OCR

C h e m i s t r y
for A2

Graham Hill ■
Andrew Hunt ■
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 OCR
C h e m i s t r y
for A2

Graham Hill ■
Andrew Hunt ■
A Note for Teachers
OCR Chemistry for A2 Network disc
The OCR Chemistry for A2 Network disc which accompanies the Student’s
Book and Dynamic Learning Student website provides a complete bank of
resources for teachers and technicians following the OCR specification.
Powered by Dynamic Learning, the Network disc contains the same
interactive version of the Student’s Book that is available on the Dynamic
Learning Student’s website, plus every resource that teachers might wish to
use in activities, discussions, practical work and assessment.
These additional resources on the Network disc include:
● a synoptic Topic overview for each of the sixteen topics showing how the
text and resources cover and follow the OCR specification, including
coverage of ‘How Science Works’. These synopses also indicate how the
resources on the Network disc can be used to create a teaching programme
and lesson plans
● Introductory PowerPoints for each topic
● Practical worksheets for students covering the entire course
● Teacher’s and technician’s notes for all practicals showing the intentions of
each practical, a suggested approach to it, health and safety considerations,
the materials and apparatus required by each group and answers to the
questions on the worksheets
● additional Weblinks
● additional Activities involving data analysis, application and evaluation
● 3D Rotatable models of molecules of interest
● answers to all Review questions in the Student’s Book, as well as answers to
all Extension questions available to students from the Dynamic Learning
Student website and to questions in the additional Activities on the
Network disc
● Interactive objective tests for each topic with answers.
All these resources are launched from interactive pages of the Student’s Book
on the Network disc. Teachers can also search for resources by resource type
or key words to allow greater flexibility in using the resource material.
A Lesson Builder allows teachers to build lessons by dragging and dropping
resources they want to use into a lesson group that can be saved and launched
later from a single screen.
The tools provided also enable teachers to import their own resources and
weblinks into the lesson group and to populate a VLE at the click of a button.

Risk assessment
As a service to users, a risk assessment for this text and associated resources has
been carried out by CLEAPSS and is available on request to the Publishers.
However, the Publishers accept no legal responsibility on any issue arising from
this risk assessment; whilst every effort has been made to check the instructions
for practical work in this book and associated resources, it is still the duty and
legal obligation of schools to carry out their own risk assessment.
Contents

Unit 4 Rings, polymers and analysis 1

1 Arenes – aromatic hydrocarbons 2
2 Carbonyl compounds 19
3 Carboxylic acids and esters 28
4 Amines 40
5 Amino acids and proteins 50
6 Polymers 62
7 Synthesis 77
8 Chromatography 93
9 Spectroscopy 105

Unit 5 Equilibria, energetics and elements 121

10 How fast? 122
11 How far? 138
12 Acids, bases and buffers 147
13 Lattice enthalpy and Born–Haber cycles 171
14 Enthalpy and entropy 186
15 Redox, electrode potentials and fuel cells 197
16 Transition elements 220
The periodic table of elements 246
Index 247

v
Introduction
Welcome to OCR Chemistry for A2. This book covers everything in the OCR
specification with 9 topics for Unit 4 and 7 topics for Unit 5. Test yourself
questions throughout the book will help you to think about what you are
studying while the Activities give you the chance to apply what you have
learned in a range of modern contexts. At the end of each topic you will find
exam-style Review questions to help you check your progress.
Student support for this book can be found on the Dynamic Learning
Student website, which contains an interactive copy of the book. Students
can access a range of free digital resources by visiting www.dynamic-learning-
student.co.uk and using the code printed on the inside front cover of this
book to gain access to relevant resources. These free digital resources include:
● Data tables, for use when answering questions
● Tutorials, which work through selected problems and concepts using a
voiceover and animated diagrams
● Practical guidance to support experimental and investigative skills
● Weblinks that provide access to relevant social, environmental and
economic contexts and help with the more demanding concepts and
practical techniques.
All diagrams and photographs can be launched and enlarged directly from the
pages. There are also Learning outcomes available at the beginning of every
topic, and answer files to all Test yourself and Activity questions. Extension
questions, covering some ideas in greater depth, are available at the end of
each topic. The Student Online icon, shown on the right, indicates where a
resource such as a Data sheet, Tutorial, Practical guidance or Extension
questions is provided on the Dynamic Learning Student website. All other
resources are linked to interactive areas on the page or associated with
particular pages in the resources menu. In addition, all these resources can be
saved to your local hard drive.
With the powerful Search tool, key words can be found in an instant,
leading you to the relevant page or alternatively to resources associated with
each key word.

Acknowledgements
We would like to acknowledge the suggestions from Ian Davis, Neil Dixon
and Tim Joliffe – teachers who commented on our initial plans. The team at
Hodder Education, led by Katie Mackenzie-Stuart, has made an extremely
valuable contribution to the development of the book and the DVD and
website resources. In particular, we would like to thank Anne Trevillion, the
project manager, Anne Wanjie, Deborah Sanderson, Anne Russell and Tony
Clappison for their skilful work on both the print and electronic resources.

Graham Hill and Andrew Hunt

February 2009
Unit 4

Rings, polymers and

analysis
1 Arenes – aromatic
hydrocarbons
2 Carbonyl compounds
3 Carboxylic acids and
esters
4 Amines
5 Amino acids and proteins
6 Polymers
7 Synthesis
8 Chromatography
9 Spectroscopy
 1 Arenes – aromatic hydrocarbons
Aspirin, paracetamol and ibuprofen are three tried and tested
painkillers. Dettol and TCP are two important and effective
antiseptics. Terylene and polystyrene are two versatile polymers
produced in millions of tonnes every year.
At the heart of all these widely different products is a remarkably
stable ring of six carbon atoms – the benzene ring, a constituent of
all arenes.

1.1 Arenes
Arenes are hydrocarbons, such as benzene, methylbenzene and naphthalene.
They are ring compounds in which there are delocalised electrons. The
simplest arene is benzene. Traditionally, chemists have called the arenes
‘aromatic’ ever since the German chemist Friedrich Kekulé was struck by the
Figure 1.1 쑿 fragrant smell of oils such as benzene. In their modern name ‘arene’, the ‘ar-’
The antiseptics used in some throat
comes from aromatic and the ending ‘-ene’ points to the fact that they are
sprays are similar in structure to TCP
and Dettol.
unsaturated hydrocarbons like the alkenes.

Definitions
Arenes are hydrocarbons with a ring
or rings of carbon atoms in which there
are delocalised electrons.
Delocalised electrons are bonding
electrons which are not fixed between
two atoms in a bond, but shared
between three or more atoms. (See also
Section 6.6 in OCR Chemistry for AS.)

Figure 1.2 씰
Benzene is an important and useful
chemical. It was first isolated in 1825 by
the fractional distillation of whale oil,
which was commonly used for lighting
homes. Later it was obtained by the
fractional distillation of coal tar. Today, it
is obtained by the catalytic reforming of
fractions from crude oil.

1.2 The structure of benzene

Friedrich Kekulé played a crucial part in our understanding of the structure of
benzene thanks to a dream. The dream helped Kekulé to propose a possible
structure for benzene, which he knew to have an empirical formula of CH and
a molecular formula of C6H6. Kekulé had been working on the problem of the
structure of benzene for some time. Then one day in 1865, while dozing in
front of the fire, he dreamed of a snake biting its own tail. This inspired him
to think of a ring structure for benzene (Figure 1.3).
Figure 1.3 씰 H
Kekulé’s snake with his structural and
skeletal formulae for benzene. Kekulé’s H C H
formula would have the systematic name C C
cyclohexa-1,3,5-triene.
C C
H C H
2
H
 The structure of benzene

Kekulé’s structure explained many of the properties of benzene. It was

accepted for many years, but still left some problems.

The absence of isomers of 1,2-dichlorobenzene

Kekulé’s structure suggests that there should be two isomers of
1,2-dichlorobenzene – one in which the chlorine atoms are linked by a single
carbon–carbon bond; the other in which the chlorine atoms are linked by a
double carbon–carbon bond (Figure 1.4).
Cl Cl Figure 1.4 씱
Possible isomers of 1,2-dichlorobenzene.
Cl Cl

In practice, it has never been possible to separate two isomers of

1,2-dichlorobenzene, or any other 1,2-disubstituted compound of benzene.
To get round this problem, Kekulé suggested that benzene molecules might
somehow alternate rapidly between the two possible structures, but this failed
to satisfy his critics.

The bond lengths in benzene

The Kekulé structure shows a molecule with alternate single and double
bonds. This implies that three of the bonds are similar in length to the
carbon–carbon single bond in alkanes, while the other three are similar in
length to the carbon–carbon double bond in alkenes. X-ray diffraction studies
show that the carbon atoms in a benzene molecule are actually at the corners
of a regular hexagon. All the bonds are the same length, shorter than single
bonds but longer than double bonds (Figure 1.5).
Figure 1.5 씱
C C Carbon–carbon bond lengths in ethane,
C C ethene and benzene.

0.154 nm 0.134 nm 0.139 nm

The resistance to reaction of benzene

An inexperienced chemist looking at the Kekulé structure might expect
benzene to behave chemically like a very reactive alkene and to take part in
addition reactions with bromine, hydrogen bromide and similar reagents.
Benzene does not do this. The compound is much less reactive than alkenes
and its characteristic reactions are substitutions, not additions.

The stability of benzene

A study of enthalpy (energy content) changes show that benzene is more
stable than expected for a compound with the Kekulé formula. This
conclusion is based on a comparison of the enthalpy changes of hydrogenation
of benzene and cyclohexene.
Cyclohexene is a cyclic hydrocarbon with one carbon–carbon double bond.
Like other alkenes, it adds hydrogen in the presence of a nickel catalyst at
140 °C to form cyclohexane. The enthalpy change of the reaction, ΔH , is
−120 kJ mol−1 (Figure 1.6).
Figure 1.6 씱
Cyclohexene is a cyclic hydrocarbon with
+ H2 ΔH = –120 kJ mol–1 one carbon–carbon double bond.

cyclohexene cyclohexane

3
 Arenes – aromatic hydrocarbons

So, if benzene has three carbon–carbon double bonds as in Kekulé’s structure,

we might reasonably predict that ΔH for the hydrogenation of benzene
should be −360 kJ mol−1. But when the hydrogenation is carried out, the
measured enthalpy change is only −208 kJ mol−1.
The measured enthalpy change is much less exothermic than the estimated
value. This suggests that the addition of hydrogen to benzene does not involve
three normal double bonds, and that benzene is actually much more stable
than expected (Figure 1.7).

Figure 1.7 씰
Comparing the measured enthalpy Kekulé’s
change of hydrogenation of benzene with + 3H2
benzene
the estimated enthalpy change of
hydrogenation for Kekulé’s structure.

benzene + 3H2
Enthalpy
(energy Estimated
content)
ΔH = –360 kJ mol–1

Measured
ΔH = –208 kJ mol–1 cyclohexane

Test yourself
1 Assume that the empirical formula of benzene is CH. What further information is
needed to show that its molecular formula is C6H6? What methods do chemists
use to obtain this information?
2 Draw one possible structure for C6H6 which does not include a ring. Why does
this structure not fit with Kekulé’s structure for benzene?
3 An arene consists of 91.3% carbon.
a) What is the empirical formula of this arene?
b) What is the molecular formula of the arene if its molar mass is 92 g mol−1?
c) Draw the structure of the arene.
4 a) Look carefully at Figure 1.7. How much more stable is the real benzene
than Kekulé’s structure for benzene?
b) Predict the enthalpy change for the complete hydrogenation of
cyclohexa-1,3-diene.

1.3 Delocalisation in benzene

The accumulation of the evidence discussed in Section 1.2 led to increased
activity in the search for a more accurate model for the structure of benzene.
The ‘quick fix’ was to treat the carbon–carbon bonds in benzene as halfway
between single and double bonds, and draw them with a full line and a dashed
line side-by-side as in the right-hand diagram in Figure 1.5. This model
explains the absence of isomers of 1,2-dichlorobenzene, the equal carbon–
carbon bond lengths in benzene and also its resistance to reaction. In recent
years, the bonding between carbon atoms in benzene has been simplified to a
circle inside a hexagon as in Figure 1.8.
Figure 1.8 쑿 Although the structure in Figure 1.8 allows an improved understanding of
The usual way of representing benzene the properties of benzene, a better insight comes from considering its
4 today. electronic and orbital structure.
 Naming arenes

Figure 1.9 shows benzene with normal covalent sigma bonds (σ bonds)
between its carbon and hydrogen atoms. Each carbon atom uses three of its
electrons to form three σ bonds with its three neighbours. This leaves each
carbon atom with one electron in an atomic p-orbital.
Figure 1.9 씱
H H p-orbital Sigma bonds in benzene, with one
electron per carbon atom remaining
H H in a p-orbital.

H H

σ bond

These six p-orbital electrons do not pair up to from three carbon–carbon

double bonds (consisting of a σ bond plus a π bond) as in the Kekulé
structure. Instead, they are shared evenly between all six carbon atoms giving
rise to circular clouds of negative charge above and below the ring of carbon
atoms (Figure 1.10). This is an example of a delocalised π electron system
which results in any molecule where the conventional structure shows
alternating double and single bonds. Within the π electron systems, the
electrons are free to move anywhere.
H Figure 1.10 씱
delocalised electrons Representation of the delocalised π
C C bonding in benzene. The circle in a
H C C H benzene ring diagram represents six
delocalised electrons.
C C

H H
benzene

Molecules with delocalised electrons, in which the charge is spread over a

larger region than usual, are more stable than might otherwise be expected. In
benzene, this accounts for the compound being 152 kJ mol–1 more stable than
expected for the Kekulé structure. This way of showing the structure explains
the shape and stability of benzene.
The development of ideas concerning the structure of benzene illustrates
the way in which theories develop and get modified as new knowledge
becomes available.

1.4 Naming arenes

The name ‘benzene’ comes from gum benzoin, a natural product containing
benzene derivatives. These derivatives of benzene are named either as substituted
products of benzene or as compounds containing the phenyl group, C6H5−.
The names and structures of some derivatives of benzene are shown in
Table 1.1.
Systematic name Substituent group Structure Table 1.1 씱
chlorobenzene chloro, −Cl C6H5−Cl The names and structures of some
derivatives of benzene.
nitrobenzene nitro, −NO2 C6H5−NO2

methylbenzene methyl, −CH3 C6H5−CH3

phenol hydroxy, −OH C6H5−OH

phenylamine amine, −NH2 C6H5−NH2 5

 Arenes – aromatic hydrocarbons

When more than one hydrogen atom is substituted, numbers are used to
indicate the positions of substituents on the benzene ring (Figure 1.11). The
ring is usually numbered clockwise, and the numbers used are the lowest ones
possible. In some cases the ring is numbered anticlockwise to get the lowest
possible numbers.
In phenyl compounds, such as phenol and phenylamine, the −OH and
−NH2 groups are assumed to occupy the ‘1’ position.
Note
Cl Cl Cl
The names used for compounds with
a benzene ring can be confusing. The Cl
phenyl group C6H5− is used to name
many compounds in which one of the
hydrogen atoms in benzene has been CH3 Br
replaced by another atom or group. 1,2-dichlorobenzene 1-chloro-3-methylbenzene 1-bromo-3-chlorobenzene
The use of phenyl in this way dates
back to the first studies of benzene. At NH2 OH
this time, ‘phene’ was suggested as
Cl
an alternative name for benzene based
on a Greek word for ‘giving light’. The
name ‘phene’ was suggested because NO2
benzene had been discovered in the
tar formed on heating coal to produce Cl
gas for lighting. 3-nitrophenylamine 2,4-dichlorophenol

Figure 1.11 쑿
Naming disubstituted products of benzene and phenol.

Test yourself
5 How does the model of benzene molecules with delocalised π electrons account
for the following?
a) The benzene ring is a regular hexagon.
b) There are no isomers of 1,2-dichlorobenzene.
c) Benzene is less reactive than cycloalkenes.
6 When chemists thought that benzene had alternate single and double bonds, it
was sometimes named cyclohexa-1,3,5-triene. Why is this now an unsatisfactory
systematic name for benzene?
7 Why is the top right compound in Figure 1.11 named 1-bromo-3-chlorobenzene
and not 1-chloro-3-bromobenzene?

1.5 The properties and reactions of arenes

Arenes are non-polar compounds with weak intermolecular forces between
their molecules. The boiling points of arenes depend on the size of the
Data molecules. The bigger the molecules, the higher the boiling point. Benzene
and methylbenzene are liquids at room temperature, while naphthalene is a
solid (Figure 1.12).

CH3

Note
Benzene is toxic. It is also a
carcinogen. Because of this, benzene Figure 1.12 쑿
is banned from teaching laboratories. Three arenes – benzene, methylbenzene and naphthalene
Arene reactions can be studied using
other compounds, such as
Arenes, like other hydrocarbons, do not mix with water, but they do mix
methylbenzene or methoxybenzene. freely with non-polar solvents such as cyclohexane.
6
 The substitution reactions of arenes

Test yourself
8 Explain the existence of weak attractive forces between benzene molecules,
which are uncharged and non-polar.
9 Explain why benzene does not mix with water.
10 Name a solvent, other than cyclohexane, with which you would expect benzene
to mix freely.

The chemical reactions of arenes

Arenes burn in air. Unlike straight-chain alkanes and alkenes of similar molar
mass, they burn with a very smoky flame because of the high ratio of carbon
to hydrogen in their molecules (Figure 1.13).
Benzene and other arenes are similar to alkenes in having a prominent and
superficial electron-dense region. In arenes this is a delocalised ring of π
electrons, while in alkenes it is a single π bond.
Because of this similarity, both arenes and alkenes react with electrophiles
in many of their reactions. However, the similarity ends there because the
overall reactions of arenes involve substitution, unlike those of alkenes which
involve addition.
It is quite easy to see why addition reactions are difficult for arenes. If, for
example, benzene reacted with bromine in an addition reaction, the ring of
delocalised π electrons would be broken (Figure 1.14). Given the stability
associated with the delocalised π system, this would require much more energy Figure 1.13 쑿
than that needed to break the one double bond in ethene. A sample of methylbenzene burning in
air showing the yellow flame and very
Br smoky fumes.
+ Br2
Figure 1.14 씱
Br Benzene does not combine with bromine
in an addition reaction because its ring of
delocalised π electrons would be broken.
So, arenes tend to retain their delocalised π electrons and undergo
substitution rather than addition reactions.

1.6 The substitution reactions of arenes

Nitration
When benzene is warmed to about 55 °C with concentrated nitric acid in the
presence of concentrated sulfuric acid, the major product is yellow, oily
nitrobenzene (Figure 1.15).
Figure 1.15 씱
H H
The reaction of benzene with
concentrated nitric acid.
H C H H C NO2
C C conc. H2SO4 C C
+ HNO3 + H2O
C C at 55 °C C C
H C H H C H

H H
benzene nitrobenzene

A substitution reaction occurs in which hydrogen is replaced by a nitro group,

–NO2.
If the reaction mixture is heated above 55 °C, further nitration occurs
forming dinitrobenzene.
Nitration of benzene and other arenes is important because it produces a
range of useful products including dyes and powerful explosives such as TNT
7
(trinitrotoluene, now called 1-methyl-2,4,6-trinitrobenzene).
 Arenes – aromatic hydrocarbons

Figure 1.16 씰
Nitrated organic compounds, like TNT
(trinitrotoluene) and nitroglycerine, are
useful explosives in mining, tunnelling
and road-building.

Halogenation
Benzene will not react with chlorine or bromine in the dark. The halogen
molecules are non-polar and have no centre of positive charge to initiate an
attack of the delocalised electron system. However, if benzene is warmed with
bromine plus a catalyst of iron or iron(III) bromide, a reaction occurs forming
bromobenzene (Figure 1.17).
Figure 1.17 씰
The reaction of benzene with bromine. H Br

H C H H C H
C C C C
warm with
+ Br2 + HBr
C C Fe or FeBr3 C C
H C H H C H

H H
bromobenzene

A similar reaction occurs when benzene is warmed with chlorine in the

presence of iron, iron(III) chloride or aluminium chloride.

Test yourself
11 Boiling benzene reacts with chlorine gas in the presence of iron(III) chloride or
aluminium chloride.
a) Sketch the apparatus which could be used to carry out this reaction on a
small scale (though not in a teaching laboratory where benzene is banned).
b) Write an equation for the reaction.
12 Three possible isomers of dinitrobenzene can be produced. One of these
isomers is called 1,2-dinitrobenzene.
a) Draw and name the structures of the other two dinitrobenzenes.
b) Why is there no isomer called 1,6-dinitrobenzene?
13 a) Draw the structure of TNT. (Hint: Look closely at its systematic name of
1-methyl-2,4,6-trinitrobenzene.)
b) Why is TNT mixed with a compound containing a high proportion of oxygen,
such as potassium nitrate, when it is used as an explosive?

8
 The mechanism of electrophilic substitution

1.7 The mechanism of electrophilic substitution

Electrophilic substitutions are the characteristic reactions of arenes, such as
benzene, in which the delocalised π electrons are attacked by strong electrophiles.

Nitration
The mixture of concentrated nitric and sulfuric acids which reacts with benzene
is called a nitrating mixture. At 55 °C, concentrated nitric acid on its own reacts
very slowly with benzene, and concentrated sulfuric acid by itself has practically
no effect. However, in a mixture of the two, sulfuric acid reacts with nitric acid
to produce nitronium ions, NO2+, which are very reactive electrophiles:
HNO3 + H2SO4 → NO2+ + HSO4− + H2O
The nitronium ions are formed by removal of OH− ions from nitric acid by
sulfuric acid. In this reaction, HNO3 is acting as a base and H2SO4 is acting as
an acid.
The NO2+ ion is a reactive electrophile which is strongly attracted to the
delocalised electrons in benzene. As it approaches the benzene ring, the NO2+
ion forms a covalent bond to one of the carbon atoms using two electrons
from the π system (Figure 1.18).

H H Figure 1.18 씱
Electrophilic nitronium ions attack the
H C H H C H delocalised electrons in benzene to form
C C C C an intermediate cation.
+ NO2
+ NO2 +
C C C C
H C H H C H

H H

The formation of a covalent bond in an intermediate cation disrupts the

delocalised ring. A large input of energy is needed to do this and the reaction
has a fairly high activation energy.
The unstable intermediate cation quickly breaks down producing
nitrobenzene. This involves the return of two electrons from a C−H bond to
the π electron system. The stability of the delocalised ring is restored and
energy is released (Figure 1.19).

H H Figure 1.19 씱
The intermediate cation breaks down to
H C H H C NO2 form nitrobenzene.
C C C C
+ NO2 + H+
C C C C
H C H H C H

H H
intermediate cation nitrobenzene

Halogenation
When benzene is warmed with bromine in the presence of iron filings, the
bromine first reacts with the iron to form iron(III) bromide:
2Fe(s) + 3Br2(l) → 2FeBr3(s)
The iron(III) bromide then acts as a catalyst for the reaction of bromine with
benzene by polarising further bromine molecules as Brδ+−Brδ− (Figure 1.20).
δ+ δ– Figure 1.20 씱
Br Br + Fe3+(Br– )3 Br Br ..... Fe3+(Br– )3 Fe3+ ions in iron(III) bromide polarise 9
bromine molecules as Brδ+−Brδ−.
 Arenes – aromatic hydrocarbons

Definition The remaining steps in the bromination of benzene are similar to nitration.
Chemists sometimes use the term The δ+ bromine atoms in the polarised Br2 molecules act as electrophiles in a
halogen carrier to describe similar way to NO2+ ions.
substances – such as iron(III) bromide, An intermediate cation is first produced when the Brδ+ atom forms a
aluminium chloride and iron – which covalent bond with two electrons from the delocalised π system leaving a Br−
catalyse the reaction of benzene with ion. This intermediate then breaks down to form bromobenzene as two
chlorine or bromine. electrons are returned from the C−H bond to the π system and the stable,
delocalised ring is restored (Figure 1.21). At the same time, an H+ ion is
released from the intermediate cation. This H+ ion immediately combines
with the Br− ion released in stage 1 to form hydrogen bromide.
Tutorial
H H H

H C H H C H H C Br
C C δ+ δ– C C C C
+ Br Br + Br + Br– + HBr
C C C C C C
H C H H C H H C H

H H H

Figure 1.21 쑿
The mechanism for the bromination of benzene.

Activity

Studying the reaction of benzene with chlorine

Figure 1.22 shows the apparatus which might once have been used
to prepare chlorobenzene by heating benzene with chlorine gas in
the presence of iron filings. This preparation is now banned in
teaching laboratories in schools and colleges.

chlorine supply

excess
oil bath chlorine
at 70 °C
benzene and
iron filings
magnetic
anti-bumping
stirrer Figure 1.22 씱
granules
hot plate Preparing chlorobenzene.

1 Why is this reaction banned in teaching laboratories in schools?

2 a) Why should the reaction be carried out in a fume cupboard?
b) Why is a hot plate used?
c) Why is the oil bath at 70 °C?
10
 Comparing the reactions of arenes and alkenes

3 During the reaction, iron reacts with chlorine to form iron(III)

chloride, which then acts as an electron pair acceptor, polarising
the Cl2 molecules as Clδ+−Clδ−. Write equations to show:
a) the formation of iron(III) chloride
b) the polarisation of Cl2 as Clδ+−Clδ− by iron(III) chloride.
4 Write a mechanism, in two steps, for the reaction of polarised
Clδ+−Clδ− molecules with benzene to form an intermediate cation
plus Cl− in the first step, and then chlorobenzene plus HCl in the
second step.
5 The reaction shown in Figure 1.22 is just as effective if aluminium
chloride or iron(III) chloride is used in place of iron. These three
substances (Fe, FeBr3 and AlCl3 ) are often described as
‘catalysts’ and ‘halogen carriers’.
a) Why are these substances described as halogen carriers for
the reaction?
b) Why is it correct to describe aluminium chloride and iron(III)
chloride as catalysts?
c) Why is it incorrect to describe iron as a catalyst for the
reaction?
6 Aluminium chloride acts as a catalyst for the chlorination of
benzene by polarising Cl2 molecules in the same way as iron(III)
chloride.
a) Do you think aluminium chloride will be more effective or less
effective than iron(III) chloride?
b) Explain your answer to part a).
7 Aluminium chloride can also be used with halogenoalkanes, such
as chloromethane, CH3Cl, to add alkyl groups to benzene and
other arenes. The aluminium chloride increases the polarity of the
Cδ+−Clδ− bond of chloromethane and promotes the action of the
methyl group, δ+CH3−, as an electrophile.
Write a possible mechanism for the electrophilic action of
CH3δ+Clδ− on benzene to form an intermediate cation, which then
breaks up to form methylbenzene and hydrogen chloride.

1.8 Comparing the reactions of arenes and

alkenes
The electrophilic substitution of benzene occurs in three distinct steps
whatever the final product.
Step 1: The formation of a reactive electrophile, such as NO2+, Brδ+−Brδ−,
Clδ+−Clδ− or δ+CH3−Clδ−.
Step 2: The attack of the delocalised π system by the reactive electrophile
forming an unstable, intermediate cation.
Step 3: The decomposition of this intermediate cation producing a
substituted-benzene (nitrobenzene, bromobenzene, methylbenzene). 11
 Arenes – aromatic hydrocarbons

Notice that the first two steps of this mechanism (Figure 1.23) are similar to
the first two steps in the electrophilic addition of electrophiles – such as
chlorine, bromine and hydrogen bromide – to alkenes.

δ+ δ–
Step 1 Formation of an electrophile, Br Br

H H H
–
+ Br
H C H H C H H C Br
C C δ+ δ– Step 2 C C Step 3 C C H+ + Br–
+ Br Br + Br +
HBr
C C C C C C
H C H H C H H C H

H H H

H H H H
H H δ+ δ– Step 2 Step 3
C C + Br Br H C C H + Br– H C C H
+
H H
ethene electrophile Br Br Br

Figure 1.23 쑿 The third step of the mechanism is, however, very different. With benzene,
Comparing the mechanisms of the
the intermediate cation loses its charge by capturing two electrons from a
reactions of bromine with benzene and
with ethene.
C−H bond and releasing an H+ ion. The delocalised, stable aromatic system is
restored and a substitution reaction occurs.
With alkenes, there is no delocalised system or its associated stability. So, in
this case the intermediate cation combines with an anion, such as Br− or Cl−
and an addition reaction occurs.
These reactions of arenes and alkenes with electrophiles also differ in
another important way – their relative reactivities.
Benzene and arenes are resistant to bromination, chlorination and nitration
because of the stability of their delocalised π electrons. They must be heated,
and catalysed as well in the case of halogenation, before a reaction occurs.
Alkenes, however, will react with halogens and hydrogen halides rapidly at
room temperature because of the localised electron density of the C=C bond.
Electrons in the π bond of ethene and other alkenes are readily available to
any attacking electrophile.

Test yourself
14 a) Describe briefly how you would prepare bromobenzene from benzene.
b) Why does benzene not react with bromine unless a halogen carrier is
present?
15 Iodine will not react with hot benzene even in the presence of iron, but good yields
of iodobenzene can be produced by reacting benzene with iodine( I ) chloride.
a) Why do you think iodine will not react with hot benzene even in the presence
of iron?
b) How is iodine( I ) chloride polarised?
c) Using your answer to part b), explain why iodine( I ) chloride reacts with
benzene to give good yields of iodobenzene.

12
 Phenols

1.9 Phenols
Phenols are examples of compounds with a functional group directly attached
to a benzene ring. In phenols, the functional group is −OH. Experiments show
that the −OH group affects the behaviour of the benzene ring, while the
benzene ring also modifies the properties of the −OH group. As a result of
this, phenols have some distinctive and useful properties.

Structures and names

In general, phenols are compounds with one or more −OH groups directly
attached to a benzene ring. The simplest and most important is phenol itself.
The −OH group gives rise to hydrogen bonding in phenol and, therefore,
much stronger intermolecular forces than in benzene. As a result of this,
phenol is a solid at room temperature (Figure 1.24). The −OH group also Figure 1.24 쑿
allows phenol to interact with and dissolve slightly in water. Crystals of phenol.
Derivatives of phenol are named in a similar way to those of benzene – by
numbering the carbon atoms in the benzene ring, starting from the −OH
group. The numbering runs clockwise or anticlockwise to give the lowest
possible numbers for the substituted groups (Figure 1.25).

OH OH OH OH Figure 1.25 씱
1 1 The structure of phenol and other
O2N 6 NO2 CH3 2 phenols.
2 6
5 3
3 5
4 4 NO2

NO2 Br

phenol 2,4,6-trinitrophenol 2-methyl-5-nitrophenol 4-bromophenol

(not 6-methyl-3-nitrophenol)

Definitions
Test yourself
A phenol is a compound with one or
16 Explain in terms of intermolecular forces why: more −OH groups directly attached to
a) phenol is a solid while benzene is a liquid at room temperature a benzene ring.
b) phenol, unlike benzene, is slightly soluble in water
c) phenol does not mix with water as freely as ethanol.
17 What would you expect to observe on heating phenol until it burns?

1.10 Reactions of the –OH group in phenol

Reaction with sodium
Phenol reacts with sodium in a similar way to ethanol. Bubbles of hydrogen
form when a small cube of sodium is added to molten phenol or to a solution
of phenol in an inert solvent. The main product of the reaction is sodium
phenoxide.

OH O–Na+ Figure 1.26 씱

The reaction of phenol with sodium.

1
+ Na + 2 H2

sodium
phenoxide
13
 Arenes – aromatic hydrocarbons

Reaction with alkalis

The benzene ring makes the −OH group more acidic in phenol than it is in
alcohols. However, phenol is not as acidic as carboxylic acids (Section 3.2). It
does not ionise significantly in water and it does not react with carbonates to
produce carbon dioxide. But phenol, unlike alcohols, is acidic enough to form
soluble salts with aqueous alkalis. So, phenol reacts readily with a solution of
sodium hydroxide to form a solution of sodium phenoxide (Figure 1.27).
Figure 1.27 씰
Phenol reacting with alkali. OH(s) + NaOH(aq) O–Na+(aq) + H2O(l)

The phenoxide ion is more stable than might be expected because the
negative charge on the oxygen atom can be spread by delocalisation over the
whole molecule (Figure 1.28). This cannot happen in alcohols.
Figure 1.28 씰
The phenoxide ion showing the H
delocalisation of the negative charge. C C
H C C O–

C C

H H

1.11 Reactions of the benzene ring in phenol

Comparing the reactivity of benzene and phenol
The −OH group in phenol activates the benzene ring and makes the ring
more reactive than in benzene itself. A lone pair of electrons on the −OH
group interacts with the delocalised electrons in the benzene ring releasing
electrons into the ring and making electrophilic attack easier. As a result,
electrophilic substitution takes place under much milder conditions with
phenol than with benzene.

Reaction with bromine

An aqueous solution of phenol reacts readily with bromine water to produce
an immediate white precipitate of 2,4,6-tribromophenol as the orange/yellow
bromine colour fades. The reaction with bromine water is rapid at room
temperature. There is no need to heat the mixture or to use a catalyst
(Figure 1.29).
Figure 1.29 씰
OH OH
The reaction of phenol with bromine
water. Br Br
(aq) + 3Br2(aq) (s) + 3HBr(aq)

Br
2,4,6-tribromophenol

A test for phenols

Phenols give a purple colour when mixed with a neutral solution of iron(III)
chloride. The colour is due to a complex ion formed between the Fe3+ ions
and phenols.
14
 Reactions of the benzene ring in phenol

Test yourself
18 Identify one way in which the reaction of the −OH group is similar in phenol and
ethanol, and one way in which it differs.
19 a) What would you expect to observe if you added enough dilute hydrochloric
acid to a solution of phenol in sodium hydroxide to make the mixture acidic?
b) Explain the reaction that occurs.
20 Dilute nitric acid reacts rapidly with phenol at room temperature to form
2-nitrophenol and 4-nitrophenol.
a) Draw the structures of the two products.
b) How do these conditions for nitrating phenol compare with the conditions for
nitrating benzene?

Activity

Manufacturing phenol
Phenol is manufactured from benzene, propene and oxygen in two
stages. The procedure is called the cumene process (Figure 1.30).

CH3 CH3

CH OH
CH3 CH3
H+ O2
+ CH3 CH CH2 + C

O
benzene propene cumene phenol propanone
(1-methylethylbenzene)

● The first stage of the process involves the acid-catalysed Figure 1.30 쑿
electrophilic substitution of benzene with propene to form The manufacture of phenol by the
cumene. cumene process.

● The second stage involves the air oxidation of cumene.

This produces equimolar amounts of phenol and propanone, a

valuable co-product. About 100 000 tonnes of phenol are
manufactured each year in the UK using the cumene process.
1 Benzene and propene are obtained from crude oil for use in the
cumene process. What processes, starting with crude oil, are
used to produce:
a) benzene b) propene?
2 In the first stage of the cumene process, H+ ions react with
propene to produce electrophiles.
a) Write the formulae of two possible electrophiles produced
when H+ ions react with propene.
b) Explain why one of these electrophiles is more stable than the
other. (Hint: alkyl groups are slightly electron-donating.)
c) Name and draw the structure of a second possible product of
this first stage, besides cumene.
15
 Arenes – aromatic hydrocarbons

3 a) Write an equation for the reaction of the stable electrophile,

identified in 2b), with benzene to produce cumene.
b) Why is this reaction described as ‘acid catalysed’?
4 Write an equation for the second stage of the process, in which
cumene is oxidised to phenol and propanone.
5 The overall yield in the cumene process is 85%. Calculate the
mass of benzene required to manufacture 1 tonne of phenol, and
the mass of propanone formed at the same time.
6 In the USA, some phenol is manufactured by refluxing
chlorobenzene with concentrated sodium hydroxide solution at
400 °C and a pressure of 150 atmospheres (Figure 1.31).

Cl OH Figure 1.31 씱
The reaction of chlorobenzene with
H C H H C H hydroxide ions to form phenol.
C C C C
+ OH– + Cl–
C C C C
H C H H C H

H H

a) What kind of reagent are OH− ions in this reaction?

b) Why do you think the reaction requires such harsh conditions
to produce phenol?

1.12 The uses and importance of phenol

The main uses of phenol are in the production of:
● antiseptics and disinfectants
● thermosetting plastics
● intermediates for the manufacture of nylon (Section 6.3).

Antiseptics and disinfectants

Definitions Phenol is a powerful disinfectant which has been used to kill germs ever since
Disinfectants are chemicals which
it was isolated from coal tar in the nineteenth century. For a time, phenol was
destroy microorganisms. Phenol is a famous as a chemical which made surgery safe. In the mid-nineteenth century
disinfectant and so is chlorine. Unlike many doctors were puzzled by the life-threatening infections in many
antiseptics, disinfectants cannot be hospitals. These were so common that most of their patients died of gangrene
used on skin and other living tissues. after serious operations. Then, in 1857, a young surgeon called Joseph Lister,
Antiseptics are chemicals which kill working in Glasgow, read Louis Pasteur’s papers about the germ theory of
microorganisms but, unlike disease. Lister realised that he could use a disinfectant chemical while
disinfectants, they can be used safely operating to prevent the onset of an infection. He developed a technique of
on the skin. spraying a solution of phenol over open wounds during operations. As a result
of this, his patients had a much better chance of their wounds healing without
becoming infected. However, Lister eventually came to the conclusion that
scrupulous attention to cleanliness was preferable to spraying with chemicals.
Unfortunately, there are also risks involved with the use of phenol. It is an
unpleasant chemical which burns the skin and is therefore unsuitable as an
antiseptic. Since Lister’s time, chemists have discovered substituted phenols
which are suitable as antiseptics. These include Dettol and TCP (Figure 1.32)
in which chlorination increases the antibacterial properties of phenol and also
16 improves its healing properties as an antiseptic.
 The uses and importance of phenol

Figure 1.32 씱
OH OH
The structure of Dettol and TCP.
Cl Cl

H3C CH3
Cl Cl
4-chloro-3,5-dimethylphenol 2,4,6-trichlorophenol
(Dettol) (TCP)

Thermosetting plastics (resins) OH OH

When phenol is heated with methanal, H2C=O, in the presence of an acid or CH2 CH2 CH2
an alkali as catalyst, a hard and brittle plastic is formed. Initially, the reaction
links phenol molecules through their 2 and 6 positions to form a linear
polymer. These linear polymers then react further with methanal molecules to OH OH
form links through their 4 positions (Figure 1.33). CH2 CH2 CH2 CH2
The final product is a molecular network in which all the benzene rings are
substituted in the 2, 4 and 6 positions. This polymer is very hard because of its
extensively cross-linked network The hard, dark brown material was OH OH
discovered in 1905 in the USA by Leo Baekeland and named ‘Bakelite’. CH2 CH2 CH2
Bakelite is an excellent thermal and electrical insulator which is still widely
used for heat-resistant handles and knobs as well as electrical plugs and
fittings.
Bakelite has the disadvantage that it sets hard as it forms and cannot be CH2 CH2
remelted or softened. This makes it difficult to mould. Polymers of this kind
are described as thermosetting and are sometimes called resins. In contrast, Figure 1.33 쑿
polymers such as polythene and pvc, soften on heating and can be moulded The thermosetting plastic produced from
into different shapes, which they retain on cooling. These polymers are phenol and methanal.
described as thermoplastic.
Figure 1.34 씱
An advert for Bakelite in the 1950s
praising its properties. Bakelite was the
first commercially successful plastic.

Definitions
Thermoplastic polymers soften on
heating and can be moulded into a
different shape which is retained on
cooling.
Thermosetting polymers (or resins)
set hard on formation and cannot be
softened or moulded into different
shapes.

17
 REVIEW QUESTIONS
Extension questions
1 a) Describe the structure and bonding in benzene and c) Naphthalene reacts with nitric acid in the presence
explain why benzene is less reactive with of sulfuric acid to form
electrophiles than alkenes. (9)
NO2
b) Describe the conditions needed for the nitration of
benzene to form nitrobenzene, and outline the
mechanism of the reaction using curly arrows where
appropriate. (5) i) Describe the conditions required for the
2 a) Chlorobenzene can be produced from benzene and reaction. (2)
chlorine with a suitable catalyst. ii) What type of reaction occurs and what is the
i) Name the catalyst. (1) reactive species? (2)
ii) Describe briefly how chlorobenzene can be d) Copy, complete and balance the following equation
prepared. (3) for the reaction of naphthalene with iodine(I)
chloride: (2)
b) Under suitable conditions benzene can be used to
make the halogenoalkane shown below.
H Cl + Cl
Cl H
H Cl
+ 3Cl2
Cl H 4 Three reactions of phenol are summarised in the flow
H Cl diagram below.
Cl H
OH
i) What type of reaction occurs? (1)
ii) What is the name of the halogenoalkane 2-nitrophenol Reaction 1 Reaction 2
+ Bakelite
produced? (2) 4-nitrophenol A B
c) The halogenoalkane from part b) reacts on warming
with excess aqueous sodium hydroxide. Reaction 3 NaOH(aq)

i) Draw the structure of the final product with C

excess sodium hydroxide solution. (1)
a) Name reagents A and B. (2)
ii) What type of reaction occurs? (2)
b) Draw the structural formula of C. (2)
3 Naphthalene is an arene containing two fused benzene
c) Under suitable conditions, nitrophenols can be
rings. Its skeletal formula is
converted to dinitrophenols.
i) Suggest the reaction conditions for converting
nitrophenols to dinitrophenols. (2)
ii) One possible dinitrophenol is 2,3-dinitrophenol.
Write the names of all the other possible
a) What is i) the molecular formula; ii) the empirical
dinitrophenols. (3)
formula of naphthalene? (2)
d) Draw the structure of the molecule produced when
b) Describe the delocalisation of electrons in
two molecules of phenol react with one molecule of
naphthalene, including the shape of the delocalised
reagent B. (2)
system and the number of delocalised electrons. (5)

18
2 Carbonyl compounds
The two types of carbonyl compounds are the aldehydes and the
ketones. The reactive carbonyl group plays an important part in the
chemistry of living things, in laboratory chemistry and in industry. As
expected for a double bond, the characteristic reactions are addition
reactions. The C=O bond is polar because oxygen is highly
electronegative. As a result, the mechanism of addition to carbonyl
compounds is not the same as the mechanism of addition to alkenes.

2.1 Aldehydes
Names and structures
Aldehydes are carbonyl compounds in which a carbonyl group (C=O) is
attached to two hydrogen atoms, or to a hydrocarbon group and a hydrogen
atom. So the carbonyl group is at the end of a carbon chain. The names are
based on the alkane with the same carbon skeleton, with the ending changed
from –ane to –anal.

Figure 2.1 씰 O O O O
Structures and names of aldehydes. The
−CHO group is the functional group H C CH3 C CH3CH2 C C
which gives aldehydes their characteristic H H H H
reactions.
methanal ethanal propanal benzenecarbaldehyde
(benzaldehyde)

Occurrence and uses

Note Biologists use a solution of methanal to preserve specimens. Since the
Always write the aldehyde group as beginning of the twentieth century it has been the main ingredient of the
−CHO. Writing −COH is fluids used by embalmers. Methanal is also an important industrial chemical
unconventional and can easily lead to because it is a raw material for the manufacture for a range of thermosetting
confusion with alcohols. plastics (see Sections 1.12 and 6.1).

O
Figure 2.3 쑿
The skeletal formula of retinal, which is a
naturally occurring aldehyde. Combined
with a protein it forms the light sensitive
part of the visual pigment in the rod cells
of the retina. When light falls on a rod Figure 2.2 쑿
cell, the retinal molecule changes shape. A coloured scanning electron micrograph of rod cells in the retina of an eye. The cells
This sets off a series of changes that lead are magnified about 3000 times. Rod cells contain a visual pigment that can respond
19
to a signal being sent to the brain. to dim light but cannot distinguish colours.
 Carbonyl compounds

Physical properties
Methanal is a gas at room temperature. Ethanal boils at 21 °C so it may be a
liquid or gas at room temperature depending on the conditions. Other
common aldehydes are all liquids. The simpler aldehydes such as methanal
and ethanal are freely soluble in water.

Test yourself
1 Write the structure of 2-methylbutanal.
2 a) Show that the boiling points of aldehydes are higher than corresponding
alkanes with similar relative molecular masses, but lower than corresponding
Data alcohols.
b) Account for the values of the boiling points of aldehydes relative to those of
alkanes and alcohols in terms of intermolecular forces.
3 Why does an aldehyde such as ethanal mix freely with water, while
benzenecarbaldehyde (benzaldehyde) is much less soluble?

Activity

Converting an alcohol to an aldehyde

A 3 g sample of sodium dichromate(VI) is added to 10 cm3 of dilute
sulfuric acid in a pear-shaped flask. Then 1.5 cm3 of propan-1-ol are
added, a few drops at a time. The flask is gently shaken to mix the
contents until all the solid has dissolved. The flask is fitted with a
condenser as shown in Figure 2.4. Then 2–3 cm3 of liquid is distilled
into a small flask from the reaction mixture.

propan-1-ol +
sodium dichromate(VI) to fume
+ dilute sulfuric acid cupboard
or sink
heat

propanal

1 What type of alcohol is propan-1-ol? Figure 2.4 쑿

Apparatus used to oxidise an alcohol.
2 What type of reagent is an acidic solution of sodium
dichromate(VI)?
3 Write an equation for the reaction.
4 Suggest a reason for adding the propan-1-ol a few drops at a
time.
5 Explain why the reaction mixture is not heated in a flask fitted
with a reflux condenser before distilling off the product.
6 Describe two tests that can be used to show that the product of
this reaction is an aldehyde and not a carboxylic acid (see
Section 2.5).
20
 Ketones

Formation
Oxidation of primary alcohols by heating with a mixture of dilute sulfuric acid
and potassium dichromate(VI) produces aldehydes under conditions which
allow the aldehyde to distil off as it forms. Unlike ketones, aldehydes are easily
oxidised further to carboxylic acids by longer heating with an excess of the
reagent.

2.2 Ketones
Names and structures
In ketones, the carbonyl group is attached to two hydrocarbon groups.
Chemists name ketones after the alkane with the same carbon skeleton by
changing the ending -ane to -anone. Where necessary, a number in the name
shows the position of the carbonyl group.

O CH3 O
6 5 4 3 2 1
CH3 C CH3 CH3 CH CH2 C CH2 CH3
propanone 5-methylhexan-3-one

Figure 2.5 쑿
Structures and names of two ketones.

Occurrence and uses

The most widely used ketone is propanone, which is a common solvent. It has
a low boiling point and evaporates quickly, making it suitable for cleaning and
drying parts of precision equipment. Propanone is also the starting point for
producing the monomer of the glass-like addition polymer in display signs,
plastic baths and the covers of car lights (see Section 6.2). Propanone, and
Figure 2.6 쑿
other ketones, form during normal metabolism, especially at night and during A bottle of peppermint oil and leaves of
fasting when the levels of propanone and other ketones in the blood rise. the peppermint plant. The oil is used in
aromatherapy. Peppermint oil contains
Physical properties menthone together with a range of
chemicals which include menthol, methyl
All the common ketones are liquids with boiling points similar to those of the
ethanoate and volatile oils.
corresponding aldehydes. The simplest ketone, propanone, mixes freely with
water.

Formation
Oxidation of secondary alcohols with hot, acidified potassium dichromate(VI) O
produces ketones which, unlike aldehydes, are not easily oxidised further.

Test yourself
4 Write the structure of 4,4-dimethylpentan-2-one.
5 What is the molecular formula of menthone (Figure 2.7)? Figure 2.7 쑿
6 Show that propanone and propanal are functional group isomers. The skeletal formula of the naturally
7 Write an equation for the oxidation of butan-2-ol to butanone. (Represent the occurring ketone called menthone, which
oxygen from the oxidising agent as [O].) is found in the oils extracted from some
plants.

21
 Carbonyl compounds

Activity

Chemicals in perfumes
The perfume ‘Chanel No. 5’ was innovative when produced for the
first time in 1921. As well as natural extracts from flowers, the scent
includes a high proportion of synthetic aldehydes such as
dodecanal. This produces a highly original perfume.

O
O
undecanal citral

OH

OH

geraniol O citronellol

O Figure 2.8 씱
hexamethyl methyl dihydrojasmonate Skeletal formulae of some
tetralin musk perfume chemicals.

The people who devise new perfumes think of the mixture as a

sequence of ‘notes’. You first smell the ‘top notes’, but the main
effect depends on the ‘middle notes’ while the more lasting
elements of the perfume are the ‘end notes’. The overall balance of
the three is critical. This means that the volatility of perfume
chemicals is of great importance to the perfumer.

Note Natural chemicals Synthetic chemicals Boiling point or Table 2.1 씱

melting point Natural and synthetic chemicals
used to make perfumes.
top citrus oils octanal (citrus) b.p. 168 °C
lavender undecanal (green) b.p. 117 °C
middle rose geraniol (floral) b.p. 146 °C
violet citronellol (rosy) b.p. 224 °C
end balsam indane (musk) m.p. 53 °C
musk hexamethyl tetralin (musk) m.p. 55 °C

1 Draw the skeletal formula of octanal.

2 Suggest two advantages for the perfumer of using synthetic
chemicals instead of chemicals extracted from living things.
3 Identify the carbonyl compounds among the compounds shown
in Figure 2.8. In each case state whether the compound includes
22 the functional group of an aldehyde or of a ketone.
 Reactions of aldehydes and ketones

4 Like many perfume chemicals, geraniol is a terpene. Terpene

molecules are built from units derived from 2-methylbuta-1,3-diene.
a) What is the structure of 2-methylbuta-1,3-diene?
b) How many 2-methylbuta-1,3-diene units are needed to make
up the hydrocarbon skeleton of geraniol?
5 Use your knowledge of intermolecular forces to explain why:
a) aldehydes are useful as top notes while alcohols are more
commonly used as middle notes
b) the musks used as ‘end notes’ also help to ‘fix’, or retain, the
more volatile components of a perfume
c) geraniol is more soluble in water than undecanal.

2.3 Reactions of aldehydes and ketones

Oxidation
Oxidising agents easily convert aldehydes to carboxylic acids. It is much harder
to oxidise ketones – this is only possible with powerful oxidising agents which
break up the carbonyl molecules. Chemical tests to distinguish aldehydes and
ketones are based on the difference in the ease of oxidation (see Section 2.5).
O O Figure 2.9 씱
Cr2O72–(aq)/H+(aq) Oxidation of propanal to propanoic acid.
CH3 CH2 C + [O] CH3 CH2 C
heat
H OH
2−
Acidified potassium dichromate(VI) is orange and contains Cr2O7 ions.
When oxidising an aldehyde to a carboxylic acid, the reagent turns green
giving a solution containing green Cr3+ ions.

Reduction
Sodium tetrahydridoborate(III), NaBH4, reduces aldehydes to primary alcohols,
and ketones to secondary alcohols.
O Figure 2.10 씱
NaBH4 Reduction of propanal and propanone.
CH3 CH2 C + 2[H] CH3 CH2 CH2OH The 2[H] comes from the reducing agent.
propanal propan-1-ol This is a shorthand way of balancing
H
complex equations involving reduction.
CH3
NaBH4
C O + 2[H] CH3 CH2OH CH3

CH3
propanone propan-2-ol

Test yourself
8 Identify the oxidation states of chromium before and after the oxidation of an
aldehyde by a solution of potassium dichromate(VI).
9 a) Outline the reagents and conditions for converting butanal to butanoic acid
b) What apparatus is used i) to carry out the reaction ii) to separate the
product from the reaction mixture?
10 Name the products of reducing butanal and butanone. Which is a primary
alcohol and which a secondary alcohol?
11 Show that reduction of an aldehyde or ketone with NaBH4 has the effect of 23
adding hydrogen to the double bond.
 Carbonyl compounds

2.4 Nucleophilic addition

The carbonyl group in aldehydes and ketones is polar because oxygen is much
more electronegative than carbon. The shared electrons in the double bond
Tutorial are drawn towards the oxygen atom. This leaves a slight positive charge on
the carbon atom. As a result, the carbon atom in a carbonyl group is open to
attack by nucleophiles.
δ+ δ–
C O

C O
C

Figure 2.11 쑿
Two ways of representing the polarity of the double bond in a carbonyl group.

The reduction of a carbonyl compound with NaBH4 is an example of a

nucleophilic addition reaction.
An incoming nucleophile uses its lone pair of electrons to form a new bond
with the carbon atom. This displaces one pair of electrons in the double bond
onto the oxygen atom. So, the oxygen atom has gained one electron from
carbon and now has a negative charge.

O O–
NaBH4
CH3CH2 C CH3CH2 C
Step 1
H H H
H–

Figure 2.12 쑿
The first step of the nucleophilic addition. The hydride ion from NaBH4 is the
nucleophile.

To complete the reaction, the negatively charged oxygen atom acts as a base
and gains a proton.
δ+
H OH–
δ+
H O δ–

O– OH

CH3CH2 C CH3CH2 C
Step 2
H H H H

Figure 2.13 쑿
The second step of the nucleophilic addition. The negatively charged oxygen atom
acts as a base and gains a proton.

Test yourself
12 Answer these questions about the nucleophilic addition of hydrogen by reaction
of a carbonyl compound with NaBH4.
a) What features of the hydride ion mean that it is a nucleophile?
b) What type of bond breaking takes place in each step?
c) Explain why there is a negative charge on the oxygen atom at the end of
step 1.
24 d) Which molecule acts as an acid in step 2?
 Tests for aldehydes and ketones

2.5 Tests for aldehydes and ketones Definition

Chemists can use derivatives to
Recognising carbonyl compounds identify unknown organic compounds.
Converting a compound to a
Today, chemists can identify aldehydes and ketones with the help of crystalline derivative produces a
instrumental techniques such as mass spectrometry and infrared spectroscopy product which can be purified by
(Topic 9). Traditionally, chemists characterised these compounds by recrystallisation and then identified by
combining them with a reagent that could convert them to a solid product. measuring its melting point.
The solid, a so-called crystalline derivative, is a chemical which can be
purified by recrystallisation and then identified by measuring its melting point.
For example, the reagent 2,4-dinitrophenylhydrazine reacts with carbonyl
compounds forming 2,4-dinitrophenylhydrazone derivatives which are solid at
room temperature and bright yellow or orange (Figure 2.14). The solid
derivative has no practical use but it can be filtered off, recrystallised and
identified by measuring its melting point. Together with the boiling point of
the original aldehyde or ketone, this makes it possible to identify the carbonyl
compound.

Distinguishing aldehydes and ketones

Tollens’ reagent (ammoniacal silver nitrate) is a mild oxidising agent which is
used to distinguish aldehydes from ketones – aldehydes are easily oxidised but
ketones are not.
Tollens’ reagent consists of an alkaline solution of diamminesilver(I) ions,
[Ag(NH3)2]+. It forms a complex with ammonia and this keeps the silver(I)
ions in solution under alkaline conditions. The silver ions can oxidise
aldehydes but not ketones. Aldehydes reduce the silver ions to metallic silver. Figure 2.14 쑿
A bright orange 2,4-
dinitrophenylhydrazone derivative.

Figure 2.15 쑿
Warming Tollens’ reagent with an aldehyde produces a precipitate of silver which
coats clean glass with a shiny layer so that it acts like a mirror (left). There is no
reaction with a ketone (right).

Test yourself
13 a) Write an equation for the reaction of Tollens’ reagent with propanal. Use the
symbol [O] to represent the reagent.
b) Use the oxidation numbers of the metal ions and atoms to show that
propanal reduces Tollens’ reagent.
14 Hydrolysis of A, C4H9Cl, with hot, aqueous sodium hydroxide produces B,
C4H10O. Heating B with an acidic solution of potassium dichromate(VI) and
distilling off the product as it forms give C, C4H8O. C gives a yellow precipitate
with 2,4-dinitrophenylhydrazine and forms a silver mirror when warmed with
Tollens’ solution. Give the names and structures of these compounds. 25
 Carbonyl compounds

Activity

Identifying an unknown carbonyl compound

Figure 2.16 shows stages in making, purifying and identifying a
carbonyl compound.

stir impure minimum volume of

impure
derivative solid ethanol needed to
dissolve the solid
5 cm3 2,4-dinitrophenyl- Hirsch funnel
hydrazine reagent

to pump

hot water

hot solution
orange of deriva-
filtrate
precipitate of tive plus
the derivative impurities

rinse with ice-cold

solvent

solvent evaporates purified

to leave dry crystals solid

to pump
ice and
water
impurities in
capillary tube
solution in
ethanol
measure the melting
pure point of a sample of filtrate with
crystals crystals impurities recrystallised 2,4-dinitro-
phenylhydrazone derivative

1 Why is it necessary to purify the derivative before measuring its Figure 2.16 쑿
melting point? Making a pure crystalline derivative
of a carbonyl compound.
2 Explain how the procedure illustrated in Figure 2.16 removes
impurities from the derivative.
3 In this instance, ethanol is the solvent used for recrystallising the
derivative. What determines the choice of solvent? Practical
guidance
4 When measuring the melting point, what are the signs that the
derivative is pure?
5 Identify the carbonyl compound which forms a
2,4-dinitrophenylhydrazone that melts at 115 °C. It boils at 80 °C. Data
The compound does not form a silver mirror with Tollens’
26 reagent.
REVIEW QUESTIONS
Extension questions
1 Copy and complete the table to show three different 4 Cinnamaldehyde is the chemical that gives cinnamon
reactions of propanal. (6) its flavour. Vanillin is the chemical mainly responsible
for the flavour of vanilla.
Reactant Reagent Organic product
OH
Name Displayed formula
OCH3
CH3CH2CHO Tollens’ H
reagent
C C
CH3CH2CHO propanoic
acid H CHO CHO
cinnamaldehyde vanillin
CH3CH2CHO NaBH4

a) i) Work out the molecular formula of vanillin. (1)

−1
2 The molar mass of a hydrocarbon W is 56 g mol and ii) Name the two functional groups (other than
it contains 85.7% carbon. W reacts with hydrogen the benzene ring) in cinnamaldehyde. (2)
bromide to form X. Heating X under reflux with
aqueous sodium hydroxide produces Y. Heating Y with iii) Name the functional group which is also
an acidified solution of potassium dichromate(VI) present in vanillin. (1)
converts it to Z. Z gives a yellow precipitate with iv) Describe a test that could be used to show that
2,4-dinitrophenylhydrazine but it does not give a silver both cinnamaldehyde and vanillin contain this
mirror with Tollens’ reagent. functional group. (2)
a) Identify W, X, Y and Z and give your reasoning. (8) b) Describe a test that could be used to distinguish
b) Write equations for the reactions of W, X and Y vanillin from cinnamaldehyde. (2)
mentioned. (3) c) Give the structure of a cis/trans isomer of
3 Describe the mechanisms for the reactions of: cinnamaldehyde. (1)

a) propene with bromine d) i) Draw the structure of the product after treating
vanillin with NaBH4. (1)
b) propanone with NaBH4.
ii) Draw the structure of the compound formed
Identify similarities and differences between the two when this product reacts with excess aqueous
mechanisms with reference to the nature of the bonds sodium hydroxide solution. (1)
and bond breaking, the reagents involved, the
formation of intermediates and the overall effects of
the change. (10)

27
 3 Carboxylic acids and esters
Many organic acids are instantly recognisable by their odours.
Ethanoic acid, for example, gives vinegar its taste and smell.
Butanoic acid is responsible for the foul smell of rancid butter, while
the body odour of goats is a blend of the three unbranched organic
acids with 6, 8 and 10 carbon atoms. Organic acids play a vital part
in the biochemistry of life because of the great variety of their
reactions. The acids are also important in laboratory and industrial
chemistry and help to give rise to a range of new materials –
especially synthetic fibres and plastics.

3.1 Carboxylic acids

Occurrence
Carboxylic acids are compounds with the formula R−COOH, where R
represents an alkyl group, aryl group or a hydrogen atom. The carboxylic acid
group −COOH is the functional group which gives the acids their
characteristic properties.

Figure 3.1 쑿
The traditional names for organic acids were based
on their natural origins. The original name for
methanoic acid was formic acid because it was first
obtained from red ants and the Latin name for ‘ant’ is
‘formica’. This red wood ant can spray attackers with
methanoic acid (magnification ×10).

Figure 3.2 씱
Many vegetables contain ethanedioic acid, which is
commonly called oxalic acid. The level of the acid in
rhubarb leaves is high enough for it to be dangerous
to eat the leaves. The acid kills by lowering the
28 concentration of calcium ions in blood to a
dangerously low level.
 Carboxylic acids

Names and structures

The carboxylic acid group can be regarded as a carbonyl group, C=O,
attached to an −OH group, but is better seen as a single functional group
with distinctive properties.
Chemists name carboxylic acids by changing the ending of the
corresponding alkane to -oic acid. So, ethane becomes ethanoic acid.

O O O

H C CH3 C CH3CH2 C

OH OH OH
methanoic acid ethanoic acid propanoic acid

O O O

C C C

HO OH OH
ethanedioic acid benzenecarboxylic acid
(benzoic acid)

Figure 3.3 쑿 Figure 3.4 쑿

Names and structures of carboxylic acids. Ball-and-stick model of a carboxylic acid.

Test yourself
1 Write out the structural formulae and give the systematic names of the three
carboxylic acids that were traditionally derived from the Latin word ‘caper’
meaning goat: caproic acid (6C), caprylic acid (8C) and capric acid (10C).
2 Give the molecular formula, skeletal formula and name of the acid shown in
Figure 3.4.

Physical properties
Even the simplest acids, such as methanoic acid and ethanoic acid, are liquids
at room temperature because of hydrogen bonding between the carboxylic
acid groups. Carboxylic acids with more than eight carbon atoms in the chain
are solids. Benzenecarboxylic acid (benzoic acid) is also a solid at room
temperature. Carbon–oxygen bonds are polar.
There is also the possibility of hydrogen bonding between water molecules
and the −OH groups and oxygen atoms in carboxylic acid molecules. This
means that the acids are soluble in water.

Test yourself
3 Draw a diagram to show hydrogen bonding between ethanoic acid molecules
and water molecules.
4 In a non-polar solvent, ethanoic acid molecules dimerise through hydrogen
bonding.
a) Suggest a reason why the acid dimerises in a non-polar solvent, but not in
water.
b) Draw a diagram to show an ethanoic acid dimer with two hydrogen bonds
between the molecules.

29
 Carboxylic acids and esters

3.2 Reactions of carboxylic acids

Reactions as acids
Carboxylic acids are weak acids (see Section 12.3). They are only slightly
ionised when they dissolve in water:
CH3COOH(aq) CH3COO−(aq) + H+(aq)
The aqueous hydrogen ions in the solutions of these compounds mean that
they show the characteristic reactions of acids with metals, bases and
carbonates.
Carboxylic acids are sufficiently acidic to produce carbon dioxide when
added to a solution of sodium carbonate or sodium hydrogencarbonate. This
reaction distinguishes carboxylic acids from weaker acids such as phenols (see
Section 1.10).

O O

CH3 C (aq) + 2HCO3–(aq) CH3 C (aq) + H2O(l) + 2CO2(g)

OH O–

Figure 3.5 쑿
The reaction of ethanoic acid with hydrogencarbonate ions.

Test yourself
5 For each of these pairs of chemicals describe what you would observe when
they react, write equations for the reactions and name the organic products:
a) methanoic acid and magnesium
b) ethanoic acid and potassium hydroxide
c) propanoic acid and sodium carbonate
d) butanoic acid with ammonia.
6 Benzenecarboxylic acid (benzoic acid) is only very slightly soluble in water but it
dissolves freely in aqueous sodium hydroxide. Use le Chatelier’s principle to
explain why this happens – start by writing an equation for the equilibrium
between solid benzenecarboxylic acid and its aqueous ions in solution.

Esterification
Carboxylic acids react with alcohols to form esters (see Section 3.3). The two
organic compounds are mixed and heated under reflux in the presence of a
small amount of a strong acid catalyst, such as concentrated sulfuric acid.

O O
H+(aq)
CH3 C (l) + CH3CH2CH3OH(l) CH3 C (l) + H2O(l)
heat
OH OCH2CH2CH3

Figure 3.6 쑿
Formation of an ester from ethanoic acid and propan-1-ol.
Test yourself This reaction is reversible. The conditions for reaction have to be arranged to
increase the yield of the ester. One possibility is to use an excess of either the
7 Use le Chatelier’s principle to
explain the methods used to
acid or the alcohol, depending on which is more available or cheaper. Using
increase the yield of an ester more concentrated sulfuric acid than needed for its catalytic effect can help
formed from an acid and an alcohol. too because the acid reacts with water. In some esterification reactions it is
possible to distil off either the ester or the water as they form.

30
 Reactions of carboxylic acids

Activity

Preparation of an ester
This sequence of diagrams shows the procedure for preparing a
small sample of an ester.
Figure 3.7 씱
Stages in the preparation of an ester.
A B

reaction mixture
after refluxing

heat
ethanol and pure
ethanoic acid with
concentrated impure
sulfuric acid product
heat

D C
E

ester
aqueous
reagent

anti-bumping
granule organic layer granules of
heat from separating calcium chloride Shake with sodium carbonate
funnel (a drying agent) solution. Run off aqueous layer,
ethyl ethanoate then shake the ester with calcium
(fraction boiling between chloride solution to remove
74°C and 79°C) unchanged ethanol

1 Identify what is happening in each of the stages A, B, C, D and E.

2 Write an equation for the reaction which forms the ester and
name the product.
3 What is the purpose of the concentrated sulfuric acid?
4 What are the visible signs of reaction during stage C, and what
practical precautions are necessary during this stage?
5 The calcium chloride in step C removes unchanged ethanol from
the impure product. What type of reaction would you expect
between the alcohol and the CaCl2?
6 A volatile by-product distils off in the boiling range 35–40 °C
before the ester in stage E. Suggest a structure for this by-
product, which has the molecular formula C4H10O. Practical
guidance
7 Calculate the percentage yield of the ester if the actual yield is
50 g from 40 g ethanol and 52 g ethanoic acid. 31
 Carboxylic acids and esters

3.3 Esters
Occurrence and uses
Many of the sweet-smelling compounds found in perfumes and fruit flavours
are esters. Some drugs used in medicine are esters, including aspirin,
paracetamol and the local anaesthetics novocaine and benzocaine. The
insecticides malathion and pyrethrin are also esters. Compounds with more
than one ester link include fats and oils as well as polyester fibres. Other esters
are important as solvents and plasticisers.

Names and structures

The general formula for an ester is RCOOR′, where R and R′ are alkyl or aryl
groups.
Figure 3.8 쑿
Natural fruit flavours are complex
O
mixtures. Some simpler esters on their O O
own have odours which resemble fruit
C
flavours. Examples are propyl ethanoate CH3 C H C
(pear), ethyl butanoate (pineapple), octyl O CH2 CH3
ethanoate (orange), 2-methylpropyl OCH3 OCH2 CH3
ethanoate (apple).
methyl ethanoate ethyl methanoate ethyl benzenecarboxylate
Definition
(ethyl benzoate)
Essential oils are the oils which
chemists extract from plants as a Figure 3.9 쑿
source of chemicals for perfumes, Names and structures of esters.
food flavourings and other uses. They
often include esters. Test yourself
8 Give the name and displayed formulae of the esters formed when:
a) butanoic acid reacts with propan-1-ol
b) ethanoic acid reacts with methanol
c) ethanoic acid reacts with butan-1-ol.

Physical properties
Common esters such as ethyl ethanoate are volatile liquids and only slightly
soluble in water.

Test yourself
9 Explain, in terms of intermolecular forces, why the boiling point of ethyl ethanoate
is similar to that of ethanol, but lower than that of ethanoic acid.
Data

Making esters with acid anhydrides

Acid anhydrides are reactive compounds that can be used to make valuable
products such as the pain-killer aspirin, which is an ester.
The functional group in an acid anhydride is formed by eliminating a
molecule of water from two carboxylic acid groups. Sometimes this happens
simply on heating the acid but, generally, anhydrides are made in other ways.
Figure 3.10 씰 O O
Structures of two acid anhydrides.
CH3 C C
O O
C
CH3 C
O
32 O

ethanoic anhydride benzene-1,2-dicarboxylic anhydride

 Esters

Acid anhydrides are acylating agents. They react with alcohols to form esters.
O O Figure 3.11 씱
Reactions of ethanoic anhydride. The
CH3 C CH3 C ethanoyl group (the acyl group) is shown
in red.
acid OH
H2 O
(l) O (aq) amide NH2
+ NH 3
+ CH3COOH + CH3COOH Definitions
CH3 C
An acyl group consists of all the
O parts of a carboxylic acid except the
+C
) 2H
−OH group. The ethanoyl group,
OH(l CH3 C 5N
H CH3CO−, is an example of an acyl
O H5 2 (a O
C 2 O q) group.
CH3 C CH3 C An acylating agent is a chemical
which substitutes an acyl group for a
ester OC2H5 N-substituted NH C2H5
hydrogen atom when it reacts with an
amide
+ CH3COOH + CH3COOH −OH group or an −NH2 group.

Test yourself
10 a) Show that butenedioic acid can exist as two cis/trans isomers. Practical
b) One of these isomers forms an anhydride quite easily on heating above its guidance
melting point. Which isomer would you expect it to be? Draw the structure of
the anhydride formed.
11 Write a balanced equation for the reaction of ethanoic anhydride
with propan-1-ol.
12 Name the type of reaction taking place when ethanoic anhydride
reacts with water.

Hydrolysis reactions
Hydrolysis is a reaction that splits an ester into an acid and an alcohol
(Figure 3.12).
O O

CH3 C + H2O CH3 C + CH3CH2OH

O CH2CH3 OH

ester acid alcohol

Figure 3.12 쑿
Hydrolysis of an ester. These are the products when an ester is heated with an
excess of dilute aqueous acid, such as hydrochloric acid. This reaction is reversible.

