Dynamic Learning is an online subscription solution that supports teachers and students with high

quality content and unique tools. Dynamic Learning incorporates elements that all work together to give
you the ultimate classroom and homework resource.

Teaching and Learning titles include interactive resources, lesson planning tools, self-marking tests
and assessment. Teachers can:
● Use the Lesson Builder to plan and deliver outstanding lessons

● Share lessons and resources with students and colleagues

● Track students’ progress with Tests and Assessments

Teachers can also combine their own trusted resources alongside those from AQA A-level Chemistry 2
which has a whole host of informative and interactive resources including:
● Engaging animations and online presentations to provide students with clearer explanations

● Interactive tests within each chapter that can be used in class or set as homework

● Numerous stretch and extension materials to encourage higher-attaining students

● Interactive flash cards, a table of the correct A-level language and a full glossary of words used in context

AQA A-level Chemistry 2 is available as a Whiteboard eTextbook which is an online interactive

version of the printed textbook that enables teachers to:
● Display interactive pages to their class

● Add notes and highlight areas

● Add double-page spreads into lesson plans

Additionally the Student eTextbook of AQA A-level Chemistry 2 is a downloadable version of the
printed textbook that teachers can assign to students so they can:
● Download and view on any device or browser

● Add, edit and synchronise notes across two devices

● Access their personal copy on the move

To find out more and sign up for free trials visit: www.hoddereducation.co.uk/dynamiclearning
 AQA
A-level

Chemistry
2
Alyn G. McFarland
Teresa Quigg
Nora Henry

1471807701_AQA_Chemistry_2_CP_ePub.indd 1 19/06/2015 12:51

 AQA material is reproduced by permission of AQA.
Although every effort has been made to ensure that website addresses are correct at time of going to
press, Hodder Education cannot be held responsible for the content of any website mentioned in this
book. It is sometimes possible to find a relocated web page by typing in the address of the home page
for a website in the URL window of your browser.
Hachette UK’s policy is to use papers that are natural, renewable and recyclable products and made from
wood grown in sustainable forests. The logging and manufacturing processes are expected to conform to
the environmental regulations of the country of origin.
Orders: please contact Bookpoint Ltd, 130 Milton Park, Abingdon, Oxon OX14 4SB. Telephone: +44
(0)1235 827720. Fax: +44 (0)1235 400454. Lines are open 9.00 a.m.–5.00 p.m., Monday to Saturday,
with a 24-hour message answering service. Visit our website at www.hoddereducation.co.uk
© Alyn McFarland and Nora Henry 2015
First published in 2015 by
Hodder Education,
An Hachette UK Company
Carmelite House, 50 Victoria Embankment, London EC4Y ODZ
Impression number 5 4 3 2 1
Year 2019 2018 2017 2016 2015
All rights reserved. Apart from any use permitted under UK copyright law, no part of this publication
may be reproduced or transmitted in any form or by any means, electronic or mechanical, including
photocopying and recording, or held within any information storage and retrieval system, without
permission in writing from the publisher or under licence from the Copyright Licensing Agency Limited.
Further details of such licences (for reprographic reproduction) may be obtained from the Copyright
Licensing Agency Limited, Saffron House, 6–10 Kirby Street, London EC1N 8TS.
Cover photo © SSilver–Fotolia
Illustrations by Aptara
Typeset in 11/13 pt ITC Berkeley Oldstyle Std by Aptara, Inc.
Printed in Italy
A catalogue record for this title is available from the British Library.
ISBN 978 1471 807701

807732_FM_AQA_Chemistry_2_i-vi.indd 2 16/06/2015 17:18

 Contents
Get the most from this book iv
Acknowledgements vi
1 Thermodynamics: Born-Haber cycles 1
2 Thermodynamics: Gibbs free energy change,
ΔG, and entropy change, ΔS 26
3 Rate equations 43
4 Equilibrium constant Kp for homogeneous
systems 68
5 Electrode potentials and cells 78
6 Acids and bases 100
7 Properties of Period 3 elements and
their oxides 135
8 Transition metals 149
9 Transition metals: Variable oxidation states 175
10 Optical isomerism 192
11 The carbonyl group 198
12 Aromatic chemistry 233
13 Amines 245
14 Polymers, amino acids and DNA 261
15 Organic synthesis, NMR spectroscopy
and chromatography 287
16 Maths for chemistry 309
Index 321
QR codes 326

807732_FM_AQA_Chemistry_2_i-vi.indd 3 13/06/15 9:29 am

 Get the most from this book
Welcome to the AQA A-level Chemistry 2 Student’s Book. This book
covers Year 2 of the AQA A-level Chemistry specification and all content
for the AQA A2 Chemistry specification.
The following features have been included to help you get the most from
this book.

Prior knowledge Thermodynamics:

2
●● Feasible reactions
This is a short list of topics that Gibbs free energy

Entropy
A reaction that can occur at a particular temperature is called a feasible

change, ∆G, and

reaction. The enthalpy change on its own is not enough to determine

you should be familiar with before

whether or not a reaction will be feasible as some feasible reactions are
endothermic. These include:

entropy change, ∆S KCl(s) +(aq) → K+ (aq) + Cl− (aq) ΔH 1 = +19 kJ mol−1

starting a chapter. The questions H2O(s) → H2O(l)

H2O(l) → H2O(g)
ΔH 1 = +6 kJ mol−1
ΔH 1 = +44 kJ mol−1

will help to test your understanding. PRIOR KNOWLEDGE

It is expected that you are familiar with all of the content of Chapter 4
Energetics in the Year 1 book of the A-level Chemistry course. The
(NH4)2CO3 (s) → 2NH3(g) + CO2(g) + H2O(g) ΔH 1 = +68 kJ mol−1
All four of these reactions above have one thing in common – an increase in
disorder. This is the disorder of the particles in the system (reaction). Gases
following are some key points of Prior Knowledge: are more disordered than liquids and solution which are more disordered
● A positive value for ∆H indicates an endothermic reaction. than solids.
● A negative value for ∆H indicates an exothermic reaction.
● Enthalpy change for a reaction may be calculated using standard
All of them show a change from an ordered system to a more random
enthalpy changes of combustion or formation. system. The degree of disorder or randomness in a system is called its
● Hess’s Law states that the enthalpy change for a chemical reaction entropy.

●
is independent of the route taken and depends only on the initial and
final states.
Enthalpy changes may be calculated from other enthalpy changes
●● Entropy
using Hess’s Law. Entropy is given the symbol S and standard or absolute entropy S 1.
Entropy is a measure of disorder within a
system. Entropy is measured in J K−1 mol−1.

TEST YOURSELF ON PRIOR KNOWLEDGE 1 Absolute entropy values (standard entropy values)
1 Calcium carbonate decomposes on heating to form calcium oxide and Absolute or standard entropy values are calculated for one mole of a
carbon dioxide. Using the standard enthalpies of formation, calculate substance based on a scale where the substance has an entropy value of
the enthalpy change for this reaction. 0 (zero) at 0 K. This assumes that the crystalline form of the substance at 0 K
CaCO3 (s) → CaO(s) + CO2(g) is a perfect crystal.
∆f H 1/kJ mol−1 Some absolute entropy (S 1) values are given in the table:
CaCO 3(s) −1207
Solids S 1/ J K−1 mol−1 Liquids S 1/ J K−1 mol−1 Gases S 1/ J K−1 mol−1
CaO(s) −636 C(s) 2.4 Br2(l) 75.8 O2(g) 205
CO2(g) –394 (diamond)
Figure 2.1 Tossing a soft drink into the Si(s) 19.0 Hg(l) 76.1 Cl 2(g) 165
2 Calculate the standard enthalpy of formation of ammonia, where the air is more likely to give a disorganised Mg(s) 32.7 C2H5OH(l) 161 N2(g) 192
enthalpy change for the reaction N2(g) + 3H2(g) → 2NH3(g) is −92 kJ mol−1. pile when it falls, than a neatly ordered
Al(s) 28.3 H2O2(l) 110 H2(g) 131
3 Ammonia reacts with oxygen to form nitrogen monoxide and steam stack. Disorder is more probable than
according to the equation. order. NaCl(s) 72.4 CS2(l) 151 NH3(g) 193
4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g) CaO(s) 39.7 NH4NO 3(aq) 190 CO2(g) 214
26 a) Using the standard enthalpies of formation, calculate the enthalpy I2(s) 58.4 NaCl(aq) 116 CO(g) 198 27
change for this reaction. H2O(s) 48.0 H2O(l) 70.0 H2O(g) 189

∆f H 1/ kJ mol−1 The higher the absolute entropy value, the higher the degree of disorder of a
NH3(g) −46 substance.
O2(g) 0 From the table it is clear to see that solids are more ordered than liquids and
NO(g) + 90 solutions, which are more ordered than gases. This can be used as a general
H2O(g) −242 rule to explain changes in entropy later.
b) Explain why oxygen has a value of zero.

Key terms and formulae

807701_C02_AQA_Chemistry_2_026-042.indd 26 27/05/2015 15:52 807701_C02_AQA_Chemistry_2_026-042.indd 27 27/05/2015 15:52

These are highlighted in the text and

definitions are given in the margin
to help you pick out and learn these
Tips important concepts.
These highlight important facts,
common misconceptions and

Le Chate
ci ple ects a
r’s prin
which aff ection so
changed
●● Le Chatelie
dir
factor is will move in a

lier’s pr
signpost you towards other relevant lier’s pri nc
Le Chate equilibrium, the
posit
that if a
iple states ion of equilibr
ium

ibrium is
in equil to reduce the

inciple
in
system change. When a
system
a direction
topics. ium is a
system
where:
t, and
constan es.
TIP
‘Us e Le
estions
Many qu atelier’s pri
Ch
’. In the
will begin e to

se qu
ncipl
es tions
ction in
as to op
Th e pri
pose the
nc
also be
sit
d, the po bance.
stated as: will move in
iple can ion of equilibrium
changes
ibrium are ctant or produ
in
ct.
c equilibr cts remain explain… to explain a rea sition disturbe of equil
a dynami d produ ceeding at equa
l rat po the distur position rticular
rea
ition of ctants an you need ving its effect of affect the entration of a pa
The defin of the rea e reactions are
pro ium mo ise any
tio ns ns equilibr ium to minim ed s wh ich may co nc
reactio re or
pli
concentra rd and revers are in
ibr
of equil that have been
ap Factor , pressu
neous nts and products
● the ure AB (g)
for wa tempe rat g) 
teroge
s
ere the change ction. sure g) + B( le of
s in pres ium: A(
● wh
and he which all the reacta to the rea equilibr and 1 mo
TIP a reacti
on in
eneous Change d B homogeneous le of A(g) e (1 mole of
Homog us reaction is one e (1 mo
in
tures of concentrations t-hand sid the right-hand
sid
Two fea : A an
ium are ducts gen eo For the on the lef on
equilibr ctants and pro rates A homo state. le they are les of gas 1 mole of gas
of the rea nstant and the se e physical  2NH 3
(g) s examp an idea
2 mo
There are as there is on
ly sition of
the sam + 3H 2(g) i.e. in thi TIP is only
ain co rev er
le: N 2(g) e state, stage it ere fts the po the pressure
rem d
ward an l. in the sam At this sition of B(g)) wh rature shi g
for For examp ducts are us, it is er the po t change, or t tempe lume. Increasin right,
of the
s are eq
ua
and pro mogeneo d products of wheth AB(g)). constan m left to er of

Examples
reaction nts ho ium do
es no or from ssure at a smaller gas vo equilibrium fro mb
All rea cta to be an equilibr m left to right se in pre th of aller nu
nsidered that all reactants for ed. An increa to the side wi ve the position tion of AB. A sm
all gases. on is co s explaining ves fro req uir
y a reacti geneous mean the reaction by mo
left tha
t is ium
equilibr uilibrium will mo in the concen
tra
laining wh homo ic to rig ht to
eq increase volume. re, at co
nstant
When exp to explain that o make it specif on this
ults in an in pressu gas
nt als r gas decrease e with a larger are
importa same state but which res has a smalle ased. A
are in the t they are all
gas es.
ction is moles of
gas is decre to the sid to left as there e.
pressure of equilibrium
Examples of questions or
ht sid
example
tha far the rea A and B erse is tru e if
move fro
m rig
right- ha nd
of how
uilibriumnotional measure the
sition
eous The rev fts the po uilibrium will gas on the
n of eq homogen ure, shi
temperat e position of eq and side and 1
mole of
Positio of equilibrium is aright-hand side. In Th r volum
e.
ion the volume. gas on the left-h gas has a greate

calculations are included to Th e po sit e or to of of

t-hand sid
iv
2 moles mber of moles
to the lef nu
A larger
example: AB(g) AB follow ing
B(g)  and the
CIPLE

A(g) + AB factured

illustrate topics and feature full AB

E1
EXAMPL process, ammonia
is manu
’S PRIN

A ber hed.
AB In the Ha establis yield of
AB AB ium is uilibrium
equilibr w the eq this equilibrium

workings and sample answers. A B AB B H 2(g) 

2NH 3(g)
e to exp
lain ho
ssure on
aTELIER

B B N 2(g) +3 principl the pre

lie r’s reasing r yield
Le Chate ected by inc a highe y.
A B 1 Use ure. a despite to safet
AB AB is aff pe rat 20 MP ere es
nc
A AB ammonia constant tem pressure of lude ref
B a not inc
D LE Ch

at
A A system try uses res. Do
A te y indus higher pressu s on
B TIP t to sta 2 Sta te wh at les of ga 157
t totally
as
nts forge of gas and ob tained an d 2 mo
AB B to the righ sent Often stu de be ing d sid e
B er of mo
les
left and left-han e
IbRIa aN

Equilibrium ducts pre on the to the sid

A B d only pro the numb te 4 moles of
sta st say answer 4 moles of gas of equil
ibrium
A t han simply You mu mark are position to
the righ
more to re AB than of right. last 1 There hand sid
e
shifts the m left
A d 2 moles gas. Also the the right- se in pressure e. ium fro
Equilibrium mo
there are B ssure an ium estion
if the qu nia
equilibr
rature, pre ion of equilibr of sition of
L EqUIL

moles

Test yourself questions

side as d as inc rea vol um po
totally
as A and
as tempe sit misse ammo An aller ga s ves the
to the left on, such to affect the po formed. is often t the yield of wit h a sm g pressure mo in pressure. ply the
Equilibrium ctants the reacti ely ou
asks ab discuss wheth es.
er the sin rease ses. s to ap
only rea rium. co nd itions of anged, this is lik or more products st as So increa pose the inc monia increa electrical pump d expensive
or decre an
ChEmICa

of equilib If the you mu op

Position tra
ch
tion, are in more reactants reases right to the yield of am e to the cost of alled vessels
Figure
6.5 conc en ult yield inc e
Therefor is expensive
du strong-w pressure.
refore res re exp ensive d the
and the su es
2 Pres re and requir ment to withs
tan

These short questions, found 2 at equil

ibrium
.
a homo
geneou
s pressu d other equip
valves
an
6

URSELF ribed as
reaction is desc
TEST YO o features of a ing equilibrium . ibrium
of a
tw (g) of eq uil
1 State why the follow O 2(g)  2SO 3
throughout each chapter, are useful
8
15 17:0
in + position 09/03/20
2 Expla ium: 2SO 2(g) ect the
could aff
156 equilibr s which
tw o factor
3 State .
reaction
for checking your understanding as h6.indd
157
mistry_C

you progress through a topic.

QA_Che
7671_A
8 147180
15 17:0
09/03/20

156
h6.indd
mistry_C
QA_Che
7671_A
147180

807732_FM_AQA_Chemistry_2_i-vi.indd 4 13/06/15 9:30 am

 Activities

Get the most from this book

These practical-based activities will help consolidate your learning and test
your practical skills.
In this edition the authors describe many important experimental procedures
as “Activities” to conform to recent changes in the A-level curriculum. Teachers
should be aware that, although there is enough information to inform students
of techniques and many observations for exam-question purposes, there is not
enough information for teachers to replicate the experiments themselves or
with students without recourse to CLEAPSS Hazcards or Laboratory worksheets
which have undergone a thorough risk assessment procedure.

aC TIVIT Y
Preparati
on of methylpro
Methylprope
ne pene gas Figure 13.
20
methylpropa gas can be prepar halogenoa Classification of
ne in the app ed by heati lkanes.
wool is soa aratus sho ng 2-c
hydroxide
ked in 2-c
hloro-2-m wn in Figure hloro-2- H
. ethylprop 13.22. The
ane and eth mineral
anolic pot
R
Mineral woo
l soakedin ethanolic
assium R
potassium
hydr
2-chloro-2-m oxide and R C
ethylpropan
X

Reaction sum
e
R C X R C X
H
primary H
one R gro
up R

mary
Methylprope to C bonded attached secondary
opene gas to halogen two R gro
ups
HEAT l● Rea to C bonded attached
to halogen
tertiary
three R gro
ups
to C bonded attached
Reagent ction sum to halogen

Condition
s
mary
potassium aqueous rea Mechanis
Figure 13. water hydroxide gent; dissol m
19 Labora halogenoa ve Produc t
tor y prepar lka
1 Dr aw the ation of me
thylprope ethanol; ref ne in a little nucleophi
lic
displayed ne. lux
2 Explain formula of potassium substitutio
aqueous rea n alcohol
why 2-chlo 2-chloro- cyanide gent; dissol
3 a) Write ro-2-meth 2-methylp halogenoa ve
an equation ylp ropane is ropan e. lkane in a
for the rea insoluble ethanol; ref little nucleophi
with ethan in water lux lic
olic
potassium ction
of 2-chloro- . substitutio
b) State the hydroxide 2-methylp concentra
ted
n nitr ile car bon cha
in length
4 A potent name of thi . ropane ammonia excess am by 1 is increased
ial s type of rea monia; in
danger in ction. tube; und a sealed
product ove heating rea er pressu
aLKaNES

gents and nucleophi

r re lic
delivery tub water is that after col excess am
e. heating, wa lecting the gaseou substitutio
n amine a high yie
monia enc
our ages
danger cou Explain why this ha ter s potassium dissolve rea ld of prima
ld be rem ppens and rises back up into hydroxide gent in eth discourag ry amine;
5 Calculat oved. suggest ho the dissolve rea anol; es produc
tion of fur
e the volum w this pot no water
ctants in
ethanol;
substitute
d amines ther
e of gaseou ential
GENO

temper atu present elimination

re of 298 K s methylpr
2-chloro- and a pre ope
2-methylp ssure of 100 ne formed at a alkene product ma
y be a mix
(Density of ropane. kPa, from
Practice qu ture of
13 HaLO

positional
2-chloro- 2 cm 3 of liq isomers
6 2-chloro- 2-methylp uid
to form an
2-methylp
ropane wil
ropane: 0.8
gcm −3) estions
alcohol. l react wit 1 Methane
a) Write a h aqueous
sodium hyd reacts
bal
b) State the anced symbol equati roxide chlorometha with chlorine to pro
name for on for this ne and a gas duce
this type of reaction. , G. c) Draw the
reaction. a) State the displayed for
conditions
Concurren reaction. necessary for product pro mula
292 t elimi nation and the duced by the for the organic
In practice, nucleophil 2 b) ii) abo reaction in
bo b) Name gas ve.
By manipula th elimination and sub ic substitu
tion reacti , G, produ
ced in the
(1)
d) Explain
ting the con stitution rea ons c) Using a reaction. why the (1)
nucleophil ditions the ctions occur series of equ (1) especially use reaction in 2 b) ii)
ic substituti chemist can simultaneou ations describ ful in organi is
on product mechanism
However, the
conditions or a high yie ensure a high yield of sly. for this reactio e the 3 The follow c synthesis.
factors which imposed on ld of the n. (1)
determine the reaction the elimination produ d) Name the
type of me (4)
ing
synthesised five compounds can be
group can the main pro mi ct.
also have an duct. The po xture are not the only 2 Bromoeth
chanism. fro
homologou m compounds belon
more likely effect on the sition of the ane is suscep (1) s ser ging
for nat
primary hal a tertiar y halogenoalk ure of the product. Eli
functional such as hyd tible to nucle case give the ies of halogenoalkane to the
ogenoalkane ane mination is roxide ions ophiles reagents and s. In each
(Figure 13.20 and substitution is a) What is
and cyanid
e ions.
for their pro
duction and conditions necessary
). more likely a nucleophil starting hal the name of
for a e? ogenoalkane the
b) Write a bal . 293
anced symbol (1) a) pent-2-en
reaction of bro equation for e
moethane wit the b) propaneni
solution of: h an aqueou trile (2)
s
14718076
71_AQA_ i) potassiu c) propan-2- (2)
Chemistry_C
h13.indd m hydroxide ol
292
ii) potassiu d) methylam (2)
m cyanide. (1) ine
e) diethylam (2)
(1) ine.
09/03/2015
(2)
17:17 1471
807671_AQA_
Chemistry_C
h13.indd
293

Practice questions 09/03/2015

17:17

You will find practice questions, including multiple-choice questions,

at the end of every chapter. These follow the style of the different types
of questions with short and longer answers that you might see in your
examination, and they are colour coded to highlight the level of difficulty.
v
● Green – Basic questions that everyone should be able to answer without
difficulty.
157
● Orange – Questions that are a regular feature of exams and that all
competent candidates should be able to handle.
e
ve
● Purple – More demanding questions which the best candidates should be
able to do.
8
15 17:0
09/03/20

A dedicated chapter for developing your Maths can be found at the back of
this book.

807732_FM_AQA_Chemistry_2_i-vi.indd 5 13/06/15 9:30 am

 Photo credits
The Publisher would like to thank the following for permission to reproduce copyright material:
p. 16 Courtesy of Morgan Riley – Wikipedia Commons (http://creativecommons.org/licenses/by/3.0/deed.en);
p. 27 both © Hodder Education; p. 27 © Hodder Education; p. 32 © CHARLES D. WINTERS/SCIENCE PHOTO
LIBRARY; p. 32 both © ANDREW LAMBERT PHOTOGRAPHY/SCIENCE PHOTO LIBRARY; p. 35 left © Pumehana
– Fotolia.com; p. 35 right © WLADIMIR BULGAR/SCIENCE PHOTO LIBRARY; p. 45 © CHARLES D. WINTERS/
SCIENCE PHOTO LIBRARY; p. 43 and p.46 © minifilm – Fotolia.com; p. 56 © MARTYN F. CHILLMAID/
SCIENCE PHOTO LIBRARY; p. 68 and p.76 © CHARLES D. WINTERS/SCIENCE PHOTO LIBRARY; p. 78 and
p.79 © SCIENCE PHOTO LIBRARY; p. 80 © ANDREW LAMBERT PHOTOGRAPHY/SCIENCE PHOTO LIBRARY;
p. 87 © ANDREW LAMBERT PHOTOGRAPHY/SCIENCE PHOTO LIBRARY; p. 90 © DR P. MARAZZI/SCIENCE
PHOTO LIBRARY; p. 100 and 107 © ANDREW LAMBERT PHOTOGRAPHY/SCIENCE PHOTO LIBRARY; p. 104
© somjring34 – Fotolia.com; p.106 © Max Tactic – Fotolia.com; p. 113 © vlad61_61 – Fotolia.com; p. 116 ©
photongpix –Fotolia.com; p. 135 and p.137 © MARTYN F. CHILLMAID/SCIENCE PHOTO LIBRARY; p. 138
© ANDREW LAMBERT PHOTOGRAPHY/SCIENCE PHOTO LIBRARY; p. 141 © MIKE WALKER, VISUALS
UNLIMITED /SCIENCE PHOTO LIBRARY; p. 142 © fotosuper - iStock via Thinkstock; p. 143 © ANDREW
LAMBERT PHOTOGRAPHY/SCIENCE PHOTO LIBRARY; p. 150 © ANDREW LAMBERT PHOTOGRAPHY/
SCIENCE PHOTO LIBRARY; p. 153 © airborne77 – Fotolia.com; p. 154 © janeness – Fotolia.com; p. 160 ©
LAGUNA DESIGN/SCIENCE PHOTO LIBRARY; p. 167 © ANDREW LAMBERT PHOTOGRAPHY/SCIENCE
PHOTO LIBRARY; p. 149 and p.168 © JERRY MASON/SCIENCE PHOTO LIBRARY; p. 169 © ANDREW
LAMBERT PHOTOGRAPHY/SCIENCE PHOTO LIBRARY; p. 171 © ANDREW LAMBERT PHOTOGRAPHY/
SCIENCE PHOTO LIBRARY; p. 175 and 186 © adam88xx – Fotolia.com; p. 176 © ANDREW LAMBERT
PHOTOGRAPHY/SCIENCE PHOTO LIBRARY; p. 179 © SCIENCE PHOTO LIBRARY; p. 187 © uckyo – Fotolia.
com; p. 188 © SCIENCE PHOTO LIBRARY; p. 198 and p.200; © DAVID MUNNS/SCIENCE PHOTO LIBRARY;
p. 202 © SATURN STILLS/SCIENCE PHOTO LIBRARY; p. 206 top © ANDREW LAMBERT PHOTOGRAPHY/
SCIENCE PHOTO LIBRARY; p. 206 bottom © ANDREW LAMBERT PHOTOGRAPHY/SCIENCE PHOTO LIBRARY;
p. 215 © MARTYN F. CHILLMAID/SCIENCE PHOTO LIBRARY; p. 224 © ANDREW LAMBERT PHOTOGRAPHY/
SCIENCE PHOTO LIBRARY; p. 233 and p.235 © valdis torms – Fotolia.com; p. 236 © ANDREW LAMBERT
PHOTOGRAPHY/SCIENCE PHOTO LIBRARY; p. 245 © Nutthaphol – iStock via Thinkstock; p. 263 © CHARLES
D. WINTERS/SCIENCE PHOTO LIBRARY; p. 276 © ST. BARTHOLOMEW’S HOSPITAL/SCIENCE PHOTO
LIBRARY; p. 278 © geogphotos / Alamy; p. 261 and p.279 © RUSSELL KIGHTLEY/SCIENCE PHOTO LIBRARY;
p. 293 © DENNIS SCHROEDER, NREL/US DEPARTMENT OF ENERGY/SCIENCE PHOTO LIBRARY; p. 298 ©
A. BENOIST/BSIP/SCIENCE PHOTO LIBRARY; p. 302 © Photos contributed by Natrij, Wikimedia
(http://creativecommons.org/licenses/by-sa/3.0/); p. 287 and p.303 © MAXIMILIAN STOCK LTD/SCIENCE
PHOTO LIBRARY; p. 305 © DR JURGEN SCRIBA/SCIENCE PHOTO LIBRARY; p. 309 © SL-66 – Fotolia.com;
p. 318 © Maurice Crooks / Alamy.
Every effort has been made to trace all copyright holders, but if any have been inadvertently overlooked, the
Publisher will be pleased to make the necessary arrangements at the first opportunity.

vi

807732_FM_AQA_Chemistry_2_i-vi.indd 6 16/06/2015 17:18

 1 Thermodynamics:
Born-Haber cycles
PRIOR KNOWLEDGE
It is expected that you are familiar with all of the content of the
Energetics unit in Year 1 of the A-level Chemistry course. The following
are some key points of Prior Knowledge:
● The enthalpy change in a chemical reaction is represented by ΔH.
● ΔH is the heat energy change measured under conditions of constant
pressure.
● For exothermic reactions, ΔH has a negative value.
● For endothermic reactions, ΔH has a positive value.
● The standard enthalpy change of combustion is the enthalpy change
when 1 mole of a substance is burned completely in excess oxygen
with all substances in standard states under standard conditions.
● The standard enthalpy change of formation is the enthalpy change
when 1 mole of a compound is formed from its constituent elements
in their standard states under standard conditions.
● Hess’s Law states that the enthalpy change for a chemical reaction
is independent of the route taken and depends only on the initial and
final states.
● Hess’s Law can be used to calculate enthalpy changes for chemical
reactions from the enthalpy changes of other reactions.
● Temperature changes may be used to calculate enthalpy changes
using q = mcΔT.
● The mean bond enthalpy is a measure of the energy required to break
one mole of a covalent bond measured in kJ mol−1 averaged across
compounds containing that bond.
● Mean bond enthalpy values may be used to calculate the enthalpy
change for a chemical reaction by considering the covalent bonds
broken (endothermic) and the covalent bonds made during the reaction.

TEST YOURSELF ON PRIOR KNOWLEDGE 1

1 Write equations, including state symbols, to represent the standard
enthalpies of formation given below:
a) Formation of magnesium oxide, MgO(s).
1
b) Formation of hydrogen chloride, HCl(g).
2 Write equations, including state symbols to represent the standard
enthalpies of combustion given below:
a) Combustion of propane, C 3H8(g).
b) Combustion of methanol, CH3OH(l).

807701_C01_AQA_Chemistry_2_001-025.indd 1 13/06/15 8:50 am

 3 The standard enthalpies of formation of ethane, carbon dioxide and
water are −85, −394 and −286 kJ mol−1, respectively.
a) State Hess’s Law.
b) Write an equation, including state symbols, to represent the
standard enthalpy of combustion of ethane.
c) C alculate a value for the standard enthalpy of combustion of
ethane.
4 In an experiment the temperature of 200 g of water rose by 22.4 °C
when 0.015 mole of ethanol were burned in air and the heat used
to warm the water. Calculate a value for the enthalpy change when
one mole of ethanol is burned. The specific heat capacity of water is
4.18 J K−1 g−1).
5 The mean bond energy values for certain covalent bonds are given
below:
Bond Mean bond enthalpy (kJ mol−1)
C–H 412
C–C 348
O–H 463
O=O 496
C=O 803
Calculate a value for the following reaction using these values:
C 3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g)

●● Enthalpy changes in ionic compounds

1    THERMODYNAMICS: BORN-HABER CYCLES

The changes that occur during the formation of an ionic compound are
considered in this unit. The dissociation or formation of an ionic compound
may be calculated from other values using Hess’s Law in the form of a
Born-Haber cycle.

Notations
● ΔH represents an enthalpy change.
● ΔH is measured under stated conditions, i.e. ΔH298 is the enthalpy
change at 298 K and the pressure is 100 kPa.
● The enthalpy change is the heat energy change at constant pressure.
● Standard Enthalpy Values are the ΔH value for enthalpy changes of
specific reactions measured under standard conditions.
● Standard conditions are represented by the symbol 1 which is used
after ΔH to indicate that an enthalpy changes occurs under standard
conditions.
● Standard conditions are 298 K, 100 kPa pressure, all solutions of
2 concentration 1 mol dm−3 and all substances are present in their standard
states.

807701_C01_AQA_Chemistry_2_001-025.indd 2 13/06/15 8:50 am

 The definitions of the enthalpy changes associated with ionic compounds
must be understood to be able to link the enthalpy changes together,

Enthalpy changes in ionic compounds

particularly in terms of what the ‘per mol’ in kJ mol−1 means.

A positive value of △H The enthalpy of the products is

(change in enthalpy) greater than the enthalpy of the
indicates an endothermic reactants so energy has been

Enthalpy (H)
reaction absorbed from the surroundings.

TIP
This is an enthalpy profile for
an endothermic reaction. The Products
△H = +ve
enthalpy change is positive. Make
sure you can draw and recognise Reactants
the enthalpy profile diagram for Progress of reaction
an exothermic reaction as well The value of the enthalpy change (△H) in this endothermic
from the Energetics topic in AS reaction is positive. This is because there has been an increase
Year 1. in enthalpy from reactants to products. This is a standard
feature of endothermic reactions and it must be remembered
that △H is positive.

Figure 1.1 Enthalpy profile for an endothermic reaction.

The word enthalpy is based on the Greek noun enthalpos, which means
heating. It comes from the classical Greek prefix ε’ ν-, meaning ‘to put into’,
and the verb θα’ λπειν, thalpein, meaning ‘to heat’. The word enthalpy first
appeared in scientific literature in 1909. Many different symbols were
used to denote enthalpy and it was not until 1922 that the symbol ‘H’ was
accepted as standard.

Lattice enthalpy
Lattice enthalpy can be represented as ΔLH 1 or ΔlattH 1.
The enthalpy of lattice dissociation is the enthalpy change when one
mole of an ionic compound is separated into its component gaseous ions.
The phrase ‘at infinite separation’ is often used in the definition because all
bonding between the ions must be broken so the ions must be infinitely
separated.
The enthalpy of lattice dissociation is also called the lattice dissociation
enthalpy. It is an endothermic process and has a positive value measured
in kJ mol−1. Energy is required to overcome the strong attraction between
the positive and negative ions. The ‘per mol’ refers to one mole of the ionic
compound.
The enthalpy of lattice formation is the enthalpy change when one mole
of an ionic compound is formed from its constituent ions in the gaseous 3
state. It is an exothermic process and has a negative value measured in
kJ mol−1. Again, the ‘per mol’ refers to one mole of the ionic compound.

807701_C01_AQA_Chemistry_2_001-025.indd 3 13/06/15 8:50 am

 Equations for lattice dissociation and formation
Equations, including state symbols, are often asked for the process which
occurs when the lattice of an ionic compound dissociates or forms.

EXAMPLE 1
Write an equation, including state symbols, for the reaction that has an
enthalpy change equal to the lattice dissociation enthalpy of sodium
chloride.

Answer
This question is asking for an equation for the dissociation of one mole of
sodium chloride into its constituent gaseous ions as that is the definition
of the enthalpy of lattice dissociation.

NaCl(s) → Na+(g) + Cl–(g)

One mole of Constituent

sodium chloride gaseous ions

TIP
Make sure you include the state symbols. The notes below the equation
1    THERMODYNAMICS: BORN-HABER CYCLES

are used for clarity and are not expected in the answer.

EXAMPLE 2
Write an equation, including state symbols, for the reaction that has an
enthalpy change equal to the enthalpy change of lattice formation of
calcium chloride.

Answer
This question is asking for an Ca2+(g) + 2Cl–(g) → CaCl2(s)
equation for the formation of one
mole of calcium chloride from its
Constituent One mole of
constituent gaseous ions as that gaseous ions calcium chloride
is the definition of the enthalpy of
lattice formation.

4 Enthalpy of formation
TIP Enthalpy of formation can be represented as ΔfH 1. The enthalpy (change)
You will have written equations of formation is the enthalpy change when one mole of a compound is
for enthalpies of formation in AS. formed from its elements when all reactants and products are in their
standard states under standard conditions.
Again equations for the process of formation are asked with state symbols.

807701_C01_AQA_Chemistry_2_001-025.indd 4 13/06/15 8:50 am

 Enthalpy changes in ionic compounds
EXAMPLE 3
Write an equation, including state symbols, for the process that has an
enthalpy change equal to the standard enthalpy of formation of silver(i)
fluoride.

Answer Ag(s) + 1
F (g) → AgF(s)
2 2
This question asks for an
equation for the formation of one
mole of silver fluoride from its Elements in their One mole of
standard states silver fluoride
constituent elements when all
reactants and products are in
their standard states under standard conditions.

EXAMPLE 4
TIP Write an equation, including state Ca(s) + Cl2(g) → CaCl2(s)
Do not confuse the enthalpy of symbols, for the process that has
lattice formation with enthalpy an enthalpy change equal to the
of formation of a compound as standard enthalpy of formation of Elements in One mole of
their standard calcium
these can also be asked. For calcium chloride. states chloride
calcium chloride, as shown in the
examples above, these equations Answer
are different. Do not forget the This question asks for an equation for the formation of one mole of
diatomic elements in enthalpy calcium chloride from its constituent elements when all reactants and
change of formation equations. products are in their standard states under standard conditions.

EXAMPLE 5
Write an equation, including state Mg(s) + 1
2
O2(g) → MgO(s)
symbols, for the process that has
an enthalpy change equal to the
standard enthalpy of formation of Elements in their One mole of
standard states magnesium oxide
magnesium oxide.

Enthalpy of atomisation
Enthalpy of atomisation can be represented as ΔaH 1 or ΔatH 1. The enthalpy
of atomisation of an element is the enthalpy change for the formation of
one mole of gaseous atoms from the element in its standard state.
5
Again equations for the process of formation may be asked with state
symbols but it is more likely you have to understand the process in a
Born-Haber cycle. For diatomic elements, the equation must produce one
mole of gaseous atoms so 12 X2 is used where 12 X2 represents half a mole of
the diatomic element.

807701_C01_AQA_Chemistry_2_001-025.indd 5 13/06/15 8:50 am

 EXAMPLE 6
Write an equation, including state symbols, for the process that has an
enthalpy change equal to the enthalpy of atomisation of sodium.
Na(s) → Na(g)

TIP EXAMPLE 7
A common mistake here is to Write an equation, including state symbols, for the process that has an
list Br2 as a gas but the element enthalpy change equal to the enthalpy of atomisation of bromine.
must be in its standard state. The
1
atomisation of iodine would be
1 2 Br2 (l) → Br(g)
I2 (s) → I(g).
2

EXAMPLE 8
Write an equation, including state symbols, for the process that has an
enthalpy change equal to the enthalpy of atomisation of oxygen.
1 O (g) → O(g)
2 2

Bond dissociation enthalpy (bond enthalpy)

1    THERMODYNAMICS: BORN-HABER CYCLES

Bond dissociation enthalpy can be represented as ΔBDEH 1 or ΔdisH 1 or

ΔdissocH1. The bond dissociation enthalpy is a value for the enthalpy change
when one mole of a covalent bond is broken under standard conditions in
the gaseous state. It takes a positive value as one mole of the covalent bond
is broken (endothermic).
For example, the bond dissociation enthalpy for chlorine is +242 kJ mol−1. This
means that 242 kJ of energy is required to convert 1 mol of chlorine molecules
(containing 1 mol of the covalent bond) into 2 mol of gaseous chlorine atoms.
The equation for this process is: Cl2(g) → 2Cl(g)

● It is important to note that mean bond enthalpy values were met in AS

TIP and are a measure of the energy required to break one mole of a covalent
The definition of bond dissociation bond measured in mol−1 (the ‘per mole’ is per mole of the covalent
enthalpy is usually asked for with bond) averaged across many compounds containing the bond.
reference to a specific bond or ● For diatomic molecules, the bond enthalpy is not averaged across many
diatomic molecule. It is used in compounds containing the bond as the bond only occurs in the diatomic
Born-Haber cycles with diatomic molecules.
6 elements. ● Also for mean bond enthalpy calculations the enthalpy of bond breaking
is endothermic and the enthalpy of bond making is exothermic as will
be considered again later in this unit, but bond dissociation enthalpy is
always endothermic as it is for the dissociation of the bond.

