

describe the reactions of carboxylic acids in the formation of:

salts, by the use of reactive metals, alkalis or carbonates

alkyl esters, by reaction with alcohols

primary alcohols, by reduction using LiAlH4.
BEFORE YOU START

1 Which statement below describes what happens to an organic compound when it is reduced and
then oxidised?

A It loses hydrogen, then loses oxygen

B It gains hydrogen, then gains oxygen

C It gains hydrogen, then loses oxygen

D It loses hydrogen, then gains oxygen

2 Discuss with a partner how to complete these general equations:

a acid + base →

b acid + metal →

c acid + carbonate →

3 a Give the skeletal formula for:

i propan-2-ol

ii butanone

iii ethanal

iv ethanoic acid.

b Give the displayed formula for:

i ethyl ethanoate

ii pentanenitrile.

4 a Discuss with another learner what happens to an organic molecule during hydrolysis and
dehydration.

b Discuss the Brønsted–Lowry theory to explain strong and weak acids.

MAKING ETHANOL AS A BIOFUEL

Ethanol, C2H5OH, is the most widely used of the homologous series of alcohols. The sugar extracted
from crops such as sugar cane and sugar beet can be fermented with yeast to make ethanol (Figure
17.1). Ethanol is a ‘biofuel’ and burns with a clean flame. This process is becoming increasingly
important as our supplies of crude oil run out and cleaner, easier to produce biofuels are needed to
take the place of petrol and diesel.
Figure 17.1: The sugar extracted from sugar cane can be fermented with yeast to make ethanol.

The industrial production of ethanol uses ethene as a reactant. As you saw in the introduction to
Chapter 15, we get ethene by the cracking of fractions from crude oil. The ethene reacts with steam,
using a catalyst of phosphoric(V) acid, H3PO4, to make ethanol (see Section 15.3):

This is a relatively cheap, continuous process, especially for countries with their own reserves of crude
oil. But ethanol made this way still costs more than petrol, as well as using up our remaining oil
reserves.

Brazil is one country that has started making ethanol on a large scale. However, they do not use
ethene. They start with sugar extracted from sugar cane. The sugar solution is fermented in a batch
process with yeast to produce ethanol as fuel for cars. The fermentation only needs a warm
temperature to take place.

The ethanol made needs to be distilled from the reaction mixture. This requires energy but more sugar
cane (or sugar beet in colder climates) can be grown each year. So ethanol made this way is a
renewable biofuel, unlike fossil fuels.

The ethanol itself can be used in cars with adapted engines or in normal cars as a mixture with petrol.

But the environment could really benefit if we start using more ethanol as a fuel. The huge volume of
carbon dioxide given off from fossil fuels is causing global climate change. But carbon dioxide is also
given off during the fermentation of sugar, as well as when ethanol burns:

However, the carbon dioxide released into the atmosphere is offset by carbon dioxide absorbed during
photosynthesis as sugar cane grows:

Questions for discussion

Discuss with another learner or group of learners:

It is difficult to achieve 100% carbon-neutrality, a perfect balance between CO2 released and CO2
absorbed. This might be because fossil fuels are often used in manufacturing fertilisers, harvesting
and transporting the crops for processing, and distributing the ethanol.

Discuss in small groups how we could make ethanol biofuel even more environmentally friendly.
Make a list of suggestions to share with the whole group.
17.1 The homologous series of alcohols
Alcohols are organic molecules containing the hydroxyl group, OH. With one hydroxyl group substituted
into an alkane molecule, the general formula is CnH2n+1OH.

The alcohols are named by adding ‘-anol’ to the alkane stem. For example, CH3OH is called methanol.

Classifying alcohols
For alcohol molecules with three or more carbon atoms, the position of the hydroxyl group is shown by
inserting a number to indicate which carbon atom is bonded to the ─OH group. Figure 17.2 gives some
examples.

Figure 17.2: Note that the numbering to show the position of the ─OH group in an alcohol starts from the end of the
molecule that gives the smaller number.