Acids or bases can catalyse the hydrolysis. Hydrolysis catalysed by acid is a

reversible reaction. It is the reverse of the reaction used to synthesise esters
from carboxylic acids (see Section 3.2).
Base catalysis is generally more efficient because it is not reversible Test yourself
(Figure 3.13). This is because the acid formed loses its proton by reacting
13 Identify the products of heating:
with excess alkali. This turns it into a negative ion which does not react with a) propyl butanoate with dilute
the alcohol. hydrochloric acid
O O b) ethyl methanoate with aqueous
– sodium hydroxide.
CH3 C + OH CH3 C + CH3CH2OH 14 The reaction of ethyl ethanoate with
O CH2CH3 O– water is reversible under acid
conditions.
ester salt alcohol
a) What conditions favour the
hydrolysis of the ester?
Figure 3.13 쑿 b) How do these conditions
The result of hydrolysing ethyl ethanoate by heating it with an aqueous alkali, such as compare with those for the
sodium hydroxide. The salt and alcohol produced do not react with each other so this synthesis of the ester? 33
reaction is not reversible.
 Carboxylic acids and esters

3.4 Triglycerides
Fats, oils and fatty acids
Fats and vegetable oils are esters of long-chain carboxylic acids and the
alcohol propane-1,2,3-triol, better known as glycerol. There are three −OH
groups in a glycerol molecule so the alcohol can form three ester links with
carboxylic acids, giving rise to triglycerides (Figure 3.14).

H O

H C O C R
O
H C O C R′
O
Figure 3.15 쑿
A farmer inspecting sunflowers in a field. H C O C R′′
He is growing the flowers for their seeds
which will be compressed to extract oil H
for cooking. from from fatty acid
glycerol
three ester links
Definitions
Figure 3.14 쑿
A triglyceride is an ester of glycerol
The general structure of a triglyceride. In natural fats and vegetable oils, the
(propane-1,2,3-triol) and three
hydrocarbon chains may all be the same or they may be different.
carboxylic acid molecules. The
carboxylic acids may or may not all be Fats and oils belong to the family of compounds called lipids. Lipids are a
the same. broad class of biological compounds which are soluble in organic solvents such
Fatty acids are the naturally occurring as ethanol but insoluble in water. Lipids are very varied and include fatty
carboxylic acids in triglycerides. The acids, fats, vegetable oils, phospholipids and steroids. Lipids release more
acids have long hydrocarbon chains. energy per gram when oxidised than carbohydrates. This makes lipids
Saturated fatty acids do not have important as a concentrated energy store in living organisms.
double bonds in the hydrocarbon
The carboxylic acids in fats are usually referred to as ‘fatty’ acids (Table
chain. There is at least one C=C
3.1). Saturated fatty acids do not have double bonds in the hydrocarbon
double bond in a molecule of an
unsaturated fatty acid. chain, but there are double bonds in the molecules of unsaturated fatty acids.
Fatty Chemical name Formula
acid

palmitic hexadecanoic CH3(CH2)14COOH

stearic octadecanoic CH3(CH2)16COOH

oleic cis-octadec-9-enoic CH3(CH2)7CH=CH(CH2)7COOH

Table 3.1 씰
Examples of fatty acids. linoleic cis, cis-octadec-9,12-dienoic CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH

Fats are solid at around room temperature (below 20 °C). Fats contain a high
proportion of saturated fatty acids. Solid triglycerides are generally found in
animal fats. In lard, for example, the main fatty acids are palmitic acid (28%),
stearic acid (8%) and 56% oleic acid.
The triglycerides with unsaturated fatty acids have a less regular structure
than saturated fats (see Figure 3.16). The molecules do not pack together so
easily to make solids so they have lower melting points and have to be cooler
before they solidify. Triglycerides of this kind occur in plants and are liquids at
around room temperature. In a vegetable oil such as olive oil the main fatty
acids are oleic acid (80%) and linoleic acid (10%).
In the food industry, some fatty acids are labelled omega-3 or omega-6. This
naming system is based on omega, Ω, the last letter of the Greek alphabet.
The numbers 3 and 6 refer to the carbon atoms numbered from the end of the
34 chain furthest from the carboxylic acid group – the last carbon atom in the
 Triglycerides

chain. Counting in this way, omega-3 fatty acids have the first double bond
between carbon atoms 3 and 4, while omega-6 acids have the first double
bond between carbon atoms 6 and 7.
Figure 3.16 씱
OH Skeletal formulae to compare the shape
of palmitic acid and linoleic acid.
palmitic acid
O
O
9 1
10
OH

12

13 linoleic acid

18

Test yourself
15 Classify each of the acids in Table 3.1 as saturated or unsaturated.
16 Draw the skeletal formula of cis, cis, cis-octadec-9,12,15-trienoic acid.
17 Is octadec-9,12,15-trienoic acid (linolenic acid) an omega-3 or an omega-6 fatty
acid?

Hydrolysis
Hydrolysis of triglycerides produces soaps and glycerol. Soaps are the sodium
or potassium salts of fatty acids (Figure 3.17).

H O
H
H C O C (CH2)16CH3
O H C O H O

H C O C (CH2)16CH3 + 3Na+OH– H C O H + 3Na+ –O C (CH2)16CH3

O
H C O H
H C O C (CH2)16CH3
H
H glycerol sodium stearate (soap)

Figure 3.17 쑿
The hydrolysis of a fat or vegetable oil (triglyceride) with alkali to make soap. This
process is also called saponification.

Soaps are surfactants which help to remove greasy dirt because they have an
ionic head (water-loving) and a long hydrocarbon tail (water-hating). Soaps
first help to separate greasy dirt from surfaces. Then they keep the dirt
dispersed in water so that it rinses away. Test yourself
Most toilet soaps are made from a mixture of animal fat and coconut palm
oil. Soaps from animal fat are less soluble and longer lasting. Soaps from palm 18 Why is hydrolysis with alkali
oils are more soluble, so they lather quickly but wash away more quickly. Bars preferred to acid hydrolysis when
of soap also often contain dyes and perfumes, together with an antioxidant to making soaps from fats and oils?
stop the soap and air combining to make irritant chemicals.
35
 Carboxylic acids and esters

Hydrogenation
Margarine was invented as a cheap substitute for butter. The production of
margarine originally depended on adding hydrogen to the double bonds in
vegetable oils to turn them into saturated fats. This process turns a liquid oil
into a solid fat, so it is sometimes called ‘hardening’.
The catalyst for hydrogenating a vegetable oil is finely divided nickel which
is suspended in the oil during hydrogenation and then recovered by filtration.
It is not necessary to hydrogenate all the double bonds in an oil for it to be
sufficiently hardened for use in foods.
Margarine, and other non-dairy spreads, are blends of vegetable oils. Some
of them contain partly-hardened fats to make the product a spreadable solid.
Fats made by hardening vegetable oils are also used to manufacture products
such as cakes and biscuits.
Definitions Naturally occurring fatty acids exist as the cis-isomers. In the presence of
Polyunsaturated fats contain fatty the nickel catalyst used for hydrogenation, some of the cis-isomers become
acids with two or more double bonds trans. This means that there is a proportion of trans-fats in products made
in the chain. using partially hardened oils. There is growing concern that trans-fats may be
Some fats or oils provide fatty acids bad for health.
which are essential in the human diet. The formation of trans-fats contributes to the hardening process because a
Two essential fatty acids are linoleic molecule of a trans-fat is straight, rather than kinked. This means that its
and linolenic acids. shape is very much like the straight chain of a fully saturated fat.
Cholesterol plays an important part in
metabolism. It makes up part of cell Test yourself
membranes and is converted in the
body to steroid hormones, such as 19 Name the fatty acid formed by completely hydrogenating linoleic acid (see Table
the sex hormones testosterone and 3.1).
progesterone. High levels of 20 a) Draw skeletal formulae for cis-octadec-9-enoic acid (oleic acid) and trans-
cholesterol in the blood may lead to octadec-9-enoic acid (elaidic acid).
deposits building up in arteries, b) What has to happen during hydrogenation for the cis-isomer to turn into the
resulting in heart disease. trans-isomer?
c) Suggest a reason why a triglyceride with three elaidic acid molecules has a
higher melting point than a triglyceride with oleic acid molecules.

Rearranging esters in food

Food scientists have now found ways of turning vegetable oils into solid
spreads without hydrogenation. Instead they use a process which allows
triglycerides to swap fatty acid molecules. The result of this process of ‘inter-
esterification’ is a product with a higher melting point. This happens because
the process happens in a way that allows the molecules to pack together more
neatly to make a denser material.
Inter-esterification does not produce trans-fats but it does produce
triglycerides that are not found naturally. Catalysts for inter-esterification
include sodium methoxide and the enzyme lipase.

Test yourself
21 Draw a simple diagram to represent the process of inter-esterification.
22 Sodium methoxide is used as a catalyst for inter-esterification. Suggest reasons
why:
a) this can be hazardous
b) the catalyst is destroyed if there is water present in the vegetable oil.

36
 Triglycerides

Activity

Health risks and fats

The Food Standards Agency advises the public about diet and
health. The agency explains on its website that it is important to
have some fat in our diet because fat helps the body to absorb
some vitamins, it’s a good source of energy and a source of the
essential fatty acids that the body cannot make itself. However, the
agency also warns that having a lot of fat makes it easy to have
more energy than we need, which means we might be more likely to
put on weight.
We are told that we should be cutting down on food that is high in
saturated fats or trans-fats, or replacing these foods with ones that
are high in unsaturated fats instead. We should also be having more Figure 3.18 쑿
omega-3 fatty acids, which are found in oily fish. Milk, full-fat yogurt, cheeses and eggs
are rich in saturated fats. Having too
much saturated fat can increase the
amount of cholesterol in the blood,
which increases the chance of
developing heart disease.

Figure 3.19 씱
Foods containing hydrogenated
vegetable oil. Hydrogenated vegetable
oil is used because it both cheap and
extends the shelf-life of foods. Trans-
fats in these foods can have a similar
effect on blood cholesterol as
saturated fats – they raise the type of
cholesterol in the blood that increases
the risk of heart disease.
Unsaturated fats can be a healthy choice. These types of fats can
actually reduce cholesterol levels and provide us with the essential
fatty acids that the body needs. They include the unsaturated fats
found in oily fish, which may help prevent heart disease. Oily fish is
also the best source of omega-3 fatty acids.
A person who has never studied advanced chemistry has looked at
the Food Standards Agency website but wants to know more about
fats in the diet. Give answers to these questions using words and
diagrams suitable for a non-specialist.
1 What is the difference between a fat and a fatty acid?
2 Why are some fatty acids essential in the diet, while others are
not?
3 What is the difference between a saturated fat and an
unsaturated fat?
4 Why are trans-fats unnatural and how do they get into the food
we eat? Figure 3.20 쑿
Mackerel and sardines, walnuts and
5 Why do some spreads include trans-fats while others do not? flax seeds are rich in omega-3 fatty
acids. These fatty acids have been
6 What are omega-3 fatty acids, and what makes them special? shown to help protect against heart
disease. 37
 Carboxylic acids and esters

Esters for biodiesel

Biodiesel is a renewable fuel made from triglycerides in vegetable oils or
animal fats. The triglyceride is heated with methanol or ethanol in the
presence of a base to act as catalyst. If the base catalyst is sodium hydroxide, it
can be dissolved in the alcohol before being added to the triglyceride. When
the reaction is complete, the fatty acids are converted to methyl or ethyl
esters and glycerol separates as a by-product. Chemists call this ‘trans-
esterification’.
Figure 3.21 씰
Trans-esterification of fatty acids in a O O
triglyceride with methanol. R1, R2 and R3
represent the hydrocarbon chains of the CH2 O C R1 R1 C O CH3 CH2 OH
fatty acids. O O

CH O C R2 + 3CH3OH R2 C O CH3 + CH OH
O O

CH2 O C R3 R3 C O CH3 CH2 OH

The use of biodiesel is increasing because of the urgent need to reduce carbon
dioxide emissions to the atmosphere. The carbon dioxide released when
biodiesel burns is equivalent to the carbon dioxide taken in by photosynthesis
during growth. However, across the whole life cycle of these fuels they are not
carbon neutral because of the energy resources used during the production of
the fuel, including the manufacture of fertilisers, plant cultivation, harvesting,
extraction of oil and processing of the oil into fuel.
Some studies have investigated the carbon dioxide emissions resulting from
preparing rainforests, peatlands and grasslands to grow palms or soya beans for
biodiesel. Clearing the land can release between 17 and 420 times more
carbon than the annual savings from replacing fossil fuels.

Test yourself
23 Suggest a reason why the product of the reaction of a vegetable oil with
methanol produces a better fuel than the original oil itself.
24 Suggest a reason why the alcohol and the triglyceride must be very dry to
ensure a good yield of biodiesel.
Figure 3.22 쑿 25 a) Explain why the production and use of biodiesel could, in theory, be carbon
A tube of biofuel made from soy oil neutral.
extracted from soybeans at a biodiesel b) Why, in practice, is the production of biodiesel not carbon neutral?
plant in Argentina.

38
REVIEW QUESTIONS
Extension questions
1 a) Describe two examples of test-tube reactions that 3 Ibuprofen is a painkiller with this skeletal formula:
you could use to show the similarities and
differences between ethanoic acid and
OH
hydrochloric acid. (6)
b) Explain, with the help of equations, the O
observations you have described in part a). (6)
2 This question is about the reaction scheme involving a) What it the molecular formula of ibuprofen? (1)
2-hydroxybenzenecarboxylic acid shown below. b) Suggest whether or not ibuprofen is soluble or
insoluble in water. Explain your answer in terms
an ester of intermolecular forces. (3)
c) Draw the displayed formula of the organic products
ethanol
COOH when ibuprofen reacts with:
OH i) dilute sodium hydroxide solution (1)

ethanoic ii) ethanol and a little sulfuric acid on warming.(1)

anhydride COOH
4 Octadecanoic acid and cis-octadec-9-enoic acid are
2-hydroxybenzenecarboxylic OCOCH3 fatty acids present in the triglycerides that make up
acid (salicylic acid) fats and vegetable oils.
a) Suggest an explanation for the fact that
aspirin octadecanoic acid is a solid while
cis-octadec-9-enoic acid is a liquid at room
temperature. (3)
a) Give the formula of the product when
2-hydroxybenzenecarboxylic acid reacts with b) Describe a chemical test that could be used to
excess dilute sodium hydroxide. (2) distinguish between the two fatty acids. (3)
b) i) Write the structure of the ester formed by its c) Explain what is meant by a triglyceride. (2)
reaction with ethanol. (1)
d) Reaction with hydrogen in the presence of a nickel
ii) What are the conditions for making the ester catalyst is used to harden vegetable oils for the food
from 2-hydroxybenzoic acid? (2) industry. During partial hydrogenation, some of the
fatty acids change from the cis to the trans form.
c) i) Write the displayed formula of ethanoic
anhydride. (1) i) What happens to cis-octadec-9-enoic acid when
it reacts with hydrogen? (1)
ii) Which functional group is present in aspirin as
a result of the reaction of ii) What is the difference between cis-octadec-9-
2-hydroxybenzenecarboxylic acid with ethanoic enoic acid and trans-octadec-9-enoic acid? (2)
anhydride? (1)
iii) Why should people be concerned by the use of
d) i) Give the structural formula of the product when partial hydrogenation to prepare ingredients for
aspirin reacts with cold, dilute sodium foodstuffs? (2)
hydroxide solution. (1)
ii) Suggest an advantage of using the product in
part d i) as a drug instead of the form of aspirin
shown at the start of this question. (1)

39
 4 Amines
Amines can be very smelly. Ethylamine, for example, has a fishy smell.
However, the importance of the amine functional group is not its
smell, but the role it plays in biochemistry and medicine. The amine
group is present in amino acids, the monomers for proteins (Topic 5).
As a result of this, the amine group plays an important part in
metabolism and it appears in the structures of many medical drugs.
In the chemical industry, aromatic amines have commercial value
because they are the basis of the manufacture of a wide range of
colourful dyes.

Figure 4.1 쑿
The active constituent of asthma
inhalers is salbutamol, which
contains the amine group.

Figure 4.2 씰
The smell of fish is partly due to
ethylamine.

4.1 Structures and names

Amines are nitrogen compounds in which one or more of the hydrogen atoms
in ammonia, NH3, is replaced by an alkyl or an aryl group. The number of
these groups determines whether the compound is a primary amine, a
secondary amine or a tertiary amine. If one H atom in ammonia is replaced by
an alkyl or aryl group, the compound is a primary amine; if two H atoms are
Note replaced, the compound is a secondary amine; and if all three H atoms in
Notice that the terms primary, ammonia are replaced, the compound is a tertiary amine.
secondary and tertiary do not have Chemists have two systems for naming amines.
the same meaning with amines as
they do with alcohols. Simple amines
Simple amines are treated as a combination of the alkyl or aryl group followed
by the ending –amine. So, CH3CH2NH2 is ethylamine, C6H5NH2 is
phenylamine and CH3CH2NHCH3 is ethylmethylamine. The prefixes di- and
tri- are used when there are two or three of the same alkyl or aryl group
(Figure 4.3).

H CH3 CH3

Figure 4.3 씰 CH3 N CH3 N CH3 N

The structures and names of primary,
secondary and tertiary amines containing H H CH3
the methyl group.
methylamine dimethylamine trimethylamine
40 (a primary amine) (a secondary amine) (a tertiary amine)
 The properties and reactions of amines

More complex amines

The prefix ‘amino-’ is used in compounds that have a second functional group
which appears at the end of the name. This is the case with amino acids that
O
contain the C group.

OH
So, the systematic name for NH2CH2COOH is aminoethanoic acid. The
prefix ‘diamino-’ is used for compounds containing two amino groups.

Test yourself
1 Draw the structures of:
a) diethylamine
b) ethylmethylpropylamine
c) 1,6-diaminohexane
d) 1,2-diaminopentane, which contributes to the smell of rotting flesh and has
the common name cadaverine
e) 1-phenyl-2-aminopropane, an amphetamine which is an addictive stimulant.
2 Salbutamol is the active ingredient in asthma inhalers.

HOCH2 CHOH N
CH2 C(CH3)3
HO
Figure 4.4 쑿
The structure of salbutamol.

a) Is its amine group primary, secondary or tertiary?

b) What other functional groups does salbutamol contain?

4.2 The properties and reactions of amines

The physical and chemical properties of the simplest amines are similar to
those of ammonia. So, methylamine and ethylamine are gases at room
temperature and they smell like ammonia, though with a fishy character.
Alkyl amines with short hydrocarbon chains are freely soluble in water, like
ammonia. Phenylamine, with its large non-polar benzene ring, is only slightly
soluble in water.

Test yourself
3 Methylamine, like ammonia, will mix with and dissolve in water whatever
proportions are mixed together. Why is this?
4 Ethane (b.p. −89 °C) and methylamine (b.p. −6 °C) have very similar molar
masses, but very different boiling points. Why is this?
5 Look at the boiling points of methylamine, dimethylamine and trimethylamine on
the data sheets on the Dynamic Learning Student website. Why do you think the
boiling point of trimethylamine, (CH3)3N, is lower than that of dimethylamine?
Data

Amines as bases
Primary amines, like ammonia, can act as bases. The lone pair of electrons on the
nitrogen atom of ammonia and amine molecules is a proton (H+ ion) acceptor.
H CH3 Figure 4.5 씱
Comparing the structures and basic 41
H N H H N H character of methylamine and ammonia.
 Amines

Reaction with water

Methylamine and other simple amines dissolve freely in water because they
react with it. The amines act as bases removing H+ ions (protons) from water
molecules to form an equilibrium mixture containing ions.

H H H H
+ –
H C N + H O H H C N H + O H

H H H H

CH3NH2(aq) + H2O(l) CH3NH3+(aq) + OH–(aq)

methylamine methylammonium ion

Figure 4.6 쑿
glass rod dipped The reaction of methylamine with water.
in conc. HCI
The reactions of simple amines, like methylamine, with water are very similar
to that of ammonia with water:
NH3(aq) + H2O(l) NH4+(aq) + OH−(aq)

Reaction with acids

Amines react even more readily with acids than they do with water. The lone
pair on the nitrogen atom rapidly accepts an H+ ion (proton) from an acid to
form a substituted ammonium salt.
white smoke When ethylamine vapour reacts with hydrogen chloride gas, the product is
ethylammonium chloride. This forms as a white smoke which settles as a
white solid (Figure 4.7).
CH3CH2NH2(g) + HCl(g) → CH3CH2NH3+Cl−(s)
ethylamine ethylammonium chloride
This reaction is very similar to that of ammonia with hydrogen chloride to
concentrated solution form ammonium chloride.
of ethylamine
NH3(g) + HCl → NH4+Cl−(s)
Figure 4.7 쑿
The vapours from ethylamine solution Phenylamine, C6H5NH2, is only slightly soluble in water, but it dissolves in
and concentrated hydrochloric acid react concentrated hydrochloric acid very easily. This is because it reacts with H+
to form a white smoke. ions in the acid to form phenylammonium ions, which are soluble in the
aqueous mixture.
C6H5NH2(l) + H+(aq) → C6H5NH3+(aq)
If a strong base, such as sodium hydroxide, is added to the aqueous
phenylammonium ions, H+ ions are removed from the phenylammonium ions
and yellow, oily phenylamine reforms.
C6H5NH3+(aq) + OH−(aq) → C6H5NH2(l) + H2O(l)
phenylamine

42
 The preparation of amines

Amines as nucleophiles Test yourself

Amines are strong nucleophiles as well as strong bases, just like ammonia. As
nucleophiles, their lone pair of electrons is attracted to any positive ion or 6 a) Write an equation to show the
positive centre in a molecule. formation of a salt when
So, amines will react with the δ+ carbon atoms in the C−Hal bond of propylamine vapour reacts with
halogenoalkanes (Figure 4.8). hydrogen bromide gas.
b) Explain why the reactants are
both gases, but the product is a
H H H H H H
solid.
δ+ δ– 7 Write equations for the following
H C C Cl H C C N+ C H Cl–
reactions and name the products:
a) ammonia with concentrated
H H N H H H H sulfuric acid
CH3 H ethylmethylammonium b) methylamine with concentrated
H chloride sulfuric acid
c) dimethylamine with
Figure 4.8 쑿 concentrated sulfuric acid.
The reaction of methylamine with chloroethane

4.3 The preparation of amines

Two key reactions are used in the preparation of amines – one for aliphatic
amines, the other for aromatic (aryl) amines.

Preparing aliphatic amines

An aliphatic amine can be prepared by heating the corresponding
halogenoalkane in a sealed flask with excess ammonia in ethanol. Ammonia
acts as a nucleophile during the reaction. The initial product is a salt of the
amine. The free amine can be liberated from its salt by adding dilute sodium
hydroxide solution (Figure 4.9).

H H H H Reflux H H H H H H H H H
H
δ+ δ– with excess +
–
Add
H C C C C Br H C C C C N H Br H C C C C N + H2O + Br–
conc. NH3 NaOH(aq)
H H H H in ethanol H H H H H H H H H H
N
H OH–
H
H

Figure 4.9 쑿
The preparation of butylamine from 1-bromobutane and excess concentrated
ammonia in ethanol.

Preparing aromatic amines

The usual laboratory method for introducing an amine group into an aromatic
compound is a two-step process – first nitration to make a nitro compound,
and then reduction (Figure 4.10).

NO2 NH2
conc. HNO3 Sn metal
conc. H2SO4 + conc. HCl
50–60°C heat
benzene nitrobenzene phenylamine

Figure 4.10 쑿
The two-step preparation of phenylamine from benzene.

43
 Amines

Test yourself The reduction of the nitroarene is achieved by boiling under reflux with tin
and concentrated hydrochloric acid (Figure 4.11). The aromatic amine
8 Describe the mechanism, using dissolves in excess concentrated HCl forming a salt. The free amine can be
appropriate curly arrows, for the liberated from the solution by adding sodium hydroxide solution and is then
nucleophilic substitution of separated from the mixture by steam distillation.
1-chloropropane with ammonia.
9 When preparing primary alkylamines
from halogenoalkanes:
a) excess ammonia is used. Why
is this? (Hint: How would the
alkylamine which forms react water out
with any excess
halogenoalkane?)
concentrated
b) a solution of ammonia in
hydrochloric acid
ethanol is used rather than
ammonia in water. Why is this? water in
(Hint: ammonia reacts with
water to produce an alkaline
solution containing OH− ions.)

Figure 4.11 씰
Reducing nitrobenzene to phenylamine cold water while adding
by refluxing with tin and hot, nitrobenzene
the acid, then boiling to
concentrated hydrochloric acid. tin complete the reaction

4.4 Diazonium salts

Alkyl and aryl amines react with nitrous acid, HNO2, below 10 °C to produce
diazonium salts containing the diazo group, N≡N+−. The diazonium salts of
aryl amines are important intermediates in the manufacture of azo dyes.
Diazonium salts are unstable. However, the diazonium salts of aryl amines
are stabilised by delocalisation and they are useful reagents if kept cool.
Benzenediazonium chloride is prepared by adding a cold solution of sodium
nitrite, NaNO2, to a solution of phenylamine in concentrated hydrochloric
acid at 5 °C.
Initially, the sodium nitrite reacts with the hydrochloric acid to form
nitrous acid. This then reacts with the phenylamine and more conc. HCl to
produce benzenediazonium chloride.
Figure 4.12 씰 H H
Preparing benzenediazonium chloride
+
from phenylamine.
H C NH2 H C N N Cl–
C C 5°C C C
+ HNO2 + HCl + 2H2O
C C C C
H C H H C H

H H
benzenediazonium chloride

The diazonium salts of alkyl amines are much more unstable and decompose
immediately to form the corresponding alcohol and nitrogen gas, even at 5 °C.
5 °C
CH3CH2−NH2 + HNO2 + HCl ⎯→ CH3CH2−N+≡NCl− + 2H2O
then CH3CH2−N+≡NCl− + H2O → CH3CH2OH + N2 + HCl
Nitrous acid itself is also unstable. It is a weak acid which looks very pale blue
in aqueous solution. At room temperature, nitrous acid starts to decompose
forming water, nitrogen monoxide and nitrogen dioxide:
44
2HNO2(aq) → H2O(l) + NO(g) + NO2(g)
 Azo dyes

The nitrogen dioxide is very soluble in water, but the nitrogen monoxide
escapes into the air and turns brown as it reacts with oxygen to form nitrogen
dioxide:
2NO(g) + O2(g) → 2NO2(g)
As the nitrous acid is unstable, it is usually prepared as and when needed by
adding hydrochloric acid to sodium nitrite. The nitrous acid is said to be
generated in situ.

Test yourself
10 a) Write an equation for the formation of nitrous acid, HNO2, in situ from
sodium nitrite solution and hydrochloric acid.
b) Write an ionic equation for the formation of nitrous acid, excluding spectator
ions and showing only the ions involved.
c) The structural formula of nitrous acid is H−O−N=O. Draw a ‘dot-and-cross’
diagram for nitrous acid showing outer shell electrons only.
11 When nitrous acid decomposes, it disproportionates (gets oxidised and reduced
at the same time).
a) Write an equation for the decomposition of nitrous acid.
b) Calculate the oxidation numbers of the different atoms before and after
decomposition and explain why disproportionation has occurred.
12 A solution of benzenediazonium chloride decomposes forming phenol above 10 °C.
a) What are the other products of the decomposition?
b) Write a balanced equation, with state symbols, for the decomposition.
13 What kind of reactants would you expect diazonium ions with the diazo group,
N≡N+−, to be?

4.5 Azo dyes

The positive charge on the N≡N+− group means that diazonium ions are
strong electrophiles. So, we would expect them to attack aryl compounds with
delocalised π electrons, particularly those that have an electron-donating
group, such as −OH in phenols (Figure 4.13) and −NH2 in aromatic amines.

+ cold
N N + OH N N OH + H+
solutions
in NaOH(aq) 4-hydroxyazobenzene

Reactions like this between diazonium ions and phenols or aromatic amines are Figure 4.13 쑿
called coupling reactions. If a cold solution of benzenediazonium chloride is The reaction between benzenediazonium
added to a cold solution of phenol in sodium hydroxide, an orange precipitate ions and phenol.
forms. The precipitate is 4-hydroxyazobenzene, which is an azo dye.
The commercial importance of diazonium salts is based on their coupling
reactions with phenols and aromatic amines to form azo dyes. Most of these
dyes are red, orange or yellow. As we have already seen, benzenediazonium
chloride reacts with phenol to give an orange dye. With phenylamine it
produces a yellow dye 4-aminoazobenzene (Figure 4.14).
+
N N Cl– + NH2 N N NH2 + HCl

4-aminoazobenzene

Unlike diazonium compounds, azo compounds are very stable and unreactive. Figure 4.14 쑿
The bright colours of azo compounds result from the extended delocalised The reaction of benzenediazonium
electron systems that spread across the whole molecule through the azo group, chloride with phenylamine to form the
−N=N−. These delocalised azo systems absorb light in the blue region of the yellow dye 4-aminoazobenzene.
spectrum which results in the yellow, orange and red dyes. 45
 Amines

When azo dyes were first discovered in the late nineteenth century, they
heralded a new regime for the dyeing of different fabrics. Vegetable dyes,
which had been used in the past, faded easily. Azo dyes fade much more
slowly as a result of atmospheric oxidation and are not removed by water,
soap or other cleaning agents because they attach themselves more strongly
to fabrics.

Test yourself
14 a) Write an equation for the coupling reaction
OH
between benzenediazonium chloride and
naphthalen-2-ol (Figure 4.16) to form an azo dye.
b) Why is the reaction usually carried out with the
naphthalen-2-ol dissolved in sodium hydroxide
Figure 4.16 쑿
solution?
Figure 4.15 쑿
15 a) Draw the structures of the diazonium compound and the amine which could
This shirt is dyed with azo dyes.
be used to make the red form of the acid–base indicator, methyl orange, in
Figure 4.17.
O
H3C
N N N S OH
H3C
O
Figure 4.17 쑿
The red form of methyl orange.
b) Draw the structure of the amine used to make the diazonium compound in
part a).
c) Draw the structure of the yellow form of methyl orange which is produced in
an alkaline solution such as NaOH(aq).

Azo dyes are also used in some foods (Figure 4.18) in spite of their toxicity.
Fortunately, azo dyes are so strongly coloured that the quantities used amount
to only milligrams per kilogram of food. Even so, some azo dyes have been
banned from use in food (see the Activity on page 96). The toxicity arises not
from the azo dyes themselves, but when they are metabolised and broken
down in the body. Their breakdown produces aromatic amines, some of which
are carcinogenic.
Some azo dyes were once thought to increase, or possibly cause,
Figure 4.18 쑿 hyperactivity in children. Since the late 1970s, there have been several studies
Azo dyes are used to colour foods such into the effects of azo dyes on hyperactivity, but most have proved
as sweets and fruit drinks. inconclusive.
However, there is more substantial evidence to suggest that certain azo
dyes, especially tartrazine (Figure 4.19), increase the allergic reactions to some
drugs and cause increased breathing problems in people with asthma.
O
Figure 4.19 씰
Tartrazine. Na+ –O C C C N N S O– Na+

O N C O

N OH

O S O

46 O– Na+
 Azo dyes

Activity

Synthesising the azo dye, dispersol fast yellow

Azo dyes account for about 60–70% of all the dyes used in food and textile
manufacture. In theory, they can provide a complete spectrum of colours, but
red, orange and yellow dyes are more common than blues and greens.
One important azo dye used with textiles is dispersol fast yellow. This can be
synthesised from phenylamine using the five-step process shown in Figure 4.20.
Figure 4.20 씱
NH2 NH2 NH2 NH2
The synthesis of
dispersol fast yellow.
Step 1 Step 2 Step 3

NO2 NH2 NH C CH3

O Step 4
phenylamine Substance A Substance B Substance C
+
N N Cl–
CH3
CH3
C O
Step 5
N N NH
NH C CH3
OH
O
dispersol fast yellow Substance D
1 Name substances A and B.
2 In aromatic amines, the −NH2 group contributes the lone pair of electrons
on the nitrogen atom into the delocalised electron system of the benzene
ring, in a similar manner to the −OH group in phenols. With this in mind,
predict the reagent and conditions required for step 1.
3 Name the reagents and conditions required for step 2.
4 The reagent used to carry out step 3 is ethanoyl chloride, CH3 C Cl .
a) What is the other product of step 3 besides
O
substance C?
b) Is ethanoyl chloride acting as an electrophile or a nucleophile in step 3?
c) Why is step 3 likely to be inefficient?
5 State the names of the reagents, in addition to substance C, and the
reaction conditions required for step 4.
6 a) Give the name and structural formula of the reagent used with
substance D in step 5.
b) Why do you think that coupling in step 5 is to one of the carbon atoms
next to that to which the −OH group is attached?
7 Suggest two essential properties which a commercial dye must have in
addition to being coloured.

47
 REVIEW QUESTIONS
Extension questions
1 Diazonium compounds are important intermediates in 3 A series of tests were carried out on three organic
the manufacture of synthetic azo dyes. compounds A, B and C. The results of the tests are
described below.
a) What reaction conditions and reagents are used to
make an aqueous solution of the diazonium ion State the deductions you can make from the tests on
C6H5−N+≡N Cl− from phenylamine? (3) each of A, B and C.
b) Explain the following including appropriate You are not expected to identify compounds A, B and
equations in your answer. C.
i) Solid benzenediazonium chloride, a) i) A is a colourless liquid which does not mix with
C6H5−N+≡NCl−, is not usually isolated because water. (1)
it is explosive. (3)
ii) After warming a few drops of A with aqueous
ii) Stable solutions of diazonium ions cannot be sodium hydroxide, the resulting solution was
obtained from aliphatic primary amines like acidified with nitric acid. Silver nitrate solution
propylamine. (3) was then added and a cream-coloured
precipitate formed. (2)
c) The benzenediazonium ion reacts with phenol
in alkaline solution to form the azo dye b) i) B is a white solid which chars on heating, and
4-hydroxyazobenzene as shown below. gives off a vapour which condenses to a liquid
that turns cobalt chloride paper from blue to
+ pink. (2)
N N + OH
ii) A solution of B turns universal indicator red. (1)
iii) A solution of B reacts with aqueous sodium
carbonate to produce a colourless gas which
turns limewater milky. (2)
iv) When a little of B is warmed with ethanol and
N N OH + H+
one drop of concentrated sulfuric acid, a sweet-
smelling product can be detected on pouring
the reaction mixture into cold water. (2)
i) What type of reagent is the diazonium ion in
this reaction? (1) c) i) C is a liquid which burns with a very smoky,
yellow flame. (1)
ii) Suggest two reasons why the reaction is carried
out in alkaline solution. (2) ii) C does not react with sodium carbonate
solution. (1)
2 Describe the main reactions of amines, pointing out the
similarities and differences between aliphatic amines iii) C fizzes with sodium and gives off a gas which
such as butylamine and aromatic amines such as produces a ‘pop’ with a burning splint. (2)
phenylamine.
Write balanced equations where appropriate. (12)

48
 REVIEW QUESTIONS

4 The diagram below shows a series of reactions a) i) What characteristic physical property of
beginning with the amine, cadaverine. Cadaverine is cadaverine would you expect to notice if you
formed when proteins decompose. were provided with a sample of it? (1)
ii) What is the systematic name of cadaverine? (1)
CH2 CH2 NH2
iii) Draw the structural formula of
CH2 compound W. (1)
CH2 CH2 NH2 iv) Write the name and formula of
cadaverine compound X. (2)
2HCl(aq) v) Write the formulae of compounds Y and Z. (2)
Compound W b) Amines are classed as primary, secondary and
tertiary.
heat
i) Describe the differences in structure between
CH2 CH2 the three types of amine. (3)
CH2 N+H2 Cl– + Compound X ii) Which type(s) do cadaverine and piperidine
belong to? (2)
CH2 CH2
c) How will the infrared spectrum of cadaverine
NaOH(aq) compare with that of piperidine? Explain your
answer. (2)
CH2 CH2

CH2 NH + Compound Y + Compound Z

CH2 CH2
piperidine

49
 5 Amino acids and proteins
Proteins make up about 15% of the human body. There are many
different protein molecules in our bodies, each able to do its own
special job (Figure 5.1).
Skin, muscle and hair consist of fibrous proteins. Other proteins coil
up into a globular shape and dissolve in body fluids where they act
as enzymes and hormones. Proteins are polymers, and amino acids
are the monomers which are used to make them.

hair is made
of protein

the surface of the the enzyme

skin is protein amylase, found in
saliva, is a protein

the hormone insulin the red

is a protein made by haemoglobin
the pancreas in blood cells
is a protein

the fibres of nerve

cells are surrounded
by protein

muscle fibres are

made of protein
bones consist of
minerals embedded in the tendons which
collagen, which is a join muscle to bone
protein contain protein

toenails and fingernails

are made of protein
Figure 5.1 쑿
Proteins in the human body.

5.1 Amino acids

Amino acids are the compounds which join together in long chains to make
proteins. They are compounds with two functional groups – the amino group,
−NH2; and the carboxylic acid group, −COOH. About 20 different amino
acids are found widely in naturally occurring proteins. Some proteins contain
thousands of amino acid units.

Structures and names

50 The structures and names of six naturally occurring amino acids are shown in
Figure 5.2. The simplest amino acid is glycine, H2N−CH2−COOH.
 The acid–base properties of amino acids

H H H Figure 5.2 씱
Six of the amino acids which occur in
H2N C COOH H2N C COOH H2N C COOH proteins.

H CH3 CH2 SH
glycine (gly) alanine (ala) cysteine (cys)
H H H

H2N C COOH H2N C COOH H2N C COOH

CH2 CH2OH CH2

serine (ser)
CH2COOH
glutamic acid (glu)

phenylalanine (phe)

Notice in Figure 5.2 that all six structures have the amino group attached to the
carbon atom next to the carboxylic acid group. This is the case with all the
amino acids that occur naturally. The carbon atom next to the carboxylic acid
group is sometimes described as the alpha (α) carbon atom, or the 2-carbon
atom in systematic names. So, all the amino acids in proteins are α-amino acids
(2-amino acids) and their general formula can be written as RCH(NH2)COOH.
R stands for the sidegroups in different amino acids (Table 5.1). The
common names and R groups of several other amino acids are shown on a
data sheet on the Dynamic Learning Student website.
Common name Abbreviated name R sidegroup

glycine gly H−
Data
alanine ala CH3−

cysteine cys HS−CH2−

phenylalanine phe C6H5−CH2−

Test yourself
aspartic acid asp HOOC−CH2−
1 What is the systematic name for:
Table 5.1 쑿 a) alanine
The R sidegroups in some amino acids. b) phenylalanine
c) serine?
As many of the natural amino acids have complex structures, it is simpler and 2 A dipeptide contains two amino
more convenient to use their common names rather than systematic names. acids linked together. How many
different dipeptides can be formed
These common names are sometimes abbreviated to a 3-letter code, which is
from the naturally occurring amino
usually the first three letters in the name. So, H2NCH2COOH is normally called
acids? (Assume that there are
‘glycine’ rather than 2-aminoethanoic acid and its abbreviated name is ‘gly’. 20 different naturally occurring
amino acids.)
5.2 The acid–base properties of amino acids
As amino acids carry an amino group, −NH2, and a carboxylic acid group,
−COOH, they show both the basic properties of primary amines and the
acidic properties of carboxylic acids.

Zwitterions and isoelectric points

In aqueous solution, carboxylic acid groups ionise producing hydrogen ions,
H+(aq); at the same time amino groups are basic and attract hydrogen ions
(protons). As a result of this, amino acids form ions in aqueous solution
(Figure 5.3). However, the ions formed are unusual in that they have both
positive and negative charges. Chemists call them zwitterions, from the 51
German word ‘zwei’ meaning two.
 Amino acids and proteins

H H O H H O

H+ N C C H N+ C C
proton from another
H H O H H H O–
carboxylic acid group
Figure 5.3 씰 proton taken up
by an amine group zwitterion
Glycine forming a zwitterion.

An amino acid will form zwitterions only at a particular pH. If the pH is too
high, the solution is too alkaline. In these conditions, OH− ions will remove
H+ ions from the zwitterions forming negative ions (Figure 5.4). On the other
hand, if the pH is too low then the solution is too acidic. In this case, H+ ions
react with the zwitterions producing positive ions (Figure 5.4).

R R R
+ OH– + OH–
H3N C COOH H3N C COO– H2N C COO–
H+ H+
H H H
(aq) (aq) (aq)
At a lower, more At the isoelectric At a higher, more
acidic pH, a positive point, the zwitterion alkaline pH, a
ion forms. forms. negative ion forms.

Figure 5.4 쑿
The ions formed by an amino acid at different pH values.

Definitions Amino acids can therefore exist in three forms depending on the pH – a
cation form, a zwitterion form and an anion form. However, at one particular
A zwitterion is an ion with both a
positive and a negative charge. pH, virtually all the molecules of the amino acid will be in the zwitterion form
and this pH value is called the isoelectric point.
The isoelectric point of an amino
Notice from Figure 5.4 that the net charge on an amino acid molecule will
acid is the pH value at which it exists
as a zwitterion. vary with the pH. The net charge will be positive in acid solutions and
negative in alkaline solutions. At the isoelectric point, the positive and
negative charges balance and the net charge on the zwitterion is zero.
All amino acids form zwitterions along the lines described above, but their
isoelectric points may differ because of the different character of their R
groups. In fact, some amino acids, like glutamic acid, have two −COOH
groups and others have two −NH2 groups which influences their isoelectric
point significantly.
The movement of H+ ions from the −COOH group of an amino acid to its
−NH2 group will occur in solution and hence before a solid amino acid
crystallises out. This means that amino acids also exist as zwitterions in the
solid state. This ionic character of amino acids accounts for their high
solubility in water and their high melting points.

Test yourself
3 The relative molecular masses of butylamine, CH3(CH2)3NH2, propanoic acid,
CH3CH2COOH, and glycine, H2NCH2COOH, are very similar. But glycine (m.p.
262 °C) is a solid at room temperature whereas butylamine (m.p. −49 °C) and
propanoic acid (m.p. −21 °C) are liquids. Why is this?
4 a) Write equations to show the reactions of alanine with:
i) dilute hydrochloric acid
ii) aqueous sodium hydroxide.
b) How do the products (from alanine) of these two reactions differ from the
zwitterions of alanine at its isoelectric point?
5 Why do zwitterions of amino acids exist just as readily in the solid state as they
52 do in aqueous solution?
 From amino acids to peptides and proteins

5.3 From amino acids to peptides and proteins

Peptides are compounds made by linking amino acids together in chains. The
simplest example is a dipeptide with just two amino acids linked together by a Tutorial
peptide bond. Figure 5.5 shows the formation of a peptide bond between
alanine and glycine to form the dipeptide, ‘ala–gly’.
CH3 H Figure 5.5 씱
O H O
The formation of a peptide bond
H2N C C + N C C between two amino acids.

H OH H H OH

ala gly

CH3 O H
Definitions
H2N C C N C COOH + H2O
A condensation reaction is one in
which molecules join together by
H H H
splitting off a small molecule, such as
peptide bond water or hydrogen chloride.
ala–gly Condensation polymerisation
involves a series of condensation
For chemists, the peptide bond is simply an example of the amide bond. reactions between the functional
However, the tradition in biochemistry is to call it a ‘peptide bond’. groups of monomers to produce a
Notice in Figure 5.5 that when a peptide linkage forms between amino acid polymer.
molecules, a molecule of water is eliminated at the same time. This is an
example of a condensation reaction. CH3 O H O
Further condensation reactions can occur between the dipeptide and other
amino acid molecules to produce polypeptides and eventually proteins. This is H2N C C N C C + H2O + 2H+
what happens when proteins are synthesised from amino acids in our bodies.
H H H OH
The overall process is an example of condensation polymerisation (Section 6.3).
Polypeptides are long-chain peptides. There is no agreed dividing line reflux with
between peptides and polypeptides, or between polypeptides and proteins. conc. HCl
However, some chemists do make a distinction between polypeptides and the CH3 O H O
longer amino acid chains in proteins. They restrict the definition of + +
polypeptides to chains with 10 to 50 or so amino acids. H3 N C C + H3N C C

H OH H OH
The hydrolysis of peptides and proteins
Digestive enzymes in the stomach and small intestine catalyse the hydrolysis of add water
+ 2H2O
peptide bonds, splitting proteins into polypeptides and then polypeptides into
amino acids. Chemists can achieve the same result by hydrolysing the peptide CH3 O H O
bond in proteins and peptides with suitable enzymes or by heating in acidic or
alkaline solution. Heating alone will start to hydrolyse some of the peptide links. H2 N C C + H2N C C + 2H3O+
When proteins and peptides are hydrolysed by refluxing with concentrated OH OH
H H
hydrochloric acid, the product contains the cation forms of the α-amino acids.
alanine glycine
These are converted to the α-amino acids on dilution with water (Figure 5.6).
If proteins and peptides are hydrolysed by refluxing with sodium hydroxide Figure 5.6 쑿
solution, the product contains carboxylates – these are anion forms of the Hydrolysing a peptide with acid to
amino acids (Figure 5.7) in which the carboxylic acid group, −COOH, exists produce α-amino acids.
as a carboxylate ion, −COO−.
CH3 O H O CH3 O H O

H2N C C N C C + 2OH– H2N C C + H2N C C + H2O

–
H H H OH H O H O–

carboxylate ions
Figure 5.7 쑿 53
Hydrolysing a peptide with alkali to produce carboxylates.
 Amino acids and proteins

Test yourself
6 Draw the structures of the two dipeptides that can be produced from serine and
phenylalanine.
Data 7 Show that splitting a dipeptide into two amino acids is an example of hydrolysis.
8 a) Identify the functional groups in the sweetener, aspartame (Figure 5.8).

O H H O CH2 O
C C C C N C C

HO H NH2 H H OCH3

Figure 5.8 쑿
The structure of aspartame (Nutrasweet).
b) How does aspartame differ from a dipeptide?
c) Suggest a reason why aspartame cannot be used to sweeten food that will
be cooked.
d) Why do you think that soft drinks sweetened with aspartame carry a warning
for people with the genetic disorder which means that they must not
consume phenylalanine?

Activity

The structure of proteins

A protein molecule consists of one or more polypeptide chains.
Chemists describe the structure of proteins at four different
levels.
H
● The primary structure of a protein is the sequence of amino
C
acids in the polypeptide chain or chains. This includes any C N R
disulfide bridges, −S−S−, formed by oxidation of the HS− R O
O
groups between neighbouring cysteine units. R
H
H
● The secondary structure describes the repeating patterns C
in the structure of sections of the polypeptide chains. X-ray R N
N C
diffraction methods have shown that helices and pleated O
R
sheets are common repeating structures in proteins. Fibrous O
H R
proteins, such as α-keratin in hair and wool, have helical H C
chains of amino acids held together by hydrogen bonds (Figure N
R C O
5.9). N
R
Stringy α-keratin in silk fibres forms pleated sheets of parallel O
polypeptide chains held together side-by-side with hydrogen
bonds.
● The tertiary structure describes the overall 3D folding and
shape of a protein. This is held together by hydrogen bonds
Figure 5.9 쑿
and other weak interactions between the R groups. Proteins The alpha helix is an important example of
tend to fall into two groups in terms of their tertiary structure: the secondary structure in some proteins.
Fibrous proteins – long molecules forming fibres of structural
54 material such as α-keratin in hair and collagen in muscle fibres.
 From amino acids to peptides and proteins

Globular proteins – compact, well-folded molecules such as

enzymes and protein hormones.
● The quaternary structure describes the linking between chains
in proteins with two or more polypeptide chains. For example,
haemoglobin molecules in blood consist of four chains fitting
together tightly to form a compact globular assembly.
These four levels of description for the structure of proteins are
illustrated in Figure 5.10.

R′′
O C
N H
R′
C O

H N
R
O C
N H

Primary Secondary Tertiary Quaternary

(sequence of (helical coil or sheets) (fibrous or globular) (the association of
amino acids) two or more chains)

Figure 5.10 쑿
The four levels of protein structure.

1 The structure in Figure 5.11 shows a short section of a protein

molecule.

CH2OH H O CH3 H O

C N C C N C
N C C N C C

H O CH2 H O CH2COOH

Figure 5.11 쑿

a) Identify the amino acids that are joined to make this section of
a protein.
b) Which of these amino acids have sidechains that: Data

i) are non-polar ii) are polar iii) can ionise?

55
 Amino acids and proteins

2 Write an equation to show how the HS− groups on neighbouring

cysteine units in a protein can be oxidised to form a disulfide
bridge. (Use [O] to represent the oxidising agent.)
3 Describe the way in which hydrogen bonds hold the helices
together in fibrous proteins such as α-keratin.
4 Haemoglobin, the oxygen carrier in blood, is a protein with a
relative molecular mass of 66 000.
a) Write one word to describe the tertiary structure of
haemoglobin.
b) Assuming that the average mass of an amino acid unit in
proteins is equal to that of an aspartic acid unit, calculate the
approximate number of amino acid molecules that are needed
to produce one molecule of haemoglobin.
5 How does hydrogen bonding explain:
a) the solubility of many proteins in water
b) the precise 3D structure of those enzymes which are proteins
c) the elasticity of natural protein fibres such as wool and silk?
6 Biochemists talk about enzymes being ‘denatured’ by strong
acids, strong bases or by a rise in temperature.
a) What do you think ‘denatured’ means?
b) Suggest a reason for the loss of catalytic activity when an
enzyme is denatured by acids, bases or a rise in temperature.

Figure 5.12 씱
A computer graphic of a haemoglobin
molecule showing the quaternary
structure. Each of the four protein
chains (blue and yellow) also carries
a haem group (white).

56
 Isomerism in amino acids – mirror image molecules

5.4 Isomerism in amino acids – mirror image

molecules
Every molecule has a mirror image. Generally, the mirror image of a molecule
can be turned around to show that it is identical to the original molecule.
Sometimes, however, it turns out that a molecule and its mirror image are
not quite the same. The molecule and its mirror image cannot be
superimposed.
A molecule is chiral if, like one of your hands, it cannot be superimposed Note
on its mirror image. The word ‘chiral’ (pronounced kiral) comes from the
Chemists have a convention for
Greek for ‘hand’. drawing 3D molecules on paper.
Chirality and optical isomerism bond behind
Chiral molecules are asymmetric. This means that they have mirror image bonds in the plane of
plane of the paper
forms which are not identical. The commonest chiral compounds are organic C
molecules in which there is a carbon atom attached to four different atoms or the paper
groups. Look closely at the two molecules of alanine in Figure 5.13. The two
molecules each have the same four different atoms or groups attached to their bond in front of the
central carbon atom – a CH3 group, an NH2 group, a COOH group and an H plane of the paper
atom. Can you see that it is impossible to superimpose the mirror images of
alanine? No matter how you turn the molecules around, you cannot get the
two to look identical with groups and atoms in the same position in space.

Figure 5.13 씱
CH3 CH3
Molecules of alanine are chiral. It is not
C possible to superimpose the two mirror
C
image molecules.
H2N COOH HOOC NH2
H H

Definitions
Asymmetric molecules are
molecules with no centre, axis or
plane of symmetry. Asymmetric
molecules are chiral and exist in mirror
image forms.
Optical isomers are non-
superimposable mirror images with a
chiral centre consisting of a carbon
atom to which four different groups or
atoms are attached.
Any carbon atom with four different
mirror groups or atoms attached to it is
asymmetric and chiral.
The two forms of alanine behave identically in all their chemical reactions
and all their physical properties – except for their effect on polarised light.
This optical property is the only way of telling the two forms of alanine apart.
So, chemists call them optical isomers. The term ‘enantiomers’ is also used to
describe mirror image molecules which are optical isomers. The word R R
‘enantiomer’ comes from a Greek word meaning ‘opposite’. C C
Amino acid structures H2N COOH HOOC NH2
H H
All the natural amino acids which occur in proteins, except glycine, have a
mirror
central carbon atom attached to four different groups. So, except for glycine,
all these amino acids have chiral molecules which can exist as mirror images Figure 5.14 쑿
(Figure 5.14). Mirror image forms of all naturally
occurring amino acids, except glycine. 57
 Amino acids and proteins

Test yourself
9 Identify the chiral objects in Figure
5.15.
10 With the help of molecular models,
decide which of the following
molecules are chiral:
NH3, CH2Cl2, CH2ClBr, CH3CHClBr,
CH3CHOHCOOH.
11 Explain why the amino acid glycine
is not chiral.

Figure 5.15 쑿

Optical isomerism and polarised light

A light beam becomes polarised after passing through a sheet of polaroid, the
material used to make sunglasses. The polaroid prevents vibrations of the light
waves in all but one plane. So, in polarised light all the waves are vibrating in
the same plane (Figure 5.16).
Figure 5.16 씰
Ordinary light and polarised light.
sheet of polaroid

ordinary
light plane
polariser polarised
light

As stated above, light is said to be plane polarised after passing through a sheet
of polaroid. If the polarised light is then directed at a second sheet of polaroid,
all the polarised beam passes through if the second sheet of polaroid is aligned in
the same way as the first (Figure 5.17a). However, no light gets through if the
second sheet is rotated through 90° relative to the first sheet (Figure 5.17b).
Figure 5.17 씰
The effect of a second sheet of polaroid a)
on polarised light.

b)

58
 Isomerism in amino acids – mirror image molecules

When polarised light passes through a solution of just one form of a chiral Note
compound, it rotates the plane of polarisation. One isomer rotates the plane of Two systems of naming chiral
polarised light clockwise. This is named the (+)isomer. The other isomer compounds are in use: the (+)/(−)
rotates the plane of polarised light anticlockwise, and this is named the system described in this section and
(−)isomer. The direction of rotation of the plane polarised light (clockwise or the D/L system. The (+)/(−) system
anticlockwise) is that viewed by an observer looking towards the source of depends on the effect that optical
light. For accurate results, chemists measure the rotations with monochromatic isomers have on plane polarised light.
light (light of one colour or frequency) in an instrument called a polarimeter The D/L system, on the other hand, is
(Figure 5.18). based on the actual stereochemical
structure at the chiral centre.
tube containing solution Based on the D/L system, all naturally
of sample rotates the second polaroid must be rotated occurring amino acids are the L
plane-polarised light to allow the maximum amount of isomers, but some of these L amino
plane-polarised light through acids are (+)isomers and others are
(−)isomers.
angle of
rotation

first polaroid
produces
plane-polarised light
plane-polarised
has been rotated
light
anticlockwise
Figure 5.18 쑿
The effect of passing plane-polarised light through a solution of a chiral compound.

Test yourself
12 How could you distinguish between the two mirror image forms of an amino acid
by experiment?
13 Which of the following alcohols are chiral: butan-1-ol, butan-2-ol, pentan-1-ol,
pentan-2-ol, pentan-3-ol?
14 Use the Data sheet: ‘Common names and R sidegroups of some amino acids’
on the Dynamic Learning Student website to help you to draw the structural
formula of isoleucine. Put an asterisk on those atoms which are chiral centres in
Data
isoleucine.
15 The chemists who synthesise new drugs must pay close attention to chirality.
Dextropropoxyphene, for example, is a painkiller. The molecule has two
asymmetric carbon atoms. Its mirror image is useless for treating pain, but it is a
useful ingredient in cough mixtures.
Redraw the structure of dextropropoxyphene (Figure 5.19) and indicate the chiral
centres with asterisks.

CH3 H
CH2 C CH3
C CH2 N
O CH3

C CH2 CH3

Figure 5.19 쑿
Dextropropoxyphene.

59
 Amino acids and proteins

5.5 Stereoisomerism
If two molecules have the same molecular formula, but a different arrangement
of their atoms, they are isomers. The isomers are different compounds with
different physical properties and, in most cases, different chemical properties.
Isomers and isomerism occur most commonly with carbon compounds because
of the way in which carbon atoms can form chains and rings.
There are two ways in which the atoms can be arranged differently in isomers:
● The atoms are joined together in a different order forming different
structures. This is called structural isomerism (Figure 5.20).
Figure 5.20 씰
A simple example of structural H H H H H H
isomerism.
H C C C Cl H C C C H

H H H H Cl H
1-chloropropane 2-chloropropane

● The atoms are joined together in the same order, but they occupy different
positions in space. This is called stereoisomerism.
Figure 5.21 shows how the two different types of isomerism are further
divided. Structural isomerism can be divided into three different types –
chain, position and functional group isomerism, which we explored in Section
10.5 of OCR Chemistry for AS.

Figure 5.21 씰
A ‘family tree’ showing the relationships Isomerism
between different forms of isomerism.
Structural isomerism Stereoisomerism

Definitions Chain Position Functional group E/Z(cis/trans) Optical

In many cases, such as 1,2- isomerism isomerism isomerism isomerism isomerism
dibromoethene in Figure 5.22 and
but-2-ene, the Z-isomer may also be
described as the cis-isomer and the There are two different types of stereoisomerism – E/Z (cis/trans) isomerism,
E-isomer as the trans-isomer. which we met in Section 12.2 in OCR Chemistry for AS, and optical
However, this is not always the case. isomerism. In both forms of stereoisomerism, the stereoisomers have the same
For example, in 2-bromobut-2-ene, molecular formula and the same structural formula, but different 3D shapes in
the E-isomer is the cis-isomer and the which their atoms occupy different positions in space.
Z-isomer is trans. E/Z isomerism occurs in alkenes and other compounds with C=C double
bonds. These isomers are labelled E and Z or cis and trans. In the Z-isomer,
the atoms with higher atomic mass attached to each carbon atom in the
double bond are on the same side of the double bond. In the E-isomer, the
atoms with higher atomic mass attached to each carbon atom in the double
bond are on opposite sides of the double bond (Figure 5.22).

Br Br H Br
C C C C
H H Br H
Z-1,2-dibromoethene E-1,2-dibromoethene
m.p. –53°C, b.p. 110°C m.p. –9°C, b.p. 108°C

Figure 5.22 쑿
E/Z isomers of 1,2-dibromoethene are distinct compounds with different melting
points and different boiling points.
60
 Review questions

Test yourself
16 Which of the following compounds have E/Z isomers:
but-1-ene; but-2-ene; 1,2-dichloroethane; 1-chloroprop-1-ene;
2-chloroprop-1-ene; 3 chloroprop-1-ene?
17 Look at the isomers of 1,2-dibromoethene in Figure 5.22. Why do you think
the Z-isomer has a higher boiling point than the E-isomer?
18 The female silk moth secretes a pheromone called bombycol (Figure 5.23) which
attracts the male silk moth strongly. Chemists are interested in pheromones
because they offer an alternative to pesticides for controlling insect pests. By
baiting insect traps with pheromones, it is possible to capture large numbers of
insects before they mate (Figure 5.24).

1 2 3 9
HOCH2CH2CH2CH2CH2CH2CH2CH2CH2 H
10 11 15 16
C C CH2CH2CH3
12 13
H C C
H H

Figure 5.23 쑿
The structure of bombycol, the sex attractant for silk moths.
a) Are the groups across the double bonds in bombycol E or Z?
b) How many different E/Z isomers are there with the structural formula shown
in Figure 5.23?
c) Write the systematic name of bombycol, assuming that the straight-chain
Figure 5.24 쑿
alkane with 16 carbon atoms is called hexadecane.
Silk moths (male right and female lower)
d) Why are there no stereoisomers for bombycol?
with eggs on a discarded cocoon.

REVIEW QUESTIONS
Extension questions
1 An incomplete structure of the dipeptide 2 The technique of electrophoresis allows a solution of
threonylisoleucine is shown below. amino acids to be separated by observing their relative
movements on chromatography paper under the
H H influence of an applied voltage.
H2N C C COOH a) At pH 3, glycine molecules migrate towards the
cathode. At pH 6 (the isoelectric point) glycine
H C OH H C CH3 molecules show no movement; but at pH 11 glycine
molecules migrate towards the anode. Explain these
CH3 CH2
observations. (7)
CH3 b) When lysine, H2N(CH2)4CH(NH2)COOH,
undergoes electrophoresis, it moves faster towards
a) i) Redraw the structure of the dipeptide inserting the cathode at pH 3 than it moves towards the
the missing peptide link. (2) anode at pH 11, even though the voltage remains
ii) On your structure, circle all the chiral constant. Why is this? (4)
centres. (3)
b) What does the presence of a chiral centre tell you 3 Explain the term stereoisomerism and describe the
about a compound? (1) different types of stereoisomerism, illustrating your
answer with suitable examples. (15)
c) Draw the structures of the products obtained when
the dipeptide is refluxed with:
i) excess concentrated hydrochloric acid (2)
ii) excess sodium hydroxide solution. (2) 61
 6 Polymers
Polymers are long-chain molecules. Natural polymers include
proteins, rubber and carbohydrates such as starch and cellulose.
Synthetic polymers include those such as polythene and pvc
produced by the addition polymerisation of compounds with carbon–
carbon double bonds, and others such as polyesters and polyamides
formed by condensation polymerisation.
The first synthetic polymers were produced more by good luck than
good management. Nowadays, chemists are capable of developing
new polymers with specific properties by applying the theories of
bonding and structure. In many respects, polymers have changed the
way we live, but the big disadvantage of most of them is that they are
not biodegradable.

6.1 Polymer chemistry

Polymer chemistry is the study of the synthesis, structure and properties of
polymers. It is a branch of chemistry that has developed rapidly since Leo
Baekeland first discovered Bakelite in 1905 (Section 1.12). People were very
excited about Bakelite, which could be used instead of ceramics and wood in
the home and in industry. This first thermosetting polymer was discovered
well before chemists understood the structure of big molecules.
Figure 6.1 씰
A false-colour computer graphic of low-
density polythene showing the branches
which prevent the chains from packing
close together. Carbon atoms are
coloured green and pink. Hydrogen
atoms are blue and orange.

It was not until 1922 that a German chemist, Hermann Staudinger, published
his theory about large molecules. Staudinger suggested that substances like
rubber and cellulose consist of long-chain molecules and he had to fight hard
to persuade other chemists to accept his ideas. Today his theory is taken for
granted.
One person who was convinced by Staudinger’s theory was the American
industrial chemist Wallace Carothers. In 1931, Carothers wrote an article
introducing the terms addition polymerisation and condensation
polymerisation. Carother’s research team at the Du Pont chemical company
produced synthetic rubber, neoprene, by addition polymerisation. Then, in
Figure 6.2 쑿 1935, the team synthesised nylon – the first completely synthetic
A false-colour electron micrograph of condensation polymer.
Gore-tex. The pink outer layers are nylon.
The 1930s were probably the most important years in the development of
The yellow and white layers consist of
Teflon (ptfe). Magnification is ×160.
polymers and the plastics industry. During this period polythene, pvc,
Gore-tex is used to line outdoor wear polystyrene and Perspex all came onto the market. Since then, research and
such as anoraks and hiking boots development in the second half of the twentieth century has led to the
62 because it is waterproof but allows production of many new and specialised polymers including Teflon (ptfe), the
perspiration to evaporate. polyamide Kevlar and biodegradable polymers.
 Addition polymerisation

Figure 6.3 씱
Expanded polystyrene has low density
and it is an excellent thermal insulator. It
is used for packaging fragile goods as it
absorbs shocks. Its correct name is
poly(phenylethene).

Definitions
Polymerisation is a process in which
many small molecules (monomers) join
up in long chains by addition or
condensation reactions.
In addition polymerisation, the
polymers form by addition reactions of
monomers containing double bonds.
In condensation polymerisation, the
polymers form by condensation
6.2 Addition polymerisation reactions in which small molecules,
such as water, are split off between
Addition polymerisation is a process for making polymers from compounds the functional groups of the
containing double bonds. The most important addition polymers are formed monomers.
from compounds of general formula CH2=CHX, in which the nature of X
determines the properties of the polymer.
Ethene, for example, in which X is H, polymerises to form poly(ethene),
commonly called polythene (Figure 6.4).
H H Figure 6.4 씱
H H
The formation of poly(ethene) from
n C C C C ethene.

H H H H
n
ethene poly(ethene)
Other widely used addition polymers include poly(propene),
poly(phenylethene) – better known as polystyrene, poly(tetrafluoroethene) –
often abbreviated to ptfe, and poly(chloroethene) – usually called pvc. In
these addition polymers, the repeat unit in the polymer chain has the general
structure shown below.
H H

C C

H X

Figure 6.5 씱
Inside the domes at the Eden Project in
Cornwall, scientists have created the
varying climatic conditions required by
plants growing in different parts of the
world. These domes consist of
interconnecting steel pentagons and
hexagons glazed with etfe – this is an
addition polymer made by polymerising a
mixture of the two monomers, ethene
and tetrafluoroethene. The polymer is
lightweight and lets through the ideal
spectrum of light for plants to
photosynthesise.
63
 Polymers

Another important addition polymer, developed in recent years as a water-

soluble plastic, is poly(ethenol) – sometimes called polyvinyl alcohol. 90–98%
of poly(ethenol) is composed of the following repeat unit.

H H

C C

H OH

Poly(ethenol) is used to make plastic bags which dissolve in water. These are
ideal for use as hospital laundry bags which can be handled without touching
any infected contents. When washing begins, the bags dissolve in the water
and the laundry is washed.

Making addition polymers

One technique for making addition polymers using an initiator involves a
radical chain reaction at high temperature and pressure. The initiator is often
a peroxo compound, or an organic peroxide such as benzoyl peroxide. These
peroxo compounds and peroxides act as a source of free radicals to initiate
addition polymerisation (Figure 6.6).

Figure 6.6 씰
A molecule of benzoyl peroxide splitting C O O C
to form two radicals. The O−O bond is
relatively weak. O O

C O + O C

O O

Using the symbol RO• for a free radical, the addition polymerisation can be
followed through the stages of initiation, propagation and termination as
shown in Figure 6.7.

Figure 6.7 씰 Initiation

The radical chain reaction involved in
the formation of an addition polymer. R O O R R O + O R
peroxide

Propagation

H H H H

R O + C C R O C C
H H H H
H H H H H H H H

R O C C + C C R O C C C C

H H H H H H H H

repeated many times

Termination
2 R O ( CH2 )n CH2 R O ( CH2 )n CH2 CH2 ( CH2 )n O R

64
 Addition polymerisation

An alternative method that speeds up the polymerisation of alkenes such as

ethene and propene is to use Ziegler–Natta catalysts. These catalysts enable
the production of addition polymers at relatively low temperatures and
pressures. The catalysts are combinations of titanium(IV) chloride and
aluminium alkyls (such as triethyl aluminium) in a hydrocarbon solvent.
There is very little chain branching in the polymers so the poly(ethene)
chains produced by this method can pack more closely together forming the
high-density form of poly(ethene).
Figure 6.8 씱
Extruding poly(ethene) to make plastic
sheeting for the building industry. A high-
pressure, high-temperature process with
a peroxide initiator produces low-density
poly(ethene) with branched chains. A
low-pressure, low-temperature process
with a Ziegler–Natta catalyst produces
high-density poly(ethene) in which the
polymer chains have very few branches
and pack much closer.

Test yourself
1 Draw two repeat units of the polymer chain formed from each of the monomers
below and write the systematic IUPAC name of the polymer.

H H H H
a) C C b) propenamide, C C
H H C O
H2N

2 Identify the following polymers and write the name and displayed formulae of
their monomers.
H H H H

a) C C b) C C

CH3 H H Cl
n n
3 Explain the terms ‘homolytic fission’ and ‘radical’ using the action of benzoyl
peroxide as an initiator for your example.
4 The paste supplied with DIY wood fillers often contains phenylethene. The paste
is supplied with a small tube of hardener.
a) Why is the hardener supplied in a separate tube and only mixed with the
paste shortly before use?
b) Suggest a chemical name for the hardener.
c) What factors will determine how quickly the wood filler sets?
5 Why is poly(ethenol) soluble in water, unlike poly(ethene) which is insoluble? 65
 Polymers

Activity

Covering the O2
The O2 Dome at Greenwich,
sometimes called ‘the O2’,
provided an important focus for
celebrations of the Millennium in
2000. The huge structure is a
triumph for science and
engineering. Its construction
would have been impossible
without the availability of a tough,
lightweight, inert and non-
flammable material for the roof.
The roof of the O2 has an area of
about 150 000 square metres. It
is covered by 144 panels of ptfe-
coated fibreglass supported by a Figure 6.9 쑿
network of steel cables suspended from 12 masts which reach to a The O2 at Greenwich, London.
height of 100 metres. The correct systematic name for ptfe is
poly(tetrafluoroethene). However, it is better known by its trade
name Teflon – it is also used to coat non-stick saucepans and skis.
Teflon is manufactured by polymerising tetrafluoroethene with a
small amount of ammonium peroxodisulfate.

1 a) Draw the displayed formula of tetrafluoroethene and a short

section of the ptfe polymer showing two repeat units.
b) Why is the polymer called ptfe?
2 Explain fully why ammonium peroxodisulfate is used in the
synthesis of ptfe.
3 Predict the conditions used to synthesise ptfe.
4 Describe the general shape of ptfe molecules and the forces that
hold these molecules together.
5 Poly(tetrafluoroethene) is an ideal material to cover the roof of the
O2 because its strong C−F bonds are resistant to chemical
attack. What other properties does ptfe have that make it ideal
for the O2?
6 Suggest two advantages that ptfe-coated fibreglass has over
ordinary glass to form the roof covering of the O2.
7 Suggest two disadvantages that ptfe-coated fibreglass has
compared to ordinary glass as the roof covering of the O2.
8 The roof of the O2 is expected to be self-cleaning.
Why is this?

66
 Condensation polymerisation

6.3 Condensation polymerisation

Condensation polymers are produced by a series of condensation reactions in
which small molecules such as water or hydrogen chloride are split off
between the functional groups of the monomers.
Condensation reactions are sometimes described as ‘addition-plus-
elimination’ reactions because the monomers undergo addition but this occurs
only by elimination of a small molecule between each repeating unit.
There are two important classes of condensation polymers – polyesters and Definitions
polyamides. When each monomer has two functional groups, polymerisation Polyesters are polymers with ester
produces chains. Cross-linking is possible if one of the polymers has three links between monomer units.
functional groups.
Polyamides are polymers with amide
links between monomer units.
Polyesters
Polyesters are polymers formed by condensation polymerisation between:
● either acids with two carboxylic acid groups and alcohols with at least two
−OH groups
● or monomers which have both a carboxylic acid group and an −OH group.
The repeating units in the polyester chains are linked by a series of ester
bonds.
The most common polyester is Terylene, used widely in fabrics. It is usually
referred to simply as ‘polyester’. Terylene is made by condensation reactions
between benzene-1,4-dicarboxylic acid and ethane-1,2-diol (Figure 6.10). The
traditional names for these two compounds are terephthalic acid and ethylene
glycol – hence the commercial name, Terylene. An alternative name for the
polymer is polyethylene terephthalate, which gives rise to the name PET
when the same polymer is used to make plastic bottles for drinks.