807701_C01_AQA_Chemistry_2_001-025.indd 6 13/06/15 8:50 am

 TIP

Enthalpy changes in ionic compounds

EXAMPLE 9
The value for the bond Write an equation, including state symbols, for the process that has an
dissociation enthalpy for the enthalpy change equal to the bond dissociation enthalpy of fluorine.
diatomic molecules is twice
the value for the enthalpy of F2(g) → 2F(g)
atomisation of these elements. This equation shows the dissociation of one mole of diatomic fluorine, F2,
This is important in deciding what into two moles of gaseous fluorine atoms.
value to use in a Born-Haber
cycle later in this unit.

Sometimes the definition of bond dissociation enthalpy is asked as applied

to a particular diatomic element and the answer must be in terms of this
element. The initial element should be in the gaseous state even if it is
bromine or iodine.

EXAMPLE 10
Define bond dissociation enthalpy as applied to fluorine.
Answer
The enthalpy change to break the bond in one mole of fluorine to form
two moles of gaseous fluorine atoms.

Ionisation enthalpies
Ionisation enthalpies can be represented as ΔIEH1. A number after IE can
be used to indicate if it is a first or second, etc., ionisation enthalpy, for
example ΔIE1H 1 represents the first ionisation enthalpy. At AS, ionisation
enthalpies (or they were called ionisation energies in Atomic Structure)
were examined as evidence for the existence of energy levels.
The first ionisation enthalpy is the enthalpy change when one mole of
electrons is removed from one mole of gaseous atoms to form one mole of
gaseous ions with a single positive charge.
The second ionisation enthalpy is the enthalpy change when one mole of
electrons is removed from one mole of gaseous ions with a single positive
charge to form one mole of gaseous ions with a 2+ charge.
The third ionisation enthalpy is the enthalpy change when one mole of
electrons is removed from one mole of gaseous ions with a 2+ charge to
form one mole of gaseous ions with a 3+ charge.
7
For the purposes of Born-Haber cycles, you would be expected to be able
to define and carry out calculations using first, second and sometimes third
ionisation enthalpies.

807701_C01_AQA_Chemistry_2_001-025.indd 7 13/06/15 8:50 am

 EXAMPLE 11
Write an equation, including state symbols, for the process that has an
enthalpy change equal to the first ionisation enthalpy of magnesium.
Answer
Mg(g) → Mg+(g) + e−
Remember that both the atoms and ions have to be gaseous. The value
for the above first ionisation enthalpy is +736 kJ mol−1. Remember also
TIP that first ionisation enthalpies decrease down a group. The first ionisation
To go from Ca(g) to Ca2+(g) enthalpy of calcium is +590 kJ mol−1.
requires a total of the first and
second ionisation enthalpies.
The first ionisation enthalpy of
calcium is +590 kJ mol−1.
The second ionisation enthalpy of EXAMPLE 12
calcium is +1150 kJ mol−1. Write an equation, including state symbols, for the process that has an
The change in enthalpy required enthalpy change equal to the second ionisation enthalpy of calcium.
for Ca(g) → Ca2+(g) + 2e− is + 590
Ca+(g) → Ca2+(g) + e−
+ 1150 = +1740 kJ.

Electron affinity
Electron affinity can be represented as ΔEAH 1. Again a number after EA can
be used to represent the first or second electron affinities.
1    THERMODYNAMICS: BORN-HABER CYCLES

The first electron affinity is the enthalpy change when one mole of gaseous
atoms forms one mole of negative ions with a single negative charge. An
equation, including state symbols, representing the first electron affinity of
fluorine would be:
F(g) + e− → F−(g)
The second electron affinity is the enthalpy change when one mole of
gaseous ions with a single negative charge forms one mole of gaseous ions
with a double negative charge.

EXAMPLE 13
Write an equation, including state symbols, for the process that has an
enthalpy change equal to the second electron affinity of oxygen.
O−(g) + e− → O2−(g)

8 TIP
When the definition of electron
affinity is asked give the definition Values for second electron affinities are positive as the process is
of first electron affinity. endothermic. This is due to the repulsion of the negative ion for the
negative electron being added.

807701_C01_AQA_Chemistry_2_001-025.indd 8 13/06/15 8:50 am

 TEST YOURSELF 2

Born-Haber cycles
1 Write equations, including state symbols, for the process that has an
enthalpy change equal to the following processes:
a)Enthalpy of lattice formation of calcium chloride.
b)Bond dissociation enthalpy of fluorine.
c)First electron affinity of oxygen.
d)Enthalpy of formation of silver fluoride.
e)First ionisation enthalpy of potassium.
2 Name the enthalpy changes represented by the following equations:
a) Ca+(g) → Ca2+(g) + e−
b) Na(s) → Na(g)
c) Cl(g) + e− → Cl−(g)
d) Na(s) + 12 F2(g) → NaF(s)
e) Mg2+(g) + 2Cl−(g) → MgCl 2 (s)
3 Define the following:
a) Standard enthalpy of formation.
b) Enthalpy of lattice formation.
c) Lattice dissociation enthalpy.
d) Enthalpy of atomisation of chlorine.
e) First ionisation enthalpy of lithium.

●● Born-Haber cycles
The Born-Haber cycle is a technique for applying Hess’s Law to the standard
enthalpy changes that occur when an ionic compound is formed.
The Born-Haber cycle for NaCl can be drawn simply as shown in the
diagram below. It should be noted that this cycle is simply being used to
explain the processes but would not be accepted as a Born-Haber cycle in
an examination question.
Δ xH
Na(s) + 12 Cl2(g) Na+(g) + Cl–(g)

Enthalpy of Enthalpy of lattice

formation dissociation
NaCl(s)

ΔxH is the sum of all the changes required to convert Na(s) to Na+(g) and
1 −
2 Cl2(g) to Cl (g).
These can be summarised in the table below.

Process Name of enthalpy change ΔH 1 /kJ mol−1 9

Na(s) → Na(g) Enthalpy of atomisation of sodium +109
Na(g) → Na+(g) + e − First ionisation enthalpy of sodium +494
1 Cl (g) → Cl(g) Enthalpy of atomisation of +121
2 2 chlorine
Cl(g) + e − → Cl− (g) First electron affinity of chlorine −364

ΔxH 1 = ΔaH 1 + ΔIE1H 1 + ΔaH 1 + ΔEA1H 1

ΔxH1 = + 109 + 494 + 121 − 364 = +360 kJ

807701_C01_AQA_Chemistry_2_001-025.indd 9 13/06/15 8:50 am

 Hess’s Law states that the enthalpy change for a chemical reaction is
independent of the route taken and depends only on the initial and final
states.
This means that ΔxH = Enthalpy of formation + Enthalpy of lattice
dissociation
This can be written as: ΔxH = ΔfH + ΔLH
The standard symbols are often left out when writing these expressions.
The value for the enthalpy of formation of sodium chloride is −411 kJ mol−1.
The enthalpy of lattice dissociation (ΔLH) can be calculated.

Δx H = Δf H + ΔLH

+360 = −411 + ΔLH

ΔLH = + 360 + 411 = +771 kJ mol−1

The enthalpy of lattice dissociation for sodium chloride is +771 kJ mol−1.
The enthalpy of lattice formation is –771 kJ mol−1.

Drawing a Born-Haber cycle

The diagram below shows a Born-Haber cycle for a Group 1 halide, in this
case for sodium chloride, NaCl.
For all Born-Haber cycles, the arrows for the enthalpy changes are not to scale.
1    THERMODYNAMICS: BORN-HABER CYCLES

metal single
positive ions Na+(g) + Cl(g) + e–
and non-metal
gaseous atoms ΔEAlH1
Na+(g) + Cl–(g)
ΔaH1 gaseous ions

metal single Na+(g) + 12 Cl2(g) + e–

positive ion

ΔIEIH1
metal Na(g) + 12 Cl2(g)
gaseous
atoms
ΔLH1

ΔaH1

elements in Na(s) + 12 Cl2(g)

standard states
ΔfH1
10
NaCl(s) solid
compound

Features of the cycle

● The arrows that are going up represent endothermic processes.
● The arrows that are going down represent exothermic processes.
● ΔLH 1 is the enthalpy of lattice dissociation in this Born-Haber cycle.
● The labels at the left and right of the different enthalpy levels show the
species which should be present on these levels. These labels are there

807701_C01_AQA_Chemistry_2_001-025.indd 10 13/06/15 8:50 am

 only to help you understand the cycle but are not essential if you are
asked to draw one.

Born-Haber cycles
● You may be expected to complete some of the levels in a cycle with the
species present or even to complete part of the cycle as shown in the
examples which follow.

EXAMPLE 14
Complete the Born-Haber cycle shown on the right for The correct direction of the arrows representing
potassium fluoride by drawing the missing energy levels, the changes should be given.
symbols and arrows. The completed cycle with annotations is shown below.
Answer K+(g) + 12 F2(g) + e–
In this type of question you would be expected to complete
the levels in the diagram as shown in the previous +420
K(g) + 12 F2(g)
example, with endothermic changes having levels above
the previous one and exothermic changes having levels
below. +90
K(s) + 12 F2(g)
The symbols for the species (atoms, ions and electrons)
on each enthalpy level with appropriate state symbols –569
would also be expected. KF(s)

F(g) formed from 12 F2(g);

the arrow represents the K+(g) + F(g) + e–
enthalpy of atomisation or F–(g) formed from F(g);
half the bond dissociation the arrow represents the
enthalpy of fluorine K+(g) + F–(g)
first electron affinity of
fluorine
The K+ ion is formed with K+(g) + 12 F2(g) + e–
e–; the arrow represents
the first ionisation
enthalpy of potassium +420
This arrow represents
K(g) + 12 F2(g)
the enthalpy of lattice
dissociation of potassium
fluoride
+90

K(s) + 12 F2(g)

–569
KF(s)

Calculations from a Born-Haber cycle

In calculations, the enthalpy of atomisation of chlorine may be given or,
alternatively, the bond dissociation enthalpy. It is vital that you understand
that for gaseous diatomic elements like the first two halogens, the bond
11
dissociation enthalpy is twice the enthalpy of atomisation. For Group 1
halides and other halides where the oxidation number of the metal is +1,
like the one shown in the cycle below, the change required is
1
2
Cl2(g) → Cl(g). This is the value of the enthalpy of atomisation of chlorine
or half the value for the bond dissociation enthalpy of chlorine.
Calculations may be of other values in the Born-Haber cycle, if the lattice
enthalpy is known.

807701_C01_AQA_Chemistry_2_001-025.indd 11 13/06/15 8:50 am

 EXAMPLE 15 Ag+(g) + F–(g) + e–
Using the Born-Haber cycle shown on the right, calculate the
enthalpy of formation of silver(i) fluoride using the enthalpy Ag+(g) + F–(g)
changes given. The diagram is not to scale.
Ag+(g) + 12 F–2(g) + e–

Name of enthalpy change ΔH 1  /kJ mol−1

Enthalpy of lattice dissociation of silver Ag(g) + 12 F–2(g)
+967
fluoride
Bond dissociation enthalpy of fluorine +158
Electron affinity of fluorine −348
First ionisation enthalpy of silver +732 Ag(s) + 12 F–2(g)
Enthalpy of atomisation of silver +289
AgF–(s)
Answer
The most important point in this Born-Haber cycle is If you go through an arrow in the wrong direction
the type of value given for the conversion of fluorine to change the sign of the enthalpy value.
fluorine atoms.
For example, the enthalpy of lattice dissociation of AgF
The value given is the bond dissociation enthalpy
which is +158 kJ mol−1 and this is the enthalpy value = − Δf H 1 + ΔaH 1 + ΔIE1H 1 + 12 ΔBDEH 1 + ΔEA1H 1
for the change F2(g) → 2F(g).
However in this cycle the change required is:
1 F (g) → F(g) Ag+(g) + F(g) + e–
2 2
1    THERMODYNAMICS: BORN-HABER CYCLES

First electron
Half of the bond –348 affinity of fluorine
The enthalpy value for this change is half of dissociation enthalpy + –
Ag (g) + F (g)
+79
the value for the bond dissociation enthalpy. of fluorine
1
Ag+(g) + F (g) + e–
It is good practice to add the values for the 2 2
Enthalpy of lattice
enthalpy changes to the Born-Haber cycle First ionisation dissociation of
+732 enthalpy of silver silver fluoride
as this makes the calculations simpler. The
Ag(g) + 12 F2(g)
diagram below shown the Born-Haber cycle
for silver fluoride with the known enthalpy Enthalpy of +967
changes added. atomisation
+289
of silver
From the cycle, the enthalpy of formation of Ag(s) + 12 F2(g)
silver fluoride is calculated by going round the
Enthalpy of
cycle in the other direction. formation of
silver fluoride AgF(s)
Start at the start of the arrow for the enthalpy
change you want to find and go around the
cycle in the other direction.

Calculating Δf H 1
12
ΔfH1 = + 289 + 732 + 79 − 348 − 967
ΔfH1 = − 215 kJ mol−1
The calculations are sometimes carried out without a cycle. The values may
be given and you would be expected to remember the sequence of enthalpy
changes as shown in the next example.

807701_C01_AQA_Chemistry_2_001-025.indd 12 13/06/15 8:50 am

 Born-Haber cycles
EXAMPLE 16
The table below gives some values for standard Answer
enthalpy changes. Use these values to calculate the
The enthalpy of lattice dissociation (ΔL H 1) can be
standard enthalpy of lattice dissociation of potassium
calculated from the other values:
bromide.

Name of enthalpy change ΔH 1/kJ mol−1 ΔLH 1 = − Δf H 1 (KBr) + ΔaH 1 (K) + ΔIE1H 1 (K)
Enthalpy of formation of potassium -392 + Δa H 1(Br) + ΔEA1H 1(Br)
bromide (Δ f H 1 )
ΔLH = +392 + 90 + 420 + 112 + (−342)
Enthalpy of atomisation of bromine +112
(Δ a H 1(Br))
ΔLH = +672 kJ mol−1
Electron affinity of bromine (Δ EA1 H 1) -342
First ionisation enthalpy of potassium +420
(Δ IE1 H 1)
Enthalpy of atomisation of potassium +90
(Δ aH 1(K))

Born-Haber cycles for metals with oxidation state +2

Born-Haber cycles for compounds of metals where the metal has an
oxidation state of +2 are slightly more complex. The cycle below represents
the Born-Haber cycle for magnesium chloride.
metal double
positive ions Mg2+ (g) + 2Cl (g) + 2e–
and non-metal 2ΔEAIH 1
gaseous atoms 2ΔaH 1 or ΔBDEH 1
Mg2+ (g) + 2Cl– (g) gaseous
metal double Mg2+ (g) + Cl2 (g) + 2e– ions
positive ion
ΔIE2H 1

metal single Mg+ (g) + Cl2 (g) + e–

positive ion
ΔIEIH 1
metal gaseous Mg (g) + Cl2 (g)
atoms

ΔaH 1 ΔLH 1

elements in Mg (s) + Cl2 (g)

standard states

ΔfH 1

MgCl2 (s) solid

compound

For all these diagrams the enthalpy changes are not to scale. The labels at 13
the left and right of the different enthalpy levels show the species which
should be present on these levels. These labels are there only to help you
understand the cycle but are not essential if you are asked to draw one.
Metals such as Group 2 metals and many transition metals will have the
metal in the oxidation state of +2. This means that an additional enthalpy
change is required, the second ionisation enthalpy of the metal (ΔIE2 H 1).
As the compounds require two moles of halide ions per mole of the metal
ion, the enthalpy of atomisation for the halogen is multiplied by 2 (2ΔatH 1)

807701_C01_AQA_Chemistry_2_001-025.indd 13 13/06/15 8:50 am

 or the bond dissociation enthalpy is used (ΔBDE H 1) and the first electron
affinity is multiplied by 2 (2ΔEA1H 1) as seen on the cycle.

Calculations using this type of cycle

The calculations using this Born-Haber cycle are similar to the calculations
with the previous one.

Name of enthalpy change ΔH 1/kJ mol−1

Enthalpy of formation of magnesium chloride (Δ f H 1) −642
Bond dissociation enthalpy of chlorine (Δ BDE H1) +242
Electron affinity of chlorine (Δ EA1 H1) −364
First ionisation enthalpy of magnesium (Δ IE1H1) +736
Second ionisation enthalpy of magnesium (Δ IE2 H1) +1450
Enthalpy of atomisation of magnesium (Δ aH1(K)) +150

ΔLH 1= −Δf H 1+ ΔaH 1+ ΔIE1H1+ ΔIE2H 1+ ΔBDEH1+ 2ΔEA1H1

(MgCl2) (Mg)   
(Mg)   (Mg)      
(Cl2)        (Cl)

= +642 + 150 + 736 + 1450 + 242 − 2(364) = +2492 kJ mol−1

Enthalpy of lattice formation

The Born-Haber cycle for magnesium chloride where enthalpy of lattice
1    THERMODYNAMICS: BORN-HABER CYCLES

formation is used is exactly the same, except the arrow for lattice enthalpy
goes down as it is an exothermic process.

Mg2+ (g) + 2Cl (g) + 2e–

2∆EAIH 1
2∆aH 1 or ∆BDEH 1
Mg2+ (g) + 2Cl– (g)
Mg2+ (g) + Cl2 (g) + 2e–

∆IE2H 1
Mg+ (g) + Cl2 (g) + e–

∆IEIH 1
Mg (g) + Cl2 (g)

∆aH 1 ∆LH 1

Mg (s) + Cl2 (g)

14
∆fH 1

MgCl2 (s)

807701_C01_AQA_Chemistry_2_001-025.indd 14 13/06/15 8:50 am

 The calculation of the lattice enthalpy can be carried out as before and the
sign changed to − at the end to show the exothermic enthalpy of lattice

Born-Haber cycles
formation.
Alternatively the following expression may be used:

Δf H 1= ΔaH 1+ ΔIE1H 1+ ΔIE2H 1+ ΔBDEH 1+ 2ΔEA1H 1+ ΔLH 1

(MgCl2) (Mg) (Mg) (Mg) (Cl2) (Cl) (MgCl2)

−642 = +150 + 736 + 1450 + 242 + 2(−364) + ΔH1L

ΔLH1= −642 − 150 − 736 − 1450 − 242 + 728

ΔLH1= −2492 kJ mol−1

TIP This is using the cycle in a slightly different way. The expression may use
The use of enthalpy of lattice 2ΔaH 1 in place of ΔBDEH1 for chlorine but ΔBDEH 1 = 2ΔaH 1 for diatomic
formation means that the molecules.
enthalpy of formation is simply
a total of all the other changes Any unknown in the expression may be calculation from given data.
in the cycle. This can be done
for previous examples as well Born-Haber cycle for magnesium oxide
but beware if enthalpy of lattice When drawing a Born-Haber cycle for the oxide of a metal with oxidation
dissociation is to be calculated. state +2, there is an additional enthalpy change. The second electron affinity
of oxygen is required.
● The first electron affinity (ΔEA1H 1) of oxygen is represented by the
equation:
O(g) + e− → O−(g)
● This is an exothermic process due to the net attraction between the
nucleus of the oxygen atom and the incoming electron.
● The second electron affinity (ΔEA2H 1) of oxygen is represented by the
equation:
O−(g) + e− → O2−(g)
● The second electron affinity of oxygen is endothermic because of the
repulsion between the negatively charged O−(g) ion and the incoming
negative electron.
The values required to calculate the enthalpy of lattice dissociation for
magnesium oxide are given below.

Name of enthalpy change ΔH 1  /kJ mol−1

Enthalpy of formation of magnesium oxide (Δ f H 1) −602
15
Enthalpy of atomisation of oxygen (Δ aH 1) +248
First electron affinity of oxygen (Δ EA1H 1) −142
Second electron affinity of oxygen (Δ EA2 H 1) +844
First ionisation enthalpy of magnesium (Δ IE1 H 1) +736
Second ionisation enthalpy of magnesium (Δ IE2 H 1) +1450
Enthalpy of atomisation of magnesium (Δ aH 1(K)) +150

807701_C01_AQA_Chemistry_2_001-025.indd 15 13/06/15 8:50 am

 When drawing the Born-Haber cycle for magnesium oxide, it is important
to realise that the second electron affinity of oxygen is endothermic.
The Born-Haber cycle below is for magnesium oxide. The values for the
enthalpy changes have been added to the cycle.

Mg2+ (g) + O2– (g)

Mg2+ (g) + O (g) + 2e–

∆ EAIH –148 ∆ EA2H +844
∆aH 1 +248 Mg2+ (g) + O– (g) + e–
Mg2+ (g) + 12 O2 (g) + 2e–

∆ IE2H +1450

Mg+ (g) + 12 O2 (g) + e–

∆ LH

∆ IE1H +736
Figure 1.2 A refractory material is one
that is physically and chemically stable Mg (g) + 12 O2 (g)
at high temperatures and is used to
∆ aH +150 Mg (s) + 12 O2 (g)
line furnaces. Magnesium oxide is a
commonly used refractory material due
to its high lattice enthalpy.
∆fH 1 –602

MgO (s)
1    THERMODYNAMICS: BORN-HABER CYCLES

The cycle is different from previous ones as it includes the endothermic second
electron affinity of oxygen so there is a level above Mg2+(g) + O−(g) + e−. Also
as the second electron affinity is +844 and the first electron affinity is −142, the
level with Mg2+(g) + O2−(g) must be above the level for Mg2+(g) + O(g) + 2e−.
The calculation of the enthalpy of lattice dissociation of magnesium oxide is:
TIP
ΔLH 1 = − Δf H 1 + ΔaH 1 + ΔIE1H 1 + ΔIE2H 1 + ΔaH 1 + ΔEA1H 1 + ΔEA2H 1
Remember that the enthalpy of
lattice formation is simply the (MgO) (Mg) (Mg) (Mg) (O) (O) (O)
negative value of the enthalpy of
lattice dissociation. The enthalpy = + 602 + 150 + 736 + 1450 + 248 – 142 + 844
of lattice formation of magnesium
oxide is −3888 kJ mol−1. = +3888 kJ mol−1
Understanding enthalpy changes in a Born-Haber cycle

Exothermic Endothermic
Enthalpy change (ΔH negative) (ΔH positive)
16
Enthalpy of lattice dissociation ✓
Enthalpy of formation ✓ (mostly)
Enthalpy of atomisation ✓
Bond dissociation enthalpy ✓
First ionisation energy ✓
Second ionisation energy ✓
First electron affinity ✓
Second electron affinity ✓

807701_C01_AQA_Chemistry_2_001-025.indd 16 13/06/15 8:50 am

 The enthalpy of lattice dissociation is endothermic whereas the enthalpy of
lattice formation would be exothermic and have the same numerical value

Born-Haber cycles
but be a negative enthalpy change.

Comparison of lattice enthalpy values

lattice enthalpy/kJ mol−1

1000
The value of the lattice enthalpy gives a measure of the strength of the ionic
800
bond and this depends on the charge on the ions and the size of the ions.
600
400
The greater the value of the lattice enthalpy, the stronger the ionic bond.
200
Smaller ions and higher charge ions give stronger ionic bonding.
0 ● Smaller ions are more closely packed in the lattice and so are more
NaF NaCI NaBr NaI
Figure 1.3 The bar chart shows the attracted to each other.
effect of ion size on lattice enthalpy of ● Ions with a high charge are more attracted to each other as well.
sodium halides as Group 7 is descended. ● For example, the lattice enthalpy for NaCl is +771 kJ mol−1 but that for
The negative ions get bigger and so NaF is +915 kJ mol−1.
the distance between the centres of ● The ions have the same + and − charges but the F− ion is smaller than the
the oppositely charged ions is greater
and the attraction less, resulting in a
Cl− ion so the ions in NaF can pack closer together in the lattice and so
decrease in lattice enthalpy. lattice enthalpy is greater as the attraction between the ions is greater in
NaF compared to NaCl.
● The lattice enthalpy for MgCl2 is +2492 kJ mol−1 but that for MgO is
4000 +3888 kJ mol−1.
The lattice enthalpy for MgCl2 is greater than that for MgO due to the
lattice enthalpy/kJ mol−1

3500 ●
3000 2− charge on the O2− ion compared to the − charge on the Cl− ion. The
2500 O2− ion is also smaller than the Cl− ion so there is a stronger attraction
2000 between Mg2+ and O2− ions than between the Mg2+ and Cl− ions.
1500
● Note the lattice enthalpy for MgO is very high (and hence it is very stable
1000
and has a very high melting point) due to the 2+ and 2− charge on the
500
0
small ions.
MgCl2 MgO
The balance of enthalpy values in a Born-Haber cycle may be examined.
Figure 1.4 The larger the charge on the
ion, the stronger the electrostatic force You may be asked to comment on the difference in lattice enthalpy values
of attraction between the ions which based on other enthalpy values in the cycle. For the difference between
results in high lattice enthalpy. NaCl and NaF, it is the halogen bond enthalpy values that are different as
well as the enthalpy of formation. The enthalpy of atomisation of sodium
and first ionisation energy of sodium are the same in both cycles.

TEST YOURSELF 3
1 The enthalpy changes below can be used to a) Explain the difference between the enthalpy
calculate the enthalpy of lattice dissociation of of lattice dissociation of rubidium chloride
rubidium chloride. compared to the enthalpy of lattice dissociation
of potassium chloride.
Step Process ΔH 1  /kJ mol−1 b) The enthalpy of formation of potassium chloride
is −437 kJ mol−1 and the enthalpy of atomisation
1 Rb(s) + 12 Cl 2(g) → RbCl(s) −435
of potassium is +90 kJ mol−1. Calculate the first
2 Rb(s) → Rb(g) +81 ionisation enthalpy of potassium from this data 17
3 Rb(g) → Rb+(g) + e − +403 and the data given in the table in question 1.
1 Cl (g) → Cl(g) 3 The bond dissociation enthalpy of fluorine is
4 +121
2 2 +158 kJ mol−1.
5 Cl(g) + e− → Cl− (g) −364 a) Write an equation, including state symbols,
a) Name the enthalpy change represented by representing the bond dissociation of fluorine.
step 1. b) What is meant by the enthalpy of atomisation of
b) Calculate the enthalpy of lattice dissociation of fluorine.
rubidium chloride. c) The first electron affinity of fluorine is
2 The enthalpy of lattice dissociation of potassium −348 kJ mol−1. Calculate the enthalpy change for
1
chloride is +715 kJ mol−1. the process 2 F2(g) + e− → F− (g).

807701_C01_AQA_Chemistry_2_001-025.indd 17 13/06/15 8:50 am

 ●● Perfect ionic model
The distinction between ionic and covalent compounds is not black and white.
100% covalent
(non-polar) ● Some covalent compounds or molecules are 100% covalent as they are
δ+ δ– non-polar.
Polar covalent
(covalent with ionic ● Covalent compounds can have some ionic character for example polar
character) covalent compounds have some ionic character, i.e. the molecules are polar.
+ – ● Ionic compounds can be perfectly ionic with no covalent character.
Ionic with covalent character
(ions are not spherical) ● A small, large charge cation can distort a large anion so that there is covalent
character to the ‘ionic compound’. This means that ions are distorted and
+ – 100% ionic not spherical as would be assumed in the perfect ionic model.
(perfectly spherical
ions) It is a sliding scale from covalent to ionic. The diagram on the left shows the
scale between 100% covalent and 100% ionic.
The value of lattice enthalpy calculated using a Born-Haber cycle is the real
value (i.e. that found by experiment).
TIP The perfect ionic model of ionic compounds allows the calculation of the
Make sure that you fully lattice enthalpy based on two assumptions:
understand the perfect ionic model. 1 the bonding in the compound is 100% ionic.
It is the last two categories which
are of interest in this section as 2 the ions are regarded as point charges or perfect spheres and are not distorted.
100% ionic compounds will have If the values of the experimental lattice enthalpy and the lattice enthalpy
an experimental lattice enthalpy
calculated from the perfect ionic model are different then the compound
(calculated from a Born-Haber
cycle) roughly equal to the lattice
has some covalent character. The forces of attraction in the compound are
1    THERMODYNAMICS: BORN-HABER CYCLES

enthalpy calculated from the found to be greater than predicted by the perfect ionic model so there is
perfect ionic model. covalent character to the ionic compound. The greater the difference in the
values, the greater the covalent character in the compound.

EXAMPLE 17
The following lattice dissociation enthalpy values were from calculations using the perfect ionic model) are
determined. almost the same, the bonding in the compound is
100% ionic.
NaBr(s) AgBr(s) If the experimental value is greater than the
Δ LH 1 (experimental)/kJ mol−1 +732 +891 experimental value, there is additional covalent
Δ H 1 (theoretical)/kJ mol−1
L +731 +760 bonding in the lattice which means that the ionic
compound has some covalent character.
1 State what you would deduce about the bonding in
NaBr using the data in the table. Answers
2 State what you would deduce about the bonding in 1 NaBr is ionic as the values are almost identical.
AgBr using that data in the table. 2 AgBr is ionic with some covalent character due to
If the values for the experimental (determined from the additional strength of the covalent bonding.
18 a Born-Haber cycle) and the theoretical (determined

EXAMPLE 18
The experimental lattice enthalpy of Answer
magnesium iodide is −2327 kJ mol−1. The The experimental value is greater than the theoretical
theoretical value calculated using the perfect ionic value.
model is −1944 kJ mol−1.
Magnesium iodide has covalent character.
Explain the difference in the values.
There is additional covalent bonding in magnesium
iodide.

807701_C01_AQA_Chemistry_2_001-025.indd 18 13/06/15 8:50 am

 ●● Enthalpy of solution

Enthalpy of solution
Ionic compounds dissolve in water when the ionic lattice breaks up
(enthalpy of lattice dissociation) and the polar water molecules form bonds
with the ions (enthalpy of hydration).

Enthalpy of solution = Enthalpy of lattice dissociation + Enthalpy of

hydration
For sodium chloride:

ΔsolH 1 = ΔLH 1 + Δhyd H 1 + ΔhydH 1

(NaCl) (NaCl) (Na+) (Cl−)

The balance of the break-up of the ionic lattice and the bonds forming with
water determines the enthalpy of solution.
The enthalpy of solution is defined as the enthalpy change when one mole
of a solute dissolves in water. It can be determined from other enthalpy
values. For example:
NaCl(s) → Na+(aq) + Cl−(aq)
The enthalpy of lattice dissociation for sodium chloride is represented by
the equation
NaCl(s) → Na+(g) + Cl−(g) ΔLH 1 = +776 kJ mol−1
The enthalpy of hydration is defined as the enthalpy change when one mole
of gaseous ions is converted into one mole of aqueous ions.

Na+(g) → Na+ (aq) ΔhydH 1 = −407 kJ mol−1

Cl−(g) → Cl− (aq) ΔhydH 1 = −364 kJ mol−1

TIP
Some texts may use ‘+(aq)’ when writing the equation for solution of a
substance to represent the addition of water on the left-hand side of the
equation. This is acceptable but do not write ‘+ H2O’. This also applies to
equations for hydration of ions. It is best to keep the equations as shown
in the example for NaCl.

These enthalpy changes fit together in the following cycle.

Na+(g) + Cl–(g) 19

ΔLH 1 ΔhydH 1

Na+(aq) + Cl–(aq)

NaCl(s) ΔsolH 1

Δsol H 1 = (+776) + (−407) + (−364) = +5 kJ mol−1

807701_C01_AQA_Chemistry_2_001-025.indd 19 13/06/15 8:50 am

 5 kJ of energy are released when 1 mole of NaCl dissolves in water to form
a solution. The enthalpy of solution may be exothermic depending on the
balance between the lattice enthalpy and the enthalpies of hydration.
It is not suggested that when NaCl dissolves in water, the ionic lattice
breaks up into scattered gaseous ions which then dissolve. However, it
allows an alternative route for calculation enthalpy of solution values which
according to Hess’s Law should give the same overall enthalpy change as the
process the ions really undergo.
A simpler diagram for calculation of solution may be like the diagram below.
∆solH 1
NaCl(s) Na+(aq) + Cl–(aq)

∆LH 1 ∆hydH 1 ∆hydH 1

Na+(g) + Cl–(g)

Be careful with enthalpy of solution for Group 2 halides, as 2× enthalpy of

hydration for the halide ion is required as there are two moles of halide ion
in one mole of the ionic compound.
When ionic compounds dissolve in water the polar water molecules are
attracted to the charged ions. The δ − O atoms in H2O molecules are attracted
to the positive ions and the δ+ H atoms in H2O molecules are attracted to the
negative ions.
1    THERMODYNAMICS: BORN-HABER CYCLES

O
H H H H H
TIP H O H δ+
O
Remember to show the polarity δ− δ+
O δ− Na+ δ− O H Cl−
of the water molecules and H
the charge on the ions if you H
δ−
H O
δ+
O δ+
are asked for this type of H H H H
diagram. The diagram shows the H
O
interaction of 4 water molecules
with the ions. There would
normally be 6 for each ion. The
Values for enthalpy of hydration
ones above and below the plane Enthalpy of hydration values are exothermic as energy is released when the
of the paper are not shown so ions are attracted to the polar water molecules.
that we can see the ions.
The enthalpy of hydration for fluoride ions is −506 kJ mol−1 which is more
negative than the enthalpy of hydration for chloride ions (−364 kJ mol−1).
This is because a smaller ion with the same charge has a higher charge
density so the negative charge on the ion attracts the δ+ H of the water
20 more strongly.
The same applies to cations: The enthalpy of hydration of the Mg2+
ion is −1920 kJ mol−1 whereas the enthalpy of hydration of Ca2+ ions is
−1650 kJ mol−1. The Mg2+ ion is smaller and has a higher charge density
than the Ca2+ ion so the ions attracts the δ− O of the water more strongly.

807701_C01_AQA_Chemistry_2_001-025.indd 20 13/06/15 8:50 am

 Halides of metals with oxidation state +2

Enthalpy of solution
For halides of Group 2 and other metals with an oxidation state of +2, 2×
the enthalpy of hydration of the halide ion is required.
For calcium chloride:

Name of enthalpy change ΔH 1  /kJ mol−1

Enthalpy of solution of calcium chloride −141
Enthalpy of lattice dissociation of calcium chloride +2237
Enthalpy of hydration of calcium ions −1650

ΔsolH 1 = ΔLH 1 + ΔhydH 1(Ca2+) + 2ΔhydH 1(Cl−)

−141 = +2237 +(−1650) + 2ΔhydH 1(Cl−)

TIP −141 − 2237 + 1650 = 2ΔhydH 1(Cl−)

The dissolution of calcium
chloride also depends on 2ΔhydH 1(Cl−) = −728
entropy considerations so
−728 = −364 kJ mol−1
this information may be used ΔhydH 1(Cl−) =
2
to predict how the amount of
The enthalpy of hydration of the chloride ions is −364 kJ mol−1.
calcium chloride which dissolves
changes as temperature changes The enthalpy of solution of calcium chloride is −141 kJ mol−1.
but it is not the whole picture.
The process CaCl2(s) ⇋ Ca2+(aq) + 2Cl−(aq) is exothermic. When treating this
process as a reversible reaction, increasing the temperature would move the
position of equilibrium in the direction of the reverse endothermic process.
This would theoretically decrease the amount of calcium chloride which would
dissolve as the position of equilibrium would be moved to the left.

ACTIVITY
Experimental determination of the enthalpy of solution of
sodium hydroxide and ammonium nitrate
100 cm3 of deionised water was measured into a polystyrene cup and the
temperature recorded. A mass of solid was quickly dissolved in the
water, stirred with the thermometer and the final temperature recorded.
The results are shown in the table below.

Initial Final Temperature

Substance Mass/g temperature/°C temperature/°C change/°C
Sodium 3.99 24.9 30.0
hydroxide
Ammonium 2.02 25.0 23.6
nitrate 21

1 Describe how approximately 2 g of ammonium nitrate was weighed

out accurately in this experiment.
2 Explain any safety precautions which should be taken when using
solid sodium hydroxide pellets.