Propan-1-ol is classified as a primary alcohol. The carbon atom bonded to the ─OH group is attached to
one other carbon atom (alkyl group). Propan-2-ol is a secondary alcohol as the carbon atom bonded to
the ─OH group is attached to two other carbon atoms (alkyl groups). With three alkyl groups attached, 2-
methylpropan-2-ol is an example of a tertiary alcohol.

There are also alcohols with more than one ─OH group. We came across an example in Section 15.4 when
an alkene is oxidised to form a ‘diol’, ethane-1,2-diol. Its structural formula is HOCH2CH2OH. Both the
hydroxy groups are bonded to a ─CH2 group, so both are classified as primary. On the other hand, a diol
such as propane-1,2-diol, HOCH2CH(OH)CH3, has one primary and one secondary ─OH group within its
molecules.

Properties of alcohols
The alcohols have higher boiling points than expected when compared with other organic molecules with
similar relative molecular masses. Even methanol, the alcohol with the lowest molar mass, is a liquid at
room temperature. This occurs because of hydrogen bonding between alcohol molecules (see Section 4.8).
Hydrogen bonding also explains why the smaller alcohol molecules are so miscible (mix and dissolve well)
in water.

Comparing the acidity of alcohols and water

Once dissolved in water, ethanol molecules do not dissociate (split up) to any great extent, although there
is a very small degree of dissociation:

The position of equilibrium lies well over to the left, favouring the undissociated C2H5OH molecules. Even
compared to the dissociation of water molecules:

the concentration of H+(aq) ions is much lower. So we can say that ethanol is a weaker acid than water: its
molecules are less likely to dissociate and form H+ ions. This is because of the electron-donating alkyl
(ethyl) group bonded to the negatively charged oxygen atom in the ethoxide ion. The positive inductive
effect of the ethyl group (see Section 27.1) has the effect of concentrating more negative charge on this
oxygen atom. So the ethoxide ion more readily accepts an H ion than the hydroxide ions, OH−, from the
dissociation of water. The hydroxide ion only has a hydrogen atom bonded to its negatively charged
oxygen, and no alkyl groups.

Question
1 a Explain how hydrogen bonds arise:

i between ethanol molecules

ii between ethanol and water molecules.

b Explain why ethanol mixes with water in all proportions but hexan-1-ol is less miscible with water.

c Give the structural formula of 2-methylbutan-2-ol, and classify it as a primary, secondary or

tertiary alcohol.

d i Give the structural difference that makes an alcohol a weaker acid than water.

ii Suggest which type of alcohol is the weakest acid:

A a primary alcohol

B a secondary alcohol

C a tertiary alcohol

D no difference

Working as a pair, with your book closed, explain to your partner why ethanol is a weaker acid than
water. Then listen while your partner talks about why water is a stronger acid than ethanol.

Finish by opening the book and checking how you did.

17.2 Reactions to make alcohols
Alcohols do occur in nature, for example, in rotting fruit that undergoes fermentation. There are also plenty
of ways that chemists can produce alcohols. Here is a summary of the reactions you need to know:

electrophilic addition of steam, H2O(g), to an alkene, using a concentrated phosphoric(V) acid, H3PO4,
catalyst (see Section 15.3):

oxidation of alkenes with cold, dilute, acidified potassium manganate(VII) to form a diol (see Section
15.4). Remember that we can use the symbol [O] to represent oxygen provided by an oxidising agent
in organic reactions:

nucleophilic substitution (hydrolysis in this case) of a halogenoalkane by heating with NaOH(aq) (see
Section 16.2):

reduction of an aldehyde (to form a primary alcohol) or of a ketone (to form a secondary alcohol) using
a reducing agent, such as NaBH4 or LiAlH4 (see Section 18.3):

reduction of a carboxylic acid using NaBH4 or LiAlH4 (see Section 17.4):

or H2(g) / Ni and heat

hydrolysis of an ester by heating with a dilute acid or alkali (see Section 17.3):

with acid

with alkali
17.3 Reactions of the alcohols

Combustion
When ignited, the alcohols react with oxygen in the air (Figure 17.3). The products of complete combustion
are carbon dioxide and water.

alcohol + oxygen → carbon dioxide + water

For example, ethanol burns with a clean blue flame in a good supply of air:

Figure 17.3: The fuel called ‘gasohol’ is a mixture of ethanol and petrol.