O O O O
C C C C

HO OH HO OH
HO CH2 CH2 OH HO CH2 CH2 OH

O O O O

C C O CH2 CH2 O C C O CH2 CH2 OH

HO
+ H2O + H2O + H2O

The condensation reactions shown in Figure 6.10 can be repeated again and Figure 6.10 쑿
again to produce a polymer with the repeat unit shown in Figure 6.11. Condensation polymerisation to produce
the polyester Terylene.
O O

HO C C O CH2 CH2 O H
Figure 6.11 씱
n The repeat unit and structure of Terylene.
repeat unit

Polyesters have high tensile strength and, because of this, they are widely used
as fibres in clothing and as the bonding resin in glass fibre plastics.
Perhaps the most important development in polyester chemistry in recent
years concerns poly(2-hydroxypropanoic acid), commonly called poly(lactic
acid) or PLA. Poly(lactic acid) is possibly the most useful and most versatile
of the new biodegradable plastics. It is already used in such diverse goods as
67
plant pots, disposable nappies and absorbable surgical sutures (stitches).
 Polymers

Poly(lactic acid) is manufactured by the condensation polymerisation of a

single monomer which contains both a carboxylic acid group, −COOH, and
an alcohol group, −OH (Figure 6.13).
CH3 O CH3 O
lactic acid
HO C C + HO C C monomers
H OH H OH

CH3 O CH3 O
HO C C O C C + H2O

H H OH

many more reactions at

each end of the molecule

CH3 O
Figure 6.12 쑿
The blazer, tie, shirt and trousers that this H O C C OH
schoolboy is wearing may all contain
polyester (Terylene). The fabrics are hard H
n
wearing, washable and relatively cheap.
Figure 6.13 쑿
The synthesis of poly(lactic acid) by condensation polymerisation.

Polyamides
Polyamides are polymers in which the monomers are linked by an amide
bond. This is exactly the same as the amide bond in proteins, in which it is
usually called the peptide bond (Figure 6.14). So, proteins and polypeptides
O are naturally occurring polyamides.
Earlier work in Topic 5 showed that polypeptides and proteins are
C N
synthesised in living things by condensation reactions between amino acids.
H In these reactions, the amine group, −NH2, of one amino acid reacts with the
carboxylic acid group, −COOH, of another amino acid to split out water and
peptide
form an amide link (Figure 5.5).
bond
This process is then repeated time after time to produce a polymer (protein)
Figure 6.14 쑿 with tens, hundreds or, in some cases, thousands of units.
The amide bond is usually called the The first synthetic and commercially important polyamides were various forms
peptide bond in proteins.
of nylon. However, these were not produced from amino acids. Instead, they
were formed by condensation polymerisation between diamines and
dicarboxylic acids. One of the commonest forms of nylon is nylon-6,6. This is
made by a condensation reaction between 1,6-diaminohexane and
hexanedioic acid (Figure 6.15). The product is called nylon-6,6 because both
monomers contain six carbon atoms.
Figure 6.15 씰 O O H H O O H
Condensation
polymerisation to make C (CH2)4 C N (CH2)6 N C (CH2)4 C N (CH2)6 NH2
nylon-6,6.
HO OH H H HO OH H

O O O O

C (CH2)4 C N (CH2)6 N C (CH2)4 C N (CH2)6 NH2

HO H H H
68
+ H2O + H 2O + H2O
 Condensation polymerisation

Nylon-6,6 can be produced more readily in the laboratory using the more
reactive hexanedioyl dichloride in place of hexanedioic acid. Hexanedioyl
dichloride reacts readily with 1,6-diaminohexane at room temperature to
produce nylon-6,6. In this case, hydrogen chloride molecules are eliminated in
the condensation reaction.

O O H H

n Cl C(CH2)4C Cl + nH N(CH2)6N H

O O H H

C(CH2)4C N(CH2)6N + 2nHCl

n

Figure 6.16 쑿
The reaction used to make nylon-6,6 in the laboratory.
Figure 6.17 쑿
Although nylon is similar in structure to wool and silk, it does not have the The American firm Du Pont patented
softness of the natural fibres. But it is much harder wearing, and one of its nylon in February 1938. The first nylon
earliest uses was as a substitute for silk in the manufacture of ladies’ stockings. stockings went on sale in the USA on 15
Apart from their obvious use in stockings and tights, nylon fibres are used May 1940. In New York alone, four
in various forms of clothing. In fact, about 75% of the UK nylon consumption million pairs were sold in a few hours.
goes on clothing, but its uses are many and varied. Nylon is used to make
ropes that don’t rot, machine bearings that don’t wear out and it is mixed
with wool to make durable carpets.
Test yourself
Nylon is the collective name for polymers with aliphatic hydrocarbon 6 a) What type of polymerisation will
sections linked by amide bonds. They are aliphatic polyamides in which the produce the polymer with a
polar amide bonds are fixed and inflexible, but the non-polar hydrocarbon repeat unit like that below?
sections are free to flex, rotate and twist. So, as the hydrocarbon sections
become longer we would expect the nylon polymers to become more flexible O O
with weaker bonding between the molecules. C CH2 CH2 C
This suggests that the properties of polyamides can be modified by changing O O
the length and nature of the hydrocarbon sections. Chemists have followed up
these ideas to develop polyamides in which the hydrocarbon sections are repeat unit
aromatic rather than aliphatic. These polymeric aromatic amides are described b) Draw the structure of the
as aramids. Aramids, such as Kevlar (Figure 6.18), are extremely strong, rigid, monomer or monomers that
fire-resistant and lightweight. would be used to prepare the
polymer.
O O O O
7 The compound shown below can
form a polymer.
C C N N C C N N
O
H H H H
C NH2
HO
Figure 6.18 쑿
A section of the polymer chain in Kevlar.
a) Identify the functional groups
Test yourself involved in forming the polymer.
b) What type of polymerisation will
8 State two similarities and two differences between the structure of nylon-6,6 and the monomer undergo?
the structure of a protein. c) What other product forms
9 Identify the types of intermolecular forces which act between the polymer chains during polymerisation?
in: d) Draw a short length of the
a) poly(ethene) polymer chain showing two
b) nylon. repeat units.

69
 Polymers

Activity

Modelling and synthesising polyamides

Experiments show that nylons with longer hydrocarbon sections to
their chains are more flexible than those with shorter sections. Kevlar
is similar to nylon-6,6 but with benzene rings rather than aliphatic
chains linked by the amide group. The repetition of benzene rings in
its structure makes Kevlar exceptionally strong and very inflexible
compared with nylon-6,6. Because of this, it is used extensively in
tyres, brakes and clutch fittings, in ropes and cables and in
protective clothing (Figure 6.19).
1 Look closely at the structure of one chain of Kevlar in Figure 6.18.
a) Explain how Kevlar is a condensation polymer of benzene-
1,4-dicarboxylic acid and benzene-1,4-diamine.
b) Weight-for-weight, Kevlar is five times stronger than steel.
This exceptional strength is due to hydrogen bonding
between the separate chains. Use Figure 6.18 to explain why
inter-chain hydrogen bonding is so strong in Kevlar. Figure 6.19 쑿
This policeman is wearing a bulletproof
c) Suggest a reason why Kevlar is made from monomers with jacket made from Kevlar.
functional groups in the 1 and 4 positions, and not from
isomers with functional groups in the 1 and 2, or 1 and 3
positions.
2 Using a molecular model kit, make one repeat unit for the
structure of Kevlar and explore the flexibility of the structure.
(Hint: Use the Kekulé structure with alternating double and single
bonds for the benzene ring.)
Repeat the model making and flexibility testing with one repeat
H2N(CH2)3CHCH2NH2
unit for the structure of nylon-6,6. Why is nylon-6,6 flexible
whereas Kevlar is inflexible? CH2OH

3 A condensation polymer can be prepared by mixing equal

amounts of the monomers in Figure 6.20 at room temperature. O O

a) Draw the structure of one repeat unit of the polymer formed C(CH2)2CHCH2C
from the two monomers. Cl Cl
COOH
b) The polymer forms even more rapidly if the reaction mixture Figure 6.20 쑿
contains sodium carbonate. Why is this?
c) The polymer molecules obtained at room temperature can be
linked to one another (cross-linked) by a second reaction.
Explain how this cross-linking can be achieved and state the
conditions needed for it to happen.
d) Explain how the choice of reaction conditions can control the
extent of polymerisation and the extent of cross-linking.

70
 Comparing addition and condensation polymerisation

6.4 Comparing addition and condensation

polymerisation
Although both addition and condensation polymerisation result in the
formation of long-chain organic molecules, known as polymers, from relatively
small organic molecules, known as monomers, there are some clear differences
between the two processes.
The first difference concerns the type of reaction involved. As its name
suggests, addition polymerisation involves only addition reactions, whereas
condensation polymerisation involves addition plus elimination. As monomer
units join together a small molecule, usually water or hydrogen chloride, is
eliminated and split off.
The second difference between addition and condensation polymerisation
involves the type of links along the polymer chain. In addition polymers, the
central chain consists of carbon atoms linked by carbon–carbon single bonds.
In condensation polymers, the central chain consists of short aliphatic or aryl
sections linked by
● ester groups, C O or ● amide groups, C N

O O H
The third difference concerns the type of monomer involved. In addition
polymerisation, the monomers have molecules with carbon–carbon double
bonds. In condensation polymerisation, the monomers have molecules with at
least two functional groups which may be the same or different.
A fourth difference concerns the conditions for preparation of the Definitions
polymers. In general, addition polymerisations require an initiator together Plastics are materials made of long-
with high temperatures and high pressures, unless a catalyst is involved. In chain molecules, which at some stage
contrast, condensation polymerisations do not require initiators and usually can be moulded into shapes which
occur at much lower temperatures and atmospheric pressure. are retained.
Elastomers are materials made of
Polymer properties long-chain molecules, which can be
These differences between addition and condensation polymerisation lead to moulded into new shapes but which
considerable variation in the properties of polymers. Polymeric materials spring back to their original shape
include plastics, fibres and elastomers. As polymer science has grown, chemists when the pressure is removed.
and material scientists have learnt how to develop new materials with Biodegradable materials break
particular properties. down due to the action of
Some of the ways of modifying the properties of polymers include: microorganisms.
● altering the average length of polymer chains Photodegradable materials break
● changing the structure of the monomer to one with different side groups down when exposed to sunlight.
and different intermolecular forces Co-polymers are polymers made
● varying the extent of cross-linking between chains from two or more monomers, each of
● selecting a monomer which produces a polymer which is biodegradable or which could produce a polymer.
photodegradable Composites are materials made up of
● producing a co-polymer, such as etfe (Figure 6.5), which is made from two two or more recognisable constituents
or more monomers, each of which could produce a polymer each of which contributes to the
● adding fillers and pigments properties of the composite.
● making composites.

Figure 6.21 씱
An electron micrograph of a glass fibre
composite showing rods of glass fibre
embedded in a polyester matrix. 71
Magnification is ×660.
 Polymers

6.5 The hydrolysis of polyesters and polyamides

Esters and polyesters
In Topic 3, we found that an ester can be hydrolysed to form an acid and an
alcohol.
Figure 6.22 씰 O O
The hydrolysis of a simple ester, ethyl
CH3 C + H2O CH3 C + CH3CH2OH
ethanoate.
O CH2CH3 OH
ethyl ethanoate ethanoic acid ethanol

Both acids and alkalis can catalyse the hydrolysis. Hydrolysis catalysed by acid
is the reverse of the reaction used to synthesise esters from carboxylic acids
and alcohols.
Base catalysis is generally more efficient because it is not reversible. This is
because the acid reacts with the base as soon as it is produced to form its
carboxylate salt, which does not react with the alcohol.
CH3COOH(aq) + OH−(aq) → CH3COO−(aq) + H2O(l)
ethanoic acid ethanoate
Polyesters can be hydrolysed in a similar way to simple esters forming products
with carboxylic acid and alcohol groups (Figure 6.23).

Figure 6.23 씰
CH3 O CH3 O
The hydrolysis of poly(lactic) acid.
H O C C + (n – 1)H2O nH O C C

H OH H OH
n
lactic acid
(2-hydroxypropanoic acid)

If the reaction is catalysed by an acid, the product is lactic acid

(2-hydroxypropanoic acid). If the reaction is catalysed by a base, the lactic
acid produced reacts with the base to form a salt.
HO−CH(CH3)−COOH(aq) + NaOH(aq)
→ HO−CH(CH3)−COONa(aq) + H2O(l)

Polyamides
In Topic 5, we found that peptides and proteins could by hydrolysed to form
amino acids, and that the hydrolysis was catalysed by both acids and bases.
However, when the reaction is catalysed by acid, H+ ions from the acid react
with −NH2 groups in the amino acids produced to form cations containing the
−NH3+ group.
But, when the reaction is catalysed by base, ions such as OH− from the base
react with −COOH groups in the amino acids produced to form carboxylate
anions containing the −COO− group.
Polyamides which contain the amide group, C N , like proteins, are
hydrolysed in the same way.
The products are compounds containing O H
carboxylic acid groups, −COOH, and amine groups, −NH2. If the hydrolysis is
catalysed by acid, the −NH2 groups are converted to −NH3+; and if the
reaction is catalysed by base, the −COOH groups are converted to −COO−
(Figure 6.24).

72
 The development of degradable polymers

O O

N ( CH2 )6 N C ( CH2 )4 C

H H n

+ 2nH2O + 2nH+ + 2nH2O + 2nOH–

acid hydrolysis base hydrolysis

H H O O H H O O
+ +
nH N ( CH2 )6 N N + nC ( CH2 )4 C nN ( CH2 )6 N + nC ( CH2 )4 C
–
H H HO OH H H O O–

+ 2nH2O
Figure 6.24 쑿
The hydrolysis of nylon-6,6 by acid and base.

Test yourself
10 A bottle made of poly(phenylethene) can be used to store dilute potassium
hydroxide, but holes gradually appear in a polyester lab coat which has soaked
up splashes of the same reagent. Account for the difference in the behaviour of
the two polymers.
11 Suggest a reason why many polyesters and polyamides are degradable while
poly(alkenes) are not.
12 a) Which type of plastic makes up most of the plastic waste from households –
condensation or addition polymers?
b) What are the implications of this when it comes to disposing of the waste?
13 Explain the difference between a co-polymer and a composite.
14 Nylon-6 contains the repeat unit shown below.
H

N ( CH2 )5 C

Draw the structures of the products formed when it is hydrolysed by refluxing

with:
a) dilute hydrochloric acid
b) sodium hydroxide solution.

6.6 The development of degradable polymers

As it becomes more and more expensive to dump waste in landfill sites,
plastics are seen as an increasing problem. The major problem with most
plastic waste is that it is non-biodegradable. This means that the only choices
for dealing with plastic waste are recycling and energy recovery.
Figure 6.25 쑿
Although some progress has been made, the separation, sorting and The managing director of a Dutch
recycling of different plastics is difficult to mechanise and automate. recycling company standing in a pile of
Modern incinerators, which burn plastic waste in order to recover the plastic bottle tops and holding a roll of
energy from its combustion, have to meet tough environmental standards. recycled plastic made from them.
Despite these higher standards, many people remain suspicious of the Separation and sorting was no problem
emissions from incinerators and worry that they are a health risk. in this case!

73
 Polymers

These concerns over incineration and the difficulties in recycling have led
chemists to look for other ways of minimising the waste from plastics. The
most promising approach involves the development of biodegradable
polymers, such as poly(lactic acid) described in the Activity on the next page.
Another important approach is the development and use of condensation
polymers that are either photodegradable or readily degraded by hydrolysis.

Photodegradable condensation polymers

The C=O bond in condensation polymers can absorb the photons in radiation
of a particular frequency. In some cases, sufficient energy can be captured by
the polymer to facilitate its decomposition.

Hydrolysis of condensation polymers

Polyamides such as nylon and polyesters containing aromatic groups are fairly
resistant to hydrolysis unless the reaction is catalysed by acid or base. But
polyesters made from purely aliphatic monomers hydrolyse slowly at pH 7
without acid or base catalysts. This has led to the use of poly(glycolic) acid
(Figure 6.26) for stitching internal wounds. Once the stitches (sutures) have
been inserted and the surgical incision closed, the stitches dissolve slowly in
the patient’s tissue fluid.

H O H O

nH O C C H O C C OH + (n – 1) H2O

H OH H n
glycolic acid poly(glycolic acid)

Figure 6.26 쑿
An equation for the synthesis of poly(glycolic acid).

Figure 6.27 쑿
Polyamides such as nylon and aromatic polyesters are used for stitches (sutures) on
external wounds. These are not degradable and have to be removed manually when
the wound has healed.

74
 The development of degradable polymers

Activity

Developing and using poly(lactic acid) O

Poly(lactic acid) is an aliphatic, thermoplastic, biodegradable
O
polyester (Figure 6.28). Its name is sometimes abbreviated to PLA.
Polylactic acid can be produced from renewable resources such as n
the sugar from canes and the starch from wheat and sweetcorn. As
Figure 6.28 쑿
such, it is a sustainable alternative to oil-based plastics. PLA is more
The skeletal formula of
expensive to produce than its oil-based alternatives, but its cost has poly(lactic acid).
fallen with increased production and the increase in oil prices.
The manufacture of PLA from starch or sugar requires two stages.
In the first stage, starch or sugar is converted to lactic acid by
bacterial fermentation. The lactic acid then undergoes condensation
polymerisation to produce PLA by heating with a catalyst of tin(II)
octanoate.
Like most thermoplastics, PLA can be processed into fibres or film
for a variety of uses.
Poly(lactic acid) is already used for waste sacks, compost bags,
disposable plastic plates, packaging and a number of biomedical
applications. These include stitches, dialysis bags and capsules
containing various medicinal drugs. Packaging made from PLA will
degrade to lactic acid in less than two months, but this relatively
rapid breakdown is only possible in the ideal conditions of a
commercial composting plant.
1 Explain what is meant by each of the following adjectives when
applied to poly(lactic acid):
a) aliphatic b) thermoplastic c) biodegradable.
2 Why is poly(lactic acid) described as a sustainable alternative to
petroleum-based plastics?
3 Why is poly(lactic acid) becoming more financially viable in the
manufacture of different goods?
4 How can poly(lactic acid) reduce the problems of plastic waste
polluting the environment?
5 Draw the displayed formula of lactic acid and write its molecular
formula.
6 Write an equation for the polymerisation of lactic acid to form
poly(lactic acid).
7 How does poly(lactic acid) degrade when it is used to stitch an
internal wound where there are no microorganisms? Figure 6.29 쑿
This bag is made from poly(lactic acid)
8 Which do you think will degrade the faster when used for – a biodegradable polymer.
stitching internal wounds – poly(lactic acid) or poly(glycolic acid)
(Figure 6.26)? Explain your answer.
9 Films of poly(lactic acid) and poly(glycolic acid) are used to coat
the tablets and capsules of certain drugs. How does this help
with the delivery of the drug into the body? 75
 REVIEW QUESTIONS
Extension questions
1 An elastic tape consists of 60% polyester and 40% a) Draw the simplest repeat unit for each polymer. (2)
neoprene. Neoprene is a polymer similar to
b) Draw and name the structural formula of the
synthetic rubber. It is manufactured by polymerising
monomer used to make polymer A. (2)
2-chlorobuta-1,3-diene as in the partially-completed
equation below. c) i) Draw the structural formulae of the two
monomers that could be used to make
polymer B. (2)
nC C C C C C C C
ii) Name one of the two monomers. (1)
n
d) During the last decade, degradable polymers have
a) Copy and complete the equation above, showing
been developed to reduce the quantity of plastic
the atoms or groups attached to the carbon
waste that is dumped in landfill sites.
skeletons. (2)
State and explain two reasons why polymer B is
b) What type of polymerisation is illustrated by the
more likely to be a degradable polymer than
manufacture of neoprene? (1)
polymer A. (4)
c) What general name is given to polymers like
3 Describe three differences between addition
neoprene and natural rubber? (1)
polymerisation and condensation polymerisation using
d) Polyester is manufactured by a reaction between poly(ethene) and nylon-6,6 as your examples. (12)
benzene-1,4-dicarboxylic acid and ethane-1,2-diol.
i) Draw the structural formulae of these two
monomers. (2)
ii) Draw the structural formula of the molecule
which forms when one molecule of each of
these monomers reacts to produce an ester. (1)
e) Why do you think that manufacturers use a mixture
of polyester and neoprene in the elastic tape? (2)
f) i) What reagent could you use to show the
presence of neoprene in the elastic tape? (1)
ii) State and explain what you would observe if
you used the reagent with some of the tape. (2)
g) Suggest two other properties, not covered earlier in
this question, which should be considered in
choosing a polymer for use in clothing. (2)
2 Short sections of the molecular structures of two
polymers are shown below.

H CH3 H CH3 H CH3

C C C C C C

CH3 H CH3 H CH3 H

polymer A

O H H H O O H H H O

O O C C C C C O O C C C C C

H H H H H H
polymer B
Figure 6.30 쑿

76
7 Synthesis
Much of the purpose and pleasure of chemistry comes from making
new materials such as pigments, perfumes, drugs and dyes. This
making of new materials is called synthesis. Synthesis is at the heart
of much of the chemical research that goes on today. We depend on
synthesis for processed foods, for our fuels, for the clothes we wear
and for many of the modern materials we use everyday. Synthesis is
also important to our understanding of reactions and molecular
structure, particularly those of organic molecules. It is not until
someone has synthesised a molecule that chemists can be confident
that they have determined its structure precisely.

7.1 Organic synthesis

Many features of modern life depend on the skills of chemists and their ability
to synthesise new and complex materials. New colours and fabrics for the
fashion industry are synthetic organic molecules. So also are many compounds
synthesised every day for testing in pharmaceutical laboratories as potential
drugs to cure one disease or another. Lightweight, flat-screen computer
monitors depend on liquid organic crystals. These organic compounds in the
computer screen have been tailor-made by chemists so that they will respond Figure 7.1 쑿
to an electric field and affect light. Liquid crystals photographed through a
microscope using polarised light. Liquid
crystals are used in the flat screens of
modern computers and in the displays of
O
calculators, digital cameras and digital
O watches.
O O

Figure 7.2 쑿
The structure of a liquid crystal molecule.

The essential job of synthetic organic chemists is to consider the proposed

structure for a target molecule and then devise a way of making it from
simpler, readily available starting materials. The scale of work involved and an CH2 CH CH3
indication of the difficulties encountered in a complex organic synthesis are
illustrated by the painstaking and ingenious synthesis of chlorophyll by a team H3C CH2CH3
of 17 scientists led by Robert Woodward at Harvard University in 1959. N N
Mg2+
The synthesis of chlorophyll N N
Chlorophyll (Figure 7.3) is the green pigment in plants. Its structure was first H3C CH3
proposed in 1940 by the famous chemist Hans Fischer. When Woodward and
his team started work in 1956, they could not be sure that Fischer’s proposed CH2 C O
structure was correct.
From the start, the project was planned in great detail. The chemists read CH2 CO2CH3
all the papers concerning previous studies of chlorophyll to ensure that no
clues to a successful synthesis were missed. They drew on their understanding CO2C20H39
of the mechanisms of organic reactions to predict the likely products at each Figure 7.3 쑿 77
stage and suggest routes to their target molecule. The structure of chlorophyll.
 Synthesis

The synthesis of chlorophyll would have been impossible without the newer
methods of separation, purification and identification that had become
available. The variety of spectroscopy techniques were crucial to success.
Woodward’s team published their paper describing the successful synthesis of
chlorophyll in 1960, opening up a new stage of research into the part that
chlorophyll plays in photosynthesis.

Organic analysis
After complex molecules, such as chlorophyll, have been synthesised,
chemists must use a variety of methods to analyse them in order to identify
their precise composition and structure.
Traditionally, chemical tests were used to identify functional groups in
organic molecules, together with combustion and quantitative analysis.
Nowadays, modern laboratories rely on a range of highly sensitive automated
and instrumental techniques to identify products of synthesis. These include
chromatography, mass spectrometry and various kinds of spectroscopy.

7.2 Functional groups – the keys to organic

molecules
Functional groups provide the key to organic molecules. A knowledge of the
properties and reactions of a limited number of functional groups has opened
up our understanding of most organic compounds.
A functional group is the atom or set of atoms which give a series of organic
compounds their characteristic properties and reactions. Chemists often think
Definitions of an organic molecule as a relatively unreactive hydrocarbon skeleton with
one or more functional groups in place of one or more hydrogen atoms. The
A functional group is the atom or set
functional group in a molecule is responsible for most of its reactions. In
of atoms which give an organic
compound its characteristic properties.
contrast, the carbon–carbon bonds and carbon–hydrogen bonds are relatively
unreactive, partly because they are both strong and non-polar.

tertiary
alcohol primary
CH2OH alcohol
carbonyl
group HO
CH3 C O
O CH2 C carbonyl
CH2 group
C C
CH3
CH2 CH CH CH2
carbonyl H2C C CH
group
C C CH2
O C CH2

H
double bond
as in an alkene

Figure 7.4 쑿
The structure of the steroid cortisone, labelled to show the reactive functional groups
and the hydrocarbon skeleton.

Table 7.1 shows the major functional groups which you have met during your
A-level studies, together with an example of one compound containing each
group.
The characteristic properties and tests for most of these functional groups
are shown on the data sheets headed ‘Tests and observations on organic
78 Data compounds’ on the Dynamic Learning Student website.
 Functional groups – the keys to organic molecules

Functional group Example Test yourself

alcohol −OH propan-1-ol, CH3CH2CH2OH 1 a) Write the empirical, molecular,
structural, displayed and
alkene propene, CH3CH=CH2
C C skeletal formulae of the
hydrocarbon in Figure 7.5.
b) What is the name of this
halogenoalkane −Hal 1-chloropropane, CH3CH2CH2Cl
compound?
ether methoxyethane, CH3OCH2CH3
C O C

aldehyde O propanal, CH3CH2CHO

C
H
ketone propanone, CH3COCH3
C O Figure 7.5 쑿
Ball-and-stick and space filling
carboxylic acid O propanoic acid, CH3CH2COOH models of a hydrocarbon.

C 2 Anaerobic respiration in muscle cells

breaks down glucose to simpler
CH compounds including the following
O C two molecules. Identify the
ester methyl ethanoate, CH3OCOCH3
functional groups in these
O molecules.
a) CH2OH−CHOH−CHO
amine −NH2 propylamine, CH3CH2CH2NH2 b) CH3−CO−COOH
3 Pheromones are messenger
Table 7.1 쑿 molecules produced by insects to
The major functional groups attract mates or to give an alarm
signal. Identify the functional groups
in the pheromone below produced
Test yourself by queen bees.
O
4 Use the data sheets on the Dynamic Learning Student website headed ‘Tests
and observations on organic compounds’ and the reaction flow charts from CH3CCH2CH2CH2CH2CH2 H
previous topics to predict six important properties or reactions of each of the
following compounds. C C
a) (−)Carvone, which is responsible for the taste of spearmint. H COOH
O
C CH2
H
CH3 C C CH3

C CH2 C
Data
H CH2

b) The painkiller dextropropoxyphene and its mirror image which is an

ingredient of cough mixtures.

CH3 H H CH3
N(CH3)2 N(CH3)2
O
O
COCH2CH3
CO
painkiller CH3CH2 cough suppressant
79
 Synthesis

7.3 Organic routes

Organic chemists synthesise new molecules using their knowledge of
functional groups, reaction mechanisms and molecular shapes – as well as the
factors which control the rate and extent of chemical change.
A synthetic pathway leads from the reactants to the required product in one
step or several steps. Organic chemists often start by examining the ‘target
molecule’. Then, they work backwards through a series of steps to find suitable
starting chemicals that are available and cheap enough. In recent years,
chemists have developed computer programs to help with the process of
working back from the target molecule to a range of possible starting
molecules.
Figure 7.6 shows an example of the systematic way in which working back
can be used in synthesising one ‘target molecule’ from a starting molecule. In
this case, the ‘target molecule’ is butanoic acid and the starting molecule is
1-bromobutane.

CH3CH2CH2CH2OH CH3CH2CH2CHO
alcohol aldehyde
halogenoalkane O O
CH3CH2CH2CH2Br CH3CH2CH2C CH3CH2CH2C
ester OCH3 OH
starting target
molecule CH3CH2CH2CH2NH2 CH3CH2CH2CH2OH molecule
amine alcohol

Figure 7.6 쑿 ● Begin by writing down the formulae of those compounds which could be
Working back from the target molecule to readily converted to butanoic acid, the target molecule. These include the
find a two-stage synthesis of butanoic aldehyde, butanal, the alcohol, butan-1-ol and the ester, methyl butanoate.
acid from 1-bromobutane. ● Then look at your starting molecule, 1-bromobutane, to see if it could be
converted to one of the compounds which would readily form butanoic
acid. If necessary, write down the formulae of compounds which might be
produced from 1-bromobutane. These include the alcohol, butan-1-ol and
the amine, butylamine.
● With any luck, you should now see a possible two-stage synthetic route
from your starting molecule to the target molecule. In this case, the route
can go via butan-1-ol.
● If a two-stage route is not clear at this point, then you might need to
consider a three-stage route involving the conversion of one of the products
from the starting material to one of the reactants which will readily form
the target material.
Figure 7.7 씰
This photo shows a combinatorial
chemistry lab. Using the computer-
controlled techniques of combinatorial
chemistry, vast numbers of new
compounds can be made and tested in a
short time.

80
 Organic routes

Chemists normally seek a synthetic route which has the least number of stages
and produces a high yield of the product. The larger the scale of production,
the more important it is to keep the yield high so as to avoid producing large
quantities of wasteful by-products.

Changing the functional groups

All the reactions in organic chemistry convert one compound to another, but
there are some reactions which are particularly useful for developing synthetic
routes. These useful reactions include:
● the addition of hydrogen halides to alkenes
● substitution reactions which replace halogen atoms with other functional
groups such as −OH or −NH2
● elimination of a hydrogen halide from a halogenoalkane to introduce a
carbon–carbon double bond
● oxidation of primary alcohols to aldehydes and then carboxylic acids
● reduction of carbonyl compounds to alcohols.

Activity

Converting one functional group to another

Make a copy of the flow chart in Figure 7.8. Beside each arrow, write
the reagents and conditions needed for the conversion. You may need
to refer to the reaction flow charts from previous topics to do this.

Alkane Halogenoalkane Amine

Alkene Alcohol Ketone

Dihalogenoalkane Aldehyde Ester

Carboxylic acid

Figure 7.8 쑿
A flow diagram summarising the methods for converting one functional group to another.

Using your completed copy of Figure 7.8, suggest two-stage

syntheses showing the reagents and conditions for each of the
following conversions:
1 ethene to ethanoic acid
2 butan-1-ol to butan-2-ol
3 ethanol to ethyl ethanoate (using ethanol as the only carbon
compound)
4 propan-2-ol to propane.

81
 Synthesis

Test yourself
5 Draw the structural formula of the main organic product in each of the following
reactions.
Classify each reaction as addition, substitution or elimination and classify the
reagent attacking the organic reactant as a free radical, nucleophile, electrophile
or base.
HBr(g)
a) CH2=CH2(g)
KOH(aq)
b) CH3CH2CH2Br(l)
H3PO4(l) catalyst
c) CH3CHOHCH3(l)
heat
conc. HNO3
d) C6H6
benzene conc.H2SO4
6 Give the reagents and conditions for converting:
a) butanone to butane in three stages
b) ethanol to ethane-1,2-diol in three stages.
7 Identify substances A to H in the flow diagrams below.
Excess A HCl(g) Conc. NH3
a) CH3CH2OH B CH3CH2Cl C
then heat in ethanol

NO2 NH2
D+ E + conc. F
b)
conc. H2SO4 heat

(i) G + dil. HCI at 5°C

N N OH
(ii) H + dil. NaOH at 5°C

7.4 Synthetic techniques

Chemists have developed a range of practical techniques for the synthesis of
solid and liquid organic compounds. These methods allow for the fact that
water out reactions involving molecules with covalent bonds are often slow and that it
is difficult to avoid side reactions which produce by-products. There are five
key stages in the preparation of an organic compound.

vapour escaping Stage 1: Planning

from the flask The starting point of any synthesis is to choose an appropriate reaction or series
condenses here of reactions as described in the last section. The next step is to work out suitable
water in reacting quantities from the equation and decide on the conditions for reaction.
condensed liquid flows An important part of the planning stage is a risk assessment to ensure that
back to the flask there are no unnecessary hazards and the procedure is carried out as safely as
reaction mixture possible.
with volatile liquids
Stage 2: Carrying out the reaction
anti-bumping granules The reactants are measured out and mixed in a suitable apparatus. Most
heat organic reactions are slow at room temperature so it is usually necessary to
Figure 7.9 쑿 heat the reactants using a flame, heating mantle or hotplate. One of the
Heating in a flask with a reflux condenser commonest techniques is to heat the reaction mixture in a flask fitted with a
prevents vapours escaping while the reflux condenser (Figure 7.9).
reaction is happening. Vapours from the Organic reagents do not usually mix with aqueous reagents. So another
reaction mixture condense and flow back common technique is to shake the immiscible reactants in a stoppered
(reflux) into the flask. container.

82
 Synthetic techniques

Stage 3: Separating the product from the reaction mixture

Chemists talk of ‘working up’ the reaction mixture to obtain their crude
product. If the product is a solid, it can be separated (‘worked up’) by filtration
using a Buchner or Hirsch funnel with suction from a water pump. This is
illustrated in part of Figure 2.16.
Liquids can often be separated by simple distillation, fractional distillation
or steam distillation. Distillation with steam at 100 °C allows the separation of
compounds which decompose if heated near their boiling points. The
technique only works with compounds that do not mix with water. When
used to separate the products of organic preparations, steam distillation leaves
behind those reagents and products which are soluble in water.
Figure 7.10 씱
Setting up a distillation apparatus to
separate chemicals synthesised during
research to develop new anti-cancer
drugs.

Stage 4: Purifying the product

The ‘crude’ product separated from the reaction mixture is usually
contaminated with by-products and unused reactants. The method of
purifying this ‘crude’ product depends on whether it is a solid or a liquid.

Purifying organic solids

The usual technique for purifying solids is recrystallisation, which is illustrated
in part of Figure 2.16. The procedure for recrystallisation is based on using a
solvent which dissolves the product when hot, but not when cold. The choice
of solvent is usually made by trial and error. Use of a Buchner or Hirsch
funnel and suction filtration speeds up filtering and facilitates recovery of the
purified solid from the filter paper. The procedure is as follows:
● Dissolve the impure solid in the minimum volume of hot solvent.
● If the solution is not clear, filter the hot mixture through a heated funnel to
remove insoluble impurities.
● Cool the filtrate so that the product recrystallises, leaving the smaller
amounts of soluble impurities in solution.
● Filter to recover the purified product.
● Wash the purified solid with small amounts of pure solvent to wash away
any solution containing impurities.
83
● Allow the solvent to evaporate from the purified solid in the air.
 Synthesis

Purifying organic liquids

Chemists often begin to purify organic liquids which are insoluble in water by
shaking with aqueous reagents in a separating funnel to extract impurities.
This is followed by washing with pure water, drying and finally fractional
distillation.
Fractional distillation separates mixtures of liquids with different boiling
points. On a laboratory scale, the process takes place in a distillation apparatus
which has been fitted with a fractionating column between the flask and the
still-head (Figure 7.11). Separation is improved if the column is packed with
inert glass beads or rings to increase the surface area so that the rising vapour
can mix with the condensed liquid running back to the flask. The column is
hotter at the bottom and cooler at the top. The thermometer reads the boiling
point of the compound passing over into the condenser.

Figure 7.11 씰
The apparatus for fractional distillation of
a mixture of liquids.
thermometer

still head

condenser

fractionating
column

receiver

starting material
anti-bumping
granules
heat

Definitions If the flask contains a mixture of liquids, the boiling liquid in the flask
A volatile liquid evaporates easily, produces a vapour which is richer in the most volatile of the liquids present –
turning to a vapour. the one with the lowest boiling point.
Most of the vapour condenses in the column and runs back. As it does so, it
Vapours are gases formed by
evaporation of substances that are meets more of the rising vapour. Some of the vapour condenses and some of
usually liquids or solids at room the liquid evaporates. In this way, the mixture evaporates and condenses
temperature. repeatedly as it rises up the column. But every time it does so, the vapour
Chemists talk about ‘hydrogen gas’ becomes richer in the most volatile liquid present. At the top of the column,
but ‘water vapour’. Vapours are easily the vapour contains 100% of the most volatile liquid. So, during fractional
condensed by cooling or increased distillation, the most volatile liquid with the lowest boiling point distils over
pressure because of their relatively first, then the liquid with the next lowest boiling point and so on.
strong intermolecular forces.
84
 Synthetic techniques

Stage 5: Measuring the yield, identifying the product and

checking its purity

Measuring the yield

Comparing the actual yield with the yield expected from the chemical equation
is a good measure of the efficiency of a process. The yield expected from the
equation, assuming that the reaction is 100% efficient, is called the
theoretical yield.
The efficiency of a synthesis, like that of other reactions, is normally
calculated as a percentage yield. This is given by the relationship:
actual yield of product
percentage yield = × 100%
theoretical yield of product

Worked example
a) What is the theoretical yield of glycine (2-aminoethanoic acid) from 15.5 g
of 2-chloroethanoic acid?
b)What is the percentage yield if the actual yield of glycine is 7.9 g?
Notes on the method
Start by writing an equation for the reaction. This need not be a full balanced
equation, so long as it includes the limiting reactant and the product in their
correct molar ratio.
In this case, we must assume that any other reagents are in excess and the
limiting reactant is chloroethanoic acid.
Answer
Test yourself
a) The equation: ClCH2COOH ⎯→ H2NCH2COOH
The molar mass of chloroethanoic acid, ClCH2COOH = 94.5 g mol−1 8 A possible two-stage synthesis of
1,2-diaminoethane first converts an
The molar mass of glycine, H2NCH2COOH = 75 g mol−1 alkene to a dihalogenoalkane, and
then reacts this with ammonia.
According to the equation: a) Write out a reaction scheme for
1 mol of chloroethanoic acid produces 1 mol of glycine the synthesis giving reagents
and conditions.
So, 94.5 g of chloroethanoic acid produces 75 g of glycine b) Calculate the mass of the
75 alkene needed to make 2 g of
So, 15.5 g of chloroethanoic acid produces × 15.5 g of glycine the 1,2-diaminoethane
94.5
= 12.3 g of glycine assuming a 60% yield in stage
1 and a 40% yield in stage 2.
actual yield of product
b) Percentage yield = × 100% Which chemicals should be in
theoretical yield of product excess?
7.9 c) What hazards does the
= × 100%
12.3 synthesis pose and what safety
= 64% precautions should be taken?

Identifying the product and checking its purity

● Qualitative tests
Simple chemical tests for functional groups can help to confirm the identity
of the product. These tests for functional groups are shown in the data
sheets headed ‘Tests and observations on organic compounds’ on the Data
Dynamic Learning Student website.

85
 Synthesis

● Measuring melting points and boiling points

Pure solids have sharp melting points, but impure solids soften and melt
over a range of temperatures. So, watching a solid melt can often show
whether it is pure or not. As databases now include the melting points of all
known compounds, it is possible to check the identity and purity of a
product by checking that it melts sharply, at the expected temperature.
Figure 7.12 씰
stirrer
Two methods of measuring the melting
point of a solid.
capillary tube
containing the
sample
thermometer

oil with a high

boiling point
capillary tube
containing
the sample

very gentle heat

Like melting points for solids, boiling points can be used to check the
purity and identity of liquids. If a liquid is pure, it should all distil over a
narrow range, at the expected boiling point. The boiling point can be
measured as the liquid distils over during fractional distillation.
● Chromatography and spectroscopy
The uses of chromatography and spectroscopy in identifying products and
checking their purity are covered in Topics 8 and 9.

Test yourself
9 Give three reasons why the actual yield in an organic synthesis is always less
than the theoretical yield.
10 A two-stage synthesis converts 18 g of benzene first to 22 g of nitrobenzene and
then to 12 g of phenylamine.
a) State the reagents and conditions for each stage.
b) Calculate the theoretical yield and the percentage yield for each stage.
c) What is the overall percentage yield?
11 Read the sub-section headed ‘Purifying organic solids’ in Section 7.4 again and
then answer the following questions.
a) Why should the impure solid be dissolved in the minimum volume of hot
solvent?
b) Why is the solution sometimes cooled in ice when the pure product is being
recrystallised?
c) How could you improve the evaporation of excess solvent from the purified
solid in the final stage?

86
 Stereochemical synthesis

7.5 Stereochemical synthesis

When organic compounds are prepared synthetically in the laboratory, the
product is sometimes a mixture of two optical isomers.
One process in which this can happen fairly frequently is the reaction of
carbonyl compounds with H− ions in sodium tetrahydridoborate(III), NaBH4,
and with cyanide ions, CN−, in potassium cyanide. Both of these reactions
with H− and CN− involve nucleophilic addition. The initial product in each
case is an intermediate anion, which is converted to the final product
containing an −OH group by adding dilute sulfuric acid (Figure 7.13).
Figure 7.13 씱
H H The nucleophilic addition of hydrogen
H cyanide to ethanal.
Reflux with Add dil.
NC– + C O NC C O– NC C OH
KCN(s) in H2SO4
CH3 ethanol
CH3 CH3
Definitions
The reaction of ethanal with cyanide ions followed by dilute sulfuric acid A racemic mixture is a mixture of
increases the number of groups attached to the carbon atom in the carbonyl equal amounts of the two mirror
group from three to four. In this case, there are now four different groups image forms of a chiral compound.
attached to the carbon atom. This means that the final product will be a The mixture does not rotate polarised
mixture of two optical isomers. As the CN− ions can attack the flat ethanal light because the two optical isomers
molecule equally well from either side, the mixture will contain equal amounts have equal and opposite effects, so
of the two optical isomers. Mixtures of this kind are called racemic mixtures. they cancel each other out.
The reaction which we have just considered is used as the first stage in the ‘Racemic’ is pronounced ‘raseemic’.
two-stage laboratory synthesis of lactic acid (2-hydroxypropanoic acid) from
ethanal. In the second stage, the product shown in Figure 7.13 is refluxed with
the dilute acid and this converts the −CN group to a carboxylic acid group,
−COOH (Figure 7.14).
Figure 7.14 씱
The laboratory synthesis of lactic acid
H3C H3C CH3 CH3 (2-hydroxypropanoic acid) from ethanal
produces a racemic mixture.
NC– C C C C –
CN
H H
H O NC CN O H
OH HO
+ +
H H
H+(aq) H+(aq)
reflux reflux
H3C CH3

C C
H H
HOOC COOH
OH mirror HO

In contrast to the lactic acid produced synthetically in the laboratory, that

formed in our muscles during excessive activity is the single (+) isomer. The
reason for this is that the lactic acid formed in our muscles is produced
naturally through processes catalysed by enzymes.
In fact, most optically active compounds in living systems are present as
just one optical isomer. For example, all the glucose in living systems is the
(+) isomer.
Almost all the chemical reactions in living organisms are controlled by
enzymes, which are natural catalysts consisting of proteins (see Section 5.3).
When enzymes act as catalysts, the reactions take place at an active site
somewhere on the enzyme molecule. The shape of the active site and the
functional groups around it are very stereospecific and give the enzyme its
catalytic properties. Figure 7.15 쑿
The stereospecific nature of the active site means that enzymes can usually Paula Radcliffe winning the London
accommodate only one particular molecule at their active site and this Marathon in 2005. All the lactic acid in 87
molecule is often only one of the optical isomers. her weary muscles is the (+) isomer.
 Synthesis

7.6 Stereochemistry and drugs

Pharmaceutical chemists seek to discover and synthesise drugs
(pharmaceuticals) which will prevent diseases, cure them or, at least, alleviate
the symptoms. Drugs act on molecules within the cells in our bodies, and most
drugs act on proteins either in enzymes or in sensitive receptors on the surface
of cells. Receptors make cells responsive to the chemicals from nerve endings
and hormones.
One of the ways in which drugs act is to target the active site of a specific
enzyme. Many drugs which kill harmful bacteria or stop their reproduction
work by targeting enzymes. The sulfonamide drugs and penicillin antibiotics
work in this way. What is crucial is that the drug affects an enzyme vital to
the biochemistry of harmful bacteria, but does not damage any of the enzymes
in humans.

Figure 7.16 씰
A computer graphic of an anti-HIV drug
(yellow) blocking the active site of the
enzyme reverse transcriptase (green).
The drug stops the HIV virus from
reproducing.

Drugs which target receptor proteins are also very important and these include
the active ingredients in medicines to treat pain, heart failure, asthma and
Parkinson’s disease.

Chirality in drugs
Many molecules in our bodies interact selectively with the active sites in the
protein structures of enzymes and receptors. These molecules are all chiral but
our body chemistry works with only one of the mirror image forms. This
means that most drugs are also chiral, and often the two optical isomers act on
the body in different ways.
Often, one isomer is active while the other is inactive, but this is not always
the case (Figure 7.17).
Figure 7.17 씰
The optical isomers of isoleucine produce HOOC COOH
CH3 H3C
completely different tastes.
C C
H2N CHC2H5 H5C2CH NH2
H H
L-isoleucine D-isoleucine
bitter sweet
The pharmaceutical industry was alerted to the crucial importance of chirality
early in the 1960s. A new drug, called thalidomide, was introduced to treat
morning sickness in the first few months of pregnancy. Soon it was realised
88 that this drug was responsible for serious malformations in babies who were
born with stunted limbs.
 Stereochemistry and drugs

O
CH2OH
OH CH3 HO CH2 CH C

NH2 H
HO CH CH2 NH C CH3
HO
CH3
salbutamol levodopa (one of the optical isomers is
(used to treat asthma) CH2OH O used to treat Parkinson’s disease)

O2N CH CH NH C CHCl2

OH
chloramphenicol (an optical isomer is the active
antibiotic used to treat typhoid)

Figure 7.18 쑿
Test yourself Drugs which are chiral.

12 a) Write an equation for the nucleophilic attack of ethanal by H− ions in NaBH4

followed by the addition of dilute sulfuric acid similar to that in Figure 7.13.
b) In what crucial way is the product different from that in Figure 7.13?
c) Give the name and structure of the simplest carbonyl compound which will
give a chiral product with H− ions followed by dilute acid.
13 Copy the molecules shown in Figure 7.18 and then identify their chiral centres
with asterisks.
14 Explain in your own words, with the help of Figure 7.14, why a laboratory
synthesis of a chiral compound usually produces a racemic mixture.

Activity

Thalidomide
Thalidomide first appeared in Germany in October 1957. It was
marketed as a sedative with very few side-effects. The
H
pharmaceutical company that developed thalidomide thought it
was so safe that it could be prescribed to women in their first few O N O
months of pregnancy to alleviate morning sickness. No one could C C O
have imagined what would follow.
CH2 CH C CH
At the beginning of the 1960s, some babies were born with CH2 N C CH
shortened, flipper-like limbs. The disabilities were traced to
C C CH
thalidomide and the drug was withdrawn, but not before an
O CH
estimated 20 000 babies had been affected.
Drug testing was much less thorough in the 1950s. Tests had been Figure 7.19 쑿
The structure of thalidomide.
conducted with thalidomide on rats and mice, but not on primates
or humans. Years later, research showed that rodents metabolised
thalidomide in a different way to humans.
Thalidomide is a chiral molecule (Figure 7.19) and the drug was a
racemic mixture of the two isomers. Pharmacologists have since
discovered that the (+) isomer is an effective and harmless sedative,
while the (−) isomer is harmful to unborn babies. The adjective for
this is teratogenic.
A vast amount of time and money has gone into researching the
properties of thalidomide and its devastating effects on the
development of limbs in the uterus. 89
 Synthesis

Research has shown that:

● the (−) isomer blocks the development of blood
vessels
● the body can convert one optical isomer of
thalidomide to the other
● a few of the women with thalidomide deformities
have given birth to babies with limb defects.
Today, the testing of drugs and other pharmaceutical
products has become much more rigorous. However,
there is still a risk that any new drug may have
unforeseen side-effects.
In recent years, suggestions have been made that
thalidomide would be effective in the treatment of
certain cancers and in curtailing weight loss in HIV
patients. This has led to rigorous clinical research trials.
1 What functional groups are present in thalidomide?
2 a) What is the molecular formula of thalidomide? Figure 7.20 쑿
These technicians are preparing
b) What is its empirical formula? bottles of pills for a clinical trial.

3 Use a model-building kit to construct a molecular

model of one of the isomers of thalidomide.
a) Identify the chiral centre.
b) Is the character of thalidomide acidic, basic or neutral?
Explain your answer.
4 Thalidomide is moderately soluble in both water and non-polar
solvents. Which groups in thalidomide help to make it:
a) soluble in water
b) soluble in non-polar solvents?
5 Why were tests of thalidomide on rodents flawed?
6 Why would the harmful effects of thalidomide still have happened
even if the pure (+) isomer had been prescribed to pregnant
women?
7 What conclusions can be drawn from the fact that a few children
born to the first victims of thalidomide have limb deformities, even
though their mothers have not taken the drug.
8 Suggest a reason why thalidomide may be effective in the
treatment of certain cancers. (Hint: cancer cells grow faster than
normal cells.)
9 Suggest three precautions that should be taken in the recent
clinical research trials with thalidomide.

90
 Synthesising drugs

7.7 Synthesising drugs

The testing of drugs and other pharmaceuticals is now much more thorough
than it was in the 1950s and 1960s. When chiral molecules are involved,
licensing authorities require pharmaceutical companies to carry out research
with both isomers and to identify their individual properties. Very often this
leads to a requirement to produce a single optical isomer.
This synthesis and production of pharmaceutical products which contain a
single optical isomer has clear benefits for both patients and drug companies:
● it reduces the possible side-effects of the product
● it reduces the risk of companies being taken to court for negligence
● it improves pharmacological activity, and therefore reduces the quantity
needed for each dose. It is therefore more economical.
However, there is one massive and very significant disadvantage. This is the
increased cost of production when it is necessary to separate optical isomers
with almost identical properties.
In order to overcome the problems of producing a pure single optical isomer
of a pharmaceutical product, chemists have employed some very innovative
techniques. These include the use of:
● enzymes or bacteria which metabolise only one of the optical isomers and
introduce the required stereoselectivity
● natural chiral molecules, such as L-amino acids or D-glucose, as starting
molecules
● chiral catalysts, possibly attached to a polymer support with reactants
flowing over them.
In some processes, supercritical carbon dioxide is used as a substitute for
organic solvents. The supercritical carbon dioxide can dissolve materials like a
liquid and diffuse through solids like a gas, which it does when used to
decaffeinate instant coffee.

Figure 7.21 쑿
A molecular model of ibuprofen in which some of the atoms have non-standard
colours. Ibuprofen, CH3CH(COOH)–C6H4–CH2CH(CH3)2, is a chiral drug.

91
 REVIEW QUESTIONS
Extension questions
1 The following steps are taken from one method of 3 Salbutamol is used in inhalers to relieve the symptoms
synthesising ethyl ethanoate (b.p. 77 °C). of asthma. Its displayed formula is shown below.
A: Heat ethanol and ethanoic acid under reflux for H H OH H
about 45 minutes with a little concentrated CH3 H
sulfuric acid. N C C
C C
B: Then, distil the reaction mixture collecting all OH
CH3
the liquid which distils over below 84 °C. CH3 H H OH
C: Shake the distillate with aqueous sodium a) Identify the chiral centre in salbutamol. (1)
carbonate solution and then discard the aqueous
layer. b) List three reasons why salbutamol is used as a single
optical isomer in pharmaceutical products. ( 3)
D: Add two spatula measures of anhydrous sodium
sulfate or anhydrous calcium chloride to the c) Draw a displayed formula of the organic products
organic product. which form when salbutamol is refluxed for some
time with acidified potassium dichromate(VI). (2)
E: Finally, redistill the organic product collecting
the liquid which boils between 75 and 79 °C. 4 The skeletal formula of compound X is shown below.
X is a constituent of jasmine oil and it is partly
a) Draw a diagram of the apparatus for heating under responsible for the taste and smell of black tea.
reflux in step A. (3)
O
b) State the reasons for each of the procedures in steps
A to E. (8)
2 Salicylic acid has been used as a painkiller. Its displayed
formula is shown below.
O O O
Compound X
C
OH
a) What is the molecular formula of X? (1)
OH
b) Name the functional groups in X. (3)
c) Compound X is a stereoisomer.
a) Identify the functional groups in salicylic acid. (2)
i) Draw the structure of X and identify each
b) Write the molecular formula of salicylic acid. (1) stereochemical component with an asterisk. (3)
c) Draw the displayed formula of the organic product ii) Label each of these components with the type
that forms when salicylic acid: of stereoisomerism involved. (2)
i) is heated under reflux with ethanol and iii) How many stereoisomers are there with the
concentrated sulfuric acid (1) skeletal formula shown? Explain your answer.(3)
ii) reacts with bromine water (1) d) Point out four important factors that
iii) is warmed with aqueous sodium hydroxide. (2) pharmaceutical companies must consider in their
production of chiral compounds that are intended
for use in medicines. (4)

92
8 Chromatography
Chromatography is very important for modern chemistry. The various
techniques provide a powerful method for separating mixtures. They
range from the cheap and simple method of paper chromatography
to the sophisticated methods based on high-precision instruments
with sophisticated detectors used in gas chromatography.

8.1 Principles of chromatography

In 1903, the Russian botanist Michel Tswett developed the technique of
column chromatography to study plant pigments. He extracted the coloured
chemicals from leaves. He added a sample to the top of a column of powdered
chalk. Then he allowed a hydrocarbon solvent to flow through the column to Figure 8.1 쑿
separate the colours in the mixture. A scientist studying paper
chromatograms of a range of dyes. Each
of these chromatograms was made by
placing a small amount of the dye at the
solvent centre of a piece of filter paper, then
(mobile
slowly dripping a solvent onto the centre
phase)
of the paper. The solvent spread out over
the paper carrying with it the chemicals in
adsorbent components the dye at different rates.
solid of a mixture
(stationary separating on
phase) the column

glass wool

Figure 8.2 쑿 Figure 8.3 쑿

Column chromatography. A solution of the Coloured chemicals from a plant leaf
mixture to be analysed is added to the top separating on a chromatography column.
of the column. Then a solvent is run slowly
through the column. The substances in the
mixture separate and emerge at different
times from the column.
Definitions
‘Chroma’ means ‘colour’. The name chromatography was chosen because the The stationary phase in
technique was first used to separate coloured chemicals from mixtures. chromatography may be a solid or a
There is now a range of chromatography techniques which can be used to: liquid held by a solid support. The
mobile phase moves through the
● separate and identify the components of a mixture of chemicals
stationary phase and may be a liquid
● check the purity of a chemical or a gas.
● identify the impurities in a chemical preparation
In column chromatography, the liquid
● purify a chemical product.
flowing through the column is the
Every type of chromatography has a stationary phase and a mobile phase eluent. It washes the components of
that flows through it. Chemicals in a mixture separate because they differ in the mixture through the column. This
the extent to which they mix with the mobile phase or stick to the stationary is the process of elution.
phase. 93
 Chromatography

Powdered solids now used in column chromatography include silicon oxide

and aluminium oxide. Both of these can adsorb chemicals onto their surfaces.
The greater the tendency for molecules to be adsorbed by the stationary
phase, the slower they move during chromatography.

tiny granule of the

stationary phase
Definitions
A sponge absorbs water into its
pores as it soaks up the liquid. Paper
is absorbent and soaks up the moving molecule adsorbed
solvent during paper chromatography. onto the surface of molecule
Solids can adsorb very thin films of the stationary phase dissolved in the
liquids or gases onto their surfaces. mobile phase

Figure 8.4 쑿
In column chromatography, there is an equilibrium between molecules adsorbed onto
the surface of the stationary phase and molecules dissolved in the solvent.

Test yourself
1 In Michel Tswett’s column chromatography method, identify:
a) the stationary phase
b) the mobile phase.
2 In Figure 8.2. state the colour of the component of the mixture being separated
that has the greater tendency to:
a) dissolve in the eluting solvent
b) stick to the stationary phase.
3 Name two other techniques, other than chromatography, that can be used to
determine whether a product of chemical synthesis is pure or not.

8.2 Liquid chromatography

The column chromatography developed by Michel Tswett was an example of
liquid chromatography. Modern versions of the column technique continue to
be widely used. Other variants include thin-layer chromatography and high-
performance liquid chromatography.

Thin-layer chromatography
Thin-layer chromatography (TLC) is a another type of liquid chromatography
in which the stationary phase is a thin layer of a solid, such as silicon dioxide
or aluminium oxide, supported on a glass or plastic plate. As in column
chromatography, the rate at which a sample moves up a TLC plate also
depends on the equilibrium between adsorption on the solid and solution in
the solvent. The position of equilibrium varies from one compound to
another, so the components of a mixture separate.
TLC is fast, cheap and needs only a very small sample for analysis. The
technique is widely used both in research laboratories and in industry. TLC
can be used to quickly check that a chemical reaction is going as expected and
is making the required product. After attempting to purifying a chemical, TLC
can show whether or not all the impurities have been removed.

94
 Liquid chromatography

lid

solvent rises up
plate by solvent tank – atmosphere
capillary action saturated with solvent
vapour by lining it with
paper soaked in the solvent

compounds in an thin-layer chromatography

impure sample plate
separating out
spots of solutions applied
here, including one or more
reference compounds

P Q R S

solvent
Figure 8.5 씱
Apparatus for thin-layer chromatography. Spots of chemicals for the analysis are
placed on the start line at P, Q, R and S.

Coloured compounds are easy to see on a TLC plate. However, the technique
is often used with colourless compounds as well. A quick way of finding the
position of colourless organic spots is to stand the plate in a covered beaker
with iodine crystals. The iodine vapour stains the spots.
An alternative is to use a TLC plate impregnated with a fluorescent
chemical. Under a UV-lamp the whole plate glows, except in the areas where
organic compounds absorb radiation – so they show up as dark spots.
Rf values can be used to record the distances moved by chemicals in a
mixture relative to the distance moved by the solvent. The values are ratios Definition
calculated using this formula where x and y are as shown in Figure 8.6:
The Rf value is the ratio of the
distance moved by chemical distance moved by the chemical in a
Rf =
distance moved by solvent front mixture to the distance moved by the
solvent front. Rf values are used in
x
= thin-layer and paper chromatography.
y

Test yourself
solvent front
4 Why is the start line for spotting
TLC samples on a plate drawn in
pencil and not with ink?
y 5 Why is the air inside the container of
the TLC solvent saturated with the
x vapour of the solvent before adding
the TLC plate?
6 Which of the four samples P, Q, R
and S in Figure 8.5:
start line a) is the mixture being analysed
b) are reference compounds also
present in the mixture
Figure 8.6 쑿 c) is a reference compound not
A diagram of a TLC plate showing the distances used to calculate Rf values. present in the mixture?
Rf values can help to identify components of mixtures so long as the conditions are 7 Estimate the Rf values for the yellow
carefully controlled. The values vary with the type of TLC plate (or paper) and the dye in Figure 8.5.
nature of the solvent.

95
 Chromatography

High-performance liquid chromatography

High-performance liquid chromatography (HPLC) is a sophisticated version
of column chromatography. The technique is able to separate components in
a mixture that are very similar to each other.
High performance is achieved by packing very small particles of a solid,
such a silica, into a steel column (Figure 8.7). A typical column is about 10–
30 cm long and has an internal diameter of about 4 mm.
The use of fine particles increases the surface area of the stationary phase.
This makes the separation efficient but it means that a high-pressure pump is
necessary to force the solvent through the tightly packed column. As a result,
the technique is sometimes called high-pressure liquid chromatography.
Figure 8.7 씰
A scientist checking a sample tube in
front of a set of high-performance liquid
chromatography columns.

An advantage of HPLC is that it is carried out at room temperature and so

can analyse mixtures that decompose before they vaporise – this applies to
many biological molecules. Organic molecules that break down on heating
cannot be studied using gas chromatography (see Section 8.3). This makes
HPLC suitable for separating biological molecules such as proteins. One
important application of HPLC is to study what happens to drugs as they are
metabolised in the body.

Activity

Food colours and children

The Food Standards Agency recommends that parents should avoid
letting their children eat foods with some colours in them, especially
if their children show signs of hyperactivity (see Section 4.5).
The colours to avoid include these dyes (with their E-numbers):
● sunset yellow (E110)
● quinoline yellow (E104)
● carmoisine (E122)
● tartrazine (E102).
These colours are used in a foods such as soft drinks, sweets,
cakes and ice cream.
Manufacturers must state the colours they use in the list of ingredients
by giving the ‘colour’ and either naming the chemical or showing the
E-number. Analysts can use thin-layer chromatography to check Figure 8.8 쑿
whether or not the claims made by manufacturers are correct. Soft drinks at a party for children.

96
 Gas chromatography

The chromatogram in Figure 8.9 shows the results of analysing the solvent front
colours extracted from two soft drinks. The colours from the soft
drinks are compared with reference compounds.
1 Tartrazine, sunset yellow and carmoisine are examples of azo
dyes.
a) Which functional group is present in an azo dye?
b) How, in general, are azo dyes made?
2 Suggest a reason for carrying out this analysis by TLC rather
than HPLC.
3 Which of the reference dyes is not a pure compound?
4 What is the Rf value for carmoisine under the conditions used to
make this TLC plate?
5 What can you conclude from the chromatogram about:
a) soft drink A 1 2 3 4 5 6
b) soft drink B?
Figure 8.9 쑿
6 What advice could the analyst give to parents of a hyperactive TLC plate showing the results of the
child about the two soft drinks, based on this chromatogram? analysis for two soft drinks and four
dyes for reference: 1 quinoline yellow;
7 What further investigations should the analyst carry out to 2 colour from soft drink A; 3 carmoisine;
confirm the advice given? 4 sunset yellow; 5 tartrazine; 6 colour
from soft drink B.

8.3 Gas chromatography

Gas chromatography (GC) is a sensitive technique for analysing complex
mixtures. The technique is used for compounds which vaporise on heating
without decomposing. This type of chromatography not only separates the
chemicals from a sample, but also gives a measure of how much of each is
present.
In GC the mobile phase is a gas, such as helium, which carries the mixture
of volatile chemicals through a long tube containing the stationary phase. The
column is coiled inside an oven. Heating the column makes it possible to
analyse any chemicals that turn to vapour at the temperature of the oven.
The analyst injects a small sample into the column where it enters the
oven. Volatile solids are dissolved in a solvent before injection. The chemicals
in the sample turn to gases and mix with the carrier gas. The gases then pass
through the column.

dried Figure 8.10 씱

carrier The main features of gas
gas in chromatography. The carrier gas takes
replaceable the mixture of chemicals through the
silicon rubber column where they separate. As the
septum detector recorder compounds leave the column they are
detected and measured.
injector exit
port
detector oven
injector
oven column

column oven 97
 Chromatography

The components in the mixture separate as they pass through the column.
After a time the chemicals emerge one by one. They pass into a detector,
Definition which sends a signal to a recorder as each compound appears. A series of
peaks, one for each compound in the mixture, make up the chromatogram.
The retention time in gas
The position of a peak on a GC print-out is a record of how long it took for
chromatography is the time it takes
for a compound in a mixture to pass
a particular compound to pass through the column. This is the retention time.
through a chromatographic column The area underneath each peak gives an indication of the relative amounts of
and reach the detector. the compounds in the mixture. If the peaks are narrow it is good enough to
measure the peak heights.

Figure 8.11 씰 10
Print-out from a gas chromatography
instrument.

Recorded response 8

Test yourself
4
8 Suggest a reason for choosing
helium as the carrier gas in gas
chromatography.
9 Refer to Figure 8.11.
2
a) How many chemicals were
there in the mixture?
b) What was the retention time of
the least abundant chemical in
0
the mixture? 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210

Time/s
Some GC instruments have capillary columns. These are 20–60 metres long
with a very small internal diameter. Capillary columns are often made of silica
with an outer coating of a polymer. The stationary phase is the inner surface
of the column which adsorbs chemicals to a greater or lesser extent. The inner
surface may be coated with a solid adsorbent or a thin film of a liquid.
Figure 8.12 씰
A scientist changing the capillary column
in the oven of a gas chromatography
instrument. Capillary columns are very
long, but they are so flexible that they
can be wound into a tight coil.

98
 Gas chromatography

Other GC columns are steel or glass tubes that are packed with a powder. The
powder is an inert solid coated with a thin film of liquid. In these columns,
the stationary phase is the liquid coating. Chemicals in the carrier gas separate
in these columns because they differ in their solubility in the liquid of the
stationary phase.

tiny granule of the

molecule dissolved in
fine powder packing
the liquid on the
a GC column
surface of the solid
packing the column

thin coating of a molecule in the mobile

liquid on the surface phase (the carrier gas)
of the inert solid

Test yourself
Figure 8.13 쑿
In some gas chromatography columns there is an equilibrium between molecules 10 Why must the liquid for the
dissolved in a liquid coating on the surface of the stationary phase and molecules in stationary phase in gas–liquid
the carrier gas. Chemicals separate because they differ in their relative solubility in the chromatography have a high boiling
stationary liquid. When this type of column is used the technique is sometimes called point?
gas–liquid chromatography (GLC). 11 What are the implications of the fact
that similar compounds may have
Applications of GLC include: very similar retention times in gas
chromatography?
● tracking down the source of oil pollution from the pattern of peaks, which 12 Explain why it is not possible to
acts like a fingerprint for any batch of oil identify a previously unknown
● measuring the level of alcohol in blood samples from drivers chemical by gas chromatography.
● detecting pesticides in river water.

Activity

Forensic investigations of arson

Arsonists sometimes use flammable liquids such as
petrol or paraffin to accelerate fires. Firefighters collect
samples from burnt-out homes which forensic scientists
can analyse in the search for clues as to how the fire
started.
Suitable samples for analysis come from areas where
furniture and fittings have not been completely
destroyed. Useful samples include carpet underlays, soil
from pot plants, bedding, clothing and material
collected from underneath floor boards.
1 Suggest a reason why firefighters collect only partially
burned materials for analysis.
2 Suggest a reason why soil from pot plants can
provide good evidence that there have been
Figure 8.14 쑿
flammable liquids present.
Firefighters searching through the wreckage of a
burnt-out house. They are looking for evidence of
how the fire started to determine whether it was
an accident or arson.
99
 Chromatography

Analysts use solvents to extract chemicals from the samples, and

then investigate the solutions by gas chromatography. They
compare the chromatograms with those from standard samples of
common flammable substances.

Fresh paraffin Fresh petrol

Detector current

Detector current
Time/min Time/min
Partially evaporated paraffin Partially evaporated petrol
Detector current

Detector current

Time/min Time/min

3 The reference chromatogram for fresh petrol is very different Figure 8.15 쑿
from the chromatogram for fresh paraffin. Describe and explain GC chromatograms of standard
the differences. samples of fuels.

4 Suggest why the chromatogram for partially evaporated petrol

differs from the chromatogram for fresh petrol.
The two chromatograms in Figure 8.16 show the results of analysing
the chemicals from samples collected from a burnt-out house.
Sample A was collected from the charred floorboards just inside the
front door. Sample B came from the partly burned carpet under a
table near the window of the front room.

Sample A Sample B
Detector current

Detector current

Time/min Time/min

5 What can you conclude from the chromatogram for sample A? Figure 8.16 쑿
GC chromatograms of chemical
6 What can you conclude from the chromatogram for sample B? extracts from two samples collected
from a burnt-out house.
7 Suggest further evidence that the analysts would need to collect
before deciding whether the house fire was an accident or the
result of arson.
100
 Chromatography combined with mass spectrometry

8.4 Chromatography combined with mass

spectrometry
Coupling gas chromatography (GC) with mass spectrometry (MS) gives a very
powerful method for separating, identifying and measuring complex mixtures
of chemicals. The combined technique (GC–MS) is widely used in drug
detection, investigation of fires and environmental monitoring, as well as in
airport security. Some space probes carry tiny GC–MS systems for analysing
samples collected in space or on the surface of planets such as Mars.

Ion detector gives an

Gas chromatography The chemicals from Mass analyser
electrical signal which is
column in which the the GC column are separates ions by
sample converted to a digital
chemicals in the separately ionised mass-to-charge
response that is stored in a
injected mixture separate and by bombardment ratio, e.g. by
computer. There is a separate
leave the column with electrons or magnetic field or
mass spectrum for each
one by one other methods time of flight
chemical in the mixture

GC–MS overcomes some of the limitations of gas chromatography. Similar Figure 8.17 쑿
compounds often have similar retention times in GC which means that they Schematic diagram showing the key
cannot be identified by chromatography alone, even if the conditions are features of a GC–MS system.
carefully standardised. Also, GC alone cannot identify any novel chemicals
because there are no standards that can be used to determine retention times
under given conditions.

Figure 8.18 쑿
A gas chromatography machine (left) connected to a mass spectrometer (right) in a
forensic laboratory. This equipment is sensitive enough to detect minute quantities of
illegal drugs in the hair of a suspect – weeks after any drugs were taken.