807701_C01_AQA_Chemistry_2_001-025.indd 21 13/06/15 8:50 am

 3 Both of the substances used in this experiment consist of ions. Give
the chemical formulae of the two ions that make up each of the
compounds.
4 For each of the solutes, calculate the change in temperature of
the water.
5 Calculate the mass of water in the polystyrene cup. The density of
water at 25 °C is 0.998 g/cm3.
6 Calculate the enthalpy change that occurred in each solution. The
specific heat capacity of water is 4.18 J K−1 g−1.
7 Calculate the number of moles of each solute and use this to calculate
the molar enthalpy of solution for each solute.
8 Data books give the enthalpy of solution of NaOH as −44.20 kJ mol−1
and for NH4NO 3, it is +25.40 kJ mol−1. Calculate the percentage error,
in this experiment for each solute.
9 State one source of error in this
experiment and describe how this
source of error can be minimised.
10 If excess solute was used in this
experiment, a saturated solution would
be formed, with the excess solute in
equilibrium with the solution.
NH4NO 3(s) + aq ⇋ NH4+(aq) + NO 3 − (aq)
By applying Le Chatelier’s principle
to this equilibrium determine if Figure 1.8 A temperature
the solubility of ammonium nitrate probe may be used to
1    THERMODYNAMICS: BORN-HABER CYCLES

will increase or decrease when the measure temperature

temperature is raised. changes accurately.

TEST YOURSELF 4
1 The experimental enthalpy of lattice dissociation of silver chloride
is +905 kJ mol−1. The theoretical value of the enthalpy of lattice
dissociation of silver chloride is +770 kJ mol−1. Explain the difference
in these values.
2 The table below gives some enthalpy changes. Calculate the enthalpy
of solution of potassium chloride.

Name of enthalpy change ΔH 1  /kJ mol−1

Enthalpy of lattice dissociation of +715
potassium chloride
Enthalpy of hydration of potassium −320
ions
22 Enthalpy of hydration of chloride ions −364

3 The enthalpy of hydration of fluoride ions is −506 kJ mol−1. Explain why

the enthalpy of hydration of fluoride ions is more negative than the
enthalpy of hydration of chloride ions given in question 2.

807701_C01_AQA_Chemistry_2_001-025.indd 22 13/06/15 8:50 am

 Practice questions a) Write equations, including state symbols, to

Practice questions
represent the following enthalpy changes.
1 Which one of the following enthalpy changes i) The first ionisation energy of lithium
is exothermic? (1)
A enthalpy of atomisation of magnesium ii) The enthalpy of formation of lithium
B enthalpy of bond dissociation of chlorine fluoride (1)

C first electron affinity of chlorine iii) The first electron affinity of fluorine (1)

D enthalpy of lattice dissociation of iv) The enthalpy of lattice formation of

magnesium chloride. (1) lithium fluoride. (1)

2 Which one of the following equations b) Calculate the enthalpy of lattice formation
represents the second ionisation energy of of lithium fluoride. (2)
strontium? 5 The Born-Haber cycle below is for sodium
A Sr(s) → S2+(g) + 2e− chloride.
Na+(g) + Cl(g) + e–
B Sr(g) → Sr2+(g) + 2e−
F
C Sr+(s) → Sr2+(g) + e− E Na+(g) + Cl–(g)
Na+(g) + 12 Cl2(g) + e–
D Sr+(g) → Sr 2+(g) + e− (1)
3 Nitrogen triiodide decomposes on contact D
Na(g) + 12 Cl2(g)
according to the equation. The reaction is A
exothermic.
C
2NI3(g) → N2(g) + 3I2(g) Na(s) + 12 Cl2(g)

B
Calculate the enthalpy change for the reaction NaCl(s)
using the mean bond enthalpy values given in
the table below. (3)
a) The table below shows the enthalpy
Mean bond enthalpy changes A to F. Complete the table by
Bond (kJ mol−1) giving the names of the missing enthalpy
N–I 159 changes. (4)
N≡N 944
I–I 151 Step Name of enthalpy change ∆H 1/ kJ mol−1
A Enthalpy of lattice to be calculated
4 Lithium fluoride is formed from lithium and dissociation of sodium
fluorine. The following data may be used to chloride
calculate the enthalpy of lattice formation of B −411
lithium fluoride.
C +109
∆H1/kJ mol−1
D +494
First ionisation enthalpy of lithium +520 E Enthalpy of atomisation of +121 23
chlorine
Enthalpy of atomisation of lithium +159
F −364
Enthalpy of formation of lithium fluoride −612
Enthalpy of atomisation of fluorine +79 b) Calculate a value for enthalpy change A
using the data in the table. (2)
Electron affinity of fluorine atoms −348

807701_C01_AQA_Chemistry_2_001-025.indd 23 16/06/2015 17:19

 c) The enthalpy of lattice dissociation for b) Use the information in the table and the
potassium chloride is +710 kJ mol−1. Born-Haber cycle to calculate the enthalpy
Explain why the value for sodium chloride of formation of magnesium chloride. (3)
calculated in (b) is greater than the value
7 The following data gives the enthalpy of
for potassium chloride. (2)
hydration of some ions.
6 The Born-Haber cycle shown below is for
magnesium chloride. The table gives the values Enthalpy of hydration
Ion (kJ mol−1)
for the enthalpy changes involved in the cycle
below. Chloride to be calculated
Bromide −335
Mg2+ (g) + 2e– + 2Cl (g)
Iodide −293
Lithium −519
Mg2+ (g) + 2e– + Cl2 (g)
Sodium −406
Mg2+ (g) + 2Cl– (g) Potassium −320
Iron(II) −1950

Mg+ (g) + e– + Cl2 (g)

a) Explain why the enthalpy of hydration of
the bromide ion is more exothermic than
the enthalpy of hydration of an iodide ion.
Mg (g) + Cl2 (g) (2)
b) The enthalpy of solution for potassium
Mg (s) + Cl2 (g)
iodide is +20.5 kJ mol−1. Calculate the
enthalpy of lattice formation for potassium
1 THERMODYNAMICS: BORN-HABER CYCLES

MgCl2 (s)
iodide. (3)
c) The enthalpy of lattice dissociation of
Name of enthalpy iron(II) chloride calculated from a Born-
change ∆H 1/kJ mol−1
Haber cycle is +2631 kJ mol−1 and the
Bond dissociation +242 enthalpy of solution of iron(II) chloride
enthalpy of chlorine
is −47 kJ mol−1 Calculate the enthalpy of
Electron affinity of −364 hydration of a chloride ion. (3)
chlorine
First ionisation enthalpy +736 d) The theoretical value for the enthalpy of
of magnesium lattice dissociation for iron(II) chloride
Second ionisation +1450 calculated from the perfect ionic model is
enthalpy of magnesium +2525 kJ mol−1.
Enthalpy of atomisation +150 i) Explain the meaning of perfect ionic
of magnesium
model. (1)
Enthalpy of lattice −2492
formation of magnesium ii) Explain why the enthalpy of lattice
chloride formation of iron(II) chloride calculated
from the Born-Haber cycle, given
24 a) Copy out the cycle and put the correct in (c), is greater than the theoretical
values on the arrows to show the enthalpy value calculated from the perfect ionic
change represented by the arrows in the model. (2)
Born-Haber cycle. (4)

807701_C01_AQA_Chemistry_2_001-025.indd 24 15/06/2015 15:21

 Stretch and challenge
2Al3+ (g) + 6e– + 3O (g)

Practice questions
8 The diagram below gives part of the Born-Haber
cycle for aluminium oxide. Examine the data 1
2Al3+ (g) + 6e– + 1 2 O2 (g)
given in the table and complete the cycle.
1
2Al2+ (g) + 4e– + 1 2 O2 (g)
Calculate the second electron affinity of oxygen
based on the data given below. 1
2Al+ (g) + 2e– + 1 2 O2 (g)
Compare the value you obtain for the second
electron affinity for the given value for the first 1
2Al (g) + 1 2 O2 (g)
electron affinity. (If you have not been able to
1
obtain a value for the second electron affinity, 2Al (s) + 1 2 O2 (g)
use +701 kJ mol−1. This is not the correct
value). (10) Al2O3 (s)

Name of enthalpy change ΔH 1/kJ mol−1

Enthalpy of atomisation of +249.2
oxygen
First electron affinity of −141.0
oxygen
First ionisation enthalpy of +580
aluminium
Second ionisation enthalpy of +1800
aluminium
Third ionisation enthalpy of +2700
aluminium
Enthalpy of atomisation of +324.3
aluminium
Enthalpy of lattice formation −15 178.9
of aluminium oxide
Enthalpy of formation of −1675.7
aluminium oxide

25

807701_C01_AQA_Chemistry_2_001-025.indd 25 13/06/15 8:50 am

 Thermodynamics:
2 Gibbs free energy
change, ΔG, and
entropy change, ΔS
PRIOR KNOWLEDGE
It is expected that you are familiar with all of the content of Chapter 4
Energetics in the Year 1 book of the A-level Chemistry course. The
following are some key points of Prior Knowledge:
● A positive value for ΔH indicates an endothermic reaction.
● A negative value for ΔH indicates an exothermic reaction.
● Enthalpy change for a reaction may be calculated using standard
enthalpy changes of combustion or formation.
● Hess’s Law states that the enthalpy change for a chemical reaction
is independent of the route taken and depends only on the initial and
final states.
● Enthalpy changes may be calculated from other enthalpy changes
using Hess’s Law.

TEST YOURSELF ON PRIOR KNOWLEDGE 1

1 Calcium carbonate decomposes on heating to form calcium oxide and
carbon dioxide. Using the standard enthalpies of formation, calculate
the enthalpy change for this reaction.
CaCO3 (s) → CaO(s) + CO2(g)
Δf H 1/kJ mol−1
CaCO 3(s) −1207
CaO(s) −636
CO2(g) –394

2 Calculate the standard enthalpy of formation of ammonia, where the

enthalpy change for the reaction N2(g) + 3H2(g) → 2NH3(g) is −92 kJ mol−1.
3 Ammonia reacts with oxygen to form nitrogen monoxide and steam
according to the equation.
4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)
26 a) Using the standard enthalpies of formation, calculate the enthalpy
change for this reaction.
Δf H 1/ kJ mol−1
NH3(g) −46
O2(g) 0
NO(g) + 90
H2O(g) −242

b) Explain why oxygen has a value of zero.

807701_C02_AQA_Chemistry_2_026-042.indd 26 13/06/15 8:58 am

 ●● Feasible reactions

Entropy
A reaction that can occur at a particular temperature is called a feasible
reaction. The enthalpy change on its own is not enough to determine
whether or not a reaction will be feasible as some feasible reactions are
endothermic. These include:
KCl(s) +(aq) → K+ (aq) + Cl− (aq) ΔH 1 = +19 kJ mol−1
H2O(s) → H2O(l) ΔH 1 = +6 kJ mol−1
H2O(l) → H2O(g) ΔH 1 = +44 kJ mol−1
(NH4)2CO3 (s) → 2NH3(g) + CO2(g) + H2O(g) ΔH 1 = +68 kJ mol−1
All four of these reactions above have one thing in common – an increase in
disorder. This is the disorder of the particles in the system (reaction). Gases
are more disordered than liquids and solution which are more disordered
than solids.
All of them show a change from an ordered system to a more random
system. The degree of disorder or randomness in a system is called its
entropy.

●● Entropy
Entropy is a measure of disorder within a Entropy is given the symbol S and standard or absolute entropy S 1.
system.
Entropy is measured in J K−1 mol−1.

Absolute entropy values (standard entropy values)

Absolute or standard entropy values are calculated for one mole of a
substance based on a scale where the substance has an entropy value of
0 (zero) at 0 K. This assumes that the crystalline form of the substance at 0 K
is a perfect crystal.
Some absolute entropy (S 1) values are given in the table:
Solids S 1/ J K−1 mol−1 Liquids S 1/ J K−1 mol−1 Gases S 1/ J K−1 mol−1
C(s) 2.4 Br2(l) 75.8 O2(g) 205
(diamond)
Figure 2.1 Tossing a soft drink into the Si(s) 19.0 Hg(l) 76.1 Cl 2(g) 165
air is more likely to give a disorganised Mg(s) 32.7 C2H5OH(l) 161 N2(g) 192
pile when it falls, than a neatly ordered
Al(s) 28.3 H2O2(l) 110 H2(g) 131
stack. Disorder is more probable than
order. NaCl(s) 72.4 CS2(l) 151 NH3(g) 193
CaO(s) 39.7 NH4NO 3(aq) 190 CO2(g) 214
I2(s) 58.4 NaCl(aq) 116 CO(g) 198 27
H2O(s) 48.0 H2O(l) 70.0 H2O(g) 189

The higher the absolute entropy value, the higher the degree of disorder of a
substance.
From the table it is clear to see that solids are more ordered than liquids and
solutions, which are more ordered than gases. This can be used as a general
rule to explain changes in entropy later.

807701_C02_AQA_Chemistry_2_026-042.indd 27 13/06/15 8:58 am

 Entropy linked to changes in state
A crystalline solid with a highly ordered arrangement has low entropy.
When it melts, the system becomes less ordered (it is impossible to tell
exactly where each ion or atom or molecule is relative to each other) so the
entropy has increased.
In Year 1 of the course (AS) the four types of crystalline solids studied are:
1 metallic
2 ionic
3 molecular
2    THERMODYNAMICS: GIBBS FREE ENERGY CHANGE, ΔG, AND ENTROPY CHANGE, Δ S

4 macromolecular
From the previous table, examples of these were given.

Type of crystalline solid Solids S 1 /J K−1 mol−1

Macromolecular C(s) (diamond) 2.4
Macromolecular Si(s) 19.0
Metallic Mg(s) 32.7
Metallic Al(s) 28.3
Ionic NaCl(s) 72.4
Ionic CaO(s) 40
Molecular I2 (s) 58.4
Molecular H2O(s) 41

From the table it is clear that macromolecular substances have a very

low entropy value and this property results from their very regular
macromolecular structure.
Metallic substances also have low entropy values based on them having
a very ordered metallic lattice, and similarly with ionic compounds and
their ionic lattice. Even molecular crystals such as iodine and ice have low
entropy values as they are regular ordered crystalline substances.
There is an increase in entropy from solid to liquid, but the increase in
entropy from liquid to gas is much larger as gases are very disordered. This
is shown most clearly by the S1 values of water as a solid, liquid and gas
below.

Solid S 1 / J K−1 mol−1 Liquid S 1 /J K−1 mol−1 Gas S 1 /J K−1 mol−1

H2 O(s) 48 H2 O(l) 70 H2 O(g) 189

28

Solid Liquid Gas

Figure 2.2 The changes in the arrangement of water molecules when ice melts, to
form a liquid and then evaporates, show an increase in disorder.

807701_C02_AQA_Chemistry_2_026-042.indd 28 13/06/15 8:58 am

 A graph of the entropy values of water against temperature is shown below.

Entropy
250
Solid Gas
200 Liquid

–1
mol
150
Boiling

–1
S 1/J K
100

Melting
50

0
273 373
Temperature/K

● At 0 K the entropy of a perfect crystalline substance is 0 (zero).

● The graph shows a general increase in entropy as temperature increases.
● Within a solid the entropy increases as temperature increases as the
particles gain energy and vibrate more.
● As the solid melts and forms a liquid there is a large increase in disorder
at a particular temperature. This temperature is called the melting point.
● Again within a liquid there is an increase in entropy (disorder) increases
as temperature increases.
● There is a very large increase in entropy at the boiling point when a
liquid changes into a gas as gases are very disordered.

Entropy related to Mr
Some absolute entropy values of gases are given below with their Mr values.

H2(g) N2(g) CO(g) O2(g) CO2(g)

Mr 2 28 28 32 44

S 1 /J K−1 mol−1 131 192 198 205 214

In general the higher the Mr value of substances in the same state, the
higher the entropy value.
This is a general rule but can be used to predict the entropy values of
substances in the same state.

Entropy change (Δ S 1)
The entropy change in a reaction can be calculated from absolute entropy values.
Absolute entropy values are quoted with units J K−1 mol−1 (joules per Kelvin 29
per mole).
The entropy change in a reaction can be calculated from the absolute
entropy values.
ΔS 1 = Sum of entropy values of products − Sum of entropy values of reactants
This can be summarised mathematically as:
ΔS 1 = ΣS 1products − ΣS 1reactants
where Σ represents the ‘sum of’.

807701_C02_AQA_Chemistry_2_026-042.indd 29 13/06/15 8:58 am

 The ‘per mole’ must be considered here as absolute entropy values are per
mole of the substance.
If two moles of substance appear in the reaction, the absolute entropy value
must be multiplied by two before being used in the expression.

EXAMPLE 1
Calcium carbonate decomposes on heating according to the equation:
CaCO3 (s) → CaO(s) + CO2(g)
2    THERMODYNAMICS: GIBBS FREE ENERGY CHANGE, ΔG, AND ENTROPY CHANGE, Δ S

Some entropy values are given below.

CaCO3 (s) CaO(s) CO2(g)

S 1
/J K −1 mol−1 93 40 214

Calculate a value for the standard entropy change for this reaction.
Answer
ΔS 1 = ΣS 1products − ΣS 1reactants
ΔS 1 = (214 + 40) − 93 = +161 J K−1 mol−1
TIP It would be expected that this reaction would have a positive entropy
In the next section you will be change.
expected to judge whether
The decomposition of a solid to produce a solid and a gas would show an
a reaction has a positive or
increase in entropy (disorder) as the gas would have a greater level of
negative entropy change based
disorder than any solid.
on the reactants and products
and their states. 1 mol of solid produces 1 mol of solid and 1 mol of gas.

EXAMPLE 2
The equation for the thermal decomposition of NaHCO3 is:
    2NaHCO3 (s) → Na2CO3 (s) + CO2(g) + H2O(l)
Absolute entropy values are given in the table below.

NaHCO3 (s) Na2CO3 (s) CO2(g) H2O(l)

S /J K −1 mol−1
1
102 135 214 70

Calculate a value of ΔS1 for this reaction.

Answer
30 ΔS 1 = ΣS products
1
− ΣS 1reactants
ΔS 1 = (135 + 214 + 70) − (2 × 102) = + 215 J K−1 mol−1
This reaction shows an increase in entropy as system becomes more
disordered. There are 2 mol of solid producing 1 mol of solid and 1 mol of
liquid and 1 mol of gas. The liquid and gas are more disordered and so
have a higher entropy value. Entropy increases in this reaction.

807701_C02_AQA_Chemistry_2_026-042.indd 30 13/06/15 8:58 am

 Entropy
EXAMPLE 3
Nitrogen reacts with hydrogen to form ammonia according to the
equation:
    N2(g) + 3H2(g) → 2NH3(g)

N2(g) H2(g) NH3(g)

S 1
/J K −1 mol−1 192 131 193

Calculate a value of the entropy change for this reaction.

Answer
    ΔS 1 = ΣS 1products − ΣS 1reactants
    ΔS 1 = (2 × 193) − (192 + 3 × 131) = −199 J K−1 mol−1
TIP
The units of S 1 (absolute entropy) This reaction shows a decrease in entropy as it becomes more ordered,
and ΔS 1 (entropy change) are i.e. 4 mol of gas becomes 2 mol of gas. Fewer moles of gas are more
J K−1 mol−1. ordered so the reaction shows a decrease in entropy.

Entropy change predicted from an equation

From the equation of a reaction, it is often possible to tell if ΔS 1 is positive
or negative.
A reaction is often called a system, so often we say that the entropy of the
system has decreased or increased meaning that ΔS 1 is negative or positive,
respectively.

EXAMPLE 4
Predict whether the entropy change of the reaction is positive or negative
and explain your answer.
   NH4NO3 (s) → N2O(g) + 2H2O(g)
TIP Answer
Under standard conditions the 1 mol of solid ammonium nitrate forms 1 mol of dinitrogen oxide gas and
water formed in the equation 2 mol of water vapour (gas).
above would be a liquid which is
more ordered than a gas, so the This will have a positive ΔS 1 value as the gases are much more
ΔS 1 would be less positive. disordered than the crystalline solid (ammonium nitrate).

31
TIP EXAMPLE 5
Only ΔS1 values need to have
a positive or negative sign. S 1 Predict whether the entropy change of the reaction is positive or negative
values are always positive in and explain your answer.
the same way as H 1 values     CaO(s) + H2O(l) → Ca(OH)2 (s)
are always positive. Values for
S 1 may be quoted to different Answer
numbers of decimal places or as ΔS 1 is negative as 1 mol of solid and 1 mol of liquid produce 1 mol of solid
whole number values. so the reaction becomes more ordered. Entropy decreases.

807701_C02_AQA_Chemistry_2_026-042.indd 31 13/06/15 8:58 am

 EXAMPLE 6
TIP Predict whether the entropy change of the reaction is positive or negative
When all the reactants and and explain your answer.
products are in the same state,     4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)
the increase in entropy can be
caused by an increase in the Answer
number of moles in the same ΔS 1 is positive as 9 mol of gas produces 10 mol of gas so the reaction
state. becomes more disordered. Entropy would be expected to increase.
2    THERMODYNAMICS: GIBBS FREE ENERGY CHANGE, ΔG, AND ENTROPY CHANGE, Δ S

TEST YOURSELF 2
1 Predict whether the entropy of the following reactions will increase or
decrease?
a) 2H2(g) + O2(g) → 2H2 O(l)
b) CaCO 3 (s) + 2HCl(aq) → CaCl 2 (aq) + CO2(g) + H2 O(l)
c) 2Na(s) + Cl 2(g) → 2NaCl(s)
Figure 2.3 Hydrated crystals of copper d) CaO(s) + 2NH4Cl(s) → CaCl 2(s) + 2NH3(g) + H2 O(l)
sulfate are shown above, with a copper
2 Calculate the entropy change of the following reaction using the
sulfate solution made from the same
standard entropy data given below.
mass of crystals. Which has the highest
entropy?
Substance S 1 value/J K−1 mol−1
KNO 3 (s) 133
KNO2 (s) 152
O2(g) 205
Fe(s) 27
Fe3O 4 (s) 146
(NH4)2 SO 4 (s) 220
Ca(OH)2 (s) 83
CaSO 4 (s) 107
NH3(g) 193
H2O(l) 70

a) 2KNO 3 (s) → 2KNO2 (s) + O2(g)

b) 3Fe(s) + 2O2(g) → Fe3O4 (s)
c) (NH4)2SO4 (s) + Ca(OH)2 (s) → CaSO4 (s) + 2NH3(g) + 2H2O(l)

32
●● Feasibility of a reaction
The feasibility of a chemical reaction depends on the enthalpy change of the
reaction, the entropy change of the reaction and the temperature at which
the reaction is occurring.
Gibbs free energy or the free energy change is written as ΔG 1 and this links
these three properties.
ΔG 1 is calculated using the expression:

ΔG 1 = ΔH 1 − TΔS 1

807701_C02_AQA_Chemistry_2_026-042.indd 32 13/06/15 8:58 am

 ● ΔG 1 is used to predict the feasibility of a chemical reaction.
For a reaction to be feasible, ΔG must be equal to or less than 0 (zero).

Feasibility of a reaction
●
● You can determine if a reaction is feasible at a certain temperature by
calculating ΔG 1.
● Also you can calculate the temperature at which a reaction becomes
TIP feasible using ΔG 1 and ΔH 1 assuming that ΔG 1 = 0 for a feasible
A reaction for which ΔG1 = 0
reaction.
is in equilibrium so both the
forward and reverse reactions are ● ΔG 1 and ΔH 1 have units of kJ mol−1. ΔS 1 has units of J K−1 mol−1.
feasible. ΔG  0 is normally used ● The value given or calculated for ΔS 1 in J K−1 mol−1 must be divided by
for a reaction to be feasible. 1000 to change into kJ K−1 mol−1 before it is used to calculate ΔG 1 or
used in the ΔG 1 expression.

Feasible and spontaneous

TIP There is a difference between a reaction being feasible and a reaction being
This is the most often forgotten spontaneous. A feasible reaction may not occur at a particular temperature
step in these calculations. ΔS1 as the activation energy may be too high for it to proceed. A spontaneous
must be converted to kJ K−1 mol−1
reaction is one that is feasible and occurs under standard conditions. For a
by dividing the given value by
reaction to be spontaneous, ΔG 1 must be less than zero and the activation
1000 before using it in the ΔG1
expression. energy for the reaction must be low enough for the reaction to proceed
under standard conditions.

TIP EXAMPLE 7
The terms feasible and The reaction below shows the possible decomposition of sodium
spontaneous are often used carbonate into sodium oxide and carbon dioxide.
interchangeably but it is    Na2CO3 (s) → Na2O(s) + CO2(g)
important to realise that the
activation energy has a part to For this reaction, ΔH 1 = +323.0 kJ mol−1 and ΔS 1 = +153.7 J K−1 mol −1
play in the spontaneous nature a) Show that the thermal decomposition of sodium carbonate is not
of a reaction. If a reaction is feasible at 1200 K.
feasible but does not occur b) Calculate the temperature at which the value of ΔG = 0 for this
spontaneously, the activation reaction. Give your answer to 1 decimal place.
energy is high.
Answer
a) ΔG1 has units of kJ mol−1 exactly like ΔH 1, so the units of ΔS must be
changed to kJ K−1 mol−1. This is achieved by dividing the ΔS 1 value by
1000 to convert to kJ K−1 mol−1.
So ΔS 1 = +0.1537 kJ K−1 mol−1
ΔG 1 = ΔH 1 − TΔS 1
ΔG 1 = 323.0 − (1200 × 0.1537) = +138.6 kJ mol−1
Because ΔG 1 is positive at this temperature the reaction is not feasible.
b) ΔG 1 = ΔH 1 − TΔS 1
When ΔG 1 = 0
Then ΔH 1 − TΔS 1 = 0 33
MATHS +323.0 − T(0.1537) = 0
2101.5 K is the same as 1828.5 °C; T(0.1537) = 323
to convert between the Kelvin and
T = 323.0 = 2101.4964 K.
Celsius temperature scale, simply 0.1537
subtract 273. To convert between T = 2101.5 K (to 1 decimal place)
Celsius and Kelvin, add 273. T must be equal to or greater than 2101.5 K for the reaction to be feasible.

807701_C02_AQA_Chemistry_2_026-042.indd 33 13/06/15 8:58 am

 To determine the temperature at which a reaction changes from not feasible to
feasible divide ΔH1 by ΔS1 but remember to make sure ΔS is in kJ K−1 mol−1.

EXAMPLE 8
The table below gives some enthalpy and entropy data for some elements
and compounds.

N2(g) H2(g) O2(g) NO(g) NH3(g) H2O(g)

Δf H 1
/kJ mol−1 0 0 0 +90 −46 −242
2    THERMODYNAMICS: GIBBS FREE ENERGY CHANGE, ΔG, AND ENTROPY CHANGE, Δ S

S 1
/J K −1 mol−1 192 131 205 211 193 189

1 Explain why the entropy value of oxygen is greater than that of

hydrogen.
2 Explain why the standard enthalpy of formation of oxygen is 0 (zero).
3 The equation for the catalytic oxidation of ammonia is:
   4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)
a) Calculate the enthalpy change for the reaction using the data in the
table.
b) Calculate the entropy change for the reaction. State the units.
c) Explain why this reaction is feasible at any temperature.
Answer
1 O2 has a higher Mr than H2. TIP
Higher entropy value as the This type of Hess’s Law
particles are heavier. calculation should be
2 Oxygen is an element. revised from Year 1 of the
3 a) ΔH = 4(+90) + 6(−242) −4(−46)
1 course (AS).
= −908 kJ mol −1

b) ΔS1 = ΣS 1products − ΣS 1reactants

= (4 × 211 + 6 × 189) − (4 × 193 + 5 × 205) = +181 J K−1 mol−1.
c) Exothermic reaction and entropy increases so reaction is feasible at
all temperatures.

Factors affecting feasibility of a reaction

The feasibility of a reaction depends on whether a reaction is endothermic
or exothermic and also whether there is an increase in entropy or a decrease
in entropy. The table below shows how these factors affect ΔG and the
feasibility of a reaction.

ΔH 1 ΔS 1 ΔG 1 Feasibility
34 May be positive or Feasible below certain
Negative Negative
negative temperatures
Negative Positive Always negative Feasible at any temperature
Positive Negative Always positive Not feasible at any temperature
May be positive or Feasible above certain
Positive Positive
negative temperatures

807701_C02_AQA_Chemistry_2_026-042.indd 34 13/06/15 8:58 am

 Feasibility of a reaction
EXAMPLE 9
The equation for the combustion of ethanol is given below:
C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(g)
Write an expression for ΔG 1.
Use this expression to explain why this reaction is feasible at all
temperatures.

TIP Answer
This kind of qualitative ΔG 1 = ΔH 1 − TΔS 1
understanding of the relationship
1 mol of liquid and 3 mol of gas become 5 mol of gas so entropy increases.
between ΔH 1, ΔS 1, T and ΔG 1 is
important as well as being able It is a combustion reaction which is exothermic.
to carry out the calculations. A
As ΔH 1 is negative and ΔS 1 is positive, ΔG 1 is negative at all
reaction which is exothermic and
temperatures.
shows an increase in entropy will
be feasible at all temperatures. So the reaction is feasible at all temperatures.

Physical changes using ΔG  1

● During a change of state ΔG 1 = 0 (zero) kJ mol−1.
● ΔG 1 is positive for temperatures below the melting point as it is not
feasible.
● ΔG 1 is negative for temperatures above the melting point as it is feasible.
● The same is true of ΔG 1 for boiling around the boiling point.
● When ΔG 1 = 0, the system is at equilibrium and this is what is
Figure 2.4 The value for ΔG is positive
1 happening when a change of state occurs.
for photosynthesis. The reaction is not ● If ΔG 1 is given, then other quantities can be calculated by rearranging
feasible until sunlight is present. the expression.

EXAMPLE 10
ΔG 1 = 0 kJ mol−1 for the melting of ice to water. This physical reaction is
endothermic and occurs at 273 K.
H2O(s) → H2O(l)
The absolute entropy values for ice and water are given below.

H2O(s) H2O(l)
S 1
/J K −1 mol−1 48 70

1 Explain why the melting of water is feasible at 273 K even though this
change is endothermic. 35
2 Calculate the entropy change for the reaction.
3 Calculate the enthalpy change for the reaction.
4 Show that the conversion of ice to water is feasible at 298 K (25 °C) but
not feasible at 268 K (−5 °C).
Figure 2.5 Melting ice is an
endothermic reaction. It is feasible
only at certain temperatures.

807701_C02_AQA_Chemistry_2_026-042.indd 35 13/06/15 8:58 am

 Answer
1 Water molecules become more disordered when the
solid changes to a liquid so ΔS 1 is positive/entropy
increases.
TIP
TΔS1 being equal to or a greater numerical
ΔG 1 is = 0 so TΔS = ΔH
value than ΔH 1 is important in ensuring that
2 ΔS 1 = ΣS 1products − ΣS 1reactants ΔG 1 is equal to or less than zero so the reaction
= 70 − 48 = +22 J K−1mol−1 is feasible. In a change of state ΔG 1 = 0.
3 ΔG = 0 kJ mol−1
1

T = 273 K
ΔS 1 = +22 J K−1 mol−1
2    THERMODYNAMICS: GIBBS FREE ENERGY CHANGE, ΔG, AND ENTROPY CHANGE, Δ S

ΔG 1 = ΔH 1 − TΔS 1
ΔH 1 = ΔG 1 + TΔS 1
ΔH 1 = 0 +273(0.022)
ΔH 1 = +6 kJ mol−1
This value was given on the first page of this topic.
4 At 298 K
ΔG 1 = ΔH 1 − TΔS 1
ΔG 1 = +6 − 298(0.022) = −0.556 kJ mol−1
ΔG 1 is less than zero so the conversion of ice to
water at 298 K is feasible. TIP
At 268 K The same theory can be applied to any change
ΔG 1 = ΔH 1 − TΔS 1 in state as ΔG1 = 0 for a change in state as
ΔG 1 = +6 − 268(0.022) = +0.104 kJ mol−1 the change of state is viewed as a reaction at
ΔG 1 is greater than zero so the conversion of ice to equilibrium.
water at 268 K is not feasible

EXAMPLE 11
The following data is given for the condensation of ΔS 1 = 23.35 = −0.09729 kJ K−1 mol−1 = −97.29 J K−1 mol−1
−240
ammonia.
ΔS = ΣS 1products − ΣS 1reactants = S 1 (NH3 (l)) − 193
1
   NH3(g) → NH3 (l)   ΔH 1 = −23.35 kJ mol−1
= −97.29 J K−1 mol−1
The absolute entropy value for NH3(g) = 193 J K−1 mol−1
S 1 (NH3 (l)) = −97.29 + 193 = 95.71 J K−1 mol−1
The boiling point of ammonia is 240 K.
Calculate the absolute entropy value of NH3 (l).

Answer TIP
You would expect this change to have a negative
For a change of state, ΔG 1 = 0 kJ mol−1 entropy change as the liquid is more ordered
ΔG 1 = ΔH 1 − TΔS 1 than the gas.
0 = −23.35 − 240(ΔS 1 )
36

TIP
Being able to rearrange an expression to calculate another quantity is
important. You can check your answers are correct on the way through
a calculation by substituting them back into the expression you used to
ensure it gives you the expected answer.

807701_C02_AQA_Chemistry_2_026-042.indd 36 13/06/15 8:58 am

 Feasibility of a reaction
EXAMPLE 12
The change of state from liquid to gas for water has an entropy change
of +119 J K−1 mol−1. The enthalpy change for the physical change is:
+44.39 kJ mol−1.
   H2O(l) → H2O(g)
Calculate the boiling point of water. Assume that ΔG 1 = 0 kJ mol−1 for the
change of liquid water to a gas.

Answer
ΔG 1 = ΔH 1 − TΔS 1
ΔG 1 = 0
ΔH 1 − TΔS 1 = 0
+44.39 − T (0.119) = 0
44.39 = T (0.119)
44.39
T= = 373 K
0.119
The boiling point of water is 100 °C which equals 373 K.

TEST YOURSELF 3
1 Two reactions which are involved in the extraction 3 For the reaction C2H4(g) + H2(g) → C2H6(g)
of iron in the blast furnace are: a) Calculate the enthalpy change for the reaction
A Fe2O 3 (s) + 3CO(g) → 2Fe(s) + 3CO2(g) given the following standard enthalpies of
   ΔH1 = −25.0 kJ mol−1 combustion (in kJ mol−1) C2H4 (g) = −1411; H2(g)
   ΔS 1 = +15.2 J K−1 mol−1 = − 286; C2H6(g) = −1560
B Fe2O 3 (s) + 3C(s) → 2Fe(s) + 3CO(g) b) Calculate ΔS1 given the following standard
   ΔH 1 = +491.0 kJ mol−1 entropies.
   ΔS 1 = +542.9 J K−1 mol−1
S 1/ J K−1 mol−1
Which reactions are feasible at
a) 800 K C2H4 (g) 220
b) 1800 K H2(g) 131
2 For the reaction Cu(s) + 2H2O(l) → Cu(OH)2 (s) + H2(g) C2H6(g) 230
a) Calculate the enthalpy change for the reaction
given the following enthalpies of formation. c) Calculate the temperature at which the
reaction becomes feasible.
Δf H 1/ kJ mol−1 4 The change of state of bromine from liquid to gas
H2O(l) −286 is represented by the equation:
Cu(OH)2 (s) −450
Br 2 (l) → Br 2(g)   ΔH 1 = +30 kJ mol−1
The standard entropy values of bromine are given
b) Calculate ΔS1 given the following absolute below:
entropy values. 37
Br2 (l) Br2(g)
S 1/ J K−1 mol−1 S 1 /J K−1 mol−1 75.8 166.4
Cu(s) 33 a) Calculate the entropy change for this reaction.
H2O(l) 70 b) Assuming ΔG 1 = 0 for a change of state,
Cu(OH)2 (s) 75 calculate the boiling point, in K, of bromine.
H2(g ) 131

c) Calculate the temperature at which ΔG 1 = 0.

807701_C02_AQA_Chemistry_2_026-042.indd 37 13/06/15 8:58 am

 ●● Graphical calculations
MATHS ● The equation ΔG 1 = ΔH 1 − TΔS 1 can be plotted as a straight line graph.
y = mx + c is the equation of a
straight line on a graph. Any
● This follows the pattern y = mx + c.
straight line is in this form where ΔG 1 = ΔH 1 − TΔS 1
m is the gradient of the line ● For the straight line graph y = mx + c, m is the gradient and c is in the
and c is the intercept with the y intercept on the y axis.
axis. For more detail on this see ● If a graph of ΔG 1 against T is plotted, the gradient is −ΔS 1 and the
chapter 16, Maths for chemistry. intercept with the ΔG 1 axis is ΔH 1.
2    THERMODYNAMICS: GIBBS FREE ENERGY CHANGE, ΔG, AND ENTROPY CHANGE, Δ S

The gradient of this

line is –∆S1. A positive
gradient like this one
The intercept The gradient of this
means a negative
of the line on line is –ΔS 1. A negative
value of ∆S1
the ΔG1 axis gradient like this one The intercept
gives the means a positive of the line
DG DG
value of ΔH 1 value of ΔS 1 on the ∆G1
0 axis gives the 0
T/K value of ∆H1 T/K

This is the temperature at which This is the temperature at which

ΔG 1 = zero. This is the minimum ∆G1 = zero. This is the maximum
temperature for the reaction to be temperature for the reaction to be
feasible. At all temperatures feasible. At all temperatures below
above this the reaction is feasible. this the reaction is feasible.

● ΔG 1 and ΔH 1 have the same units of kJ mol−1.

● When T = 0, ΔG 1 = ΔH 1 from the expression ΔG 1 = ΔH 1 − TΔS 1.
● The gradient of the line has units of kJ K−1 mol−1. The gradient can be
calculated from the graph and the negative of this value gives ΔS 1.
● ΔS 1 can be calculated in J K−1 mol−1 by multiplying the negative gradient
by 1000.