Substitution to form a halogenoalkane

In this substitution reaction with a hydrogen halide, such as hydrogen chloride, the ─OH group in the
alcohol is replaced by a halogen atom. This produces a halogenoalkane.

IMPORTANT

The general equation is:

alcohol + hydrogen halide → halogenoalkane + water

For example:
The dry hydrogen chloride gas for this reaction can be made in situ (in the reaction vessel). Sodium
chloride and concentrated sulfuric acid are used for this:

NaCl + H2SO4 → NaHSO4 + HCl

PRACTICAL ACTIVITY 17.1

Halogenation of an alcohol
The alcohol is heated under reflux (see apparatus in Section 16.2) with the reactants to make the
halogenoalkane. The halogenoalkane made can then be distilled off from the reaction mixture and
collected as oily droplets under water (Figure 17.4).

Figure 17.4: Bromoethane being distilled off following the reaction between ethanol and hydrogen bromide. The
white solid visible in the pear-shaped flask is sodium bromide (crystals). The sodium bromide reacts with concentrated
sulfuric or phosphoric(V) acid to make the hydrogen bromide needed for the reaction.

For a substitution reaction with hydrogen bromide, the HBr can be made using potassium bromide and
concentrated phosphoric (or sulfuric) acid.

The nucleophilic substitution by the halide ion takes place after the ─OH group has accepted an H+ ion
from the acid. This makes the C─O bond in the alcohol easier to break, and water is given off.

Sulfur dichloride oxide, SOCl2, can also be used to substitute a chlorine atom into an alcohol molecule, as
shown below:

C2H5OH + SOCl2 → C2H5Cl + HCl + SO2

Note that in this reaction the two by-products of the reaction (HCl and SO2) are both gases. These gases
escape from the reaction mixture. The halogenoalkane is formed, without the need to heat the reaction
mixture.

We can also use phosphorus halides to provide the halogen atoms for this substitution reaction with
alcohols.

For chloroalkanes we can use solid phosphorus(V) chloride, PCl5:

C2H5OH + PCl5 → C2H5Cl + HCl + POCl3

The release of acidic hydrogen chloride gas from this reaction can be used as a test for the hydroxyl group.
You can see acidic steamy fumes from the HCl gas produced.

Phosphorus(III) chloride can also be used to halogenate an alcohol, but this reaction does require heating.

3C2H5OH + PCl3 3C2H5Cl + H3PO3

For bromoalkanes and iodoalkanes, we can make the phosphorus(III) halide, PBr3 or PI3, needed for the
reaction. Red phosphorus and bromine or iodine are warmed with the alcohol.

For example:

Question
2 a Starting with an alkene, give the reactants and conditions needed to produce:

i propanol

ii propane-1,2-diol.

b Write a balanced equation for the complete combustion of:

i propan-1-ol

ii butan-1-ol.

c i Write a balanced equation to show the reaction between ethanol and hydrogen bromide.

ii What are the reagents and conditions used for this reaction?

iii What do we call this type of reaction?

Now go through your answers to Question 2 with a fellow learner and discuss any differences. Then
check against the actual answers.

Reaction with sodium metal

In the reaction with hydrogen halides, the C─O bond in the alcohol breaks as it loses its ─OH group.
However, in some other reactions the O─H bond in the alcohol breaks. The reaction with sodium metal is an
example:

The reaction is similar to sodium’s reaction with water, but less vigorous. In both cases hydrogen gas is
given off and a basic ionic compound is formed. With ethanol, if the excess ethanol is allowed to evaporate
off after the reaction, a white crystalline solid is left. This is sodium ethoxide.