GC–MS produces a mass spectrum for each of the chemicals separated on the
GC column. These spectra can be used like fingerprints to identify the
compounds because every chemical has a unique mass spectrum.
A computer connected to a GC–MS system stores all the data. The
computer can be linked to a library of spectra of known compounds. The
computer compares the mass spectrum of each chemical in a mixture to mass
spectra in the library. It automatically reports a list of likely identifications
along with the probability that the matches are correct.
101
 Chromatography

Activity

Solving a pollution problem with GC–MS

With complex mixtures, a computer can help an analyst look for a Figure 8.19 쑼
‘needle in a haystack’. Figure 18.19 shows the chromatogram from Gas chromatogram for chemicals
sampled from the air in a house. The
an investigation of the air in a home where the family was feeling
numbers 1–700 on the time axis
very sick. During the analysis by GC–MS, the computer stored 700 indicate the points at which mass
mass spectra as the mixture of chemicals emerged from the spectra were recorded and stored.
chromatography column. Underneath these numbers are the
retention times.
100 231
Relative abundance/%

80 152
131
60
51 101

40
356 382
584
20 345
519
646

0
100 200 300 400 500 600 700
1:50 3:40 5:30 7:19 9:09 10:59 12:49
Sample number for mass spectra
Retention time/min

The analysts suspected that the chemicals might have come from
petrol, so they asked the computer to plot a chromatogram showing
only those chemicals producing a peak with mass/charge ratio of 91
in their spectra. The result is shown in Figure 18.20, which indicates
that methylbenzene, ethylbenzene and three dimethylbenzenes were Figure 8.20 쑼
present in the mixture. These are all chemicals that are distinctive for GC–MS print out for the same
the mixture of hydrocarbons found in petrol. With this evidence the sample as in Figure 18.19 – but
investigators carried out further searches and tracked down the showing only the chemicals with a
source of the petrol vapour. prominent peak with a mass/charge
ratio of 91 in their mass spectra.
231
100
Relative abundance/%

80 methylbenzene
1,3-and 1,4-dimethylbenzene
60
356 382

40 1,2-dimethylbenzene
ethylbenzene 345

20

0
100 200 300 400 500
Sample number for mass spectra

102
 REVIEW QUESTIONS

1 Why, in a mass spectrometer, does each chemical:

a) have to be ionised
b) pass through a region with electric and/or magnetic fields
c) produce a spectrum with several peaks?
2 Suggest the identity of the ion fragment with a mass/charge ratio
of 91 in the mass spectra of methylbenzene and related
compounds.
3 How does the computer identify a chemical with a mass
spectrum recorded at a particular retention time?
4 Suggest two reasons why forensic scientists find GC–MS
particularly valuable.
5 HPLC can also be combined with MS. Give an example of a
sample that could be analysed by HPLC–MS but not by GC–MS.
Explain your choice.

REVIEW QUESTIONS
1 Draw up a table to summarise and compare three methods of chromatography, using an
enlarged version of Table 8.1. (12)
Type of Method of separation: adsorption Example of an Advantages Limitations
chromatography or relative solubility application
TLC
HPLC
GC

Table 8.1 쑿

2 Figure 8.21 shows the results of paper distance moved Amino acid Rf
by solvent
chromatography to separate amino acids. The
alanine 0.38
solvent was a mixture of butan-1-ol, ethanoic
butan-1-ol/ethanoic acid

acid and water. arginine 0.16

a) Amino acids are colourless. Suggest a glycine 0.26
method that could be used to show up leucine 0.73
the spots on the chromatogram. (1)
tyrosine 0.50
b) Why is it important to specify the type of
chromatography and the solvent used? (1) valine 0.60

c) Identify the three amino acids with Table 8.2 쑿

the help of Table 8.2. (2) Rf values for paper chromatography using a
solvent which is a mixture of butan-1-ol,
ethanoic acid and water.

Figure 8.21 씰

103
 Chromatography

3 Gas chromatography can be used to analyse the Compound Retention time/min

chemicals formed during the production of beer. Figure
8.22 shows a GC chromatogram for a sample taken methanol 19.5
during beer-making. The instrument was fitted with a
capillary column using a solid stationary phase. Table ethanol 20.5
8.3 gives the retention times for several relevant propan-1-ol 20.9
compounds.
propan-2-ol 22.5
a) Suggest a reason for the trend in the retention times
2-methylpropan-1-ol 22.7
for the four primary alcohols. (2)
butan-2-ol 24.6
b) Suggest a reason why 2-methylpropan-1-ol has a
shorter retention time than butan-2-ol. (2) ethanal 20.2

c) i) Use Figure 8.22 and Table 8.3 to identify the propanal 24.5
chemicals in the beer sample. (3) butanal 25.5
ii) How certain can you be of the answers you have propanone 23.8
given in part a)? Which peaks were hard to
ethanoic acid 24.2
identify and why? (2)
butanoic acid 26.2
d) The mixture was analysed by GC–MS. Figure 8.23
shows the mass spectrum of the fifth peak to emerge Table 8.3 쑿
from the GC column. Use this mass spectrum to
decide whether this peak is butan-2-ol or propanal. 100
Explain how you decide on your answer. (3)
e) How does the chemical with the shortest retention
80
time form during brewing? (2)
Relative abundance/%

60

40
Relative abundance

20

0.0
20 30 40 50 60
m/z
Figure 8.23 쑿

19 20 21 22 23 24 25 26 27
Retention time/min
Figure 8.22 쑿

104
9 Spectroscopy
In a modern laboratory, organic analysis is based on a range of
automated and instrumental techniques including nuclear magnetic
resonance spectroscopy, mass spectrometry and infrared
spectroscopy.

Figure 9.1 씱
Using a mass spectrometer in a forensic
laboratory to detect drugs in urine
samples.

Spectroscopy is a term which covers a range of practical techniques for

studying the composition, structure and bonding of compounds. Spectroscopic
techniques are now the essential ‘eyes’ of chemistry.

9.1 Nuclear magnetic resonance spectroscopy

Nuclear magnetic resonance spectroscopy (NMR) is a powerful analytical
technique for finding the structures of carbon compounds. The technique is
used to identify unknown compounds, to check for impurities and to study the
shapes of molecules.
1000 10 0.1 0.0001 Approximate energy Figure 9.2 씱
per photon/kJ mol–1
The uses of the electromagnetic
nuclei flipping

spectrum in spectroscopy.
in magnetic
transitions

molecular
electronic

vibration

fields

Effect on atoms
and molecules

Region of
waves
visible

radio
UV

IR

electromagnetic
spectrum

10–7 10–6 10–5 10–4 10–3 10–2 0.1 1 10 Wavelength/m

This type of spectroscopy studies the behaviour of the nuclei of atoms in

magnetic fields. It is limited to those nuclei that behave like tiny magnets
because they have a property called spin – in common organic compounds,
the only nuclei to do this are those of carbon-13 atoms, 13C, and of hydrogen
atoms, 1H. The nuclei of the much commoner carbon-12, oxygen-16 and
nitrogen-14 atoms do not show up in NMR spectra. 105
 Spectroscopy

Figure 9.3 씰 radio- radio-

Diagram of an NMR spectrometer frequency frequency computer recorder
oscillator detector
showing the key features of the
technique. probe at room temperature
containing the sample which is
spun at 20 times per second to
average any inhomogeneity
N S in the sample or the glass tube

powerful
magnet

When placed in a very strong magnetic field, the magnetic nuclei can line up
either in the same direction as or in the opposite direction to an external
magnetic field. There is a small energy jump when the nuclei flip from one
alignment to the other. The size of the energy jump corresponds to the
energies of quanta of radiowaves.
The tube with the sample is supported in a strong magnetic field. The
operator turns on a source of radiation at radio frequencies. The radio-
Definition frequency detector records the intensity of the signal from the sample as the
oscillator emits pulses of radiation across a range of wavelengths.
The horizontal scale of an NMR
The sample is dissolved in a solvent. Also in the solution is some
spectrum shows the chemical shifts
of the peaks measured in parts per tetramethylsilane (TMS), which is a standard reference compound that
million (ppm). The symbol δ stands for produces a single, sharp absorption peak well away from the peaks produced by
the chemical shift relative to the zero samples for analysis.
on the scale, which is given by the Each peak corresponds to one or more magnetic atoms in a particular
signal from tetramethylsilane (TMS). chemical environment. Nuclei in different parts of a molecule experience
slightly different magnetic fields in an NMR machine. This is because they are
shielded to a greater or lesser extent from the field applied by the spectrometer
by the tiny magnetic fields associated with the electrons of neighbouring
bonds and atoms.
The recorder prints out a spectrum that has been analysed by computer to
show peaks wherever the sample absorbs radiation strongly. The zero on the
scale is fixed by the absorption of magnetic atoms in the reference chemical.
The distances of the sample peaks from this zero are called their chemical
shifts (δ).

Carbon-13 NMR
Carbon-13 NMR relies on the magnetic properties of the carbon-13 isotope.
Carbon-13 makes up only about 1% of all naturally occurring carbon atoms
but this is enough for a signal to be detected in an NMR machine.
Figure 9.4 shows the carbon-13 NMR spectrum for ethanol. Spectra of this
kind are available from the Spectral Database System (SDBS) for Organic
Compounds at the National Institute of Materials and Chemical Research in
Japan.
Figure 9.4 씰
Carbon-13 NMR spectrum for ethanol
dissolved in CDCl3.
Signal strength

106 200 180 160 140 120 100 80 60 40 20 0

Chemical shift, δ/ppm
 Nuclear magnetic resonance spectroscopy

There are two peaks in the carbon-13 NMR spectrum for ethanol. This Test yourself
reflects the fact that there are two carbon atoms in an ethanol molecules and
they are in different chemical environments. The carbon in the CH3 group is 1 What is the difference in the
attached to 3 hydrogen atoms and a carbon atom. The carbon in the CH2 structure of the nuclei of carbon-12
group is attached to 2 hydrogen atoms, a carbon atom and an oxygen atom. and carbon-13 atoms?
Spectra of the type shown in Figure 9.4 are usually recorded with the 2 What is the difference between the
sample in solution. The chosen solvent is commonly CDCl3. Molecules of formula of CDCl3 and the formula of
CDCl3 contain one carbon atom and they produce a line in carbon-13 spectra trichloromethane?
which is easy to recognise. This line is usually removed from the spectra in 3 TMS is related to silane, SiH4, but
databases such as SDBS to avoid any confusion. The line produced by the has the four hydrogen atoms
solvent is not shown in any of the carbon-13 spectra in this book. replaced by methyl groups. Why
does this reference chemical
The chemical shifts are measured relative to the TMS peak at the zero mark
produce just one peak in carbon-13
– but this peak is also generally removed from the spectra in databases for NMR spectra?
clarity.
Figure 9.5 illustrates the principles of carbon-13 NMR in a more complex
example. Here too, every carbon atom, or group of carbon atoms, in a
chemically distinct environment gives a separate peak in the NMR spectrum.
Figure 9.5 씱
Carbon-13 NMR spectrum for
4-methylpentan-2-one dissolved
in CDCl3.
Signal strength

200 180 160 140 120 100 80 60 40 20 0

Chemical shift, δ/ppm

There are six carbon atoms in 4-methylpentan-2-one but only five peaks in
the carbon-13 NMR spectrum. The reason is shown in Figure 9.6. The carbon
atoms of two of the methyl groups (E) in the molecule are in exactly the same
environment, so they give rise to only one peak. The other four carbon atoms,
including the carbon atom in the third methyl group (A), are in slightly
different environments and give rise to separate peaks.

E Figure 9.6 씱
A The structure of 4-methylpentan-2-one
O CH3 labelled to show the five different
environments for the six carbon atoms.
H3C C CH2 C CH3
The two carbon atoms labelled E are in
exactly the same chemical environment.
H
B C D

107
 Spectroscopy

Generally, carbon atoms attached to electronegative atoms, such as oxygen, show

the largest chemical shifts. Chemists have found that it is possible to draw up
tables to show the likely range of values for the chemical shifts of carbon-13 atoms
in different environments. For example, carbon-13 atoms in alkanes typically give
chemical shifts in the range 10–35 ppm while carbon atoms in the carbonyl
groups of aldehydes and ketones give chemical shifts in the range 190–200 ppm.

Note Test yourself

You are only expected to interpret
carbon-13 NMR spectra in which 4 Predict the number of peaks in the carbon-13 NMR spectrum of:
each chemical environment for carbon a) pentane
atoms is represented by a single b) propyl ethanoate
peak. Also note that you cannot draw c) pentanal.
any conclusions by looking at the size 5 Predict the number of peaks in the carbon-13 NMR spectrum for
of the peaks in these spectra. a) benzene
Carbon-13 NMR differs from proton b) methylbenzene.
NMR in these two ways. 6 Explain how you could distinguish between propanal and propanone by
inspection of the carbon-13 NMR spectra of the two compounds.
7 Refer to the data sheet showing chemical shifts for carbon-13 NMR. To what
extent does the data show that the presence of electronegative atoms increases
the chemical shift values?
Data 8 Use the data sheet showing chemical shift values to suggest which carbon
atoms give rise to which peaks in the spectrum of:
a) ethanol (Figure 9.4)
b) 4-methylpentan-2-one (Figure 9.5).

Proton NMR
Proton NMR relies on the magnetic properties of the hydrogen-1 isotope. As
with carbon-13 NMR, the number of main peaks in the spectrum shows how
many different chemical environments there are for hydrogen atoms. Also, the
values for the chemical shifts are a useful indication of the types of chemical
environment for the hydrogen atoms corresponding to each peak.
Even more information can be deduced from a proton NMR spectrum
because it is possible to work out the number of hydrogen atoms in each
environment. In a proton NMR spectrum, the area under a peak is
proportional to the number of nuclei.
An NMR instrument is set up to integrate the curve and work out the
ratios. Sometimes the results of the calculation are shown by an integration
trace such as the blue line shown in the spectrum for methyl ethanoate in
Figure 9.8 – this shows the proton NMR spectrum for methyl ethanoate. This
is a low-resolution spectrum which shows the main peaks but no fine detail.

Figure 9.7쑿
A researcher adding a sample to a
nuclear magnetic resonance
Signal strength

spectrometer.

integration trace

10 9 8 7 6 5 4 3 2 1 0
Chemical shift, δ/ppm

Figure 9.8 쑿
108 Proton NMR spectrum of methyl ethanoate in CDCl3.
 Nuclear magnetic resonance spectroscopy

Alternatively, the instrument’s computer prints a number below each peak

that is a measure of the relative area under the curve – as shown for the
spectrum in Figure 9.9.
Figure 9.9 씱
Proton NMR spectrum of a compound
C5H10O in CDCl3.
Signal strength

Definition
Integration is a mathematical
technique that works out the area
under a curve. The ratios of the
17.3 integration value 155.4 results of integrating the peaks in a
proton NMR spectrum show the
10 9 8 7 6 5 4 3 2 1 0 relative numbers of hydrogen atoms in
Chemical shift, δ/ppm each chemical environment.

Proton NMR spectra, like carbon-13 NMR spectra, are usually recorded with
the sample in solution. It is important that the solvent does not contain
hydrogen atoms that would give peaks with chemical shifts similar to those in
the sample. One option is to use a solvent that contains no hydrogen atoms,
such as tetrachloromethane, CCl4. The other is to use a solvent in which
atoms of the hydrogen-1 isotope have been replaced by deuterium atoms – a
compound that is often used is CDCl3. Deuterium atoms produce peaks in
regions of the spectrum well away from the chemical shifts for proton NMR.
The reference chemical for proton NMR is again tetramethylsilane (TMS).
There are twelve hydrogen atoms in a molecule of TMS but they all have the
same chemical environment. TMS provides a single strong peak which marks
the zero on the scale of chemical shifts

Test yourself
9 NMR based on hydrogen nuclei is sometimes called 1H-NMR, and sometimes
proton NMR. Show that these are equivalent names.
10 Refer to the proton NMR spectrum in Figure 9.8 and the data sheet of chemical
shifts from the Dynamic Learning Student website.
a) Explain why there are two peaks in the spectrum.
Data
b) Use the chemical shift values to decide which hydrogen atoms give rise to
each peak.
c) Show that the integration trace is as you would expect for methyl ethanoate.
11 Refer to the proton NMR spectrum in Figure 9.9 and the data sheet of chemical
shifts.
a) How many different chemical environments are there for hydrogen atoms in
C5H10O?
b) Use the integration values under each peak to work out the ratios of
hydrogen atoms in each environment.
c) Use your answers to parts a) and b) and chemical shift values to suggest a
structure for this compound.
d) Describe two chemical tests that could be used to confirm the presence of
the main functional group in this molecule. State what you would do and
what you would expect to observe.
12 With the help of the data sheet of chemical shifts, sketch the low-resolution NMR
spectrum you would expect for:
a) butanone
b) 2-methylpropan-2-ol. 109
 Spectroscopy

Coupling
Note At high resolution, it is possible to produce proton NMR spectra with more
detail that provide even more information about molecular structures. The
Protons with the same chemical shift
do not couple with each other.
spins of protons connected to neighbouring carbon atoms interact with each
other. Chemists call this interaction spin–spin coupling and they find that the
effect is to split the peaks into a number of lines.

Signal strength

Data 5

Test yourself
13 Use the Data sheet: ‘NMR chemical TMS
reference
shifts’ from the Dynamic Learning
Student website to suggest a
structure for the aromatic
10 9 8 7 6 5 4 3 2 1 0
hydrocarbon with the proton NMR
spectrum shown in Figure 9.10. Chemical shift, δ/ppm
14 Sketch the high-resolution NMR
spectrum you would expect to Figure 9.10 쑿
observe with: High-resolution proton NMR spectrum for an aromatic hydrocarbon. Note the extra
a) propane peaks compared with the low-resolution spectrum.
b) ethoxyethane.
In simple examples, the ‘n + 1’ rule makes it possible to work out the numbers
of coupled protons. A peak from protons bonded to an atom that is next to an
atom with two protons splits into three lines. A peak from protons bonded to
an atom which is next to an atom with three protons splits into four lines.

number of splitting pattern and

equivalent protons relative intensity of
causing splitting the peaks
1 1 1
2 1 2 1
δ– 3 1 3 3 1
O
δ+ 4 1 4 6 4 1
C2H5 H C2H5
O δ–
Figure 9.11 쑿
H δ+ Pascal’s triangle predicts the pattern of peaks and the relative peak heights.

Oδ– Labile protons

H C2H5 Hydrogen bonding affects the properties of compounds that have molecules
containing hydrogen atoms attached to highly electronegative atoms such as
Figure 9.12 쑿 oxygen or nitrogen. These molecules can exchange protons rapidly as they
Hydrogen bonding in ethanol. move from one electronegative atom to another. Chemists describe these
protons as labile.
Definition
Labile protons do not couple with protons linked to neighbouring atoms.
An atom (or compound) is labile if it This means that the NMR peak for a proton in an −OH group appears as a
quickly and easily moves (or reacts). single peak in a high-resolution spectrum.

110
 Nuclear magnetic resonance spectroscopy

(3H) Figure 9.13 씱

The high-resolution NMR spectrum of
ethanol. Note that there is no coupling
between the proton in the −OH group
Signal strength

and the protons in the next-door −CH2

group.
(2H)

(1H)
TMS
reference

6 5 4 3 2 1 0
Chemical shift, δ/ppm
A useful technique for detecting labile protons is to measure the NMR Chemical Number of Integration
spectrum in the presence of deuterium oxide (heavy water), D2O. Deuterium shift lines ratio
nuclei can exchange rapidly with labile protons. Deuterium nuclei do not
show up in the proton NMR region of the spectrum and so the peaks of any 1.2 triplet 3
labile protons disappear. 2.4 quartet 2

Test yourself 11.7 singlet 1

Table 9.1쑿
15 Write an equation to show the reversible exchange of deuterium and hydrogen
nuclei between ethanol and deuterium oxide.
16 Account for the splitting pattern shown by the peaks in the proton NMR
spectrum of ethanol in Figure 9.13.
17 Table 9.1 shows the main features of the high-resolution NMR spectrum of a
compound containing carbon, hydrogen and oxygen. The peak with a chemical
shift of 11.7 disappears in the presence of D2O. Deduce the structure of the
compound.

NMR in medicine
In medicine, magnetic resonance imaging (MRI) uses NMR to map hydrogen
nuclei in the human body, especially in water and lipids. A computer
translates the information from a body scan into 3D images of the soft tissue
and internal organs, which are normally transparent to X-rays.
Figure 9.14 씱
Researcher preparing a test subject for
scanning in an advanced magnetic
resonance imaging machine.

Test yourself Figure 9.15 쑿

A coloured 3D MRI scan of a normal
18 Suggest a reason why doctors and radiographers refer to ‘MRI scanning’ rather human brain. The front of the brain is on
than to ‘NMR imaging’ even though the technologies used in medicine and the left. The coloured lines indicate the
many neural pathways that exist in the
chemical research are essentially the same. 111
brain.
 Spectroscopy

Definitions 9.2 Combined techniques

The instruments used for analysis are Analytical chemists use a combination of techniques to identify organic
variously called spectroscopes compounds and determine their structures.
(emphasising the uses of the ● Mass spectrometry gives the relative molecular mass of a compound and can
techniques for making observations) suggest a likely structure for a compound.
or spectrometers (emphasising the ● Infrared spectroscopy shows the presence of particular functional groups by
importance of measurements). detecting their characteristic vibration frequencies.
● Nuclear magnetic resonance techniques help to detect carbon atoms and
groups with hydrogen atoms in particular environments in molecules.

Mass spectrometry
Mass spectrometry is used to determine the relative molecular masses and
molecular structures of organic compounds. In this way it can be used to
identify unknown compounds.
The combination of gas–liquid chromatography with mass spectrometry is
of great importance in modern chemical analysis (see Section 8.4). First, gas
chromatography separates the chemicals in an unknown mixture, such as a
sample of polluted water; then mass spectrometry detects and identifies the
components.
All mass spectrometers have the components shown in Figure 9.16.

Ionisation of the Mass analyser Ion detector giving an

Gaseous sample sample by separating ions by electrical signal which is
bombardment mass-to-charge converted to a digital
from inlet system with electrons or ratio, e.g. by magnetic response that is stored in
other methods field or time of flight a computer

Figure 9.16 쑿
Schematic diagram to show the key features of a mass spectrometer.
Definition
The mass-to-charge ratio (m/z) is the There are five main types of mass spectrometer. They differ in the method
ratio of the relative mass of an ion to used to separate ions with different mass-to-charge ratios. One type uses an
its charge, where z is the number of electric field to accelerate ions into a magnetic field which then deflects the
charges (1, 2 and so on). In all the ions onto the detector. A second type accelerates the ions and then separates
examples that you will meet, z = 1. them by their flight time through a field-free region. A third type, the so-
called transmission quadrupole instrument, is now much the most common
because it is very reliable, compact and easy-to-use. It varies the fields in the
instrument in a subtle way to allow all ions with a particular mass-to-charge
ratio to pass through to the detector at the same time.
Figure 9.17 씰
The smaller instrument on the right is a
mass spectrometer being used to
analyse samples from the gas
chromatography instrument on the left.

112
 Combined techniques

Inside a mass spectrometer there is a high vacuum. This allows ionised atoms
and molecules from the chemical being tested to be studied without
interference from atoms and molecules in the air.
In a mass spectrometer, a beam of high-energy electrons bombards the Definition
molecules of the sample. This turns them into ions by knocking out one or A carbocation is an unstable
more electrons. intermediate in which a carbon atom
Bombarding molecules with high-energy electrons not only ionises them carries a positive charge. A
but usually splits them into fragments. As a result, the mass spectrum consists carbocation with the charge on a
of a ‘fragmentation pattern’. tertiary carbon atom is more stable
Molecules break up more readily at weak bonds or at bonds which give rise than one with the charge on a
to stable fragments. The highest peaks correspond to positive ions which are secondary carbon atom, which in turn
relatively more stable, such as tertiary carbocations or ions such as RCO+ (the is more stable than one with the
acylium ion) or the fragment C6H5+ from aromatic compounds. charge on a primary carbon atom.
After ionisation and fragmentation, the charged species are separated to
produce the mass spectrum, which distinguishes the fragments on the basis of
their mass-to-charge ratios. When analysing molecular compounds, the peak
of the ion with the highest mass is usually the whole molecule ionised. So the
mass of this ‘parent ion’, M+, is the relative molecular mass of the compound.
Chemists study mass spectra with these ideas in mind and as a result can Test yourself
gain insight into the structure of new molecules. They identify the fragments
from their masses and then piece together likely structures with the help of 19 An organic molecule, M, can be
evidence from other methods of analysis such as infrared spectroscopy and represented as a combination of
NMR spectroscopy. two parts: m1 and m2. Draw a
diagram to represent the ionisation
Chemists have also built up a very large database of mass spectra of known
and then fragmentation of the
compounds for use in analysis. Chemists regard the spectra in a database as a set molecule, and explain why only one
of ‘fingerprints’ for identifying chemicals. The computer of a mass spectrometer of the two fragments shows up in
is programmed to search the database to find a good match between the the mass spectrum.
spectrum of a compound being analysed and a spectrum in the database.

Analysing mass spectra

When analysing molecular compounds, the peak of the ion with the highest
mass is usually the whole molecule ionised. So the mass of this parent ion is
the relative molecular mass of the compound.

100 105

80
Relative intensity/%

77
60

40 136
51

20
Data

0
25 50 75 100 125 Test yourself
m/z
20 Suggest the identity of the peaks
Figure 9.18 쑿 labelled in the mass spectrum
Mass spectrum of methyl benzenecarboxylate (methyl benzoate). The pattern of shown in Figure 9.18.
fragments is characteristic of this compound.

113
 Spectroscopy

Note The presence of isotopes shows up in spectra of organic compounds that

Some spectra show a very small peak contain chlorine or bromine atoms. Chlorine has two isotopes, 35C and 37C.
that is 1 unit to the right of the peak Chlorine-35 is three times more abundant than chlorine-37. If a molecule
for the parent ion. This is the ‘M + 1’ contains one chlorine atom, the molecular ion shows as two peaks separated
peak which is present because some by 2 mass units. The peak with the lower value of m/z is three times higher
molecules include carbon-13 atoms. than the peak with the higher value.
Carbon-13 makes up 1.1% of natural Bromine consists largely of two isotopes, 79Br and 81Br, which are roughly
carbon, so in a molecule with two equally abundant. If a molecule contains one bromine atom, the molecular ion
carbon atoms, for example, the height shows up as two peaks separated by 2 mass units with roughly equal intensity.
of the ‘M + 1’ peak is 2.2% of the
height of the molecular ion peak.
64
100

28

Relative intensity/%
29

50 27

49 66
26

51

0
0 20 40 60 80 100
m/z

15
100
94
Relative intensity/%

50

79

28 47
0
0 20 40 60 80 100
m/z
Figure 9.19 쑿
Mass spectra of two compounds containing halogen atoms.

Test yourself
21 Account for these facts about the mass spectrum of dichloroethene:
a) it includes three peaks at m/z values of 96, 98 and 100 with intensities in the
ratio 9 : 6 : 1
Data b) it includes two peaks at m/z values 61 and 63 with intensities in the ratio
of 3 : 1.
22 One of the mass spectra in Figure 9.19 is bromomethane and the other is
chloroethane. Match the spectra to the compounds, and identify as many
fragments in the spectra as you can.

114
 Combined techniques

Test yourself
23 Figure 9.20 shows the mass spectra of two isomers, benzenecarboxylic acid
(benzoic acid) and 3-hydroxybenzenecarbaldehyde (3-hydroxybenzaldehyde).
a) Match the compounds to the spectra and give your reasons. Data
b) Identify the peaks at 77 and 105 in the top spectrum.
c) Identify the peaks at 39 and 93 in the bottom spectrum.

105
100
122

77
Relative intensity/%

50
51

28 39 57 65 94
0
20 40 60 80 100 120
m/z
122
100
Relative intensity/%

93
50
65

39

53 74
0
20 40 60 80 100 120
m/z
Figure 9.20 쑿
Two mass spectra.

Infrared spectroscopy
Most compounds absorb infrared (IR) radiation. The wavelengths of the
radiation they absorb correspond to the natural frequencies at which vibrating
bonds in the molecules bend and stretch. However, it is only molecules that
change their polarity as they vibrate which interact with IR.

radiation sample detector computer printer Definition

source
An absorption spectrum is a plot
showing how strongly a sample
Figure 9.21 씱 absorbs radiation over a range of
The essential features of a modern single-beam IR spectrometer. frequencies. Absorption spectra from
infrared spectroscopy give chemists
Spectroscopists have found that it is possible to correlate absorptions in the
valuable information about the
region 4000–1500 cm−1 with the stretching or bending vibrations of particular composition and structure of
bonds. As a result, an infrared spectrum gives valuable clues to the presence of chemicals.
functional groups in an organic molecule.
115
 Spectroscopy

The important correlations between different bonds and observed absorptions

are shown in Figure 9.22. Hydrogen bonding broadens the absorption peaks of
−OH groups in alcohols, and even more so in carboxylic acids.
Figure 9.22 씰
Chart to show the main regions of the Wavenumber ranges
–1 –1
infrared spectrum and important 4000 cm 2500 cm 1900 cm–1 1500 cm–1 650 cm–1
correlations between bonds and C H C C C C
observed absorptions.
O H C N C O
N H fingerprint
region
single bond triple bond double bond
stretching stretching stretching
vibrations vibrations vibrations

Molecules with several atoms can vibrate in many ways because the vibrations
Note
of one bond affect others close to it. The complex pattern of vibrations can be
Most organic molecules contain C−H used as a ‘fingerprint’ to be matched against the recorded IR spectrum in a
bonds. As a result, most organic database.
compounds have a peak at around
3000 cm−1 in their IR spectrum
100
Transmittance/%

50

A B

0
4000 3000 2000 1500 1000 500
Wavenumber/cm–1
100
Transmittance/%

50

C
Figure 9.23 씰 0
Two IR spectra. 4000 3000 2000 1500 1000 500
116 Wavenumber/cm–1
 Combined techniques

Test yourself
24 Figure 9.23 shows the infrared spectra of ethyl ethanoate and ethanamide. Use
the Data sheet: ‘Characteristic IR absorptions in organic molecules’ from the
Dynamic Learning Student website to work out: Data
a) which bonds give rise to the peaks marked with letters
b) which spectrum belongs to which compound.
25 Compound P is a liquid which does not mix with water. Its molecular formula is
C7H6O and it has an infrared spectrum with strong sharp peaks at 2800 cm−1,
2720 cm−1 and 1700 cm−1 with a weaker absorption peak between 3000 and
3100 cm−1. Oxidation of P gives a white crystalline solid Q with a strong broad IR
absorption band in the region 2500–3300 cm−1 and another strong absorption at
1680–1750 cm−1.
a) Suggest possible structures for P and Q.
b) What chemical tests could you use to check on your suggestions?

Activity

Analysing a perfume chemical

Jasmine blossom is a source of chemicals used in perfumes.
Analysis of an extract from the blossom by gas chromatography
shows that it can contain over 200 compounds. Two of the
compounds in the mixture are mainly responsible for the smell of the
blossom. One of these chemicals is jasmone, which has the
empirical formula C11H16O.
The structure of jasmone has been studied by mass spectrometry, IR
spectroscopy and NMR with the results shown in Figures 9.24 to 9.26.

Figure 9.24 쑿
A harvester gathering jasmine flowers for the French perfume industry.

117
 Spectroscopy

100 Figure 9.25 씱

Mass spectrum of the perfume
chemical jasmone.
80
Relative intensity/%

60

40

20

0
25 50 75 100 125 150
m/z

Figure 9.26 씱
Carbon-13 NMR spectrum of
the perfume chemical jasmone.
Signal strength

200 180 160 140 120 100 80 60 40 20 0 Figure 9.27 쑼

Chemical shift, δ/ppm IR spectrum of the perfume
chemical jasmone.

100
Transmittance/%

50

0
4000 3000 2000 1500 1000 500
118 Wavenumber/cm–1
 Combined techniques

1 Why is gas chromatography a suitable technique for separating

the compounds in natural perfume chemicals?
2 a) Use the mass spectrum of jasmone to determine its relative
molecular mass.
b) What is the molecular formula of jasmone?
c) How many double bonds and/or rings are there in the
molecule?
3 Refer to the carbon-13 NMR spectrum in Figure 9.26.
a) How many different environments for carbon atoms are there
in the molecule?
b) Use the data sheet of NMR chemical shifts on the Dynamic
Learning Student website to suggest which chemical
environments for carbon are in the molecule. Data

c) What can you conclude about the structure of the molecule

from the spectrum?
4 Refer to the IR spectrum in Figure 9.27 and the data sheet of
characteristic IR absorptions in organic molecules from the
Dynamic Learning Student website. The peak at 1650 cm−1 Data
indicates the presence of C=C. What other parts of your answers
to question 3 are confirmed by the spectrum?
5 Suggest a possible structure for jasmone that is consistent both
with the information from the spectra and with the fact that the
full name of the compound is cis-jasmone.
6 Describe what you would expect to observe if you tested a
sample of cis-jasmone with:
a) a solution of bromine in an organic solvent
b) Tollens’ reagent
c) 2,4-dinitrophenylhydrazine reagent.

119
 REVIEW QUESTIONS
Extension questions
1 Predict the number of peaks you would expect in the 3 Identify the compound containing only carbon,
carbon-13 NMR spectra of each of the four isomeric hydrogen and oxygen that gives rise to the mass, NMR
alcohols with the molecular formula C4H10O. (4) and IR spectra below. Draw the displayed formula of
the compound and name it. Give your reasoning and
2 Two isomeric ketones with the molecular formula
show how you can account for the key features in the
C5H10O have the mass spectra shown below.
three spectra. (10)
43
100

100 27
80 55 72
Relative intensity/%

60 80

Relative intensity/%
40 60

86
20 40
71 45

0 20
10 20 30 40 50 60 70 80 90
m/z
0
100
57 25 50 75
m/z

80
Relative intensity/%

29
60
Signal strength

40

86
20

0
10 20 30 40 50 60 70 80 90 200 180 160 140 120 100 80 60 40 20 0
m/z Chemical shift, δ/ppm

100
a) Draw the skeletal formula of the two ketones and
name them. (2)
Transmittance/%

b) Why do both spectra have peaks at m/z values of

86? (2)
50
c) i) Suggest possible identities for the four fragments
in the two spectra with m/z values of 29, 43, 57
and 71. (4)
ii) Hence show which spectrum belongs to which
compound. (1) 0
4000 3000 2000 1500 1000 500
d) Use the data table showing chemical shifts from the Wavenumber/cm–1
Dynamic Learning Student website to predict the
appearance of:
i) the carbon-13 NMR spectrum of
pentan-2-one (3)
ii) the proton NMR spectrum of pentan-3-one. (4) Data 1 Data 2 Data 3

120
Unit 5

Equilibria, energetics and

elements
10 How fast?
11 How far?
12 Acids, bases and buffers
13 Lattice enthalpy and
Born–Haber cycles
14 Enthalpy and entropy
15 Redox, electrode
potentials and fuel cells
16 Transition elements
 10 How fast?
Reaction kinetics is the study of the rates of chemical reactions.
Several factors influence the rate of chemical change including the
concentration of the reactants, the surface area of solids, the
temperature of the reaction mixture and the presence of a catalyst.
Chemists have found that they can learn much more about reactions
by studying these effects quantitatively. They can then set up models
to simulate the data and make predictions about the impact of
changing the conditions.
Chemists apply these models to drug design and to the
formulation of medicines to make sure that patients receive
treatments that are effective for some time without causing harmful
side-effects. The models can also account for the damage arising
from pollutants in the atmosphere and help chemists to suggest ways
of reducing or preventing the problems.

Figure 10.1 쑿
Understanding the factors which determine the rate and direction of chemical change
is essential to the design of productive, safe and profitable chemical processes.

10.1 Measuring reaction rates

Balanced chemical equations tell us nothing about how quickly the reactions
occur. In order to get this information, chemists have to do experiments to
measure the rates of reactions under various conditions.
The amounts of the reactants and products change during any chemical
reaction – products form as reactants disappear. The rates at which these
Definition changes happen give a measure of the rate of reaction.
The rate of reaction measures the Chemists define rate of reaction as the change in concentration of a
rate of formation of a product or the product, or a reactant, divided by the time taken for the change. Usually the
rate of removal of a reactant: rate is not constant but varies as the reaction proceeds. The first step in
analysing the results of an experiment is to plot a concentration–time graph.
change in measured property
122 rate = The gradient (or slope) of the graph at any point gives a measure of the rate of
time
reaction at that time.
 Measuring reaction rates

A C

rate at time t

[Reactant]/mol dm–3
[Product]/mol dm–3

PQ
= mol dm–3 s–1
P QR

rate at time t
AB
= mol dm–3 s–1
AC
B

Q R
t t
Time/s Time/s

Figure 10.2 쑿 Figure 10.3 쑿

Concentration–time graph for the formation of a product. The Concentration–time graph for the disappearance of a reactant.
rate of formation of product at time t is the gradient of the curve The rate of loss of reactant at time t is the gradient of the curve
at that time. at that time.

Definition
Test yourself
Writing the formula of a chemical in
1 Each of the following factors can change the rate of a reaction. Give an example square brackets is the usual
of a reaction to illustrate each one: shorthand for concentration in mol
a) the concentration of reactants in solution dm−3. For example, [A] represents the
b) the pressure of gaseous reactants concentration of A in mol dm−3.
c) the surface area of a solid
d) the temperature
e) the presence of a catalyst.
2 How does the collision theory account for the effects of altering each of the
factors a) to e) in question 1?
3 In a study of the hydrolysis of an ester, the concentration of the ester fell from
0.55 mol dm−3 to 0.42 mol dm−3 in 15 seconds. What was the average rate of
reaction in that period?
4 The gaseous oxide N2O5 decomposes to NO2 gas and oxygen.
a) Write a balanced equation for the reaction.
b) If the rate of disappearance of N2O5 is 3.5 × 10−4 mol dm−3 s−1, what is the
rate of formation of NO2?

Practical methods
Ideally, chemists look for methods for measuring reaction rates that do not
interfere with the reaction mixture, as shown in Figures 10.4–10.6.
Figure 10.4 씱
Following the course of a reaction over
time by collecting and measuring the
volume of a gas formed.

gas syringe

dilute hydrochloric acid

magnesium turnings 123
 How fast?

Figure 10.5 씰
Using a colorimeter to follow the
formation of a coloured product or the
removal of a coloured reactant.

light source filter reaction light sensitive meter

mixture cell

Figure 10.6 씰
Using a conductivity cell and meter to
measure the changes in electrical
conductivity of the reaction mixture as
the number or nature of the ions
changes.

conductivity
platinum meter
electrode

However, sometimes it is necessary to withdraw samples of the reaction

mixture at regular intervals and analyse the concentration of a reactant or
product by titration, as illustrated in Figure 10.7.
Figure 10.7 씰
Following the course of a reaction that
involves an acid by removing measured
samples of the mixture at intervals,
stopping the reaction by cooling in an ice
bath, and then determining the
concentration of the sample by titration.
Further samples are taken at regular
graduated
intervals. pipette

Practical standard
guidance solution of alkali

reaction mixture
containing an acid

ice cold water sample after

stopping reaction

Test yourself
5 Suggest a suitable method for measuring the rate of each of these reactions:
a) Br2(aq) + HCOOH(aq) → 2HBr(aq) + CO2(g)
b) CH3COOCH3(l) + H2O(l) → CH3COOH(aq) + CH3OH(aq)
124 c) C4H9Br(l) + H2O(l) → C4H9OH(l) + H+(aq) + Br−(aq)
 Measuring reaction rates

Activity

Investigating the effect of concentration on the rate of a reaction

Bromine oxidises methanoic acid in aqueous solution
to carbon dioxide. The reaction is catalysed by
hydrogen ions:
Br2(aq) + HCOOH(aq) → 2Br−(aq) + 2H+(aq) + CO2(g)
The reaction can be followed using a colorimeter.
Table 10.1 shows some typical results. The
concentration of methanoic acid was kept constant
throughout the experiment by having it present in
large excess.
Figure 10.8 쑿
1 Explain why it is possible to follow the rate of this A colorimeter can be used to follow the changes in
reaction using a colorimeter. concentration of coloured chemicals during a reaction.

2 Suggest a suitable chemical to use as the catalyst

for the reaction.
3 Explain the purpose of adding a large excess of methanoic acid.
4 Plot a graph of concentration against time using the results in
Table 10.1.
5 Draw tangents to the graph and measure the gradient to obtain Time/s Concentration of
values for the rate of reaction at two points during the bromine/10−3 mol dm−3
experiment. Use the values at 100 s and 500 s. (Remember when 0 10.0
calculating the gradients that the bromine concentrations are
10 9.0
1000 times smaller than the numbers in the table.)
30 8.1
6 Table 10.2 shows values for the reaction rate obtained by
drawing gradients at other times on the concentration–time 90 7.3
graph. Plot a graph of rate against concentration using the two 120 6.6
values you calculated in question 4 and the values in Table 10.2. 180 5.3
Time/s Concentration of Rate of reaction from gradients 240 4.4
bromine/10−3 mol dm−3 to the concentration time
graph/10−5 mol dm−3 s−1 360 2.8

50 8.3 2.9 480 2.0

200 5.0 1.7 600 1.3

300 3.5 1.2 Table 10.1 쑿

Results of an experiment to investigate
400 2.5 0.8 the rate of reaction of bromine with
methanoic acid. Note that the bromine
Table 10.2 쑿
concentrations are multiplied by 1000.
Rate values obtained by measuring gradients of tangents to the
The actual bromine concentration at
concentration–time graph. Note that the bromine concentrations are
90 seconds, for example, was
multiplied by 100 000. The actual rate at 300 seconds, for example,
0.0073 mol dm−3.
was 1.2 × 10−5 mol dm−3 s−1.

7 How does the bromine concentration change with time?

8 How does the rate of reaction change with time?
9 How does the rate of reaction depend on the bromine
concentration?
125
 How fast?

10.2 Rate equations

Chemists have found that they can summarise the results of investigating the
rate of a reaction in the form of a rate equation. A rate equation shows how
changes in the concentrations of reactants affect the rate of a reaction.
Take the example of a general reaction in which x moles of A react with y
moles of B to form products:
xA + yB → products

Note
The equation which describes how the rate varies with the concentrations
of the reactants takes this form:
A rate equation cannot be deduced
from a balanced equation – it has to rate = k[A]n[B]m
be found by experiment. In this
general example, the values of n and
where [A] and [B] represent the concentrations of the reactants in moles per
m in the rate equation may or may not cubic decimetre (litre).
be the same as the values of x and y The powers n and m are the reaction orders. The reaction above is order n
in the balanced equation for the with respect to A and order m with respect to B. The overall order is (n + m).
reaction. The rate constant, k, is only constant at a particular temperature. The value
of k varies with temperature (see Section 10.3). The units of the rate constant
depend on the overall order of the reaction, as shown in Table 10.3.
Overall order Units of the rate
constant Worked example
zero mol dm−3 s−1 The decomposition of ethanal to methane and carbon monoxide is second
order with respect to ethanal. When the concentration of ethanal in the gas
first s−1 phase is 0.20 mol dm−3, the rate of reaction is 0.080 mol dm−3 s−1 at a certain
second mol−1 dm3 s−1 temperature. What is the value of the rate constant at this temperature?
Notes on the method
Table 10.3 쑿
Start by writing out the rate equation based on the information given. There
is no need to write the equation for the reaction because the rate equation
cannot be deduced from the balanced chemical equation.
Definitions
Substitute values in the rate equation, including the units as well as the
In a rate equation, such as values. Then rearrange the equation to find the value of k. Check that the
rate = k[A]m[B]n, the k is the rate units are as expected for a second order reaction.
constant. The powers n and m are
the orders of the reaction with Answer
respect to the reactants A and B that The rate equation: rate = k[ethanal]2
appear in this equation. The overall
order of the reaction is (n + m). Substituting: 0.080 mol dm−3 s–1 = k × (0.20 mol dm−3)2
0.080 mol dm−3 s−1
Rearranging: k=
(0.20 mol dm−3)2

Hence, k = 2.0 mol−1 dm3 s−1

Test yourself
6 The rate of decomposition of di(benzenecarbonyl) peroxide is first order with
respect to the peroxide. Calculate the rate constant for the reaction at 107 °C if
the rate of decomposition of the peroxide at this temperature is
7.4 × 10−6 mol dm−3 s−1 when the concentration of peroxide is 0.02 mol dm−3.
7 The hydrolysis of the ester methyl ethanoate in alkali is first order with respect to
the ester and first order with respect to hydroxide ions. The rate of reaction is
0.000 69 mol dm−3 s−1, at a given temperature, when the ester concentration is
0.05 mol dm−3 and the hydroxide ion concentration is 0.10 mol dm−3. Write out
the rate equation for the reaction and calculate the rate constant.

126
 Rate equations

First order reactions

A reaction is first order with respect to a reactant if the rate of the reaction is
proportional to the concentration of that reactant. The concentration term
for this reactant is raised to the power 1 in the rate equation:
rate = k[X]1 = k[X]
This means that doubling the concentration of the chemical X leads to a
doubling of the rate of reaction. The rate of reaction is proportional to the
concentration of the reactant – this means that a plot of rate against
concentration gives a straight line passing through the origin.
Figure 10.9 씱
Variation of reaction rate with
concentration for a first order reaction.
Rate of reaction

The graph is a straight line through the

origin, showing that the rate is
proportional to the concentration of
the reactant.

Concentration of reactant

One of the easier ways to spot a first order reaction is to plot a concentration–time
graph and then work out the time taken for the concentration to fall by half. At a
constant temperature, the half-life of a first order reaction is the same wherever it
is measured on a concentration–time graph.
Concentration of a reactant

Time
equal half-lives
Figure 10.10 쑿
Variation of concentration of a reactant plotted against time for a first order reaction.
The half-life for a first order reaction is a constant, so it is the same wherever it is read
off the curve. It is independent of the initial concentration.

Test yourself
8 Refer to your answers to the activity in Section 10.1.
a) From your rate–concentration graph, what is the order of the reaction of
bromine with methanoic acid with respect to bromine?
b) i) Determine three values for half-lives for the reaction from your
Definition
concentration–time graph.
ii) Are your values consistent with your answer to that in part a)? The half-life of a reaction is the time
9 Explain how the rate constant can be found from a rate–concentration graph for the concentration of one of the
such as that in Figure 10.9. reactants to fall by half.

127
 How fast?

Second order reactions

A reaction is second order with respect to a reactant if the rate of the reaction is
proportional to the concentration of that reactant squared. This means that the
concentration term for this reactant is raised to the power 2 in the rate equation.
At its simplest, the rate equation for a second order reaction takes the form:
rate = k[reactant]2
This means that doubling the concentration of X increases the rate by a factor
of four.

Concentration of a reactant
second order

Time
unequal half-lives
Figure 10.11 쑿
Variation of concentration of a reactant plotted against time for a second order
reaction. The half-life for a second order reaction is not a constant. The time for the
concentration to fall from c to c/2 is half the time for the concentration to fall from c/2
to c/4. The half-life is inversely proportional to the starting concentration.

Note The variation of rate with concentration for a second order reaction can be
It can be shown mathematically that found, as before, by drawing tangents to the curve of the concentration–time
for a second order reaction, with a graph. However, a rate–concentration graph is not a straight line for a second
rate equation in the form rate = k[A]2, order reaction, but instead is a curve as shown in Figure 10.12.
1
a plot of [A] against time is a straight
t
line, where [A]t is the concentration of
reactant A at time t. The slope of the
line is equal to the value of the rate
Rate of reaction

constant, k.

Figure 10.12 씰
A concentration–time graph for a second
order reaction. Concentration of reactant

Test yourself
10 The rate of reaction of 1-bromopropane with hydroxide ions is first order with
respect to the halogenoalkane, and first order with respect to hydroxide ions.
a) Write the rate equation for the reaction
b) What is the overall order of reaction?
c) What are the units of the rate constant?

128
 Rate equations

Zero order reactions

At first sight, it seems odd that there can be zero order reactions. A reaction is
zero order with respect to a reactant if the rate of the reaction is unaffected by
changes in the concentration of that reactant (Figures 10.13 and 10.14).
Chemists have found a way to account for zero order reactions in terms of the
mechanisms of these reactions (Section 10.4).
In a rate equation for a zero order reaction, the concentration term for the
reactant is raised to the power zero:
Note
rate = k[reactant]0
Any term raised to the power zero
= k (a constant) equals 1. So [reactant]0 = 1.
Concentration of a reactant

Rate of reaction
Time Concentration of reactant
Figure 10.13 쑿
Variation of concentration of a reactant plotted against time for a zero order reaction. Figure 10.14 쑿
The gradient of this graph measures the rate of reaction. The gradient is a constant so Variation of reaction rate with
the rate stays the same even though the concentration of the reactant is falling. concentration for a zero order reaction.

The nitration of methylbenzene is an example where the conditions can be

such that the reaction is zero order with respect to the aromatic compound.
The methylbenzene reacts with nitronium ions formed from nitric acid (see
Sections 1.6 and 1.7). The reaction creating the NO2+ ions is relatively slow,
but as soon as the ions form they react with methylbenzene. As a result, the
rate is not affected by the methylbenzene concentration.

Test yourself
11 Ammonia gas decomposes to nitrogen and hydrogen in the presence of a hot
platinum wire. Experiments show that the reaction continues at a constant rate
until all the ammonia has disappeared.
a) Sketch a concentration–time graph for the reaction.
b) Write the balanced chemical equation and the rate equation for this reaction.

The initial rate method

The most general method for determining reaction orders is the initial rate
method. This is based on finding the rate immediately after the start of a
reaction. This is the one point when all the concentrations are known.
The investigator makes up a series of mixtures in which all the initial
concentrations are the same, except one. A suitable method is used to
measure the change of concentration with time for each mixture (see Section
10.1). The results are used to plot concentration–time graphs. The initial rate
for each mixture is then determined by drawing tangents to the curve at the
start and calculating their gradients.

129
 How fast?

Worked example
The initial rate method was used to study the reaction:
BrO3−(aq) + 5Br−(aq) + 6H+(aq) → 3Br2(aq) + 3H2O(l)

Experiment Initial concentration Initial concentration Initial concentration Initial rate of

of BrO3–/mol dm−3 of Br−/mol dm−3 of H+/mol dm−3 reaction/mol dm−3 s−1

1 0.1 0.10 0.10 1.2 × 10–3

2 0.2 0.10 0.10 2.4 × 10–3
3 0.1 0.30 0.10 3.6 × 10–3
4 0.2 0.10 0.20 9.6 × 10–3

Table 10.4쑿
The initial rate was calculated from four graphs plotted to show how the
concentration of BrO3−(aq) varied with time for different initial
concentrations of reactants, with the results shown in Table 10.4.
What is:
a) the rate equation for the reaction
b) the value of the rate constant?
Notes on the method
Remember that the rate equation cannot be worked out from the balanced
equation for the reaction.
First, look at the experiments in which the concentration of BrO3− varies
but the concentration of the other two reactants stays the same. How does
doubling the concentration of BrO3− affect the rate?
Then, in turn, look at the experiments in which the concentrations of first
Br− and then H+ vary while the concentrations of the other two reactants stay
the same. How does doubling or tripling the concentration of a reactant affect
the rate?
Substitute the values for any one experiment in the rate equation to find
the value of the rate constant, k. Take care with the units.
Tutorial
Answer
From experiments 1 and 2: doubling [BrO3−]initial increases the rate by
a factor of 2. So rate ∝ [BrO3−]1
From experiments 1 and 3: tripling [Br−]initial triples the rate. So rate ∝ [Br−]1
From experiments 2 and 4: doubling [H+]initial increases the rate by
a factor of 4 (22). So rate ∝ [H+]2
The reaction is first order with respect to BrO3– and Br– but second order with
respect to H+.
The rate equation is: rate = k [BrO3−][Br−][H+]2
Rearranging this equation, and substituting values from experiment 4:
rate
k=
[BrO3−][Br−] [H+]2

9.6 × 10−3 mol dm−3 s−1

=
0.2 mol dm × 0.1 mol dm−3 × (0.2 mol dm−3)2
−3

k = 12.0 mol−3 dm9 s−1

130
 The effect of temperature on reaction rates

Test yourself
12 Hydrogen gas reacts with nitrogen monoxide gas to form steam and nitrogen.
Doubling the concentration of hydrogen doubles the rate of reaction. Tripling the
concentration of nitrogen monoxide increases the rate by a factor of nine.
a) Write the balanced equation for the reaction.
b) Write the rate equation for the reaction.
13 This data refers to the reaction of the halogenoalkane 1-bromobutane (represented
as RBr here) with hydroxide ions. The results are shown in Table 10.5.

Experiment [RBr]/mol dm−3 [OH−]/mol dm−3 Rate of reaction/mol dm−3 s−1

1 0.020 0.020 1.36

2 0.010 0.020 0.68
3 0.010 0.005 0.17
Table 10.5쑿
a) Deduce the rate equation for the reaction.
b) Calculate the value of the rate constant.
14 This data refers to the reaction of the halogenoalkane 2-bromo-2-methylbutane
(represented as R′Br here) with hydroxide ions. The results are shown in Table 10.6.

Experiment [R'Br]/mol dm−3 [OH−]/mol dm−3 Rate of reaction/mol dm−3 s−1

1 0.020 0.020 40.40

2 0.010 0.020 20.19
3 0.010 0.005 20.20

Table 10.6쑿
a) Deduce the rate equation for the reaction.
b) Calculate the value of the rate constant.

10.3 The effect of temperature on reaction rates

Raising the temperature often has a dramatic effect on the rate of a reaction,
especially reactions which involve the breaking of strong covalent bonds. This
explains why the practical procedure for most organic reactions involves
heating the reaction mixture. With the help of collision theory, it is possible
to make predictions about the effect of temperature changes on rates. Definitions
The constant k in a rate equation is only a constant at a specified A reaction profile is a plot which
temperature. Generally, the value of the rate constant increases as the shows how the total energy of the
temperature rises – and this means that the rate of reaction increases. atoms, molecules or ions changes
Collision theory accounts for the effect of temperature on reaction rates by during the progress of a change from
assuming that chemical changes pass through a transition state. The transition reactants to products.
state is at a higher energy than the reactants, so there is an energy barrier or A transition state is the state of the
activation energy. Reactant molecules must collide with enough energy to reacting atoms, molecules or ions when
overcome this activation energy barrier. This means that the only collisions they are at the top of the activation
that lead to reaction are those with enough energy to break existing bonds energy barrier for a reaction step.
and allow the atoms to rearrange to form new bonds in the product molecules.
Figure 10.15 씱
A reaction profile showing the activation
energy for a reaction.
transition state
Energy

activation energy
reactants

products

131
Progress of reaction
 How fast?

Activation energies account for the fact that reactions go much more slowly
than would be expected if every collision in a mixture of chemicals led to
reaction. Only a very small proportion of collisions bring about chemical
change because molecules can only react if they collide with enough energy to
overcome the energy barrier. At around room temperature, for many
reactions, only a small proportion of molecules have enough energy to react.
The Maxwell–Boltzmann curve describes the distribution of the kinetic
energies of molecules. As Figure 10.16 shows, the proportion of molecules
with energies greater than the activation energy is small at around 300 K.

300 K

Number of molecules with

number of molecules with
energy greater than the
310 K

kinetic energy E
activation energy at 310 K

number of molecules with

energy greater than the
activation energy at 300 K

activation energy

Kinetic energy E

Figure 10.16 쑿
The Maxwell–Boltzmann distribution of molecular kinetic energies in a gas at two
temperatures. The modal speed increases as the temperature rises. The area under
the curve gives the total number of molecules in the reaction mixture. This does not
change as the temperature rises so the peak height falls as the curve widens.

The shaded areas in Figure 10.16 show the proportions of molecules having at
least the activation energy for a reaction at the two temperatures. This area is
bigger at the higher temperature. So at a higher temperature there are more
molecules with enough energy to react when they collide, and the reaction
goes faster.

Test yourself
15 Why is it that many reactions have activation energies ranging between about
50 kJ mol−1 and 250 kJ mol−1?
16 Table 10.7 shows the value of the rate constant for the reaction of
benzenediazonium chloride in aqueous solution with water at four temperatures.

Temperature/K Rate constant/10−5 s−1

278 0.15
298 4.1
308 20
323 140

Table 10.7쑿
a) What do the units of the rate constant tell you about the form of the rate
equation?
b) What do the values tell you about the effect of temperature on the rate of the
reaction?
c) What is the effect of a 10 degree rise in temperature on the rate of the
reaction?
17 The activation energy for the decomposition of ammonia into nitrogen and
hydrogen is 335 kJ mol−1 in the absence of a catalyst, but 162 kJ mol−1 in the
presence of a tungsten catalyst. Explain the significance of these values in terms
132 of the transition-state theory.
 Rate equations and reaction mechanisms

10.4 Rate equations and reaction mechanisms

Rate equations were one of the first pieces of evidence which set chemists
thinking about the mechanisms of reactions. They wanted to understand why
a rate equation cannot be predicted from the balanced equation for the
reaction. They were puzzled that similar reactions turned out to have different
forms of rate equations.

Multi-step reactions
The key to understanding reaction mechanisms was the realisation that most
reactions do not take place in one step, as suggested by a balanced equation,
but in a series of steps.
It is unexpected that the decomposition of ammonia gas in the presence of
a hot platinum wire is a zero order reaction. How can it be that the
concentration of the only reactant does not affect the rate? A possible
explanation is illustrated in Figure 10.17.

Diffusion away from

Diffusion to the catalyst (fast)
the catalyst (fast)

Definitions
The mechanism of a reaction
describes how the reaction takes
Bonds breaking and new bonds forming. place showing the bonds which
Rate determined by the surface area of the break, and the new bonds which
catalyst which is a constant (rate-determining)
form, step by step.
The rate-determining step in a multi-
step reaction is the slowest step – the
Figure 10.17 쑿 one with the highest activation energy.
Three steps in the decomposition of ammonia gas in the presence of a platinum
catalyst.

Ammonia diffuses to the surface of the metal rapidly and is adsorbed onto the Test yourself
surface. This happens quickly. Bonds break and atoms rearrange to make new
molecules on the surface of the metal. This is the slowest process. Once 18 Give an analogy from the everyday
formed, the nitrogen and hydrogen rapidly break away from the metal into the world to explain the idea of a rate-
gas phase. determining step. You could base
your example on people getting
So there is a rate-determining step that can only happen on the surface of
their meals in a busy self-service
the platinum. The rate of reaction is determined only by the surface area of canteen, or cars on a motorway
the platinum, which is constant. This means that the rate of reaction is with lots of traffic but affected by
constant, so long as there is enough ammonia to be adsorbed all over the lane closures.
metal surface. The rate is independent of the ammonia concentration.

Hydrolysis of halogenoalkanes
Another puzzle for chemists was the discovery that there are different rate
equations for the reactions between hydroxide ions and the two isomers with
the formula C4H9Br (see questions 13 and 14 in Section 10.2).
The hydrolysis of a primary halogenoalkane, such as 1-bromobutane, is
second order overall. The rate equation has the form:
rate = k[C4H9Br][OH−] 133
 How fast?

To account for this chemists have suggested a mechanism showing the C−Br
bond breaking at the same time as the nucleophile, OH−, forms a C−OH
bond. In this mechanism, both reactants are involved in the single, rate-
determining step.

Figure 10.18 씰 H H H H
A one-step mechanism for the hydrolysis H H
– δ– δ–
of 1-bromobutane. HO C Br HO C Br HO C + Br–

C3H7 C3H7 C3H7

1-bromobutane transition state butan-1-ol

In this example of a substitution reaction, the nucleophile is the hydroxide

ion. Chemists label this mechanism SN2 – the ‘2’ shows that there are two
Tutorial molecules or ions involved in the rate-determining step.
On the other hand, the hydrolysis of tertiary halogenoalkanes, such as
2-bromo-2-methylpropane, is first order overall. The rate equation has the
form:
rate = k[C4H9Br]
The suggested mechanism shows the C−Br bond breaking first to form an
ionic intermediate. Then the nucleophile, OH−, rapidly forms a new bond
with carbon.

Figure 10.19 씰 CH3

CH3 CH3 CH3
A two-step mechanism for the hydrolysis slow step
of 2-bromo-2-methylpropane. C Br C+ + Br–
rate-determining
CH3 CH3
carbocation
intermediate
Definitions (planar)
An SN1 reaction is a nucleophilic
substitution reaction with a CH3 CH3 CH3
CH3
mechanism that involves only one – fast
molecule or ion in the rate-determining C+ OH C OH
step
step.
CH3 CH3
An SN2 reaction is a nucleophilic
substitution reaction with a In this example of a substitution reaction, the nucleophile is also the
mechanism that involves two
hydroxide ion. In this case, chemists label the mechanism SN1 – the ‘1’ shows
molecules or ions in the rate-
determining step.
that there is just one molecule or ion involved in the rate-determining step.
The concentration of the hydroxide ions does not affect the rate of reaction
because hydroxide ions are not involved in the rate-determining step.
What these examples show is that it is generally the molecules or ions
involved (directly or indirectly) in the rate-determining step that appear in
the rate equation for the reaction.
Tutorial
Test yourself
19 Explain, in terms of bonding, why the first step in the SN1 mechanism is slow but
the second step is fast.
20 In the proposed two-step mechanism for the reaction of nitrogen dioxide gas
with carbon monoxide gas, the first step is slow and the second step is fast:
2NO2(g) → NO3(g) + NO(g) slow
NO3(g) + CO(g) → NO2(g) + CO2(g) fast
a) What is the overall equation for the reaction?
b) Suggest a rate equation which is consistent with this mechanism.
c) What, according to your suggested rate equation, is the order of reaction
134 with respect to carbon monoxide?
 Rate equations and reaction mechanisms

Activity

A model for explaining how enzymes work

The lock-and-key model
Enzymes are natural catalysts. They are much more
powerful than inorganic catalysts, and are also highly
specific. Most enzymes catalyse only one reaction or
one type of reaction. An example is catalase – this
enzyme occurs in most living tissues where it
dramatically speeds up the decomposition of
hydrogen peroxide. It has no effect on any other
reactions in cells.
A proposed model to explain how enzymes work is
based on an analogy with a lock and a key. Enzymes
are proteins. Like all proteins, they have a precise
molecular shape (see Section 5.3). The lock-and-key
model suggests that each enzyme molecule has an
active site.
Figure 10.20 쑿
This computer graphic shows a
molecule of the enzyme lysozyme.
active Lysozyme catalyses the hydrolysis
site reactions that damage the cell walls of
bacteria. In this image the protein is
shown in blue. The backbone is traced
out by a magenta ribbon. The
enzyme substrate enzyme–substrate substrate is shown in yellow, bound to
complex the active site.

Figure 10.21 씱
enzyme products enzyme–product A diagram to illustrate the lock-and-key
complex model for enzyme action.
Molecules of the main reactant (the substrate) fit into the active site.
Typically, the active site is a cleft formed by the folding of the protein
chain where substrate molecules can be held by intermolecular
forces such as hydrogen bonds.
The substrate is converted to products at the active site. These
products then separate from the enzyme leaving the active site free
to accept another molecule of the substrate:
enzyme (E) + substrate (S) → enzyme–substrate complex (ES)
→ enzyme–product complex (EP) → enzyme (E) + products (P)

135
 How fast?

Investigating urease
The enzyme urease speeds up the reaction of urea Concentration of Initial rate of reaction/
(H2N−CO−NH2) with water to form carbon dioxide and urea/mol dm−3 mol dm−3 min−1
ammonia. Two series of experiments were carried out to 0.000 0
investigate the rate equation for the reaction. The
0.005 1.7 × 10−6
experiments were designed to measure the initial rate of
the reaction under different conditions. 0.010 2.3 × 10−6

Part 1: This involved a series of runs in which the 0.020 3.2 × 10−6
concentration of the enzyme was kept constant but the 0.050 4.4 × 10−6
concentration of the substrate, urea, was varied from one
0.100 5.9 × 10−6
run to the next as shown in Table 10.8.
0.200 7.2 × 10−6
Part 2: In a second series of runs, the concentration of
0.300 7.7 × 10−6
the substrate, urea, was kept constant while the
concentration of the enzyme, urease, was varied from one 0.400 8.0 × 10−6
run to the next. This was done by adding different volumes
Table 10.8쑿
of urease solution to the reaction mixture keeping the total
volume constant by adding water. The results are given in
Table 10.9. Volume of urease Initial rate of reaction/
solution/cm3 mol dm−3 min−1
1 How can the lock-and-key model explain why enzymes
are highly specific? 0.00 0
0.005 0.6 × 10−6
2 Write an equation for the reaction of urea with water.
0.10 0.8 × 10−6
3 Plot the rate of reaction against substrate concentration
for the results from part 1 of this investigation. 0.20 1.8 × 10−6
0.30 3.2 × 10−6
4 What does your graph show about the order of reaction
with respect to the substrate urea when: 0.50 4.8 × 10−6

a) the substrate concentration is high 1.00 10.4 × 10−6

1.50 14.9 × 10−6
b) the substrate concentration is low?
2.00 19.5 × 10−6
5 Plot the rate of reaction against volume of enzyme
solution for the results from part 2 of the investigation. Table 10.9쑿
(Note that the volume of the urease solution is a
measure of the enzyme concentration.)
6 What is the order of reaction with respect to the enzyme?
7 Write the full rate equation for the reaction when:
a) the substrate concentration is low
b) the substrate concentration is high.
8 Show how the mechanism for the reaction of enzyme with
substrate can account for your answers to questions 4, 6 and 7.
E + S → ES → EP → E + P
9 Suggest reasons why an understanding of the mechanisms of
enzyme-catalysed reactions is important in the development of
new drugs.

136
REVIEW QUESTIONS
Extension questions
1 The data in Table 10.10 refers to the decomposition of c) i) Use your results from part b) to plot a graph to
hydrogen peroxide, H2O2. confirm that the reaction is second order with
respect to iodine. (3)
Time/s [H2O2]/mol dm−3
ii) Explain how to interpret the graph you have
0 20.0 × 10−3 drawn. (2)
12 × 103 16.0 × 10−3 3 Hydrogen peroxide oxidises iodide ions to iodine in the
24 × 103 13.1 × 10−3 presence of hydrogen ions. The other product is water.
36 × 103 10.6 × 10−3 The reaction is first order with respect to hydrogen
peroxide, first order with respect to iodide ions, but
48 × 103 8.6 × 10−3 zero order with respect to hydrogen ions.
60 × 103 6.9 × 10−3
a) Write a balanced equation for the reaction. (1)
72 × 103 5.6 × 10−3
b) Write the rate equation for the reaction. (2)
96 × 103 3.7 × 10−3
c) What is the overall order of the reaction? (1)
120 × 103 2.4 × 10−3
d) A proposed mechanism for the reaction involves
Table 10.10쑿 three steps:
a) Plot a concentration–time graph for the H2O2 + I− → H2O + IO−
decomposition reaction (3)
H+ + IO− → HIO
b) Read off three half-lives from the graph and show HIO + H+ + I− → I2 + H2O
that this is a first-order reaction. (3)
Which step is likely to be the rate-determining
c) Draw tangents to the curve in your graph at four step and why? (2)
different concentrations, and calculate the gradient
of the curve at each point. (4) 4 Two gases, X and Y, react according to this equation:
d) Plot a graph of rate against concentration using X(g) + 2Y(g) → XY2(g)
your results from part c), and hence find the This reaction was studied at 400 K giving the results
value for the rate constant at the temperature shown in Table 10.12.
of the experiment. (4)
Experiment Initial Initial Initial rate of
2 The results in Table 10.11 come from a study of the
number concentration concentration formation of
rate of reaction of iodine with a large excess of of X/mol dm–3 of Y/mol dm–3 XY2/mol dm–3 s–1
hex-1-ene dissolved in ethanoic acid.
1 0.10 0.10 0.0001
Time/s [I2]/mol dm−3
2 0.10 0.20 0.0004
0 20.0 × 10−3 3 0.10 0.30 0.0009
1 × 103 15.6 × 10−3 4 0.20 0.10 0.0001
2 × 103 12.8 × 10−3 5 0.30 0.10 0.0001
3 × 103 11.0 × 10−3
Table 10.12쑿
4 × 103 9.4 × 10−3
a) What is the order of the reaction with respect to:
5 × 103 8.3 × 10−3
i) X
6 × 103 7.5 × 10−3 ii) Y? (4)
7 × 103 6.8 × 10−3 b) Write a rate equation for the reaction of X with Y. (2)
8 × 103 6.2 × 10−3 c) Use the results of experiment 1 in Table 10.12
Table 10.11쑿 to calculate the value of the rate constant and
give its units. (2)
a) Plot a concentration–time graph and show that the
half-life is not a constant. (5) d) Suggest a possible mechanism for the reaction. (3)

b) From your graph, find the rate of reaction at a e) Explain why chemists are interested in determining
series of concentrations. (3) rate equations and measuring rate constants. (5)

137
 11 How far?
All chemical reactions tend towards a state of dynamic equilibrium.
Chemists have discovered a law which allows them to predict the
concentrations of chemicals expected in equilibrium mixtures. This
law is one of several approaches which chemists use to answer the
questions ‘How far?’ and ‘In which direction?’. An understanding of
equilibrium ideas helps to explain changes in the natural
environment, the biochemistry of living things and the conditions
used in the chemical industry to manufacture new products.

Figure 11.1 쑿
Red blood cells flowing through a blood
vessel magnified 2500 times. The protein
haemoglobin has just the right properties
to take up oxygen in the lungs and
release it to cells throughout the body.
The position of equilibrium of this
reversible process varies with the
concentration of oxygen.

Figure 11.2 씰
Solvent extraction is used to separate
and purify chemicals. A compound
dissolved in one liquid can be extracted
into another liquid in which it is more
soluble. After shaking the mixture in a
tap funnel, the two solutions are in 11.1 Reversibility and equilibrium
equilibrium but with more of the solute
Reversible reactions tend towards a state of balance. They reach equilibrium
in one of the solvents.
when neither the forward change nor the backward change is complete, with
both changes still going on at equal rates. They cancel each other out and
there is no overall change – this is dynamic equilibrium.
Under given conditions, the same equilibrium state can be reached either
by starting with the chemicals on one side of the equation for a reaction, or by
starting with the chemicals on the other side. Figures 11.3 and 11.4 illustrate
this for the reversible reaction between hydrogen and iodine:
H2(g) + I2(g) 2HI(g)

[H2(g)] = [I2(g)] [HI(g)]

Concentration

Concentration

Test yourself
[HI(g)]
1 Explain, with the help of an
example, the idea of dynamic
equilibrium. [H2(g)] = [I2(g)]
2 Describe what is happening to the
molecules in the gas mixtures from
time zero to the time at which each Time Time
mixture reaches equilibrium as
described by: Figure 11.3쑿 Figure 11.4쑿
a) Figure 11.3 Reaching an equilibrium state by the Reaching the same equilibrium state by the
138 b) Figure 11.4. reaction of equal amounts of hydrogen decomposition of hydrogen iodide under
gas and iodine gas. the same conditions as for Figure 11.3.
 Reversibility and equilibrium

The equilibrium law

The equilibrium law is a quantitative law for predicting the amounts of
reactants and products when a reversible reaction reaches a state of dynamic
equilibrium. In general, for a reversible reaction at equilibrium:
aA + bB cC + dD

[C]c[D]d
Kc =
[A]a[B]b
Note
This is the form for the equilibrium constant, Kc, when the concentrations of Equilibrium constants are constant for
the reactants and products are measured in moles per cubic decimetre. [A], [B] a particular temperature.
and so on are the equilibrium concentrations, sometimes written as [A]eqm and
Unlike rate equations, the form of the
[B]eqm to make this clear. expression for an equilibrium constant
The concentrations of the chemicals on the right-hand side of the equation can be deduced from the balanced
appear on the top line of the expression. The concentrations of reactants on chemical equation.
the left appear on the bottom line. Each concentration term is raised to the
power of the number in front of its formula in the balanced equation.