EXAMPLE 13 700
When lead (ii) nitrate is heated it decomposes
600
according to the equation
500
2Pb(NO3)2 (s) → 2PbO(s) + 4NO2(g) + O2(g)
The graph shows how the free energy change (ΔG 1 ) 400
for this reaction varies with temperature. 300
Use the graph to find ΔH and ΔS .
1 1
200
ΔG 1/kJ mol–1

What is the minimum temperature required for the 100

decomposition of lead(ii) nitrate?
38 0
Answer 300 600 900 1200
–100 T/K
Extrapolating back to T = 0 the line intercepts the ΔG 1

axis at +600 kJ mol−1. –200

From the expression ΔG = ΔH − TΔS , when T = 0,

1 1 1
–300
ΔG 1 = ΔH 1.
–400
ΔH 1 = +600 kJ mol−1.
–500
The gradient is found by dividing rise by run − 600 =
690 –600
−0.875 kJ mol−1 K−1.

807701_C02_AQA_Chemistry_2_026-042.indd 38 16/06/2015 17:05

 The gradient is negative as the line falls from left to 700

Graphical calculations
right. 600
The gradient is −ΔS 1 so ΔS 1 = 0.875 kJ mol−1 K−1, 500
which equals +875 J K−1 mol−1.
400
The temperature at which the line crosses the T axis
is the temperature at which ΔG 1 = 0. This value is 300 600
690 K. The minimum temperature required for the
200
decomposition of lead(ii) nitrate is 690−K.

ΔG 1/kJ mol–1
100
690
0
300 600 900 1200
–100 T/K

–200

–300

–400

–500

–600

TIP
If you are unsure about how to calculate the gradient of a graph, refer to
page 314 in the mathematics chapter of this book.

ACTIVITY
The production of ammonia The graph shows how the free energy change (ΔG 1 )
for this reaction varies with temperature.
Ammonia has a major use in making fertilisers and
is used to produce many other chemicals as shown in
Figure 2.6.
1 Write a balanced symbol equation for the Polyamides 5%
production of ammonium sulfate fertiliser from Nitric acid 5%
ammonia. Fertilisers
Other uses 5%
2 Nitric acid is manufactured by the oxidation of 85%
ammonia, which initially produces nitrogen monoxide
and water. The nitrogen monoxide is further oxidised
to nitrogen dioxide, which is then reacted with more
air and water to produce nitric acid. Write balanced
symbol equations for each of the three steps in this Figure 2.6 The major uses of ammonia. 39
manufacture.
In the Haber process, nitrogen reacts with hydrogen
to form ammonia according to the equation:
   N2(g) + 3H2(g) ⇌ 2NH3(g)

807701_C02_AQA_Chemistry_2_026-042.indd 39 16/06/2015 17:06

 100
3 a) Use the graph to determine ΔS 1.
b) Use the graph to determine ΔH 1 . 80
c) Calculate the temperature above which the
60
reaction is no longer feasible.
d) The line is not drawn below a temperature of 40

ΔG 1/kJ mol–1
240 K because its gradient changes at this point.
20
Suggest what happens to the ammonia at 240 K
that causes the slope of the line to change. 0
e) In terms of the reactants and products and 100 200 300 400 500 600 700 800
–20 T/K
their physical states, account for the sign of the
2    THERMODYNAMICS: GIBBS FREE ENERGY CHANGE, ΔG, AND ENTROPY CHANGE, Δ S

entropy change that you calculated in part (a). –40

–60

–80

–100
Figure 2.7 Graph of ΔG 1 against T for the
production of ammonia.

TEST YOURSELF 4 100

1 What is the gradient of a ΔG against temperature
1
80
graph?
2 Explain how the value of ΔH 1 is determined from a 60
ΔG 1 against temperature graph.
3 Consider the following graph of ΔG 1 against T for a 40
ΔG 1/kJ mol–1

reaction.
20
a) Give an estimate of the value of ΔH 1 for this
reaction using the graph. 0
200 400 600 800
b) Explain using the graph whether the reaction shows –20
an increase or decrease in entropy. T/K
c) At what temperature does ΔG 1 = 0? –40

–60

–80

–100

40

807701_C02_AQA_Chemistry_2_026-042.indd 40 16/06/2015 17:06

 Practice questions a) Calculate the free energy change, ΔG 1, for

Practice questions
this reaction at:
1 Which one of the reactions shown below would i) 400 K (1)
show a decrease in entropy?
ii) 600 K and comment on the
1
A Ca(s) + 2 O2(g) → CaO(s) feasibility of this reaction at this
B Ca(s) + 2HCl(aq) → CaCl2(aq) + H2(g) temperature. (2)
C CaCO3(s) → CaO(s) + CO2(g) b) Calculate the temperature at which
D CaCO3(s) + 2HNO3(aq) → Ca(NO3)2 (aq) + CO2(g) + H2O(l) (1) ΔG 1 has a value of 0 for the
decomposition of silver(I) oxide. (2)
2 Carbon can reduce carbon dioxide to carbon
monoxide according to the equation: 5 For the reaction:

C(s) + CO2(g) → 2CO(g) ΔH 1 = +173 kJ mol−1 CaO(s) + H2O(l) → Ca(OH)2(s)

ΔH 1 = −65 kJ mol−1
If ΔS 1 = +175.9 J K−1 mol−1, at which of the
following temperatures is the reaction feasible? a) Calculate ΔS 1 given the following
absolute entropy values (in J K−1 mol−1):
A 750 K B 850 K C 950 K D 1050 K (1) CaO(s) = 39.7; H2O(l) = 70;
3 The reaction of copper with steam is represented Ca(OH)2 (s) = 83.4. (2)
by the equation: b) Calculate the temperature at which
Cu(s) + H2O(g) → CuO(s) + H2(g) ΔG 1 = 0. (2)

The table gives the standard entropy values and 6 Magnesium carbonate and barium carbonate
the standard enthalpies of formation. both decompose on heating according to the
equation:
Cu(s) H2O(g) CuO(s) H2(g) XCO3(s) → XO(g) + CO2(g)
Standard 0 −242 −155 0
enthalpy of The table below details the values of
formation Δf H1 and absolute entropy.
(kJ mol−1)
MgCO3(s) MgO(s) CO2(g) BaCO3(s) BaO(s)
Standard entropy 33 189 43.5 131
Δf H1/ −1096 −602 −394 −1216 −554
value
kJ mol−1
(J K−1 mol−1)
S 1 /J K−1 66 27 214 112 70
Which one of the following correctly describes mol−1
the reaction of copper with steam? a) Calculate ΔH 1 and ΔS 1 for both
A Feasible at any temperature. reactions, and use these values to
B Not feasible at any temperature. calculate ΔG 1 at 900 K for both reactions.
Which (if either) of the carbonates will
C Feasible at low temperature but not feasible decompose on heating to 900 K? (4)
at high temperature.
b) Calculate the minimum temperature
D Not feasible at low temperature but
needed to decompose each carbonate
feasible at high temperature. (1)
based on when ΔG 1 = 0. (4) 41
4 On heating, silver(I) oxide decomposes into
7 When heated strongly, copper(II) sulfate
silver and oxygen
decomposes according to the equation:
2Ag2O(s) → 4Ag(s) + O2(g)
CuSO4(s) → CuO(s) + SO3(g)
ΔH 1 = +62 kJ mol−1
The graph below shows how the free energy
ΔS 1 = +132.8 J K−1 mol−1 change (ΔG 1) for this reaction varies with
temperature.

807701_C02_AQA_Chemistry_2_026-042.indd 41 13/06/15 8:58 am

 a) Use the graph to find ∆H 1 and ∆S 1. (2) a) Calculate the enthalpy change of the
reaction shown above using the
b) At what temperature does ∆G = 0? 1
(1)
enthalpies of formation. (2)
c) What is the minimum temperature
b) Explain why the enthalpy of formation of
required for the decomposition of
aluminium is 0 (zero). (1)
copper(II) sulfate? (1)
250
c) Calculate the entropy change for this
reaction. (2)
200
d) Calculate the value of ∆G 1 for this
150 reaction at 298 K. State the units. (2)
2 THERMODYNAMICS: GIBBS FREE ENERGY CHANGE, ∆G, AND ENTROPY CHANGE, ∆ S

ΔG 1/kJ mol–1

100 e) Explain whether the reaction is feasible

at 298 K. Explain your answer. (1)
50
f) Calculate the temperature at which this
0
400 800 1200 1600 reaction becomes feasible. (2)
–50 T/K
Stretch and challenge
–100
10 The following reaction becomes feasible at
temperatures above 5440 K.
8 Sodium melts at 371 K.
H2O(g) → H2(g) + 12 O2(g)
The absolute entropy value of Na(s) is
51.0 J K−1 mol−1. The entropies of the species involved are
shown in the following table.
For the change:
Na (s) → Na(l) ∆H 1 = +2.6 kJ mol−1. H2O(g) H2(g) O2(g)
Calculate the absolute entropy value of Na(l). (3)
S 1/J K−1 mol−1 189 131 205
9 Aluminium oxide can be reduced using carbon
as shown in the equation below. a) Calculate the entropy change ∆S 1 for
Al2O3(s) + 3C(s) → 2Al(s) + 3CO(g) this reaction. (1)
The table below gives values for standard b) Calculate a value, with units, for the
enthalpy of formation and absolute entropy for enthalpy change for this reaction at
the reactants and products. 5440 K. State the units. (4)

Al2O3(s) C(s) Al(s) CO(g)

c) The standard enthalpy of formation of
water is −286 kJ mol−1. Using Hess’s Law,
∆ f H 1/kJ mol−1 −1669 0 0 −111
calculate the enthalpy change for the
S 1
/J K−1 mol−1 51 6 28 198 change H2O(l) → H2O(g). (3)

42

807701_C02_AQA_Chemistry_2_026-042.indd 42 16/06/2015 17:06

 3 Rate equations
PRIOR KNOWLEDGE
It is expected that you are familiar with all of the content of the Kinetics
unit in Year 1 (AS) of the A-level Chemistry course. The following are
some key points of Prior Knowledge:
● The rate of reaction is the change in concentration of a reactant or
product in a given period of time.
● The rate of a reaction is dependent on the frequency of successful
collisions.
● A successful collision is a collision that has the minimum amount of
energy for the reacting particles to react.
● The activation energy is the minimum amount of energy that the
reacting particles require for a successful collision.
● A catalyst increases the rate of reaction without being used up.
● A catalyst works by providing an alternative reaction pathway (or
route) of lower activation energy.
● A Maxwell-Boltzmann distribution is a plot of the number of gaseous
molecules against the energy they have at a fixed temperature.
● The energy value of the peak on a Maxwell-Boltzmann distribution is
the most probable energy (Emp) of the molecules.
● Emp is only affected by changes in temperature.
● Increasing temperature increases Emp and increases the number of
molecules above the activation energy.

TEST YOURSELF ON PRIOR KNOWLEDGE 1

1 State three factors that can affect the rate of a chemical reaction.
2 State the effect, if any, on the most probable energy of decreasing the
temperature.
3 State the effect, if any, on the most probable energy of changing the
concentration.
4 From the reactions below:
Reaction A: C2H4 (g) + Br 2(aq) → C2H4Br 2(l)
Reaction B: C 3H6(g) + H2(g) → C2H6(g)
Reaction C: C2H5OH(l) + 3O 2(g) → 2CO2(g) + 3H2 O(l)
a) Which reaction is homogeneous?
b) Explain your answer to part (a).
5 What is meant by the term activation energy? 43

807701_C03_AQA_Chemistry_2_043-067.indd 43 13/06/15 8:59 am

 ●● Conventions
● Kinetics is the study of the rate of a chemical reaction.
● The rate of a reaction can be measured based on how fast the
TIP
The concentrations of gases concentration of a reactant is decreasing or how fast the concentration of
and solutions are frequently a product is increasing, i.e. the change in concentration per unit time.
measured in mol dm−3 as it ● The units of rate are concentration per unit time, for example
expresses the number of moles mol dm−3 s−1 (mol per dm3 per second).
of a substance in a volume ● Square brackets around a substance, for example [A] or [H+] or [CH3OH]
(solution or space) of 1 dm3. This or [O2] all indicate concentration of the substance which is inside the
convention is used in equilibrium brackets.
calculation as well as kinetics. ● Concentration is always measured in mol dm−3 (mol per dm3).
● For example [H+] = concentration of hydrogen ions measured in mol dm−3.
● Initial rates of reaction are often used as the initial rate of reaction at t =
0 s (time = zero seconds, i.e. when the reaction has just started) is directly
related to the concentrations of the reactants which were used in setting
up the experiment. As the experiment progresses the reactants are being
used up so it is more difficult to relate the concentrations of reactants to
the rate as the reaction proceeds.

●● The rate equation

The rate equation is an expression showing how the rate of reaction is linked
to the concentrations of the reactants.
● Rate is equal to the rate constant (k) multiplied by the concentration of
each reactant raised to certain whole number powers (called orders).
● Some reactants may be zero order which means they do not appear in the
rate equation as [X]0 = 1.
● The rate equation for general reaction: A + B → C + D
is: rate = k[A]m[B]n
where m is the order of reaction with respect to reactant A
and n is the order of reaction with respect to reactant B
and k is the rate constant
● The order of reaction with respect to a particular reactant is the power
3    R ATE EQUATIONS

to which the concentration of this reactant is raised in the rate equation.

● The overall order of the reaction is the sum of all the orders in the rate
equation. In this general example it would be m + n.
● The rate constant is the proportionality constant which links the rate of
TIP
Make sure that the rate constant reaction to the concentrations in the rate equation.
is included in a rate equation Wilhelm Ostwald was a German physical chemist and was the first person
as it is easily forgotten. Also to introduce the term ‘reaction order’. He identified the action of catalysts
make sure it is a lower case k in lowering activation energy. As a result, Ostwald was awarded the 1909
44 as a capital K is an equilibrium
Nobel Prize in Chemistry. Ostwald is usually credited with inventing the
constant.
Ostwald process used in the manufacture of nitric acid.

807701_C03_AQA_Chemistry_2_043-067.indd 44 13/06/15 8:59 am

 Effect of changes in concentration on rate
MATHS

The rate equation

For the reaction: B + C + D → E + F, the rate equation is: rate = k [B]2[D].
Any value raised to the power This means that the order of reaction with respect to B is 2, the order of
zero is equal to 1. 50 = 1; [A]0 = reaction with respect to C is zero (as it does not appear in the rate equation)
1. A power of 1 is not usually and the order of reaction with respect to D is 1. The overall order of
written, for example rate = k[A]
reaction is 3 (2+1).
means that the order of reaction
with respect to A is 1. ● Doubling the concentration of B would increase the rate by a factor of 4
as (×2)2 = ×4.
● Doubling the concentration of C would have no effect on the rate as
(×2)0 = ×1.
Doubling the concentration of D would double the rate as (×2)1 = ×2.
TIP ●

Orders with respect to reactants ● Doubling the concentration of B, C and D would increase the rate by a
are 0 (zero), 1 or 2. In terms of factor of 8 as (×2)2(×2)0(×2)1 = ×8 or using the overall order (×2)3 = ×8.
rate of reaction, the concentration
of a zero order reactant has no Units of the rate constant
effect on the rate of the reaction. ● Rate has units of mol dm−3 s−1 and concentration has units of mol dm−3.
Third order reactions are not ● The units of the rate constant, k, depend on overall order of reaction and
common but examples are used the units can be calculated as shown:
to illustrate the principles. ● For a general rate equation = k[A]2[B] the overall order is 3 (2 + 1).
[B] = [B]1 so the order with respect to B is 1.
● rate = k × (concentration)3
● Putting in the units: mol dm−3 s−1 = k (mol dm−3)3
Overall order Units of rate −3   −1 −3   −1
of Reaction constant, k ● Rearranging to find k: k = mol dm s = mol dm s
(mol dm−3)3 mol3 dm−9
1 s−1
−3
2 mol−1 dm3 s−1 ● Treat each term separately: mol = mol−2 and dm−9 = dm−3−(−9) = dm6.
3 mol−2 dm6 s−1 mol 3 dm
−2
Units of the rate constant k = mol dm s 6 −1
4 mol−3 dm9 s−1 ●
5 mol−4 dm12 s−1 The table shows the units of the rate constant for common overall orders.

TEST YOURSELF 2
1 The reaction C + 2D → E + 2F is zero order with respect to C and
second order with respect to D. Write a rate equation for the
reaction.
2 In the rate equation: rate = k[A]2[B]
a) What is represented by k?
b) What is the order of reaction with respect to A?
c) What is the order of reaction with respect to B?
d) What is the overall order of reaction?
3 For the reaction P + Q → S + T the rate equation is rate = k[P]2 45
a) What is the order of reaction with respect to P?
b) What is the order of reaction with respect to Q?
c) What are the units of the rate constant (k)?
4 For the following general rate equation: rate = k[X]x[Y]y
a) What is meant by [A]?
b) What are the units of rate?
c) What is the overall order of reaction in terms of x and y?
Figure 3.1 The photochemical reaction d) What are the units of the rate constant if x = 0 and y = 1?
of hydrogen and chlorine is a zero order e) What are the units of the rate constant if x = 1 and y =2?
reaction.

807701_C03_AQA_Chemistry_2_043-067.indd 45 13/06/15 8:59 am

 Deducing and using orders of reaction and the rate
constant and its units
Often questions are set with experimental data at a constant temperature and
you are asked to deduce the order of reaction with respect to one or several
reactants or write a rate equation and calculate the value and units of the
rate constant.
The key to these types of questions is understanding that if you change the
concentration of one reactant, the effect it has on the rate is determined by
the order with respect to this reactant.

TIP
‘At a constant temperature’ is very important as temperature affects the
rate of reaction so the data are only able to be used to deduce orders
of reaction if the series of experiments are carried out at constant
temperature.

Using the orders of reaction from a given rate equation

With a given rate equation the orders can be used to work out the effect of
the changing concentrations of reactants on the rate.
Also you may be given a table of data with values missing which have to be
completed using the orders of reaction from the rate equation.

EXAMPLE 1
For the general reaction A + B + C → D + E, the rate equation is:
rate = k[B]2[C]
State the effect on the rate of reaction of trebling the concentration of
each reactant individually.
State the effect on the rate of reaction of trebling the concentrations of all
3    R ATE EQUATIONS

three reactants.

Answer
The order is zero with respect to A, second with respect to B and first with
respect to C.
If you treble the concentration of A, this will not change the rate as
(×3)0 = (×1)
Remember anything to the power of zero is equal to 1 so that the
concentration of a reactant with order zero has no effect on the rate of the
46 reaction.
If you treble the concentration of B, this will multiply the rate by a factor
of nine as (×3)2 = (×9)
Figure 3.2 Many important biological If you treble the concentration of C, this will triple the rate as (×3)1 = (×3)
reactions, such as the formation
of double-stranded DNA from two If you treble all the reactants, A, B and C, this will multiply the rate by a
complementary strands, can be factor of 27 as (×3)0(×3)2(×3)1 = (×1)(×9)(×3) = (×27)
described using second order kinetics.

807701_C03_AQA_Chemistry_2_043-067.indd 46 13/06/15 8:59 am

 The rate equation
EXAMPLE 2
In the reaction A + B → C + D, at constant You can write rate = k[A][B]0, but the zero order
temperature, doubling the concentration of A doubles reactants are usually left out.
the rate of reaction, whereas when the concentration
of B is doubled, this has no effect on the rate.
Determine the orders of reaction with respect to A and
B and write a rate equation for the reaction. TIP
Answer The concentration of a catalyst may be included
in the rate equation and the order with respect
Doubling the concentration of A doubles the rate so
to a catalyst can be determined in the same
order with respect to A is 1.
way as for any reactant. Often reactions that are
Doubling the concentration of B has no effect on the acid catalysed are given and concentrations of
rate so the order with respect to B is 0 (zero). [H+] are given with rate values to allow you to
determine the order with respect to H+ ions.
Rate equation is: rate = k[A].

EXAMPLE 3
The kinetics of the reaction of nitrogen(ii) oxide with Looking at the differences between the experiments
hydrogen were investigated. 2 and 3: It is best to choose these as between these
rows only the concentration of H2 is changing.
2NO(g) + 2H2(g) → 2H2O(g) + N2(g)
[H2] is doubled (×2) but [NO] does not change (×1) and
The following data were obtained in a series of the rate is doubled (×2).
experiments about the rate of reaction between NO
and H2 at a constant temperature. It follows that y = 1 here as (×2)1 = (×2) so the order
with respect to H2 is 1.
Initial Initial
concentration concentration Initial rate/ Rate equation is: rate = k[NO]2[H2]
Experiment of NO/mol dm−3 of H2/mol dm−3 mol dm−3 s−1
1 2.0 1.0 2.0 × 10 −5
2 6.0 1.0 18.0 × 10 −5 Factor by which
(×3)x = (×9)
3 6.0 2.0 36.0 ×10 −5 rate has increased

Factor by which Order (x) with respect

Deduce the order of reaction with respect to NO. concentration of to NO which we are
NO has increased trying to determine
Deduce the order of reaction with respect to H2.
Write a rate equation for this reaction.
Factor by which
Answer (×2)y = (×2)
rate has increased
Each row in the table above corresponds to a different Factor by which Order (y) with respect
experiment. Write the general rate equation as: concentration of to H2 which we are
H2 has increased trying to determine
rate = k[NO]x[H2] y 47
If you look at the differences between experiments
1 and 2. [NO] is tripled (×3) but [H2] does not change
(×1) and the rate increased by a factor of 9.
x = 2 here as (×3)2 = (×9) so the order with respect to
NO is 2.

807701_C03_AQA_Chemistry_2_043-067.indd 47 13/06/15 8:59 am

 EXAMPLE 4
The data in the table below were obtained in a series of experiments
about the rate of reaction between substances P and Q at a constant
temperature.
Deduce the orders of reaction with respect to P and Q and write a rate
equation for this reaction.

Initial
Initial concentration concentration
Experiment of P/mol dm−3 of Q/mol dm−3 Initial rate/mol dm−3 s−1
1 0.12 0.22 0.17 × 10 −4
2 0.36 0.22 0.51 × 10 −4
3 0.48 0.44 2.72 × 10 −4

Answer
Write the general rate equation as:
rate = k[P]x[Q]y
If you look at the differences Factor by which
(×3)x = (×3)
rate has increased
between experiments 1
and 2. [P] is tripled (×3) but Factor by which Order (x) with respect
concentration of to P which we are
[Q] does not change (×1) P has increased trying to determine
and the rate increased by a
factor of 3.
It follows that x = 1 here as (×3)1 = (×3) so the order with respect
to P is 1.
Looking at the differences between experiments 1 and 3 (1 and 3 were
chosen as there is a whole number factor increase in the concentrations
of both P and Q).
[P] is ×4 and [Q] is doubled (×2). The rate increases by a factor of 16 (×16).
We already know the order of reaction with respect to P is 1.
This simplifies to:
3    R ATE EQUATIONS

×4 (×2)y = ×16
Order (y) with respect to
(×2)y = ×16 = ×4 Q which we are trying to determine
×4
(×2)y = ×4 Factor by which
(×4)1 (×2)y = (×16)
rate has increased
y = 2 (as 22 = 4)
Factor by which Factor by which
The order of reaction concentration of Q
concentration of P
with respect to Q is 2. has increased has increased

Rate equation is: Order with

48 respect to P = 1
rate = k[P][Q]2

807701_C03_AQA_Chemistry_2_043-067.indd 48 13/06/15 8:59 am

 The rate equation
EXAMPLE 5
−3
The initial rate of reaction between two gases G and H rate changes by a factor of = 1.92×10−3 = 6
was measured in a series of experiments at a constant 0.32×10
temperature. [G] changes by a factor of ×3; rate changes by a factor
of ×6
The rate equation was determined to be:
So using rate equation:
rate = k[G]2[H]
Complete the table of data for the reactions between rate = k[G]2[H] ×6 = k (×3)2(×a)
G and H. k is a constant can be ignored at constant
temperature.
Initial [G]/ Initial [H]/ Initial rate/
Experiment mol dm−3 mol dm−3 mol dm−3 s−1 ×6 = ×9 ×a
1 0.20 0.15 0.32 × 10 −3
Missing concentration in experiment 3 = 0.15 × 2 =
2 0.40 0.30 0.1 mol dm−3. 3
3 0.60 1.92 × 10 −3
Missing data in experiment 4
4 0.45 8.64 × 10 −3
Between experiments 1 and 4 (chosen as the factor by
Answer which [H] increases is a whole number):

Missing data in experiment 2 [G] ×b (unknown)

Between experiments 1 and 2: [H] ×3
−3
[G] ×2 rate changes by a factor of = 8.64 × 10−3 = ×27
0.32 × 10
[H] ×2 [H] changes by a factor of ×3; rate changes by a factor
of ×27
rate × x(unknown)
So using rate equation:
Using rate equation:
rate = k[G]2[H] rate = k (×2)2(×2) rate = k[G]2[H] ×27= k(×b)2(×3)

k is a constant and can be ignored at constant k is a constant can be ignored at constant

temperature. temperature.

rate = ×4×2 = ×8 ×27 = ×b2 × 3

Missing rate in experiment 2 = 0.32 × 10−3 × 8 = 2.56 × b2 = ×27
10−3 mol dm−3 s−1 ×3
b = ×9
2 b = ×3
Missing data in experiment 3
Missing concentration in experiment 4 = 0.2 × b = 0.2 ×
Between experiments 1 and 3 (chosen as the factor by 3 = 0.6 mol dm−3
which [G] increases is a whole number):

[G] ×3
[H] ×a (unknown)
49

TIP Determining the value and units of the rate constant

In these calculations you can Often having deduced the orders of reaction for all the reactants (including
generally ignore that × or ÷ in the a catalyst if present) you can be asked to write the rate equation and
calculations but these are here to calculate a value of the rate constant and deduce its units. This combines
help you to remember to × or ÷ at many of the skills from the previous section.
the end.

807701_C03_AQA_Chemistry_2_043-067.indd 49 13/06/15 8:59 am

 EXAMPLE 6
The oxidation of nitrogen monoxide is represented by So order with respect to NO is 2 as (×2)2 = (×4)
the equation:
Experiments 2 and 4:
2NO(g) + O2(g) → 2NO2(g)
[NO] ×1
The kinetics of this reaction were studied at a constant
temperature and the following results recorded.
[O2] ×2
Initial Initial
concentration concentration rate ×2
of NO/ of O2 / Initial rate/
Factor by which
Experiment mol dm−3 mol dm−3 mol dm−3 s−1 (×2)y = (×2)
rate has increased
1 4 × 10 −3 1 × 10 −3 6 × 10 −4
Factor by which Order (y) with respect
2 8 × 10 −3 1 × 10 −3 24 × 10 −4 concentration of to O2 which we are
3 12 × 10 −3 1 × 10 −3 54 × 10 −4 O2 has increased trying to determine
4 8 × 10 −3 2 × 10 −3 48 × 10 −4
5 12 × 10 −3 3 × 10 −3 162 × 10 −4 So order with respect to O2 is 1 as (×2)1 = (×2)

Using these results, deduce the order of the reaction Rate equation: rate = k[NO]2[O2]
with respect to nitrogen monoxide and oxygen. To calculate a value of the rate constant at this
Write a rate equation for the reaction. temperature, substitute in any values from the table.

Calculate a value for the rate constant at this If we use experiment 1:

temperature and deduce its units.
[NO] = 4 × 10−3 mol dm−3
Calculate the rate when the initial concentrations of
NO and O2 are both 5 × 10 mol dm−3. [O2] = 1 × 10−3 mol dm−3
A general rate equation would be:
rate = 6 × 10−4 mol dm−3 s−1
rate = k[NO]x[O2]y The rate equation determined was: rate = k[NO]2[O2]
Answers So substituting the values from experiment 1 into the
Experiments 1 and 2: equation:

[NO] × 2 6 × 10−4 = k(4 × 10−3)2(1 × 10−3)

3    R ATE EQUATIONS

[O2] × 1 6 × 10−4 = k(1.6 × 10−8)

Units of the rate constant were discussed previously.
rate × 4 The units of an overall order 3 reaction are
mol−2 dm6 s−1.
Factor by which
(×2)x = (×4) k = 37 500 mol−2 dm6 s−1.
rate has increased

Factor by which Order (x) with respect Using the rate equation and the value of k.
concentration of to NO which we are
NO has increased trying to determine
50 rate = k[NO]2[O2] = 37 500 × (5 × 10−3)2(5 × 10−3) =
4.6875 × 10−3 mol dm−3 s−1

TIP
In this type of question it may tell you which experiment to use to
calculate the rate constant but if it does not, use the first one as this is
often the simplest one.

807701_C03_AQA_Chemistry_2_043-067.indd 50 13/06/15 8:59 am

 The rate equation
EXAMPLE 7
Gases Y and Z react according to the following Order (y) with respect to Z which
equation. we are trying to determine

2Y(g) + Z(g) → S(g) + T(g) Factor by which

(×5)1 (×0.5)y = (×1.25)
rate has increased
The initial rate of reaction was measured in a series of
experiments at a constant temperature. Factor by which Factor by which
concentration of Y concentration of Z
Initial [Y]/ Initial [Z]/ Initial rate/ has increased has increased
Experiment mol dm−3 mol dm−3 mol dm−3 s−1 Order with
1 1.7 × 10 −2 2.4 × 10 −2 7.40 × 10 −5 respect to Y = 1
2 5.1 × 10 −2 2.4 × 10 −2 2.22 × 10 −4
3 8.5 × 10 −2 1.2 × 10 −2 9.25 × 10 −5 This simplifies to:
4 3.4 × 10 −2 4.8 × 10 −2 5.92 × 10 −4
×5 (×0.5)y = ×1.25
Deduce the orders of reaction with respect to Y and Z.
Write a rate equation for the reaction at this (×0.5)y = ×1.25 = ×0.25
×5
temperature.
(×0.5)y = ×0.25
Calculate a value for the rate constant (k) at this
temperature and deduce its units. y = 2 (as 0.52 = 0.25)
A general rate equation would be: The order of reaction
TIP
with respect to Z is 2.
rate = k[Y]x[Z]y Remember that orders
The rate equation is rate of reaction have to be 0
Answers = k[Y][Z]2 (zero), 1 or 2.
Experiments 1 and 2: To calculate a value of
the rate constant at this temperature, substitute in any
[Y] × 3
values from the table.
[Z] × 1 If we use experiment 1:
rate ×3
[Y] = 1.7 × 10−2 mol dm−3
Factor by which
(×3)x = (×3)
rate has increased [Z] = 2.4 × 10−2 mol dm−3
Factor by which Order (x) with respect
concentration of to Y which we are rate = 7.40 × 10−5 mol dm−3 s−1
Y has increased trying to determine
The rate equation determined was:
So order with respect to Y is 1 as (×3)1 = (×3)
rate = k[Y][Z]2
There are no two experiments in which the
So substituting the values from experiment 1 into the
concentration of Y does not change so you can choose
equation:
any two experiments now that you know the order of
reaction with respect to Y.
7.40 × 10−5 = k(1.7 × 10−2)(2.4 ×10−2)2
Experiments 1 and 3: 51
7.40 × 10−5 = k(9.792 × 10−6)
[Y] × 5 Units of the rate constant were discussed previously.
The units of an overall order 3 reaction are
[Z] × 0.5
mol−2 dm6 s−1.
rate ×1.25 k = 7.56 mol−2 dm6 s−1.

807701_C03_AQA_Chemistry_2_043-067.indd 51 13/06/15 8:59 am

 Effect of temperature on the rate constant
All of the previous work in calculating a value of the rate constant (k) has
depended on the measurements being taken at a constant temperature.
The rate constant is dependent on temperature. If a constant temperature
had not been maintained, the rate would have varied based on changes in
concentrations of reactants as well as temperature.
k

● As temperature increases, the rate constant increases.

● The rate constant increases exponentially as temperature increases.
● A graph of the rate constant (k) against temperature (measured in Kelvin)
T would be as shown on the left.

●● The Arrhenius equation

The Arrhenius equation links the rate constant with activation energy and
temperature. It is written as
Ea
–
k = Ae RT

where k is the rate constant, A is the Arrhenius constant, e is a mathematical

constant (2.71828), Ea is the activation energy, R is the gas constant
TIP (8.31 J K−1 mol−1) and T is the temperature measured in kelvin (K).
ex can be accessed on your
calculator as it will be the shift In this equation Ea has units of J mol-1. This means that ERTa does not have any
Ea
function of natural log (which is units as J mol−1 is divided by (J K−1 mol-1 × K). e – RT will not have any units
written ln). Check you can use either, so the Arrhenius constant will have the same units as the rate constant.
ex; e1 should be 2.71828 with the
1828 recurring.
EXAMPLE 8
A reaction has an activation energy of 120 kJ mol−1 at room temperature
(298 K). The gas constant R is 8.31 J K−1 mol−1. A = 2.2 × 1012 s−1. Calculate
a value for this rate constant at this temperature. State its units.

Answer
E
Initially determine RTa . Ea = 120 000 J mol−1; R = 8.31 J K−1 mol−1 and T = 298 K
3    R ATE EQUATIONS

Ea 120 000
= = 48.46.
RT 8.31 × 298
Ea
k = Ae– RT = 2.2 × 1012 × e−48.46 = 1.98 × 10−9 s−1.
The units of the rate constant are the same as the units of the Arrhenius
constant.

52
Effect of changes in temperature and presence
of a catalyst
Recalculating the value of k at 308 K using the same value for the Arrhenius
constant used in Example 8 gives
Ea
= 120 000 = 46.88.
RT 831 × 308
E
k = Ae– RT = 2.2 × 1012 × e−46.88 = 9.61 × 10−9 s−1.
a

807701_C03_AQA_Chemistry_2_043-067.indd 52 13/06/15 8:59 am

 This shows an almost five-fold (9.61 × 10−9/1.98 × 10−5 = 4.85) increase in
the rate of reaction with a small increase in temperature.

The Arrhenius equation

TIP
Remember that doubling the concentration of a first order reactant will
only double the rate of reaction so increasing temperature will have a
greater effect on the rate of the reaction than changing the concentration.
This was discussed at AS.

However, adding a catalyst has a much more dramatic effect on the rate of
reaction. A catalyst for this reaction lowers the activation energy to
100 kJ mol−1 at 298 K. The Arrhenius constant is unchanged.
Recalculating the value of k at 298 K:
E 100 000 = 40.38.
− a =
RT 8.31 × 298
E
k = Ae RT = 2.2 × 1012 × e−40.38 = 6.39 × 10−6 s−1.
a
–

A catalyst which lowers the activation energy from 120 kJ mol−1 to

100 kJ mol−1 increases the rate of reaction by a factor of 3228
(6.39 × 10−6/1.98 × 10−9 = 3228.1). Catalysts have a very
significant effect on the rate of a chemical reaction.

Graphical analysis
The Arrhenius equation can be converting using natural logs (represented
by ln) to:
E
ln k = − a + ln A.
RT
● This is in the form of y = mx + c so a graph of ln k against 1/T is drawn.
E
● The gradient of this graph will be − a and the intercept with the ln k axis
R
will be ln A.
● As the gas constant, R, is given as (8.31 J K−1 mol−1), Ea can be calculated
from the gradient of the line.
● The intercept is ln A. This can be converted to A using the inverse or
shift function on your calculator.

EXAMPLE 9
The rate constant for a reaction was calculated at The quantities 1/T and ln k were calculated and
different temperatures as shown below. presented in the table below.

Temperature/K k/s−1 1/T ln k

53
300 1.75 × 10 −3 3.33 × 10 −3 −6.35
310 6.60 × 10 −3 3.23 × 10 −3 −5.02
320 2.50 × 10 −2 3.13 × 10 −3 −3.69
330 7.60 × 10 −2 3.03 × 10 −3 −2.58
340 2.40 × 10 −1 2.94 × 10 −3 −1.43

807701_C03_AQA_Chemistry_2_043-067.indd 53 13/06/15 8:59 am

 Answer 50

These results are plotted on the graph of ln k against 1/T as

40
shown below:
The intercept on the ln k axis is at 37. This would indicate that ln 30

ln k
A = 37 so A = e37. A = 1.17 × 1016 s−1. A has the same units as k
given in the table. 20 37

The gradient of the line is negative as the line has a negative 10

slope and is −37/0.00285 = −12982.5. This is equal to −Ea/R so
0.00285
Ea = 12982.5 × R = 12982.5 × 8.31 = 107884.6 J mol−1. This is 0
converted to kJ mol−1 by dividing by 1000. So Ea for the reaction 0 0.001 0.002 0.003
at this temperature is 107.9 kJ mol−1. 1/T

TIP TEST YOURSELF 3

In these types of question, the 1 In the rate equation: rate = k[C][D]2
equations and any constants a) State the order of reaction with respect to C and D.
required would be given to you with b) State the units of the rate constant (k).
the required units. Remember 2 A series of experiments were carried out on the rate of reaction
that Ea should be in J mol−1 in the between A and B at a constant temperature.
Arrhenius equation and A has the The rate equation for the reaction is rate = k[A]2
same units as the rate constant. The data obtained are given in the table below. Complete the table.