Other alcohols react in a similar way with sodium. For example, propan-1-ol would produce sodium
propoxide plus hydrogen gas.

IMPORTANT
In general:

alcohol + sodium → sodium alkoxide + hydrogen

We find that the longer the hydrocarbon chain in the alcohol, the less vigorous the reaction with sodium
metal (Figure 17.5).
Figure 17.5: Sodium reacting with ethanol. The pink colour is from a colourless phenolphthalein indicator that has been
added to the ethanol, showing the basic nature of the sodium ethoxide formed in the ethanol.

Question
3 Lithium reacts with alcohols in a similar way to sodium.

A small piece of lithium metal is dropped onto a watch-glass containing propan-1-ol.

a Describe what you would observe.

b Name the products of the reaction.

c Suggest what difference you would see if you used sodium instead of lithium in this reaction.

Esterification
Another reaction that involves the breaking of the O─H bond in alcohols is esterification, i.e. the making
of esters. An esterification reaction can take place between an alcohol and a carboxylic acid. It can be
classified as a condensation reaction.

IMPORTANT
The general equation is:

REFLECTION

1 At this point, review your knowledge of the reactions of the alcohols covered so far in this chapter.
Go back to Section 17.2 ‘Reactions to make alcohols’ and look at each chemical equation since
then, covering the products with a sheet of paper. Try to complete each equation on your sheet of
paper, checking your answers as you go along. How did you do?

2 If you know the type of reaction taking place it is a lot easier to identify the products formed.
Discuss with a partner any strategies you have found useful to help remember organic equations.

PRACTICAL ACTIVITY 17.2

Alcohol plus carboxylic acid

For esterification to take place, the carboxylic acid and alcohol are heated under reflux with a strong
acid catalyst (usually concentrated sulfuric acid, but also phosphoric(V) acid). The reaction is
reversible, so an equilibrium mixture can be established with all the reactants and products shown in
the general equation present.

The esters formed usually have sweet, fruity smells.

Here is an example of an esterification reaction:

The ester formed is called ethyl ethanoate.

But what would be the name of the ester formed if ethanol was reacted with propanoic acid?

Would it be propyl ethanoate or ethyl propanoate?

The answer is ethyl propanoate. That’s because the first part of an ester’s name comes from the alcohol: in
this case ethanol, giving ‘ethyl …’. The second part comes from the carboxylic acid, in this case propanoic
acid, giving ‘… propanoate’. This makes ‘ethyl propanoate’ as the name of the ester formed (Figure 17.6).
Figure 17.6: Esters contribute to the complex mixture of substances blended in a perfume. They are also present
naturally in fruits, and we use them in artificial flavourings and as solvents, e.g. in nail varnish remover.

Hydrolysis of esters

IMPORTANT

Esters can be hydrolysed by heating under reflux with either an acid or a base.

Refluxing with an acid, such as dilute sulfuric acid, simply reverses the preparation of the ester from an
alcohol and a carboxylic acid. The reaction is reversible and an equilibrium mixture is established. In acid
hydrolysis, there are always both reactants (ester + water) and products (carboxylic acid + alcohol)
present after the reaction.

The equation for the acid hydrolysis of the ester ethyl ethanoate is:

However, when an ester is refluxed with an alkali (a soluble base), such as aqueous sodium hydroxide, it is
fully hydrolysed. Unlike acid hydrolysis, this is not a reversible reaction, so all the ester present can be
broken down by excess alkali. An alcohol and the sodium salt of the carboxylic acid are formed.

The equation for the base hydrolysis of ethyl ethanoate is:

Question
4 a Name the ester formed in each of the following reactions :

i butan-1-ol + ethanoic acid

ii ethanol + hexanoic acid

iii pentan-1-ol and methanoic acid.

b Write the structural formula of each ester formed in part a.