Worked example
Calculate the value of Kc for the reaction which forms an ester from ethanoic
acid and ethanol (see Section 3.3) from this data. Practical
guidance
CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l) + H2O(l)
When 0.50 mol of CH3COOH(l) is dissolved in 0.5 dm3 of an organic solvent
with 0.09 mol of C2H5OH(l) and allowed to come to equilibrium at 293 K, the
amount of the ester, CH3COOC2H5(l), formed at equilibrium is 0.086 mol.
Notes on the method
● Write down the equation.
● Underneath write first the initial amounts, and then write the amounts at
equilibrium.
● Use the equation to calculate the amounts not given.
● Calculate the equilibrium concentrations given the volume of the solution.
● Substitute the values and units in the expression for Kc.

Answer
Equation: CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l) + H2O(l)
Initial amounts/mol 0.50 0.09 0 0
At equilibrium:
● amount given/mol: 0.086
● amounts calculated/mol: (0.50 − 0.086) (0.09 − 0.086) 0.086
= 0.414 = 0.004
Equilibrium concentrations/mol dm−3 0.414 ÷ 0.5 0.004 ÷ 0.5 0.086 ÷ 0.5 0.086 ÷ 0.5
= 0.828 = 0.008 = 0.172 = 0.172
[CH3COOC2H5(l)][ H2O(l)]
Kc =
[CH3COOH(l)][ C2H5OH(l)]

0.172 mol dm−3 × 0.172 mol dm−3

= 0.828 mol dm−3 × 0.008 mol dm−3

= 4.47
In this example the units cancel, so Kc has no units.

139
 How far?

Test yourself
3 On mixing 1.68 moles of PCl5(g) with 0.36 moles of PCl3(g) in a 2.0 dm3
container and allowing the mixture to reach equilibrium, the amount of PCl5 in
the equilibrium mixture was 1.44 mol. Calculate Kc for the reaction
PCl5(g) PCl3(g) + Cl2(g).
4 Kc = 170 mol−1 dm3 at 298 K for the equilibrium system 2NO2(g) N2O4(g).
If a 5 dm3 flask contains 1.0 × 10−3 mol of NO2 and 7.5 × 10−4 mol of N2O4, is the
system at equilibrium? Is there any tendency for the concentration of NO2 to
change and, if so, will it increase or decrease?

Equilibrium constants and balanced equations

An equilibrium constant always applies to a particular chemical equation and
can be deduced directly from the equation.
There are two common ways of writing the reaction of sulfur dioxide with
oxygen. As a result, there are two forms for the equilibrium constant which
have different values. So long as the matching equation and equilibrium
constant are used in any calculation, the predictions based on the equilibrium
law are the same. For:

Test yourself 2SO2(g) + O2(g) 2SO3(g) Equation 1

2
[SO3(g)]
Kc =
5 Consider the equilibrium between [SO2(g)]2[O2(g)]
sulfur dioxide, oxygen and sulfur
trioxide. But for:
a) Show that the units for the
SO2(g) + ½O2(g) SO3(g) Equation 2
equilibrium constant, Kc , for
equation 1 are mol−1 dm3. [SO3(g)]
b) Kc = 1.6 × 106 mol−1 dm3 for Kc =
[SO2(g)][O2(g)]½
equation 1 at a particular
temperature, So, it is important to write the balanced equation and the equilibrium
what is the value of Kc for constant together.
equation 2? Reversing the equation also changes the form of the equilibrium constant
c) What is the value of Kc for because the concentration terms for the chemicals on the right-hand side of
equation 3?
the equation always appear on the top of the expression for Kc.
So, for:
2SO3(g) 2SO2(g) + O2(g) Equation 3
[SO2(g)]2[O2(g)]
Kc =
[SO3(g)]2

Test yourself
6 Write the Kc expressions for the following equations and state the units of the
equilibrium constant for each example:
a) CO2(g) + H2(g) CO(g) + H2O(g)
b) N2(g) + 3H2(g) 2NH3(g)
c) 2O3(g) 3O2(g)
d) 4PF5(g) P4(g) + 10F2(g)

140
 Reversibility and equilibrium

Activity

Testing the equilibrium law

The reversible reaction involving hydrogen, iodine and hydrogen
iodide has been used to test the equilibrium law experimentally. In a
series of six experiments, samples of the chemicals were sealed in
reaction tubes and then heated at 731 K until the mixtures reached
equilibrium. Four of the tubes started with different mixtures of
hydrogen and iodine. Two of the tubes started with just hydrogen
iodide.
Once the tubes had reached equilibrium, they were rapidly cooled to
stop the reactions. Then the contents of the tubes were analysed to
find the compositions of the equilibrium mixture. The results for six
of the tubes are shown in Table 11.1.

Tube Initial concentrations/mol dm−3 Equilibrium concentrations/mol dm−3

[H2(g)] [I2(g)] [HI(g)] [H2(g)] [I2(g)] [HI(g)]

1 2.40 × 10−2 1.38 × 10−2 0 1.14 × 10−2 0.12 × 10−2 2.52 × 10−2
2 2.40 × 10−2 1.68 × 10−2 0 0.92 × 10−2 0.20 × 10−2 2.96 × 10−2
3 2.44 × 10−2 1.98 × 10−2 0 0.77 × 10−2 0.31 × 10−2 3.34 × 10−2
4 2.46 × 10−2 1.76 × 10−2 0 0.92 × 10−2 0.22 × 10−2 3.08 × 10−2
5 0 0 3.04 × 10−2 0.345 × 10−2 0.345 × 10−2 2.35 × 10−2
6 0 0 7.58 × 10−2 0.86 × 10−2 0.86 × 10−2 5.86 × 10−2

Table 11.1쑿

1 Write the equation for the reversible reaction to form hydrogen

iodide from hydrogen and iodine.
2 Show that the equilibrium concentration of:
a) hydrogen in tube 1 is as expected given the value of [I2(g)]eqm
b) hydrogen iodide in tube 2 is as expected given the value
of [I2(g)]eqm.
3 Explain why [H2(g)]eqm = [I2(g)]eqm in tubes 5 and 6.
4 For each of the tubes work out the value of:
[HI(g)]eqm
a)
[H2(g)]eqm[I2(g)]eqm

[HI(g)]2eqm
b) [H2(g)]eqm[I2(g)]eqm

c) Enter your values in a table and comment on the results.

5 What is the value of Kc for the reaction of hydrogen with iodine
at 731 K?

141
 How far?

11.2 Equilibrium constants and the direction of

change
If the value of an equilibrium constant is large then the position of equilibrium
is over to the right-hand side of the equation. Broadly speaking, if Kc is about
100 or larger at a given temperature then the products predominate.
Conversely, if the value of the equilibrium constant is small then the
position of equilibrium is over to the left-hand side of the equation. If Kc is
about 0.01 or smaller at a given temperature then the reactants predominate.
If the value of Kc is close to 1, then there are significant quantities both of
reactants and of products present at equilibrium.
It is very important to keep in mind that equilibrium constants say nothing
about the time it takes for a reaction mixture to reach equilibrium. The
system may reach equilibrium rapidly or slowly – the value of Kc says nothing
about the rate of change.
For example, the value of Kc for the reaction of hydrogen with chlorine to
make hydrogen chloride is about 1031 at room temperature, but in the absence
of a catalyst or ultraviolet light there is no reaction.

Note Test yourself

Changing any or all of the
concentrations does not alter the 7 What can you conclude about the direction and extent of change in each of
value of the equilibrium constant, so these examples?
long as the temperature stays a) Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) Kc = 1 × 1037 at 298 K
constant. Changing the pressure b) 2HBr(g) H2(g) + Br2(g) Kc = 1 × 10−10 at 298 K
changes the concentration of c) N2(g) + 3H2(g) 2NH3(g) Kc = 2.2 at 623 K
molecules in a gas. This does not 8 In general, if the equilibrium constant for a forward reaction is large what will be
affect the value of the equilibrium the size of the equilibrium constant for the reverse of the reaction?
constant either.
The effect of changing concentrations on systems at equilibrium
The equilibrium law makes it possible to explain the effect of changing the
concentration of one or more of the chemicals in an equilibrium mixture.
An example is the equilibrium involving chromate(VI) and dichromate(VI)
ions in water:
2CrO42−(aq) + 2H+(aq) Cr2O72−(aq) + H2O(l)
yellow orange
At equilibrium:
[Cr2O72–(aq)]
Kc =
[CrO42–(aq)]2[H+(aq)]2
where these are equilibrium concentrations.
In dilute solution, [H2O(l)] is constant so it does not appear in the
equilibrium law expression.
Figure 11.5쑿 Adding a few drops of concentrated acid increases the concentration of
On the left, a yellow solution of H+(aq) on the left-hand side of the equation.
chromate(VI) ions in water. On the right, a This briefly upsets the equilibrium. For an instant after adding acid:
solution of chromate(VI) ions in water after
[Cr2O72–(aq)]
adding a few drops of strong acid – the < Kc
solution has turned orange as more
[CrO42–(aq)]2[H+(aq)]2
dichromate(VI) ions form.
The system restores equilibrium as chromate(VI) ions react with hydrogen ions
to produce more of the products. There is very soon a new equilibrium – and
once again:
[Cr2O72–(aq)]
= Kc
[CrO42–(aq)]2[H+(aq)]2
142
but now with new values for the various concentrations.
 Equilibrium constants and the direction of change

Chemists sometimes say that adding the acid makes the ‘position of
equilibrium shift to the right’. The effect is visible here because the yellow
colour of the chromate(VI) ions turns to the orange colour of dichromate(VI)
ions. This is as le Chatelier’s principle predicts. The advantage of using Kc is
that it makes quantitative predictions possible.

Test yourself
9 Show that it is reasonable to assume that the concentration of water is
constant in dilute aqueous solutions by calculating the concentration of water in
a 0.1 mol dm−3 solution of a solute.
10 Describe and explain the effect of adding alkali to a solution of dichromate(VI)
ions.
11 a) Use the equilibrium law to predict and explain the effect of adding pure
ethanol to an equilibrium mixture of ethanoic acid, ethanol, ethyl ethanoate
and water:
CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l) + H2O(l)
b) Show that your prediction is consistent with le Chatelier’s principle.
12 Use the equilibrium law to predict the effect of the following changes on an
equilibrium mixture of hydrogen, carbon monoxide and methanol:
2H2(g) + CO(g) CH3OH(g)
a) adding more hydrogen to the gas mixture at constant total pressure
b) compressing the mixture to increase the total pressure.

The effect of temperature changes on systems at equilibrium Note

Le Chatelier’s principle predicts that raising the temperature makes the If ΔH for a forward reaction is
equilibrium shift in the direction which is endothermic. For example, for the negative, then ΔH for the reverse
reaction that produces sulfur trioxide during the manufacture of sulfuric acid, reaction will have the same magnitude
raising the temperature lowers the percentage of sulfur trioxide at equilibrium. but the opposite sign. So, if a forward
reaction is exothermic, then the
2SO2(g) + O2(g) 2SO3(g) ΔH = −98 kJ mol−1 reverse reaction is endothermic.
The equilibrium shifts to the left as the temperature increases because this is
the direction in which the reaction is endothermic.

100
Percentage conversion to SO3

80

60

40

20

0
600 700 800 900
Temperature/K

Figure 11.6쑿
The effect of raising the temperature on the equilibrium between SO2, O2 and SO3.

143
 How far?

Note The reason that temperature changes cause a shift in the position of
The value of an equilibrium constant equilibrium is that the value of the equilibrium constant changes. This is
for an exothermic reaction decreases illustrated by the values in Table 11.2.
as the temperature increases.
Temperature/K Kc/mol−1 dm3
The value of the equilibrium constant
for an endothermic reaction increases 293 9.9 × 1025
as the temperature increases.
500 1.0 × 1012
700 1.7 × 106

Table 11.2쑿
Values of Kc at three temperatures for the equilibrium 2SO2(g) + O2(g) 2SO3(g).

Test yourself
13 Show that the values in Table 11.2 are consistent with predictions for the
equilibrium based on le Chatelier’s principle.
14 The values of Kc for the equilibrium N2O4(g) 2NO2(g) are 1.44 mol dm−3 at
400 K and 41 mol dm−3 at 500 K.
a) What is the effect of increasing the temperature on the position of
equilibrium?
b) How can your answer to part a) account for the appearance of the gas
mixtures in Figure 11.7?
c) What is the sign of ΔH for the reaction?
15 For the reaction between hydrogen and iodine to form hydrogen iodide, the
value of Kc is 794 at 298 K but 54 at 700 K. What can you deduce from this
information?

The effect of catalysts on systems at equilibrium

Figure 11.7쑿
Catalysts speed up reactions but are not used up as they do their job. It is
Tubes containing mixtures of N2O4(g) and important to note that while a catalyst speeds up the rate at which a reaction
2NO2(g). The tube in the middle is at gets to an equilibrium state, it has no effect on the final position of
room temperature; the tube on the left in equilibrium. In other words, a catalyst provides a faster route to the same
hot water; and the tube on the right in equilibrium state. The alternative route with a catalyst has a lower activation
iced water. energy, but speeds up the forward and back reactions to the same extent so
that the dynamic equilibrium is unchanged.

Tutorial

Figure 11.8씰
Crystals of palladium seen under an
electron microscope. Palladium is a rare
144 and precious metal which is used to
catalyse hydrogenation reactions.
 Equilibrium constants and the direction of change

Activity

City smog and equilibrium

Smog is a problem on still, sunny days in cities with many
motor vehicles. Smog starts with the release of nitric oxide
(NO) from motor vehicles. The NO reacts with oxygen and
ozone in the air to form nitrogen dioxide (NO2). In sunlight,
NO2 decomposes to form NO and free oxygen atoms, O.
The oxygen atoms combine with oxygen molecules to
form ozone, O3. Ozone alone is a serious pollutant, but it
can lead to further harm when it mixes with unburnt
hydrocarbons. The ozone reacts with hydrocarbons to
form a complex mixture of irritant chemicals which, in the
absence of any wind, builds up to create photochemical
smog.
Nitrogen in the air is usually inert but inside the cylinders of
a petrol engine the temperature is over 2000 K. Under
these conditions, nitrogen reacts with oxygen to form
some NO. Data about the reversible decomposition of NO
is given in Table 11.3. Figure 11.9쑿
Photochemical smog over Hong Kong, China.
Temperature/K ΔH /kJ mol−1 Kc

298 −43.16 2.2 × 1030

900 −43.22 2.5 × 109
2300 −43.20 605

Table 11.3 쑿
Data for the reversible reaction 2NO N2(g) + O2(g) .

1 Why is city smog described as ‘photochemical smog’?

2 Show that the trend in values for Kc in Table 11.3 is as expected
from the values of the enthalpy change for the reaction.
3 Why does the size of the enthalpy change vary so little with
temperature?
4 Calculate the equilibrium concentration of NO present in a 1 dm3
steel cylinder containing 0.04 mol of N2 and 0.01 mol of O2 at
equilibrium:
a) at 2300 K
b) at 298 K.
5 Explain why the NO formed in a car engine actually does cause
pollution when it leaves the hot cylinder and enters the cold air,
despite your answer to question 4 b).
6 How are oxides of nitrogen removed from the exhausts of petrol
engines?

145
 REVIEW QUESTIONS Extension questions

1 a) A flask contains an equilibrium mixture of hydrogen 3 At 473 K, the value of Kc for the decomposition of PCl5
gas (0.01 mol dm−3), iodine gas (0.01 mol dm−3) and is 8 × 10−3 mol dm−3.
hydrogen iodide gas (0.07 mol dm−3) at a constant
PCl5(g) PCl3(g) + Cl2(g) ΔH = +124 kJ mol−1
temperature. Calculate Kc for the reaction of
hydrogen with iodine to form hydrogen iodide at a) Write the expression for Kc for the reaction. (1)
this temperature. (3)
b) What is the value of Kc for the reverse reaction
b) Enough hydrogen is added to the mixture in part a) at 473 K, and what are its units? (2)
to suddenly double the hydrogen concentration in
c) A sample of pure PCl5 is heated to 473 K in a
the flask to 0.02 mol dm−3. After a while, the
vessel containing no other chemicals. At
mixture settles down with a new iodine
equilibrium the concentration of PCl5 is
concentration of 0.007 mol dm−3 at the same
5 × 10−2 mol dm−3. What are the equilibrium
temperature as before.
concentrations of PCl3 and Cl2? (3)
i) What are the new concentrations of
d) Explain how the concentrations of PCl5, PCl3 and
hydrogen and hydrogen iodide? (2)
Cl2 change in the equilibrium mixture if:
ii) Show that the new mixture is at equilibrium.(2)
i) more PCl5 is added (2)
c) Why does a sudden doubling of the hydrogen
ii) the pressure is increased (2)
concentration affect the position of equilibrium? (2)
iii) the temperature is increased. (2)
2 At 298 K the value of Kc for the following equilibrium
is 1010: e) What is the effect on the value of Kc if:
Sn2+(aq) + 2Fe3+(aq) Sn4+(aq) + 2Fe2+(aq) i) more PCl5 is added (1)
a) i) Write the expression for Kc. (2) ii) the pressure is increased (1)
ii) What are the units of Kc for this reaction? iii) the temperature is increased? (2)
Explain your answer. (2)
4 Explain what is wrong with each of the following
b) What is the value of Kc for: statements. To what extent, if any, are these
statements true?
i) Sn4+(aq) + 2Fe2+(aq) Sn2+(aq) + 2Fe3+(aq)
a) Once a reaction mixture reaches equilibrium
ii) ½Sn2+(aq) + Fe3+(aq) ½Sn4+(aq) + Fe2+(aq)?
there is no further reaction. (3)
(4)
b) Adding more of one of the reactants to an
equilibrium mixture increases the yield of
products because the value of Kc increases. (3)
c) Adding a catalyst to make a reaction go faster can
increase the amount of product at equilibrium. (3)
d) Raising the temperature to make a reaction
go faster can increase the amount of product
at equilibrium. (3)

146
12 Acids, bases and buffers
Acids and bases are very common not only in laboratories but also in
living things, in the home and in the natural environment. Acid–base
reactions are reversible and are governed by the equilibrium law. This
means that chemists can predict reliably and quantitatively how acids
and bases behave. This is important for the supply of safe drinking
water, the care of patients in hospitals, the formulation of shampoos
and cosmetics – as well as the processing of food and many other
aspects of life.

Chemists have several theories to explain the behaviour of acids, but the Definition
preferred theory for discussing acid–base equilibria is the Brønsted–Lowry A proton is the nucleus of a hydrogen
theory. This theory describes acids as proton donors and bases as proton atom – so a hydrogen ion, H+, is just a
acceptors. proton.

Figure 12.1쑿
A composite, false-colour image
produced by combining ultraviolet and
infrared images from instruments on the
European Space Agency’s Venus
Express spacecraft in July 2007. There
is a very thick cloud layer at around
Figure 12.2쑿 60 kilometres altitude around the planet.
Polyrhachis laboriosa ants attacking an intruder from a different colony. They are This lies between the lower and middle
about to kill the intruder by spraying a jet of methanoic acid from their abdomens. This layers of Venus’s atmosphere. Scientists
species of ant lives in trees at the edges of tropical forests in Cameroon. now know that the upper part of this
layer is composed mostly of tiny droplets
of sulfuric acid.
12.1 Acids and bases
Acids
According to the Brønsted–Lowry theory, hydrogen chloride molecules give
hydrogen ions (protons) to water molecules when they dissolve in water,
producing hydrated hydrogen ions called oxonium ions. The water acts as a base.

H+
Note
HCI(g) + H2O(l) H3O+(aq) + Cl–(aq)
It is more correct to represent
hydrogen ions in aqueous solution as
Figure 12.3쑿 H3O+(aq) – however, chemists
Proton transfer between hydrogen chloride molecules and water molecules. This is commonly use a shorter symbol for
reversible – a proton from the oxonium ion can transfer back to the chloride ion to hydrated protons, H+(aq).
give hydrogen chloride and water. 147
 Acids, bases and buffers

Definitions Hydrogen chloride is a strong acid. What this means is that it readily gives up
A strong acid is an acid which is fully its protons to water molecules and the equilibrium in solution lies well over to
ionised when it dissolves in water. the right. Hydrogen chloride is effectively completely ionised in solution.
Monobasic acids are acids that can
Other examples of strong acids are sulfuric acid and nitric acid.
give away (donate) one proton per The typical reactions of dilute acids in water are the reactions of aqueous
molecule. Examples are hydrochloric hydrogen ions:
acid, HCl; nitric acid, HNO3; and ● with metals: Mg(s) + 2H+(aq) → Mg2+(aq) + H2(g)
ethanoic acid, CH3COOH. These are
● with carbonates: CO32−(s) + 2H+(aq) → CO2(g) + H2O(l)
also called monoprotic acids.
● with bases: O2−(s) + 2H+(aq) → H2O(l)
Dibasic acids are acids that can give
away (donate) two protons per
molecule. Examples are sulfuric acid,
Test yourself
H2SO4; and ethanedioic acid,
1 a) What type of bond links the water molecule to a proton in an oxonium ion?
HOOC−COOH. These are also called
b) Draw a dot-and-cross diagram to show the bonding in an oxonium ion.
diprotic acids.
c) Predict the shape of an oxonium ion.
2 Write a balanced ionic equation for the reaction of 1 mol of ethanedioic acid with
2 mol of sodium hydroxide showing the displayed formulae (see Section 10.3 in
OCR Chemistry for AS) for the acid and for the ethanedioate ion formed.
3 a) Identify the products of the reaction when concentrated sulfuric acid reacts
with sodium chloride.
b) Show that this is a proton transfer reaction
c) Account for the fact that this reaction can give a good yield of hydrogen
chloride gas.
4 Write ionic equations to show the reactions of nitric acid with:
a) zinc b) potassium carbonate
c) calcium oxide d) lithium hydroxide.

Bases
A base is a molecule or ion which can accept a hydrogen ion (proton) from an
acid. A base has a lone pair of electrons, which can form a dative covalent
bond with a proton.
Figure 12.4 씰 2–

Oxide ions have lone pairs of electrons O H+ O H–

which can form dative covalent bonds
with hydrogen ions. An ionic oxide, such as calcium oxide, reacts completely with water to form
calcium hydroxide. The calcium ions do not change. But the oxide ions, which
are powerful proton acceptors, all take protons from water molecules. The
oxide ion is a strong base. Common bases include the oxide and hydroxide
ions, ammonia, amines, as well as the carbonate and hydrogencarbonate ions.
Figure 12.5 씰 H+
There is a lone pair on the nitrogen atom
of ammonia which allows it to act as a NH3(g) + HNO3(g) NH4+NO3–(s)
base. base acid

In biochemistry, the term ‘base’ often refers to one of the five nitrogenous
bases which make up nucleotides and the nucleic acids DNA and RNA.
These compounds (adenine, guanine, cytosine, uracil and thymine) are bases
in the chemical sense because they have lone pairs on nitrogen atoms which
can accept hydrogen ions.
Figure 12.6 씰 NH2
The displayed formula of adenine. This is
one of the bases in DNA. C N
N C
C H
C C
H N N
148
H
 The pH scale

Note
Test yourself
Many compounds of the Group 1 and
5 Show that the reactions between the following pairs of compounds are acid– Group 2 metals form alkaline
base reactions, and identify as precisely as possible the molecules or ions which solutions. This is because metals such
are the acid and the base in each example. as sodium, potassium, magnesium
a) MgO + HCl and calcium (unlike other metals) form
b) H2SO4 + NH3 oxides, hydroxides and carbonates
c) NH4NO3 + NaOH that are soluble (to a greater or lesser
d) HCl + Na2CO3 extent) in water. It is important to
6 a) What type of bond links the ammonia molecule to a proton in an ammonium realise that it is the oxide, hydroxide or
ion? carbonate ions in these compounds
b) Draw a dot-and-cross diagram to show the bonding in an ammonium ion. which are bases, and not the metal
c) Predict the shape of an ammonium ion. ions.
7 How many lone pairs of electrons are there in a molecule of adenine (Figure 12.6)?

Conjugate acid–base pairs

Any acid–base reaction involves competition for protons. This is illustrated by
a solution of an ammonium salt, such as ammonium chloride, in water:
NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)
acid 1 base 2 base 1 acid 2
Definitions
In this example there is competition for protons between ammonia molecules
and water molecules. On the left-hand side of the equation, the protons are An acid turns into its conjugate base
held by lone pairs on the ammonia molecules. On the right-hand side, they are when it loses a proton. A base turns
held by lone pairs on water molecules. The position of equilibrium shows into its conjugate acid when it gains
which of the two bases has the stronger hold on the protons. a proton.
Chemists use the term ‘conjugate acid–base pair’ to describe a pair of Any pair of compounds made up of
molecules or ions which can be converted from one to the other by the gain an acid and a base that can be
or loss of a proton. The equilibrium in a solution of an ammonium salt above converted from one to the other by
proton transfer is a conjugate acid–
involves two conjugate acid–base pairs:
base pair.
● NH4+ and NH3
● H3O+ and H2O.

Test yourself
8 Identify and name the conjugate bases of these acids: HNO3, CH3COOH,
H2SO4, HCO3−
9 Identify and name the conjugate acids of these bases: O2−, OH–, NH3, CO32−,
HCO3−, SO42−.
10 Explain and illustrate these two statements:
a) the stronger the acid, the weaker its conjugate base
b) the stronger the base, the weaker its conjugate acid.

12.2 The pH scale

The concentration of hydrogen ions in aqueous solutions commonly ranges
from 2 mol dm−3 to 1 × 10−14 mol dm−3. The concentration of aqueous hydrogen
ions in dilute hydrochloric acid is about 100 000 000 000 000 times greater than
the concentration of hydrogen ions in dilute sodium hydroxide solution.
Given such a wide range of concentrations, chemists find it convenient to
use a logarithmic scale to measure the concentration of aqueous hydrogen ions
in acidic or alkaline solutions – this is the pH scale. The definition of pH is:
pH = −log [H+(aq)]
Figure 12.7쑿
A scientist measuring the pH of glacier
melt water during research into air and
149
water pollution.
 Acids, bases and buffers

pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
[H+(aq)]/mol dm–3 100 10–1 10–2 10–3 10–4 10–5 10–6 10–7 10–8 10–9 10–10 10–11 10–12 10–13 10–14

increasingly acidic neutral increasingly alkaline

Figure 12.8쑿 Worked examples

The pH scale showing the colours of full-
range indicator at the different pH values. 1 What is the pH of 0.020 mol dm−3 hydrochloric acid?
Notes on the method
Note
Hydrochloric acid is a strong acid so it is fully ionised.
Note that 1 mol HCl gives 1 mol H+(aq).
Strictly speaking, the definition of pH Use the log button on your calculator.
is given by:
[H+(aq)] Do not forget the minus sign in the definition of pH.
pH = −log10
1 mol dm−3 Answer
because mathematically it is only [H+(aq)] = [HCl(aq)] = 0.020 mol dm–3
possible to take logarithms of numbers
and not of quantities with units. pH = –log (0.020) = 1.70
Dividing by a standard concentration 2 The pH of human blood is 7.40.What is the aqueous hydrogen ion
of 1 mol dm−3 does not change the
concentration in blood?
value, but does cancel the units.
Notes on the method
pH = −log [H+(aq)]
From the definition of logarithms, this rearranges to [H+(aq)] = 10−pH
Tutorial
Use the inverse log button (10x) on your calculator – not forgetting the
minus sign in the definition of pH.
Definition Answer
Chemists use logarithms to base 10 pH = 7.4
to handle values that range over
several orders of magnitude. [H+(aq)] = 10−7.4
Logarithms to base 10 are defined = 4.0 × 10−8 mol dm−3
such that:
• log 103 = 3
• log 102 = 2 Test yourself
• log 101 = 1
11 What is the pH of solutions of hydrochloric acid with these concentrations?
• log 100 = 0
a) 0.1 mol dm−3
• log 10−1 = −1 b) 0.01 mol dm−3
• log 10−2 = −2 c) 0.001 mol dm−3
In general, log 10 x = x. For example, 12 Calculate the pH of a 0.08 mol dm−3 solution of nitric acid.
2 = 100.301, so log10 2 = 0.301. 13 What is the concentration of hydrogen ions in these solutions?
a) orange juice with a pH of 3.3
By definition:
b) coffee with a pH of 5.4
log xy = log x + log y c) saliva with a pH of 6.7
and d) a suspension of an antacid in water with a pH of 10.5
log xn = n log x.
So it follows that The ionic product of water
1
log
x
= log x−1 = −log x. There are hydrogen ions and hydroxide ions even in pure water because of the
transfer of hydrogen ions between water molecules. This only happens to a
very slight extent:
H2O(l) + H2O(l) H3O+(aq) + OH−(aq)
This can be written more simply as:
H2O(l) H+(aq) + OH−(aq)
[H+(aq)][OH−(aq)]
The equilibrium constant Kc =
150 [H2O(l)]
 The pH scale

There is a very large excess of water, so [H2O(l)] = a constant, so the

relationship simplifies to:
Kw = [H+(aq)][OH−(aq)]
where Kw is the ionic product of water.
The pH of pure water at 298 K is 7.0. So, the hydrogen ion concentration
at equilibrium is given by [H+(aq)] = 1 × 10−7 mol dm−3.
Also, in pure water [H+(aq)] = [OH−(aq)]. So, the concentration of
hydroxide ions is given by [OH–(aq)] = 1 × 10−7 mol dm−3.
Hence, the ionic product of water is given by Kw = 1 × 10−14 mol2 dm−6.
Kw is a constant in all aqueous solutions at 298 K. This makes it possible to
calculate the pH of alkalis.

Worked example
What is the pH of a 0.05 mol dm−3 solution of sodium hydroxide?
Notes on the method
Sodium hydroxide is fully ionised in solution.
So in this solution [OH−(aq)] = 0.05 mol dm−3 and pH = −log [H+(aq)].
Answer
For this solution:
Kw = [H+(aq)] × 0.05 mol dm−3
= 1 × 10−14 mol2 dm−6
1 × 10−14 mol2 dm−6
So [H+(aq)] =
0.05 mol dm−3
= 2 × 10–13 mol dm−3
Hence, pH = −log (2 × 10−13) = 12.7

Test yourself
14 The value of Kw varies with temperature. At 273 K its value is
1.1 × 10−15 mol2 dm−6, while at 303 K it is 1.5 × 10−14 mol2 dm−6.
a) Is the ionisation of water an exothermic process or an endothermic process?
b) What happens to the hydrogen ion concentration in pure water as the
temperature increases? What happens to the pH?
c) Does pure water stop being neutral if its temperature is above or below 298 K?
15 Calculate the pH of these solutions:
a) 1.0 mol dm−3 NaOH b) 0.02 mol dm−3 KOH
−3
c) 0.001 mol dm Ba(OH)2.

Figure 12.9 씱
Tufa towers at Lake Mono, California.
They were first exposed when the water
level in the lake dropped because water
was diverted, to Los Angeles, from rivers
feeding the lake. These pillars of calcium
carbonate were created underwater
when water from underground streams
rich in calcium salts mixed with the lake
water, which was alkaline because it was
rich in hydrogencarbonates.

151
 Acids, bases and buffers

Working in logarithms
The logarithmic form of equilibrium constants is particularly useful for pH
calculations. Taking logarithms produces a conveniently small scale of values.
Kw = [H+(aq)][OH−(aq)] = 1 × 10−14 at 298 K
Taking logarithms, and applying the rule that log xy = log x + log y, gives:
log Kw = log [H+(aq)] + log [OH−(aq)] = log 10−14 = −14
Multiplying through by −1 reverses the signs:
−log Kw = − log [H+(aq)] − log [OH−(aq)] = 14

Note Hence, pKw = pH + pOH = 14, where, by analogy with pH:

Don’t try to remember the formula ● pKw is defined as −log Kw
pH = 14 − pOH. Only use it if you can ● pOH is defined as −log [OH−(aq)].
work it out quickly for yourself from
the definition of Kw.
So, you can see that pH = 14 − pOH, which makes it easy to calculate the pH
of alkaline solutions.

Worked example
What is the pH of a 0.05 mol dm−3 solution of sodium hydroxide?
Notes on the method
Sodium hydroxide, NaOH, is a strong base so it is fully ionised.
Find the values of logarithms with the log button of your calculator.
Answer
[OH−(aq)] = 0.05 mol dm−3
pOH = −log 0.05 = 1.3
pH = 14 − pOH = 14 − 1.3 = 12.7

12.3 Weak acids and bases

Most organic acids and bases ionise to only a slight extent in aqueous
solution. Carboxylic acids (see Section 3.2) such as ethanoic acid in vinegar,
citric acid in fruit juices and lactic acid in sour milk are all weak acids.
Ammonia and amines (see Section 4.2) are weak bases.

Weak acids
Weak acids, such as ethanoic acid, are only slightly ionised when they dissolve
in water. In a 0.1 mol dm−3 solution of ethanoic acid, for example, only about
1 in a 100 molecules ionise to produce hydrogen ions:
CH3COOH(aq) CH3COO−(aq) + H+(aq)
This means that the pH of a 0.1 mol dm−3 of ethanoic acid is 2.9, and not 1 as
it would be if it were a strong acid.
There is a very important distinction between acid strength and concentration
Figure 12.10쑿
Bacteria added to milk ferment the
– strength is the extent of ionisation; concentration is the amount, in moles, of
lactose sugar and turn it into lactic acid. acid in a cubic decimetre. It takes just as much sodium hydroxide to neutralise
The acid turns the milk into yogurt and 25 cm3 of a 0.1 mol dm−3 solution of a weak acid as it does to neutralise 25 cm3 of
also restricts the growth of food 0.1 mol dm−3 of a solution of a strong acid such as hydrochloric acid.
poisoning bacteria.
Test yourself
16 Explain why measuring the pH of a solution of an acid does not provide enough
evidence to show whether the acid is strong or weak.
17 Explain why it takes the same amount of sodium hydroxide to neutralise 25 cm3
152 of 0.1 mol dm−3 ethanoic acid as it does to neutralise 25 cm3 of 0.1 mol dm−3
hydrochloric acid.
 Weak acids and bases

Weak bases
Weak bases are only slightly ionised when they dissolve in water. In a
0.1 mol dm−3 solution of ammonia, for example, 99 in every 100 molecules do
not react and remain as dissolved molecules. Only 1 molecule in a 100 reacts
to form ammonium ions:
NH3(aq) + H2O(l) NH4+(aq) + OH−(aq)
As with weak acids, it is important to distinguish between strength and
concentration.

Acid dissociation constants

Chemists use the equilibrium constant, Ka, for the reversible ionisation of a
weak acid as a measure of its strength. Such an equilibrium constant shows
the extent to which an acid dissociates into ions in solution. Data
A weak acid can be represented by the general formula HA, where A− is
the ion produced when the acid ionises:
HA(aq) H+(aq) + A−(aq)
Test yourself
According to the equilibrium law, the equilibrium constant takes this form:
[H+(aq)][A−(aq)] 18 If a weak acid is shown as HA, what
Ka = is A− in the particular case of:
[HA(aq)]
a) hydrogen fluoride
In this context, the equilibrium constant, Ka, is called the acid dissociation b) methanoic acid
constant. Given a value of Ka it is possible to calculate the pH of a solution of c) phenol?
a weak acid.

Worked example
Calculate the hydrogen ion concentration and the pH of a 0.01 mol dm−3
solution of propanoic acid. Ka for the acid is 1.3 × 10−5 mol dm−3.
Notes on the method Tutorial
Two approximations simplify the calculation.
1 The first assumption is that [H+(aq)] = [A−(aq)] at equilibrium. In this
example A− is the propanoate ion CH3CH2COO−. This assumption seems
obvious from the equation for the ionisation of a weak acid, but it ignores
the hydrogen ions from the ionisation of water. Water produces far fewer
hydrogen ions than most weak acids so its ionisation can usually be ignored.
This assumption is acceptable so long as the pH of the acid is below 6.
2 The second assumption is that so little of the propanoic acid ionises in water
that [HA(aq)] ≈ 0.01 mol dm−3 at equilibrium – HA represents propanoic
acid here. This is a riskier assumption that has to be checked because in very
dilute solutions the degree of ionisation may become quite large relative to
the amount of acid in the solution. Chemists generally accept that this
assumption is acceptable so long as less than 5% of the acid ionises.
Answer
CH3CH2COOH(aq) H+(aq) + CH3CH2COO−(aq)
[H+(aq)][CH3CH2COO−(aq)]
Ka =
[CH3CH2COOH(aq)]
[H+(aq)]2
=
0.01 mol dm−3
= 1.3 × 10−5 mol dm−3

153
 Acids, bases and buffers

Therefore, [H+(aq)]2 = 1.3 × 10–7 mol2 dm−6

So, [H+(aq)] = 3.6 × 10−4 mol dm−3
So, pH = −log [H+(aq)]
= −log (3.6 × 10−4)
= 3.4
Check the second assumption – in this case, less than 0.0004 mol dm−3 of
the 0.0100 mol dm−3 of acid (4%) has ionised. In this instance, the degree
of ionisation is small enough to justify the assumption that
[HA(aq)] ≈ the concentration of un-ionised acid.

One method which can, in principle, be used to measure Ka for a weak acid is
to measure the pH of a solution when the concentration of the acid is known
Practical accurately. This is not a good method for determining the size of Ka because
guidance the pH values of dilute solutions are very susceptible to contamination – for
example by dissolved carbon dioxide from the air.

Worked example
Calculate the Ka of lactic acid given that the pH of a 0.10 mol dm−3 solution
of the acid is 2.43.
Notes on the method
The same two approximations simplify the calculation:
1 Assume that [H+(aq)] = [A−(aq)], where A−(aq) represents the aqueous
lactate ion. Since the pH is well below 6 this is certainly justified.
2 Also assume that so little of the lactic acid ionises in water that at
equilibrium [HA(aq)] ≈ 0.1 mol dm−3. Here HA represents lactic acid. This
is a riskier assumption which can be checked during the calculation.
Answer
pH = 2.43
[H+(aq)] = 10−2.43 = 3.72 × 10−3 mol dm−3
[H+(aq)] = [A−(aq)] = 3.72 × 10−3 mol dm−3
In this example, less than 5% of the acid is ionised (less than 0.004 out of
0.100 mol in each cubic decimetre.)
So [HA(aq)] ≈ 0.1 mol dm−3
Substituting in the expression for Ka:
[H+(aq)][A−(aq)]
Ka =
[HA(aq)]

= (3.72 × 10 mol−3
−3
dm−3)2
0.1 mol dm
= 1.38 × 10−4 mol dm−3

154
 Weak acids and bases

Test yourself
19 Calculate the pH of a 0.01 mol dm−3 solution of hydrogen cyanide given that
Ka = 4.9 × 10−10 mol dm−3.
20 Calculate the pH of a 0.05 mol dm−3 solution of ethanoic acid given that
Ka = 1.7 × 10−5 mol dm−3.
21 Calculate Ka for methanoic acid given that the pH of a 0.050 mol dm−3 solution of
the acid is 2.55.
22 Calculate Ka for butanoic acid, C3H7COOH, given that the pH of a 0.01 mol dm−3
solution of the acid is 3.42.

Working in logarithms
Chemists find it convenient to define a quantity pKa = −log Ka when working
with weak acids. This definition means that hydrocyanic acid, HCN, with a
pKa value of 9.3 is a much weaker acid than nitrous acid, HNO2, with a pKa
value of 3.3. Books of data tabulate pKa values.
The relationship between acid strength and pH can be expressed more
simply because both are logarithmic quantities.
[H+(aq)][A−(aq)]
Ka =
[HA(aq)]
The two common assumptions when using this expression in calculations are
that:
● [H+(aq)] = [A−(aq)]
● [HA(aq)] = cA, where cA = the concentration of the un-ionised acid.
Substituting in the expression for Ka gives:
[H+(aq)]2
Ka =
cA

Hence, Ka × cA = [H+(aq)]2 Note

Taking logarithms: log (Ka × cA) = log [H (aq)]
+ 2 Do not try to remember this
logarithmic form of the equilibrium
Applying the rules that log xy = log x + log y and that log xn = n log x, gives: law. The relationship is easy to use,
log Ka + log cA = 2 × log [H+(aq)] but only apply it if you can derive it
quickly from first principles as shown
which, on multiplying by −1, becomes: here. Do not forget that this form of
the law has two built-in assumptions,
− log Ka − log cA = −2 × log [H+(aq)]
so it only applies when these
Hence, pKa − log cA = 2 × pH assumptions are acceptable.

This shows that for a solution of a weak acid which is less than 5% ionised:
pH = ½(pKa − log cA)
which rearranges to pKa = 2pH + log cA.

Test yourself
23 What is the value of pKa for methanoic acid given that Ka = 1.6 × 10−4 mol dm−3?
24 What is the value of Ka for benzoic acid given that pKa = 4.2?
25 Show that the logarithmic relationship pKa = 2pH + log cA gives the same
answers from the data as the methods used in the worked examples from
pages 153 and 154.

155
 Acids, bases and buffers

Activity

The acid strength of halogenated carboxylic acids

Introducing a halogen atom into the structure of a carboxylic acid
can have a marked effect on its acid strength. This is illustrated by
the values in Table 12.1.

Acid Ka /mol dm−3 pKa

ethanoic acid 1.7 × 10−5 4.8

fluoroethanoic acid 2.2 × 10−3 2.7
chloroethanoic acid 1.3 × 10 −3
2.9
iodoethanoic acid 7.6 × 10−4 3.1
dichloroethanoic acid 5.0 × 10−2 1.3
trichloroethanoic acid 2.3 × 10 −1
0.7
butanoic acid 1.5 × 10−5 4.8
2-chlorobutanoic acid 1.4 × 10−3 2.8
3-chlorobutanoic acid 8.7 × 10−5 4.0
4-bromobutanoic acid 3.0 × 10−5 4.5

Table 12.1쑿

1 Calculate the pH of a 0.1 mol dm−3 solution of:

a) butanoic acid
b) trichlorethanoic acid.
2 a) What is the pattern in the acid strength of fluoro-, chloro- and
iodoethanoic acids when compared with the value for
ethanoic acid?
b) Suggest an explanation for the pattern.
3 a) What is the pattern in the acid strength of chloro-, dichloro-
and trichloroethanoic acids when compared with the value for
ethanoic acid?
b) Is the pattern consistent with your suggested explanation in
question 2 b)?
4 a) What is the pattern in the acid strength of the chlorinated
butanoic acids when compared with the value for butanoic
acid?
b) Suggest an explanation for the pattern.

156
 Buffer solutions

12.4 Buffer solutions

Buffer solutions contain mixtures of molecules and ions in solution which help
to keep pH more or less constant. Buffer solutions help to stabilise the pH of
blood, medicines, shampoos, swimming pools and of many other solutions in
living things, domestic products and in the environment.
A buffer solution cannot prevent pH changes, but can even out the large
swings in pH that can happen without a buffer.
Buffers are important in living organisms. For example, the pH of blood is
closely controlled by buffers within the narrow range 7.35 to 7.45. Chemists
use buffers when they want to investigate chemical reactions at a fixed pH.

Figure 12.11쑿
Eye drops contain a buffer solution to
make sure that they do not irritate the
sensitive surface of the eye.

Figure 12.12쑿
Many shampoos for animals, as well as for people, contain a buffer solution. They are
marketed as ‘pH balanced’ shampoos.

Buffers are equilibrium systems which illustrate the practical importance of the
equilibrium law. A typical buffer mixture consists of a solution of a weak acid
and one of its salts – for example, a mixture of ethanoic acid and sodium
ethanoate. There must be plenty of both the acid and its salt.
Figure 12.13 씱
CH3COOH(aq) + H2O(l) CH3COO–(aq) + H3O+(aq) The action of a buffer solution.
acid molecules base ions – with
are a reservoir the capacity to stays roughly
of H+ ions accept H+ ions constant so the pH
plenty of weak acid plenty of the ions hardly changes
to supply more H+ from the salt able to
ions if alkali is added combine with H+
ions if acid is added

Le Chatelier’s principle provides a qualitative explanation of the buffering

action. Adding a small amount of a strong acid temporarily increases the
concentration of H+(aq), so the equilibrium shifts to the left to counteract the
change. Adding a small amount of a strong alkali temporarily decreases the
concentration of H+(aq), so the equilibrium shifts to the right to counteract
the change.

Test yourself
26 Show that the buffer solution in Figure 12.13 consists of a conjugate acid–base
pair.
27 Explain why a weak acid on its own cannot make a buffer solution, but a mixture
of a weak acid and one of its salts can. 157
 Acids, bases and buffers

The pH of buffer solutions

By choosing the right weak acid, it is possible to prepare buffers at any pH
value throughout the pH scale. If the concentrations of the weak acid and its
salt are the same, then the pH of the buffer is equal to pKa for the acid. The
pH of a buffer mixture can be calculated with the help of the equilibrium law.
[H+(aq)][A−(aq)]
Ka =
[HA(aq)]
This rearranges to give [H+(aq)] = Ka × [HA(aq)] , from which the pH can be
calculated. [A−(aq)]
So the equilibrium law makes it possible to calculate the pH of a buffer
solution made from a mixture of a weak acid and its conjugate base.
In a mixture of a weak acid and its salt, the weak acid is only slightly
ionised, while the salt is fully ionised. This means that it is often accurate
enough to assume that:
● all the HA molecules come from the added acid
● all the negative ions, A–(aq), come from the added salt.
So the calculation of the hydrogen ion concentration of a buffer solution can
be based on the expression:
[acid]
[H+(aq)] = Ka ×
[salt]
Diluting a buffer solution with water does not change the ratio of the
concentrations of the salt and acid, so the pH does not change unless the
dilution is so great that the assumptions used to arrive at this formula
break down.

Worked example
What is the pH of a buffer solution containing 0.40 mol dm−3 methanoic acid
and 1.00 mol dm−3 sodium methanoate?
Tutorial
Notes on the answer
Look up the value of Ka in a table of data: Ka for methanoic acid is
1.6 × 10−4 mol dm−3.
Make the assumptions that all the methanoic acid molecules come from the
added acid, and that all the methanoate ions come from the added salt.
Answer
From the information in the question, [acid] = 0.40 mol dm−3 and
[salt] = 1.00 mol dm−3.
Substituting in the expression gives:
[acid]
[H+(aq)] = Ka ×
[salt]
0.40 mol dm−3
= 1.6 × 10−4 mol dm−3 ×
1.00 mol dm−3
[H+(aq)] = 6.4 × 10−5 mol dm−3
So, pH = −log [H+(aq)]
= −log [6.4 × 10−5]
= 4.2

158
 Buffer solutions

Test yourself
28 Calculate the pH of these buffer mixtures.
a) A solution containing equal amounts, in moles, of H2PO4−(aq) and
HPO42−(aq). Ka for the dihydrogenphosphate(V) ion is 6.3 × 10−7 mol dm−3.
b) A solution containing 12.2 g of benzenecarboxylic acid (C6H5COOH) and
7.2 g of sodium benzenecarboxylate in 250 cm3 of aqueous solution. Ka for
benzenecarboxylic acid is 6.3 × 10−5 mol dm−3.
c) A solution containing 12.2 g benzenecarboxylic acid (C6H5COOH) and 7.2 g
of sodium benzenecarboxylate in 1000 cm3 of aqueous solution.
29 What is the ratio of the concentrations of the ethanoate ions and the ethanoic
acid molecules in a buffer solution with pH = 5.4? Ka for ethanoic acid is
1.7 × 10−5 mol dm−3.

Activity

Blood buffers
In a healthy person, the pH of blood lies within a
narrow range (7.35–7.45). Chemical reactions in
cells tend to upset the normal pH. Respiration, for
example, produces carbon dioxide all the time.
The carbon dioxide diffuses into the blood, where
it is mainly in the form of carbonic acid, H2CO3.
However, the blood pH stays constant because
it is stabilised by buffer solutions – in particular
by the buffer system based on the equilibrium
between carbon dioxide, water and
hydrogencarbonate ions. This is the carbonic
acid–hydrogencarbonate buffer.
CO2(g) + H2O(l) H+(aq) + HCO3−(aq)
Proteins in blood, including haemoglobin, can also
contribute to the buffering of blood pH. This is
because the molecules contain both acidic and
basic functional groups (see Sections 5.1 and 5.3).
Figure 12.14쑿
Two major organs help to control the total The lungs have a vital part to play in maintaining the
amounts of carbonic acid and hydrogencarbonate pH of the blood.
ions in the blood. The lungs remove excess carbon
dioxide from the blood and the kidneys remove
excess hydrogencarbonate ions.
The brain responds to the level of carbon dioxide
in the blood. During exercise, for example, the
brain speeds up the rate of breathing.
The consequences can be fatal if the blood pH
moves outside the normal range. Patients who
have been badly burned or suffered other serious
injuries are treated quickly with a drip into a vein.
One of the purposes of an intravenous drip is to
help to maintain the pH of the blood close to its
normal value.

159
 Acids, bases and buffers

Figure 12.15씱
Paramedics transferring a patient into
a helicopter ambulance. One of the
paramedics is holding an intravenous
drip bag.

1 Write an equation to show aqueous carbon dioxide reacting with

water to form hydrogen ions and hydrogencarbonate ions.
2 Explain why breathing faster and more deeply tends to raise the
blood pH.
3 a) Suggest two reason why the blood pH tends to fall during
strenuous exercise.
b) Why do people breathe faster and more deeply when
running?
4 a) Write the Ka expression for the equilibrium between carbon
dioxide, water, hydrogen ions and hydrogencarbonate ions.
b) In a sample of blood, the concentration of hydrogencarbonate
ions is 2.5 × 10−2 mol dm−3. The concentration of aqueous
carbon dioxide is 1.25 × 10−3 mol dm−3. The value of
Ka = 4.5 × 10−7 mol dm−3. Use this information to calculate:
i) the hydrogen ion concentration in the blood
ii) the pH of the blood.
iii) What can you conclude about the person who gave the
blood sample?
5 Explain why a mixture of carbon dioxide, water and
hydrogencarbonate ions can act as a buffer solution.
6 Give one example each of an acidic functional group and a basic
functional group that means that a protein can help to buffer
blood pH.
7 Why are blood buffers on their own unable to maintain the correct
blood pH for any length of time?
8 Suggest reasons why people may need treatment to adjust their
blood pH if they have been rescued after breathing thick smoke
during a fire.
160
 Acid–base titrations

12.5 Acid–base titrations

The equilibrium law helps to explain what happens during acid–base titrations
and it provides a basis for the selection of the right indicator for a titration.

Figure 12.16 쑿
Chemist operating a computer controlled automatic titrator.

The pH changes during a titration as a solution of an alkali runs from a

burette and mixes with an acid in a flask. Plotting the pH against the volume
of alkali added gives a shape that is determined by the nature of the acid and
the base. Usually there is a marked change in pH near the equivalence point
and it is this that makes it possible to detect the end-point of the titration
with an indicator. Figure 12.17쑿
Apparatus for measuring the changes in
It is common to use an indicator to find the end-point during a titration.
pH during an acid–base titration.
This is the point at which the colour change of the indicator shows that
enough of the solution in the burette has been added to react with the
amount of the acid in the flask. In a well-planned titration, the colour change
observed at the end-point corresponds exactly with the equivalence point.
The equivalence point is the point during any titration when the amount,
in moles, of the reactant added from a burette is just enough to react exactly
with all the measured amount of the acid in the flask as shown by the
balanced equation.
An alternative method of following the course of a titration and
determining the equivalence point is to use a pH meter. 161
 Acids, bases and buffers

Activity

Titration of a strong acid with a strong base

Strong acids and strong bases are fully ionised in solution.
Figure 12.18 shows the shape of the pH curve for a titration of a
strong acid, such as hydrochloric acid, with a strong base, such as
sodium hydroxide.
Figure 12.18씱
12
The pH change on gradually adding
10 0.1 mol dm−3 NaOH(aq) from a burette
to 25 cm3 of 0.1 mol dm−3 HCl(aq) .
8 equivalence
point pH = 7
pH

0
0 5 10 15 20 25 30
Titre/cm3

1 Show that pH = 1 for a solution of 0.1 mol dm−3 HCl(aq).

2 Why does the pH equal 7 at the equivalence point of a titration of
a strong acid with a strong base?
3 Calculate the pH of 25 cm3 of a solution of sodium chloride after
adding:
a) 0.05 cm3 (1 drop) of 0.1 mol dm−3 of HCl(aq)
b) 0.05 cm3 (1 drop) of 0.1 mol dm−3 of NaOH(aq).
(In both instances assume that the volume change on adding the
single drop is insignificant.)
4 Calculate the pH of the solution produced by adding 5 cm3 of
0.1 mol dm−3 NaOH(aq) to 25 cm3 of a solution of sodium chloride.
5 Show that your answers to questions 1, 2 and 3 are consistent
with Figure 12.18.
6 What features of the curve plotted in Figure 12.18 are important
to the practical accuracy of acid–base titrations of this kind?

Titration of a weak acid with a strong base

If the acid in the titration flask is weak, then the equilibrium law applies and
the pH curve up to the equivalence point can be calculated with the help of
the expression for Ka.
Consider, for example, the reaction of ethanoic acid with sodium hydroxide
during a titration. At the start, the flask contains the pure acid:
CH3COOH(aq) H+(aq) + CH3COO−(aq)
The pH of the pure acid can be calculated from Ka as shown in Section 12.3.
When some strong alkali runs in from the burette, some of the ethanoic
acid reacts to produce sodium ethanoate. Once this has happened
[H+(aq)] ≠ [CH3COO−(aq)] and the method of calculating the pH has to
162
change to account for this. After adding some alkali, and before reaching
 Acid–base titrations

the end-point, the titration flask contains a buffer solution. The pH is

calculated using the same method as for buffer solutions (see Section 12.4).
Figure 12.19 씱
12 The pH change on adding 0.1 mol dm−3
10 NaOH(aq) from a burette to 25 cm3 of a
equivalence point
0.1 mol dm−3 solution of CH3COOH(aq).
solution of
8 acid
sodium ethanoate
half-neutralised
pH = 8.7
pH

6 pH = 4.8
4
pure ethanoic acid
2 pH = 2.9
0
0 5 10 15 20 25 30
Titre/cm3

Worked example
What is the pH of the mixture formed during a titration after adding 20.0 cm3
of 0.10 mol dm−3 NaOH(aq) to 25.0 cm3 of a 0.10 mol dm−3 solution of
CH3COOH(aq) if Ka = 1.7 × 10−5 mol dm−3?
Notes on the method
The pH of the mixture can be estimated quite accurately using the
equilibrium law by assuming that:
● the concentration of ethanoic acid molecules at equilibrium is determined
by the amount of acid which has yet to be neutralised
● the concentration of ethanoate ions is determined by the amount of acid
converted to sodium ethanoate.
This is the same as the assumptions made when calculating the pH of buffer
solutions.
Answer
The total volume of the solution is 45.0 cm3.
5.0 cm3 of the 0.1 mol dm−3 ethanoic acid solution remains not neutralised and
this has been diluted to a total volume of 45 cm3 solution.
5.0 cm3
So the concentration of ethanoic acid molecules = × 0.10 mol dm−3
45.0 cm3
20.0 cm3
Also, the concentration of ethanoate ions = × 0.10 mol dm−3
45.0 cm3
[acid] [CH3COOH(aq)]
So the ratio =
[salt] [CH3COO–(aq)]
5.0
=
20.0
Substituting in the rearranged expression for the equilibrium law gives:
[H+(aq)] = Ka × [acid]
[salt]
5.0
= 1.7 × 10−5 mol dm−3 ×
20.0
= 4.25 × 10−6 mol dm−3
So, pH = −log [H+(aq)]
= −log [4.25 × 10−6]
= 5.4

Note in Figure 12.19 that at halfway to the equivalence point, the added
alkali has converted half of the weak acid to its salt. In this example, at this
163
point [CH3COOH(aq)] = [CH3COO−(aq)].
 Acids, bases and buffers

[CH3COOH(aq)]
So, [H+(aq)] = Ka × = Ka
[CH3COO–(aq)]
Hence, pH = pKa halfway to the equivalence point (Figure 12.20). The pH
changes rather slowly in the range of added volumes of alkali from about 5 cm3
to 20 cm3, In this range the titration flask contains a series of buffer solutions.
At the equivalence point itself, the solution contains sodium ethanoate. As
Figure 12.19 shows, the solution is not neutral at this point. A solution of a
salt of a weak acid and a strong base is alkaline. Sodium ions have no effect
on the pH of a solution, but ethanoate ions are basic. The ethanoate ion is
the conjugate base of a weak acid.
Beyond the equivalence point, the curve is determined by the excess of
strong base and so the shape is the same as for Figure 2.18.

Test yourself
30 Calculate the pH of a 0.1 mol dm−3 buffer
solution of CH3COOH(aq); range
pH 7 pH = pKa
Ka = 1.7 × 10−5 mol dm−3.
31 Calculate the pH of the mixture halfway to the
formed during a titration after end-point
adding 10.0 cm3 of 0.10 mol dm−3 0
NaOH(aq) to 25.0 cm3 of a 0 25
0.10 mol dm−3 solution of Added alkali/cm3
CH3COOH(aq).
Figure 12.20쑿
32 Explain why a solution of sodium
In the buffering range, the pH changes little on adding substantial volumes of strong
ethanoate is alkaline.
alkali. Over this range the flask contains significant amounts of both the acid and the
33 Why is the equivalence point
salt formed from the acid.
reached at 25 cm3 in both of the
titrations illustrated in Figures 12.18
and 12.19? Titration of a strong acid with a weak base
During the titration of a strong acid with a weak base, the flask contains a
strong acid at the start and the titration curve follows the same line as in
Figure 12.18. In a titration of hydrochloric acid with ammonia solution, for
example, the salt formed at the equivalence point is ammonium chloride.
Since ammonia is a weak base, the ammonium ion is an acid. So a solution
of ammonium chloride is acidic and the pH is below 7 at the equivalence
point. After the equivalence point, the curve rises less far than in Figure 12.18
because the excess alkali is a weak base and is not fully ionised.

12
10

8
equivalence
pH

6
point
4

0
0 5 10 15 20 25 30
Titre/cm3
Figure 12.21쑿
The pH change on gradually adding a 0.1 mol dm−3 solution of the weak base NH3(aq)
from a burette to 25 cm3 of a 0.1 mol dm−3 solution of HCl(aq), a strong acid.

Test yourself
164 34 Explain why a solution of ammonium chloride is acidic.
 Acid–base titrations

Titration of a weak acid with a weak base

In practice, it is not usual to titrate a weak acid with a weak base. As shown
in Figure 12.22, the change of pH around the equivalence point is gradual and
not very marked. This means that it is hard to fix the end-point precisely. If
the dissociation constants of the weak acid and of the weak base are
approximately equal (as is the case for ethanoic acid and ammonia) then the
salt formed at the equivalence point is neutral and the pH is 7 at this point.
12
10

8
pH

0
0 5 10 15 20 25 30
Titre/cm3
Test yourself
Figure 12.22 쑿
The pH change on gradually adding 0.1 mol dm–3 NH3(aq) from a burette to 25 cm3 of a 35 Write a balanced equation for the
0.1 mol dm−3 solution of CH3COOH(aq). Before the end-point the curve is essentially the neutralisation of ethanoic acid by
same as in Figure 12.19, but after the end-point it is as in Figure 12.21. Note the resulting ammonia solution.
small change of pH around the equivalence point

Working with logarithms

There can be advantages from working with a logarithmic form of the
equilibrium law when calculating the pH of a mixture of a weak acid and one
of its salts, both in buffer solutions and during titrations.
In general, for a weak acid HA:
HA(aq) H+(aq) + A−(aq)
[H+(aq)][A−(aq)]
Ka =
[HA(aq)]
This rearranges to give:
[HA(aq)]
[H+(aq)] = Ka ×
[A−(aq)]
Taking logs and substituting pH for −log [H+(aq)] and pKa for −log Ka gives:
⎧ [A−(aq)] ⎫
pH = pKa + log⎪ ⎪
⎩ [HA(aq)] ⎭
Note the change of sign and the inversion of the log ratio. This follows because:
⎧ [A−(aq)] ⎫ ⎧ [HA(aq)] ⎫
−log⎪ ⎪ = +log⎪ [A−(aq)] ⎪
⎩ [HA(aq)] ⎭ ⎩ ⎭
Again it is possible to make the assumption that in a mixture of a weak acid
and its salt, the weak acid is only slightly ionised and the salt is fully ionised.
This means that it is often accurate enough to assume that all the anions
come from the salt present, and all the un-ionised molecules come from the Note
acid. Hence: If you want to use the logarithmic form
⎧ [salt] ⎫ of the equilibrium law, make sure that
pH = pKa +log⎪ ⎪ you can derive it for yourself. Also
⎩ [acid] ⎭
check that you understand the
This form of the equilibrium law cannot be used to calculate the pH of a assumptions made in deriving this
solution of a weak acid on its own. However, it can help to account for the form of the law so that you know just
behaviour of buffer solutions (Section 12.4), and to explain the properties of when it applies.
acid–base indicators (Section 12.6). 165
 Acids, bases and buffers

12.6 Indicators
Acid–base indicators change colour when the pH changes. They signal the
end-point of a titration. No single indicator is right for all titrations and the
equilibrium law can help chemists to choose the indicator which will give
accurate results.
The indicator chosen for a titration must change colour completely in the
pH range of the near vertical part of the pH curve (see Figures 12.18, 12.19
and 12.21). This is essential if the visible end-point is to correspond to the
equivalence point when exactly equal amounts of acid and base are mixed.
Table 12.2 gives some data for four common indicators. Note that each
indicator changes colour over a range of pH values, which differs from one
indicator to the next.

Indicator pKa Colour change pH range over which the

HIn/In− colour change occurs
methyl orange 3.6 red/yellow 3.2–4.2
Figure 12.23쑿
The flowers of this variety of hydrangea methyl red 5.0 yellow/red 4.2–6.3
respond to soil pH. In acid soils they
bromothymol blue 7.1 yellow/blue 6.0–7.6
produce blue flowers; elsewhere the
flowers are pink. phenolphthalein 9.4 colourless/red 8.2–10.0

Table 12.2쑿

Figure 12.24쑿 Figure 12.25쑿

The colours of screened methyl orange indicator The colours of phenolphthalein
at pH 6 (left), pH 4 (middle) and pH 2 (right). This indicator at pH 7 (left) and pH 11
indicator includes a green dye to make the (right).
colour change easier to see.

Test yourself
36 Using le Chatelier’s principle, explain qualitatively why methyl red is yellow at
pH 3 but red at pH 7.
37 a) Why is methyl orange an unsuitable indicator for the titration illustrated by
Figure 12.19?
b) Why is phenolphthalein an unsuitable indicator for the titration illustrated by
Figure 12.20?
c) Identify the indicators that can be used to detect the end-points of the
titrations illustrated by Figures 12.18, 12.19 and 12.21.
Figure 12.26쑿 d) Explain why it is not possible to use an indicator to give a sharp and
The colours of bromothymol blue accurate end-point for the titration illustrated by Figure 12.22.
indicator at pH 5 (left) and pH 8 (right).
166
 Indicators

Indicators are themselves weak acids or bases which change colour when they Note
lose or gain hydrogen ions. When added to a solution, an indicator gains or The theory of acid–base indicators
loses protons, depending on the pH of the solution. It is conventional to and the theory of buffer solutions is
represent a weak acid indicator as HIn, where ‘In’ is a shorthand for the all of essentially the same. The difference is
the rest of molecule other than the ionisable hydrogen atom. In water: that a large amount of buffer mixture
is added to control the pH of a
HIn(aq) H+(aq) + In−(aq) solution, whereas the drop or two of
un-ionised indicator after an indicator in a titration flask is too
indicator losing a proton little to affect the pH. An indicator
colour 1 colour 2 follows the pH changes dictated by
the mixture of acid and alkali during
the titration.
Note that an analyst adds only a drop or two of indicator during a titration.
This means that there is so little indicator that it cannot affect the pH of the
mixture. The pH is determined by the nature of the titration (as shown in
Figures 12.18, 12.19 and 12.21). The position of the equilibrium for the
ionisation of the indicator shifts one way or the other as dictated by the pH of
the solution in the titration flask.
The pH range over which an indicator changes colour is determined by its
acid strength. Typically the range is given roughly by pKa ± 1.The logarithmic
form of the equilibrium law derived at the end of Section 12.5 shows why this
is so. For an indicator, it takes the form:

⎧ [In–(aq)] ⎫
pH = pKa + log⎪ ⎪
⎩ [HIn(aq)] ⎭

When pH = pKa, [HIn(aq)] = [In−(aq)] and the two different colours of the
indicator are present in equal amounts. The indicator is midway through its
colour change range.
Add a few drops of acid and the pH falls. If the two colours of the indicator
are equally intense, it turns out that our eyes see the characteristic acid colour
of the indicator clearly when [HIn] = 10 × [In−(aq)].
At this point, pH = pKa + log 0.1 = pKa − 1, since log 0.1 = −1.
Add a few drops of alkali and the pH rises. Similarly our eyes see the
characteristic alkaline colour of the indicator clearly when
[In−(aq)] = 10 × [HIn(aq)].
At this point, pH = pKa + log 10 = pKa + 1, since log 10 = +1.

+ H+ +
– –
O3S N N N CH3 O3S N N N CH3
+
–H
CH3 H CH3
yellow red

Figure 12.27쑿
The structures of methyl orange in acid and alkaline solutions. In acid solution, the
added hydrogen ion (proton) localises two electrons to form a covalent bond. In
alkaline solution, the removal of the hydrogen ion allows the two electrons to join the
other delocalised electrons. The change in the number of delocalised electrons
causes a shift in the peak of the wavelengths of light absorbed – so the colour
changes and the molecule acts as an indicator.

Test yourself
38 Suggest an explanation for the fact that the indicators shown in Table 12.2 do
not all change colour over a pH range of 2 units.

167
 Acids, bases and buffers

12.7 Neutralisation reactions

Chemists use the term ‘neutralisation’ to describe any reaction in which an
acid reacts with a base to form a salt – even when the pH is not exactly 7 on
mixing equivalent amounts of the acid and the alkali.

The pH of salts
Mixing equal amounts (in moles) of hydrochloric acid with sodium hydroxide
produces a neutral solution of sodium chloride. Strong acids, such as
hydrochloric acid, and strong bases, such as sodium hydroxide, are fully
ionised in solution – as is the salt formed in the reaction, sodium chloride.
Writing ionic equations for reactions such as this shows that neutralisation is
essentially a reaction between aqueous hydrogen ions and hydroxide ions.
(This similarity is also supported by the values for enthalpies of neutralisation
– see the next part in this section.)
H+(aq) + OH–(aq) H2O(l)
Figure 12.28쑿 The surprise is that ‘neutralisation’ reactions do not always produce neutral
Limestone etched by rainwater made solutions. ‘Neutralising’ a weak acid such as ethanoic acid with an equal
acidic by dissolved carbon dioxide. amount, in moles, of a strong base, such as sodium hydroxide, produces a
Bloody cranesbill is a plant that can only solution of sodium ethanoate that is alkaline.
flourish when growing in soil where the ‘Neutralising’ a weak base such as ammonia with an equal amount of the
minerals, such as limestone, neutralise strong acid hydrochloric acid produces a solution of ammonium chloride that
acids and keep the soil water alkaline. is acidic.
Where a salt has either a ‘parent’ acid or a ‘parent’ base which is weak, it
dissolves to give a solution which is not neutral. The strong ‘parent’ in the
partnership ‘wins’:
● weak acid + strong base – the salt formed is alkaline in solution
● strong acid + weak base – the salt formed is acidic in solution.

Test yourself
39 Predict, with the help of a table of Ka or pKa values, whether the salt
formed on mixing equivalent amounts of these acids and alkalis gives
Data a solution with pH of 7, pH above 7 or pH below 7:
a) nitric acid and potassium hydroxide
b) chloric(I) acid and sodium hydroxide
c) hydrobromic acid and ammonia
d) propanoic acid and sodium hydroxide.

Enthalpy change of neutralisation

Strong acids and bases
The ‘enthalpy change of neutralisation’ is the enthalpy change for a reaction
when an acid neutralises an alkali. For example:
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l) ΔH neutralisation = –57.5 kJ mol−1
The standard enthalpy of neutralisation for dilute solutions of a strong acid
with a strong base is always close to 57.5 kJ mol–1. The reason is that these
acids and alkalis are fully ionised. So in every instance the reaction is the
same:
H+(aq) + OH−(aq) → H2O(l) ΔH = −57.5 kJ mol−1
Approximate values of enthalpies of neutralisation can be measured by mixing
solutions of acids and alkalis in a calorimeter.

168
 Neutralisation reactions

Worked example
50 cm3 of 1.0 mol dm−3 dilute nitric acid was mixed with 50 cm3 of
1.0 mol dm−3 dilute potassium hydroxide solution in an expanded polystyrene
thermometer –10 to 50°C
cup. The temperature rise was 6.7 °C. Calculate the enthalpy change of
neutralisation for the reaction.
Notes on the method
Note that the total volume of solution on mixing is 100 cm3. polystyrene cup and lid

Assume that the density and specific heat capacity of the solutions is the same
as for pure water. reaction mixture

The specific heat capacity of water is 4.18 J g−1 K−1.