Initial [A]/ Initial [B]/ Initial rate/

Experiment mol dm−3 mol dm−3 mol dm−3 s−1
1 1.5 × 10 −2 2.4 × 10 −2 1.2 × 10 −5
2 3.0 × 10 −2 2.4 × 10 −2
3 3.6 × 10 −2 4.8 × 10 −5

3 R reacts with S. The kinetics of the reaction were studied at a

constant temperature. The data obtained are given in the table below.
Initial [R]/ Initial [S]/ Initial rate/
Experiment mol dm−3 mol dm−3 mol dm−3 s−1
1 0.25 0.15 0.0225
3    R ATE EQUATIONS

2 0.25 0.30 0.0900

3 0.50 0.30 0.1800
4 0.75 0.45 0.6075

a) Deduce the order of reaction with respect to R and S.

b) Write a rate equation for the reaction.
c) Calculate a value of the rate constant (k) at this constant
temperature and deduce its units.
Ea
4 What do k, A, R, T and Ea stand for in the expression k = Ae– RT ?
54
●● Methods of determining rate of reaction
Measuring the rate of a chemical reaction depends on being able to follow
the progress of the reaction against time. This involves being able to
measure a change in the amount or concentration of a reactant or product
during the reaction.
From the equation of the reaction identify a reactant or a product which can
be measured. Examples will include:
1 a gaseous product which can be monitored using a gas syringe or by loss in
mass

807701_C03_AQA_Chemistry_2_043-067.indd 54 13/06/15 8:59 am

 2 a coloured reactant or product which can be monitored using colorimetry

Methods of determining rate of reaction

3 a titratable reactant or product which can be monitored by sampling,
gas syringe quenching and titrating
4 a directly measurable reactant or product, i.e. H+ ions or OH− ions by
measuring pH using a pH meter.
conical flask

reaction mixture Measuring gas volume

● A gas syringe is a ground glass syringe which is attached to a sealed
reaction vessel and measures the volume of gas produced.
● This is measured against time and a graph of gas volume against time is
plotted.
● The gradient of the tangent at t = 0 s gives the initial rate of reaction.
● This is the rate of reaction.

Example of gas volume graph

As reaction nears completion
gradient of tangent approaches 0

Gradient of tangent taken at

Gas volume/cm3

t = 40 is less than at t = 0

Gradient of tangent taken at t = 0 is greater than

gradients at later times-this gives the initial rate

0 20 40 60 80 100 120 140 160

Time/s

Measuring change in mass

● A reaction in which a gas is produced may also be monitored by
measuring the mass over a period of time.
● The curve of the graph decreases again and initial tangent at t = 0 s gives
a measure of initial rate of reaction.
Mass/g

55

TIP
Mass and gas volume in a
specified volume are equivalent Time/s
to mol dm−3 s−1 as the gas volume
would be divided by a constant
(Vm) and the mass lost would be Example of a graph showing change in mass against time
divided by a constant Mr and the Gas syringe measurements and change in mass measurements are used for
reaction would be carried out in a
initial rate monitoring.
constant volume.

807701_C03_AQA_Chemistry_2_043-067.indd 55 13/06/15 8:59 am

 ● This means several experiments changing the concentration of the each
reactant are carried out and initial rate measurement taken.
● A typical table of results for changes in the concentration of reactant A
for the reaction A + B → C would be:
[A]/mol dm−3 Rate/mol dm−3 s−1
0.01 0.0025
0.02 0.0050
0.03 0.0075
0.04 0.0100
0.05 0.0125

● The initial rate can be related to the initial concentration and the order
determined as shown before or a graph of rate against concentration
can be drawn. The shape of this graph gives the order of reaction with
respect to the reactant the concentration of which you were changing.
● It could be worked out that the order of reaction with respect for A is 1
as when the concentration doubles the rate doubles.
● A graph of rate against concentration for a first order reaction such as this
would look like the graph below.

TIP
Graphs of rate against
Rate/mol dm–3 s–1

concentration will be examined in

more detail later in the chapter.

Concentration/mol dm–3

Measuring a coloured reactant or product

A colorimeter measures colour intensity of a solution. It must be done
3    R ATE EQUATIONS

with an appropriate coloured filter. For example if you are measuring the
intensity of a blue solution, you should use a red filter as the solution is
absorbing red light. The amount of red light absorbed relates directly to
the concentration. A calibration curve should be set up first with known
concentrations of the reactant or product so that you can directly relate the
colorimeter reading to the concentration.
Figure 3.3 A colorimeter
A calibration curve
This calibration curve allows absorbance values to be directly converted to
56
concentration. Graphs of concentration against time can then be drawn.
Absorbance

Concentration/mol dm–3

807701_C03_AQA_Chemistry_2_043-067.indd 56 13/06/15 8:59 am

 Example of a graph for colorimeter readings for a coloured product

Methods of determining rate of reaction

The gradient of the tangent at t = 0 s gives the initial rate of reaction.

Absorbance
Time/s

Measurement of a coloured product is used for initial rate monitoring.

● This means several experiments are carried out changing the
concentration of each reactant.
● The gradient of the tangents at t = 0 s for each concentration give the
initial rate of reaction for each of the concentrations used.
● The initial rate can then be related to the initial concentration to
determine the order. The order can be determined from a graph of
rate against concentration. The shape of this graph gives the order of
reaction with respect to the reactant the concentration of which you were
changing.

Example of a graph of colorimeter reading for a coloured reactant

Measurement of a coloured reactant can be used for continuous rate
monitoring.
● This means one experiment is carried out
The gradient is of this line is the rate
0.04 of reaction when the concentration and the colorimeter readings are converted to
is 0.04 mol dm-3 concentration using the calibration curve.
● A graph of concentration against time is drawn
Concentration/mol dm-3

and the shape of this curve can give the order

The gradient is of this line is the rate with respect to the coloured reactant.
of reaction when the concentration ● A gradient of a tangent at any concentration
is 0.02 mol dm-3 on the graph is a measure of rate at that
0.02 concentration.
● The rate can then be related to the concentration
The gradient is of this line is
and the order determined or a graph of rate
the rate of reaction when the
concentration is 0.01 mol dm-3 against concentration can be drawn. The shape of
0.01
this graph gives the order of reaction with respect
to the reactant, the concentration of which you
were changing.
Time 57

Measuring a reactant or product by titration

Sampling, quenching and titrating allows a titratable reactant or product
to be measured during the course of the reaction.
A sample is taken at various times, and the reaction is quenched – this
means the reaction is stopped. Methods of quenching include rapid cooling,
adding a chemical to remove a reactant which is not being monitored or
adding a large known volume of water to the sample. The sample may then
be titrated to find the concentration of the reactant or product.

807701_C03_AQA_Chemistry_2_043-067.indd 57 13/06/15 8:59 am

 From the data, a graph of concentration against time can be drawn.
Measurement of a titratable product is used for initial rate monitoring.
● This means several experiments changing the concentration of each
reactant are carried out and initial rate measurement taken from the
graphs of concentration against time.
● The initial rate can then be related to the initial concentration and
the order determined as shown before or a graph of rate against
concentration can be drawn. The shape of this graph gives the order of
reaction with respect to the reactant the concentration of which you were
changing.
Measurement of a titratable reactant may be used for continuous rate
monitoring.
● This means one experiment is carried out and a graph of concentration
against time is drawn and often the shape of this curve can give the order
with respect to the titratable reactant.
● A gradient of a tangent at any concentration on the graph is a measure of
rate at that concentration.
● The rate can then be related to the concentration and the order
determined as shown before or a graph of rate against concentration
can be drawn. The shape of this graph gives the order of reaction
with respect to the reactant the concentration of which you were
changing.

pH monitoring
TIP
The interconversion between pH = −log10[H+], so [H+] = 10(−pH)
pH and [H+] will be covered in ● pH values can be taken over time and using the above equation they can
detail in the Acids and bases unit be converted directly to [H+]
(Chapter 6). ● A graph of [H+] against time can be drawn.
● If the H+ ions are a reactant the shape of this curve can give the rate or
again gradients of tangents at various [H+] can be taken which equal rate.
● The rate can then be related to the concentration and the order
3    R ATE EQUATIONS

determined as shown before or a graph of rate against concentration

can be drawn. The shape of this graph gives the order of reaction with
respect to the reactant the concentration of which you were changing.

●● Rate monitoring
The rate of reaction may be measured in various ways but the methods used
depend on either initial rate monitoring or continuous rate monitoring.
58
Initial rate monitoring
Use a reactant or product which is measurable to enable the initial rate of
reaction to be measured. For example:
● gas production – measured using a gas syringe
● coloured substance – measured using a colorimeter
● hydrogen ions/hydroxide ions – measured using a pH meter or by
quenching and titrating.

807701_C03_AQA_Chemistry_2_043-067.indd 58 13/06/15 8:59 am

 Method

Rate monitoring
1 Pick one reactant for which you will determine the order of reaction.
2 Carry out several experiments at different concentrations for this reactant
measuring the quantity against time, for example gas volume against time.
3 Plot graphs of the measurable quantity (for example gas volume) against
time.
4 Draw a tangent at t = 0 s and determine the initial gradient of this tangent.
5 The gradient of the tangent at t = 0 s is the initial rate of the reaction.
6 Repeat for variety of concentrations of this reactant.
7 Plot a graph of the initial rate of reaction against concentration and the
shape of the graph gives the order of reaction with respect to the reactant
for which the concentration was varied.
8 Repeat for all other reactants to determine order of reaction for each one.

First order Second order

Zero order

Rate

Rate
Rate

Concentration Concentration
Concentration
For a first order reactant For a second order reactant
For a zero order reactant the graph of rate will be a the graph of rate will be a
the graph of rate will be straight line where as the curved line where as the
a straight line where concentration of the concentration of the
concentration has no effect reactant doubles the rate reactant doubles the rate
on the rate of reaction. of reaction also doubles. of reaction quadruples (×4).

Continuous rate monitoring

If the concentration of a reactant can be determined directly, for example:
● hydrogen ions determined directly from pH measurements or by
quenching and titrating
● coloured reactant determined from colorimeter readings using calibration
curve.
● a specific reactant may be titrated.

Method
1 Allow the reaction to progress and take readings (colorimeter/pH) or 59
samples at various times.
2 Any samples taken should be quenched to stop the reaction and titrated –
quenching can be carried out by rapid cooling/adding large quantities of
cold water or by adding a chemical which will remove a reactant and stop
the reaction.
3 Plot a graph of concentration against time for this reactant and the shape
of the graph gives the order with respect to this reactant.
Here are the three types of graphs, for orders of reaction 0, 1 and 2.

807701_C03_AQA_Chemistry_2_043-067.indd 59 13/06/15 8:59 am

 Zero order First order Second order
TIP

Concentration
Concentration

Concentration
If you are asked to sketch the
graphs, ensure the line or curve
starts on the concentration (y)
axis.

Time Time Time

A few rate values are determined at different concentrations and then a rate
TIP against concentration graph may be plotted in order to determine a clearer
For reactants which are zero
order, the gradient of the
order.
concentration against time graph The shape of the rate against concentration graphs can help to determine
is equal to the rate constant, k. the order of reaction. These graphs will have the same shapes as shown on
page 59 depending on the order of reaction.

Using concentration against time graphs

Gradients of tangents may be taken at various concentrations to determine
rate.
For example the graph below shows the concentration of reactant A against
time. A tangent to the curve is drawn at a concentration of 0.200 mol dm−3.
At a concentration of A of 0.200 mol dm−3 the gradient of the tangent:

= 0.240 = 6.86 × 10−5 mol dm−3 s−1.

3500
0.35

0.30 Concentration of 0.200

mol dm–3

0.25
[Ester]/mol dm–3
3    R ATE EQUATIONS

0.20 Tangent to the curve at

0.200 mol dm–3

0.15
0.240
0.10

0.05
3500

0.0
60 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Time/s

TIP
Any sensible value will be accepted as long as you draw the tangent
carefully and use the scale to calculate rise over run. This tangent would
have a negative gradient but in terms of rate is taken as the positive
value as it is the disappearance of a reactant. You can learn more about
tangents and gradients in the maths chapter.

807701_C03_AQA_Chemistry_2_043-067.indd 60 13/06/15 8:59 am

 Rate monitoring
EXAMPLE 10
Methanoic acid undergoes an acid-catalysed reaction the shape of this graph to determine the order with
with bromine according to the equation: respect to Br2.
H+(aq)
Br2(aq) + HCOOH(aq) 2Br−(aq) + 2H+(aq) + CO2(g) The second answer involves using initial rate
monitoring based on the CO2 being produced. Several
Describe an experimental method that could be used
experiments with different initial concentrations of
to determine the order of reaction with respect to
Br2 were carried out and the volume of carbon dioxide
bromine.
measured using a gas syringe against time. Graphs
The rate equation was found to be: of gas volume against time were plotted and the
gradient of the tangent at t = 0 were taken which gave
rate = k[Br2][HCOOH]
the initial rate. A graph of initial rate against the initial
Deduce the units for the rate constant. concentrations of Br2 was plotted and the shape of
this graph is used to determine the order with respect
On the axes below, sketch the expected shape of the
to Br2.
graphs in this reaction.
The reaction is second order overall.
rate = k(concentration)2
[HCOOH]

mol dm−3 s−1 = k × (mol dm−3)2

Rate

mol dm−3 s−1 = k × mol2 dm−6

−3 −1
k = mol dm s = mol1−2 dm−3−(−6) s−1 = mol−1 dm3 s−1
Time [HCOOH] mol 2 dm−6
The units of the rate constant are mol−1 dm3 s−1
Answers From the rate equation, the reaction is first order with
Measuring absorbance with a colorimeter respect to HCOOH

Br2(aq) is brown so use colorimetry with a blue filter: A concentration against time graph for a first order
reactant should look like this:
● measure absorbance against time
● use calibration curve of known concentrations of A common mistake is not starting the curve on
bromine the y axis. It must start touching the y axis as
● plot bromine concentration against time or rate the reactant has an initial concentration.
[HCOOH]

against bromine concentration and determine order

from shape of graph.
Do not make the curve too steep as it needs to
Alternative method: measure gas volume: look different from the second order.
Time
● measure CO2 volume using gas syringe against time
● repeat with different bromine concentrations A rate against concentration graph for a first order
● plot volume against time and measure tangent reactant should look like this:
at t = 0
● plot rate against [Br2] and determine order from A common error here is not to make it go through
shape of graph. the origin. When the concentration of a first or
second order reactant is zero, the rate will be
The answer could be either progressive rate
Rate

zero so it must go through (0, 0).

monitoring of the concentration of bromine against 61
time with a colorimeter. A calibration curve may be
used to convert from absorbance to concentration.
[HCOOH]
Plotting [Br2] against time and use the shape of the
graph to determine order with respect to Br2, or take
tangents to the [Br2] against time graph at various
concentrations and plot a rate vs [Br2] graph and use

807701_C03_AQA_Chemistry_2_043-067.indd 61 13/06/15 8:59 am

 REQUIRED PRACTICAL 7
Investigation of the reaction of iodate(v) All of the concentrations were constant except the
ions in acidic solution with sulfate(IV) ions concentration of acid, hence the rate equation for this
reaction simplifies to:
to determine the order of the reaction with
respect to hydrogen ions rate = k[ H+] z
The iodate(v) ion is an oxidising agent and reacts with where z is the order of reaction with respect to
sulfate(iv) ions in acidic solution to produce iodine in hydrogen ion concentration.
solution, according to the following equations:
We could write
Stage 1: IO 3− + 3SO 32− → I− + 3SO42−
log(rate) = zlog[H+] + constant
Stage 2: IO 3− + 5I− + 6H+ → 3H2 O + 3I2
The event being measured is fixed, i.e. the first
Overall: 2IO3− + 5SO32− + 2H+ → I2 + 5SO42− + H2O appearance of the blue–black colour, so it is possible
for the rate to be expressed as:
Iodine is only liberated when acid is added. It is
possible to determine the effect of changing the Rate = 1/t
concentration of acid on the initial rate of this
The total volume of solution in each experiment is
reaction by timing how long it takes for iodine to
constant and so the [H+] can be represented by the
be produced. This is indicated by the formation of a
volume of sulfuric acid. Therefore the rate expression
blue-black colour with starch.
becomes:
log(1/t) = zlog(volume of sulfuric acid) + constant
1 For all the time results in the table
a) Calculate 1/t (to 3 significant figures).
Colourless Blue–black b) Calculate log 1/t (to 3 significant figures).
c) Calculate log (volume of sulfuric acid).
2 Plot a graph of log (1/t) (y axis) against log V
Figure 3.4 When the colourless solutions of acid, iodate(v)
(volume)(x axis). Draw a best-fit straight line
and sulfate(iv) are mixed in the presence of starch, there
is no visible reaction. After a short time delay, the colour
through the points.
changes suddenly from colourless to blue–black. The colour 3 Use your graph to determine the gradient of the
change is sharp and dependable like a clock – the abrupt straight line that you have drawn. Give your answer
colour change occurs in a reproducible time lapse. This to 2 decimal places.
reaction is therefore known as an ‘iodine clock reaction’. 4 The experiment was designed to determine the
order of reaction with respect to hydrogen ions
3    R ATE EQUATIONS

Method in the reaction. What changes would you make to

15 cm3 of the potassium iodate(v) solution, 85 cm3 of the experiment so that the order of reaction with
deionised water and 5 cm3 of starch were placed in a respect to iodate(v) ions could be determined?
beaker. 15 cm3 of sodium sulfate(iv) solution was mixed 5 a) The reaction is first order with respect to
with 85 cm3 of 0.1 mol dm−3 sulfuric acid and poured into hydrogen ions. In an experiment to determine
the beaker. The stop-clock was started simultaneously. the order of this reaction a value of 0.963 was
The contents were stirred with a glass rod and the time obtained. Calculate the percentage error in this
taken (t, seconds) for the blue-black colour to appear result.
was recorded. The experiment was repeated, varying b) The experimental error resulting from the use
62 the concentration of sulfuric acid by changing the of the apparatus was determined to be 2.1%.
volume of sulfuric acid and making the total volume of Explain what this means in relation to the
the up to 100 cm3 by the addition of deionised water. The practical technique used.
results are presented in the table below.

Table 3.1 Data from the iodine clock experiment

Expt 1 2 3 4 5 Initial TIP
Acid volume/cm3 25 35 45 55 70 85 The graph is of the type y = mx + c and
therefore the gradient m will give a
Water volume/cm3 60 50 40 30 15 0
value for the order, z. See Chapter 16 for
Na2 SO 3 volume/cm3 15 15 15 15 15 15
more information about logarithms.
t(s) 42 28 20 15 11 9

807701_C03_AQA_Chemistry_2_043-067.indd 62 13/06/15 8:59 am

 TEST YOURSELF 4

Order linked to mechanism of a reaction

1 For the reaction:
CaCO 3(s) + 2HCl(aq) → CaCl 2(aq) + CO2(g) + H2 O(l)
Suggest a method of monitoring the rate of reaction including
practical detail.
2 For the reactions:
Reaction A: 2H2 O2(aq) → 2H2 O(l) + O2(g)
Reaction B: CH3COCH3(aq) + I2(aq) → CH3COCH2I(aq) + H+(aq) + I−(aq)
Reaction C: 2Na2 S2 O 3(aq) + I2(aq) → Na2 S 4O6(aq) + 2NaI(aq)
a) Explain how reaction A is monitored using initial rate monitoring
using a gas syringe.
b) Explain why reaction B may be monitored in two ways.
c) Explain how reaction C is monitored using initial rate monitoring.

●● Order linked to mechanism of a reaction

The order of a reactant is clear from the rate equation and this may give a
clue as to the details of the mechanism for the reaction.

Mechanisms
The mechanism for a reaction is a series of reactions which shows how the
reaction occurs.
For example, the reaction
A + 2B → AB2
may occur in two stages:
A + B → AB
AB + B → AB2

Adding equations to determine an overall equation

Taking the steps shown above, if these steps are added together, you will get
the overall equation for the reaction.
A + B → AB
AB + B → AB2

Write down all the species on the left-hand side of both equations and then
cancel out anything which appears on both sides of the overall equation.
A + B + AB + B → AB + AB2 63

The overall equation is:

A + 2B → AB2

807701_C03_AQA_Chemistry_2_043-067.indd 63 13/06/15 8:59 am

 EXAMPLE 11
In the chlorination of methane the Answer
following reactions occur:
Cl2 → 2Cl· Cl2 + CH4 + Cl· + CH3· + Cl2 + 2Cl· → 2Cl· + CH3· + HCl + CH3Cl + Cl· + Cl2

This simplifies to:

CH4 + Cl· → CH3· + HCl
2Cl2 + CH4 + 3Cl· + CH3· → 3Cl· + CH3· + HCl + CH3Cl + Cl2
CH3 + Cl2 → CH3Cl +
· Cl· This may be written:
2Cl· → Cl2 Cl2 + CH4 → CH3Cl + HCl
Write an overall equation for the reaction. This is the overall equation for this reaction.

EXAMPLE 12
For the following two-step process:
6NO(g) + 3O2(g) → 6NO2(g)
2NO(g) + O2(g) → 2NO2(g)
6NO2(g) + 2H2O(l) → 4HNO3(aq) + 2NO(g)
3NO2(g) + H2O(l) → 2HNO3(aq) + NO(g)
Adding the equations gives:
Write an overall equation for this reaction.
6NO(g) + 3O2(g) + 6NO2(g) + 2H2O(l) → 6NO2(g) + 4HNO3(aq) + 2NO(g)
Answer
The overall equation is:
The key to this is the fact that 2NO2 is
produced in the first reaction but 3NO2 4NO(g) + 3O2(g) + 2H2O(l) → 4HNO3(aq)
is used in the second reaction.
Multiply the first reaction by 3 and the
second reaction by 2 before adding them.

Rate-determining step
3    R ATE EQUATIONS

Any of the steps in a mechanism for a reaction may be the rate-determining

step. The rate-determining step is the slowest step and it dictates the overall
rate of the reaction.
The species (atoms, molecules, ions or molecules) that react in the rate-
determining step are the species which are present as concentrations with
non-zero orders in the rate equation.
Reactants in the overall equation which have zero order are not involved in
the rate-determining step.
64
Finding the rate-determining step
The rate-determining step may be determined by examining the rate
equation and the steps in the mechanism for the reaction.
If there is a reactant in the overall equation which is zero order (i.e. it does
not appear in the rate equation), this reactant should not appear in the rate-
determining step.

807701_C03_AQA_Chemistry_2_043-067.indd 64 13/06/15 8:59 am

 Order linked to mechanism of a reaction
EXAMPLE 13 The rate equation for the reaction is:
In the hydrolysis of C4H9Br, the following overall rate = k[C4H9Br]
reaction occurs:
Deduce the rate-determining step in this two-step
C4H9Br + OH− → C4H9OH + Br− process. Explain your answer.
The mechanism for the reaction can be described in Answer
two steps:
The rate-determining step is step 1.
Step 1: C4H9Br → C4H9+ + Br−
Explanation: OH− ions are zero order so therefore not
Step 2: C4H9+ + OH− → C4H9OH part of the rate-determining step. Step 1 does not
involve OH− ions.

EXAMPLE 14 The first step in the mechanism shows X and Y

For the overall reaction: reacting in a 1:1 ratio.

X + 2Y → XY2 This suggests that step 1 is the rate-determining step

and both X and Y are present in the rate equation in a
The mechanism for the reaction occurs in two steps: 1:1 ratio.
Step 1: X + Y → XY
Step 2: XY + Y → XY2
TIP
The rate equation for this reaction is given as:
If the rate equation had been rate = k[X][Y]2
rate = k[X][Y] then the second step would be the rate-
determining step as it (when combined
Determine which step in the reaction is the rate-
with the first step) gives the ratio of X:Y as
determining step.
1:2. The orders of reaction are equal to the
Answer number of reacting particles.
This rate equation shows that the orders of reaction
with respect to both X and Y are 1.

TEST YOURSELF 5
1 For the reaction: a) State the overall order of reaction.
2X + Y → Z b) Write a rate equation for the hydrolysis of ester
The reaction occurs in a two-step process A using A to represent the ester.
Step 1: 2X → X 2 c) State the units of the rate constant.
Step 2: X 2 + Y → Z 3 For the following two-step process
The overall rate equation for the reaction is: Step 1: A + B → AB
rate = k[X]2 Step 2: AB + A → A 2B
a) What is order of reaction with respect to X? a) Write an overall equation for the reaction.
65
b) What is order of reaction with respect to Y? b) The order of reaction with respect to A is 1 and
c) State and explain which step is the rate- the order of reaction with respect to B is 1.
determining step. i) State the overall order of reaction.
2 In the hydrolysis of an ester A (CH3COOCH3) with ii) Write a rate equation for the reaction.
OH− ions, the order of reaction with respect to the iii) State and explain which step is the rate-
ester, A, is first order and first order with respect determining step.
to OH− ions.

807701_C03_AQA_Chemistry_2_043-067.indd 65 13/06/15 8:59 am

 Practice questions a) Deduce the order of reaction with respect to A. (1)
b) Deduce the order of reaction with respect to B. (1)
1 For the rate equation: rate = k[A][B]2
c) Write a rate equation for the reaction. (1)
Which one of the following are the units of the
rate constant, k? d) Calculate a value for the rate constant (k) at
constant temperature and deduce its units. (2)
A s−1 C mol−2 dm6 s−1
5 P reacts with Q. The kinetics of the reaction were
B mol−1 dm3 s−1 D mol−3 dm9 s−1 (1) studied at a constant temperature.
2 X reacts with Y to form Z according to the The data obtained are given in the table below.
overall equation:
Initial [P]/ Initial [Q]/ Initial rate/
X + 2Y → Z Experiment mol dm−3 mol dm−3 mol dm−3 s−1
1 0.10 0.10 0.0020
The mechanism for the reaction is:
2 0.20 0.10 0.0040
2Y → W (slow step) 3 0.30 0.10 0.0060
4 0.40 0.20 0.0160
W+X→Z (fast step)
a) Deduce the order of reaction with respect to P
Which one of the following is most likely to be and Q. (2)
the rate equation for the overall reaction?
b) Write a rate equation for the reaction. (1)
A rate = k [Y] C rate = k [X][Y]
c) Calculate a value of the rate constant (k) at
B rate = k [Y]2 D rate = k [X][Y]2 (1) this temperature and deduce its units. (2)
3 The following experimental data were 6 Two experiments were carried out on the rate
determined for the reaction: of reaction between B and C at a constant
X+Y→Z temperature.

initial rate
The rate equation for the reaction is rate = k[B][C]2
of reaction/ The data obtained are given in the table below.
[X]/mol dm−3 [Y]/mol dm−3 mol dm−3 s−1
0.1 0.1 0.007 Initial [B]/ Initial [C]/ Initial rate/
0.2 0.1 0.028 Experiment mol dm−3 mol dm−3 mol dm−3 s−1
0.2 0.2 0.056 1 2.0 × 10 −2 4.0 × 10 −2 2.7 × 10 −7
2 4.0 × 10 −2 5.0 × 10 −2 To be
3 RATE EQUATIONS

a) Deduce the orders with respect to calculated

X and Y. (2)
a) Calculate a value for the rate constant (k)
b) What is the overall order of reaction? (1) at this temperature using the results of
experiment 1 and deduce its units. (2)
c) Write a rate equation for this reaction. (1)
b) Calculate a value for the initial rate in
d) Calculate a value of the rate constant (k)
experiment 2. (1)
and deduce its units. (2)
7 a) Write the Arrhenius equation. (1)
66 4 In the following series of reactions of A and
B at constant temperature the following data b) A graph of ln k against 1/T was plotted for
were obtained. a first order reaction and the gradient of the
line found to be −15024. The intercept on the
Initial [A]/ Initial [B]/ Initial rate/
Experiment mol dm−3 mol dm−3 mol dm−3 s−1
ln k axis was 21.4. The gas constant,
R, = 8.31 J K−1 mol−1.
1 1.4 × 10 −2 2.0 × 10 −2 3.760 × 10 −4
2 2.8 × 10 −2 2.0 × 10 −2 7.520 × 10 −4 Using the expression: ln k = -Ea/RT + ln A
3 2.8 × 10 −2 4.0 × 10 −2 1.504 × 10 −3
Calculate the value of A and Ea for this reaction.
State the units. (4)

807701_C03_AQA_Chemistry_2_043-067.indd 66 13/06/15 8:59 am

 c) Given that e = 2.71828, calculate a value i) What is the order of reaction with

Practice questions
for k at 300 K using the value of Ea and A respect to iodine? (1)
calculated in (b). If you did not calculate a
ii) Sketch a graph of rate of reaction against
value for Ea or A in (b) use Ea = 130 kJ mol−1
concentration of iodine. (1)
and A =2.00 × 1010. State the units. (3)
c) The rate equation for the reaction is
8 The kinetics of the acid-catalysed hydrolysis of
an ester were studied and the concentration of rate = k[CH3COCH3][H+]
the ester plotted against time as shown below. i) How does this rate equation support
0.600 your answer to (b)(i). (1)
0.500 ii) The table below gives some initial rate
data for this reaction. Use this data to
[Ester]/mol dm-3

0.400
calculate a value for the rate constant
0.300 and state its units. (2)

0.200
Initial [H+]/ [CH3COCH3]/ Initial [I2]/ Initial rate/
mol dm−3 mol dm−3 mol dm−3 mol dm−3 s−1
0.100 0.50 8.00 0.04 1.20 × 10 −4

0.000 Stretch and challenge

0 2000 4000 6000 8000
Time/s
10 For the reaction D + E → F + G
a) Draw a tangent to the curve when the The rate equation is rate = k[D][E]2
concentration is 0.300 mol dm−3. Use this
The table below gives details of a series of
tangent to determine the rate of reaction at
experiments for this reaction.
this concentration of the ester. (3)
Initial Initial
b) Based on the shape of the graph what is
concentration concentration Initial rate/
the order of reaction with respect to Experiment of D/mol dm−3 of E/mol dm−3 mol dm−3 s−1
the ester? (1) 1 0.05 0.10 2.25 × 10 −3
9 The reaction between propanone and iodine is 2 0.05 0.20
catalysed by the presence of hydrogen ions, H+. 3 0.10 4.50 × 10 −3
4 0.20 2.70 × 10 −2
CH3COCH3 + I2 → CH3COCH2I + HI 5 0.10 8.82 × 10 −2
a) Suggest a method by which the order 6 5.76 × 10 −4
of reaction with respect to iodine could
a) Complete the missing data in the table for
be determined using continuous rate
experiments 2 to 5. (4)
monitoring. (2)
b) Determine a value for the rate constant
b) The graph below shows iodine
using the results of experiment 1 and state
concentration against time.
its units. (2)
0.500 c) In experiment 6, the initial concentrations
of D and E were in the ratio 1:4. The initial
0.400 67
[Iodine]/mol dm-3

rate of reaction was determined to be

0.300 5.76 × 10−4 mol dm−3 s−1. Using the value
of the rate constant determined in (b) and
0.200 the rate of reaction, determine the initial
0.100
concentrations of D and E and fill these
values into the table.
0.000
0 500 1000 1500 2000 2500 If you were unable to calculate a value for
Time/s the rate constant in (b) use 10.0. This is
not the correct value. (4)

807701_C03_AQA_Chemistry_2_043-067.indd 67 16/06/2015 17:19

 4 Equilibrium constant
Kp for homogeneous
systems
PRIOR KNOWLEDGE
It is expected that you are familiar with all of the content of the Chemical
equilibria, Le Chatelier’s principle and Kc units in Year 1 of the A-level
Chemistry course. The following are some key points of Prior Knowledge:
● A ‘dynamic equilibrium’ is an equilibrium where both the forward
and reverse reactions are occurring at the same rate and the
concentrations of the reactants and product remain constant.
● A homogeneous equilibrium is one in which all the reactants and
products are in the same state.
● Le Chatelier’s principle states that if a factor is changed which affects
a system in equilibrium, the position of equilibrium will move in a
direction so as to oppose the change.
● The position of equilibrium is often affected by changes in
temperature, changes in concentrations of reactants or products,
changes in pressure.
● For an equilibrium reaction where the enthalpy change is positive
(endothermic), an increase in temperature moves the position of
equilibrium from left to right.
● For an equilibrium reaction where the enthalpy change is negative
(exothermic), an increase in temperature moves the position of
equilibrium from right to left.
● For an equilibrium reaction, an increase in the total pressure moves
the position of equilibrium to the side with the fewer moles of gas.
● For an equilibrium reaction, an increase in the concentration of a
reactant will move the position of equilibrium from left to right.
● For an equilibrium reaction, an increase in the concentration of a
product will move the position of equilibrium from right to left.
● A catalyst allows equilibrium to be achieved more rapidly but it has no
effect on the position of equilibrium.
● The equilibrium constant, K c, for the reaction
N2(g) + 3H2(g) ⇋ 2NH3(g) is given by the expression:
[NH3]2
68 Kc =
[N2][H2]3
and the units of this Kc would be mol −2 dm6.
● The value of Kc is only affected by a change in temperature.

807701_C04_AQA_Chemistry_2_068-077.indd 68 13/06/15 8:59 am

 Mole fractions
TEST YOURSELF ON PRIOR KNOWLEDGE 1
1 What is meant by dynamic equilibrium?
2 State Le Chatelier’s principle.
3 For the equilibrium:
A(g) + 2B(g) ⇋ C(g) Δ H =  −52 kJ mol −1
a) Explain how the yield of C would change if the temperature were
increased.
b) Explain how the yield of C would change if the total pressure were
increased.
c) Explain why a catalyst does not affect the position of equilibrium.
d) Explain why this equilibrium is described as a homogeneous
equilibrium.
4 For the gaseous homogeneous equilibrium given below:
CH4(g) + 2H2O(g) ⇋ CO2(g) + 4H2(g)
a) Write an expression for the equilibrium constant Kc for the reaction
b) 1.00 mol of CH4 is mixed with 2.00 mol of H2O(g) in a container of
volume 5.00 dm3. At equilibrium there are 2.20 mol of hydrogen
present in the equilibrium mixture. Calculate a value of the
equilibrium constant, Kc, and state its units. Give your answer to 3
significant figures.

●● Mole fractions
The mole fraction of a component, A, in a gaseous mixture is denoted
xA and is calculated by dividing the amount, in moles, of A by the total
amount of moles of gas in the mixture:
For
A(g) + B(g) ⇋ C(g)
nA
xA = n + n + n
A B C

where nA, nB and nC are the amounts, in moles, of A, B and C present in the
mixture.
Mole fractions can only have values in the range 0 to 1. The sum of the
mole fractions of all of the components in a mixture will be equal to 1.

EXAMPLE 1
A mixture contains 1.42 g of nitrogen and 2.41 g of oxygen. Calculate the
69
mole fraction of the gases in this mixture.

Answer
1.42
Moles of N2 = = 0.0507 mol
28.0
Moles of O2 = 2.41 = 0.0753 mol
32.0
Total moles of gas = 0.0507 + 0.0753 = 0.126 mol
TIP
The total of the mole fractions 0.0507
Mole fraction of N2 = = 0.402
should add up to 1 mol. For 0.126
Example 1: 0.402 + 0.598 = 1.00 Mole fraction of O2 = 0.0753 = 0.598
0.126

807701_C04_AQA_Chemistry_2_068-077.indd 69 13/06/15 8:59 am

 ●● Partial pressure
The partial pressure of a component, A, in a mixture of gases is the
contribution which that gas makes to the total pressure of the gas mixture.
It is also the pressure if the same amount of A were the only substance
present in a container of the same size. The partial pressure of A is denoted
by pA or p(A) or pA or PA.
The partial pressure of a component can be calculated by multiplying the
total pressure of the mixture by the mole fraction of that component.
For example the partial pressure of A, p(A), in a mixture is given by the
expression:
p(A) = xA × P
where xA is the mole fraction of A and P is the total pressure.
Although partial pressures and concentrations are not the same thing, they
are both proportional to the amount of the substance present.
4    EQUILIBRIUM CONSTANT K P FOR HOMOGENEOUS SYSTEMS

EXAMPLE 2
A mixture contains 1.00 g of ammonia and 1.00 g of nitrogen. The total
pressure is 5.00 × 105 Pa. Calculate the partial pressure of each gas in the
mixture.

Answer
1.00
Moles of NH3 = = 0.0588 mol
17.0
1.00
Moles of N2 = = 0.0357 mol
28.0
Total moles of gas = 0.588 + 0.0357 = 0.0945 mol
0.0588
Mole fraction of NH3 = = 0.622
0.0945
Mole fraction of N2 = 0.0357 = 0.378
0.0945
Checking the calculation, the sum of the mole fractions is (0.622+0.378) = 1.
Partial pressure of NH3 = mole fraction × total pressure
= 0.622 × 5.00 × 105 = 3.11 × 105 Pa
Partial pressure of N2 = mole fraction × total pressure
= 0.378 × 5.00 × 105 = 1.89 × 105 Pa
Again a check that the sum of the partial pressures is equal to the total
70 pressure (3.11 × 105 + 1.89 × 105) = 5.00 × 105 Pa.
All given values are to 3 significant figures in this calculation so the
answers should also be given to 3 significant figures.

807701_C04_AQA_Chemistry_2_068-077.indd 70 13/06/15 8:59 am

 TEST YOURSELF 2

Kp
1 A mixture contains 2.00 g of oxygen and 2.00 g of nitrogen. Calculate
the mole fraction of each gas in the mixture.
2 Two gases were mixed and the total pressure was 100 kPa. One of
the gases had a partial pressure of 40.0 kPa. Calculate the partial
pressure of the other gas.
3 In the equilibrium, N2(g) + 3H2(g) ⇋ 2NH3(g), the equilibrium mixture
of nitrogen, hydrogen and ammonia at 350 °C contains 7.00 g of
nitrogen, 4.50 g of hydrogen and 36.5 g of ammonia.
a) Calculate the mole fraction of each substance in the equilibrium
mixture.
b) Calculate the partial pressure of each gas in the mixture if the
total pressure is 100 kPa.