Dehydration
Alcohols can also undergo elimination reactions in which water is lost, and in this case, alkenes are formed.
As the small molecule removed from the alcohol molecule is H2O, this reaction is also known as
dehydration.

The reaction takes place when alcohol vapour is passed over a hot catalyst of aluminium oxide powder.
Pieces of porous pot or pumice, as well as a concentrated acid, also catalyse the reaction.

For example:

Figure 17.7 shows how you would collect the ethene gas formed.
Figure 17.7: The dehydration of ethanol to give ethene.

Question
5 Concentrated sulfuric acid or phosphoric acid can be used to catalyse the dehydration of an alcohol.

The alcohol and concentrated acid are heated to about 170 °C. The concentrated acid does not
change chemically during the reaction.

a Write an equation showing the dehydration of ethanol using concentrated sulfuric acid.

b If propan-1-ol was used instead of ethanol, name the organic product formed.

Oxidation
In Section 17.1 we saw how alcohols can be classified as primary, secondary or tertiary. For most of their
reactions, the class of alcohol makes no difference to the type of products formed. In organic chemistry, we
can usually generalise for the whole homologous series. However, when alcohols are oxidised, primary,
secondary and tertiary alcohols each behave differently.

IMPORTANT

Primary and secondary alcohols can be oxidised by potassium dichromate(VI) solution, K2Cr2O7,
acidified with dilute sulfuric acid. Tertiary alcohols are not oxidised by acidified potassium
dichromate(VI) solution.

The orange colour of acidified potassium dichromate(VI) solution is caused by the dichromate(VI) ions,
Cr2O72−(aq). When the dichromate(VI) ions behave as an oxidising agent, the ions themselves are reduced.
They become chromium(III) ions, Cr3+(aq), which form a green solution. The reaction mixture needs to be
warmed before the oxidation takes place.
The product formed when you attempt to oxidise an alcohol can be used to distinguish between primary,
secondary and tertiary alcohols.

With tertiary alcohols, a mixture of the tertiary alcohol, dilute sulfuric acid and potassium dichromate(VI)
solution remains orange when warmed. No reaction takes place.

A secondary alcohol, such as propan-2-ol, will be oxidised to form a ketone. In this case propanone is
formed and the reaction mixture turns green:

Remember that simplified oxidation equations use [O] to show the oxygen added from the oxidising agent
(see Section 14.8).

With a primary alcohol, such as ethanol, the alcohol is oxidised to an aldehyde. Ethanol is oxidised to
ethanal:

PRACTICAL ACTIVITY 17.3

Distinguishing tertiary alcohols

Given three unknown alcohols, one primary, one secondary and one tertiary, it is easy to distinguish
the tertiary alcohol. Figure 17.8 shows the results of warming each class of alcohol with a solution of
acidified potassium dichromate(VI).

Figure 17.8: Before warming with the labelled alcohol, each of these tubes contained orange acidified potassium
dichromate(VI) solution. After warming, the orange dichromate(VI) ions have been reduced to green chromium(III) ions
by the primary and secondary alcohols. This shows that both the primary and secondary alcohols have been oxidised,
but the tertiary alcohol, 2-methylpropan-2-ol, has not.

The ethanal formed can be further oxidised to form ethanoic acid, a carboxylic acid. This is achieved by
refluxing with excess acidified potassium dichromate(VI):

Question
Working with a partner, discuss and answer these questions:

6 Propan-1-ol can be oxidised to propanal, CH3CH2CHO, and then further oxidised to propanoic acid,
CH3CH2COOH.

a Give the reagents and conditions that should be used to oxidise propan-1-ol to propanal.

b Write a balanced chemical equation for this oxidation. Represent oxygen from the oxidising agent
as [O].

c Give the reagents and conditions that should be used to oxidise propan-1-ol to propanoic acid.

d Write a balanced chemical equation for this oxidation. Again, show oxygen from the oxidising
agent as [O].