The density of water is 1 g cm−3 so the mass of 100 cm3 is 100 g.
Figure 12.29쑿
A change of 6.7 °C is the same as a temperature change of 6.7 K on the Kelvin Apparatus for measuring the enthalpy
scale. change of the neutralisation of an acid by
The energy from the exothermic reaction is trapped in the system by the a base.
expanded polystyrene, so it heats up the mixture.
Answer
The energy change = 4.18 J g−1 K−1 × 100 g × 6.7 K = 2800 J
50
Amount of acid neutralised = dm3 × 1.0 mol dm−3 = 0.05 mol
1000
HNO3(aq) + KOH(aq) → KNO3(aq) + H2O(l)
–2800 J
ΔHneutralisation = = −56 000 J mol−1 = −56.0 kJ mol−1
0.05 mol

Weak acids and bases

The standard enthalpy changes for neutralisation reactions involving weak
acids and weak bases are less negative than those for neutralisation reactions
between strong acids and strong bases. For example, the standard enthalpy
change for the neutralisation of ethanoic acid by sodium hydroxide
is −56.1 kJ mol−1.
This is partly because the weak acids and weak bases are not fully ionised at
the start, so bonds have to be broken and the neutralisations cannot be
described simply as reactions between readily available aqueous hydrogen ions
and aqueous hydroxide ions. Another reason is that the solutions are not
neutral at the equivalence point.

Test yourself
40 Account for the discrepancy between the value calculated in the worked
example from experimental results and the expected value of about
−57.5 kJ mol−1.
41 Suggest an explanation for the difference in the values of ΔH neutralisation for
HCl/NaOH and CH3COOH/NaOH.
42 Here are three pairs of acids and bases that can react to form salts: HBr/NaOH,
HCl/NH3, CH3COOH/NH3.
Here are three values for standard enthalpy changes of neutralisation:
−50.4 kJ mol−1, −53.4 kJ mol−1, −57.6 kJ mol−1.
Write the equations for the three neutralisation reactions, and match each with
its corresponding value of ΔH neutralisation.

169
 REVIEW QUESTIONS Extension questions

1 a) Write an equation for the reaction which occurs 3 a) Give examples to explain the difference between a
when weak acid HX is added to water. (1) strong acid and a weak acid. (4)
b) Write an expression for the acid dissociation b) At 298 K, what is the pH of:
constant of the weak acid. (1)
i) 0.01 mol dm−3 HNO3(aq) (1)
c) The ionisation of HX in aqueous solution is
ii) 0.01 mol dm−3 KOH(aq)? (2)
endothermic. Predict the effect, if any, of:
c) Butanoic acid, C3H7COOH, has an acid dissociation
i) an increase in temperature on the value of its
constant, Ka, of 1.5 × 10−5 mol dm−3 at 298 K.
acid dissociation constant (1)
i) Calculate the pH of a 0.020 mol dm−3 solution
ii) an increase in temperature on the pH of an
of butanoic acid at this temperature. (2)
aqueous solution of the weak acid (1)
ii) Draw a sketch graph to show the pH changes
iii) a decrease in concentration of the acid on the
when 0.020 mol dm−3 NaOH(aq) is added to
value of its acid dissociation constant. (1)
25 cm3 of 0.020 mol dm−3 butanoic acid. (4)
2 a) Describe and explain the use of buffer solutions with
iii) Choose, from the table below, the indicator
the help of examples. (6)
that would be most suitable for detecting the
b) i) What is the pH of a buffer solution in which end-point of a titration between butanoic acid
the concentration of ethanoic acid is and sodium hydroxide. Give your reasons. (2)
0.080 mol dm−3 and the concentration of
sodium ethanoate is 0.040 mol dm−3. Ka for Indicator Colour change pH range over
ethanoic acid is 1.7 × 10−5 mol dm−3. (2) acid/alkaline which colour
change occurs
ii) Calculate the new pH value if 0.020 mol NaOH
is dissolved in 1 dm3 of the buffer solution in thymol blue red/yellow 1.2–2.8
part a). (2) congo red violet/red 3.0–5.0

iii) Calculate the pH of a solution of thymolphthalein colourless/blue 8.3–10.6

0.020 mol NaOH in 1 dm3 of water. (2)
iv) Comment on the effectiveness of the buffer 4 A solution containing 0.050 mol dm−3 chloric(I) acid
solution (1) (HClO) and 0.050 mol dm−3 sodium chlorate(I) has a
pH of 7.43 at 298 K.
a) i) Write an equation for the ionisation of
chloric(I) acid. (1)
ii) Write an expression for the acid dissociation
constant of chloric(I) acid. (1)
b) Work out the values of Ka and pKa for chloric(I)
acid showing your working. (5)

170
13 Lattice enthalpy and Born–Haber cycles
Some compounds are stable and remain unchanged even when
heated to high temperatures. Other compounds decompose very
readily forming their elements or other compounds at relatively low
temperatures. By measuring the enthalpy changes of the various
stages which occur when metals react with non-metals, it is possible
to compare the stability of different ionic compounds. The enthalpy
(energy) cycles which chemists draw up to link the relevant changes
and investigate the stability of ionic compounds are called Born–
Haber cycles.

13.1 Ionic bonding and structures

Compounds of metals with non-metals, such as sodium chloride and magnesium
oxide, are composed of ions. When compounds form between metals and non-
metals, the metal atoms lose electrons and form positive ions (cations). At the
same time, the non-metal atoms gain electrons and form negative ions (anions).
For example, when sodium reacts with chlorine (Figure 13.1), each sodium atom Figure 13.1쑿
loses its one outer electron forming a sodium ion, Na+. Chlorine atoms gain Hot sodium reacting with chlorine.
these electrons and form chloride ions, Cl− (Figure 13.2).

Na Cl

sodium atom, Na chlorine atom, Cl

2,8,1 2,8,7

+ –

Na Cl

Figure 13.2씱
+ – The formation of ions in sodium chloride
sodium ion, Na chloride ion, Cl
2,8 2,8,8 when sodium reacts with chlorine.

From your studies in AS Chemistry, you should know that diagrams like that
in Figure 13.2, in which the electrons of one element are shown as dots and
those of the other element are shown as crosses, are called dot-and-cross
diagrams. These diagrams provide a useful balance sheet for keeping track of
the electrons when ionic compounds form.
Very often it is sufficient to show simply the outer shell electrons in dot-and-
cross diagrams and two of these simplified diagrams are shown in Figure 13.3.

–
Na + Cl Na+ + Cl
sodium atom chlorine atom sodium ion chloride ion
(2, 8, 1) (2, 8, 7) (2, 8) (2, 8, 8)
Figure 13.3씱
Dot-and-cross diagrams for the
– –
Ca + F F Ca2+ + F F formation of sodium chloride and
calcium fluoride showing only the
calcium atom two fluorine atoms calcium ion two fluoride ions
electrons in the outer shells of the 171
(2, 8, 8, 2) (2, 7) (2, 8, 8) (2, 8) reactant atoms and product ions.
 Lattice enthalpy and Born–Haber cycles

When metals react with non-metals, the ions produced form ionic crystals.
These ionic crystals are giant lattices containing billions of positive and
negative ions packed together in a regular pattern. Strong ionic bonds hold
the ions firmly together in ionic lattices like that shown in Figure 13.4.

Figure 13.4 쑿
A 3D model of the structure of sodium chloride. The red balls represent Na+ ions; the
larger green balls represent Cl− ions.

Many other compounds have the same lattice structure as sodium chloride
including the chlorides, bromides and iodides of lithium, sodium and
potassium, and the oxides and sulfides of magnesium, calcium and strontium.

Test yourself
1 Draw dot-and-cross diagrams, similar to those in Figure 13.3, for:
a) potassium oxide
b) magnesium sulfide.
2 Why do metals form positive ions, whereas non-metals form negative ions?
3 Why do you think the melting point of magnesium oxide (2852 °C) is so much
higher than that of sodium fluoride (993 °C)?

13.2 Enthalpy changes and ionic bonding

When sodium reacts with chlorine, a very exothermic reaction occurs and
energy is given out to the surroundings. When the product, sodium chloride,
cools down to room temperature, it is clear that the system has less energy
than it had before the reaction took place. Figure 13.5 shows an enthalpy
profile (level) diagram for the reaction that occurs.
Figure 13.5씰
An enthalpy profile diagram for the Reactants: Na(s) + 12 Cl2(g)
formation of sodium chloride.
(energy content)
Enthalpy

ΔHf = –411 kJ mol–1

Product: Na+Cl–(s)

172
Course of reaction
 A closer look at the enthalpy changes when ions form

The enthalpy change shown in Figure 13.5 relates to the formation of 1 mole
of sodium chloride from its elements sodium and chlorine. If the
measurements have been made at 25 °C (298 K) and 1 atmosphere pressure
(105 Pa), the result is described as the standard enthalpy change of formation
of sodium chloride. This can be written either as:
Na(s) + 12 Cl2(g) → Na+Cl−(s) ΔH f = −411 kJ mol−1
or as: ΔH f [NaCl(s)] = −411 kJ mol−1

Standard enthalpy changes

In order to compare energy changes, such as enthalpy changes of formation,
fairly and consistently, it is important to make thermochemical measurements
under the same conditions. The conditions chosen for comparing enthalpy
changes and other thermochemical measurements are called standard
conditions. These standard conditions are:
● a temperature of 25 °C (298 K)
● a pressure of 1 atmosphere (1 × 105 Pa = 100 kPa)
● all reactants and products in their standard (stable) states at 25 °C and
1 atmosphere pressure
● all solutions at a concentration of 1 mol dm−3.
The symbol for these standard enthalpy changes is ΔH , and ΔH f for standard Definition
enthalpy changes of formation. The standard enthalpy change of
From the standard conditions just described, you will appreciate how formation of a compound, ΔH f , is
important it is to specify the states of the chemicals involved in any relevant the enthalpy change when one mole
process. Equations should always include state symbols, and in this respect the of the compound forms from its
state for water in all standard enthalpy changes should relate to water liquid, elements under standard conditions
H2O(l), not water vapour, H2O(g). In addition, the standard state for carbon with the elements and the compound
is graphite, C(graphite), and not diamond, C(diamond), because graphite is in their standard (stable) states.
energetically more stable than diamond at 25 °C and 1 atmosphere pressure.
Notes
13.3 A closer look at the enthalpy changes when The superscript sign in ΔH shows
that the value quoted is for standard
ions form conditions. The symbol is pronounced
Figure 13.2 shows the formation of sodium chloride from its elements, but it ‘delta H standard’.
simplifies the process in many ways. As far as sodium is concerned, Figure 13.2 The definition of standard enthalpy
ignores the fact that: changes of formation means that
ΔH f = 0 kJ mol−1 for all elements
● sodium starts as a giant lattice of atoms
because there is no change when an
● energy is required to separate the sodium atoms in the giant lattice. This
element forms from itself, and
process is called the enthalpy change of atomisation of sodium therefore no enthalpy change. In other
● energy is also required to remove one electron from each sodium atom in words, the standard enthalpy change
order to form positive sodium ions, Na+. This is the first ionisation energy of formation of any element is zero.
of sodium.
As far as chlorine is concerned, Figure 13.2 ignores the fact that:
● chlorine consists of Cl2 molecules
● energy is required to break the bonds between Cl atoms in the Cl2
molecules and form separate Cl atoms. This process is the enthalpy change
of atomisation of chlorine
● an energy change also occurs when one electron is added to each Cl atom
forming chloride ions, Cl−. This process is called the electron affinity of
chlorine.
Finally, but equally importantly, Figure 13.2 ignores the fact that energy is
given out when gaseous Na+ and Cl− ions come together forming a giant ionic
lattice of sodium chloride, Na+Cl−(s). This process is called the lattice
enthalpy of sodium chloride. 173
 Lattice enthalpy and Born–Haber cycles

Definitions
The standard enthalpy change of atomisation of an element is the energy
needed to produce one mole of gaseous atoms of the element under standard
conditions. For sodium this is:
Na(s) → Na(g) ΔH at [Na(s)] = +107 kJ mol−1
And for chlorine this is:
1
2 Cl2(g) → Cl(g) ΔH at [ 12 Cl2(g)] = +122 kJ mol−1
The first ionisation energy of an element is the energy needed to remove one
electron from each atom in one mole of gaseous atoms of the element under
standard conditions. For sodium this is:
Na(g) → Na+(g) + e− ΔH i.1 [Na(g)] = + 496 kJ mol−1
Successive ionisation energies for the same element measure the energy needed
to remove a second, third, fourth electron and so on. For example, the third
ionisation energy of sodium relates to the process:
Na2+(g) → Na3+(g) + e−
The first electron affinity of an element is the energy change when each atom in
one mole of gaseous atoms gains one electron to form one mole of gaseous ions
with a single negative charge.
The following two equations define the first and second electron affinities for
oxygen:
O(g) + e− → O− (g) E aff.1 = −141 kJ mol−1
O−(g) + e− → O2−(g) E aff.2 = +798 kJ mol−1
The gain of the first electron is exothermic, but adding a second electron to a
negatively charged ion is endothermic.

Lattice enthalpies
The lattice enthalpy of a compound is usually defined as the standard
enthalpy change when one mole of an ionic compound is formed from free
gaseous ions. For sodium chloride, this is summarised by the equation:
Na+(g) + Cl−(g) → Na+Cl− (s) ΔH lattice[NaCl(s)] = −787 kJ mol−1
This lattice enthalpy process is shown diagrammatically in Figure 13.6.
Figure 13.6씰
Lattice enthalpy is the energy that would
be given out to the surroundings (red
arrows) if one mole of a compound could
be formed directly from free gaseous ions
coming together (black arrows) and
arranging themselves into a crystal lattice.

Definition
The lattice enthalpy of an ionic
compound is the standard enthalpy
change when one mole of the
compound forms from free gaseous Na
ions.
Some chemists use the term ‘lattice
energy’ as an alternative to lattice Cl
174 enthalpy.
 Born–Haber cycles

Lattice enthalpies are important because they can be used as a measure of the Test yourself
strength of ionic bonds in different ionic compounds.
The strengths of ionic bonds, measured as lattice enthalpies in kJ mol−1, 4 Write equations for the
arise from the energy given out as billions upon billions of positive and following processes.
negative ions come together to form a crystal lattice. a) The enthalpy change Data
The force of attraction between the ions is stronger, and this results in a of formation of
more exothermic lattice enthalpy, if: magnesium chloride.
b) The lattice energy of
● the charges on the ions are large magnesium chloride.
● the ionic radii are small, allowing the ions to get closer to each other. c) The second ionisation energy of
It is important to distinguish between the lattice enthalpy of an ionic magnesium.
d) The enthalpy change of
compound and its standard enthalpy change of formation. The lattice
atomisation of magnesium.
enthalpy relates to the formation of 1 mole of a compound from its free e) The first electron affinity of
gaseous ions, whereas the standard enthalpy change of formation relates to the chlorine.
formation of 1 mole of the compound from its elements in their normal states 5 Draw an enthalpy profile diagram for
under standard conditions. the formation of aluminium oxide:
During the early part of the twentieth century, scientists found ways of ΔH f [Al2O3(s)] = −1676 kJ mol−1
measuring enthalpy changes of formation and atomisation, ionisation energies 6 Why should the state of water in
and electron affinities of various elements. This led the German scientists standard enthalpy changes relate to
Max Born (1882–1970) and Fritz Haber (1868–1934) to analyse the energy H2O(l) and not H2O(g)?
changes in the formation of different ionic compounds. Their work resulted in 7 Why is the standard enthalpy
Born–Haber cycles which are thermochemical cycles for calculating lattice change of formation of copper
equal to zero?
enthalpies and for investigating the stability and bonding in ionic compounds.
8 Why is the first electron affinity of
chlorine exothermic, but its second
13.4 Born–Haber cycles electron affinity endothermic?
9 Why are ionisation energies always
Born–Haber cycles are an application of Hess’s law (Section 16.5 in endothermic?
OCR Chemistry for AS). They provide a model for the determination Tutorial 10 Why is the second ionisation energy
of lattice enthalpies which cannot be measured experimentally. They of any element more endothermic
also enable chemists to test the ionic model of bonding in different than its first ionisation energy?
substances. 11 Why does the lattice enthalpy of
A Born–Haber cycle identifies all the enthalpy changes that contribute to lithium fluoride indicate that the ionic
the standard enthalpy change of formation of a compound. These changes, bonding in lithium fluoride is
stronger than that in sodium
shown in Figure 13.7, involve:
chloride?
● the energy (enthalpy changes) required to create free gaseous ions by (ΔH lattice [LiF(s)] = −1031 kJ mol−1;
atomising and then ionising the elements ΔH lattice [NaCl(s)] = −780 kJ mol−1)
● the energy given out (the lattice enthalpy) when the ions come together to
form a crystal lattice.

gaseous ions

total enthalpy
change for atomising
and ionising the
two elements
lattice
enthalpy
metal element and
non-metal element

enthalpy change
of formation of
the compound compound

Figure 13.7 쑿
The overall structure of a Born–Haber cycle.
175
 Lattice enthalpy and Born–Haber cycles

A Born–Haber cycle is usually set out like an enthalpy profile diagram, with
enthalpy changes one after another. All the processes in the cycle can be
measured experimentally except the lattice enthalpy. So, by using Hess’s law it
is possible to calculate the lattice enthalpy.
Figure 13.8 shows the Born–Haber cycle for sodium oxide, Na2O.

Sum of the first and second

2Na+(g) + O2–(g)
electron affinities of O(g)
Eaff.1 + Eaff.2 = –141 + 798
Eaff.1 + Eaff.2 = +657 kJ mol–1 2Na+(g) + 2e– + O(g)

Atomisation to form 1 mol O(g) 2Na+(g) + 2e– + 12 O2(g)

ΔHat = +249 kJ mol–1

Ionisation of 2 mol Na(g)

2 × ΔHi1 = +992 kJ mol–1 Lattice enthalpy of
2Na(g) + 12 O2(g) sodium oxide,
ΔHlattice[Na2O(s)] = ?
Atomisation to form 2 mol Na(g) 2Na(s) + 12 O2(g)
2 × ΔHat = +214 kJ mol–1

Standard enthalpy change

of formation of Na2O(s)
ΔHf [Na2O(s)] = –414 kJ mol–1
Na2O(s)

Figure 13.8쑿
The Born–Haber cycle for sodium oxide.

Starting with the elements sodium and oxygen, the measured value for the
standard enthalpy change of formation of sodium oxide has been written
downwards on the cycle, showing that it is exothermic. Above that, the terms
and values for the atomisation and then ionisation of sodium are written
upwards as endothermic processes.
Notice also that the amount of sodium required is 2 mol because there are 2
moles of sodium in 1 mole of sodium oxide.
These terms and values for sodium are followed by those required for the
conversion of half a mole of oxygen molecules, 12 O2(g), to one mole of oxide
ions, O2−(g). This involves the atomisation of oxygen followed by its first and
second electron affinities. From the experimentally determined values, which
we now have in the cycle, it is possible to calculate the lattice enthalpy.

Worked example
Calculate the lattice enthalpy of sodium oxide, ΔH lattice [Na2O(s)] using the
data in Figure 13.8.
Note
Notes on the method
Lattice enthalpies, as usually defined, Apply Hess’s law to the cycle in Figure 13.8 remembering that an exothermic
are negative. This means that the change in one direction becomes an endothermic change with the opposite
descriptions ‘larger’ and ‘smaller’ can sign in the reverse direction.
be ambiguous in comparing lattice
enthalpies. For this reason, it is better Answer
to describe one lattice enthalpy as ΔH lattice [Na2O(s)] = (− 657 − 249 − 992 − 214 − 414) kJ mol−1
being more exothermic or less
exothermic than another. = −2526 kJ mol−1

176
 Testing the ionic model – ionic or covalent?

Test yourself
Tutorial
12 Why are lattice enthalpies:
a) always negative
b) impossible to measure directly?
13 Explain why a Born–Haber cycle is an application of Hess’s law.
14 Look carefully at Figure 13.9, which is a Born–Haber cycle for magnesium
chloride.
Mg2+(g) + 2e– + 2Cl(g)
ΔH6 = –698 kJ mol–1
ΔH5 = +244 kJ mol–1 2+ –
Mg (g) + 2e + Cl2(g)
Mg2+(g) + 2Cl–(g)

ΔH4 = +1451 kJ mol–1

Mg+(g) + e– + Cl2(g)
ΔH7
ΔH3 = +738 kJ mol–1
Mg(g) + Cl2(g)
–1
ΔH2 = +148 kJ mol Mg(s) + Cl2(g)

ΔH1 = –641 kJ mol–1

MgCl2(s)

Figure 13.9 쑿
A Born–Haber cycle for magnesium chloride.

a) Identify the enthalpy changes ΔH 1, ΔH 2 , ΔH 3 , ΔH 4 , ΔH 5 , ΔH 6 and ΔH 7 .

b) Calculate the lattice enthalpy of magnesium chloride.

13.5 Testing the ionic model – ionic or covalent?

Note
One way in which scientists can test their theories and models is by
comparing the predictions from their theoretical models with the values Electrostatic forces operate between
obtained by experiment. Born–Haber cycles are very helpful in this respect the ions in a crystal. Oppositely
because they enable chemists to test the ionic model and check whether the charged ions attract each other, and
ions with like charges repel each
bonding in a compound is truly ionic. The experimental lattice enthalpy
other. The size of the electrostatic
obtained from a Born–Haber cycle can be compared with the theoretical value
force, F, between two charges is
calculated by using the laws of electrostatics and assuming that the only given by the equation:
bonding in the crystal is ionic. Q1 × Q2
Using the laws of electrostatics, it is possible to calculate a theoretical value F∝ d2
for the lattice enthalpy of an ionic compound by summing up the effects of all
● the larger the charges, Q1 and Q2,
the attractions and repulsions between the ions in the crystal lattice (Figure
the stronger the force
13.10).
● the greater the distance, d,
+ between the charges, the smaller
+ –
the force – this has a big effect
because it is the square of the
distance that matters.
– + –

Figure 13.10씱
– + – Some of the many attractions (red)
and repulsions (blue) which must be
taken into account in calculating a
+ – + theoretical value for the lattice 177
enthalpy of an ionic crystal.
 Lattice enthalpy and Born–Haber cycles

Table 13.1 shows the experimentally determined lattice enthalpies and the
theoretical lattice enthalpies for some ionic compounds.
Compound Experimental lattice Theoretical lattice enthalpy
enthalpy from a Born–Haber calculated assuming that the
cycle /kJ mol−1 only bonding is ionic / kJ mol−1

NaCl −780 −770

NaBr −742 −735

NaI −705 −687

KCl −711 −702

KBr −679 −674

KI −651 −636

AgCl −905 −833

MgI2 −2327 −1944

Table 13.1쑿

Pure ionic bonding arises solely from the electrostatic forces between the ions
in a crystal. Notice that there is close agreement between the experimental
and theoretical values of the lattice enthalpies for sodium and potassium
halides in Table 13.1. In all these halides, the difference between the two
values is less than 3%. This shows that ionic bonding can account almost
entirely for the bonding in sodium and potassium halides.
But look at the experimental and theoretical lattice enthalpies of silver
chloride and magnesium iodide in Table 13.1. In these two compounds, the
experimental values are much larger than the theoretical values, which
assume that the only bonding is ionic. The bonding is clearly stronger than
that predicted by a pure ionic model. This suggests that there is some covalent
bonding as well as ionic bonding in these substances.

Polarisation of ions
In ionic compounds, positive metal ions will attract the outermost electrons of
negative ions, pulling these electrons into the spaces between the ions. This
distortion of the electron clouds around anions by positively charged cations is
an example of polarisation. As a result of polarisation, there is a significant
degree of covalent bonding in some ionic compounds.
Definition This makes the size of the lattice enthalpy greater numerically than that
Polarisation is the distortion of the expected from the purely ionic model, because the calculation does not allow
electron cloud in a molecule or ion by for the extra attraction resulting from the distortion of the anions. The values
a nearby positive charge. in Table 13.1 show clearly that both silver chloride and magnesium iodide,
although mainly ionic, have a significant degree of covalent bonding.
Figure 13.11 shows three examples of ionic bonding with increasing degrees
of electron sharing as a positive cation polarises the neighbouring negative
ion. In general, results show that:
● the polarising power of a cation increases as its charge increases and as its
radius decreases
● the polarisability of an anion increases as its radius increases.
As the negative anion gets larger, its outermost electrons are further from the
attraction of its positive nucleus. Consequently, these outermost electrons are
more readily attracted to a neighbouring positive ion and the anion is
therefore more polarisable.
178
 Testing the ionic model – ionic or covalent?

ion pair

increasing polarisation
size of the of the negative ion by
unpolarised the positive ion
ion
substantial
covalent
bonding

Figure 13.11쑿
Ionic bonding with increasing amounts of electron sharing as a positive cation
polarises neighbouring negative anions. (Dotted circles show the size of
unpolarised ions.)

This means that iodide ions are more polarisable than bromide ions, bromide
ions are more polarisable than chloride ions and fluoride ions are very difficult
to polarise. In fact, fluorine, with its small, singly charged fluoride ion, forms
compounds which are more ionic than any other non-metal.

Test yourself
15 Look at Table 13.2, which lists the ionic radii of some ions.
Ion Li+ Na+ K+ Mg2+ Al3+
Ionic radius/nm 0.074 0.102 0.138 0.072 0.053
Ion N3− O2− F−

Ionic radius/nm 0.171 0.140 0.133

Table 13.2쑿
Use the data in Table 13.2 to explain why:
a) the ionic radii decrease from N3− through O2− to F−
b) the polarising power of Mg2+ is greater than that of Li+
c) the polarising power of Li+ is greater than that of K+
d) the polarising power of Al3+ is greater than that of Na+
e) the polarisability of N3− is greater than that of F−.
16 The lattice enthalpy of LiF is −1031 kJ mol−1 and that of LiI is −759 kJ mol−1.
a) Why is the lattice enthalpy of LiI less exothermic than the lattice enthalpy
of LiF?
b) Which compound would you expect to have the closer agreement between
the Born–Haber experimental value of its lattice enthalpy and its theoretical
value based on the ionic model?
c) Explain your answer to part b).
17 Here are four values for lattice enthalpy in kJ mol−1: −3791, −3299, −3054 and
−2725.
The four ionic compounds to which these values relate are BaO, MgO, BaS
and MgS.
Match the formulae with the values and justify your choices.

179
 Lattice enthalpy and Born–Haber cycles

Activity

The stability of ionic compounds

Almost all the compounds of metals with non-metals are regarded
as ionic, and these compounds have standard enthalpy changes of
formation which are exothermic. This means that the compounds
are at a lower energy level and therefore more stable than their
elements.
If you look at the Born–Haber cycles in Figures 13.8 and 13.9, you
will see that an ionic compound will have an exothermic standard
enthalpy of formation if its negative lattice enthalpy outweighs the
total energy needed to produce gaseous ions from the elements.
Using a Born–Haber cycle with a theoretically calculated value for
the lattice enthalpy, it is possible to estimate the standard enthalpy
change of formation for compounds which do not normally exist. For
example, consider the Born–Haber cycle for the hypothetical
compound MgCl in Figure 13.12.
Mg+(g) + e– + Cl(g)

ΔHat [ 12 C l 2 ( g )]= +122 kJ mol–1 Mg+(g) + e– + 1 Cl (g)

Ea f f [ Cl] = –349 kJ mol–1
2 2

Mg+(g) + Cl–(g)
–1
ΔHi.1 [ Mg ]= +738 kJ mol

Mg(g) + 12 Cl2(g) Theoretical

ΔHla ttic e [ MgCl( s) ] = –753 kJ mol–1
ΔHat [ M g( g )]= +148 kJ mol–1 Mg(s) + 12 Cl2(g)

ΔHf [MgCl( s) ]
MgCl(s)

1 Use Figure 13.12 to calculate a value for the standard enthalpy Figure 13.12쑿
change of formation of MgCl(s). A Born–Haber cycle for the
hypothetical compound MgCl.
2 What does your answer to question 1 suggest about the stability
of MgCl(s)?
3 Using the Hess cycle in Figure 13.13, calculate the standard
enthalpy change for the reaction
2MgCl(s) → MgCl2(s) + Mg(s)
knowing that ΔH f [MgCl2(s)] = −641 kJ mol−1.

Figure 13.13씱
2MgCl(s) MgCl2(s) + Mg(s) A Hess cycle for the reaction
2MgCl(s) → MgCl2(s) + Mg(s).

2Mg(s) + Cl2(g)

180
 Enthalpy changes during dissolving

4 What does your result for question 3 tell you about the stability of
MgCl(s)?
5 The Born–Haber cycle for the hypothetical compound MgCl3
suggests that ΔH f [MgCl3(s)] = +3950 kJ mol−1.
a) What does the value of ΔH f [MgCl3(s)] tell you about the
stability of MgCl3(s)?
b) Suggest why the value of ΔH f [MgCl3(s)] is so endothermic.
6 The estimated lattice enthalpy of MgCl3(s) is −5440 kJ mol−1.
a) Write an equation to summarise the lattice enthalpy of MgCl3.
b) Why is the lattice enthalpy of MgCl3 more exothermic than
that of MgCl2(s)?

13.6 Enthalpy changes during dissolving

Why do ionic crystals dissolve in water, even though ions in the lattice are
strongly attracted to each other? What, in general, are the factors which
determine the extent to which an ionic salt dissolves in water?
Chemists look for answers to questions of this kind by analysing the energy
changes which take place as crystals dissolve.

Figure 13.14씱
The concentration of sodium chloride in
the Dead Sea in Israel is so high that salt
crystallises out in some places.

An ionic compound such as sodium chloride does not dissolve in non-polar

solvents like hexane, but it will dissolve in a polar solvent like water. When
one mole of sodium chloride dissolves in water to produce a solution of
concentration 1 mol dm−3 under standard conditions, there is an enthalpy
change of +3.8 kJ mol−1. This enthalpy change is described as the standard
enthalpy change of solution, ΔH solution, of sodium chloride. The process can be
summarised by the equation:
NaCl(s) + aq → Na+(aq) + Cl− (aq) ΔH solution = +3.8 kJ mol−1
or simply as ΔH solution [NaCl(s)] = +3.8 kJ mol−1.
In the equation above, ‘+ aq’ is short for the addition of water.
Enthalpy changes of solution are often measured and tabulated for 1 mole of a
compound dissolving in different amounts of water under standard conditions.
For example, if 1 mole of sodium chloride is dissolved in 100 moles of water
under standard conditions, the enthalpy change is represented by the equation:
181
NaCl(s) + 100H2O(l) → NaCl(aq, 100 H2O) ΔHsoln = +4.1 kJ mol−1
 Lattice enthalpy and Born–Haber cycles

Sodium chloride dissolves readily in water despite the fact that the process is
slightly endothermic. This is another example which shows that the sign of
ΔH is not a reliable guide to whether or not a process will happen. This is
particularly the case when the magnitude of ΔH is small.
It is not immediately obvious why the charged ions in a crystal, such as
sodium chloride, separate and go into solution in water. Where does the
energy come from to overcome the attractive forces between oppositely
charged ions?
When sodium chloride dissolves in water, the overall process can be
pictured in two stages and these are shown in Figure 13.15.

Figure 13.15씰 Na+(g) + Cl–(g) + aq

The Born–Haber cycle for sodium
chloride dissolving in water.

–ΔHlattice = +787 kJ mol–1 ΔHhyd[Na+] + ΔHhyd[Cl–] = –784 kJ mol–1

Na+(aq) + Cl–aq
+ –
Na Cl (s) + aq ΔHsolution = +3 kJ mol–1

Definitions ● First of all, Na+ and Cl− ions must be separated from the solid NaCl crystals
The standard enthalpy change of
to form well-spaced ions in the gaseous state, Na+(g) and Cl−(g). This is
solution, ΔH solution, is the enthalpy the reverse of the lattice enthalpy and is labelled −ΔH lattice = +787 kJ mol−1
change when one mole of a in Figure 13.15.
compound dissolves to form a ● In the second stage, gaseous Na+(g) and Cl−(g) ions are hydrated by polar
solution containing 1 mol dm−3 under water molecules forming a solution of sodium chloride, Na+(aq) + Cl−(aq).
standard conditions. Under standard conditions, this process is the sum of the standard
Enthalpy changes of solution are often enthalpy changes of hydration of Na+(g) and Cl−(g). This is written as
calculated and quoted for one mole of ΔH hyd [Na+] + ΔH hyd [Cl−] = −784 kJ mol−1 in Figure 13.15.
a compound dissolving in different
amounts of water.
It is now possible to see from Figure 13.15 why sodium chloride dissolves so
readily in water. The explanation is that the Na+ and Cl− ions are so strongly
The standard enthalpy change of
hydrated by polar water molecules that the exothermic enthalpy changes of
hydration is the enthalpy change
when one mole of gaseous ions is
hydration nearly balance the energy required to separate the ions (the reverse
hydrated under standard conditions to lattice enthalpy).
form a solution in which the The enthalpy change of solution is the difference between the energy
concentration of ions is 1 mol dm−3. needed to separate the ions from the crystal lattice (the negative lattice
For example, for sodium ions: enthalpy) and the energy given out as the ions are hydrated (the sum of the
Na+(g) + aq → Na+(aq) hydration enthalpies).
ΔH hyd = −444 kJ mol−1 Figure 13.16 shows the structure of hydrated sodium and chloride ions. In
Enthalpy changes of hydration are water molecules, there is a δ+ charge in the region between the hydrogen
sometimes just called hydration atoms and a δ− charge on the oxygen atoms. This means that the polar water
enthalpies or hydration energies. molecules are attracted to both positive cations and negative anions. The
bond between the ions and the water molecules is an electrostatic attraction.
With cations, the electrostatic attraction involves the positive charge on the
cations and the δ− charges on the oxygen atoms of the water molecules. In
contrast, with anions, the attraction involves the negative charge on the
anions and the δ+ charge on the hydrogen atoms in the water molecules.

182
 Enthalpy changes during dissolving

δ– Figure 13.16씱
Sodium and chloride ions are hydrated
δ+ when sodium chloride dissolves in water.
δ– Polar water molecules are attracted to
δ+ δ– δ+ δ+
δ+ δ– δ+ both cations and anions.
δ–
δ– Cl–
Na+ δ+ δ+
δ– δ–
δ– δ–
δ+ δ– δ+
δ+

δ+
δ–

Test yourself
Data
18 Look at the data sheet on the Dynamic Learning Student website headed
‘Enthalpy changes of hydration’.
a) How is the enthalpy change of hydration affected by increasing ionic charge?
b) List an appropriate series of ions and their enthalpy changes of hydration to
illustrate your conclusion in part a).
19 Look at Table 13.2 showing the radii of some ions, and the data sheet headed
‘Enthalpy changes of hydration’.
a) How is the enthalpy change of hydration affected by increasing ionic radius?
b) List an appropriate series of ions, their radii and their enthalpy changes of
hydration to illustrate your conclusion in part a).

The effect of ionic charge on enthalpy change of hydration

and lattice enthalpy
Enthalpy changes of hydration and lattice enthalpies both involve
electrostatic attractions between opposite charges. Because of these
attractions, both processes are exothermic.
Furthermore, both processes become more exothermic as the charges on the
ions increase because the charge density of an ion increases and therefore its
attraction for any opposite charge increases.
This is illustrated very well by the enthalpy changes of hydration for Na+
and Mg2+ and the lattice enthalpies of NaF and MgO in Table 13.3.

Table 13.3씱
Enthalpy change of hydration /kJ mol−1 Lattice enthalpy /kJ mol−1
Comparing enthalpy changes of
Na+ −444 NaF −918 hydration and lattice enthalpies.

Mg2+ −2003 MgO −3791

Li+ −559 LiF −1031
K+ −361 KF −817

The effect of ionic radius on enthalpy change of hydration and

lattice enthalpy
As the radius of an ion increases, its charge density decreases. This results in a
weaker attraction for oppositely charged ions and for the δ+ or δ− charges on
polar molecules such as water. So, an increase in ionic radius leads to less
exothermic values for enthalpy changes of hydration and lattice enthalpies.
This point is neatly illustrated by the enthalpy changes of hydration for Li+
and K+ and the lattice enthalpies of LiF and KF in Table 13.3.

183
 Lattice enthalpy and Born–Haber cycles

Trends in solubility
It is difficult to use enthalpy cycles, like that in Figure 13.15, to account for
trends in the solubilities of ionic compounds for three reasons.
First, the enthalpy change of solution is generally a small difference
between two large enthalpy changes, neither of which can be measured
directly. So, even small errors in estimating trends in the values of lattice
enthalpies and hydration enthalpies can lead to large percentage errors in the
predicted enthalpy changes of solution.
Second, both lattice enthalpies and hydration enthalpies are affected in the
same way, as we have seen, by changes in the size of ions and their charges.
This tends to reduce the likelihood of any clear trends in enthalpy changes of
solution.
Finally, it is clear from the small endothermic value for sodium chloride
that the sign and magnitude of the enthalpy change of solution is not a
reliable guide as to whether or not a solid will dissolve. Other factors must be
taken into account – these are considered in Topic 14.

Test yourself
20 a) Use the equation
energy change = m/g × c/J g−1 K−1 × ΔT/K
to calculate the temperature change when 1 mole of sodium chloride is used
to make 1 dm3 of a solution containing 1.0 mol dm−3 of solute.
(ΔH soln [NaCl(s)] = +3.8 kJ mol−1)
(Assume that the density and specific heat capacity of the solution are the
same as those of water.)
b) Explain how the temperature of the solution will change.
21 a) Use the data sheets on the Dynamic Learning Student website headed
‘Lattice enthalpies of some ionic compounds’ and ‘Enthalpy changes of
hydration’ to calculate the enthalpies of solution of lithium fluoride and lithium
Data 1 Data 2 iodide.
b) Account for the relative values of the lattice enthalpies and hydration
enthalpies of the two compounds in terms of ionic radii.
c) To what extent, if any, can your answers to part a) explain the differences in
the solubilities of the two compounds?
(Solubilities: LiF = 5 × 10−5 mol in 100 g water; LiI = 1.21 mol in 100 g water)
22 Why do you think the lattice enthalpy of magnesium oxide (ΔH lattice [MgO (s)] =
−3791 kJ mol−1) is roughly four times more exothermic than that of sodium
fluoride (ΔH lattice [NaF(s)] = −918 kJ mol−1)?
23 Suggest a reason why the nitrates of Group 1 elements are all soluble in water,
but the sulfates of most Group 2 elements are insoluble.

REVIEW QUESTIONS Extension questions

1 a) Define the term first electron affinity. (3) c) In magnesium iodide, MgI2, the iodide ions are
polarised, but in sodium iodide they are not polarised.
b) The equation below represents the change occurring
during the second electron affinity of nitrogen: i) What is meant by the phrase ‘polarisation
of an ion’? (2)
N−(g) + e− → N2− (g)
ii) State two factors that help to explain the
i) Explain why the second electron affinity for all
polarisation of iodide ions in magnesium
elements is endothermic. (2)
iodide. (2)
ii) Write equations for the first and third electron
affinities of nitrogen. (2)
184
 REVIEW QUESTIONS

2 The following data can be used in a Born–Haber cycle 3 When calcium chloride dissolves in water, the process
for copper(II) iodide, CuI2. can be represented by the equation:
Enthalpy change of atomisation of iodine Ca2+(Cl−)2(s) + aq → Ca2+(aq) + 2Cl−(aq)
ΔH at [ 12 I2(s)] = +107 kJ mol−1
The enthalpy change for this process is called the
Enthalpy change of atomisation of copper, enthalpy change of solution. Its value can be calculated
ΔH at [Cu(s)] = +338 kJ mol−1 from a Born–Haber cycle using the following data:
First ionisation energy of copper, lattice enthalpy of calcium chloride = −2258 kJ mol−1
ΔH i.1 [Cu(g)] = +746 kJ mol−1
enthalpy change of hydration of Ca2+(g) = −1657 kJ mol−1
Second ionisation energy of copper,
enthalpy change of hydration of Cl−(g) = −340 kJ mol−1
ΔH i.2 [Cu(g)] = +1958 kJ mol−1
a) Draw and label the Born–Haber cycle linking the
Electron affinity of iodine,
enthalpy change of solution of calcium chloride
ΔH aff.1 [I(g)] = −295 kJ mol−1
with the enthalpy changes in the data above. (4)
Lattice enthalpy of copper(II) iodide,
b) Use your Born–Haber cycle to calculate the
CuI2(s), ΔH lattice [CuI2(s)] = −963 kJ mol−1
enthalpy change of solution of calcium chloride. (3)
a) The following diagram shows an outline of the
c) What factors will affect the size of the enthalpy
Born–Haber cycle for copper(II) iodide:
change of hydration of Ca2+(g) compared with that
of Li+(g)? (2)
F
Cu2+(g) + 2I–(g) CuI2(s) d) Why are the hydration enthalpies of both anions
and cations negative? (2)
D 4 The lattice enthalpy of rubidium iodide, RbI, can be
E determined indirectly using a Born–Haber cycle.
B
a) Use the data in the table below to construct a
Born–Haber cycle for rubidium iodide. (6)
C
Enthalpy change Energy/kJ mol−1
Formation of rubidium iodide −334
A
Atomisation of rubidium +81
Atomisation of iodine +107
First ionisation energy of rubidium +403
Cu(s) + I2(s)
First electron affinity of iodine −295

i) Write the formulae and state symbols of the species

b) Determine a value for the lattice enthalpy of
that should appear in boxes A, B and C. (3)
rubidium iodide. (2)
ii) Name the enthalpy changes D, E and F. (3)
c) Explain why the lattice enthalpy of lithium iodide,
b) Define the term lattice enthalpy. (2) LiI, is more exothermic than that of rubidium
iodide. (2)
c) Use the diagram and the data supplied to calculate
the enthalpy change of formation of copper(II) iodide. d) Theoretical values for the lattice enthalpies of LiI
Give a sign and units in your answer. (3) and RbI can be calculated by assuming that the
compounds are purely ionic. When this is done, the
d) When the lattice enthalpy of copper(II) iodide is
experimentally determined value of the lattice
calculated from ionic radii and charges, the result is
enthalpy of lithium iodide is greater than the
about 14% smaller than the one obtained from the
calculated value by 21 kJ mol−1, whereas the
Born–Haber cycle.
experimental value for rubidium iodide is greater
i) What does this suggest about the nature of the than the calculated value by only 11 kJ mol−1.
bonding in copper(II) iodide? (1) Explain the difference in these values. (4)
ii) Draw a diagram to show how the smaller copper
ion influences the larger iodide ion. (1)
185
 14 Enthalpy and entropy
Chemists have devised a range of ways of predicting the direction
and extent of chemical changes. They use equilibrium constants
(Topics 11 and 12) and electrode potentials (Topic 15) to explain why
some reactions go while others do not. How are these quantities
related, and is there a more fundamental concept which links them
together? The answer is yes – and the unifying concept is entropy.

Figure 14.1 쑿
Energy can drive change against its
natural direction. Photosynthesis
effectively reverses the changes of
respiration. Leaves on plants harness
energy from the Sun to convert carbon
dioxide and water into carbohydrates.

Figure 14.2 씰
A cheetah hunting its prey in Kenya. The
cheetah gets its energy from respiration
taking advantage of the natural direction
of change. Carbohydrates react with
14.1 Entropy changes
oxygen in muscle cells forming carbon
dioxide and water and giving out energy.
Spontaneous changes
A spontaneous reaction is a reaction which tends to ‘go’ without being driven
by any external agency. Spontaneous reactions are the chemical equivalent of
water flowing downhill. Any reaction that naturally tends to happen is
spontaneous in this sense, even if it is very slow – just as water has a tendency
to flow down a valley even when held up behind a dam. The chemical
equivalent of a dam is a high activation energy for a reaction.

Figure 14.3쑿
Theory shows that the change of
diamond to graphite is spontaneous.
Graphite is more stable than diamond. Figure 14.4쑿
Fortunately for owners of valuable Metals such as magnesium, iron and aluminium react spontaneously with oxygen.
186 jewellery, the change is very, very slow. They are ingredients of fireworks – they burn when heated by the spontaneous
reactions between sulfur, carbon and potassium nitrate in gunpowder.
 Entropy changes

In practice, chemists also use the word ‘spontaneous’ in its everyday sense to
describe reactions which not only tend to go but also go quickly on mixing
the reactants at room temperature. Here is a typical example:
‘The hydrides of silicon catch fire spontaneously in air, unlike methane
which has an ignition temperature of about 500 °C.’
The reaction of methane with oxygen is also spontaneous in the
thermodynamic sense, even at room temperature. However the activation Definition
energy for the reaction is so high that nothing happens until the gas is heated A feasible (or spontaneous) reaction
in air with a flame. is one which naturally tends to
The possible ambiguity in the use of the word ‘spontaneous’ means that happen, even if it is very slow
chemists often prefer an alternative term. They describe a reaction as feasible if because the activation energy is high.
it tends to go naturally.

Test yourself
1 Classify these changes as feasible/fast, feasible/slow or not feasible:
a) ice melting at 5 °C
b) ammonia gas condensing to a liquid at room temperature
c) diamond reacting with oxygen at room temperature
d) water splitting up into hydrogen and oxygen at room temperature
e) sodium reacting with water at room temperature.

Enthalpy changes and feasible reactions

Most reactions that are feasible are also exothermic. They have a negative
standard enthalpy change of reaction. This is such a common pattern that
chemists often use the sign of ΔH to decide whether or not a reaction is likely
to go.
However, some endothermic processes are feasible too. This shows the
limitations of using the enthalpy change to decide the likely direction of
change. One example is the reaction of citric acid with sodium
hydrogencarbonate – the mixture fizzes vigorously while getting colder and
colder. ΔH for this reaction is positive.

Figure 14.5쑿
Alka-Seltzer tablets contain citric acid and sodium hydrogencarbonate. They fizz when
added to water. The reaction of the acid and the hydrogencarbonate is a
spontaneous endothermic reaction.

A more colourful example is the reaction of sulfur dichloride oxide with the
dark red crystals of cobalt(II) chloride. The reaction looks violent and a large
quantity of fuming hydrogen chloride gas bubbles out of the mixture while a
thermometer dipping into the chemicals shows that the temperature falls 187
sharply.
 Enthalpy and entropy

Entropy
Entropy, S, is a thermochemical quantity which makes it possible to decide
whether or not a reaction is feasible – change happens in the direction which
leads to a total increase in entropy. When considering chemical reactions, it is
essential to calculate the total entropy change in two parts – the entropy
change of the system and the entropy change of the surroundings:
ΔStotal = ΔSsystem + ΔSsurroundings
The entropy of a system measures the number of ways, W, of arranging the
molecules involved and sharing out the energy between the molecules.
The relationship between S and W was derived by Ludwig Boltzmann
(1844–1906), the Austrian physicist who was the first person to explain the
laws of thermodynamics in terms of the behaviour of atoms and molecules in
motion:
S = k ln W
where S is the entropy of the system, k the Boltzmann constant and ln W the
natural logarithm of the number of ways of arranging the particles and energy
in the system.
Chemists sometimes describe entropy as a measure of disorder or
randomness. These descriptions have to be interpreted with care because the
disorder refers not only to the arrangement of the particles in space but, much
more significantly, to the numbers of ways of distributing the energy of the
system across all the available energy levels.

Standard molar entropies

Nothing seems to be happening in a closed flask of a gas kept at a constant
temperature. However, kinetic theory tells us that the molecules are in rapid
motion colliding with each other and with the walls of the container. The gas
stays the same while the molecules are constantly rearranged and the energy
redistributed. The ‘number of ways’, W, is large for a gas. Gases generally have
higher entropies than comparable liquids, which have higher entropies than
similar solids.
Figure 14.6씰
The structure of a solid. Solids have
relatively low values for standard molar
entropies. In diamond, the carbon atoms
are held firmly in place by strong, highly
directional covalent bonds – the standard
molar entropy of diamond is low. Lead
has a higher value for its standard molar
entropy because metallic bonds are not
directional – the heavier, larger atoms
can vibrate more freely and share out
their energy in more ways than can
carbon atoms in diamond.

Figure 14.7씰
The structure of a liquid. In general,
liquids have higher standard molar
entropies than comparable solids
because the atoms or molecules are free
to move. There are many more ways of
distributing the particles and energy –
there is more disorder. The standard
molar entropy of mercury is higher than
that of lead. Molecules with more atoms
have higher standard molar entropies
188 because they can vibrate, rotate and
arrange themselves in yet more ways.
 Entropy changes

Figure 14.8쑿
The atoms of a noble gas. Gases have even higher standard molar entropies than
comparable liquids because the atoms or molecules are not only free to move but also
widely spaced. There are even more ways of distributing the particles and energy – the
disorder is even greater. The standard molar entropy of argon is higher than that of
mercury. As with liquids, molecules with more atoms have even higher standard molar
entropies because they can vibrate, rotate and arrange themselves in more ways.

Solids S /J mol−1 K−1 Liquids S /J mol−1 K−1 Gases S /J mol−1 K−1

carbon (diamond) 2.4 mercury 76.0 argon 155
magnesium oxide 26.9 water 69.9 ammonia 192
copper 33.2 ethanol 160 carbon dioxide 214
lead 64.8 benzene 173 propane 270

Table 14.1쑿
Standard molar entropies for selected solids, liquids and gases. Definition
Standard molar entropy, S , is the
Test yourself entropy per mole of a substance under
standard conditions. Chemists use
2 Refer to Table 14.1. Why is the value of the standard molar entropy of: values for standard molar entropies to
a) mercury higher than the value for copper calculate entropy changes, and hence
b) ammonia higher than the value for water to predict the direction and extent of
c) propane higher than the value for argon? chemical change.
3 Which substance in each of the following pairs is expected to have the higher The units for standard molar entropy
standard molar entropy at 298 K? are joules per mole per kelvin
a) Br2(l), Br2(g) (J mol−1 K−1). Note that the units are
b) H2O(s), H2O(l) joules and not kilojoules.
c) HF(g), NH3(g)
d) CH4(g), C2H6(g)
e) NaCl(s), NaCl(aq)
f) ethene, poly(ethene)
g) pentene gas, cyclopentane gas.

The entropy change of the system

Tables of standard molar entropies make it possible to calculate the entropy
change of a system of chemicals during a reaction.
S system = the sum of the standard − the sum of the standard
molar entropies molar entropies
of the products of the reactants

189
 Enthalpy and entropy

Worked example
Calculate the entropy change of the system, S system , in the synthesis of
ammonia from nitrogen and hydrogen. Comment on the value.
Notes on the method
Write the balanced equation for the reaction.
Look up the standard molar entropies in the data table, taking careful note of
Data the units.
Answer
The balanced equation is:
N2(g) + 3H2(g) → 2NH3(g)
Sum of the standard molar entropies of the products = 2 × S [NH3(g)]
= 2 × 192.4 J mol−1 K−1 = 384.8 J mol−1 K−1
Sum of the standard molar entropies of the reactants
= S [N2(g)] + 3S [H2(g)]
= 191.6 J mol−1 K−1 + (3 × 130.6 J mol−1 K−1) = 583.4 J mol−1 K−1
Tutorial
ΔS system = 384.8 J mol−1 K−1 − 583.4 J mol−1 K−1
= −198.6 J mol−1 K−1
Test yourself This shows that the entropy of the system decreases when nitrogen and
hydrogen combine to form ammonia. This is not surprising since the change
4 Without doing any calculations,
predict whether the entropy of the halves the number of molecules, so the amount of gas decreases.
system increases or decreases as a
result of these changes:
a) KCl(s) + aq → KCl(aq) The entropy change of the surroundings
b) H2O(l) → H2O(g) It is not enough to consider just the entropy of the system. What matters is
c) Mg(s) + Cl2(g) → MgCl2(s) the total entropy change, which is the sum of the entropy changes of the
d) N2O4(g) → 2NO2(g) system and the entropy change in the surroundings.
e) NaHCO3(s) + HCl(aq) →
NaCl(aq) + H2O(l) + CO2(g) ΔS total = ΔS system + ΔS surroundings
5 Use values from the data sheet to It turns out that the entropy change of the surroundings during a chemical
calculate the entropy change of the reaction is determined by the size of the enthalpy change, ΔH, and the
system for the catalytic reaction of temperature, T. The relationship is:
ammonia with oxygen to form nitric
−ΔH
oxide, NO, and steam. Comment ΔSsurroundings =
on the value.
T
The minus sign is included because the entropy change is larger as more
energy is transferred to the surroundings. For an exothermic reaction, which
transfers energy to the surroundings, ΔH is negative, so −ΔH is positive.
What this relationship shows is that the more energy transferred to the
surroundings by an exothermic process, the larger the increase in the entropy
of the surroundings. It also shows that, for a given quantity of energy, the
increase in entropy is greater when the surroundings are cool than when they
are hot. Adding energy to molecules in a cool system has a proportionately
greater effect on the number of ways of distributing matter and energy than
adding the same quantity of energy to a system that is already very hot.
Bearing in mind that a reaction is only feasible if the total entropy change,
ΔStotal, is positive:
● Most exothermic reactions tend to go because at about room temperature
the value of −ΔH/T is much larger and more positive than ΔSsystem, which
means that ΔStotal is positive.
● An endothermic reaction can be feasible so long as the increase in the
Figure 14.9쑿 entropy of the system is greater than the decrease in the entropy of the
The thermite reaction is highly exothermic surroundings.
– it gives out a great deal of energy to its ● A reaction which does not tend to go at room temperature may become
190 surroundings. The entropy change in the feasible as the temperature rises because ΔSsurroundings decreases in magnitude
surroundings is large and positive. as T increases.
 Free energy

14.2 Free energy

A chemical change is feasible if the total entropy change is positive. There is
no doubt about this. The problem is that using entropy to decide on the
direction change involves three steps – first, working out the entropy change
of the system, then working out the entropy change of the surroundings, and
then putting the two together to calculate the total entropy change. This can
be laborious and chemists are grateful to the American physicist Willard
Gibbs who discovered an easier way of unifying all that chemists know about
predicting the extent and direction of change.

Free energy and entropy

Willard Gibbs (1839–1903) was the first to define the thermochemical
quantity ‘free energy’. The symbol for a free energy change is ΔG. If ΔG is
negative then the reaction is feasible and tends to go.
The advantage of ΔG values for chemists is that tables of standard free
energies of formation can be used to calculate the standard free energy change
for any reaction. The calculations follow exactly the same steps as the
calculations to calculate standard enthalpy changes for reactions from
standard enthalpies of formation.
The quantity ‘free energy’ is closely related to the idea of entropy and can
be thought of as the ‘total entropy change’ in disguise. Willard Gibbs defined
free energy as:
ΔG = −TΔS total
Given that:
ΔS total = ΔS system + ΔS surroundings
and that for a change at constant temperature and pressure:
−ΔH
ΔS surroundings = T

It follows that:
ΔS total = ΔS system + ( −ΔH
T )
Hence, −TΔS total = −TΔS system + ΔH
From Gibb’s definition this becomes ΔG = ΔH − TΔS system
The great advantage of this equation is that all the terms refer to the system,
and so it is no longer necessary to calculate changes in the surroundings.
Given that this is the case, the equation is usually written as below, with the
understanding that the entropy change is ΔS system:
ΔG = ΔH − TΔS
Table 14.2 summarises the implications of this important relationship.

Enthalpy change Entropy change Is the reaction feasible?

of the system
exothermic (ΔH –ve) increase (ΔS +ve) yes, ΔG is –ve
exothermic (ΔH –ve) decrease (ΔS –ve) yes, if the number value of ΔH is
greater than the magnitude of TΔS
endothermic (ΔH +ve) increase (ΔS +ve) yes, if the magnitude of TΔS is
greater than the number value of ΔH
endothermic (ΔH +ve) decrease (ΔS –ve) no, ΔG is +ve

Table 14.2쑿 191

 Enthalpy and entropy

The possibilities listed in Table 14.2 show why chemists sometimes say that
the feasibility of a reaction depends on the balance between the enthalpy
change and the entropy change for the process.
Table 14.2 also shows that a change that is not feasible at a lower
temperature may become feasible if the temperature increases. Generally the
values of ΔH and ΔS do not change markedly with temperature, so it is
possible to estimate the temperature at which a reaction which is not feasible
at room temperature becomes feasible at a higher temperature.
Full data is not available for all reactions so it is not always possible to
calculate the free energy change. At relatively low temperatures, the TΔS
Tutorial term is often relatively small compared to the enthalpy change so that
ΔG ≈ ΔH .
This means that chemists can often use the sign of ΔH as a guide to
feasibility. This can be misleading if the magnitude of the entropy change of
the reaction system is large. Also, the approximation becomes less justified at
higher temperatures when T is bigger and so the magnitude of TΔS is bigger.

Test yourself
6 Can an exothermic reaction which is not feasible at room temperature become
feasible at a higher temperature if the entropy change of the reaction is negative?
7 a) Calculate ΔS and ΔH for the synthesis of methanol from carbon
monoxide and hydrogen, taking the information you need from the data
Data sheets on the Dynamic Learning Student website.
b) Work out the temperature at which the synthesis ceases to be feasible.
8 Consider the reaction of magnesium with oxygen:
2Mg(s) + O2(g) → 2MgO(s) ΔH = −602 kJ mol−1; ΔS = −217 J mol−1 K−1
a) Why does the entropy of the system decrease?
b) Show why the reaction of magnesium with oxygen is feasible at 298 K
despite the decrease in the entropy.
9 Consider the reduction of iron(III) oxide by carbon:
2Fe2O3(s) + 3C(s) → 4Fe(s) + 3CO2(g) ΔH = +468 kJ mol−1;
ΔS = +558 J mol−1 K−1
a) Why does the entropy of the system increase for this reaction?
b) Show that the reaction is not feasible at room temperature (298 K).
c) Assuming that ΔH and ΔS do not vary with temperature, estimate the
temperature at which the decomposition becomes feasible.

How far and in which direction?

Gibbs’s concept of free energy makes it possible to unify all the means that
chemists use to predict the extent and direction of change.
For many reactions, such as acid–base reactions, the easiest guide to the
direction and extent of change is the equilibrium constant, Kc. It is possible to
show that the standard free energy change is related to the value of the
equilibrium constant:
ΔG ∝ −log Kc
For redox reactions, standard electrode potentials offer an alternative way of
deciding whether or not reactions tend to go (see Topic 15). The free energy
change for a redox reaction and a corresponding cell e.m.f. are closely related:
ΔG ∝ −E cell
So, if the cell e.m.f is positive the redox reaction in the cell will tend to go.
What this shows is that ΔG , E cell and Kc values can all answer the same
questions for a reaction:
● will the reaction go?
● how far will it go?
192
 Free energy

In practice, chemists use the quantity which is most convenient to measure.

Knowing the value of one of the three quantities it is possible to calculate the
other two.
However, it is always important to bear in mind that even if a reaction is
feasible it may be very slow.

Stable or inert?
The study of energetics (thermochemistry) and rates of reaction (kinetics)
helps to explain why some chemicals are stable while others react rapidly.
Compounds are stable if they have no tendency to decompose into their
elements or change into other compounds. For example, magnesium oxide has
no tendency to split up into magnesium and oxygen. However, a compound
which is stable at room temperature and pressure may become more or less
stable as conditions change.
Chemists often use standard enthalpy change as an indicator of stability.
Strictly they should use standard free energy, ΔG f , values – but in many cases
ΔG f ≈ ΔH f .
A chemical is inert if it has no tendency to react even when the reaction is
feasible. The lighter noble gases helium and neon live up to the original name
for Group 8 elements – they are inert towards all other reagents. Figure 14.10쑿
Roofer fitting copper to a roof in Boston,
USA. Copper in air and water – stable or
inert?

Definitions
A chemical, or mixture of chemicals, is
thermodynamically stable if there is
no tendency for a reaction to occur.
Figure 14.11씱 A positive free energy change, ΔG,
Coils of aluminium at a processing plant. Aluminium in air – stable or inert? indicates that the reaction does not
tend to occur.
Nitrogen is a relatively unreactive gas which can be used to create an ‘inert’ Kinetic inertness is a term used
atmosphere free of oxygen (which is much more reactive). However, nitrogen is when a reaction does not go even
not inert in all circumstances. It reacts with hydrogen in the Haber process to though the reaction appears to be
form ammonia, and with oxygen at high temperatures to form nitrogen oxides. feasible. The reaction should tend to
A compound such as the gas N2O, for example, is thermodynamically go according to its equilibrium
unstable but it continues to exist at room temperature because it is kinetically constant, or its standard electrode
inert (ΔH f = +82 kJ mol−1 and ΔG f = +104 kJ mol−1). The free energy change potential, or its free energy change –
for the decomposition reaction is negative, so the compound tends to yet nothing happens. There is no
change because the rate of reaction is
decompose into its elements, but the rate is very slow under normal conditions.
too slow to be noticeable. There is a
Examples of kinetic inertness are: barrier preventing change – usually a
● a mixture of hydrogen and oxygen at room temperature high activation energy. The compound
● a solution of hydrogen peroxide in the absence of a catalyst or mixture is inert.
● aluminium metal in dilute hydrochloric acid. 193
 Enthalpy and entropy

‘Kinetic stability’ is a term sometimes used for ‘kinetic inertness’. However, it

helps to make a sharp distinction between two quite different types of
explanation. For clarity, chemists refer to:
● systems with no tendency to react as ‘stable’
● systems which should react but do not do so for a rate (kinetic) reason, as
‘inert’.

ΔG (≈ ΔH ) Activation Change
energy observed
positive high no reaction reactants stable relative to products
negative high no reaction reactants unstable relative to products
but kinetically inert
Test yourself positive low no reaction reactants stable relative to products

10 Suggest examples of reactions to negative low fast reaction reactants unstable relative to products
illustrate each of the four
Table 14.3쑿
possibilities in Table 14.3.
11 Draw a reaction profile to show the Sometimes there is no tendency for a reaction to go because the reactants are
energy changes from reactants to stable. This is so if the free energy change for the reaction is positive.
products for reactants which are Sometimes there is no reaction even though thermochemistry suggests that it
thermodynamically unstable relative should go. The free energy change is negative, so the change is feasible, but a
to the products, but kinetically inert.
high activation energy means that the rate of reaction is very, very slow.

Activity

The thermal stability of Group 2 carbonates

The decomposition of Group 2 metal carbonates is used on a large
scale to make oxides such as magnesium and calcium oxides.
The carbonates of Group 2 metals do not decompose at room
temperature. They do decompose on heating:
MgCO3(s) → MgO(s) + CO2(g)
ΔH = +117 kJ mol−1; ΔS = +175 J mol−1 K−1
BaCO3(s) → BaO(s) + CO2(g)
ΔH = +268 kJ mol−1; ΔS = +172 J mol−1 K−1
1 Why does the entropy increase when a Group 2 carbonate
decomposes?
2 a) Calculate the free energy change for the room temperature Figure 14.12 쑿
Crystals of dolomite (foreground) and
(298 K) decomposition of:
magnesite (background) from Brazil.
i) magnesium carbonate Dolomite is a calcium–magnesium
carbonate rock. Magnesite is pure
ii) barium carbonate. magnesium carbonate. Large crystals
of magnesite are rare.
b) Are these two compounds stable or unstable relative to
decomposition into their oxide and carbon dioxide at room
temperature?

194
 Free energy

3 Assuming that ΔH and ΔS for the reactions do not vary with

temperature, estimate the temperatures at which the two
decomposition reactions become feasible.
4 Down Group 2, do the metal carbonates become more stable or
less stable relative to decomposition into the oxide and carbon
dioxide?
Chemists seek to explain the trend in thermal stability of the Group 2
carbonates by analysing the energy changes.

enthalpy change Figure 14.13씱

2+ for breaking An energy cycle for the
M (g) + CO32–(g) 2+ 2–
M (g) + O (g) + CO2(g)
bonds in the decomposition of the carbonate
carbonate ion of a Group 2 metal, M.
lattice enthalpy for
the metal carbonate lattice enthalpy
for the metal oxide

enthalpy change
for the decomposition
M2+CO32–(s) M2+O2–(s) + CO2(g)
of the metal carbonate
to the metal oxide

Figure 14.14씱
2– Decomposition of the Group 2
CO3
O2– carbonate into its oxide.

CO32– M2+ CO32– O2– M2+ O2–

2–
O2–
CO3

5 Which of the enthalpy changes in Figure 14.13 are exothermic

and which are endothermic?
6 Why is the lattice enthalpy of magnesium oxide more negative
than the lattice enthalpy of barium oxide?
7 Why is the lattice enthalpy of magnesium oxide more negative
than the lattice enthalpy of magnesium carbonate?
8 Why is the difference between the lattice enthalpies of the metal
carbonates and oxides significant in explaining the trend in
thermal stability of the Group 2 carbonates?
9 How does the trend in thermal stability of the metal carbonates
down Group 2 relate to the polarising power of the metal ions?

195
 REVIEW QUESTIONS Extension questions

1 The graph below shows how the entropy of water c) Calculate the standard entropy change for the
changes from 0 K to 450 K. reduction reaction. (3)
d) i) Calculate the standard free energy change for
the reduction at 298 K. (2)
Entropy/J mol–1 K–1

ii) What does you answer to part d) i) tell you

about the feasibility of the reaction at 298 K?(1)
e) Calculate the minimum temperature at which
the reduction of aluminium oxide by carbon
becomes feasible. (2)
f) Suggest a reason why the reaction between
0 aluminium oxide and carbon does not happen to a
0 T1 T2
significant extent until the temperature is about 1000
Temperature/K
degrees higher than your answer to part d). (1)
a) Explain why the molar entropy of water 3 Carbon monoxide is one of the products when
is zero at 0 K. (2) methane burns in a limited supply of air.
b) Account for the entropy changes at temperatures CH4(g) + 32 O2(g) → CO(g) + 2H2O(g)
T1 and T2. Explain why one is bigger than the ΔH = −519 kJ mol−1; ΔS = +82 J mol−1 K−1
other. (3) a) Calculate ΔG for the reaction. (2)
c) i) Why does ΔG = 0 kJ mol−1 for the change of b) i) Plot a graph to show how ΔG for this reaction
water to steam at 373 K and 1 atmosphere varies with temperature, using your answer to
pressure? (2) part a) and these values: (2)
ii) The enthalpy change of vaporisation of water is
Temperature/K 1500 3000 4000
41.1 kJ mol−1 at 373 K. Calculate the value of
ΔS for the conversion of water into steam at ΔG/kJ mol−1 −640 −765 −845
373 K and 1 atmosphere pressure. (3)
ii) From the shape of the line on the graph, what
2 Electrolysis is usually used to extract aluminium metal. can you conclude about the variation with
In principle, it should be possible to extract the metal temperature of ΔS for this reaction? (2)
by heating its oxide with carbon. Use the data in the
table to answer the questions. c) i) Is the reaction of methane with oxygen to form
carbon monoxide and steam feasible in the
Al2O3(s) C(s) Al(s) CO(g) temperature range 200 K to 3000 K? (2)
ΔH f /kJ mol−1 −1669 0 0 −111 ii) Why does methane not burn in air at 298 K? (2)
S /J mol−1 K−1 50.9 5.7 28.3 198 d) Sooty carbon is another of the products when
methane burns in a limited supply of air.
a) Write the equation for the reduction of aluminium CH4(g) + O2(g) → C(s) + 2H2O(g)
oxide by carbon, assuming that the carbon is ΔS = −8 J mol−1 K−1
converted to carbon monoxide. (1)
How do you account for the difference in the values
b) Calculate the standard enthalpy change for the for ΔS for the reaction producing carbon
reduction reaction. (3) monoxide and the reaction that forms soot? (4)

196
15 Redox, electrode potentials and fuel cells
Redox reactions are very important in the natural environment, in
living things and in modern technology. It should be no surprise that
the Earth, with its oxygen-containing atmosphere, has an extensive
range of redox chemistry.
Redox reactions involve electron transfer and chemists have
developed the concept of electrode potentials in electrochemical
cells in order to explain redox changes more fully. Some
electrochemical cells have great practical and technological
importance, while others, particularly fuel cells, are becoming a
serious alternative to oil-based fuels for vehicles. Measurements of
the electrode potentials of cells help us to assess the feasibility and
likelihood of redox reactions.

15.1 Redox reactions

About one million million (1012) moles of oxygen are removed from the
atmosphere every year in the process of oxidising ions such as iron(II), Fe2+,
from weathered rocks, and molecules such as hydrogen sulfide, carbon
monoxide and methane in volcanic gases.
Figure 15.1씱
Volcanoes release millions of tonnes of
reducing gases into the atmosphere,
where they react with oxygen. This photo
shows Mount St Helens in British
Columbia erupting in 1980.

Redox reactions are also involved in the metabolic pathways of respiration.

These pathways produce adenosine triphosphate (ATP). ATP transfers the
energy released during the oxidation of food into movement, growth and all
the other reactions in living things which need a source of energy.
In addition, the voltages of chemical cells are obtained from the energy of
redox reactions, and redox is also involved in manufacturing processes that
use electrolysis to make products such as chlorine and aluminium.

Definitions of redox
Descriptions and theories of oxidation and reduction have developed over the
years and, although there are now several definitions of redox, oxidation and
reduction always occur together. 197
 Redox, electrode potentials and fuel cells

From your AS studies, you should recall that oxidation originally meant
addition of oxygen, but the term now covers all reactions in which atoms,
molecules or ions lose electrons. Chemists have further extended the
definition of oxidation to cover reactions which do not appear to involve
electron transfer by defining oxidation as a change in which the oxidation
number of an element becomes more positive, or less negative.
Similarly, reduction originally meant removal of oxygen, but the term now
covers all reactions in which atoms, molecules or ions gain electrons. Defining
reduction as a change in which the oxidation number of an element becomes
more negative, or less positive, further extends the definitions of reduction
like that of oxidation.

Oxidation states and oxidation numbers

Most elements in the p block and d block of the periodic table form
compounds in which their atoms have different oxidation states. Displaying
the compounds of an element on an oxidation state diagram provides a ‘map’
of its chemistry and shows the different oxidation numbers that it can have.
Figure 15.2 shows such a map for sulfur.