●● Kp
For the general case of a gaseous homogeneous equilibrium:
aA(g) + bB(g) ⇋ cC(g) + dD(g)
the equilibrium law states that
p(C)c p(D)d
Kp =
p(A)a p(B)b
where p(A)a is the partial pressure of A raised to the power of a, etc.
N2(g) + 3H2(g) ⇋ 2NH3(g)
p(NH3)2
Kp =
p(N2) p(H2)3
Partial pressures in Pa
(Pa)2 (Pa)2 1
units of Kp = = = = Pa−2
(Pa) (Pa)3 (Pa)4 (Pa)2
Calculation of Kp
Calculations to find Kp are similar to those to find Kc. The only difference
is that after finding the number of moles at equilibrium, instead of using
concentration = moles , partial pressures are used where
volume
partial pressure = mole fraction × total pressure.

71
MATHS
The unit most commonly used for pressure is Pascal (Pa). kPa (103 Pa)
and MPa (106 Pa) may also be used. If the total pressure is given in
kPa, then the partial pressure will also be in kPa. 100 kPa is the most
frequently used value.

807701_C04_AQA_Chemistry_2_068-077.indd 71 13/06/15 8:59 am

 EXAMPLE 3
For the equilibrium Initial amounts in moles (given in the example):
2NO(g) + O2(g) ⇋ 2NO2(g) 0.357 mol of NO is mixed with 0.229 mol of O2
10.7 g of nitrogen(ii) oxide and 7.33 g of oxygen were Amount in moles of one substance at equilibrium
mixed and at equilibrium 13.4 g of nitrogen(iv) oxide (given in the example):
were formed at a total pressure of 100 kPa and a
0.291 mol of NO2 is present in the equilibrium mixture
temperature of 400 K.
Reacting moles of this substance (calculated from
1 Calculate the partial pressures of the three gases
given information)
present in the equilibrium mixture.
2 Calculate a value for Kp at 400 K. 0.291 mol of NO2 has formed (+0.291)

Answers Reacting moles of other substances (calculated from

10.7 balancing numbers in the equation):
1 Initial moles of NO = = 0.357 mol
30.0
0.291 mol of NO reacts with 0.146 mol of O2 and
7.33 formed 0.291 mol of NO2
Initial moles of O2 = = 0.229 mol
32.0
13.4 Equilibrium moles of other substances (the initial
Equilibrium moles of NO2 = = 0.291mol
46.0 moles minus the reacting moles):
4    EQUILIBRIUM CONSTANT K P FOR HOMOGENEOUS SYSTEMS

2NO + O2 ⇋ 2NO2 0.357 − 0.291 = 0.066 mol of NO remaining;

Initial 0.357 0.229 0.00 0.229 − 0.146 = 0.083 mol of O2 remaining.
moles The total equilibrium moles present is =
Reacting moles − 0.291 − 0.146 +0.291 0.066 + 0.083 + 0.291 = 0.440 mol
Equilibrium 0.066 0.083 0.291
moles

2NO O2 2NO2
Initial 0.357 0.229 0.00
moles
Reacting moles − 0.291 − 0.146 +0.291
Equilibrium 0.066 0.083 0.291 Total equilibrium moles =
moles 0.440
Mole 0.066 0.083 0.291 Check total of mole
fraction = 0.150 = 0.189 = 0.661 fractions = 1
0.440 0.440 0.440
0.150 + 0.189 + 0.661 = 1.00

Partial 0.150 × 100 0.189 × 100 0.661 × 100 Check total of partial
pressure = 15.0 kPa = 18.9 kPa = 66.1 kPa pressures = 100 kPa
15.0 + 18.9 + 66.1 =
100 kPa

p (NO2)2 (66.1)2
2 Kp = = = 1.03 kPa −1
p (NO)2 p(O2) (15.0)2(18.9)

72

TIP
Check the colour code system used at AS for Kc calculations in the
Equilibrium, Le Chatelier’s Principle and Kc chapters.

807701_C04_AQA_Chemistry_2_068-077.indd 72 13/06/15 8:59 am

 Kp
EXAMPLE 4
Hydrogen reacts with bromine according to the
equilibrium: TIP
P is used for the total
H2(g) + Br2(g) ⇋ 2HBr(g) pressure as the total
1.00 mol of hydrogen was mixed with 1.00 mol of pressure is not given in
bromine and the mixture allowed to attain the question. P will cancel
equilibrium. 0.824 mol of hydrogen bromide were out in the Kp expression.
present in the equilibrium mixture. Calculate a
value for Kp.

Answer
H2 + Br2 ⇋ 2HBr
Initial 1.00 1.00 0.00
moles
Reacting moles −0.412 −0.412 +0.824
Equilibrium moles 0.588 0.588 0.824 Total equilibrium
moles
= 0.588 + 0.588 +
0.824 = 2.00
Mole 0.588 0.588 0.824 Check total of mole
fraction = 0.294 = 0.294 = 0.412 fractions = 1
2.00 2.00 2.00
0.294 + 0.294 +
0.412 = 100
Partial pressures 0.294 P 0.294 P 0.412 P 0.294 P + 0.294 P +
0.412 P = P

p (HBr)2 (0.412 P)2

Kp = = = 1.96
p (H2) p(Br2) (0.294 P) (0.294 P)

Note that using the equilibrium moles will give the

same value, i.e.

p (HBr)2 (0.824)2
Kp = = = 1.96.
p (H2)p(Br2) (0.588) (0.588)
TIP
It is advisable to use the partial pressures as this Kp has no units because
is correct for the Kp expression. If a total pressure the pressures cancel out
had been given then use this to calculate the in the expression.
partial pressures.

Using Kp
TIP Some calculations may give a value of Kp and you may be expected to
Practise carrying out the calculate the equilibrium moles of one component or the mole fraction 73
calculation shown above on your or partial pressure.
calculator as it is easy to make
mistakes with the bottom line
(denominator) of the fraction.

807701_C04_AQA_Chemistry_2_068-077.indd 73 13/06/15 8:59 am

 EXAMPLE 5
For the following gaseous homogeneous equilibrium:
2HI(s) ⇋ H2(g) + I2(g)
2.00 mol of hydrogen iodide was allowed to reach equilibrium at 500 K.
Kp for this equilibrium at 500 K is 0.360. Calculate the partial pressure of
hydrogen in the equilibrium mixture if the total pressure is 100 kPa.

Answer
TIP As the number of moles which reacts is not known, 2x moles of HI
Using 2x moles of HI avoids react to form x moles of H2 and x moles of I2.
x
moles of H2 and I2 but the
2 2HI ⇋ H2 + I2
calculation would work either way.
Initial 2.00 0 0
moles
Reacting −2x +x +x
moles
Equilibrium 2.00 − 2x x x Total equilibrium moles
moles = 2  − 2x + x + x = 2
4    EQUILIBRIUM CONSTANT K P FOR HOMOGENEOUS SYSTEMS

Mole 2.00 − 2x x x Check total

fraction 2 2 2 of mole fractions = 1
Partial 2.00 − 2x x x 2.00 − 2x x
pressure × 100 ×100 × 100 × 100+ × 100
2 2 2 2 2
x 200
+ ×100 = = 100
2 2
100 x 2
p (H2) p (I2) 2 x2
Kp = = = = 0.360
p (HI)2 200 − 200 x 2 (2−2x)2
2
x2 x 2
= = 0.360
(2 − 2x)2 2 − 2x
x
= = 0.600 as √0.360 = 0.600
2 − 2x
x = 0.600 (2 − 2x)
x = 1.20 − 1.20x
2.20x = 1.20
1.20
x= = 0.545
2.20
The partial pressure of hydrogen in the equilibrium mixture is given by
x 0.545
74 × 100 so the partial pressure is × 100 = 27.3 kPa.
2 2

Calculations of this sort are more complex and should be worked through
TIP carefully. You can check the value of x you obtain by substituting it into
In a calculation where Kp is either the partial pressures or the mole fractions. The sum of the mole
unitless, the mole fractions or the fractions should add up to 1 and the sum of the partial pressures should
equilibrium moles may be used add up to the total pressure in this case 100 kPa.
in the Kp expression and will give
the same answer. However, as Also in an equilibrium where 1 mol of two products are formed, the
the total pressure is given in this equilibrium moles, mole fractions and partial pressures of these two
question it is best practice to use it. products are the same throughout for any equilibria at any temperature.

807701_C04_AQA_Chemistry_2_068-077.indd 74 13/06/15 8:59 am

 Calculating total pressure

Kp
The total pressure in a Kp calculation may be represented by the letter P. P is
used in the Kp expression and the expression may be solved to find P.

EXAMPLE 6
At equilibrium, 0.200 mol of nitrogen, 0.400 mol of hydrogen and 0.400 mol
of ammonia are present during the Born-Haber process:
N2(g) + 3H2(g) ⇋ 2NH3(g)
Calculate a value for the total pressure on the system at 390 K if Kp has a
value of 0.172 K Pa −2.

N2 + 3H2 ⇋ 2NH3
Equilibrium 0.200 0.400 0.400 Total equilibrium
moles moles
= 0.200 + 0.400 +
0.400 = 1.00
Mole 0.200 0.400 0.400 Check total of
fraction = 0.200 = 0.400 = 0.400 mole fractions
1.00 1.00 1.00
=1
0.200 + 0.400 +
0.400 = 1.00
Partial 0.200 P 0.400 P 0.400 P
pressure

p (NH3)2 (0.400P)2
Kp = = = 0.172
p (N2) p(H2)3 (0.200P) (0.400P)3
Cancelling (0.400P)2
(0.400P)2 1
= = 0.172
(0.200P) (0.400P)3 (0.200P) (0.400P)
1 = 0.172(0.200P)(0.400P)

1 = 0.01376P2 as 0.172 × 0.200 × 0.400 = 0.01376 and P × P = P2

1
P2 =
(0.01376)
P2 = 72.674
TIP
All initial values were given to 3 P = √72.674 = 8.52 kPa
significant figures. This would
mean that the final answers Again this can be checked by filling the total pressure (8.52 kPa) into the
should also be given to 3 equilibrium expression and if you get the correct value for Kp, the value of
significant figures. P is correct.
75

Changes in temperature and other factors

l Kp is constant at a particular temperature.
l The equilibrium constant, Kp is affected by changes in temperature, but
it is not affected by changes in pressure, the presence of a catalyst or
changes in concentration or amount of substances present in the mixture.
l This is the same for all equilibrium constants which are constant at a
particular temperature and are not affected by changes in any other
quantities.

807701_C04_AQA_Chemistry_2_068-077.indd 75 13/06/15 8:59 am

 l For the equilibrium:
N2(g) + 3H2(g) ⇋ 2NH3(g) ∆H = −92 kJ mol −1
Increasing the temperature will favour the reverse reaction and the
position of equilibrium will move to the left. This will decrease the
partial pressure of NH3 and the value of Kp will decrease.
l Increasing the pressure will favour the forward reaction and the
position of equilibrium will move to the right. This will have no effect
on the value of Kp as long as the temperature remains constant.
l Adding more hydrogen to the mixture will increase the partial
pressure of the hydrogen and it will move the position of equilibrium
to the right. It will have no effect on the value of Kp as long as the
temperature remains constant.

TEST YOURSELF 3
1 1.00 moles of PCl 5 are allowed to reach equilibrium.
PCl5(g) ⇋ PCl3(g) + Cl 2(g)
a) At equilibrium there are 0.400 mol of Cl 2 present at 400 K.
Figure 4.1 The equilibrium between
4 EQUILIBRIUM CONSTANT K P FOR HOMOGENEOUS SYSTEMS

NO 2 and N2 O 4 is shown in cold and hot

Calculate a value for the equilibrium constant, Kp, when the total
water baths. A change in temperature pressure on the system is 100 kPa. State the units of Kp (if any).
shifts the equilibrium between the two Give your answer to 3 significant figures.
species. When more NO 2 is produced, b) State the effect, if any, of an increase in pressure on the value of Kp.
the gas inside the tube becomes 2 In the following equilibrium CO2(g) + H2(g) ⇋ CO(g) + H2O(g) at a
darker. The Kp value will change with temperature of 373 K and a pressure of 700 kPa, the amounts of
temperature. each gas present at equilibrium were 0.210 mol of CO, 0.210 mol of
H2 O, 1.04 mol of CO2 and 1.04 mol of H2. Calculate a value for Kp and
state its units (if any). Give your answer to 3 significant figures.
3 In the equilibrium N2O4(g) ⇋ 2NO2(g), the value of Kp is 0.389 MPa
at 350 K. The partial pressure of NO2 at equilibrium was found to be
0.0700 MPa. Calculate the partial pressure of N2 O4 at equilibrium
and the total pressure on the system. Give your answer to 3
significant figures.

Practice questions Value of K p Partial pressure of NO(g)

A increase decrease
1 Which one of the following could be units of
B increase no change
Kp for the reaction shown below?
C no change increase
2NH3(g) + 3O2(g) ⇋ N2(g) + 3H2O(g)
D no change decrease
A KPa C kPa 2 3 For the equilibrium below, calculate a value for
76
B kPa −1 D kPa −2 (1) Kp if the partial pressure of the gases present at
equilibrium are: O2 = 100 kPa, SO2 = 240 kPa
2 Which one of the following is correct when and SO3 = 500 kPa. Give your answer to 3
pressure is increased on the following significant figures.
equilibrium at constant temperature?
2SO2(g) + O2(g) ⇋ 2SO3(g) (3)
2NO(g) + O2(g) ⇋ 2NO2(g) (1)

807701_C04_AQA_Chemistry_2_068-077.indd 76 13/06/15 8:59 am

 4 2.00 mol of A was mixed with 2.00 moles 8 At 107 °C, the reaction

Practice questions
of B and the mixture was allowed to reach CO(g) + 2H2(g) ⇋ CH3OH(g)
equilibrium at 500 °C. The equilibrium reaches equilibrium under a pressure of
mixture was found to contain 1.00 mole of A. 1.59 MPa with 0.122 mol of CO, 0.298 mol
Calculate a value for Kp. of H2 and 0.500 mol of CH3OH present in a
vessel of volume 1.04 dm³.
2A(g) + B(g) ⇋ 3C(g) (3)
Calculate Kc and Kp and state the units of both.
5 Analysis of the equilibrium system, N2(g) +
Give both answers to 3 significant figures. (6)
3H2(g) ⇋ 2NH3(g) showed 25.1 g of NH3,
12.8 g of H2 and 59.6 g of N2. Calculate a value Stretch and challenge
for Kp if the total pressure is 1.32 × 105 Pa. 9 For the reaction, H2(g) + I2(g) ⇋ 2HI(g),
Give your answer to 3 significant figures. (4) 2.00 mol of hydrogen and 2.00 mol of iodine
6 When hydrogen iodide is heated in a sealed are heated to 700 K in a sealed vessel until
container, it reaches equilibrium according to equilibrium is attained at a pressure of
the equation: 100 kPa. The value of Kp at 700 K for this
reaction is 0.106.
2HI(g) ⇋ H2(g) + I2(g)
a) i) Write an expression for the equilibrium
Kp for this reaction at 700 K is 0.0185 and
constant, Kp. (1)
partial pressure of the hydrogen iodide in the
ii) Calculate the number of moles of each
equilibrium mixture is 1.80 MPa. Calculate the
gas present at equilibrium. (5)
partial pressures of the hydrogen and iodine in
iii) Determine the percentage of hydrogen
the equilibrium mixture. Give your answer to
which reacted. (1)
3 significant figures. (4)
b) Using the same initial amount in moles,
7 In the equilibrium
the equilibrium was re-established at
CO(g) + H2O(g) ⇋ CO2(g) + H2(g),
100 kPa pressure and 400 K. The value
1.00 mol of carbon monoxide is mixed with
of Kp at 400 K is 0.0111. Calculate the
1.00 mol of water vapour at 200 °C and
number of moles of hydrogen remaining
400 kPa pressure. The equilibrium constant,
at equilibrium and hence the percentage of
Kp, at 200 °C is 0.0625. Calculate the number
hydrogen which reacted. (4)
of moles of carbon monoxide present at
equilibrium. (4)

77

807701_C04_AQA_Chemistry_2_068-077.indd 77 13/06/15 8:59 am

 5 Electrode potentials
and cells
PRIOR KNOWLEDGE
● Oxidation state is the relative state of oxidation or reduction of an
element.
● Elements have an oxidation state of 0 (zero).
● In compounds, Group 1 elements have an oxidation state of +1.
● In compounds, Group 2 elements have an oxidation state of +2.
● In compounds, aluminium has an oxidation state of +3.
● In a simple binary compound, the more electronegative element has
the negative oxidation state.
● Oxygen has an oxidation state of -2 in all compounds except peroxides
where its oxidation state is -1 and in the compound OF2 where its
oxidation state is +2.
● Hydrogen has an oxidation state of +1 in all compounds except
hydrides where its oxidation state is -1.
● In compounds, d block and p block elements have variable oxidation
state.
● Oxidation is the loss of electrons or increase in oxidation state.
● Equations showing oxidation have +e − on the right-hand side.
● Reduction is the gain of electrons or the decrease in oxidation state.
● Equations showing reduction have +e − on the left have side.
● The number of moles of electrons is equal to the change in
oxidation state.

TEST YOURSELF ON PRIOR KNOWLEDGE 1

1 Give the oxidation state of nitrogen in the following compounds
and ions:
a) NO b) NH3 c) NO−3
d) N2H4 e) N3−
2 State the full name of the following compounds:
a) Na2SO4 b) NH4NO 3 c) N2O
d) K 2CrO4
3 For the following reactions:
78 Reaction A: Mg → Mg2+ + 2e−
Reaction B: Cl 2 + H2 O → HCl + HOCl
Reaction C: 8HI + H2 SO4 → 4I2 + 4H2 O + H2 S
Reaction D: NaCl + H2 SO4 → NaHSO4 + HI
Reaction E: NO −3 + 4H+ + 3e− → NO + 2H2 O
a) Which reaction shows only a reduction reaction?
b) Which reaction is not a redox reaction?
c) Which reaction shows only an oxidation reaction?
d) Which reaction shows the largest changes in oxidation state?

807701_C05_AQA_Chemistry_2_078-099.indd 78 13/06/15 9:00 am

 Redox reactions involve electron transfer. An electrochemical cell uses
electron transfer reactions to produce electrical energy. Most batteries

Redox equilibria
contain an electrochemical cell and as such, they are found in cameras,
laptops, phones and even hybrid cars. Figure 5.1 shows a lemon being used
as a cell which provides electrical current sufficient to power a clock.

●● Redox equilibria
When a metal in dipped into a solution containing its simple ions, an
equilibrium is established between the metal ions and the metal atoms. This
type of arrangement is called a half cell.

Zn Cu

Figure 5.1 The lemon is being used as Zn2+ (aq) Cu2+ (aq)
an electrolytic cell, the electrolyte being The zinc ions in the solution The copper ions in the solution
citric acid. Four electrodes – two copper are in equilibrium with the are in equilibrium with the
and two zinc – are placed in the lemon zinc atoms in the metal. copper atoms in the metal.
and connected together. Zinc atoms on Zn2+ (aq) + 2e- Zn (s) Cu2+ (aq) + 2e- Cu (s)
the electrode are oxidised, losing two
electrons per atom and dissolving into It is impossible to measure the equilibrium in one half cell unless another
solution. The electrons pass through
the wires to the copper electrode where
half cell is connected to it. Two half cells joined together create a cell.
they combine with hydrogen ions from An example of a cell is shown below.
the citric acid to liberate hydrogen gas.
The movement of electrons between
wire
electrodes forms the current.

Zn salt bridge Cu

TIP
In any half cell, the metal is the
electrode but often the entire half
cell is referred to as an electrode
as in the standard hydrogen
electrode. Zn2+ (aq) Cu2+ (aq)

The two metals in the half cells are connected externally using a conducting
wire and the solutions are connected using a salt bridge. A salt bridge can
be one of two things:
1 a piece of filter paper soaked in a solution of potassium chloride or
79
potassium nitrate
2 potassium chloride dissolved in agar gel and set in a U-tube.
The salt bridge has mobile ions that complete the circuit. Potassium
chloride/potassium nitrate are used to ensure that there is no precipitation
as chlorides and nitrates are usually soluble.

807701_C05_AQA_Chemistry_2_078-099.indd 79 13/06/15 9:00 am

 However, care should be taken with potassium chloride solution as chloride
ions can react with some metal ions such as Cu2+ to form complexes such as
[CuCl4]2−. Potassium nitrate is better to use for the salt bridge for solutions
in which the metal ion might form a complex with the chloride ions.
In the complete cell above, an electrochemical reaction occurs that is based
on the equilibrium for each electrode. If the circuit is connected for a while
[05_02]
and the mass of the metals measured before and after, the zinc would have
lost mass and the copper would have gained mass.
Therefore the reactions which are occurring are:
Figure 5.2 The photograph shows a
zinc copper cell. On the right, copper is Zn → Zn2+ + 2e−
dipped in a copper sulfate solution, and
on the left zinc is dipped in zinc sulfate. Cu2+ + 2e− → Cu
The zinc has a lower affinity for electrons
than copper, and zinc from the zinc strip An electrode where oxidation occurs is called the negative electrode whereas
forms ions and electrons flow along the an electrode where reduction occurs is called the positive electrode.
electrical wires and pull copper ions out
of solution to form solid copper on the ● In this cell, the zinc forms the negative electrode and the copper forms
copper strip. The salt bridge is the white the positive electrode.
filter paper soaked in potassium nitrate ● The electrons flow externally in the circuit from the zinc side to the
solution.
copper side. The zinc atoms lose electrons and the electrons flow from
the zinc metal to the copper metal and the copper ions in the solution
gain electrons to form copper.
TIP ● Copper forms on the copper electrode and increases the mass and some
Solid arrows rather than of the zinc metal forms zinc ions and this decreases the mass of the zinc
equilibrium arrows are often electrode.
used in these electrode half ● This circuit allows electrons to flow.
5    ELECTRODE POTENTIALS AND CELLS

equations. ● This shows us that the zinc is more likely to form its ions than the
copper.
● In order to measure this, a high-resistance voltmeter is connected in the
external circuit to measure the potential difference without allowing any
TIP electrons to flow in the circuit. This maintains the concentration of the
NEGATOX is a good way of ions in solution by not allowing any current to flow yet can still measure
remembering that the NEGactive the potential difference of the electrons trying to flow.
electrode is where OXidation
occurs. V

Zn salt bridge Cu

80
Zn2+ (aq) Cu2+ (aq)

The voltage measured in this circuit is +1.10 V. This indicates the potential
difference between the zinc half cell (or electrode) on the left and the
copper half cell (or electrode) on the right. This does not give a measure of
the potential difference in one half cell.

807701_C05_AQA_Chemistry_2_078-099.indd 80 13/06/15 9:00 am

 temperature = 298 K Electrode potentials

Redox equilibria
hydrogen gas at
To measure the potential difference for a single half cell, a standard must be
100 kPa pressure used to which all other potential differences can be compared. This standard
platinum wire is the standard hydrogen electrode or standard hydrogen half cell.
The standard hydrogen electrode is an electrode consisting of hydrogen gas
in contact with hydrogen ions, H+, on a platinum surface.
platinum foil covered
in porous platinum The standard conditions for this half cell (electrode) apply to all other half
cells to ensure that they can be compared. All solutions should have an ion
[H+] = 1.00 mol dm–3
concentration of 1.00 mol dm−3. All gases should be under 100 kPa pressure
Figure 5.3 Standard hydrogen and the whole cell should be at 298 K.
electrode.
Measuring standard electrode potentials
high resistance
A high-resistance voltmeter should be connected to the
temperature = 298 K voltmeter standard hydrogen electrode (half cell) and the other electrode
V (half cell) connected to the voltmeter. A salt bridge will connect
hydrogen at the two solutions.
100 kPa pressure
salt bridge
zinc [H+] = concentration of hydrogen ions; [Zn2+] = concentration
platinum wire
of Zn2+ ions. Both are measured in mol dm−3.
platinum foil covered When the standard hydrogen electrode is used, by convention,
in porous platinum
it must be the negative electrode (anode) – i.e. an oxidation
reaction must occur. This oxidation reaction is:
[H+] = 1.00 mol dm–3 [Zn2+] = 1.00 mol dm–3
H2(g) → 2H+(aq) + 2e−
This means that, by convention, a reduction occurs at the other half cell
(electrode) connected to the standard hydrogen electrode. All standard
electrode potentials are written as reductions and the value is given for the
TIP reduction reaction.
Platinum is often used in
electrochemical cells as it is a This means that the standard electrode potential for the zinc electrode is
good conductor of electricity and −0.76 V. Electrons are trying to flow from the zinc electrode to the hydrogen
it is inert. Porous platinum gives electrode and giving a negative electrode potential.
a larger surface area for reaction.
The standard electrode potential is defined as: the electrode potential
of a standard electrode with ion concentration of 1.00 mol dm−3 at 298 K
connected to a standard hydrogen electrode (1.00 mol dm−3 H+ ions,
TIP 100 kPa H2 gas at 298 K) using a high-resistance voltmeter and a salt bridge.
The standard electrode potential
can also be called a standard Electrodes containing two ions
redox potential or standard If the standard electrode potential of a reduction between two ions is to be
reduction potential. It is measured, it is set up as follows:
represented by the symbol E 1.
high resistance
temperature = 298 K voltmeter 81
V
hydrogen gas at
100 kPa pressure
salt
platinum
platinum wire

platinum foil
covered in porous
platinum in porous
[H+] = 1.00 mol dm–3 [Fe2+] = 1.00 mol dm–3
[Fe3+] = 1.00 mol dm–3

807701_C05_AQA_Chemistry_2_078-099.indd 81 13/06/15 9:00 am

 For the right-hand electrode, the solution contains two different iron ions,
Fe2+ and Fe3+, both at a concentration of 1 mol dm−3. The equilibrium is
established between them by using a platinum electrode.
Again the standard hydrogen electrode should, by convention, have an
oxidation reaction occurring. In reality this time the oxidation reaction does
occur at the standard hydrogen electrode. The value on the high-resistance
voltmeter is the actual standard electrode potential for the Fe3+ to Fe2+
reduction reaction.
This means that the value for the reduction reaction on the right-hand
side is:

Fe3+(aq) + e− → Fe2+(aq) E 1 = +0.77 V

In this case the value shown on the voltmeter in a practical setting is the
same as the actual standard electrode potential for the reduction reaction in
the right-hand cell.

TEST YOURSELF 2
1 Give two reasons why platinum is used as the contact in a standard
hydrogen electrode.
2 State the conditions required for the standard hydrogen electrode.
3 Draw a labelled diagram of the apparatus that could be connected
to a standard hydrogen electrode in order to measure the standard
electrode potential of the Cu2+(aq) + 2e− → Cu(s) electrode.
In your diagram, show how this electrode is connected to the standard
5    ELECTRODE POTENTIALS AND CELLS

hydrogen electrode and to a voltmeter. Do not draw the standard

hydrogen electrode.
State the conditions under which this cell should be operated to
measure the standard electrode potential.

●● Cell conventions and electromotive force

(EMF)
Convention means a lot in drawing a complete cell and in calculating
standard electrode potentials.
When connecting any two electrodes and drawing a diagram of the overall
cell, the oxidation electrode should be drawn on the left and the reduction
electrode on the right. All cells drawn previously have been drawn like this.

82 Obviously for the two electrodes, the oxidation and reduction reactions
must be determined before the cell is drawn. The standard electrode
potential with the more negative value will form the oxidation electrode.
The more negative electrode potential is the left-hand (oxidation) side of the cell.

807701_C05_AQA_Chemistry_2_078-099.indd 82 13/06/15 9:00 am

 Cell conventions and electromotive force (EMF)
EXAMPLE 1
A cell is made from a Zn2+|Zn electrode and a Cu2+|Cu electrode. The
values of the standard electrode potentials are:

Zn2+(aq) + 2e− → Zn(s) E1 = −0.76 V

Cu2+ (aq) + 2e− → Cu(s) E1 = +0.34 V

Calculate the EMF of this cell.

Answer
The more negative standard electrode potential is the zinc one, which
means it will form the left-hand electrode and the copper one will form
the right-hand electrode. Oxidation will occur at the zinc electrode and
reduction will occur at the copper electrode.

Zn salt bridge Cu

Zn2+ (aq) Cu2+ (aq)

The overall voltage measured on a cell like this is called the electromotive
force (EMF). For this electrochemical reaction, the zinc being oxidised
has a potential of +0.76 V and the copper being reduced has a potential of
+0.34 V so the EMF of this cell is +1.10 V.

Zn Zn2+ + 2e– +0.76 V

2+
Cu + 2e– Cu +0.34 V
Zn + Cu2+ Zn2+ + Cu +1.10 V

This is the overall ionic This is the EMF

equation for the complete of the cell
cell (without electrons)

In real terms this means that when zinc is placed in a solution containing
copper(ii) ions, the zinc will displace the copper(ii) ions to form zinc ions
and copper. Zinc is more reactive than copper.

83
Using an ammeter in a cell
The high-resistance voltmeter is only used to measure the potential of a cell
under standard conditions. Often an ammeter can be used to show the flow
of current in the cell and in particular to show the direction of electron flow
in the cell.

807701_C05_AQA_Chemistry_2_078-099.indd 83 13/06/15 9:00 am

 Cells not under standard conditions
If an electrochemical cell is created with two copper electrodes, the standard
electrode potential for Cu + 2e− → Cu would appear to be the same on both
sides, which would give an overall EMF of 0.00 V. There should be no flow
of current under standard conditions.
However this only applies if all conditions are standard. In the cell shown
below the concentration of CuSO4(aq) on the left-hand side is greater than
the concentration of the same solution on the right-hand side.
A

Copper salt bridge Copper

1.00 mol dm–3 0.20 mol dm–3

CuSO4 (aq) CuSO4 (aq)

● The ammeter allows current to flow.

● As the concentration of Cu2+ ions is greater on the left-hand side,
Cu2+ + 2e− → Cu occurs in preference on the left-hand side.
● The left-hand electrode in this diagram is the positive electrode.
● The oxidation Cu → Cu2+ + 2e− occurs at the right-hand electrode
(anode) to provide electrons for the reduction on the left-hand side.
5    ELECTRODE POTENTIALS AND CELLS

● Electrons flow through the ammeter from the right-hand side to the
left-hand side.
● In this cell the current would eventually fall to zero once the
concentrations of the solutions were equal.

●● Redox reactions and feasibility

of reactions
Redox potentials are always given as reduction reactions (always with gain
of electrons) and the feasibility of the reaction is given by the standard
electrode potential. The more positive the electrode potential the more
feasible is the reduction reaction.
Redox reactions consist of two parts.
1 an oxidation (which is a standard reduction reaction reversed) and
84 2 a reduction.
The total of the standard electrode potentials gives the overall feasibility of
the redox reaction. This value is called the EMF (electromotive force) of the
reaction. If the EMF is positive, then the redox reaction is feasible and if it is
negative then it is not feasible.
The table below gives the standard electrode potentials of some of the most
commonly used half equations.

807701_C05_AQA_Chemistry_2_078-099.indd 84 13/06/15 9:00 am

 Half reaction E1 /V

Redox reactions and feasibility of reactions

F 2(g) + 2e − → 2F− (aq) +2.87
Cl 2(g) + 2e −→2Cl(aq) +1.36
Br2(l) + 2e−→2Br – (aq) +1.07

strong reducing agents

strong oxidising agents
Fe3+(aq) + e −→Fe2+(aq) +0.77
I2(s) + 2e −→2I− (aq) +0.54
Cu2+(aq) + 2e−→Cu(s) +0.34
Sn4+(aq) + 2e− → Sn2+(aq) +0.14
2H+(aq) + 2e− → H2(g) 0.00
Pb2+(aq) + 2e− → Pb(s) −0.13
Fe2+(aq) + 2e−→Fe(s) −0.44
Zn2+(aq) + 2e−→Zn(s) −0.76
K+(aq) + e − → K(s) −2.93
Li+(aq) + e − → Li(s) −3.05
Fluorine most easily undergoes reduction to fluoride ions hence fluorine is
the strongest oxidising agent (or oxidant).
Lithium ions, Li+, are most resistant to reduction. As the reverse reaction
(oxidation) has a high positive value this means that lithium metal is the
most easily oxidised and so is the strongest reducing agent (reductant).
The overall EMF of a redox reaction can be calculated using the standard
electrode potentials.

EXAMPLE 2
In the reaction between chlorine and potassium EMF for the reaction = +1.36 + (−1.07) = +0.29 V
bromide solution, the equation for the reaction is: This would indicate that the redox reaction:
2KBr + Cl2 → 2KCl + Br2
2Br− + Cl2 → 2Cl− + Br2
The potassium ion, K+,
is the spectator ion and can
be disregarded as it does not take part in the redox is feasible and does occur.
reaction, being the same at the beginning as at the However in the following reaction:
end. With this ion removed, the equation is now an
ionic equation: 2Cl− + Br2 → 2Br− + Cl2

2Br− + Cl2 → 2Cl− + Br2 The half equations and standard electrode potentials
for these reactions are given below:
Note that this consists of two half equations:
E1 value for Cl2 + 2e− → 2Cl− +1.36 V
2Br− → Br2 + 2e− Loss of electrons = oxidation
E1 value for Br2 + 2e− → 2Br− +1.07 V
and
The top half equation must be reversed to make it an
Cl2 + 2e− → 2Cl− Gain of electrons = reduction oxidation.
The standard electrode potentials for these reactions
EMF of the redox reaction is = 1.07 − (+1.36) =
are given below: 85
−0.29 V
E1 value for Cl2 + 2e− → 2Cl− +1.36 V This would indicate that the redox reaction:
E1 value for Br2 + 2e− → 2Br− +1.07 V 2Cl− + Br2 → 2Br− + Cl2
However these are both reductions and the second is not feasible and does not occur.
must be reversed to form an oxidation step. The EMF is
the total of the standard electrode potentials when the
sign of one has been changed to make it an oxidation
reaction.

807701_C05_AQA_Chemistry_2_078-099.indd 85 13/06/15 9:00 am

 ●● Conventional cell representation
(cell notation)
It would be cumbersome to have to draw a full cell diagram every time to
represent the electrodes.
A simple representation of a cell can be used. The rules for writing
conventional cell representations are:
1 The oxidation electrode is placed on the left with the components in
order of being oxidised, e.g. Zn(s) first then Zn2+(aq).
2 The reduction electrode is written on the right with the component in
order of being reduced, e.g. Cu2+(aq) then Cu(s).
3 A double vertical line (||) is used between the two electrodes to represent
the salt bridge.
4 Single vertical lines are used between components in an electrode
to represent a phase boundary (difference in physical state), e.g.
Cu2+(aq)|Cu(s).
5 If Pt is used as a contact in an electrode for gas/ions in solution or two ions
in solution it should be placed at the extreme left of the left-hand electrode
and the extreme right of the right-hand electrode. Phase boundary lines
may also be used to separate it from other components of the electrode.
6 Commas are used to separate components in an electrode which are in
the same phase, e.g. Fe3+(aq), Fe2+ (aq).
The cell notation for the zinc copper cell is shown below.
5    ELECTRODE POTENTIALS AND CELLS

The single vertical line The single vertical

represents a phase line represents a
boundary phase boundary

Zn(s)|Zn2+ (aq)||Cu2+ (aq)|Cu(s) EMF = +1.10 V

Zn Zn2+ + 2e– Cu2+ + 2e– Cu

Oxidation reaction Reduction reaction
in left electrode in right electrode
The double vertical lines
represent the salt bridge

The single vertical lines are important between the components of an

electrode. As the zinc is a solid and the Zn2+ ions are aqueous, there should
be a vertical phase boundary line between them.
The EMF of this type of arrangement can be determined from the standard
electrode potentials using an expression which is:
86
TIP EMF = E1RHS − E1LHS (RHS = right-hand side; LHS = left-hand side)
However it is best often to work This means that the standard electrode potential of the right-hand electrode
out which electrode is undergoing minus the standard electrode potential of the left-hand electrode is equal to
oxidation and change the sign of
the EMF.
the standard electrode potential
and add it to the standard electrode The minus takes into account that there is an oxidation occurring at the
potential for the electrode left-hand electrode.
undergoing reduction. This will
also give the EMF of the cell. It can also be written:
EMF = E 1(reduction reaction) − E 1(oxidation reaction)

807701_C05_AQA_Chemistry_2_078-099.indd 86 13/06/15 9:00 am

 If a standard hydrogen electrode is used in the cell, it should be on the left
as it should always be the oxidation electrode (by convention), for example:

Conventional cell representation (cell notation)

Pt|H2(g) | H+(aq) || Zn2+(aq) | Zn(s) EMF = −0.76 V
The platinum contact in the electrode must be included. For the left-hand
electrode, Pt is placed before the component and again a phase boundary (|)
is in place. The phase boundaries are also in place between the components
of the electrodes.
The same is true of a solution containing two ions such as the Fe3+|Fe2+
electrode, for example:
Pt|H2(g)|H+(aq)||Fe3+(aq), Fe2+(aq)|Pt EMF = +0.77 V
In this example both electrodes have a platinum contact. The standard
hydrogen electrode is again always on the left-hand side.
The Pt is placed at the end of the reduction side (right-hand side) and again
a phase boundary (|) is in place.
Figure 5.4 A platinum electrode
(square, lower centre) in a solution As both Fe3+ and Fe2+ are in the same phase on the right, a phase boundary
of iron(ii) and iron(iii) ions. The iron(iii) line is not used but a comma instead.
ions are being reduced to iron(ii) ions,
gaining an electron in the process. A comma should be used between components of an electrode that are in
The electron movements are powered the same phase.
by the oxidation of hydrogen in the
smaller tube seen inside the larger Constructing a normal cell from two electrodes:
tube. Hydrogen gas is adsorbed
onto the platinum coil and loses two Zn2+(aq) + 2e− → Zn(s) E1 = −0.76 V
electrons to form two hydrogen ions
in the surrounding water. A platinum-
hydrogen electrode is the standard Mg2+(aq) + 2e− → Mg(s) E1 = −2.37 V
used to measure redox potentials of The more negative standard electrode potential is for magnesium so this
ions. In this case the iron(iii) to iron(ii)
redox potential is +0.77 V.
becomes the left-hand electrode.

Mg(s)| Mg2+(aq)|| Zn2+(aq)|Zn(s)

The overall EMF is:

ERHS − ELHS = −0.76 − (−2.37) = +1.61 V

or
Mg → Mg2+ + 2e− +2.37 V

Zn2+ + 2e− → Zn −0.76 V

Mg + Zn2+ → Mg2+ + Zn EMF = +1.61 V

87
In real terms, this means that when magnesium is placed in a solution
TIP containing zinc ions, the magnesium will displace the zinc ions to form
If a reaction is determined to be magnesium ions and zinc. Magnesium is more reactive than zinc.
feasible as it has a positive EMF,
this does not mean that it will This allows us to create a reactivity series: magnesium is more reactive
happen. The activation energy than zinc, which is more reactive than copper.
may be so high as to prevent it
reacting at any appreciable rate
Remember: a positive EMF value for a cell indicates that a reaction given by
under standard conditions. the overall cell equation is feasible. A negative EMF value for a cell indicates
that a reaction given by the overall cell equation is not feasible.

807701_C05_AQA_Chemistry_2_078-099.indd 87 13/06/15 9:00 am

 EXAMPLE 3
Which one of the following species will oxidise iron(ii) For B: Fe2+|Fe3+||Cl2 |2Cl−
to iron(iii) in aqueous solution. EMF = +1.36 − (+0.77) = +0.59 V
This is feasible – chlorine will oxidise iron(ii) ions to
Fe3+(aq) + e− → Fe2+(aq) E1 = +0.77 V
iron(iii) ions
A iodine I2 + 2e− → 2I− +0.54 V
For C: Fe2+|Fe3+||Cu2+ |Cu
B chlorine Cl2 + 2e− → 2Cl− +1.36 V
EMF = +0.34 − (+0.77) = −0.43 V
C copper(ii) ions Cu2+ + 2e− → Cu +0.34 V
D nickel(ii) ions Ni2+ + 2e− → Ni −0.25 V This is not feasible – copper (ii) ions will not oxidise
Answer iron(ii) ions to iron(iii) ions
For this question, the iron(ii) ions are to be oxidised to For D: Fe2+|Fe3+||Ni2+ |Ni
iron(iii) ions so this must be the left-hand electrode. EMF = −0.25 − (+0.77) = −1.02 V
The EMF will then be calculated for each of the
This is not feasible – nickel(ii) ions will not oxidise
substances in A to D.
iron(ii) ions to iron(iii) ions.
For A: Fe2+ |Fe3+||I2 |2I−
Hence chlorine will oxidise iron(ii) ions to iron(iii) ions.
EMF = +0.54 − (+0.77) = −0.23 V
This is not feasible – iodine will not oxidise iron(ii) ions
to iron(iii) ions

EXAMPLE 4
The table below shows some standard electrode The EMF of this cell is +1.08 V. Use the data in the
potential data. table above to calculate a value for the standard
5    ELECTRODE POTENTIALS AND CELLS

electrode potential of the chromium electrode.

Electrode half equation E1 /V
Mg2+ (aq) + 2e − → Mg(s) −2.37 Answer
Al 3+ (aq) + 3e − → Al(s) −1.66 1 The strongest reducing agent is most easily
Zn2+ (aq) + 2e − → Zn(s) −0.76 oxidised.
Fe2+ (aq) + 2e − → Fe(s) −0.44 Mg → Mg2+ + 2e− would have the most positive
value.
V2+ (aq) + 2e − → V(s) −0.26
Mg is the strongest reducing agent
Ni2+ (aq) + 2e − → Ni(s) −0.25
2 a) Zn → Zn2+ + 2e−
2H+ (aq) + 2e − → H2(g) 0.00 V2+ + 2e− → V
Cu2+ (aq) + 2e − → Cu(s) + 0.34 overall equation: Zn + V2+ → Zn2+ + V
The zinc and vanadium redox potentials show a
1 Which species in the table above is the strongest
difference of 0.50 between the values, −0.76 V and
reducing agent? Explain your answer.
−0.26 V. When the zinc is reversed it gives +0.76 V
2 a) Use the data in the table to deduce the equation
and −0.26 V is added to give +0.50 V.
for the overall cell reaction of a cell which has an
b) Zn|Zn2+||V2+|V
EMF of +0.50 V.
c) The negative electrode is where an oxidation
b) Give the conventional cell representation for this
88 occurs. The negative electrode is the zinc
cell.
electrode.
c) Identify the negative electrode.
3 Cu2+|Cu +0.34 V
3 A conventional cell representation is shown below:
Cr|Cr3+ + x V
Cr(s)|Cr3+(aq)||Cu2+(aq)|Cu(s)
= EMF = +1.08 V
x = 1.08 − 0.34 = +0.74 V
This is for the oxidation reaction (Cr → Cr3+ + 3e−)
Standard electrode potential for Cr3+ + 3e− → Cr =
−0.74 V

807701_C05_AQA_Chemistry_2_078-099.indd 88 13/06/15 9:00 am

 Conventional cell representation (cell notation)
EXAMPLE 5
The table below shows some standard electrode Answers
potential data. 1 Reaction 1: O2 + 4H+ + 4e− → 2H2O E1 = +1.23 V
Reaction Electrode half equation E1 /V
Reaction 4: Br2 + 2e− → 2Br− E1 = +1.07 V
Reverse reaction 4 and ×2
1 O 2(g) + 4H+ (aq) + 4e − → 2H2 O(l) +1.23
O2 + 4H+ + 4e− → 2H2O
2 O 2(g) + 2H+ (aq) + 2e − → H2 O 2(aq) +0.68
4Br− → 2Br2 + 4e−
3 O 2(g) + 2H2 O(l) + 4e − → 4OH − (aq) +0.40 Overall equation is:
4 Br 2(l) + 2e − → 2Br − (aq) +1.07 4H+ + 4Br− + O2 → 2H2O + 2Br2
5 Ag+ (aq) + e − → Ag(s) +0.80 The equation may also be written: 4HBr + O2 →
2H2O + 2Br2
1 A solution of hydrogen bromide reacts with EMF = +1.23 − 1.07 = +0.16 V
oxygen gas. 2 O2 + 2H+ + 2e− → H2O2   E1 = +0.68 V
Determine the overall equation for the reaction Ag+ + e− → Ag      E1 = +0.80 V
which occurs and calculate the EMF of this reaction Reverse first equation and second equation ×2
using reactions 1 and 4 above. H2O2 → O2 + 2H+ + 2e−
2 Determine the overall reaction when a solution 2Ag+ + 2e− → 2Ag
containing silver(i) ions are added to hydrogen Overall equation is:
peroxide solution. Calculate the EMF of this H2O2 + 2Ag+ → O2 + 2Ag + 2H+
reaction. EMF = +0.80 − 0.68 = +0.12 V
3 a) Using the standard electrode potentials, explain 3 a) E1 (Br2|Br–)>E1(Ag+|Ag)
why silver reacts with bromine. b) Negative electrode is where oxidation occurs. Ag
b) Identify the negative electrode. is oxidised to Ag+/silver electrode is the negative
electrode

TEST YOURSELF 3
1 A cell is set up using the following two electrodes: Half equation E1 /V
Fe3+(aq) + e− → Fe2+ = (aq)   E1 = +0.77 V Zn2+(aq) + 2e− → Zn(s) −0.76
2+ −
Zn (aq) + 2e → Zn(s)    E1 = −0.76 V O2(g) + 4H+(aq) + 4e − → 2H2O(l) +1.23
a) Calculate the EMF of the overall cell. Cl 2(g) + 2e − → 2Cl− (aq) +1.36
b) Which electrode forms the positive electrode? F2(g) + 2e − → 2F− (aq) +2.87
c) Write an overall equation for the cell reaction.
d) Write the conventional representation for the a) Name the strongest reducing agent from the
cell using platinum contacts for the Fe3+|Fe2+ table above.
electrode. b) In terms of electrons, state what happens to a
2 A conventional representation of a cell is shown reducing agent in a redox reaction.
below: c) Fluorine reacts with water, oxidising the oxygen
Fe(s)|Fe2+ (aq)||Cu2+ (aq)|Cu(s) in water to oxygen.
a) Write an equation to represent the oxidation i) Use data from the table to explain why
reaction in this cell. fluorine reacts with water. 89
b) Write an equation to represent the reduction ii) Write an equation for the reaction which
reaction in this cell. occurs.
c) Write an overall equation for the cell reaction. d) Zinc reacts with chlorine.
d) The EMF of this cell is +0.78 V. The half equation i) Write a conventional cell representation for
Fe2+(aq) + 2e− → Fe(s) has a standard electrode the reaction which occurs.
potential of −0.44 V. Determine the standard ii) Calculate the EMF of this cell.
electrode potential of the copper electrode.
3 The table below shows some redox half equations
with their standard electrode potentials.

807701_C05_AQA_Chemistry_2_078-099.indd 89 13/06/15 9:00 am

 REQUIRED PRACTICAL 8
Does the concentration of silver ions in 5 Complete the table by calculating values for
a solution affect the electrode potential Log[Ag+]B and then plot a graph of Log [Ag+]B
(x axis) against electrode potential (y axis).
of a cell?
Why is a log scale useful in this case?
A silver chloride electrode is a type of reference 6 How could you use this experiment to determine
electrode commonly used in electrochemical the silver ion concentration of an unknown
measurements. For example, it is usually the internal solution?
reference electrode in pH meters. Silver chloride
electrodes are also used in electrocardiography
(ECG).
In a laboratory experiment a silver cell was set up as
shown in the diagram below.

silver salt bridge silver

metal metal

Ag+

Figure 5.5 Electrocardiogram (ECG) electrodes

beaker A beaker B placed on a patient’s leg. The electrodes measure the
electrical activity of the heart and are also placed on
The concentration of silver ions in the solution in the chest and arms. The electrodes are silver/silver
beaker B was changed and the electrode potential chloride sensors made by coating a thin layer of silver
5    ELECTRODE POTENTIALS AND CELLS

recorded in the table below. on plastic, and the outer layer is converted to silver
chloride.
[Ag+] in beaker [Ag+] in beaker Electrode
A /mol dm−3 B /mol dm−3 Log[Ag+]B potential/V
0.1 0.00001 −0.200
0.1 0.0001 −0.150
0.1 0.001 −0.100 TIP
0.1 0.01 −0.050
Further information on plotting a
log graph is given on page 320 in
0.1 0.1 0.000
the mathematics for chemistry
1 Why is a salt bridge necessary in this experiment? chapter.
2 Suggest how the salt bridge may be made.
3 Explain why there is a zero voltage if the solutions
in both beakers are identical.
4 Why is a high-resistance voltmeter used in this
experiment?

90

●● Commercial applications
of electrochemical cells
Electrochemical cells can be used as commercial source of electrical energy.
They are commonly called cells or batteries. The electromotive force of the
electrochemical cell is the voltage of the cell or battery. The two electrodes
combine to produce the voltage. Some cells are non-rechargeable and
others are rechargeable.

807701_C05_AQA_Chemistry_2_078-099.indd 90 13/06/15 9:00 am

 Primary cells are often referred to as single-use or disposable. The materials
in the cell cannot be regenerated by recharging. Some examples include

Commercial applications of electrochemical cells

alkaline cells which are commonly used in torches. Secondary cells are
able to be recharged and the original reagents in the cell regenerated by
recharging. These include the lead-acid batteries used in cars and the
rechargeable lithium ion and nickel metal hydride cells used in many
electronic devices such as mobile phones.

Non-rechargeable cells
Common examples of non-rechargeable cells include alkaline batteries and
dry cells. These are called primary cells which can only be used once and
then discarded.
+ The diagram shows a non-rechargeable cell.
cover
The porous separator allows ions to pass through it. The carbon rod is
carbon rod made of graphite as it conducts electricity and allows the movement of
the electrons through it. The zinc is used as a container for the cell but the
MnO2 paste
cell leaks after being used for a long time as the zinc is used up. The zinc
becomes compromised and the contents may leak out of the cell.
porous separator
zinc At the negative electrode, oxidation occurs:
ZnCl2 paste Zn(s) → Zn2+(aq) + 2e−
At the positive electrode, reduction occurs:
A typical non-rechargeable cell
MnO2(s) + H2O(l) + e− → MnO(OH)(s) + OH−(aq)
The standard electrode potentials for the reduction reactions are given as:

MnO2(s) + H2O(l) + e− → MnO (OH)(s) + OH−(aq) E1 = +0.74 V

Zn2+(aq) + 2e− → Zn(s) E1 = −0.76 V

The overall EMF of this cell is: +0.74 + 0.76 = 1.50 V.
This is the voltage provided by this cell.
The oxidation state of the zinc in the oxidation reaction changes from 0
TIP in Zn to +2 in Zn2+. The manganese is reduced from +4 in MnO2 to +3 in
Try working out this overall
MnO(OH).
equation from the oxidation and
reduction reactions occurring in The overall reaction when the cell discharges is:
the cell.
Zn(s) + 2MnO2(s) + 2H2O(l) → Zn2+(aq) + 2MnO(OH)2(s) + 2OH−(aq)

91

807701_C05_AQA_Chemistry_2_078-099.indd 91 13/06/15 9:00 am

 EXAMPLE 6
The zinc-silver(i) oxide cell is non-rechargeable. It may be used as a
source of electrical energy.
Using the following standard electrode potentials:
TIP
As Ag2O and Ag are in the same Zn2+ (aq) + 2e− → Zn(s) E1 = −0.76 V
state, they should be separated
by a comma rather than a phase Ag2O(s) + 2H+ (aq) + 2e− → 2Ag(s) + H2O(l) E1 = +0.34 V
line (|). If state symbols are
required, the answer would be 1 Write the cell notation of the cell used to represent the zinc-silver(i)
Zn(s)|Zn2+ (aq)||Ag2O(s), Ag(g). oxide cell.
2 Which half equation forms the negative electrode of this cell?
3 Calculate the EMF of this cell.
4 Write an overall equation occurring when this cell is discharging.
Answers
TIP 1 Zn | Zn2+ || Ag2O, Ag
Non-rechargeable cells cannot 2 The negative electrode is where oxidation occurs. The negative
be recharged as the reaction that electrode is the zinc electrode as zinc is oxidised.
occurs is not reversible. 3 EMF = + 0.34 + 0.76 = 1.10 V
4 Zn(s) → Zn2+ (aq) + 2e−
Ag2O(s) + 2H+ (aq) + 2e− → 2Ag(s) + H2O(l)
Combining these:
Zn(s) + Ag2O(s) + 2H+ (aq) → Zn2+ (aq) + 2Ag(s) + H2O(l)

Rechargeable cells
5    ELECTRODE POTENTIALS AND CELLS

Rechargeable cells (often called secondary cells) can be used many times.
There are many types of these such as the nickel-cadmium cell and the
lithium ion cell.

Nickel-cadmium cell
In this cell the standard electrode potentials are:
Cd(OH)2(s) + 2e− → Cd(s) + 2OH−(aq) E1 = −0.88 V

NiO(OH)(s) + H2O(l) + e− → Ni(OH)2(s) + OH−(aq) E1 = +0.52 V

For the cell to work, the Ni is reduced from +3 in NiO(OH)2 to +2 in
Ni(OH)2 and the Cd is oxidised from 0 in Cd to +2 in Cd(OH)2. This gives
a positive EMF for this cell. The EMF is +0.52 + 0.88 = +1.40 V.
At the negative electrode, oxidation occurs:
92
Cd(s) + 2OH−(aq) → Cd(OH)2(s) + 2e−
At the positive electrode, reduction occurs:

NiO(OH)(s) + H2O(l) + e− → Ni(OH)2(s) + OH− (aq)

807701_C05_AQA_Chemistry_2_078-099.indd 92 13/06/15 9:00 am

 The overall reaction occurring when the cell is discharged is:
TIP

Commercial applications of electrochemical cells

Cd(s) + 2NiO(OH)(s) + 2H2O(l) → Cd(OH)2(s) + 2Ni(OH)2 (s)
The reaction that recharges
a rechargeable cell is the When the cell is recharged the reaction above is reversed to regenerate the
reverse of the reaction which reagents:
discharges it.
Cd(OH)2 (s) + 2Ni(OH)2 (s) → Cd(s) + 2NiO(OH)(s) + 2H2O(l)
Rechargeable cells are more environmentally advantageous as they can be
reused and prevent waste. Supplies of the metal and other reagents are not
depleted as quickly and less energy is used to extract metals.

Lead-acid cell
The lead-acid cell is the cell used in cars and other vehicles. It is recharged
as the vehicle moves. Sulfuric acid is used to provide the acid in these types
of battery.
The half equations for the reaction are:

PbO2(s) + 3H+(aq) + HSO4−(aq) + 2e− → PbSO4 (s) + 2H2O(l) E1 = +1.69 V

PbSO4(s) + H+(aq) + 2e− → Pb(s) + HSO4−(aq) E1 = −0.46 V

At the negative electrode, oxidation occurs:
Pb(s) + HSO4−(aq) → PbSO4(s) + H+(aq) + 2e−
At the positive electrode, reduction occurs:
PbO2(s) + 3H+(aq) + HSO4−(aq) + 2e− → PbSO4(s) + 2H2O(l)
The overall reaction occurring when the cell is discharged is:
PbO2(s) + 2H+(aq) + 2HSO4−(aq) + Pb(s) → 2PbSO4(s) + 2H2O(l)
When the cell is recharged the reaction above is reversed to regenerate the
reagents:
−
2PbSO4 (s) + 2H2O(l) → PbO2 (s) + 2H+ (aq) + 2HSO4 (aq) + Pb(s)
At the negative electrode, Pb is oxidised from 0 in Pb to +2 in PbSO4.
At the positive electrode, Pb is reduced from +4 in PbO2 to +2 in PbSO4.
The formation of lead(ii) sulfate can be a problem if a lead-acid cell is
discharged for long periods of time. The insoluble lead(ii) sulfate build up
in the cell and the cell cannot be recharged.

Lithium ion cell 93

Rechargeable lithium ion cells are rechargeable and often used to provide
electrical energy for cameras, laptops, tablets and mobile phones.
The positive electrode (cathode) in the cell is represented by the half
equation:
Li+ + CoO2 + e− → Li+[CoO2]− reduction
The negative electrode (anode) is represented by the half equation:

Li → Li+ + e− oxidation

807701_C05_AQA_Chemistry_2_078-099.indd 93 13/06/15 9:00 am

 The overall cell may be written as:
TIP
Li|Li+||Li+, CoO2|LiCoO2|Pt
Remember to use NEGATOX to
identify the negative electrode
The overall reaction is found by combining the half equations:
as the electrode at which an
oxidation occurs.
Li + CoO2 → Li+[CoO2]−
At the negative electrode, lithium is being oxidised from 0 in Li to +1 in Li+.
At the positive electrode, cobalt is being reduced from +4 oxidation state in
CoO2 to +3 oxidation state in LiCoO2.
The reactants in this electrochemical cell are absorbed into graphite powder
which acts as a support medium. The ions are able to react in this support
medium without the need for a solvent such as water. Water could not be
used as it reacts with lithium.

Fuel cells
● A fuel cell is an electrical cell which converts the chemical energy of a
redox reaction into electrical energy. The cell will continue to function as
long as the fuel and oxygen are supplied to it.
● The most common fuel cells use hydrogen or ethanol as the fuel though
hydrocarbons may also be used.
● Oxidation occurs at the anode and the electrons released travel through a
wire and into the external circuit.
● The central electrolyte allows ions and molecules to move through it
but not electrons. The ions react with another substance and this is the
reduction reaction which takes electrons from the external circuit.
5    ELECTRODE POTENTIALS AND CELLS

● The oxidation and reduction reactions are both catalysed.

Hydrogen fuel cell

The hydrogen fuel call can operate in acidic or alkaline conditions. In
the acidic hydrogen fuel cell this oxidation is the reverse of the following
standard electrode potential:

2H+ (aq) + 2e− → H2(g) E1 = 0.00 V

The oxidation reaction at the negative electrode (anode) is:

H2(g) → 2H+(aq) + 2e−

The reduction reaction at the positive electrode (cathode) is:

O2(g) + 4H+(aq) + 4e− → 2H2O(l) E1 = +1.23 V

94 The overall reaction is:

2H2(g) + O2(g) → 2H2O(l) EMF = +1.23 V.

The cell notation for a hydrogen fuel cell operating in acidic conditions is:

Pt|H2(g)|H+(aq)||O2(g)|H+(aq), H2O(l)|Pt

807701_C05_AQA_Chemistry_2_078-099.indd 94 13/06/15 9:00 am

 Electric current flowing The diagram on the left shows these processes:
in external circuit

Commercial applications of electrochemical cells

In the alkaline hydrogen fuel cell, the oxidation reaction at the anode is the
H2 in e –
Air in reverse of the following standard electrode potential:
e–
2H2O(l) + 2e− → H2(g) + 2OH− (aq) E1 = −0.83 V
e– H2O
e–
H+ The oxidation reaction at the negative electrode (anode) is:

H2 O2 H2(g) + 2OH− (aq) → 2H2O(l) + 2e−

H+
Unused
H2 out
gases The reduction reaction at the positive electrode (cathode) is:
H2O out

O2(g) + 2H2O(l) + 4e− → 4OH− (aq) E1 = +0.40 V

Anode Cathode
Electrolyte
The overall reaction is:
Hydrogen fuel cell in acidic conditions
Hydrogen fuel cell in acidic
conditions 2H2(g) + O2(g) → 2H2O(l) EMF = +1.23 V.

The conventional cell representation for a hydrogen fuel cell operating in

alkaline conditions is:
TIP
The overall reaction is the same Pt|H2(g)|OH−(aq), H2O(l)||O2(g)|H2O(l), OH− (aq)|Pt
so the EMF is the same for both
the acidic hydrogen fuel cell and Commercial alkaline hydrogen fuel cells use platinum electrodes in contact
the alkaline hydrogen fuel cell. with concentrated aqueous hydrogen hydroxide. Porous platinum is used to
give a larger surface area.
Fuel cells do not have to be recharged as the fuel is supplied continuously
to the cell so the voltage output does not change. However, fuel cells
use fuels that may have been produced using an energy source that is
not carbon neutral. Ethanol fuel cells can use ethanol produced from
fermentation of crops, which are regarded as carbon neutral as the CO2
produced in the fuel cell is captured again during photosynthesis to
generate the carbohydrates used to make the ethanol.

Ethanol fuel cell

Ethanol oxygen fuel cells are used an as alternative to the hydrogen fuel cell.
Ethanol is oxidised in the fuel cell to carbon dioxide and water. The overall
reaction is:

C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l)

The oxidation reaction occurring at the negative electrode (anode) reaction
is:
95
C2H5OH(l) + 3H2O(l) → 2CO2(g) + 12H+ (aq) + 12e−

The reduction reaction occurring at the positive electrode (cathode) is:

12H+ (aq) + 3O2(g) + 12e− → 6H2O(l)

807701_C05_AQA_Chemistry_2_078-099.indd 95 13/06/15 9:00 am

 EXAMPLE 7
The EMF of the ethanol fuel cell is +1.00 V. The standard electrode
potential of the following reaction is:

2CO2(g) + 12H+ (aq) + 12e− → C2H5OH(l) + 3H2O(l) E1 = +0.23 V

Calculate the standard electrode potential of the following reaction:

4H+ (aq) + O2(g) + 4e− → 2H2O(l)

Answer
The oxidation reaction is the reverse of the first reaction:

C2H5OH(l) + 3H2O(l) → 2CO2(g) + 12H+ (aq) + 12e−

The reduction reaction is:

12H+ (aq) + 3O2(g) + 12e− → 6H2O(l)

The EMF is the total of the oxidation and reduction potentials.

Reduction potential = to be determined = x
Oxidation potential = −0.23 V
EMF = 1.00 V = x + (−0.23)
x = +1.23 V
Standard electrode potential is +1.23 V
5    ELECTRODE POTENTIALS AND CELLS

EXAMPLE 8
The EMF of the methanol fuel cell is +1.21 V. The standard electrode
potential of the following reaction occurring at the positive electrode is:

4H+(aq) + O2(g) + 4e− → 2H2O(l) E1 = +1.23 V

1 Write an overall equation for the reaction occurring in the fuel cell.
2 Write an equation for the reaction occurring at the negative electrode.
3 Calculate the standard electrode potential for the reaction occurring at
the negative electrode.
Answer
1 The overall reaction is the oxidation of methanol:
1
CH3OH + 12 O2 → CO2 + 2H2O
2 The basic equation is:
96 CH3OH + H2O → CO2 + H+ + e−
It is balanced by balancing the atoms and the electrons balance the
charge.
CH3OH + H2O → CO2 + 6H+ + 6e−
3 The EMF is the total of the oxidation and reduction potentials.
Electrode potential to be determined = x
Reduction potential = +1.23 V
EMF = 1.21 V = 1.23 − x
x = + 0.02 V
Standard electrode potential as a reduction = +0.02 V

807701_C05_AQA_Chemistry_2_078-099.indd 96 13/06/15 9:00 am

 Practice questions
TEST YOURSELF 4
1 The reactions which occur in a lithium ion cell are:
Reaction A: Li+ + CoO2 + e− → Li+[CoO2]−
Reaction B: Li → Li+ + e−
a) Write an overall equation for the reaction occurring in the
lithium ion cell.
b) Which reaction (A or B) occurs at the electrode which is the
negative electrode in this cell? Explain your answer.
2 Explain why the voltage produced by a hydrogen fuel cell remains
constant whereas that of a lead-acid cell decreases eventually after
continued use.
3 The conventional representation of the hydrogen fuel cell operating
in acidic conditions is:
Pt|H2(g)|H+ (aq)||O2(g)|H+ (aq), H2 O(l)|Pt
a) Write an equation for the oxidation reaction which is occurring.
b) Write an equation for the reduction reaction which is occurring.
c) Write an overall equation for the reaction in the fuel cell.

Practice questions 3 Use the following data to predict which of the

reactions listed below will proceed as written.
1 Which one of the following statements about E1/V
the standard hydrogen electrode is incorrect?
Cr3+ + 3e− → Cr −0.74
A the hydrogen gas is at a pressure of 100 kPa
Fe2+ + 2e− → Fe −0.44
B the value of E1 is 1.00 V
Fe3+ + 2e− → Fe2+ +0.77
C the hydrogen ion concentration in solution
7 + 14H +6e → 2Cr + 7H2O
Cr2O2− + − 3+ +1.33
is 1.00 mol dm−3
1
D the temperature is 298 K (1) BrO3− + 6H+ + 5e− → Br2 + 3H2O
2
+1.52
2 Using the standard electrode potentials below, A 2Cr3+ + 7H2O + 3Fe2+ → Cr2O2− +
7 + 14H + 3Fe

choose the reducing agent capable of reducing B 1

Br + 3H2O + 5Fe3+ → 5Fe2+ + BrO3− + 6H+ + 5e−
2 2
vanadium from the +5 to the +3 oxidation
state but not to the +2 state. C Cr2O2−
7 + 14H + 2Cr → 4 Cr + 7H2O
+ 3+

E1/V D Br2 + 6H2O + 5Fe2+ → 2BrO3− + 12H+ + 10e− + 5Fe

(1)
Zn2+(aq) + 2e− → Zn(s) −0.76
4 V3+(aq) + e− → V2+(aq) E1 = −0.26 V
Fe2+(aq) + 2e− → Fe(s) −0.44
a) Draw a labelled diagram of the apparatus
V3+(aq) + e− → V2+(aq) −0.26 which could be connected to a standard 97
4 (aq) + 4H (aq) + 2e → 2H2O(l) + SO2(g)
SO2− + − +0.17 hydrogen electrode in order to measure the
standard electrode potential of the V3+/V2+
VO2+(aq) + 2H+(aq) + e− → V3+(aq) + H2O(l) + 0.32 electrode.
I2(aq) + 2e− → 2I−(aq) +0.54 b) In your diagram, show how this electrode
VO+2 (aq) + 2H+(aq) + e− → VO2+(aq) + H2O(l) +1.00 is connected to the standard hydrogen
electrode and to a voltmeter. Do not draw
A iodide ions B iron the standard hydrogen electrode.
C sulfur dioxide D zinc (1)

807701_C05_AQA_Chemistry_2_078-099.indd 97 13/06/15 9:00 am

 c) State the conditions under which this cell a) Au+ ions react with water.
should be operated to measure the standard
i) Use data from the table to explain why
electrode potential. (5)
Au+ ions react with water. (1)
5 For the conventional representation of a cell
ii) Write an equation for the reaction
shown below:
which would occur between Au+ ions
Pt|Fe2+(aq), Fe3+(aq)||MnO−4(aq), Mn2+(aq)|Pt and water. (1)
a) State which electrode is the negative iii) Write a conventional cell
electrode and explain your answer. (2) representation of this cell. (2)
b) Write the half equation representing the b) Silver nitrate solution is used to test for the
oxidation and reduction reactions in this presence of halide ions.
cell and combine these to write an overall
i) Explain why a redox reaction does not
equation for the cell reaction. (3)
occur when silver(i) ions are mixed with
c) The EMF of this cell is +0.74 V. The a solution containing chloride ions. (1)
standard electrode potential of the
ii) What is observed when a solution
manganate(Vii)/manganese(ii) cell is +1.51 V.
containing silver(i) ions is added to a
Calculate a value for the standard electrode
solution containing chloride ions? (1)
potential of the Fe3+/Fe2+ electrode. (2)
iii) Write an ionic equation for the
6 The half equations for two electrodes used to
reaction between silver(i) ions and
make an electrochemical cell are shown below:
chloride ions.
ClO3− (aq) + 6H+(aq) + 6e− → Cl−(aq) + 3H2O(l)
(c) Predict the products of the following
E1 = +1.45 V
reactions and write equation(s) to
VO+2 (aq) + 2H+(aq) + e− → VO2+(aq) + H2O(l) represent the reactions which occur.
E1 = +1.00 V
5 ELECTRODE POTENTIALS AND CELLS

i) Zinc metal is placed in a solution

a) Write the conventional cell representation containing Fe3+ ions. (3)
for the cell using platinum contacts. (2)
ii) Iron metal is placed in a solution
b) Write an overall equation for the cell containing Ag+ ions. (3)
reaction. (1)
iii) Copper metal is placed in silver(i)
c) Identify the oxidising agent and the nitrate solution. (3)
reducing agent in this reaction. (2)
8 The diagram below shows an electrochemical
d) Calculate the EMF of the cell. (1) cell:
e) Identify the negative electrode. (1) A
7 The table below shows some standard platinum Cu (s)
electrode potentials:
A
Electrode half equation E1 /V
Au+ (aq) + e − → Au(s) +1.68
98
Cl 2(g) + 2e − → 2Cl− (aq) +1.36
O 2(g) + 4H+ (aq) + 4e − → 2H2 O(l) +1.23 solution containing 1.0 0 mol dm–3
Ag+ (aq) + e − → Ag(s) +0.80 1.0 0 mol dm–3 V2+ ions CuSO4 (aq)
and
Fe 3+ (aq) + e − → Fe2+ (aq) +0.77 1.0 0 mol dm–3 V3+ ions
Cu2+ (aq) + 2e − → Cu(s) +0.34
Fe2+ (aq) + 2e − → Fe(s) −0.44
Zn2+ (aq) + 2e − → Zn(s) −0.76

807701_C05_AQA_Chemistry_2_078-099.indd 98 13/06/15 9:00 am

 The standard electrode potentials are: Stretch and challenge

Practice questions
V3+(aq) + e− → V2+(aq) E1 = −0.26 V 10 A table of standard electrode potentials is
Cu2+(aq) + 2e− → Cu(s) E1 = + 0.34 V given below:
a) i) Write a conventional cell
representation for this cell. (2) Half electrode equation E1/V
Zn2+ (aq) + 2e − → Zn(s) −0.76
ii) What is represented by A? (1)
Fe2+ (aq) + 2e − → Fe(s) −0.44
iii) Explain why electrons flow
Sn2+ (aq) + 2e − → Sn(s) −0.14
from left to right in this cell. (2)
Fe 3+ (aq) + e− → Fe2+ (aq) +0.77
iv) Calculate the EMF of this cell. (1) Cr2O 2− + 6e − →
7 (aq) + 14H (aq) +
3+ +1.33
v) Write an overall equation for the 2Cr (aq) + 7H2 O(l)
reaction occurring in this cell. (1)
a) i) Using the table above, write the formula
b) The copper electrode is replaced by a for the strongest oxidising agent. (1)
platinum contact in a solution containing
ii) Describe, without the use of a diagram,
VO2+ ions and VO2+ ions both of
how the standard electrode potential
concentration 1.00 mol dm−3.
of the dichromate(Vi)/chromium(iii)
The EMF of the cell using a high-resistance electrode could be determined. (4)
voltmeter is determined to be +1.26 V.
iii) Write the equation for the cell reaction
i) Determine a value for the standard when the dichromate(Vi)/chromium(iii)
electrode potential for the VO2+ |VO2+ and Fe3+ (aq)/Fe2+ (aq) half cells are
electrode. (2) combined. (2)
ii) Write an overall equation for the b) Tin plate is used to prevent rusting of
reaction which occurs in the cell. (2) steel cans. Rusting is promoted if the tin
is scratched and the steel is exposed. An
9 The conventional cell representation for
electrochemical cell is set up between the
a hydrogen fuel cell operating in alkaline
iron and tin.
conditions is:
i) Calculate the EMF of this cell. (1)
Pt|H2(g)|OH−(aq), H2O(l)||O2(g)|H2O(l), OH−(aq)|Pt
a) Write an equation for the oxidation reaction ii) Write conventional cell representation
occurring in the fuel cell. (1) for this cell. (2)

b) Write an equation for the reduction c) i) Explain using the standard electrode
reaction occurring in the fuel cell. (1) potentials how galvanising (coating in
zinc) could prevent iron from rusting
c) Write an overall equation for the reaction even if the coating is scratched. (2)
occurring in the fuel cell. (1)
ii) Write an overall equation for the
d) The EMF of the hydrogen fuel cell is reaction which occurs when the zinc
+1.23 V. The standard electrode potential coating on a piece of galvanised iron is
for the positive electrode is given below: scratched. (1)
O2(g) + 2H2O(l) + 4e− → 4OH−(aq) E 1 = +0.40 V 99

i) Calculate a value for the standard

electrode potential for the other
electrode. (2)
ii) Explain why fuel cells maintain a
constant voltage. (2)

807701_C05_AQA_Chemistry_2_078-099.indd 99 13/06/15 9:00 am

 6 Acids and bases
PRIOR KNOWLEDGE
● Acids are compounds that dissolve in water to produce hydrogen ions.
● Hydrogen ions are H+.
● Hydrochloric acid (HCl), sulfuric acid (H2 SO4) and nitric acid (HNO 3)
are strong acids.
● Ethanoic acid (CH3COOH) is a weak acid.
● The pH scale gives a numeric value that measures the strength of an
acid or base (alkali); the scale at a simple level goes from 0 to 14.
● A pH value of 7 is neutral.
● pH values <7 are acidic; 0–2 are pH values for strong acids; pH values
>2 and <7 are for weak acids.
● A base is a substance that reacts with an acid producing a salt and water.
● Alkalis are soluble bases.
● Alkalis dissolve in water to produce hydroxide ions.
● Hydroxide ions are OH−
● The ionic equation for neutralisation is H+(aq) + OH− (aq) → H2 O(l)
● In general, pH values >7 are alkaline; 12–14 are pH values for strong
alkalis; pH values >7 and <12 are for weak alkalis.
● Bases (and alkalis) react with acids forming salts.
● Sodium hydroxide and potassium hydroxide solutions are strong alkalis.
● Sulfuric acid forms salts called sulfates; hydrochloric acid forms
salts called chlorides; nitric acid forms salts called nitrates; ethanoic
acid forms salts called ethanoates.

TEST YOURSELF ON PRIOR KNOWLEDGE 1

1 From the following acids:
H2 SO4 HCl HNO 3 CH3COOH
a) Name each acid.
b) Which one of the acids is a weak acid?
2 From the following bases:
NaOH CuO KOH MgO
a) Which two bases are also alkalis?
b) Name the salt formed when CuO reacts with H2SO4.
c) Name the salt produced when MgO reacts with HCl.
3 Solution A has a pH of 9
Solution B has a pH of 1
100 Solution C has a pH of 14
Solution D has a pH of 7
Solution E has a pH of 5
a) Which solution is neutral?
b) Which solution is a weak acid?
c) Which solution is a strong alkali?
d) Which solution is a weak alkali?
e) Which solution is a strong acid?