+6 SO3 H2SO4 SO42–

+4 SO2 H2SO3 SO32–

+2

0 S

Definitions –2 H2S S2–

Redox stands for reduction +
oxidation.
Figure 15.2쑿
Oxidation involves the loss of The oxidation numbers of sulfur in its different oxidation states.
electrons, or an increase in oxidation
number. There are strict rules for assigning oxidation numbers and these are shown
Reduction involves the gain of below.
electrons, or a decrease in oxidation
number. Oxidation number rules
Remember the mnemonic OILRIG – 1 The oxidation number of the atoms in uncombined elements is zero.
Oxidation Is Loss; Reduction Is Gain 2 In simple ions, the oxidation number of the element is the charge on the ion.
of electrons.
3 In neutral molecules, the sum of the oxidation numbers of the constituent
An oxidation number is a number elements is zero.
assigned to an atom or ion to
describe its relative state of oxidation 4 In ions containing two or more elements, the charge on the ion is the sum of
or reduction. the oxidation numbers.
5 In any compound, the more electronegative element has a negative oxidation
number and the less electronegative element has a positive oxidation number.
6 The oxidation number of hydrogen in all its compounds is +1, except in metal
hydrides in which it is −1.
7 The oxidation number of oxygen in all its compounds is –2, except in
peroxides in which it is −1 and OF2 in which it is +2.

198
 Redox reactions

Half-reactions and half-equations

Half-reactions are reactions which relate to one half (either the oxidation half
or the reduction half ) of a redox reaction. Of course, no half-reaction can
take place without another half-reaction to complete both the oxidation and
reduction halves of a redox reaction.
Half-reactions can be summarised by half-equations – these are ionic
equations used to describe either the gain or the loss of electrons during a
redox reaction. Half-equations help to show what is happening during a redox
reaction. In a similar fashion to half-reactions, two half-equations can
combine to give the full equation for a redox reaction.
For example, zinc metal can reduce Cu2+ ions in copper(II) sulfate solution
forming copper metal and Zn2+ ions in zinc sulfate solution. This can be
shown as two half-equations:
● electron loss (oxidation); Zn(s) → Zn2+(aq) + 2e−
● electron gain (reduction); Cu2+(aq) + 2e− → Cu(s)
Balancing the number of electrons lost by Zn with the number gained by
Cu2+(aq), we can add the two half-equations to get the full equation:
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

Test yourself
1 Describe, in terms of gain or loss of electrons, the redox reactions in these
examples:
a) the changes at the electrodes during the manufacture of aluminium from
molten (liquid) aluminium oxide
b) the reaction of iron with chlorine to form iron(III) chloride.
2 Explain why the oxidation number of oxygen is:
a) +2 in OF2
b) −1 in peroxides such as Na2O2.
3 State the changes in oxidation number when concentrated sulfuric acid reacts
with potassium bromide:
4KBr(s) + 2H2SO4(aq) → K2SO4(aq) + K2SO3(aq) + Br2(aq) + 2HBr(aq) + H2O(l)
4 What is the oxidation number of each element in:
a) KIO3
b) NO3−
c) H2O2
d) SF6
e) NaH?
5 Which sulfur compounds in Figure 15.2 can:
a) act as an oxidising agent or as a reducing agent depending on the
conditions
b) only act as an oxidising agent
c) only act as a reducing agent?
6 Draw a chart similar to Figure 15.2 to show the main oxidation states of:
a) nitrogen
b) chlorine.
7 Are the named elements oxidised or reduced in the following conversions:
a) magnesium to magnesium sulfate
b) iodine to aluminium iodide
c) hydrogen to lithium hydride
d) iodine to iodine monochloride, ICl?

199
 Redox, electrode potentials and fuel cells

Activity

Redox reactions in the Space Shuttle

Unlike most vehicles on Earth, spacecraft must carry oxidising
agents as well as fuels. The mixtures of fuels plus oxidising agents
are called propellants.
In order to launch the Space Shuttle from ground level into the
Earth’s upper atmosphere, a solid propellant mixture of powdered
aluminium and ammonium chlorate(VII), NH4ClO4 is used. The
reaction involved is:
3Al(s) + 3NH4ClO4(s) → Al2O3(s) + AlCl3(s) + 3NO(g) + 6H2O(g)
1 What is:
a) the fuel;
b) the oxidising agent in the solid propellant?
2 What are the oxidation numbers of each element in NH4ClO4?
3 a) Which elements are oxidised in the reaction? Figure 15.3 쑿
The Space Shuttle Endeavour takes off
b) State the change in oxidation numbers of these elements.
on its journey to the International
4 Which element is reduced in the reaction, and what is the Space Station.
change in its oxidation number?
5 What actually propels the Space Shuttle?
Propulsion of the Shuttle from the upper atmosphere into orbit is
achieved using a mixture of liquid hydrogen and liquid oxygen. Once
the hydrogen and oxygen are ignited, they continue to vaporise and
burn continuously producing a clean water-vapour exhaust.
6 Write an equation for the combustion of liquid hydrogen and
oxygen during the second stage.
Once in orbit, a propulsion system is needed for manoeuvrability –
one in which the fuel and oxidising agent ignite spontaneously on
mixing and which can be readily started and stopped.
In this stage, the fuel is liquid methylhydrazine (CH3NHNH2) with
liquid dinitrogen tetroxide (N2O4) as the oxidiser. The reaction
produces water vapour, carbon dioxide and nitrogen.
7 Write a balanced equation for the reaction between CH3NHNH2
and N2O4 in this stage.
8 Explain why CH3NHNH2 acts as the reducing agent and why
N2O4 acts as the oxidising agent during the reaction.

200
 Oxidising agents and reducing agents

15.2 Oxidising agents and reducing agents

Oxidising agents (oxidants) are chemical reagents that can oxidise other
substances. They do this either by taking electrons away from these substances
or by increasing their oxidation number. Common oxidising agents include
oxygen, chlorine, bromine, hydrogen peroxide, the manganate(VII) ion in
potassium manganate(VII) and the dichromate(VI) ion in potassium or sodium
dichromate(VI).

2 × decrease in oxidation
number of –3
Cr2O72–(aq) + 14H+(aq) + 6e– 2Cr3+(aq) + 7H2O(l)

6Fe2+(aq) 6Fe3+(aq) + 6e–

6 × increase
in oxidation
number of +1

Figure 15.4쑿
Dichromate(VI) ions act as oxidising agents by taking electrons from iron(II) ions in acid
solution. An oxidising agent is itself reduced when it reacts.

Some reagents change colour when they are oxidised and this makes them Note
useful for detecting oxidising agents. For example, a colourless solution of
Iodine is only very slightly soluble in
iodide ions is oxidised to iodine, which turns the solution to a yellow–brown water, but it dissolves in a solution
colour: containing iodide ions to form triiodide
2I− (aq) → I2(aq) + 2e− ions, I3− (aq).
I2(s) + I− (aq) → I3−(aq)
electrons taken by the oxidising agent. A reagent labelled ‘iodine solution’ is
normally I2(s) in KI(aq) which forms
This can be a very sensitive test if starch is also present because starch forms
KI3(aq). The I3− (aq) ion is yellow–
an intense blue–black colour with iodine. Moistened starch–iodide paper can brown, which explains the colour
detect oxidising gases such as chlorine and bromine vapour. change when iodine is produced from
Reducing agents (reductants) are chemical reagents that can reduce other iodide ions.
substances. They do this either by giving electrons to these substances or by
reducing their oxidation number. Common reducing agents include metals Definitions
such as zinc and iron (often with acid), sulfite ions (SO32−), iron(II) ions and
Oxidising agents (oxidants) accept
iodide ions.
electrons and are reduced when they
2 × decrease in oxidation react.
number of –5 Reducing agents (reductants) give up
2MnO4–(aq) + 16H+(aq) + 10e– 2Mn2+(aq) + 8H2O(l) electrons and are oxidised when they
react.

5SO32–(aq) + 5H2O(l) 5SO42–(aq) + 10H+(aq) + 10e–

5 × increase
in oxidation
number of +2
Figure 15.5쑿
Sulfite ions act as reducing agents by giving electrons to manganate(VII) ions. A
reducing agent is itself oxidised when it reacts

201
 Redox, electrode potentials and fuel cells

Some reagents change colour when they are reduced and this makes them
useful for detecting reducing agents (Figures 15.6 and 15.7).

Figure 15.6쑿 Figure 15.7쑿

A test for reducing agents. Another test for reducing agents.
The test – add a solution of purple The test – add orange dichromate(VI)
potassium manganate(VII) acidified with solution acidified with dilute sulfuric acid
dilute sulfuric acid to the reducing agent. to the reducing agent.
The result – the purple solution turns The result – the orange solution turns
colourless as purple MnO4− ions are green as orange Cr2O72− ions are
reduced to very pale pink Mn2+ ions. reduced to green Cr3+ ions.

15.3 Constructing redox equations

The easiest way to write a balanced equation for a redox reaction is to
combine the relevant half-equations. Just write the half-equations for the
reactants involved and then balance the number of electrons given up by the
reducing agent with those taken by the oxidising agent.

Worked example
Construct a balanced equation for the redox reaction between acidified
potassium manganate(VII) and hydrogen peroxide.
Answer
Step 1: Write the relevant half-equations:
MnO4− + 8H+ + 5e−k→ Mn2+ + 4H2O
H2O2k→ O2 + 2H+ + 2e−
(Note that the oxygen in oxoanions, such as MnO4− and Cr2O72−, usually gets
converted to water by H+ ions in the acid solution, while the Mn and Cr in
the oxoanions are converted to stable simple ions.)
Step 2: Balance the number of electrons given up by the reducing agent with
those taken by the oxidising agent. In this case, we need to multiply one half-
equation by 5 and the other by 2 so that 10 electrons are given up and then
taken:
2MnO4− + 16H+ + 10e−k→ 2Mn2+ + 8H2O
5H2O2k→ 5O2 + 10H+ + 10e−
Step 3: Add the two half-equations to get the full equation. When you do
this the electrons cancel and, in this particular case, some of the H+ ions can
be cancelled as well.
2MnO4− + 6H+ + 5H2O2k→ 2Mn2+ + 8H2O + 5O2
202
 Constructing redox equations

Oxidation numbers can also help in the construction of redox equations. In Test yourself
fact, oxidation numbers can be used even when you don’t know the relevant
half-equations, provided that you do know the formulae of the atoms, ions and 8 Write half-equations to show the
molecules involved in the reaction. We can illustrate this in the following following reactants acting as
worked example. oxidising agents:
a) Fe3+(aq)
Worked example b) Br2(aq)
Construct a balanced equation for the oxidation of iron(II) ions by hydrogen c) H2O2(aq) in acid solution.
peroxide in acid solution. 9 Write half-equations to show the
following reactants acting as
Notes on the method reducing agents:
The key to this method is to set the decrease in oxidation number of the a) Zn(s)
element reduced equal to the increase in oxidation number of the element b) I−(aq)
oxidised. c) Fe2+(aq).
10 Explain why moist starch–iodide
Answer paper can be used as a very
Step 1: Write the formulae of the atoms, ions and molecules involved in the sensitive test for chlorine.
reaction. 11 a) Write the half-equations
involved in the reaction between
H2O2 + H+ + Fe2+ → H2O + Fe3+ hydrogen peroxide and iron(II)
Step 2: Identify the elements which change in oxidation number and the sulfate in acid solution.
extent of change. b) Write a full redox equation for
the reaction involved.
change of –1 in c) Describe the change you would
each of two O see in the solution when the
reaction occurs.
H2O2 + H+ + Fe2+ → H2O + Fe3+ d) How many moles of iron(II)
sulfate react with 1 mole of
change of +1 H2O2?
in one Fe 12 a) Write the half-equations
involved when dichromate(VI)
Step 3: Balance the equation so that the overall decrease in oxidation number ions in acid solution react with
of one element equals the overall increase in oxidation number of the other. sulfite ions, SO32−, to form
In this example, the overall decrease in oxygen is 2 × −1 = −2. So, this chromium(III) ions and sulfate
ions, SO42−.
must be balanced by two Fe2+ ions each increasing their oxidation number by
b) Write a full, balanced redox
+1 (2 × +1 = +2): equation for the reaction.
H2O2 + H+ + 2Fe2+ → H2O + 2Fe3+ c) Describe the change you would
see in the solution when the
Step 4: Balance for oxygen and hydrogen, if necessary. reaction occurs.
In this case, the two oxygen atoms of the H2O2 molecule form two d) How many moles of sulfite react
molecules of water and this requires two H+ ions to balance hydrogen on both with one mole of dichromate(VI)?
sides of the equation:
H2O2 + 2H+ + 2Fe2+ → 2H2O + 2Fe3+
Step 5: Finally, check that the overall charges on each side of the equation
balance and then add state symbols.
The net charge on the left is 6+, which is the same as that on the right.
After adding state symbols, the final equation is:
H2O2(aq) + 2H+(aq) + 2Fe2+(aq) → 2H2O(l) + 2Fe3+(aq)

Test yourself
13 Write balanced equations for each of the following redox reactions:
a) manganese(IV) oxide with hydrochloric acid to form manganese(II) ions
and chlorine
b) copper metal with nitrate ions, NO3−, in nitric acid to form copper(II) ions and
nitrogen dioxide gas, NO2.
203
 Redox, electrode potentials and fuel cells

15.4 Electrode potentials

Test yourself Redox reactions involve the transfer of electrons from a reducing agent to an
oxidising agent. The electron transfer can be shown by writing half-equations.
14 Write two ionic half-equations and So, for example, when zinc is added to copper(II) sulfate solution, Zn atoms
the overall balanced equation for give up electrons forming Zn2+ ions. At the same time, the electrons are
each of the following redox
transferred to Cu2+ ions, which form Cu atoms.
reactions. In each example, state
which atom, ion or molecule is
The two half-equations for the reaction are:
oxidised and which is reduced. Zn(s) → Zn2+(aq) + 2e−
a) magnesium metal with copper(II)
sulfate solution electron transfer
b) aqueous chlorine with a solution
Cu2+ (aq) + 2e → Cu(s)
−
of potassium bromide
c) a solution of silver nitrate with The overall balanced equation is:
copper metal.
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

Electrochemical cells
Instead of mixing two reagents, it is possible to carry out a redox reaction in
an electrochemical cell so that the electron transfer takes place along a wire
connecting the two electrodes. This harnesses the energy from the redox
reaction to produce an electrical potential difference (voltage).
One of the first useable electrochemical cells was based on the reaction of
zinc metal with aqueous copper(II) ions (Figure 15.8). In this cell, zinc is
oxidised to zinc ions as copper(II) ions are reduced to copper metal:
Zn(s) → Zn2+(aq) + 2e−
Cu2+(aq) + 2e− → Cu(s)

high resistance voltmeter

V

zinc strip copper strip

salt bridge

solution of Zn2+(aq) solution of Cu2+(aq)

(1mol dm–3) (1mol dm–3)

Figure 15.8쑿
An electrochemical cell based on the reaction of zinc metal with aqueous copper(II)
ions. Electrons flow from the negative zinc electrode to the positive copper electrode
through the external circuit.

In electrochemical cells, the two half-reactions happen in separate half-cells.

The electrons flow from one cell to the other through a wire connecting the
electrodes. A salt bridge connecting the two solutions completes the electrical
circuit. The salt bridge makes an electrical connection between the two
halves of the cell by allowing ions to flow while preventing the two solutions
from mixing.
204
 Electrode potentials

At its simplest, a salt bridge consists of a strip of filter paper soaked in potassium Definition
nitrate solution and folded over each of the two beakers. All potassium salts and The cell potential or e.m.f. measures
all nitrates are soluble, so the potassium nitrate in the salt bridge does not form the maximum ‘voltage’ produced by
precipitates with any of the ions in the half-cells. In more permanent cells, a salt an electrochemical cell.
bridge may consist of a porous solid such as sintered glass. The symbol for cell potential is E and
Chemists measure the tendency for the current to flow in the external its SI unit is the volt (V). The cell
circuit by using a high-resistance voltmeter to measure the maximum cell potential (e.m.f.) is the energy
voltage when no current is flowing. transferred in joules per coulomb of
In Figure 15.8, electrons flow out of the zinc electrode (negative) through charge flowing through a circuit
the external circuit to the copper electrode (positive). The maximum voltage connected to a cell. Cell potentials are
at a maximum when no current flows
of the cell, usually called the cell potential or the electromotive force (e.m.f.),
because under these conditions no
is 1.10 V under standard conditions. energy is lost due to the internal
resistance of the cell as the current
Standard conditions flows.
In order to compare the voltages (cell potentials) developed by different
electrochemical cells, scientists carry out the measurements under standard
conditions. These standard conditions for electrochemical measurements are the
same as those for thermochemical measurements that we met during the AS
course. They are:
● temperature 298 K (25 °C)
● gases at a pressure of 1 atmosphere (1.013 × 105 Pa ≈ 100 kPa)
● solutions at a concentration of 1.0 mol dm−3.
Chemists have also developed a convenient shorthand, called a cell diagram, for
describing cells. The cell diagram for the cell in Figure 15.8 is shown in Figure
15.9 with an explanation below each entry. Under standard conditions the
symbol for a cell potential is E cell and this is called the standard cell potential.

Zn(s) Zn2+(aq) Cu2+(aq) Cu(s) Ecell = +1.10 V

metal electrode materials in contact salt materials in contact metal electrode The cell potential (e.m.f.)
on the left with left electrode bridge with right electrode on the right The sign of E is the charge
on the right electrode
Figure 15.9 쑿
A cell diagram for the cell composed of the Zn(s)⎪Zn2+(aq) and Cu(s)⎪Cu2+(aq)
half-cells.

If the cell potential is positive, the reaction in the cell tends to go according
to the cell diagram reading from left to right. As a current flows in the
external circuit connecting the two electrodes in Figure 15.9, zinc atoms turn Test yourself
into zinc ions and go into solution, while copper ions turn into copper atoms
and deposit on the copper electrode as shown in Figure 15.10. 15 Consider a cell based on the redox
reaction below, which tends to go in
the direction shown:
reaction Cu(s) + 2Ag+(aq)
– +
→ Cu2+(aq) + 2Ag(s)
Zn(s) Zn2+(aq) Cu2+(aq) Cu(s) Ecell = +1.10 V The voltage between the electrodes
is 0.46 V.
Zn(s) Zn2+(aq) + 2e– 2e– + Cu2+(aq) Cu(s) a) Write the half-equations for the
electrode processes when the
ele
ex ctrons viait cell supplies a current.
ternal circu b) Write the conventional cell
diagram for the cell, including
Figure 15.10 쑿 the value for Ecell.
The direction of change in an electrochemical cell.

205
 Redox, electrode potentials and fuel cells

Standard electrode potentials

The study of many cells has shown that a half-electrode, such as the
Cu2+(aq)⎪Cu(s) electrode, makes the same contribution to the cell potential
in any cell, so long as the measurements are made under the same conditions.
But there is no way of measuring the potential (voltage) of an isolated, single
electrode because it has only one terminal.
Chemists have solved this problem by selecting a standard electrode system
as a reference electrode against which they can compare all other electrode
Note
systems. The chosen reference electrode is the standard hydrogen electrode.
It is only in a standard hydrogen By convention the electrode potential of the standard hydrogen electrode is
electrode that the platinum metal is zero. This is represented as Pt[H2(g)]⎪2H+(aq) E = 0.00 V.
covered with finely divided platinum
The standard electrode potential for any half-cell is measured relative to a
black. This helps to maintain an
equilibrium between hydrogen gas
standard hydrogen electrode under standard conditions, as shown in Figure
and hydrogen ions, and ensures a 15.11. A standard hydrogen electrode sets up an equilibrium between
reversible reaction between them. hydrogen ions in solution (1 mol dm−3) and hydrogen gas (1 atm. pressure) at
298 K on the surface of a platinum electrode coated with platinum black.

V
high resistance voltmeter
H2(g) at
298 K and copper strip
1 atm pressure

salt bridge

acid solution containing

H+(aq) (1mol dm–3) solution of Cu2+(aq)
holes in glass
for bubbles of H2 (1mol dm–3)
platinum electrode
coated with finely gas to escape
divided platinum black

Figure 15.11쑿 By convention, when a standard hydrogen electrode is the left-hand electrode
The overall potential of this cell under in an electrochemical cell, the overall cell potential is the electrode potential
standard conditions is, by definition, the of the right-hand electrode.
standard electrode potential of the So, the conventional cell diagram for the cell that defines the standard
Cu2+(aq)⎪Cu(s) electrode.
electrode potential of the Cu2+(aq)⎪Cu(s) electrode is:
Pt[H2(g)]⎪2H+(aq) Cu2+(aq)⎪Cu(s) E = +0.34 V
Definition The electrode and its standard electrode potential are often represented more
The standard electrode potential,
simply as:
E , of a standard half-cell is the Cu2+(aq) + 2e− Cu(s) E = +0.34 V
potential (voltage) of that half-cell oxidised form reduced form
relative to a standard hydrogen
electrode under standard conditions. This also serves to emphasise that standard electrode potentials represent
Standard electrode potentials are reduction processes.
sometimes called standard redox A hydrogen electrode is difficult to set up and maintain, so it is much easier
potentials or standard reduction to use a secondary standard such as a silver/silver chloride electrode or a
potentials. calomel electrode as a reference electrode. These electrodes are available
commercially and are reliable to use. They have been calibrated against a
standard hydrogen electrode. ‘Calomel’ is an old-fashioned name for
mercury(I) chloride. The cell reaction and electrode potential for a calomel
electrode relative to a hydrogen electrode are:
Hg2Cl2(s) + 2e− 2Hg(l) + 2Cl−(aq) E = +0.27 V
For the reverse reaction, E has the opposite sign so:
206
2Hg(l) + 2Cl−(aq) Hg2Cl2(s) + 2e− E = −0.27 V
 Cell potentials and the direction of change

Figure 15.11 shows how to measure the standard electrode potential of a metal
or a non-metal in contact with its ions in aqueous solution.
It is also possible to measure the standard electrode potentials of electrode
systems in which both the oxidised and reduced forms are ions in solution,
such as ions of the same element in different oxidation states. In these cases,
the electrode in the system is platinum (Figure 15.12).

V
high resistance voltmeter
H2(g) at
298 K and
1 atm pressure

salt bridge

solution of Fe3+(aq) and

Fe2+(aq) both at 1mol dm–3
platinum electrode shiny platinum electrode
coated with finely acid solution
divided platinum black containing H+(aq)
(1mol dm–3)

The cell diagram for the cell in Figure 15.12 is: Figure 15.12쑿
The diagram of a cell for measuring the
Pt[H2(g)]⎪ 2H+(aq) Fe3+(aq), Fe2+(aq)⎪Pt E = +0.77 V standard electrode potential of the redox
reaction Fe3+(aq) + e− Fe2+(aq) .
Test yourself
16 Suggest why a hydrogen electrode is difficult to set up and maintain.
17 Why do you think that platinum is used as the electrode for systems in which both
the oxidised and reduced forms are ions in solution, such as Fe3+(aq) and Fe2+(aq)?
18 What are the half-equations and standard electrode potentials of the right-hand
electrode in each of the following cells?
a) Pt[H2(g)]⎪2H+(aq) Sn2+(aq)⎪Sn(s) E = −0.14 V
b) Pt[H2(g)]⎪2H+(aq) Br2(aq), 2Br− (aq)⎪Pt E = +1.07 V
c) Pt⎪[2Hg(l) + 2Cl− (aq)],Hg2Cl2(s) Cr3+(aq)⎪Cr(s) E = −1.01 V
19 The standard electrode potential for the Cu2+(aq)⎪Cu(s) electrode is +0.34 V. For
the cell: Cu(s)⎪Cu2+(aq) Pb2+(aq)⎪Pb(s) E cell = −0.47 V.
What is the standard electrode potential for the Pb2+(aq)⎪Pb(s) electrode?
20 a) What is the standard cell potential when a standard calomel electrode is
connected to a standard Cu2+(aq)⎪Cu(s) electrode?
b) Write half-equations for the reactions at the electrodes.

15.5 Cell potentials and the direction of change

Chemists use standard electrode potentials to:
● calculate standard cell potentials and
● predict the feasibility (direction) of redox reactions.
The data sheet headed ‘Standard electrode potentials’ on the Dynamic
Learning Student website lists redox half-reactions in order of their standard
electrode (reduction) potentials from the most negative to the most positive. Data
The size and sign of a standard electrode potential tells you how likely it is
that a half-reaction will occur. The more positive the standard electrode
potential, the more likely it is that the half-reaction will occur.
So, the half-reaction H2O2(aq) + 2H+(aq) + 2e− → 2H2O(l) with a
standard electrode potential of +1.77 volts near the bottom of the table is
much more likely to happen than the half-reaction Li+(aq) + e− → Li(s) with 207
a standard electrode potential of −3.03 volts at the top of the list. Indeed, this
 Redox, electrode potentials and fuel cells

last half-reaction will be much more likely to occur in the opposite direction
when it would contribute a voltage of +3.03 volts to any electrochemical cell.
Li(s) → Li+(aq) + e− E = +3.03 V
Using a table of standard electrode potentials, it is possible to calculate
standard cell potentials by combining the standard electrode potentials of the
two half-cells that make up the full cell.
Look again at Figure 15.9 and the value of the cell potential, E cell. The
value of +1.10 V arises from the sum of the E values for two half-reactions:
Cu2+(aq) + 2e− → Cu(s) E = +0.34 V
and the reverse of:
Zn2+(aq) + 2e− → Zn(s) E = −0.76 V
So, we have:
Figure 15.13쑿
The four lithium batteries in this camera Cu2+(aq) + 2e− → Cu(s) E = +0.34 V
have a total cell potential (e.m.f.) of
Zn(s) → Zn2+(aq) + 2e− E = +0.76 V
about 6 volts.
Overall: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) E cell = +1.10 V
From this discussion, you will see that:
E cell = − E (left-hand electrode) + E (right-hand electrode)
A positive value of E cell indicates that the changes shown in the overall
equation are likely to occur. In this case, zinc atoms will go into solution as
zinc ions at the zinc electrode. Electrons will flow through the external circuit
from the zinc terminal to the copper terminal as an electric current, where
copper ions will take these electrons and form copper atoms.
The more positive the value of E cell, the more likely are the changes at the
electrodes. On the other hand, negative values for E cell indicate that the
changes summarised in the overall equation will not happen.
In fact, if the reactants are available the changes shown in an overall
equation with a negative cell potential will occur in the reverse direction, for
which the cell potential would be positive.
By setting up a cell as in Figure 15.8, it is possible to separate the two
halves of the redox reaction involving zinc and copper(II) ions. But the same
changes will also occur if zinc is added directly to a solution containing copper
ions. Zinc will go into solution as zinc ions, giving up electrons to copper(II)
ions which then form a deposit of copper (Figure 15.14).
So, a positive value for a cell potential suggests that the half-reactions which
could take place at the electrodes are feasible (likely to occur) if the reactants
are mixed together in a test tube. In fact, the more positive the cell potential,
the more feasible the reaction is on direct mixing of the reactants.

Worked example
Figure 15.14쑿 Draw the cell diagram for a cell based on the two half-equations below. Work
Crystals of copper metal have deposited out the cell potential and write the overall equation for the reaction which is
on a strip of zinc placed in copper(II) likely to occur (the spontaneous reaction).
sulfate solution.
Fe3+(aq) + e− Fe2+(aq) E = +0.77 V
Cu2+(aq) + 2e− Cu(s) E = +0.34 V
Notes on the method
Write the cell diagram with the more positive electrode on the right.
Then use the equation:
E cell = E (right-hand electrode) − E (left-hand electrode)
208 to calculate the cell potential.
 Cell potentials and the direction of change

Answer
The Fe3+(aq), Fe2+(aq) electrode is the more positive so it should be on the
right-hand side of the cell diagram. Both the oxidised and reduced forms are
in solution, so a shiny platinum electrode is needed. This is represented as
Fe3+(aq), Fe2+(aq)⎪Pt(s).
The left-hand electrode is Cu2+(aq)⎪Cu(s) so the copper metal can also be
the conducting electrode. The cell diagram is therefore:
Cu(s)⎪Cu2+(aq) Fe3+(aq), Fe2+(aq)⎪Pt(s)
and the e.m.f. of the cell is given by:
E cell = + 0.77V − (+0.34)V = +0.43 V
Balancing the two half-equations in the direction of the cell diagram gives the
overall equation:
Tutorial
Cu(s) + 2Fe3+(aq) → Cu2+(aq) + 2Fe2+(aq) E cell = + 0.43 V

Test yourself
21 Draw the cell diagram for a cell based on each of the following pairs of half-
equations. For each example look up the standard electrode potentials, work out
the cell potential and write the overall equation for the reaction which tends to
happen (the spontaneous reaction):
a) V3+(aq) + e− V2+(aq); Zn2+(aq) + 2e− Zn(s) Data
b) Br2(aq) + 2e− 2Br –(aq); I2(aq) + 2e− 2I− (aq)
c) Cl2(aq) + 2e− 2Cl− (aq); PbO2(s) + 4H+(aq) + 2e− Pb2+(aq) + 2H2O(l)
22 Using the standard electrode potential data on the Dynamic Learning Student
website, arrange the following sets of metals in order of decreasing strength as
reducing agents:
a) Ca, K, Li, Mg, Na
b) Cu, Fe, Pb, Sn, Zn.
23 Using the standard electrode potential data on the Dynamic Learning Student
website, arrange the following sets of molecules/ions in order of decreasing
strength as oxidising agents in acid solution:
a) Cr2O72−, Fe3+, H2O2, MnO4−
b) Br2, Cl2, ClO−, H2O2, O2

The electrochemical series

A list of electrode systems set out in order of their electrode potentials (in the Data
table on the Dynamic Learning Student website and in Table 15.1) is a useful
guide to the behaviour of oxidising and reducing agents. It is an Metal ion⎪metal Standard electrode
electrochemical series. electrode potential, E / V
The metal ion⎪metal electrodes with highly negative electrode potentials Li+(aq) | Li(s) −3.03
involve half-reactions for Group 1 metal ions and metals (Table 15.1).
Lithium is the most reactive of these metals when it reacts as a reducing agent K+(aq) | K(s) −2.92
forming metal ions. Consequently, the reverse reaction of Li+ ions forming Li Na+(aq) | Na(s) −2.71
metal is the least likely, and this results in the most negative standard
Al3+(aq) | Al(s) −1.66
electrode potential.
The metal ion⎪metal electrodes with positive electrode potentials involve Zn2+(aq) | Zn(s) −0.76
half-reactions of d-block metal ions and metals such as copper and silver.
Fe2+(aq) | Fe(s) −0.44
These metals are relatively unreactive as reducing agents and they do not
react with dilute acids to form hydrogen gas. However, their ions are readily Pb2+(aq) | Pb(s) −0.13
reduced to the metal and this results in positive standard electrode potentials. Cu2+(aq) | Cu(s) +0.34
So, as you might expect, the order of metal ion⎪metal systems in Table 15.1
corresponds closely to the reactivity series for metals and the reactions shown Ag+(aq) | Ag(s) +0.80
by ion⎪metal ion displacement reactions.
The electrode potentials of the half-equations involving halogen molecules Table 15.1쑿
The standard electrode potentials of
and halide ions are positive. The F2(aq)⎪2F−(aq) system is the most positive, 209
some common metals.
 Redox, electrode potentials and fuel cells

Note showing that fluorine is the most reactive of the halogens as an oxidising
In whatever order electrode agent. The next most reactive halogen is chlorine, then bromine and finally
(reduction) potentials are tabulated, it iodine is the least reactive. This corresponds to the order of reactivity of the
is always true that: halogens and the results of their displacement reactions.
● the half-cell with the most positive
electrode potential has the greatest
The limitations of predictions from E data
tendency to gain electrons, so it is In some cases, the predictions from standard electrode potentials may not be
the most powerfully oxidising. borne out in practice.
● the half-cell with the most negative Although an overall positive value of E for a redox reaction suggests that
electrode (reduction) potential has the reaction should take place, in practice the reaction may be too slow. The
the greatest tendency to give up important point to appreciate is that E values relate to the relative stabilities
electrons, so it is the most of reactants and products.
powerfully reducing. Therefore, a positive value for E indicates that the products are more stable
than the reactants and the reaction is energetically feasible. But E values do
not give any indication about the rates of reactions or their kinetic feasibility.
For example, E values predict that Cu2+(aq) should oxidise H2(g) to H+ ions:
Cu2+(aq) + H2(g) → Cu(s) + 2H+(aq) E = +0.34 V
However, nothing happens when hydrogen is bubbled into copper(II) sulfate
solution because the activation energy is so high and the reaction rate is
effectively zero.
A second important point about E values is that they relate only to standard
conditions. Changes in concentration, temperature and pressure affect electrode
potentials. In particular, all electrode (reduction) potentials become more
positive if the concentration of reactant ions is increased and less positive if their
concentration is reduced. This means that some reactions that are not possible
under standard conditions occur under non-standard conditions, and vice versa.
For example, under standard conditions MnO2 will not oxidise 1.0 mol dm−3
HCl(aq) to Cl2:
MnO2(s) + 4H+(aq) + 2e− → Mn2+(aq) + 2H2O(l) E = +1.23 V
2Cl−(aq) → Cl2(g) + 2e− E = −1.36 V
And the overall equation is:
MnO2(s) + 4H+(aq) + 2Cl− (aq) → Mn2+(aq) + 2H2O(l) + Cl2(g) E = −0.13 V
But if MnO2 is heated with concentrated HCl, the electrode potentials of both
half-equations become more positive, the overall E becomes positive and
chlorine is produced.
So, our predictions from cell potentials about the feasibility (probability) of
redox reactions may not occur in practice if the kinetics of the reactions are so
slow, or if the concentration of reactants or the temperatures differ from
Tutorial
standard conditions.

Test yourself
Data
24 Why is it not possible to measure the electrode potential for the Na+(aq)⎪Na(s)
system using the method illustrated in Figure 15.11?
25 Predict which of the following pairs of reagents will react. Write the overall
balanced equation for the reactions which you predict will tend to go:
a) Zn(s) + Ag+(aq) e) Ag(s) + H+(aq)
b) Fe(s) + Ca2+(aq) f) I2(aq) + Cl− (aq)
+
c) Cr(s) + H (aq) g) Cl2(aq) + I− (aq)
+
d) Ca(s) + H (aq)
26 a) Use the data on the Dynamic Learning Student website to find the standard
electrode potentials for the two reactions below:
Cu2+(aq) + e− → Cu+(aq)
Cu+(aq) + e− → Cu(s)
b) Using the E values, show that Cu+(aq) will disproportionate (be oxidised
210 and reduced simultaneously) under standard conditions.
 Modern storage cells

15.6 Modern storage cells

From alarm clocks to wrist watches, from radios to calculators – most of us rely Definition
on the electrical power of cells and batteries. A battery is two or more
Electrochemical cells are a useful and economic way of storing and, when electrochemical cells connected
convenient, using the energy from chemical reactions. Because of this they are in series.
sometimes called storage cells. However, the impractical cells discussed in the
last two sections have been replaced by more convenient, portable cells for
everyday use.

Activity

The dry cell

Probably the commonest, cheapest and most convenient cell in use
today is the modern dry cell shown in Figure 15.15. This is an
adaptation of a cell developed by the French chemist, Georges
Leclanché in the nineteenth century. It is sometimes called the
Leclanché dry cell. The dry cell is used in a wide range of small
electrical appliances such as radios, torches and alarm clocks.

brass terminal for Figure 15.15씱

carbon rod (+) A modern dry cell.
sealing material

zinc container (–)

carbon rod

cardboard
powdered carbon
+ manganese(IV) oxide

ammonium
chloride paste

The cell diagram for a dry cell is:

Zn(s)⎪Zn2+(aq) NH4+(aq), [2NH3(g) + H2(g)]⎪C(graphite) E = 1.5 V
The negative terminal in the cell is zinc. The positive terminal is a
carbon (graphite) rod where ammonium ions are converted to
ammonia and hydrogen when the cell delivers a current.
A single dry cell can produce a potential difference of 1.5 V, although
batteries of these cells giving 100 V or more have been used.
In recent years, a modified form of the dry cell, known as the alkaline
cell, is becoming more common. You can study the alkaline cell in
Review question 2 at the end of this topic.
1 Why is the dry cell more convenient than the cells described in
Sections 15.4 and 15.5?
2 Why is ammonium chloride used as a paste rather than as a
dry solid?

211
 Redox, electrode potentials and fuel cells

3 Write a half-equation for the reaction at:

a) the zinc terminal
b) the carbon (graphite) terminal.
4 Assuming that the electrode potential for
the Zn2+(aq)⎪Zn(s) half-cell is −0.76 V,
calculate the electrode potential of the
other half-cell in a dry cell.
5 The surface area of the positive terminal is
increased by surrounding the carbon rod
with a mixture of powdered graphite and
manganese(IV) oxide. The purpose of the
manganese(IV) oxide is to oxidise
hydrogen produced at the electrode to Figure 15.16쑿
water. This prevents bubbles of hydrogen from coating the A selection of the different sizes and
carbon terminal and reducing its efficiency. types of dry cells and alkaline cells
used in radios, clocks, torches and
a) Why do you think it is important to increase the surface area toys.
of the carbon terminal?
b) Write an equation for the reaction of manganese(IV) oxide with
hydrogen to produce water.
c) Why does ammonia not cause the same problems as
hydrogen in reducing the efficiency of the carbon terminal?

Rechargeable (secondary) cells

Dry cells and alkaline cells cannot, of course, provide continuous supplies of
electrical energy indefinitely. Nor is there any way of recharging these cells so
that they can be used again. However, there are cells which can be recharged
and used again. These are called secondary cells, in contrast to primary cells
like dry cells and alkaline cells, which cannot be recharged. When a
secondary cell is recharged, an electric current passes through it in the
opposite direction to that which the cell produces. Recharging is an example
of electrolysis as chemical reactions occur to reform the chemicals which
make up the electrodes.

Lead–acid cells (car batteries)

Almost all car batteries are composed of six lead–acid cells in series giving a
total battery potential of 12 volts. These batteries are only used to provide
electricity for lights and windscreen wipers and a spark to ignite the fuel when
a vehicle is started. Most milk floats and battery-operated wheelchairs are
actually powered by lead–acid cells.
In recent years, the increasing cost of fossil fuels has made the electrically
powered car a more viable alternative. Unfortunately, attempts to develop and
market a vehicle of this type using lead–acid cells have not been successful.
The main reasons for this are:
Figure 15.17쑿
Most battery-operated wheelchairs are ● the high cost of lead–acid batteries
powered by lead–acid cells. ● the low power/weight ratio of lead–acid batteries
● the limited mileage before recharging is necessary.

212
 Modern storage cells

The negative terminal in a lead–acid cell is lead. This gives up electrons

forming lead(II) ions when the cell is working normally (discharging):
Pb(s) → Pb2+(aq) + 2e−
The positive terminal is lead coated with lead(IV) oxide. During discharge, the
lead(IV) oxide reacts with H+ ions in the sulfuric acid electrolyte and takes
electrons:
PbO2(s) + 4H+(aq) + 2e− → Pb2+(aq) + 2H2O(l)
Notice that lead(II) ions, Pb2+(aq), are formed at both terminals during
discharge. These react with sulfate ions, SO42−(aq), in the electrolyte forming
insoluble lead(II) sulfate on both terminals:
Pb2+(aq) + SO42−(aq) → PbSO4(s)
The formation of insoluble lead(II) sulfate creates another potential problem
for lead–acid cells. If the cells are discharged for long periods, the precipitate
of lead(II) sulfate becomes coarser and thicker and the process cannot be
reversed when the cells are recharged.
When a lead–acid cell is recharged, the current is reversed and the
reactions at each terminal are reversed. This turns Pb2+ ions back to lead
metal at one terminal and back to PbO2 at the other, with sulfate ions going
back into the electrolyte.

Test yourself
27 Why have attempts to develop family cars powered by lead–acid batteries been
unsuccessful? Data
28 The milk float in Figure 15.18 is powered by lead–acid batteries. Why is this both
possible and convenient?
29 a) Use the data sheet on the Dynamic Learning Student website listing
‘Standard electrode potentials’ to write down the value of E for a
Pb2+(aq)⎪Pb(s) half-cell.
b) What is the approximate cell potential for one lead–acid cell?
c) What is the approximate electrode potential of the [PbO2(s) + 4H+(aq)],
[Pb2+(aq) + 2H2O(l)]⎪Pb(s) half-cell in a lead–acid cell?
d) Write a balanced equation for the overall reaction in a lead–acid cell when it
is supplying current.
e) Write the half-equations for the processes at the two terminals when the cell
is being recharged.
Figure 15.18쑿

Lithium cells
Modern mobile phones and laptop computers use lithium batteries. The
advantages of electrodes based on lithium are that the metal has a low density,
so cells based on lithium electrodes can be relatively light. Also, lithium is
very reactive, which means that the electrode potential of a lithium half-cell
is relatively high and each cell has a large e.m.f.
The difficulty to overcome is that lithium is so reactive that it readily
combines with oxygen in the air forming a layer of non-conducting oxide on the
surface of the metal. The metal also reacts rapidly with water. Research workers
have solved these technical problems by developing electrodes with lithium
atoms and ions inserted into the crystal lattices of other materials. In addition,
the electrolyte is a polymeric material rather than an aqueous solution.

213
 Redox, electrode potentials and fuel cells

Figure 15.19씰 device powered electron flow in

A schematic diagram of a lithium battery by the battery the external circuit
discharging. The electrode processes are
reversible, so the battery can be e– e–
recharged.

Li+
Li+ Li+

Li+ Li+

Positive electrode Polymer electrolyte Negative electrode

Layer lattice of MnO2 with Li+ ions Carbon (graphite) with a
into which Li+ ions layer lattice containing
can move lithium atoms
2MnO2(s) + 2e– + 2Li+ 2Li 2Li+ + 2e–
from from in
electrolyte electrode electrolyte
Mn2O3(s) + Li2O(s)

15.7 Fuel cells

Fuel cells are electrochemical cells in which the chemical energy of a fuel is
converted directly into electrical energy. Fuel cells differ from typical
electrochemical cells, such as dry cells and lead–acid accumulators, in having a
continuous supply of reactants from which to produce a steady electric current.
Fuel cells use a variety of fuels including hydrogen, hydrocarbons (such as
methane) and alcohols. Inside a fuel cell, energy from the redox reaction
between a fuel and oxygen is used to create a potential difference (voltage).

The hydrogen–oxygen fuel cell

One of the most important fuel cells is the hydrogen–oxygen fuel cell.
In the hydrogen–oxygen fuel cell, the negative electrode is porous graphite
impregnated with nickel and the positive electrode is porous graphite
impregnated with nickel and nickel(II) oxide.
The nickel and nickel oxide catalyse the breakdown of hydrogen and
oxygen molecules into single atoms.

external
electron circuit electron
Figure 15.20씰
flow flow
A hydrogen–oxygen fuel cell.

2e– 2e–
1
hydrogen O
2 2
oxygen

2H+

H2

excess
H2O water
hydrogen

porous graphite porous graphite

solid polymer
impregnated impregnated with
electrolyte
with nickel nickel + nickel oxide
214 – +
 Fuel cell vehicles (FCVs)

Hydrogen gas flows onto the negative electrode, where the H2 molecules split
into single H atoms on the nickel catalyst. The H atoms then lose electrons
and form H+ ions:
Negative electrode: H2 → 2H → 2H+ + 2e− Equation 1
The electrons flow into the external circuit as an electric current, while the
hydrogen ions migrate through the electrolyte.
Oxygen flows onto the positive electrode where the nickel/nickel(II) oxide
catalyses its splitting into single oxygen atoms, and then its combination with
hydrogen ions from the electrolyte and electrons to form water:
Positive terminal: O + 2H+ + 2e− → H2O Equation 2
The overall reaction in the hydrogen–oxygen fuel cell (obtained by adding
Equations 1 and 2) is:
H2 + O → H2O
This cell is no different in principle from more familiar electrochemical cells.
The innovation is that new reactants (H2 and O2) are constantly fed into the
cell and the product (H2O) is drawn off. This continuous flow of materials
allows the cell potential to remain constant at about 1.2 volts and the power
output is uninterrupted.
The great advantage of all fuel cells is that they convert chemical energy
into electricity directly and in doing so achieve a remarkable efficiency of
about 70%. In comparison, modern power plants and petrol engines using
fossil fuels have a conversion efficiency from chemical energy to electrical
energy or kinetic energy of only about 45%.

15.8 Fuel cell vehicles (FCVs)

As calls for a cleaner environment become louder and reserves of fossil fuels
become scarcer, the search for alternative fuels is on. One possible alternative
to petrol is to run vehicles on hydrogen using fuel cells that are far more
efficient than petrol engines. What is more, vehicles emitting water vapour as
the only exhaust gas are an attractive green proposition.
The idea of a car powered by hydrogen is not new, but until recently it has
not been feasible due to technological problems. These problems include the
weight of fuel cells and the difficulty of carrying and containing sufficient
hydrogen in a vehicle.
Figure 15.21씱
A technician assembling a fuel cell for
testing. The fuel cell is constructed from
lightweight polymeric materials.

215
 Redox, electrode potentials and fuel cells

In recent years, compact lightweight fuel cells have been developed, along
with the technology to store large quantities of hydrogen much more
conveniently and safely.
Three possible methods of storing hydrogen in fuel cell vehicles (FCVs) are
being considered:
● as a liquid under pressure
● adsorbed on the surface of a solid
● absorbed within a solid material.
The efficiency of fuel cells is so much better than petrol engines that fuel cell
vehicles of the future might well use hydrogen-rich fuels such as methanol,
natural gas and petrol in place of hydrogen. Although fuel cells have been
constructed which use methane and methanol directly, scientists are now
working on the development of compact catalytic ‘reformers’ which will
produce hydrogen from these fuels as on-board components of FCVs.

Limitations to the development of hydrogen FCVs

The development of lightweight hydrogen fuel cells made from polymeric
materials and an appreciation that their efficiency could be five times that of
petrol engines has led to renewed interest in the development of hydrogen-
powered FCVs.
At present, the most serious limitations to the development of a hydrogen-
powered FCV are:
● the safe storage and transport of hydrogen
● the hazards posed by highly pressurised liquid hydrogen
● the limited life cycle of solid ‘adsorbers’ and ‘absorbers’
● the finite life and high cost of fuel cells requiring regular replacement and
disposal.
Everyone knows that hydrogen is explosive, and explosions such as the
Figure 15.22쑿 Hindenburg disaster in 1937 only serve to emphasise the hazards in its storage
People have long memories over and transport.
disasters. In 1937, the Hindenburg The method of storing liquid hydrogen for industrial uses in heavy, thick
airship filled with hydrogen exploded steel vessels at pressures above 100 atmospheres would never be suitable for
when attempting to dock with its moving vehicles.
mooring mast. Liquid hydrogen is useful in industry, but the energy used in liquefying it is
a major fraction of what could be generated when it is oxidised in a fuel cell.
Furthermore, liquid hydrogen would present a serious safety problem if it were
used as a fuel for vehicles. Liquid hydrogen is extremely cold (boiling point
−253 K) and it is highly volatile and extremely flammable.
Fortunately, chemists have discovered a much safer storage arrangement for
hydrogen at normal temperatures. This involves the formation of metal
hydrides.
Most metals react with hydrogen to form a hydride. In many cases, the
reaction occurs simply by passing hydrogen over the hot metal. For example,
with magnesium the equation is:
Mg(s) + H2(g) MgH2(s)
Notice that the reaction is reversible. If the pressure is above a certain level,
the reaction goes to the right and more metal hydride is formed. If the
pressure is below that level, the metal hydride decomposes to the metal and
hydrogen gas.

216
 Fuel cell vehicles (FCVs)

The main reason why some metal hydrides can be used for the storage of
hydrogen is that they can accommodate an extremely high density of
hydrogen. In fact, it is possible to pack more hydrogen into a metal hydride
than into the same volume of liquid hydrogen.
When hydrogen reacts with a metal to form its hydride, hydrogen molecules
(H2) are first adsorbed onto the surface of the metal. Some of the molecules
dissociate into hydrogen atoms (H) and are absorbed deeper into the metal
lattice as they react to form the metal hydride (Figure 15.23).

Figure 15.23씱
hydrogen Hydrogen atoms absorbed into the
atoms crystal lattice of the metal niobium.

sections of
other niobium
atoms in the
crystal lattice

niobium
atoms

If the pressure of hydrogen in contact with the metal is increased, even greater
amounts of hydrogen can be absorbed into the spaces between metal atoms. In
most metal hydrides, the number of hydrogen atoms in the lattice will be two
to three times the number of metal atoms.
Although there is an increasing political and social desire to move to a
greener, more environmentally friendly economy including the use of FCVs
powered by hydrogen, there are still obstacles to be overcome. A ‘hydrogen
economy’ may well contribute to our future energy needs, but the obstacles
that will limit its development include:
● the public and political acceptance of hydrogen as a safe fuel
● the handling, storage, transport and maintenance of hydrogen systems in
vehicles
● a realisation that FCVs powered by hydrogen are not totally ‘green’ –
significant amounts of energy are needed to manufacture hydrogen and
there are toxic chemicals used in the manufacture of fuel cells.

Test yourself
30 Hydrogen is said to have ‘the highest density of energy per unit mass of any
fuel’. What does this expression mean?
31 Why is liquid hydrogen unsuitable for use as a fuel in motor vehicles?
32 What is the difference between hydrogen adsorbed by a metal and hydrogen
absorbed by a metal?
33 Explain briefly why some metal hydrides can accommodate a high packing-
density of hydrogen.

217
 Redox, electrode potentials and fuel cells

Activity

A greener future for transport!

Figure 15.24씱
Technicians assembling the
components of an FCV based on a
modified Honda.

Read Section 15.8 again and then answer the following questions.
1 Why are compounds such as methanol, natural gas and petrol
described as ‘hydrogen-rich’ fuels?
2 What are the major problems in developing FCVs powered by
hydrogen and hydrogen-rich fuels?
3 What are the major advantages of FCVs over conventional petrol-
engine and diesel-engine vehicles?
4 What is the main advantage of fuel cell vehicles powered by
hydrogen rather than hydrogen-rich fuels?
5 Write equations for the oxidation of hydrogen and petrol in fuel
cells, assuming that they are completely oxidised and that petrol
is pure octane.
6 a) Use the data sheet on the Dynamic Learning Student website
headed ‘Average bond enthalpies and bond lengths’ to find Data
the average bond enthalpies for the different bonds in
hydrogen, oxygen, octane, carbon dioxide and water. Figure 15.25쑼
The limited edition Honda FCX
b) Make a table showing the bonds broken and the bonds Clarity was first made available for
formed during the complete combustion of hydrogen, and lease in Southern California in 2008.
then calculate a value for the enthalpy
change of combustion of hydrogen.
c) Calculate the energy produced during the
complete combustion of 1 gram of hydrogen.
7 Repeat the calculations in questions 6b) and c)
for petrol (octane) in place of hydrogen.
8 Bearing in mind that fuel cells are approximately
70% efficient and petrol engines are about 40%
efficient, how many times more efficient is a fuel
cell vehicle powered by hydrogen compared to a
vehicle with a petrol engine per gram of fuel?
218
REVIEW QUESTIONS Extension questions

1 Use the standard electrode potentials in the table 3 A student set up the electrochemical cell shown below.
below to answer the questions that follow.
high resistance voltmeter
A Fe3+(aq) + e− → Fe2+(aq) E = +0.77 V
V
B Cu2+(aq) + 2e− → Cu(s) E = +0.34 V

C 2H+(aq) + 2e− → H2(g) E = 0.00 V copper foil silver foil

D O2(g) + 4H+(aq) + 4e− → 2H2O(l) E = +0.40 V

a) An electrochemical cell was arranged using systems salt bridge

A and B.
i) Write half-equations for the reactions which 1.0 mol dm–3
copper(II) sulfate
occur in each half-cell when a current flows.
Say which half-equation involves oxidation and 1.0 mol dm–3
silver nitrate
which involves reduction. (2)
ii) Calculate the change in oxidation number You are provided with the following standard electrode
of the oxidised and reduced elements in each potentials:
half-cell. (2)
Cu2+|Cu E = +0.34 V
iii) Determine the cell potential of the cell. (1)
Ag+|Ag E = +0.80 V
b) Fuel cells using systems C and D are increasingly
being used to generate electricity. a) How could the student have made the salt bridge?
(1)
i) Construct an overall equation for the cell
reaction and show your working. (2) b) Write a half-equation to show the reaction that
occurred in:
ii) From which half-cell do electrons flow into the
external circuit? (1) i) the Cu|Cu2+ half-cell. (1)
iii) State two advantages and two disadvantages of ii) the Ag|Ag+ half-cell. (1)
using fuel cells based on systems C and D to c) Write an equation for the overall cell reaction. (1)
generate energy rather than using fossil fuels. (4)
d) Calculate the standard cell potential for
2 A more efficient, and more expensive, form of the dry this cell. (2)
cell is the alkaline cell.
e) At which electrode does reduction occur?
The reaction at the negative terminal is again the Explain your answer. (2)
oxidation of zinc, but in contact with OH− ions to form
zinc oxide. f) The student found that the cell potential was
less than the calculated value. Suggest two
The positive terminal is manganese(IV) oxide which is reasons for this. (2)
reduced to manganese(III) oxide:
4 a) What are the principal differences between a
2MnO2(s) + H2O(l) + 2e− → Mn2O3(s) + 2OH− (aq) hydrogen–oxygen fuel cell and a conventional
a) An alkaline cell is an example of a primary cell. electrochemical cell like the dry cell? (3)
What is meant by a ‘primary’ cell? (1) b) Outline and explain two advantages that would be
b) How does a secondary cell differ from a primary gained by generating electricity using fuel cells
cell? (2) rather than in thermal power stations. (4)
c) Write a half-equation for the reaction at the c) What major advantage would hydrogen-powered
negative terminal when an alkaline cell is used. (2) fuel cells have over other fuel cells? (2)
d) State the changes in oxidation number at each d) Suggest three obstacles to the present development
terminal. (2) and production of hydrogen-powered fuel cell
vehicles. (3)
e) Why is an alkaline cell in continuous use more
efficient than a dry cell? (2)

219
 16 Transition elements
The transition elements are vital to life and bring colour to our lives.
They are also metals of great engineering and industrial importance.
Chemically, these elements, which occupy the d-block of the periodic
table, are more alike than might be expected. Across the ten elements
from scandium to zinc in Period 4, the similarities are as striking as
the differences. Chemists explain the characteristics of transition
elements in terms of the electron configurations of their atoms.
Transition metal chemistry is colourful because of the range of
oxidation states and complex ions. Transition metals matter because
their properties are fundamental, not only to life but also to modern
technology.

Figure 16.1씰
A stained glass window in Ely Cathedral.
The commonest colorants in stained
glass are the oxides of transition
elements.

Tutorial

4p
Orbitals in
16.1 Electron configurations
the 4th shell As the shells of electrons around the nuclei of atoms get further from the
3d nucleus, they become closer in energy. So the difference in energy between
4s the second and third shells is less than that between the first and second.
When the fourth shell is reached, there is, in fact, an overlap between the
3p orbitals of highest energy in the third shell (the 3d orbitals) and that of lowest
energy in the fourth shell (the 4s orbital) (Figure 16.2).
Orbitals in The 3d sub-shell is on average closer to the nucleus than the 4s sub-shell,
the 3rd shell but at a higher energy level. So, once the 3s and 3p sub-shells are filled, the
3s next electrons go into the 4s sub-shell because it occupies a lower energy level
than the 3d sub-shell.
Figure 16.2쑿
This means that potassium and calcium have the electron structure [Ar]4s1
220 Relative energy levels of orbitals in the and [Ar]4s2 respectively (Table 16.1).
third and fourth shells.
 Electron configurations

Element Symbol Electron structure

spdf notation Electrons-in-boxes notation
3d 4s
potassium K [Ar]4s1 [Ar]

calcium Ca [Ar]4s2 [Ar]

scandium Sc [Ar]3d14s2 [Ar]

titanium Ti [Ar]3d24s2 [Ar]

vanadium V [Ar]3d34s2 [Ar]

chromium Cr [Ar]3d54s1 [Ar]

manganese Mn [Ar]3d54s2 [Ar]

iron Fe [Ar]3d64s2 [Ar]

cobalt Co [Ar]3d74s2 [Ar]

nickel Ni [Ar]3d84s2 [Ar]

Table 16.1씱
copper Cu [Ar]3d104s1 [Ar] Electron configurations from potassium
to zinc in Period 4 of the periodic table.
zinc Zn [Ar]3d104s2 [Ar] ([Ar] represents the electron configuration
of argon.)

Look carefully at Table 16.1. In Period 4, the d-block elements run from
scandium (1s22s22p63s23p63d14s2) to zinc (1s22s22p63s23p63d104s2). But, notice
that the electron configurations of chromium and copper do not fit the general
pattern. The explanation of these irregularities lies in the stability associated
with half-filled and filled sub-shells. So, the electron structure of chromium,
[Ar]3d54s1, with half-filled sub-shells and an equal distribution of charge
around the nucleus, is more stable than the electron structure [Ar]3d 44s2.
Similarly, the electron structure of copper, [Ar]3d104s1, with a filled 3d sub-
shell and a half-filled 4s sub-shell, is more stable than [Ar]3d 94s2.
Along the series of d-block elements from scandium to zinc, the number of
protons in the nucleus increases by one from one element to the next. The
added electrons go into an inner d sub-shell. The outer electrons are always in
the 4s sub-shell, and this means that the changes in chemical properties across
the series are much less marked than the big changes across a series of p-block
elements such as aluminium to argon.
The chemistry of an element is determined to a large extent by its outer
shell electrons because they are the first to get involved in reactions. All the
d-block elements from Sc to Zn have their outer electrons in the 4s sub-shell, Figure 16.3 쑼
so they are similar in many ways. Specimens of some d-block elements.

221
 Transition elements

Ions of the transition metals

When transition metals form their ions, electrons are lost initially from the 4s
sub-shell and not the 3d sub-shell. This may seem somewhat illogical because,
prior to holding any electrons, the 4s level is more stable than the 3d level.
But once the 3d sub-shell is occupied by electrons, being closer to the nucleus,
these 3d electrons repel the 4s electrons to a higher energy level. The 4s
electrons are, in fact, pushed to an energy level higher than those occupying
the 3d sub-shell. So, when transition metals form ions they lose electrons from
the 4s orbital before the 3d level. This further emphasises the fact that
transition metals have similar chemical properties, which are dictated by the
behaviour of the 4s electrons in their outer shells.

Test yourself
1 Write the full spdf electron configurations of:
a) a scandium atom b) a scandium(III) ion
c) a manganese atom d) a manganese(II) ion.
2 Look at the electron structures of iron and copper in Table 16.1.
a) Write the electron structure of an iron(II) ion.
b) Write the electron structure of an iron(III) ion.
c) Which ion, Fe2+ or Fe3+, would you expect to be the more stable? Explain
your choice.
d) Write the formula for the ion of copper that you would expect to be the most
stable. Explain your choice.

16.2 Defining the transition elements

The simplest and neatest way to define the transition elements would be to
say that they are the elements in the d-block of the periodic table. But, this
simple definition leads to the inclusion of scandium and zinc as transition
elements and ignores the fact that these two metals have some clear
differences to the elements between them in the periodic table from titanium
to copper. For example:
● scandium and zinc have only one oxidation state in their compounds
(scandium +3, zinc +2), whereas the elements from titanium to copper
have two or more
● the compounds of scandium and zinc are usually white, unlike those of
transition metals which are generally coloured
● scandium and zinc, and their compounds, show little catalytic activity.

Definition As scandium and zinc do not show the typical properties of transition
elements, chemists looked for a more satisfactory definition. This definition
A transition element is a d-block
element that has at least one stable
had to exclude scandium and zinc, but include all the elements from titanium
ion with a partially filled d sub-shell. to copper. In order to achieve this, chemists describe transition elements as
d-block elements that have at least one stable ion with an incomplete
(partially filled) d sub-shell.

Characteristics of the transition metals

Transition metals share a number of common properties.
● They are hard metals with useful mechanical properties, high melting
Data points and high boiling points.
● They form compounds in more than one oxidation state.
● They form coloured compounds.
● They act as catalysts either as the elements or as their compounds.
● They form a variety of complex ions (Section 16.7).
222
 The transition elements as metals

16.3 The transition elements as metals

Most of the transition elements have a close-packed structure in which each
atom has 12 nearest neighbours. In addition, transition elements have
relatively low atomic radii because an increasingly large nuclear charge is
attracting electrons that are being added to an inner sub-shell. The dual effect
of close packing and small atomic radii results in strong metallic bonding. So,
transition metals have higher melting points, higher boiling points, higher
densities and higher tensile strength than s-block metals such as calcium and
p-block metals such as aluminium and lead. A plot of physical properties
against atomic number often has two peaks or two troughs associated with a
half-filled and then a filled d sub-shell.

2500 2163
2130
1933

1808
1814

1768
1728
2000
1517
Melting point/K

1356
1500
1112

Element Standard electrode

potential, E
1000 M2+(aq)⎪M(s)/V
693
vanadium −1.20
500 chromium −0.91
manganese −1.19
0 iron −0.44
Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn
cobalt −0.28
Figure 16.4쑿
nickel −0.25
A plot of melting point against atomic number for the elements calcium to zinc in the
periodic table. copper +0.34

The transition metals are much less reactive than the s-block metals. Table 16.2쑿
However, their electrode potentials, shown in Table 16.2, suggest that all of Standard electrode potentials of the
them, except copper, should react with dilute strong acids such as 1 mol dm−3 transition metals from vanadium to
hydrochloric acid and sulfuric acid. In practice, many of these metals react copper.
very slowly with dilute acids because the metal is protected by a thin,
unreactive layer of oxide. Chromium provides a very good example of this.
Despite the predictions from its standard electrode potential, it is used as a
protective, non-rusting metal owing to the presence of an unreactive, non-
porous layer of chromium(III) oxide, Cr2O3.

Test yourself
3 Why can scandium and zinc be described as d-block elements, but not as
transition metals?
4 Suggest a reason why zinc only forms compounds in the +2 oxidation state.
5 a) What is the general trend in standard electrode potentials of the
M2+(aq) | M(s) systems for the transition metals in Table 16.2?
b) What does this suggest about the reactivity of transition metals across
Period 4 in the periodic table?
6 Explain why the atomic radius falls from 0.15 nm in titanium to 0.14 nm in
vanadium and then 0.13 nm in chromium.

223
 Transition elements

Activity

Studying the ionisation energies of transition metals

Earlier in this topic, we used the energy-level model to predict the
electronic structures of d-block elements in Period 4 and their ions.
These electronic structures can be fully substantiated by studying
the ionisation energies of the elements concerned.
Look carefully at Figure 16.5 which shows graphs of the first, second
and third ionisation energies of the elements from scandium to zinc.

Figure 16.5씱
4000
Zn third Graphs of the first, second and third
ionisation energies of the elements from
Cu scandium to zinc in the periodic table.
3500 Ni
Mn Co

Cr
3000 V
Ti Fe
Ionisation energy/kJ mol –1

2500
Sc

Cu
2000
Ni
Cr Co second
Fe
V Mn Zn
1500 Ti
Sc

1000 Cr Mn Fe Co Ni Cu Zn
Sc Ti V first

20 21 22 23 24 25 26 27 28 29 30 31
Atomic number

1 Write the electronic structure of the following atoms and ions,

using [Ar] for the electronic structure of argon:
a) Zn b) Cu+ c) Zn+ d) Cr+ e) Mn+
2 Write an equation for:
a) the second ionisation energy of chromium
b) the third ionisation energy of iron.
3 Explain the general trend in ionisation energies as atomic number
increases.
4 Why is the first ionisation energy of zinc significantly higher than
that of any of the other elements?

224
 Oxidation states

5 Why is the second ionisation energy of every element higher than

its first ionisation energy?
6 By referring to electron structures, explain why the second
ionisation energy of both chromium and copper is higher than
that of the next element.
7 By referring to electron structures, explain why the third
ionisation energy of manganese is higher than the third ionisation
energy of iron.

16.4 Oxidation states

Most of the d-block elements in Period 4 show more than one oxidation state
in their compounds. The main reason for this is that the transition metals
from titanium to copper have electrons of similar energy in both the 3d and 4s
levels. This means that each of these elements can form ions of roughly the
same stability in aqueous solution or in crystalline solids by losing different
numbers of electrons.
The formulae of the common oxides of the elements from scandium to zinc
are shown in Figure 16.6 above the stable oxidation states of each element in
its compounds. The main oxidation states of the elements are shown in bold
blue print.

Sc Ti V Cr Mn Fe Co Ni Cu Zn Figure 16.6씱
Common Sc2O3 Ti2O3 V2O3 Cr2O3 MnO FeO CoO NiO Cu2O ZnO Oxidation states and common oxides of
oxides TiO2 V2O5 CrO3 MnO2 Fe2O3 Co2O3 CuO the elements scandium to zinc, with the
Mn2O7 main oxidation states in bold blue print.

+7
+6 +6
+5
+4 +4 +4
+3 +3 +3 +3 +3 +3 +3
+2 +2 +2 +2 +2 +2 +2 +2 +2
+1

The elements at each end of the series, scandium and zinc, give rise to only
one oxidation state. The elements near the middle of the series have the
greatest range of oxidation states. Most of the elements form compounds in
the +2 state corresponding to the use of both of the 4s electrons in bonding.
The +2 state is a main oxidation state for all the elements in the second
half of the series, whereas +3 is a main oxidation state for all elements in the
first part. Across the series, the +2 state becomes more stable relative to the
+3 state.
From scandium to manganese, the highest oxidation state corresponds to
the total number of electrons in the 3d and 4s energy levels. However, these
higher oxidation states never exist as simple ions. Typically, they occur in
compounds in which the metal is covalently bonded to an electronegative
atom, particularly oxygen as in the dichromate(VI) ion, Cr2O72− and the
manganate(VII) ion, MnO4−.
One of the most attractive and effective demonstrations of the range of
oxidation states in a transition element can be shown by shaking a solution of
ammonium vanadate(V), NH4VO3, in dilute sulfuric acid with zinc (Figure
16.7). Before adding zinc, H+ ions in the sulfuric acid react with VO3− ions to
form dioxovanadium(V) ions and the solution is yellow:
225
VO3−(aq) + 2H+(aq) → VO2+(aq) + H2O(l)
 Transition elements

When the yellow solution, containing dioxovanadium(V) ions, is shaken with

zinc, it is reduced first to blue oxovanadium(IV) ions, VO2+(aq), then to green
vanadium(III) ions, V3+(aq), and finally to violet vanadium(II) ions, V2+(aq).

Figure 16.7씰
The oxidation states of vanadium
showing the colours of its ions in the +5,
+4, +3 and +2 oxidation states.

VO2+(aq) VO2+(aq) V3+(aq) V2+(aq)

Test yourself
7 Write down four generalisations about the oxidation states of transition metals
based on Figure 16.6 and the text in Section 16.4.
8 Give examples of compounds, other than oxides, of:
a) chromium in the +3 and +6 states
b) manganese in the +2 and +7 states
c) iron in the +2 and +3 states
d) copper in the +1 and +2 states.
9 Explain why the oxidation state of vanadium in VO2+ ions is +5.
10 a) Write half-equations for:
i) the reduction of dioxovanadium(V) ions, VO2+, to oxovanadium(IV) ions,
VO2+, in acid solution
ii) the oxidation of zinc to zinc(II) ions.
b) Use the data sheet headed ‘Standard electrode potentials’ on the Dynamic
Learning Student website to show that zinc will reduce VO2+ ions to VO2+
ions in acid solution.
Data
11 a) Why do you think that copper is the only transition metal to have +1 as a
main oxidation state?
b) Which other transition metal might you expect to form some compounds in
the +1 state? Explain your answer.

16.5 Coloured ions

In many cases, coloured compounds get their colour by absorbing some of the
radiation in the visible region of the electromagnetic spectrum with
wavelengths between 400 and 700 nm. When light strikes a substance, some
of it is absorbed, some is transmitted (if the substance is transparent) and
some is usually reflected.
If all the light is absorbed, the substance looks black. If all the light is
reflected, the substance looks white. If very little light is absorbed and all the
radiations in the visible region of the electromagnetic spectrum are
transmitted equally, then the substance will be colourless like water.
However, many compounds, particularly those of transition metals, absorb
radiations in only certain areas of the visible spectrum. This means that the
substances take on the colour of the light that they transmit or reflect. For
example, if a material absorbs all radiations in the green–blue–violet region of
226 the spectrum, it will appear red–orange in white light (Figure 16.8).
 Coloured ions

Colour of Wavelength Colour of light Figure 16.8씱

compound absorbed/nm absorbed A chart showing complementary colours
in the left and right-hand columns. The
greenish yellow 400–430 violet
colour of a compound is the
yellow to orange 430–490 blue complementary colour to the light it
red 490–510 blue-green absorbs.

purple 510–530 green

violet 530–560 yellow-green
blue 560–590 yellow
greenish blue 590–610 orange
blue-green to green 610–700 red

In coloured compounds, it is the electrons which absorb radiation and jump

from their normal state to a higher excited state. According to the quantum
theory, there is a fixed relationship between the size of the energy ‘jump’ and
the wavelength of the radiation absorbed. In many compounds, the electron
‘jumps’ between one sub-level and the next are so large that the radiation
absorbed is in the ultraviolet region of the spectrum. These compounds are
therefore white or colourless because they are not absorbing any of the
radiations in the visible region of the electromagnetic spectrum.
However, the colour of transition metal ions arises from the possibility of
transitions between the orbitals within the 3d sub-shell.
In a free gaseous atom or ion, the five d orbitals are all at the same energy
level even though they do not all have the same shape. But, when the ion of a
d-block element is surrounded by other ions in a crystalline solid, or by
molecules such as water in aqueous solutions, the differences in shape cause
the five orbitals to split into two groups. Two of the 3d orbitals move to a
slightly higher energy level than the other three. Because of this, ions such as
Cu2+(aq) appear coloured because light of a particular frequency can be
absorbed from visible light as electrons jump from a lower to a higher 3d
orbital (Figure 16.9). If all the d orbitals are full, or empty, there is no
possibility of electronic transitions between them.

The d orbitals split into two groups with Figure 16.9씱

different energies in an aqueous ion The energy difference between the
d orbitals in an aqueous transition metal
ion, like Cu2+(aq), allows electron
Five d orbitals with the same
transitions from a lower orbital to a higher
energy in a free gaseous ion
Absorption of light at a orbital. The ion absorbs light with a
particular frequency can particular frequency in the visible region
promote an electron to a of the electromagnetic spectrum.
Cu2+(g) higher level

Cu2+(aq)
Note
The quantum theory states that
In explaining the colour of transition metal ions, you should appreciate the
radiation is emitted or absorbed in
limitations of our simple energy-level model of electronic structure. The need tiny, discrete amounts called energy
for more sophisticated explanations is clear, bearing in mind the existence of quanta. Quanta have energy E = hν,
sub-shells and the different shapes of orbitals within d sub-shells. where h is Planck’s constant and ν is
the frequency of the radiation.
Test yourself
12 a) By writing out their electron configurations, explain why Zn2+, Cu+ and Sc3+
ions are usually colourless in solution and white in solids.
b) What colours of light are absorbed most effectively by a Cu2+ ion? 227
 Transition elements

16.6 Catalytic behaviour

Transition elements and their compounds play a crucial role as catalysts in
industry. Table 16.3 lists some important examples of transition metals and
their compounds as catalysts.
Table 16.3씰 Transition element/compound Reaction catalysed
Some important examples of transition used as catalyst
metals and their compounds as
catalysts. vanadium(v) oxide, V2O5, or Contact process in the manufacture of sulfuric acid
vanadate, VO3− 2SO2(g) + O2(g) → 2SO3(g)

iron or iron(III) oxide Haber process to manufacture ammonia

N2(g) + 3H2(g) → 2NH3(g)

nickel, platinum and palladium manufacture of low fat spreads and margarine
RCH=CH2(g) + H2(g) → RCH2CH3(g)

platinum or platinum–rhodium conversion of NO and CO to CO2 and N2 in

alloys catalytic converters
2CO(g) + 2NO(g) → 2CO2(g) + N2(g)

platinum reforming straight chain alkanes as cyclic alkanes

and arenes
CH3(CH2)5CH3 → CH3−C6H5 + 4H2
heptane methylbenzene

Catalysts can be divided into two types – heterogeneous and homogeneous.

Heterogeneous catalysis
Heterogeneous catalysis involves a catalyst in a different state from the
reactants it is catalysing. It is used in almost every large-scale manufacturing
process such as the manufacture of ammonia in the Haber process (Table
16.3) in which nitrogen and hydrogen gas flow through a reactor containing
lumps of iron or iron(III) oxide.
Platinum metal alloyed with other metals, such as rhodium, is used in
catalytic converters. In a catalytic converter, such as that in Figure 16.10, a
honeycombed ceramic structure is coated with a very thin layer of the
expensive catalyst in order to increase its surface area in contact with the
exhaust gases.
Figure 16.10씰
A catalytic converter is an example of a
heterogeneous catalyst. Pollutant
molecules of NO and CO in the exhaust
gases become attached to the surface of
the platinum alloy where they react to
form N2 and CO2. In this computer
graphic, oxygen and nitrogen atoms are
shown conventionally as red and blue
respectively, but carbon atoms are
shown in green.

228
 Catalytic behaviour

Impurities in reactants can ‘poison’ heterogeneous catalysts, particularly Definition

metals, causing them to become less effective. Carbon monoxide ‘poisons’ the A heterogeneous catalyst is one that
iron catalyst used in the Haber process and lead compounds ‘poison’ catalytic is in a different state from the
converters, so lead-free petrol must be used. reactants. Generally, a heterogeneous
Heterogeneous catalysts work by adsorbing reactants at active sites on their catalyst is a solid while the reactants
surface. Nickel acts as a catalyst for the addition of hydrogen to unsaturated are gases or in solution.
compounds with carbon–carbon double bonds (Table 16.3). Hydrogen The advantage of heterogeneous
molecules are adsorbed on the catalyst surface where they are thought to split catalysts is that they can be
into single atoms. These highly reactive hydrogen atoms undergo addition separated from the reaction products
with molecules of unsaturated compounds, like ethene, as the unsaturated easily.
compounds approach the catalyst surface (Figure 16.11).

C
C

C
C C C
H H H H step 1 H H H step 2 H H

Ethene approaches the catalyst Ethene adds one hydrogen After adding a second
surface where hydrogen gas is atom and the CH3CH2• radical hydrogen atom the
adsorbed as single atoms. is attached to the surface. hydrocarbon, now ethane,
escapes from the surface.

If a metal is to be a good catalyst for the addition of hydrogen, it must not Figure 16.11쑿
adsorb the hydrogen so strongly that the hydrogen atoms become unreactive. A possible mechanism for the
This happens with tungsten. Equally, if adsorption is too weak, there will be hydrogenation of an alkene using a nickel
insufficient adsorbed atoms for the reaction to occur at a useful rate, as is the catalyst. The reaction takes place on the
surface of the catalyst, which adsorbs
case with silver. The strength of adsorption must have a suitable intermediate
hydrogen molecules and then splits them
value as it does with nickel, platinum and palladium.
into atoms.
Homogeneous catalysis
Homogeneous catalysis involves a catalyst in the same state as the reactants it
is catalysing. This type of catalysis is most important in biological systems in
which enzymes (proteins) catalyse the metabolic processes of all organisms.
Very often transition metal ions act as co-enzymes in these processes,
enhancing the catalytic activity of the associated enzyme. Cytochrome
oxidase is an important enzyme which contains copper. This enzyme is
involved when energy is released from the oxidation of food. In the absence of
copper, cytochrome oxidase is totally ineffective and the animal or plant is
unable to metabolise successfully.
Transition metal ions can also be effective as homogeneous catalysts
themselves because they can gain and lose electrons, changing from one
oxidation state to another. The oxidation of iodide ions by peroxodisulfate(VI)
ions using iron(III) ions as a catalyst is a good example of this:
2I−(aq) + S2O82− (aq) → I2(aq) + 2SO42− (aq)
In the absence of Fe3+ ions the reaction is very slow, but the reaction is many
times faster with Fe3+ ions in the mixture. A possible mechanism is that Fe3+
ions are reduced to Fe2+ as they oxidise iodide ions to iodine. Then the S2O82−
ions oxidise Fe2+ ions back to Fe3+, ready to oxidise more of the iodide ions,
and so on.

229
 Transition elements

Definitions Sometimes one of the products of a reaction can act as a catalyst for the
A homogeneous catalyst is one that process. This is called autocatalysis. An autocatalytic reaction starts slowly, but
is in the same state as the reactants. then speeds up as the catalytic product is formed. Mn2+ ions act as autocatalysts
Usually, the reactant and the catalyst in the oxidation of ethanedioate ions, C2O42−, by manganate(VII) ions in acid
are dissolved in the same solution. solution. This is also an example of homogeneous catalysis.
2MnO4− (aq) + 16H+(aq) + 5C2O42− (aq) →
2Mn2+(aq) + 8H2O(l) + 10CO2(g)

Test yourself
13 What is the advantage of using a solid heterogeneous catalyst in:
a) a continuous industrial process
b) an industrial batch process.
14 a) Write half-equations to explain the mechanism by which iron(III) ions catalyse
the reaction between iodide ions and peroxodisulfate ions.
b) Do you think Fe2+ ions will also catalyse this reaction? Explain your answer.
15 a) Suggest two methods of speeding up the reaction between MnO4− (aq) and
C2O42− (aq) from the start of the reaction.
b) What would you expect to see when a solution of potassium manganate(VII)
is added to an acidified solution of potassium ethanedioate:
i) at the start of the reaction
ii) as the reaction gets underway?

16.7 Ligands and complex ions

N Fe2+ N
O
C
N
OH
O
C

OH

Figure 16.12쑿 Figure 16.13쑿

Red blood cells in a small artery. The blood cells are red because A haem group with its Fe2+ ion. Haem groups are ligands
they contain haemoglobin, which is bright red when combined with forming four dative covalent bonds to the central Fe2+ ion.
oxygen. Haemoglobin is composed of complex ions with haem Each Fe2+ ion also has two dative covalent bonds from a
groups, globin molecules and Fe2+ ions. globin molecule.

During the AS course, we found that H+ ions in aqueous solution are strongly
O attached to water molecules by dative covalent bonds forming H3O+ ions. The
H structure of an H3O+ ion is shown in Figure 16.14.
H+ In the same way as H+, other cations can also exist in aqueous solution as
H hydrated ions. So, Mg2+(aq), Cu2+(aq) and Ag+(aq) can be represented more
Figure 16.14쑿 precisely as [Mg(H2O)6]2+(aq), [Cu(H2O)6]2+(aq) and [Ag(H2O)2]+(aq) in
Dative covalent bonding in an aqueous aqueous solution. But, notice that the larger size of these cations relative to
H3O+ ion. H+ enables them to associate with up to six water molecules.

230
 Ligands and complex ions

H H
H O
H
H O
O
2+ H
Cu
H
O H
O
H
H
O
H H

Figure 16.15쑿
Dative covalent bonding in an aqueous Cu2+ ion.

Other polar molecules, besides water, can also form dative covalent bonds
with metal ions. For example, in ammonia solution Cu2+ ions form
[Cu(NH3)4(H2O)2]2+ and Ag+ ions form [Ag(NH3)2]+.
In addition to polar molecules, anions can also associate with cations using Definitions
dative covalent bonds, and when anhydrous copper(II) sulfate is added to
concentrated hydrochloric acid the solution contains yellow [CuCl4]2− ions. A complex ion is an ion in which a
number of molecules or anions are
Ions such as [Cu(H2O)6]2+, [Cu(NH3)4(H2O)2]2+ and [CuCl4]2−, in which a
bound to a central metal cation by co-
metal ion is associated with a number of molecules or anions, are called ordinate bonds.
complex ions, and the anions and molecules attached to the central metal ion
A ligand is a molecule or anion bound
are called ligands. Each ligand must contain at least one lone pair of electrons,
to the central metal ion in a complex
which it uses to form a dative covalent bond with the metal ion. The number ion by co-ordinate bonding.
of ligands in a complex ion is typically two, four or six.
The co-ordination number of a metal
Chemists have an alternative name for dative covalent bonds which they
ion in a complex is the number of co-
often prefer to use when describing complex ions. The alternative name is ‘co- ordinate bonds to the metal ion from
ordinate bond’, which gives rise to the terms ‘co-ordination compound’ and the surrounding ligands.
‘co-ordination number’. A co-ordination compound is one which contains a
complex ion, and the co-ordination number of a complex ion is the number of
co-ordinate bonds from the ligands to the central metal ion.
Co-ordination compounds contain complexes which may be cations, anions
or neutral molecules. Examples of co-ordination compounds include:
● K3[Fe(CN)6] containing the negatively charged complex ion [Fe(CN)6]3−

● CuSO4.5H2O containing the positively charged complex ion [Cu(H2O)4]2+

● Ni(CO)4 which is a neutral complex between nickel atoms and carbon

monoxide molecules.

Figure 16.16씱
Crystals of six co-ordination compounds.
From left to right these are
NiSO4.7H2O, FeSO4.7H2O, CoCl2.6H2O,
CuSO4.5H2O, Cr2(SO4)3.18H2O and
K3[Fe(CN)6].

231
 Transition elements

There are two common visible signs that a reaction has occurred during the
formation of a new complex ion:
● a colour change or
● an insoluble solid dissolving.
A familiar example of a colour change occurs when excess ammonia solution
is added to copper(II) sulfate solution. Ammonia molecules displace water
molecules from hydrated copper(II) ions forming [Cu(NH3)4(H2O)2]2+(aq)
ions and the colour changes from pale blue to deep blue:
[Cu(H2O)6]2+(aq) + 4NH3(aq) → [Cu(NH3)4(H2O)2]2+(aq) + 4H2O(l)
The test for chloride ions using aqueous silver nitrate followed by ammonia
solution is an example of an insoluble solid dissolving as a complex ion forms.
Adding silver nitrate to a solution containing chloride ions produces a white
precipitate of silver chloride, AgCl. This precipitate dissolves on adding
ammonia solution because silver ions form the complex ion [Ag(NH3)2]+(aq)
with ammonia molecules:
AgCl(s) + 2NH3(aq) → [Ag(NH3)2]+(aq) + Cl−(aq)

16.8 Naming complex ions

There are four simple rules to follow when naming a complex ion.
1 Identify the number of ligands around the central cation using Greek
prefixes mono-, di-, tri-, tetra-, penta-, hexa-, etc.
2 Name the ligand using names ending in ‘-o’ for anions, e.g. chloro for Cl−,
fluoro- for F−, cyano- for CN−, hydroxo- for OH−, along with aqua- for H2O
and ammine- for NH3.
3 Name the central metal ion using the normal name of the metal for
positive and neutral complex ions, and the old-fashioned Latinised name
ending in ‘-ate’ for negative complex ions, e.g. ferrate for iron, cuprate for
copper, argentate for silver.
4 Finally, add the oxidation number of the central metal ion.
The examples in Table 16.4 illustrate how you should use the rules.
Table 16.4씰 Formula of 1 Identify the 2 Name the 3 Name the 4 Add the oxidation
Writing the systematic names of complex number of ligand central number of the
complex ions. ion ligands metal ion central metal ion
[Ag(NH3)2]+ di ammine silver (I)

[Cu(H2O)6]2+ hexa aqua copper (II)

[CuCl4]2− tetra chloro cuprate (II)

[Fe(CN)6]3− hexa cyano ferrate (III)

Test yourself
16 What is the co-ordination number of:
a) Fe2+ ions in haemoglobin b) Cu2+ ions in [Cu(H2O)6]2+
c) Fe3+ ions in [Fe(CN)6]3−?
17 Write the systematic names of the following complex ions:
a) [Cu(NH3)4]2+ b) [Zn(OH)4]2− c) [AlH4]− d) [Ni(H2O)6]2+
Note 18 What is the oxidation state of the metal ion in the following complex ions?
Notice that ammonia, NH3, in a) [NiCl4]2− b) [Ag(NH3)2]+ c) [Fe(H2O)6]3+ d) [Fe(CN)6]4−
complexes is described as ‘ammine’, 19 The fixer used to remove unexposed and undeveloped silver bromide from
whereas the −NH2 group in organic photographic film contains thiosulfate ions, S2O32−. Each silver ion forms a
compounds such as CH3NH2 is complex ion with two thiosulfate ions as the silver bromide dissolves. Write an
232
described as ‘amine’. equation for the formation of the complex.
 The shapes of complex ions

16.9 The shapes of complex ions

The shapes of complex ions depend on the number of ligands around the
central metal ion. There is no simple, definitive rule for predicting the shapes
of complexes from their formulae, but:
● in complexes with a co-ordination number of six, the ligands usually
occupy octahedral positions so that the six electron pairs around the
central atom are repelled as far as possible.
● in complexes with a co-ordination number of four, the ligands usually
occupy tetrahedral positions, although there are a few complexes with
fourfold co-ordination, such as [Pt(NH3)2Cl2], with a square planar
structure.
● in complexes with a co-ordination number of two, the ligands usually form
a linear structure with the central metal ion.
These structures are all illustrated in Figure 16.17.

NH3

Cl– Cu+ Cl–

Complexes with a
H3N co-ordination number
NH3 of 2 are usually linear
3+
Cr

H3N
NH3 Cl– Cl–
NH3

Complexes with a Pt2+

co-ordination number of Cl–
6 are usually octahedral NH3
Cr3+ A few complexes with NH3
Cl–
a co-ordination number
of 4 are planar
Cl–

Complexes with a Cl–

co-ordination number of
4 are usually tetrahedral

Types of ligand Figure 16.17쑿

Most ligands use only one lone pair of electrons to form a co-ordinate bond The shapes of complex ions.
with the central metal ion. These ligands are described as monodentate
because they have only ‘one tooth’ to hold onto the central cation (dens is
Latin for tooth). Examples of monodentate ligands include H2O, NH3, Cl−,
OH− and CN−.
Some ligands have more than one lone pair of electrons which can form
co-ordinate bonds with the same metal ion. Bidentate (‘two-toothed’) ligands,
for example, form two dative covalent bonds with metal ions in complexes.
Bidentate ligands include 1,2-diaminoethane, H2NCH2CH2NH2, the
ethanedioate ion, C2O42−, and amino acids.

233
 Transition elements

2+ 2+
H2N CH2
en
CH2
H2
N NH2

H2C
Ni2+ en Ni2+
H2C

Figure 16.18씰 N NH2

Representations of a complex formed by H2
the bidentate ligand 1,2-diaminoethane CH2 en
with nickel(II) ions. Note the use of ‘en’ as
an abbreviation for the ligand. H2N CH2

Note The hexadentate ligand edta is particularly impressive because it can form six
Edta crystals consist of the disodium
co-ordinate bonds with the central metal ion in complexes. The common
salt of ethanediaminetetraethanoic abbreviation for this hexadentate ligand is edta. It binds so firmly with metal
acid. Chemists sometimes use the ions that it holds them in solution and makes them chemically inactive. Edta
abbreviation Na2H2Y for the salt, is added to commercially produced salad dressings to extend their shelf life.
where Y represents the 4− ion. The ligand traps traces of metal ions which would otherwise catalyse the
oxidation of vegetable oils. Edta is also an ingredient of bathroom cleaners to
help remove scale by dissolving Ca2+ ions from the calcium carbonate left by
hard water.
O
– 2–
O C
O CH2
C CH2
–O N
CH2
2+
Pb
CH2

– N
O
C H2C
O –
CH2
O C

Note O
Monodentate ligands may also be Figure 16.19쑿
called unidentate ligands, and The complex ion formed by edta with a Pb2+ ion. The ligand can fold itself around
multidentate ligands are sometimes metal ions, such as Pb2+, so that four oxygen atoms and two nitrogen atoms form co-
called polydentate ligands. ordinate bonds to the metal ion. This is the ion formed when edta is used to treat lead
poisoning. The edta forms such a stable complex with Pb2+ ions that it can be
excreted through the kidneys.
Definitions
Ligands like those in Figures 16.18 and 16.19, which form more than one
Multidentate ligands are ligands
which form more than one co-ordinate co-ordinate bond with metal ions, are called multidentate ligands, and the
bond with the same metal ion. complexes which these ligands form are called chelates (pronounced ‘keelates’).
The term ‘chelate’ comes from a Greek word for a crab’s claw reflecting the
Chelates are complex ions involving
multidentate ligands. claw-like way in which chelating ligands grip metal ions. Powerful chelating
agents trap metal ions and effectively isolate them in solution.

Stereoisomerism in complex ions

As a result of the spatial positions of ligands around a central metal ion, four
co-ordinated and six co-ordinated complexes can have stereoisomers. These
234 stereoisomers have the same formula, but different spatial arrangements of
their constituent atoms.
 The shapes of complex ions

Two examples of E/Z isomerism (cis/trans isomerism) are shown in

Figure 16.20.
diamminedichloronickel(II) tetraamminedichlorocobalt(III)

Cl– Cl–

Cl– Cl– H3N H3N

NH3 NH3 NH3 NH3
Ni2+ Ni2+ Co3+ Co3+
Cl– H3N H3N H3N
NH3 Cl– NH3 Cl–

Cl– NH3
Z-isomer E-isomer E-isomer Z-isomer
(cis-isomer) (trans-isomer) (trans-isomer) (cis-isomer)

The chloride of tetraamminedichlorocobalt(III) is a particularly striking Figure 16.20쑿

example of the stereoisomerism caused by complex ions in co-ordination E/Z isomers of diamminedichloronickel(II)
compounds. In this compound, the two isomers have very different coloured and tetraamminedichlorocobalt(III).
crystals. The E-isomer forms green crystals, whereas those of the Z-isomer are
violet.
Octahedral (six co-ordinated) complex ions can also form optical
isomers because of their three-dimensional shape and an example of this is
shown in Figure 16.21. In the complex [Ni(H2NCH2CH2NH2)3]2+, three
1,2-diaminoethane molecules each bind to the central Ni2+ ion in two places.
The complex ion is asymmetric and the two stereoisomers are not
superimposable.

en en
The ligand
H2NCH2CH2NH2
en en is represented
Ni2+ Ni2+ en
as

en en
imaginary
mirror
Figure 16.21쑿
Optical isomers of [Ni(H2NCH2CH2NH2)3]2+.

Test yourself
20 Predict the likely shape of the following complex ions:
a) [Ag(CN)2] −; b) [Fe(CN)6]3−; c) [NiCl4]2−; d) [CrCl2(H2O)4]+
21 Explain how the amino acid glycine, (H2NCH2COOH), can act as a bidentate
ligand.
22 a) Why is edta described as a hexadentate ligand?
b) What is the overall shape of the edta complex in Figure 16.19?
23 a) Draw a diagram to represent the complex ion formed between a Cr3+ ion
and three ethanedioate ions, –OOC–COO–
b) What is the overall shape of this complex ion?
24 a) Predict an order of stability for the complex ions [Ni(NH3)6]2+, [Ni(en)3]2+ and
[Ni(edta)]2−
b) Explain your prediction. Figure 16.22쑿
25 Look at the painting and caption in Figure 16.22. Write the formula of: The blue pigment in this painting by
a) the hexacyanoferrate(II) ion George Romney in 1763 is called
b) iron(III) hexacyanoferrate(II). Prussian blue. Its correct chemical name 235
is iron(III) hexacyanoferrate(II).
 Transition elements

Activity

Cis-platin
The neutral complex, PtCl2(NH3)2, in which Cl− ions and NH3
molecules act as ligands, has two isomers. These isomers have
different melting points and different chemical properties. One
isomer, called cis-platin, is used in the treatment of certain cancers –
the other isomer is ineffective against cancer.
Patients are given an intravenous injection of cis-platin which
circulates all around the body including the cancerous area. Cis-platin
diffuses relatively easily through the tumour cell membrane because it
has no overall charge, like the cell membrane. Its action is shown in
Figure 16.23.
Once inside the cell, cis-platin reacts by exchanging one of its
chloride ions for a molecule of water forming [Pt(NH3)2(Cl)(H2O)]+
which is the ‘active principle’. This positively charged ion then enters
the cell nucleus where it readily bonds with two sites on the DNA.
Binding involves co-ordinate bonding from the nitrogen or oxygen
atoms in the bases of DNA to the platinum ion.
Figure 16.23씱
The action of cis-platin.
H3N Cl H3N Cl

Pt Pt

H3N Cl H3N Cl

cis-platin is neutral – Cl–

and so diffuses + H2O
through the cell +
membrane H3N Cl cell
nucleus
Pt DNA

H3N H 2O
The active principle
enters the nucleus and
binds with its DNA

The cis-platin binding changes the overall structure of the DNA helix,
pulling it out of shape and shortening the helical turn.
The badly shaped DNA can no longer replicate and divide to form
new cells, although the affected cells continue to grow. Eventually
the cells die and, if enough of the cancerous cells absorb cis-platin,
the tumour is destroyed.
Unfortunately, cis-platin is not a miracle cure without risks or
drawbacks. It is toxic, resulting in unpleasant side-effects, and can
cause kidney failure. However, clinical trials have led to the discovery
of other platinum complexes which cause fewer problems and are
already being used as anti-cancer drugs.
236
 Ligand substitution reactions

1 Why is it possible to conclude that cis-platin has a square planar

rather than a tetrahedral structure?
2 What type of isomerism do cis-platin and its isomer show?
3 a) What is the oxidation number of platinum in cis-platin?
b) Write the systematic name of cis-platin.
c) Draw the structure of cis-platin.
4 Why does cis-platin diffuse easily through the membrane of cells?
5 What is meant by the term ‘active principle’ applied to
[Pt(NH3)2(Cl)(H2O)]+?
6 When [Pt(NH3)2(Cl)(H2O)]+ has formed inside the cell, it cannot
diffuse out through the cell membrane. Why is this?
7 Why is a cell with cis-platin binding to DNA unable to replicate?
8 Why is the binding to cis-platin from nitrogen and oxygen atoms
rather than from carbon and hydrogen atoms in the bases of
DNA?
9 Why is cis-platin more likely to affect cancerous cells than normal
cells?
10 Why is any anti-cancer drug which acts like cis-platin likely to
have undesirable side-effects?

16.10 Ligand substitution reactions

Complex ions often react by swapping one ligand for another. These ligand
substitution reactions are usually reversible and the changes of ligand are often
accompanied by colour changes. For example, when excess concentrated
ammonia solution is added to pale blue copper(II) sulfate solution, ammonia
molecules are substituted for water molecules around the central Cu2+ ion and
the colour changes to a deep blue:
Cu(H2O)62+(aq) + 4NH3(aq) Cu(NH3)4(H2O)22+(aq) + 4H2O(l)
pale blue deep blue
The NH3 and H2O ligands are both uncharged and similar in size. This allows
substitution reactions between these ligands without there being a change in
co-ordination number of the metal ion.
A similar ligand substitution reaction occurs when concentrated
hydrochloric acid is added to copper(II) sulfate solution. This time, the colour
changes from pale blue to yellow as Cl− ions replace water molecules around
the Cu2+ ion:
Cu(H2O)62+(aq) + 4Cl−(aq) CuCl42−(aq) + 6H2O(l)
pale blue yellow
In this case, the ligand exchange does involve a change in co-ordination
number. Chloride ions are larger than water molecules, so fewer chloride ions
can fit round the central Cu2+ ion.

Ligand substitution in oxygen transport by haemoglobin

Ligand substitution is important in the transport of oxygen by haemoglobin
(Figures 16.12 and 16.13). The active part of haemoglobin is the Fe2+ ion.
This forms co-ordinate bonds to four nitrogen atoms in the haem ligand and 237
 Transition elements

to two nitrogen atoms in the globin. One of the latter positions can be weakly
and reversibly substituted by oxygen:

haemoglobin(aq) + O2(g) haemoglobin−O2(aq)

(oxyhaemoglobin)

This property allows haemoglobin to transport oxygen from the lungs to all
parts of the body, where the oxygen can be released for metabolic processes
such as respiration.
Unfortunately, carbon monoxide can also act as a ligand with Fe2+ ions, and
it binds more strongly than oxygen and irreversibly. Death is inevitable if
most of the haemoglobin in someone’s blood has combined with carbon
monoxide.

Stability constants
In aqueous solution, the simple compounds of most transition metals contain
complex ions with formulae such as Cu(H2O)62+, Cr(H2O)63+ and
Co(H2O)62+.
When solutions containing other ligands, such as Cl−, are added to aqueous
solutions of these hydrated cations, the mixture comes to an equilibrium in
which the water molecules of some complexes have been replaced by the
added ligands. For example, the equilibrium which results when concentrated
sodium chloride solution is added to aqueous copper(II) ions is:

Cu(H2O)62+(aq) + 4Cl−(aq) CuCl42−(aq) + 6H2O(l)

The equilibrium constant, Kc, for this reaction is given by:

[CuCl42−(aq)]eq
Kc =
[Cu(H2O)62+(aq)]eq[Cl−(aq)]4eq

[H2O(l)] is constant and therefore it is not included in the equation for Kc.
Equilibrium constants like this for the formation of complex ions in aqueous
solution are called stability constants and the symbol Kstab is normally used in
place of Kc.
Definitions Stability constants enable chemists to compare the stabilities of complex
ions of a cation with different ligands. The larger the stability constant, the
The stability constant, Kstab, of a
more stable is the complex ion compared with that containing water.
complex ion is the equilibrium
constant for the formation of the
Table 16.5 shows the stability constants of three complexes of the
complex ion from its constituent ions copper(II) ion. In order to avoid awkward powers of ten, the logarithms of the
in a solvent (usually water). values of stability constants are often quoted.
From the values for the stability constants in Table 16.5, the relative
stabilities of these three copper(II) complexes are:

Cu(edta)2– > Cu(NH3)4(H2O)22+ > CuCl42–

Table 16.5씰
Ligand Complex ion Kstab log Kstab
The stability constants of three copper(II)
complexes.
Cl− CuCl42− 4.0 × 105 5.6

NH3 Cu(NH3)4(H2O)22+ 1.3 × 1013 13.1

edta Cu(edta)2− 6.3 × 1018 18.8

238
 Redox reactions and titrations

Test yourself
26 Write equations for the ligand substitution reactions which occur when:
a) hexaaquacobalt(II) ions react with ammonia molecules to form
hexaamminecobalt(II) ions
b) hexaamminecobalt(II) ions react with chloride ions to form
tetrachlorocobaltate(II) ions
c) hexaaquairon(II) ions react with cyanide ions to form hexacyanoferrate(II) ions.
27 Explain the following changes with the help of equations.
a) Adding ammonia solution to a pale blue solution of hydrated copper(II) ions
produces a pale blue precipitate of the hydrated hydroxide.
b) On adding more ammonia solution, the precipitate dissolves to give a deep
blue solution.
28 Write expressions for the stability constants Kstab, for the following ligand Figure 16.24쑿
substitution reactions: Filter paper soaked in pink cobalt(II)
a) M2+(aq) + 6X−(aq) MX64−(aq) chloride solution and dried in an oven
b) Co(H2O)62+ + 4Cl−(aq) CoCl42−(aq) + 6H2O(l) until it is blue can be used to test for the
+
c) Ag(H2O)2 (aq) + 2NH3(aq) Ag(NH3)2+(aq) + 2H2O(l) presence of water.
29 A dilute solution of cobalt(II) chloride is pink because it contains hydrated cobalt(II)
ions. The solution turns blue on adding concentrated hydrochloric acid with the
formation of tetrachlorocobaltate(II) ions.
a) Write an equation for the reaction which occurs when concentrated HCl is
added to dilute cobalt chloride solution and indicate the colour of relevant
species.
b) Explain the chemical basis for the test illustrated in Figure 16.24.

16.11 Redox reactions and titrations

From Section 16.4 and Topic 15, you will know that transition elements can
occur in different oxidation states and exhibit a wide range of redox
behaviour. For example, chromium forms compounds in three oxidation
states, +2, +3 and +6. In the +3 state, chromium exists as Cr3+ ions and these
can be oxidised or reduced.
Under alkaline conditions, hydrogen peroxide oxidises green chromium(III)
ions, Cr3+(aq), to yellow chromium(VI) in chromate ions, CrO42−(aq):
H2O2(aq) + 2e− → 2OH−(aq)
Cr3+(aq) + 8OH− (aq) → CrO42−(aq) + 4H2O(l) + 3e−
In contrast to this, zinc reduces green Cr3+(aq) to blue–violet Cr2+(aq) ions:
Zn(s) → Zn2+(aq) + 2e−
Cr3+(aq) + e− → Cr2+(aq)
Figure 16.25씱
Solutions containing ions in the three
oxidation states of chromium. From left
to right, these test tubes contain yellow
CrO42−, orange Cr2O72−, green Cr3+ and
blue-violet Cr2+ ions in aqueous solution.

239
 Transition elements

Both potassium dichromate(VI) and potassium manganate(VII) are powerful

oxidising agents used as standard reagents in redox titrations.
In redox titrations, oxidising agents react with reducing agents. During the
titration, you will usually measure the volume of a standard solution of an
oxidising agent or a reducing agent that reacts exactly with a measured
volume of the other reactant.

Measuring reducing agents – potassium manganate(VII)

titrations
Potassium manganate(VII) is often chosen to measure reducing agents because
it can be obtained as a pure, stable solid which reacts exactly as the following
equation in acid solution:
MnO4−(aq) + 8H+(aq) + 5e− → Mn2+(aq) + 4H2O(l)
In addition, no indicator is required in manganate(VII) titrations. On adding
the potassium manganate(VII) solution from a burette, the MnO4− changes
rapidly from purple to colourless because the Mn2+ ions produced are very pale
pink. At the end-point, one drop of excess MnO4− is sufficient to produce a
permanent red–purple colour.

Worked example
Two iron tablets (total mass 1.30 g) containing iron(II) sulfate were dissolved
in dilute sulfuric acid and made up to 100 cm3 (Figure 16.26). 10 cm3 of this
solution required 12.00 cm3 of a standard solution of 0.0050 mol dm−3 KMnO4
to produce a faint red colour. What is the percentage of iron in the iron
tablets? (Fe = 55.8)

safety filter

solution containing pipette

1.30 g iron tablets KMnO4 solution,
in 100 cm3 concentration = 0.0050 mol dm–3

burette

100cm3 conical flask

solution
average accurate titration
10cm3 = 12.00 cm3 KMnO4 solution

Figure 16.26쑿 Finding the percentage of iron in iron tablets.

Notes on the method

1 Write the half-equations and work out the amounts in moles of Fe2+ and
MnO4− which react.
2 Calculate the amount of MnO4− which reacts in the titration, and hence
the amount of Fe2+ which reacts.
3 Work out the amount of Fe2+ in the whole solution, and hence in the
tablets dissolved.
4 Calculate the percentage of iron in the tablets.
240
 Redox reactions and titrations

Answer Definitions
Step 1: The half-equations for the reaction are: A standard solution is a solution with
MnO4 + 8H + 5e → Mn
− + − 2+
+ 4H2O an accurately known concentration.
The method of preparing a standard
and (Fe2+ → Fe3+ + e−) × 5 solution is to dissolve a weighed
sample of a primary standard in water,
So 5 mol Fe2+ react with 1 mol MnO4−. and then make the solution up to a
12
Step 2: Amount of MnO4− reacting = dm3 × 0.0050 mol dm−3. definite volume in a graduated flask.
1000
A primary standard is a chemical
12 which can be weighed out accurately
So the amount of Fe2+ reacting = × 0.0050 × 5 mol to make up a standard solution. A
1000
primary standard must:
12
Step 3: Amount of Fe2+ in 100 cm3 = × 0.0050 × 5 × 10 mol • be very pure
1000
of solution (2 tablets) • not gain or lose mass when
3 exposed to the air
= mol
1000 • have a relatively high molar mass
3 so that weighing errors are
Step 4: Mass of Fe2+ in two tablets = mol × 55.8 g mol−1 minimised
1000
• react exactly and rapidly as
= 0.1674 g described by the chemical equation.
0.1674 g
So, % of iron in the tablets = × 100
1.30 g
= 12.9%

Measuring oxidising agents – iodine/thiosulfate titrations

The measurement of oxidising agents usually involves a combination of
potassium iodide and sodium thiosulfate.
The oxidising agent to be estimated (e.g. iron(III) ions, copper(II) ions,
chlorine or manganate(VII) ions in acid) is first added to excess potassium
iodide. This produces iodine:
2Fe3+(aq) + 2e− → 2Fe2+(aq)
2I−(aq) → I2(aq) + 2e−
The iodine stays in solution in excess potassium iodide forming a yellow–
brown solution.
The amount of iodine produced is then determined by titration with a
standard solution of sodium thiosulfate, Na2S2O3(aq), which reduces the
iodine back to colourless iodide ions:
I2(aq) + 2e− → 2I−(aq)
2S2O32−(aq) → S4O62−(aq) + 2e−
thiosulfate tetrathionate
The greater the amount of oxidising agent added, the more iodine is formed
and the more thiosulfate is needed to react with it. On adding thiosulfate from
a burette, the colour of the iodine solution becomes paler. Near the end-point,
the solution is a very pale yellow. Adding a small amount of soluble starch
solution as an indicator at this point gives a sharp colour change from dark
blue to colourless at the end-point.
The following activity illustrates the use of iodine/thiosulfate titrations in
determining the concentration of supermarket bleaches, and then considers
the accuracy, reliability and validity of the final results.

241
 Transition elements

Activity

Supermarket bleaches
Figure 16.27씱
Supermarket bleaches.

The active reagent in household bleaches is sodium chlorate(I),

NaClO. To increase the cleaning power of these bleaches,
manufacturers usually add detergents, and to improve their smell
they add perfumes. Sodium chlorate(I) is a strong oxidising agent
which bleaches by oxidising coloured materials to colourless or
white substances.
The half-equation when sodium chlorate(I) acts as an oxidising agent
is:
ClO−(aq) + 2H+(aq) + 2e− → Cl−(aq) + H2O
A student was asked to determine the concentration of sodium
chlorate(I) in a supermarket bleach.
Using a measuring cylinder, 100 cm3 of the bleach was added to a
graduated flask and made up to a volume of 1000 cm3. 10.0 cm3 of
the diluted solution was then pipetted into a conical flask, followed
by the addition of excess potassium iodide.
The iodine produced was finally titrated with 0.10 mol dm−3 sodium
thiosulfate solution giving an average accurate titration of 26.60 cm3.
1 Write a half-equation for the oxidation of iodide ions to iodine.
2 Write a balanced equation for the reaction of chlorate(I) ions with
iodide ions in acid solution to form iodine, chloride ions and
water.
3 Write a balanced equation for the reaction of iodine with
thiosulfate ions during the titration.
4 Using your answers to questions 2 and 3, calculate the number
of moles of thiosulfate that react with the iodine produced by
1 mole of chlorate(I) ions.
242
 Redox reactions and titrations

5 Calculate the number of moles of thiosulfate in the average

accurate titration, and hence the number of moles of sodium
chlorate(I) in 10 cm3 of the diluted bleach.
6 Calculate the mass of sodium chlorate(I) in 100 cm3 of undiluted
bleach. (Na = 23.0, Cl = 35.5, O = 16.0)
7 What precautions should the student take to ensure that the
result is accurate?
8 What could the student do to improve the reliability of the result?
9 What must the student do to ensure the result is valid?
10 Use the practical guidance entitled ‘Errors and uncertainty’ on the
Dynamic Learning Student website to answer the following
questions. Practical
guidance
a) Calculate the uncertainty and percentage uncertainty in:
i) the volume of undiluted bleach taken
ii) the volume of diluted bleach pipetted
iii) the volume of thiosulfate titrated
iv) the concentration of the thiosulfate solution.
b) Calculate the total percentage uncertainty in the mass of
sodium chlorate(I) in 100 cm3 of undiluted bleach.
11 Express your result for the mass of sodium chlorate(I) in undiluted
bleach in the form x ± y g per 100 cm3.

Test yourself
30 Write half-equations for the reactions between acidified potassium manganate(VII)
and:
a) iron(II) sulfate solution
b) hydrogen peroxide solution.
31 Use your answers to question 30 to calculate the volume of 0.02 mol dm−3
potassium manganate(VII) solution required to oxidise 20 cm3 of:
a) 0.10 mol dm−3 iron(II) sulfate solution
b) 0.200 mol dm−3 hydrogen peroxide solution.
32 All the iron in 1.34 g of some iron ore was dissolved in acid and reduced to
iron(II) ions. The solution was then titrated with 0.020 mol dm−3 potassium
manganate(VII) solution. The titre was 26.75 cm3. Calculate the percentage by
mass of iron in the ore. (Fe = 55.8)
33 0.275 g of an alloy containing copper was dissolved in nitric acid, and then diluted
with water producing a solution of copper(II) nitrate. An excess of potassium
iodide was then added. The copper(II) ions reacted with the iodide ions to form a
precipitate of copper(I) iodide and iodine. In a titration, the iodine reacted with
22.50 cm3 of 0.140 mol dm−3 sodium thiosulfate solution. (Cu = 63.5)
a) Write equations for:
i) the reaction of copper(II) ions with iodide ions to form copper(I) iodide and
iodine
ii) the reaction of iodine with sodium thiosulfate during the titration.
b) Calculate the percentage by mass of copper in the alloy.

243
 REVIEW QUESTIONS Extension questions

1 Chemical reactions can be identified by two types of 3 Chromium shows its highest oxidation state in the
catalysis – homogeneous and heterogeneous. oxoanion, CrO42−.
a) Explain the term ‘homogeneous catalysis’ and state the a) Calculate the oxidation number of chromium in
most important feature of transition metal ions which CrO42−. (1)
allows them to act as homogeneous catalysts. (2)
b) The mixture changes colour when dilute acid is
b) In aqueous solution, I− ions slowly reduce S2O82− added to a solution containing CrO42− ions.
ions to SO42− ions.
State the changes in colour and write an equation
i) Write an equation (or two half-equations) for for the reaction that occurs. (3)
the reaction. (2)
c) When sulfur dioxide is bubbled into a solution of
ii) Suggest why the activation energy of the CrO42− ions, the colour changes and chromium is
reaction is high, resulting in a slow reaction in reduced to a simple ion. State the new colour and
the absence of a catalyst. (1) the formula of the new simple ion. (2)
iii) Write two equations (or two pairs of half- d) A sample of an oxochloride of vanadium, VOClx,
equations) to show the role of iron salts in containing 0.012 moles, required 20.0 cm3 of
catalysing the reaction. (2) 0.100 mol dm−3 potassium dichromate(VI) solution
for oxidation of the vanadium to its +5 oxidation
c) In Periods 5 and 6 of the periodic table, the
state.
catalytic efficiency of transition metals as
heterogeneous catalysts tends to be poor at the ends i) Copy and balance the half-equation below for
of the transition series, but high in the middle. the action of dichromate(VI) as an oxidising
agent:
i) Suggest two reasons why the efficiency of
transition metals as heterogeneous catalysts is Cr2O72−(aq) + …H+(aq) + …e−
poor at the ends of the transition series. (2) → …Cr3+(aq) + …H2O(l) (2)
ii) Suggest why their efficiency as heterogeneous ii) How many moles of dichromate(VI) reacted
catalysts is high in the middle of the transition with the oxochloride of vanadium? (1)
series. (2)
iii) How many moles of electrons were taken by the
d) In catalytic converters used to ‘clean’ the exhaust Cr2O72− ions? (1)
gases from petrol engines, a catalyst reduces
iv) Calculate the change in oxidation state of the
nitrogen oxides using another pollutant gas as the
vanadium during the reaction. (1)
reducing agent. State a suitable catalyst for catalytic
converters, identify the reducing agent and write an v) Write the formula of the oxochloride of
equation for a possible reaction that occurs. (3) vanadium showing the correct value of x. (1)
2 a) Write the electronic structure of: 4 This question concerns the chemistry of transition
metals.
i) a scandium atom (1)
a) Define and explain the terms:
ii) a copper atom (1)
i) transition metal (3)
iii) a Cu2+ ion. (1)
ii) oxidation number (3)
b) Both scandium and copper are d-block elements, but
only copper is a transition element. Explain the iii) complex ion. (3)
meaning of these terms. (3)
b) Discuss with examples, equations and observations
c) Aqueous Cu2+ ions react with excess ammonia the typical reactions of the ions of transition
solution to form [Cu(NH3)4(H2O)2]2+ ions. metals. (9)
i) Write the name of the [Cu(NH3)4(H2O)2]2+ 5 Describe, using suitable examples and diagrams, the
ion. (1) different shapes and different types of stereoisomerism
shown by the complex ions of transition metals. In your
ii) What is the overall shape of the
diagrams, show clearly the shape and/or type of
[Cu(NH3)4(H2O)2]2+ ion? (1)
stereoisomerism involved. (12)
d) Explain why the complexes of copper(II) ions are
usually coloured. (4)
244
 REVIEW QUESTIONS

6 The reaction scheme below involves various b) Describe and explain, with an equation, what you
compounds of copper. would see when solution C is diluted with excess
dilute
water. (6)
H2O(l) NH3(aq) c) When aqueous sodium hydroxide is added to
CuSO4.5H2O(s) blue solution blue precipitate
A B copper(II) sulfate solution, a blue precipitate is
excess excess formed. However, if excess edta solution is first
conc. conc.
added to the copper(II) sulfate solution, before the
HCl(aq) NH3(aq)
aqueous sodium hydroxide, no precipitate forms.
yellow-green deep-blue Write an equation for the formation of the blue
solution solution
C D
precipitate with aqueous sodium hydroxide and
explain why no precipitate forms if excess edta is
added to the copper(II) sulfate solution before the
a) Write the formulae of the species responsible for the sodium hydroxide. (5)
colour in each of the products A to D. (4)

245
246
The periodic table of elements

1 2 3 4 5 6 7 0(8)

(18)
1.0
H 4.0
hydrogen He
1 helium
(1) (2) Key (13) (14) (15) (16) (17) 2

6.9 9.0 relative atomic mass 10.8 12.0 14.0 16.0 19.0 20.2
Li Be atomic symbol B C N O F Ne
lithium beryllium name boron carbon nitrogen oxygen fluorine neon
3 4 atomic (proton) number 5 6 7 8 9 10

23.0 24.3 27.0 28.1 31.0 32.1 35.5 39.9

Na Mg Al Si P S Cl Ar
sodium magnesium aluminium silicon phosphorus sulfur chlorine argon
11 12 (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) 13 14 15 16 17 18

39.1 40.1 45.0 47.9 50.9 52.0 54.9 55.8 58.9 58.7 63.5 65.4 69.7 72.6 74.9 79.0 79.9 83.8
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
potassium calcium scandium titanium vanadium chromium manganese iron cobalt nickel copper zinc gallium germanium arsenic selenium bromine krypton
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

85.5 87.6 88.9 91.2 92.9 95.9 [98] 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
rubidium strontium yttrium zirconium niobium molybdenum technetium ruthenium rhodium palladium silver cadmium indium tin antimony tellurium iodine xenon
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54

132.9 137.3 138.9 178.5 180.9 183.8 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 [209] [210] [222]
Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
caesium barium lanthanum hafnium tantalum tungsten rhenium osmium iridium platinum gold mercury thallium lead bismuth polonium astatine radon
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86

[223] [226] [227] [261] [262] [266] [264] [277] [268] [271] [272]
Fr Ra Ac* Rf Db Sg Bh Hs Mt Ds Rg
francium radium actinium rutherfordium dubnium seaborgium bohrium hassium meitnerium darmstadtium roentgenium Elements with atomic numbers 112–116
87 88 89 104 105 106 107 108 109 110 111
have been reported but not fully authenticated

140 141 144 [147] 150 152 157 159 163 165 167 169 173 175

*Lanthanide series Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
cerium praseodymium neodymium promethium samarium europium gadolinium terbium dysprosium holmium erbium thulium ytterbium lutetium
58 59 60 61 62 63 64 65 66 67 68 69 70 71

232 [231] 238 [237] [242] [243] [247] [245] [251] [254] [253] [256] [254] [257]

*Actinide series Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
thorium protactinium uranium neptunium plutonium americium curium berkelium californium einsteinium fermium mendelevium nobelium lawrencium
90 91 92 93 94 95 96 97 98 99 100 101 102 103
Index
Page numbers in bold refer to illustrations.

A ammonia 133, 148, 152–3,

232
diazonium salts 44, 45
disubstitution reactions 6
condensation polymers 74
electrophilic substitution
absorption 94, 115, 116
coloured ions 226, 227 anhydrides 32, 33 electronic structure 4, 5 reactions 9, 10
fuel cells 216, 217 anions 182 orbital structure 4, 5 equilibria 144
acids 28–39, 147–70 amino acids 52, 53 phenols 14–16 esters 33, 38
amines 42 hydration 183 polyamides 70 fuel cells 214–15, 216
amino acids 51–2 ionic bonding 171 resistance to reaction 3 halogenation 9, 10
condensation polymers 74 ligands 231 stability 3–4, 12 heterogeneous 228–9
dissociation constant 153 see also polarisation/polarity structure 2–4 hydrolysis 72
equilibria 142–3 antibiotics 88, 89 see also arenes lock-and-key models 135
esters 32, 33 antiseptics 2, 16 bidentate ligands 233, 234 peptides/proteins 53
hydrolysis 72, 73 aramids 69 biodegradable materials 71, phenol manufacture 15
oxidation reactions 23 arenes 2–18, 6 73–4, 75 reaction rates 125
phenol manufacture 15 alkene reactions 11–12 biodiesel 38 stereochemical synthesis 87
reaction rates 124 benzene 2–5 bleach 241, 242, 243 transition elements 228–30
redox reactions 202 bromine 12, 14 blood cells 56, 138, 159, 160, triglycerides 36
activation energies 131, 132, electrophilic substitution 230, 237–8 Ziegler–Natta 65
144, 210 reactions 9–12 boiling points 84, 86 see also enzymes
active sites 87, 88, 135 naming 5–6 Boltzmann, Ludwig 188 cations
acyl groups 33 phenols 13–17 Born, Max 175 amino acids 52, 53
addition reactions properties/reactions 6, 7 Born–Haber cycles 171, arenes 9, 12
arenes 7, 12 stability 3–4, 12 175–7, 180, 182, 193 hydration 183
carbonyl compounds 19 substitution reactions 7–8, bromine ionic bonding 171
ketones 21 9–12 arenes 12, 14 ligands 230
nucleophilic reactions 24, aromatherapy 21 benzene rings 8 polarisation 178, 179
87 aromatic compounds 2–18 electrophilic substitution stability constants 238
polymerisation 63–5, 71 amides 69 reactions 9, 10 water interaction 183
adenine 148 amines 43, 44, 45, 46 halogenation 8 see also polarisation/polarity
adenosine triphosphate (ATP) condensation polymers 74 mass spectra 114 CDCl3 106, 107, 108, 109
197 esters 32 reaction rates 125 cell potentials (e.m.f.) 192,
adsorption 94, 216, 217, 229 high-resolution proton 1-bromobutane 80, 133, 134 205, 206, 207–10, 213
alanine 57 NMR 110 2-bromo-2-methylpropane 134 le Chatelier’s principle 30,
alcohols see also benzene bromothymol blue 166 143, 157
carboxylic acids 30 aspirin 32 Brønsted–Lowry theory 147 chelates 234
condensation reactions 68 asthma 40, 46 Buchner funnels 83 chemical shifts 106, 108
esters 33, 38 atomisation 174 buffers 147, 157–60, 164, 167 chiral molecules 57–9, 88, 89,
oxidation reactions 20, 21 ATP (adenosine triphosphate) 91
reduction reactions 23 197 C chloramphenicol 89
autocatalysis 230 calomel 206 chlorine
aldehydes 19, 20, 23 calorimeters 168
alcohol conversions 20 automatic titrators 161 benzene reactions 10–11
azo dyes 45–7, 46, 47 cancer 6, 46, 83, 90, 236 benzene ring 10, 16
formation 21 capillary columns 98
nucleophilic addition Born–Haber cycles 180, 182
reactions 24
B car batteries 212–13 dissolving reactions 181
bacteria 152 carbocation 113 hydration 183
Tollens’ reagent 25 Baekeland, Leo 17, 62 carbon dioxide 30, 38, 91,
aliphatic molecules 43, 69, 75 ionic bonding 171, 172,
‘Bakelite’ 17, 62 168, 186 173
Alka-Seltzer tablets 187 balanced equations see carbon monoxide 228, 229,
alkaline cells 211, 212 mass spectra 114
equilibria 238 phenol tests 14
alkalis 151, 152, 167 ball-and-stick models 29 carbon-13 NMR 106, 107,
carboxylate formation 53 chlorophyll 77, 78, 186
bases 14, 147–70, 151 108, 109, 118 cholesterol 36, 37
ethyl ethanoate 33 alkalis 14, 33, 35, 53, 72, carbonic acid 159
neutralisation 168 chromate 142, 143
168 carbonyl compounds 19–27 chromatography 78, 86,
phenol reactions 14 amines 41 aldehydes 19–21, 22, 23–5
polyamides/polyesters 72 93–104, 101
amino acids 51–2 ketones 21, 23–5, 24, 25 cis-platin 236, 237
saponification 35 condensation polymers 74 nucleophilic addition
alkenes 11–12 cis/trans isomerism 36, 60, 235
esters 33, 38 reactions 24 citric acid 187
alkyl amines 41 hydrolysis 35, 72, 73 carboxylic acids 28–32, 39,
alpha amino acids 51, 53 co-ordination numbers 231,
nucleophilic addition 152 233, 235, 237–8
alpha-helical structures 54 reactions 24 amino acids 50
amides 53, 67, 68, 69–70, co-polymers 71
peptides/proteins 53 condensation reactions 68 collision theory 131, 132
72–3 batteries 208, 211, 212, 213, halogenation 156
amines 40–9, 152 colorimeters 124, 125
214 carcinogens 6, 46 colourings 96, 220
naming/structure 40, 41 benzene 2 Carothers, Wallace 62
preparation 43–4 azo dyes 45–7, 46, 47
bond lengths 3 carrier gases 97, 99 chromatography 93, 93
properties/reactions 41–3 bromine reactions 8, 12 catalysis
amino acids 50–61 complex ions/ligands 232
carboxylic acids 29 ammonia decomposition transition elements 226, 227
acid/base properties 51–2 chlorine reactions 10–11 133
3-letter code 51 column chromatography 93–4,
delocalisation 4–5 carboxylic acids 30 96–9, 102
naming/structure 50–4
247
 Index

combinatorial chemistry 80 1,2-dichlorobenzene 3 equilibria 99, 138–46, 202–3, decomposition 133

complementary colours 227 dichromate 142, 143, 202 238 electrode potentials 205
complex ions digestive enzymes 53 see also acids; bases equilibria 138, 142
ligands 230–2 discharging 213 equivalence points 161, 162, heterogeneous catalysis 228
naming 232 disinfectants 16 165, 169 lattice enthalpies 174
shapes 233–6 dispersol fast yellow 47 essential fatty acids 32, 36 Maxwell–Boltzmann
stereoisomerism 234–5 dissociation constant 153 esterification/esters 28, 30, distribution 132
composites 71, 147 dissolving reactions 181–4, 32–9, 38 reaction rates 123
concentrations 232 biodiesel 38 redox reactions 197
electrode potentials 205, 210 distillation 44, 83, 84 polymerisation 67–8, 72–3, standard molar entropies
enthalpies 181 disubstituted compounds 6 75 188, 189
equilibria 142–3 DNA (deoxyribonucleic acid) preparation 31 GC (gas chromatography) 96,
rate equations 127, 128, 148, 236 triglycerides 34–8 97, 98, 99, 100–2, 112
129 dolomite 194 ethanediaminetetraethanoic Gibbs, Willard 191–2
rate measurements 122, 123, dot-and-cross diagrams 171 acid (edta) 234 GLC (gas-liquid
125 drugs ethanoic acid 29, 30, 168 chromatography) 99, 112
supermarket bleach 242 clinical trials 90 ethanol 20, 107, 110 globin molecules see
titrations 241 distillation 83 ethene 12, 63 haemoglobin
see also acids; bases illegal 101, 105 ethylene glycol 67 globular proteins 55
condensation reactions 53, 63, stereochemistry 88, 89, 90 exhaust gases 228 glycerol 34
67–9, 71, 74 synthesis 91 exothermic reactions 143, 144, glycine 50, 52
conductivity cells/meters 124 transition metal complexes 182, 190 Gore-tex 62
conjugate acid–base pairs 236 Born–Haber cycles 175, 176 gradients (reaction rates) 122,
149–50 dry cells 211, 212 feasibility 187 123
constants dyes 45–7, 46, 47, 93 free energy 191 graphite 173, 186, 211, 214
acid dissociation 153 ionic bonding 172 ‘green’ thinking 38, 215, 217,
equilibria 139, 140, 142–4, E eye drops 157 218
154 E/Z isomerism 60, 235 guanine 148
rate equations 126 Eden Project 63 F
reaction rates 131 edta see ethanediamine- false-colour images 62, 147 H
stability 238 tetraethanoic acid fats 34 Haber, Fritz 175
water ionic products 150–1 elastomers 71 health risks 37 Haber processes 228, 229
see also acids; bases electric fields 112 hydrogenation reactions 36 see also Born–Haber cycles
cortisone 78 electrochemical cells/series hydrolysis 35 haemoglobin 56, 138, 159,
coupling 110 204, 205, 209–10 fatty acids 34, 35, 36, 37, 38 230, 237–8
covalent bonds 148, 177–9, electrode potentials 197, FCVs (fuel cell vehicles) half-cells 206, 208
230, 231 204–10, 223 215–17, 218 half-equations/reactions 199,
arenes 5, 9, 10 electromagnetic spectra 226, feasible reactions 187, 193–4, 204, 207–8, 209–10, 242
indicators 167 227 207, 210 half-life 127, 128
‘crude’ products 83 electrons fibrous proteins 54 halogenation/halogens
see also impurities affinities 174 first order reactions 127 arenes 8, 9, 10
crystals 25, 26, 181, 194 benzene 4, 5 Fischer, Hans 77 carboxylic acids 156
cumene processes 15 bombardment 113 fish 37 electrochemical series
cyanide 87 micrographs 71 flammable substances 99–100, 209–10
cytochrome oxidase 229 see also electrode potentials; 216 hydrolysis 133, 134
cytosine 148 oxidation reactions; redox see also fuel; petrol mass spectra 114
reactions; reduction forensics 99, 100, 101, 105 see also bromine; chlorine;
D reactions fractional distillation 83, 84 iodine
d-block elements see transition electrophiles 9–12, 15, 45 fragmentation 113 ‘hardening’ 36
elements electrostatic forces 177 free energy 191–5 heart disease 36, 37
D/L chiral systems 59 eluents/elution 93 free radicals 64 helical structures 54, 148, 236
dative covalent bonds 148, e.m.f. (cell potentials) 192, fruit 32 Hess’s law 175, 176
230, 231 205, 206, 207–10, 213 fuel 38 see also Born–Haber cycles
decomposition 133, 193, 194, enantiomers 57 chromatography 99, 100 heterogeneous catalysis 228–9
195 end-points 161, 162–3, 165, gas chromatography/mass hexadentate ligands 234
degradable materials 71, 73–4, 166, 241 spectrometry 102 high-performance liquid
75 endothermic reactions 143, redox reactions 200 chromatography (HPLC)
delocalisation 144, 184, 187, 191 see also petrol 96
arenes 4, 5, 7, 9–10, 12, 14 energetics/enthalpies 143–4, fuel cell vehicles (FCVs) high-resolution proton NMR
azo dyes 45 171–96 215–17, 218 110, 111
definition 2 benzene 3, 4 fuel cells 197, 214–18, 215 Hirsch funnels 83
indicators 167 dissolving reactions 181–4 functional groups 78, 81, 115 HIV (human
deoxyribonucleic acid (DNA) neutralisation 168 immunodeficiency virus)
148, 236 entropies 186–96 G 88, 90
derivatives 5, 25, 26 enzymes gas chromatography (GC) 96, homogeneous catalysis 229–30
Dettol 2, 16, 17 homogeneous catalysis 229 97, 98, 99, 100–2, 112 hormones 36, 78
deuterium atoms 109, 111 mechanism 135 gas-liquid chromatography HPLC (high-performance
diamminedichloronickel 235 peptides/proteins 53 (GLC) 99, 112 liquid chromatography)
diamond 173, 186, 188 reaction rates 135, 136 gases 193 96
diazonium salts 44–5 stereochemical molecules chromatography 96, 97, 98, human immunodeficiency
dibasic acids 148 87, 88 99, 100–2, 112 virus (HIV) 88, 90
248 coloured ions 227
 Index

hydration 182, 183 kidneys see also electrode potentials; Tollens’ reagent 25
hydrides 216–17 buffer solutions 159 fuel cells; ionic bonds; see also redox reactions
hydrocarbons 2–18, 145 cis-platin 236 transition elements oxygen 66, 148, 148, 186,
hydrochloric acid 168 lead poisoning 234 methanal 17, 19, 20 193, 230
hydrogen/hydrogenation kinetics 122–37, 193–4 methanoic acid 28, 29, 125 Born–Haber cycles 176
reactions 30, 147, 148, methyl groups 7, 107, 108, carbonate decomposition
151, 187, 193 L 113, 129 194, 195
benzene 4 L chiral systems 59 methyl orange indicators 166, equilibria 138, 140
bonding 29, 110 labile protons 110–11 167 fuel cells 214
buffer solutions 159 lactic acid 67, 68, 72, 87, 152 4-methylpentan-2-one 107 haemoglobin 56, 138, 159,
equilibria 138, 141, 144 lattice enthalpies 171–85 mobile phases 93 230, 237–8
fuel cells 214, 215, 216, 217 Le Chatelier’s principle 30, modern storage cells 211–14 photochemical smog 145
heterogeneous catalysis 229, 143, 157 molar entropies 188–9 redox reactions 197
229 lead-acid cells 212, 213 monobasic acids 148 transition elements 220,
isotopes 108–9 Leclanché, Georges 211, 212 monodentate ligands 233, 234 225
standard electrode potentials levodopa 89 MRI see magnetic resonance transport 237–8
206 ligands 235 imaging ozone 145
triglycerides 36, 37 cis-platin 236 multi-step reactions 133–4
see also acids; bases complex ions 230–2 multidentate ligands 233–4 P
hydrolysis substitution reactions 237–9 palladium 144
condensation polymers 74 types 233–4 N palmitic acid 35
esters 33 light 58, 147 natural chemicals 22 paraffin 99–100
halogenoalkanes 133, 134 chromatography 95 natural fats 34 Parkinson’s disease 89
peptides/proteins 53 coloured ions 226, 227 neutral complexes 231 Pascal’s triangle 110
polymers 72–3 optical isomerism 59 neutralisation 168–9 peppermint 21
triglycerides 35 ultraviolet 95, 147, 227 nickel 36, 229 peptides 53–4, 68
hydroxides 13, 14, 16, 134, see also polarisation/polarity niobium 217 perfume 22, 23, 117, 118, 242
168 limestone 168 nitrations peroxides 64
linear shapes 233 arenes 7, 8, 9 peroxo compounds 64
I linoleic acid 35 aromatic amines 43 petrol 99–100, 145
ibuprofen 91 lipids 34 rate equations 129 fuel cell vehicles 215
ice baths 124 liquids nitric oxide 145, 228 gas chromatography/mass
impurities 83–4, 229 chromatography 94–7, 99 nitrogen 148, 193 spectrometry 102
incinerators 73–4 crystals 77 benzene rings 44 heterogeneous catalysis 229
indicators 161, 166, 167, 241 entropies 188, 189 city smog 145 pH 149–52, 154
inert compounds 193–4 fuel cells 216 diazonium salts 44–5 buffer solutions 157
infrared light 25, 112–13, purification 84 NMR see nuclear magnetic indicators 166, 167
115–18, 147 Lister, Joseph 16 resonance spectroscopy salts 168
initial rate methods 129 lithium 208 noble gases 189, 193 titrations 161
integration 109 lithium cells 213, 214 non-metals 171–5 zwitterions 52
inter-esterification 36 lock-and-key models 135 see also electrode potentials; see also acids; bases
intravenous drips 159, 160, logarithms 152, 155, 165, 238 ionic bonds pharmaceuticals see drugs
236 lungs 159, 238 non-polar compounds 2–18 phenolphthalein 166
iodine 138, 141, 241 lysozyme 135 nuclear magnetic resonance phenols 6, 13, 14–17, 15–16,
ion acceleration 112 spectroscopy (NMR) 45
ionic bonds 171–85 M 105–11, 108–11, 112–13, phenylamine 41, 42, 44, 45,
ionic product (water) 150–1 magnesite 194 118 47
ionisation energies 174, 224 magnesium 180 nucleophiles 24, 43, 87, 134 photochemical smog 145
iron 9, 14, 229, 240 magnetic fields 105, 106, 112 nylon 16, 68, 69, 74 photodegradable materials 71,
isoelectric points 51–2 magnetic resonance imaging 74
isoleucine 88 (MRI) 111 O photosynthesis 77, 78, 186
isomerism 59, 60–1, 87 see also nuclear magnetic octahedral shapes 233 pi-bonds 5, 7, 9, 10, 12, 45
amino acids 57–9 resonance spectroscopy odour see aromatic compounds; PLA see poly(lactic acid)
arenes 3 manganate ions 201 perfume planar shapes 233
cis-platin 236 margarine 36 “OILRIG” 198 plastics 16, 17, 19, 71
complex ions 234–5 mass spectrometry 25, 78, 101, oils 32, 34, 35, 36, 37 poly(lactic acid) production
drugs 88, 89, 90 105, 112–15 omega-fatty acids 34, 35, 37 75
hydrolysis 133–4 mass-to-charge ratio 112 optical isomerism see recycling 73, 74
triglycerides 36 Maxwell–Boltzmann isomerism cis-platin 236, 237
isotopes 108–9, 114 distribution 132 orange dichromate 202 platinum 133, 206, 207, 228
medicine 111 orbitals 4, 5, 220, 227 poison see toxicity
J see also drugs orders 126, 127, 128, 129 polarisation/polarity 178–9,
jasmone 117, 118 melting points 86, 223 overall orders 126 182, 230–1
menthone 21 oxidation reactions hydration 183
K metals alcohols 20, 21 light 58, 59, 77
Kekulé, Friedrich 2–3 carbonates 194, 195 aldehydes/ketones 23 nucleophilic addition
ketones 19, 21, 23 cell potentials 208 chromium 239 reactions 24
formation 21 enthalpy/entropies 186, 188 free energy 192 polaroid sheets 58
nucleophilic addition ionic bonding 171–5 homogeneous catalysis 229 pollution 102, 149, 228
reactions 24 redox reactions 201 numbers/states 198, 225–6, poly(chloroethene) (pvc) 63
Tollens’ reagent 25 232 poly(glycolic acid) 74
Kevlar 69, 70 phenol manufacture 15 249
 Index

poly(lactic acid) (PLA) 67, ‘reformer’ catalysts 216 stereochemical molecules toxicity
68, 72, 75 resins 16, 17, 19 87–91 azo dyes 46
polymerisation/polymers 17, respiration 197, 238 stereoisomerism 60–1, 234–5 cis-platin 236
21, 62–76 retention times 98 steroids 36, 78 heterogeneous catalysis 229
addition reactions 63–5, 71 retinal 19 stitches 74 lead 234
amides 67, 68–9, 70, 72–3 reversibility 138–9 storage cells 211–14 trans-esterification 38
condensation reactions 63, Rf values 95 strong acids/bases 148 trans-fats 36, 37
67–9, 71, 74 ribonucleic acid (RNA) 148 buffer solutions 157 trans isomerism 36, 60, 235
degradability 73–4 rod cells 19 neutralisation 168–9 transition elements 220–45
esters 67–8, 72, 75 titrations 162–4 catalysis 228–30
peptides/proteins 53 S substitution reactions colourings 226, 227
polystyrene 63 salbutamol 40, 89 arenes 6, 7–8, 9–12 definition 222
unsaturated fats 36 salts ligands 237–9 electron configurations
polystyrene 63 amines 44–5 phenol production 15 220–2
poly(tetrafluoroethene) (ptfe) bridges 204, 205, 206, 207 reaction rates 134 ionisation energies 224
63 dissolving reactions 181 substrates 135, 136 oxidation states 225–6
polyvinyl alcohol 64 pH 168 sutures 74 transition states 131
potassium 202, 240, 241, 242 titrations 164, 165 synthesis 77–92 transmission quadrupole
powdered solids 94, 99, 200 saponification 35 drugs 91 instruments 112
pressure 96 saturated fatty acids 34, 36, 37 functional groups 78, 81 triglycerides 34–8, 35
electrode potentials 210 scanning electron micrographs organics 77–8, 80–2 Tswett, Michel 93
equilibria 142 19 stereochemical molecules tungsten 229
free energy 191 second order reactions 128 87–91 two-stage routes 80
fuel cells 216 secondary cells 212 techniques 82–6 two-step mechanisms 134
primary standards 241 see also rechargeable cells synthetic chemicals 22
probability see feasible separating mixtures 83 U
reactions shampoos 157 T ultraviolet light 95, 147, 227
product identification 85–6 silver 25, 206, 229 ‘target molecules’ 80 unsaturated fatty acids 34, 36,
propanone 21 simple distillation 83 tartrazine 46 37
proteins 50–61, 54, 55 single-step mechanisms 134 TCP 2, 16, 17 uracil 148
see also enzymes smog 145 Teflon 66 urease 136
proton NMR 108, 109, 110, SN1/SN2 reactions 134 temperature 193
111 soap 35 carbonate decomposition V
proton transfer 147, 148, 230 sodium 187 194, 195 vacuum 113
see also acids; bases arenes 13 electrode potentials 205, 210 vanadium 226
Prussian blue 235 bleach 242 equilibria 143, 144 vapours 84, 102, 215
ptfe see Born–Haber cycles 176, 182 free energy 191–2 vegetable oils 34, 35, 36, 37
poly(tetrafluoroethene) dissolving reactions 181 reaction rates 127, 131–2 vibrations 116
purification/purity 83–4, 85–6 hydration 183 see also energetics/enthalpies volatile chemicals 84, 97, 216
pvc see poly(chloroethene) ionic bonding 171, 172, terephthalic acid 67 volcanoes 197
173 Terylene 67, 68 voltage 204, 215
Q neutralisation 168 tetraamminedichlorocobalt see also electrode potentials
qualitative testing 85 solids 235
quantum theory 227 boiling/melting points 86 tetrachloromethane 109 W
complex ions/ligands 232 tetrafluoroethene 63 water 151, 186
R entropies 188, 189 tetrahedral shapes 233 amine reactions 42
racemic mixtures 87 fuel cells 216 tetramethylsilane (TMS) 106, complex ions/ligands 232
radiation 115, 226, 227 purification 83 107, 109 fuel cells 215
radicals 64 solubility 184 thalidomide 88, 89, 90 ionic products 150–1
rate equations 126–31, 133–4 solvent extractions 138 thermite reaction 190 lithium cells 213
reaction profiles 131 spectrometry/spectroscopy 25, thermodynamics 193–5 pH scale 149
reaction rates 122–37 78, 86, 101, 105–20 see also urease 136
measuring 122–5 spin 105, 110 energetics/enthalpies; vapours 84
rate equations 126–31, spontaneous reactions 186–7 temperature weak acids/bases 152–6
133–4 stability 193–4 thermoplastic polymers 16, 17, indicators 166–7
temperature 131–2 arenes 3–4, 12 17, 19, 75 neutralisation 168, 169
see also catalysis benzene 3–4, 12 thermosetting plastics 16, 17, titrations 162–4, 165
rechargeable cells 212, 213, constants 238, 238 19 Woodward, Robert 77–8
214
recycling 73, 74
ionic bonds 180
standard cell potentials 205,
thin-layer chromatography
(TLC) 94, 95
Y
red blood cells 56, 138, 159, yield measurements 85
206, 207, 209 thiosulfate 241, 242
230, 237–8
redox reactions 197–219
standard enthalpy changes thymine 148 Z
173, 182 time (rate equations/reaction Z isomerism 60, 235
definition 197–8 standard molar entropies rates) 122, 123, 127, zero order reactions 129, 133
free energy 192 188–9 128, 129 Ziegler–Natta catalysts 65
fuel cells 214 standard solutions 241 titrations 124, 161–7 zwitterions 51, 52
titrations 239–41 starch 75, 201, 241 indicators 166–7
reduction reactions 23, 43, 44, starting molecules 80 redox reactions 239–41
192, 197–219, 239–41 state symbols 173 TLC see thin-layer
reference electrodes 206 stationary phases 93, 94, 99 chromatography
reflux condensers 82 Staudinger, Hermann 62 TMS see tetramethylsilane
250 steam distillation 44, 83 Tollens’ reagent 25