807701_C06_AQA_Chemistry_2_100-134.indd 100 13/06/15 9:01 am

 Many of the reactions studied in chemistry involve those of acids
and bases. Acids are important in many industrial processes from the

Brønsted-Lowry theory of acids and bases

manufacture of fertilisers, dyes, explosives, pharmaceutical drugs to
paint and pigments. Bases are used in household cleaning products,
soap manufacture, in the refining of crude oil and the manufacture of
explosives and fertilisers.

●● Brønsted-Lowry theory of acids and

bases
The Brønsted-Lowry-Lowry definition of acids and bases depends on
protons. A hydrogen ion, H+, is a proton so the term hydrogen ion and
proton are interchangeable.
● A Brønsted-Lowry acid is defined as a proton donor.
● A Brønsted-Lowry base is defined as a proton acceptor.

Strong and weak acids and bases

Acids (and bases) may be classified as strong or weak depending on the
degree to which they are dissociated in solution.
Strong acids and strong bases are completely dissociated in aqueous
solution.
Weak acids and weak bases are slightly dissociated in aqueous solution.

Strong acids
The strong acids most commonly used are hydrochloric acid (HCl), sulfuric
acid (H2SO4) and nitric acid (HNO3).
Strong acids are usually covalent molecules that dissolve in water and
dissociate (or ionise) completely.
Acidic hydrogen atoms in a molecule are the hydrogen atoms which will
produce H+(aq) or protons when the acid dissolves in water.
The acidic hydrogen atoms are often bonded to electronegative atoms such
as oxygen, fluorine and chlorine. In oxy-acids like sulfuric acid and nitric
acid, the acidic hydrogen atoms are bonded to oxygen atoms.

101

807701_C06_AQA_Chemistry_2_100-134.indd 101 13/06/15 9:01 am

 A full arrow is used Hydrogen chloride gas dissolves in water to form hydrochloric acid.
to show that the All acids produce
dissociation is H+(aq) ions Normally the ‘+(aq)’ is left out of the equation.
complete
H—Cl + (aq) → H+(aq) + Cl (aq)
– The equation on the left can be simplified to:

Covalently Added Hydrochloric acid forms

HCl → H+ + Cl−
bonded to water salts called chlorides as
hydrogen this is the anion which All of the HCl molecules in solution dissociate into ions. This makes
chloride remains in solution hydrochloric acid a strong acid as it dissociates completely.
Hydrochloric acid is described as a strong monoprotic acid as 1 mol of
hydrogen chloride produces 1 mol of H+(aq).
H O O Sulfuric acid is H2SO4. It has the structure:
acidic hydrogen
atoms S H2SO4 → 2H+ + SO42−
H O O
Sulfuric acid dissolves in water and dissociates completely (or ionises
completely).
This makes sulfuric acid a strong acid as it ionises (or dissociates)
completely.
Sulfuric acid is described as a strong diprotic acid as 1 mol of sulfuric acid
produces 2 mol of hydrogen ions (protons).

Weak acids
The most common weak acid is ethanoic acid (CH3COOH). Most
carboxylic acids are weak acids.
Weak acids are usually covalent molecules which dissolve in water and
dissociate (or ionise) slightly.
Acidic hydrogen atoms in a molecule are the hydrogen atoms which will
produce H+(aq) or protons when the acid dissolves in water.
The acidic hydrogen atoms are often bonded to electronegative atoms such
as oxygen, fluorine and chlorine. In ethanoic acid the acidic hydrogen atom
is the one bonded to the oxygen atom. The other hydrogen atoms bonded
6    ACIDS AND BASES

to carbon are not acidic hydrogen atoms.

The structure of ethanoic acid is:

A reversible arrow All acids produce

is used to show H+(aq) ions
that the dissociation
is not complete
H CH3COOH(aq) + (aq) H+(aq) + CH3COO–(aq)
O
H C C Covalently Added to Ethanoic acid forms salts
102 OH acidic hydrogen atom bonded water called ethanoates as this
H ethanoic is the anion which is
acid present in the solution

807701_C06_AQA_Chemistry_2_100-134.indd 102 13/06/15 9:01 am

 Normally the ‘+(aq)’ is left out of the equation.

Brønsted-Lowry theory of acids and bases

The above equation can be simplified to:
CH3COOH ⇋ H+ + CH3COO−
Only some of the CH3COOH molecules in solution dissociate into ions.
This makes ethanoic acid a weak acid as it dissociates slightly.
Ethanoic acid is described as a weak monoprotic acid as 1 mol of ethanoic
acid could produce 1 mol of H+(aq) if it dissociated completely.

Bases and alkalis

Any substance that reacts with an acid and accepts a proton from the acid is
classified as a base.
An alkali is any substance which produces hydroxide ions, OH− (aq), when
they are in aqueous solution.
All alkalis are bases but not all bases are alkalis.
Some substance can act as a base but they are not soluble in water and so
do not produce hydroxide ions, OH− (aq) in aqueous solution.
For example copper(ii) oxide acts as a base when it reacts with acid. The
acid donates protons to the oxide ion to form water.
O2− + 2H+ → H2O
In this way the oxide ion, O2−, in the copper(ii) oxide can act as a base as
it accepts protons. However, copper(ii) oxide does not dissolve in water
and so does not produce hydroxide ions, OH−(aq), in aqueous solution.
Copper(ii) oxide is a base but it is not an alkali.
Sodium hydroxide acts as a base when the hydroxide ion reacts with acid
and accepts a proton to produce water:
H+(aq) + OH−aq) → H2O(l)
Sodium hydroxide also dissolves in water and produces aqueous hydroxide
Bases
ions, OH−(aq). Sodium hydroxide is also an alkali.
CuO
MgO Strong bases
Alkalis
KOH A strong base is completely dissociated in aqueous solution.
NH3 Ca(OH)2
Fe2O3
NaOH
The strong bases most commonly used are sodium hydroxide and
potassium hydroxide.
Figure 6.1 This diagram shows the Strong bases are usually ionic compounds which dissolve in water and
distinction between the terms base and dissociate (or ionise) completely.
alkali. As all alkalis are bases, we will
use the term base for all substances Strong bases produce hydroxide ions OH−(aq) if the base dissolves in water. 103
discussed in this unit.
A full arrow is used When a base dissolves
to show that the in water it produces
–
dissociation is hydroxide ions, OH (aq)
complete
NaOH(s) + (aq) → Na+(aq) + OH–(aq)

Sodium Added to Sodium hydroxide forms

hydroxide water sodium salts as this is the
cation which is present in
the solution

807701_C06_AQA_Chemistry_2_100-134.indd 103 13/06/15 9:01 am

 Normally the ‘+(aq)’ is left out of the equation.
The above equation can be simplified to:
NaOH → Na+ + OH−
All of the NaOH added to water dissociates into ions. This makes sodium
hydroxide a strong base as it dissociates completely.

Weak bases
A weak base is slightly dissociated in aqueous solution.
The weak base most commonly used is ammonia.
Weak bases are often covalent substances which dissolve in water and
dissociate (or ionise) slightly.
Weak bases produce hydroxide ions OH−(aq) if the base dissolves in water.

A reversible arrow When a base dissolves

is used to show in water it produces
that the dissociation hydroxide ions, OH–(aq)
is slightly complete
NH3(g) + H2O(I) NH+4 (aq) + OH–(aq)

Ammonia Added to Ammonia forms

water ammonium salts as this
Figure 6.2 Have you ever found hair is the cation which is
present in the solution
blocking the plug hole and water pipes?
Pouring sodium hydroxide drain cleaner
down the drain will help. This strong The ‘+ H2O(l)’ is required in this equation as it is the source of hydroxide
base will hydrolyse the proteins in hair ions, OH−(aq).
and help unblock clogged pipes.
The state symbols may be left out of the equation to simplify it:
NH3 + H2O ⇋ NH4+ + OH−
Only some of the NH3 added to water dissociates into ions. This makes
ammonia a weak base as it dissociates (or ionises) slightly.

Equations for acid dissociation

6    ACIDS AND BASES

The equations for acid dissociation may be written including water.

The simplified equation for the dissociation of hydrochloric acid is given as:
HCl → H+ + Cl−
This can be rewritten including water as:
HCl + H2O → H3O+ + Cl−

104 H3O+ is the hydronium ion or hydroxonium ion or oxonium ion. It is

the ion formed when acids react with water. All three names are used
hydronium would be the most common.
This better represents the acid–base reaction as it shows the acid donating a
proton to the water and water accepting a proton and acting as a base.
However, for the majority of calculations involving acids, the simplified
equation is used.

807701_C06_AQA_Chemistry_2_100-134.indd 104 13/06/15 9:01 am

 For ethanoic acid the simplified equation is given as:

pH
CH3COOH ⇋ CH3COO− + H+
and the equation for the reaction with water is:
CH3COOH + H2O ⇋ CH3COO− + H3O+
Again the simplified equation is perfectly suitable for calculations involving
weak acids like ethanoic acid.

Identifying Brønsted-Lowry acids and bases

The English chemist Thomas Lowry and the Danish chemist Johannes
Brønsted both independently proposed the same definitions for acids and
bases in 1923. This is usually referred to as the Brønsted-Lowry theory of
acids and bases.
It is important to be able to identify Brønsted-Lowry acids and bases in a
reaction.
The Brønsted-Lowry acid is the proton donor and the Brønsted-Lowry base
the proton acceptor in the reaction.
This best applies to reversible reactions in which one molecule or ion
donates a proton and one molecule or ion accepts a proton.

EXAMPLE 1
In the following reaction:
NH3 + H2O ⇌ NH+4 + OH−
NH3 accepts a proton to become NH+4.
NH3 acts as a Brønsted-Lowry base.
H2O donates a proton.
H2O acts as a Brønsted-Lowry acid.

EXAMPLE 2
In the following reaction:
TIP
Water can act as both a CH3COOH + H2O ⇋ CH3COO− + H3O+
Brønsted-Lowry acid and base. H2O accepts a proton to become H3O+.
Other species can do this as well
such as the hydrogenphosphate H2O acts as a Brønsted-Lowry base.
ion, HPO42−, dihydrogenphosphate CH3COOH donates a proton.
ion, H2PO4− and the 105
hydrogencarbonate ion, HCO3−. CH3COOH acts as a Brønsted-Lowry acid.

●● pH
pH (always written with a small p and a capital H) is a logarithmic scale
which gives a measure of the H+ concentration, in mol dm−3, in a solution.
The H in pH relates to the hydrogen.
Neutral solutions have a pH value of 7.00 at 25°C.

807701_C06_AQA_Chemistry_2_100-134.indd 105 13/06/15 9:01 am

 Acidic solutions have a pH of less than 7.00 and alkaline solutions have a
pH of greater than 7.00.
An alkali is a soluble base and when bases dissociate in solution they are
called alkalis.

Calculating pH from [H+]

The following expression is used to calculate pH from the concentration of
hydrogen ions.
pH = −log10[H+]
● In this expression, [H+] represents the concentration of H+ ions in
solution measured in mol dm−3.
● Log10 is often written log so pH = −log[H+] is common. The square
brackets are essential to indicate the concentration of the hydrogen ions.
Figure 6.3 Dipsticks as shown in the To calculate the hydrogen ion concentration from the pH, reverse the
photo above are used by doctors to
calculation:
measure the pH of urine. Urine pH
normally ranges between 2.5 and 8. [H+] = 10(−pH)
High acidity can indicate diabetes and
high alkalinity can indicate urinary tract The H in pH relates to the hydrogen ion concentration but the origin of
infections or kidney stones. the p is disputed. The term was first used by Sørenson in the Carlsberg
Laboratory in 1909 and was supposed to mean ‘power’ of hydrogen which
would relate to the logarithmic scale. However it has also been called
TIP ‘potential of hydrogen’. For our purposes, pH means −log10[H+].
log10 is the standard log button
on your calculator. Shift log will pH of strong acids
access the antilog function which The diagram below shows the links between concentration of the acid,
may appear as 10x. Try a few [acid], concentration of hydrogen ions, [H+], and pH for a strong acid.
calculations to make sure you
can convert from [H+] to pH and Monoprotic acids like hydrochloric acid and nitric acid have a proticity of 1,
from pH to [H+]. A [H+] of 0.0100 whereas diprotic acid like sulfuric acid have a proticity of 2.
mol dm−3 will give a pH of 2.00.
× proticity of acid pH = –log10[H+]
A pH of 4.50 will give a [H+] of
[Acid] [H+] pH
3.16 × 10−5 mol dm−3.
÷ proticity of acid [H+] = 10(–pH)
6    ACIDS AND BASES

EXAMPLE 3
Calculate the pH of 0.0500 mol dm−3 hydrochloric acid.

Answer
For strong monobasic acids, the proticity is 1 so
[H+] = 1 × [acid]
106
HCl → H+ + Cl−
If [HCl] = 0.0500 mol dm−3, then [H+] = 0.0500 mol dm−3
pH = −log10[H+] = −log(0.05)
  = 1.30 (to 2 decimal places)

807701_C06_AQA_Chemistry_2_100-134.indd 106 13/06/15 9:01 am

 pH
EXAMPLE 4
Calculate the pH of 1.00 mol dm−3 sulfuric acid.

Answer
For strong diprotic acids, the proticity is 2 so [H+] = 2 × [acid]
H2SO4 → 2H+ + SO2−
4

If [H2SO4] = 1.00 mol dm−3 then [H+] = 2.00 mol dm−3

pH = −log[H+] = −log(2.00)
= −0.30 (to 2 decimal places)

TIP
pH values are normally given between 0 and 14, but values below 0 are
possible for very high [H+]. Values above 14 are also possible for very high
hydroxide ion concentrations [OH−]. pH values are almost always quoted
to 2 decimal places.

Figure 6.4 When universal indicator is added to a solution,

it changes colour depending on the solution’s pH. The tubes
contain solutions of pH 0 to 14 from left to right.

Determining concentration of an acid from its pH

If you are given the pH of a strong acid you can calculate the concentration
of the hydrogen ions and so the concentration of the acid.

107
EXAMPLE 5
Determine the concentration, in mol dm−3, of nitric acid which has a pH of
0.71. Give your answer to 3 significant figures.

Answer
[H+] = 10(−pH) = 10(−0.71) = 0.1950 mol dm−3 (to 4 significant figures)

Nitric acid (HNO3) is a strong monobasic acid so the [acid] = [H+]

The concentration of nitric acid = 0.195 mol dm−3 (to 3 significant figures).

807701_C06_AQA_Chemistry_2_100-134.indd 107 13/06/15 9:02 am

 EXAMPLE 6
Determine the concentration of sulfuric acid which has a pH of 1.00.

Answer
[H+] = 10(−pH) = 10(−1.00) = 0.100 mol dm−3

Sulfuric acid (H2SO4) is a strong diprotic acid so the [acid]

[H+ ]
=
2
0.100
= = 0.0500 mol dm−3
2
The concentration of this sulfuric acid = 0.0500 mol dm−3.

TEST YOURSELF 2
1 Write an expression for pH. values. Give your answers to 3 significant
2 Calculate the pH of the following acidic solutions. figures.
Give your answer to all questions to 2 decimal places. a) hydrochloric acid of pH 1.80
a) 0.0240 mol dm −3 hydrochloric acid b) nitric acid of pH 0.50
b) 0.0170 mol dm −3 nitric acid c) sulfuric acid of pH −0.10
c) 0.0140 mol dm −3 sulfuric acid 4 Calculate the concentration, in mol dm −3, of a
3 Calculate the concentration of the acid solution of hydrochloric acid which has the same
solution which gives a pH of the following pH as a solution of 0.185 mol dm −3 sulfuric acid.

●● Ionic product of pure water

Water slightly dissociates into hydrogen ions and hydroxide ions according
to the equilibrium.
H2O ⇋ H+ + OH−
Kw is the ionic product of water and Kw = [H+][OH−].
6    ACIDS AND BASES

The units of Kw are always mol2 dm−6.

At 25 °C, Kw = 1.00 × 10−14 mol2 dm−6.

Calculating the pH of pure water

In pure water [H+] = [OH−] so Kw = [H+]2.
[H+] = K w and pH = −log10[H+]

108 The pH of pure water can be calculated from the value of Kw.

EXAMPLE 7
Calculate the pH of water at 25 °C when In water [H+] = [OH−] so Kw = [H+]2
Kw = 1.00 × 10−14 mol2 dm−6.
[H+]2 = 1.00 × 10−14 mol2 dm−6
Answer [H+] = 100 × 10−14 = 1.00 × 10−7 mol dm−3.
At 25 °C, Kw = 1.00 × 10−14 mol2 dm−6. pH = −log10[H+] = −log10(1.00 × 10−7) = 7.00
Kw = [H+][OH−] The pH of pure water at 25 °C is 7.00.

807701_C06_AQA_Chemistry_2_100-134.indd 108 13/06/15 9:02 am

 Ionic product of pure water
EXAMPLE 8
At 40 °C, Kw = 2.92 × 10−14 mol2 dm−6.

Calculate the pH of water at 40 °C. Give your answer to 2 decimal places.

Answer
At 40 °C Kw = 2.92 × 10−14 = [H+]2

[H+] = 2.92 × 10−14 = 1.709 × 10−7 mol dm−3 (to 4 significant figures)
pH = −log10[H+] = −log10(1.709 × 10−7) = 6.7673 (to 4 decimal places)
pH = 6.77 to 2 decimal places

We have become accustomed to think that the pH of pure water is 7, but

this is only true at 25 °C. As temperature increases above 25 °C, the pH
of water drops below 7. The increase in Kw as temperature increases also
indicates that the dissociation of water into H+ and OH− ions is endothermic
as the equilibrium is moving from left to right (more H+) as temperature
increases.
Mineral water gets its name from the dissolved mineral rocks that it
contains. Mineral water from limestone rocks contains calcium hydrogen
carbonate and as a result the pH is around 8.00.
TIP
Water at 40 °C is not acidic (even Calculating Kw from the pH of pure water
though it has a pH of 6.77) as the
The pH of pure water at a certain temperature can be used to calculate [H+].
concentration of [H+] = [OH−].
In pure water [H+] = [OH−] and so Kw = [H+]2.

EXAMPLE 9
The pH of pure water at 60 °C is 6.52. Calculate the value of Kw at 60 °C.
Give your answer to 3 significant figures.

Answer
[H+] = 10(−pH) = 10(−6.52) = 3.020 × 10−7 mol dm−3 (to 4 significant figures)
Kw = [H+]2 = (3.020 × 10−7)2 = 9.12 × 10−14 mol2 dm−6

pH of strong bases
When a soluble base dissolves in water, hydroxide ions are present in the
solution.
The concentration of the hydroxide ions, [OH−] can be converted to the 109
[H+] using Kw as at 25 °C Kw = 1.00 × 10−14 mol2 dm−6.
In pure water [H+] = [OH−] but this is not true in acid or alkaline solutions.
Kw and [OH−] can be used to calculate [H+], which is then used to
determine pH.
The diagram below shows the links between concentration of the strong
bases, [base], concentration of hydroxide ions, [OH−], concentration of
hydrogen ions, [H+], and pH for a strong base.

807701_C06_AQA_Chemistry_2_100-134.indd 109 13/06/15 9:02 am

 × number of moles
of OH– produced
by 1 mole of the Kw
[H+] = ——–
base in solution [OH–] pH = –log10[H+]
[Base] [OH–] [H+] pH
÷ number of moles Kw [H+] = 10(–pH)
[OH–] = ——–
of OH– produced [H+]
by 1 mole of the
base in solution

Calculating pH of a strong bases

For strong bases, the concentration of OH− is equal to the concentration of
the base × the number of hydroxide ions produced in solution.

EXAMPLE 10
Calculate the pH of a 0.250 mol dm−3 solution of sodium hydroxide
(Kw = 1.00 × 10 −14 mol2 dm−6). Give your answer to 2 decimal places.

Answer
Sodium hydroxide is a strong base and so dissociates fully in solution.

NaOH → Na+ + OH−

Also 1 mol of sodium hydroxide contains 1 mol of OH− ions.
[NaOH] = 0.250 mol dm−3 so [OH−] = 0.250 mol dm−3
Kw 1.00 × 10−14
[H+] = = so [H+] = 4.00 × 10−14 mol dm−3
[OH−] 0.250
pH = −log10(4.00 × 10−14) = 13.3979 (to 4 decimal places)
pH = 13.40 (to 2 decimal places)

The majority of strong bases (alkalis) you will encounter will have 1 mol of
OH− ions per mole of the base. However, sometimes a question is set on a
Group 2 hydroxide where you are asked to assume that the base is strong
and so the number of moles of OH− per mole of base for Ca(OH)2 is 2.
6    ACIDS AND BASES

Sometimes the pH calculation may be at temperature other than 25 °C and

the Kw value at this temperature is given. The method is exactly the same
using the Kw value.

EXAMPLE 11
At 50 °C, Kw = 5.48 × 10−14 mol2 dm−6. Calculate the pH of 0.175 mol dm−3
potassium hydroxide solution at 50 °C.

110 Answer
Potassium hydroxide is a strong base and so dissociates fully in solution.
KOH → K+ + OH−
Also 1 mol of potassium hydroxide contains 1 mol of OH− ions.
[KOH] = 0.175 mol dm−3 so [OH−] = 0.175 mol dm−3
K 5.48 × 10−14
[H+] = w− = = so [H+] = 3.131 × 10−13 mol dm−3
[OH ] 0.175
pH = −log10(3.131 × 10−13) = 12.5043 (to 4 decimal places)
pH = 12.50 (to 2 decimal places)

807701_C06_AQA_Chemistry_2_100-134.indd 110 13/06/15 9:02 am

 Calculating the concentration of a base from its pH

Ionic product of pure water

The concentration of hydrogen ions can be calculated from pH.
The [OH−] can be calculated from [H+] using Kw.
The concentration of the base can be calculated from the concentration of
hydroxide ions.

TIP EXAMPLE 12
Concentration may be in units Calculate the concentration of potassium hydroxide solution in mol dm−3
of g dm−3 or mg dm−3 rather than with a pH of 13.70 at 25 °C. Kw = 1.00 × 10−14 mol2 dm−6 at 25 °C. Give your
mol dm−3. To convert between answer to 2 decimal places.
mol dm−3 and g dm−3, simply
multiply by the Mr. To convert Answer
between mol dm−3 and mg dm−3,
[H+] = 10(−pH) = 10(−13.70) = 1.995 × 10−14 mol dm−3 (to 4 significant figures)
multiply by the Mr of the base and
multiply by 1000 to convert mass Kw 1.00 × 10−14
[OH−] = =
in g to mass in mg. [H+] 1.995 × 10−14
−3
= 0.5013 mol dm (to 4 significant figures)
Potassium hydroxide (KOH) has 1 mol of OH− ions per mole of base so the
concentration of KOH, [KOH] = 0.5013 mol dm−3.
Concentration of KOH solution = 0501 mol dm−3 (to 3 significant figures)

Calculating a value for Kw

In some calculations the pH of a solution of a base is given with its
concentration at a particular temperature.
[H+] may be calculated from the pH, [OH−] may be calculated from the
concentration.

EXAMPLE 13
At 40 °C, a 0.270 mol dm−3 solution of sodium hydroxide has a pH of 12.98.
Calculate the value for Kw at 40 °C. Give your answer to 3 significant
figures.

Answer
Using pH to calculate [H+]

[H+] = 10(−12.98) = 1.047 × 10−13 mol dm−3 (to 4 significant figures)

As NaOH contains 1 mol of OH− per mole of NaOH
[OH−] = [NaOH] = 0.270 mol dm−3 111

Kw = [H+][OH−] = (1.047 × 10−13) × 0.270 = 2.83 × 10−14 mol2 dm−6

pKw, pH and pOH

TIP pKw may be used in place of Kw to carry out calculations involving strong bases.
Remember pKw = −log10Kw is
used, but −logKw is equally pKw = −log10Kw
acceptable without the log base
number. pKw = 14.00 at 25 °C.

807701_C06_AQA_Chemistry_2_100-134.indd 111 13/06/15 9:02 am

 pOH = −log10[OH−]
pH + pOH = pKw
This is an alternative way to use Kw values. The pOH is calculated from the
hydroxide ions concentration. The total of pH and pOH is equal to pKw.

EXAMPLE 14
Calculate the pH of a 2.00 g dm−3 solution of sodium hydroxide, NaOH,
given that pKw = 14.00 at 25 °C. Give your answer to 2 decimal places.

Answer
Mr of NaOH = 40.0
2.00
Concentration of NaOH solution = = 0.0500 mol dm−3
40.0
[OH−] = 0.050 mol dm−3 as NaOH contains 1 mol of OH− per mole of NaOH
pOH = −log[OH−] = −log(0.0500) = 1.3010 (to 4 decimal places)
pKw = 14.00 = pOH + pH
pH = 14.00 − 1.3010 = 12.699
The pH of a 2.00 g dm−3 solution of sodium hydroxide is 12.70 (to 2 decimal
places).

TEST YOURSELF 3
1 Write an expression for the ionic product of water, Kw.
2 At 15 °C, Kw = 4.65 × 10 −13 mol2 dm−6.
a) Calculate the pH of pure water at 15 °C. Give your answer to
2 decimal places.
b) Calculate the pH of a solution of 0.170 mol dm−3 potassium
hydroxide at 15 °C. Give your answers to 2 decimal places.
3 The pH of water at 45 °C is 6.70. Calculate the value of Kw at 45 °C.
6    ACIDS AND BASES

Give your answer to 3 significant figures.

4 The pH of a solution of sodium hydroxide is 13.68 at 25 °C. K w
at 25 °C is 1.00 × 10 −14 mol 2 dm −6. Calculate the concentration of
the solution of sodium hydroxide at 25 °C. Give your answer to 3
significant figures.

●● pH of weak acids
112 Weak acids are slightly dissociated in solution. This is represented using a
reversible arrow (⇋).

Ka
The equilibrium constant for the acid dissociation is represented by Ka.
For a general acid dissociation

HA ⇋ H+ + A−
[A−][H+]
Ka =
[HA]

807701_C06_AQA_Chemistry_2_100-134.indd 112 13/06/15 9:02 am

 For example:

pH of weak acids
CH3COOH ⇋ H+ + CH3COO−
[CH3COO−] [H+]
Ka =
[CH3COOH]
Ka always has units of mol dm−3.
HA is the undissociated acid. Remember that the undissociated acid does
not cause it to be acidic. It is the concentration of H+ that causes acidity
Figure 6.5 The oceans have absorbed when the acid dissociates. HA is not acidic until it dissociates.
about half of the carbon dioxide produced
by burning fossil fuels since 1800. As
The value of Ka gives a measure of the strength of the acid. A higher Ka
carbon dioxide in the ocean increases, value indicates a ‘stronger’ weak acid. For example ethanoic acid has a Ka
ocean pH decreases. This is called ocean value of 1.74 × 10−5 mol dm−3 whereas hydrocyanic acid has a Ka of 4.90 ×
acidification. With ocean acidification, 10−10 mol dm−3.
corals cannot absorb the calcium
carbonate they need to maintain their For a weak acid, [H+] is calculated from the concentration of the acid and
skeletons and the stony skeletons that the Ka value.
support corals and reefs will dissolve.
For a weak acid of concentration 1.00 mol dm−3, the following equilibrium
applies:

TIP HA ⇋ H+ + A−
It is important to be able to write Initial Concentration/mol dm−3: 1.00 0 0
Ka expressions for weak acids. It
is always the [anion] and [H+] on
the top and [undissociated acid]
Equilibrium Concentration/mol dm−3: 1.00 − x x x
on the bottom. [A−][H+] x2
Ka = =
[HA] 100 − x
But as this is a weak acid, the concentration of the acid at equilibrium
(1 − x) will be approximately equal to the initial concentration of the weak
acid (1 mol dm−3) as x is very small compared to the initial concentration.
x2
Ka = so in this example Ka = [H+]2
1.00
In general
[H+]2
Ka =    so [H+]2 = Ka × [weak acid]
[weak acid]
and

[H+] = √Ka × [weak acid]

pH is then calculated using pH = −log10[H+].

To determine the concentration of a weak acid from its pH 113

and Ka value
[H+] is determined from pH in the usual way and then the concentration of
[H+]2
the weak acid is calculated using .
Ka

807701_C06_AQA_Chemistry_2_100-134.indd 113 13/06/15 9:02 am

 The overall process is described in the diagram below. [weak acid] = the
concentration of the weak acid.

[H+] = √ Ka × [weak acid] pH = –log10[H+]

[Weak acid] [H+] pH
[H+]2 [H +] = 10(–pH)
[Weak acid] = ——–
Ka

pKa
The pKa of a weak acid may be given in place of its Ka. pKa = −log10Ka.
To convert between a pKa value and Ka, use the following: Ka = 10−pKa.
The higher the pKa value, the weaker the acid.
A lower pKa indicates a less weak acid.

Calculating the pH of a weak acid

EXAMPLE 15
TIP The Ka for ethanoic acid (CH3COOH) is 1.74 × 10−5 mol dm−3. Calculate the
The use of unusual units in these pH of a 0.105 mol dm−3 solution of ethanoic acid. Give the answer to 2
types of calculations is common. decimal places.
Remember that there are 1000
(103) mg in 1 g and 1 000 000 Answer
(106) μg in 1 g. The same applies [H+] = Ka × [weak acid] = 1.74 × 10−5 × 0.105 = 1.872 × 10−6
to volume units: 1000 (103) ml
in 1 litre and 1 000 000 (106) μl in = 1.352 × 10−3 mol dm−3 (to 4 significant figures)
1 litre. 1 cm3 = 1 ml and 1 dm3 = pH = −log10[H+] = −log10(1.352 × 10−3) = 2.8691 (to 4 decimal places)
1 litre. These questions can be
awkward as mistakes can be pH = 2.87 (to 2 decimal places)
made when converting between
units but as long as you know the
units, it makes it easier. Calculating the concentration of a weak acid
from its pH
6    ACIDS AND BASES

EXAMPLE 16
[H+]2 (3.162 × 10−3)2
Determine the concentration, in mg dm−3, of a solution [weak acid] = =
of propanoic acid (CH3CH2COOH) with a pKa value of Ka 1.288 × 10−3
2.89 with a pH of 2.50. [weak acid] = 7.76 × 10 mol dm−3 (to 3 significant figures)
−3

Mr of propanoic acid (CH3CH2COOH) = 74.0

Answer
Ka = 10(−pKa) = 10(−2.89) = 1.288 × 10−3 mol dm−3 [weak acid] = 7.76 × 10−3 × 74.0 = 0.574 g dm−3
114 (to 4 significant figures) [weak acid] = 0.574 × 1000 = 574 mg dm−3
[H+] = 10(−pH) = 10(−2.50) = 3.162 × 10−3 mol dm−3

807701_C06_AQA_Chemistry_2_100-134.indd 114 13/06/15 9:02 am

 Calculating the Ka from the pH of a weak acid and its
concentration

Dilutions and neutralisations

+ 2
For a weak acid, HA, Ka = [H ]
[HA]
If the pH of a weak acid is known, [H+] can be calculated using 10(−pH).
A value for Ka can be calculated from the concentration of the weak acid,
[HA] and the concentration of hydrogen ions, [H+].

EXAMPLE 17
A weak acid, HA, of concentration 0.0120 mol dm−3 has a pH of 4.10.
Calculate a value for the acid dissociation constant, Ka, for the weak acid.

Answer
[H+] = 10(−pH) = 10(−4.10) = 7.943 × 10−5 mol dm−3
[HA] = 0.0120 mol dm−3
Ka = [H+]2
[HA]
(7.943 × 10−5)2 = 6.309 × 10−9 = 5.26 × 10−7 mol dm−3
Ka =
0.0120 0.0120

TEST YOURSELF 4
1 Write an equation for the acid dissociation of the 4 Calculate the concentration of the solution of a
weak acid ethanoic acid, CH3COOH. monoprotic weak acid when it has a pH of 2.80
2 Write an expression for the acid dissociation and a pKa of 3.10. Give your answer to 3 significant
constant, Ka, for ethanoic acid (CH3COOH). figures.
3 Calculate the pH of a 0.270 mol dm−3 solution of 5 Calculate the pH of a 0.0540 mol dm−3 solution of
ethanoic acid. Ka for ethanoic acid at 25 °C is 1.74 × a weak acid, HX, which has an acid dissociation
10−5 mol dm−3. Give your answer to 2 decimal constant, Ka, = 1.54 × 10 −4 mol dm−3. Give your
places. answer to 2 decimal places.

●● Dilutions and neutralisations

When an acid or base is neutralised or diluted, the concentrations of the
ions in solution change. It is important to be able to calculate the new
concentration of H+ or OH− and then determine pH of the new solution.
The total volume must be taken into account to determine the new
concentration in mol dm−3.
115
Dilutions
When a solution of an acid or a base is diluted, the concentration of the
ions in the solution changes. As the concentration of the ions in solution
changes, this changes the pH.
The new concentration of a solution may be calculated by dividing the
amount of solute, in moles, in the solution by the new total volume and
multiplying by 1000.

New concentration of solution = amount in moles of solute × 1000

new total volume of solution

807701_C06_AQA_Chemistry_2_100-134.indd 115 13/06/15 9:02 am

 EXAMPLE 18
20.0 cm3 of a 0.152 mol dm−3 solution of hydrochloric acid is placed in a
250 cm3 volumetric flask and the volume made up to 250 cm3 using deion-
ised water. Determine the pH of the resulting solution.

Answer
Moles of HCl added = 20.0 × 0.152 = 3.04 × 10−3 mol
1000
New volume = 250 cm 3

3.04 × 10−3
Figure 6.6 The pH of a solution can be New concentration of solution = × 1000 = 0.01216 mol dm−3
250
accurately measured using a digital pH
meter. The pH of this solution is 8.09. As HCl is a strong monoprotic acid, [H+] = 0.01216 mol dm−3
pH = −log(0.01216) = 1.92 (to 2 decimal places)

EXAMPLE 19
10.0 cm3 of a 1.54 mol dm−3 solution of potassium hydroxide is diluted to
2.00 dm3 in a volumetric flask. Determine the pH of the resulting solution
at 25 °C if pKw = 14.0 at 25 °C. Give your answer to 2 decimal places.

Answer
Moles of KOH added = 10.0 × 1.54 = 0.0154 mol
1000
New volume = 2.00 dm (2000 cm3)
3

0.0154
Concentration of new solution = × 1000 = 0.00770 mol dm−3
2000
As 1 mol of KOH contains 1 mol of OH−, [OH−] = 0.00770 mol dm−3
pOH = −log[OH-] pOH = −log (0.00770) = 2.114 (to 4 decimal places)
pKw = 14 = pH + pOH
pH = 14.0 − 2.114 = 11.886
6    ACIDS AND BASES

pH = 11.89 (to 2 decimal places)

EXAMPLE 20
Calculate the pH of the solution formed when 15.0 cm3 of 0.114 mol dm−3
sulfuric acid are added to 485 cm3 of deionised water. Give your answer to
2 decimal places.

Answer
116 15.0 × 0.114
Moles of H2SO4 =
1000
= 1.71 × 10−3 mol
New volume = 15 + 485 = 500 cm3
−3
TIP Concentration of new solution = 1.71 × 10 = ×1000 = 3.42 × 10−3 mol dm−3
500
In this example the total volume H2SO4 is a diprotic acid so [H+] = 3.42 × 10−3 × 2 = 6.48 × 10−3 mol dm−3
of the solution is not given but it
can be calculated from the two pH = −log10[H+] = −log10(6.48 × 10−3) = 2.1649 (to 4 decimal places)
volumes (15.0 + 485 = 500 cm3). pH = 2.16

807701_C06_AQA_Chemistry_2_100-134.indd 116 13/06/15 9:02 am

 Calculating the new concentration using dilution factors

Dilutions and neutralisations

You may also determine the dilution factor to calculate the new
concentration of acid or base. In example 18 the dilution factor is 12.5. The
volume of solution initially was 20.0 cm3 and the final volume was 250 cm3.
total volume after dilution
Dilution factor = initial volume added
as long as the units of volume are
the same.
The diluted solution is 12.5 times less concentrated than the original
solution
0.152
Concentration of the diluted solution = = 0.01216 mol dm−3.
12.5

The dilution factor in Example 19 is 200

10( ), so the diluted solution of
2000

KOH is 200 times more dilute than the original solution.

1.54
Concentration of the diluted solution = = 0.00770 mol dm−3
200
The remainder of the calculation is carried out as per the examples.

Calculating the volume in a dilution

Some calculations on dilutions may focus on determining the new total
volume of the solution or the volume of water added when carrying out the
dilution.
The pH of the solution would be given and [H+] can be calculated from this
value.
The concentration of the new solution can be determined from [H+] and the
dilution factor or new total volume of the solution calculated as shown.

TIP EXAMPLE 21
You can reverse the calculation 32.0 cm3 of 0.0420 mol dm−3 hydrochloric acid were diluted. The pH of the
to check that you get 2.10 for the resulting solution was 2.10. Calculate the total volume of the solution
pH of the new solution formed. formed. Give your answer to 3 significant figures and state the units.
As the volume was given to 3
significant figures the pH may Answer
not be exactly 2.10 but it should In this example the pH is first used to calculate [H+].
be very close. In this case using
169 cm3 gives a pH of 2.099 or As hydrochloric acid is a monoprotic acid, [HCl] = [H+]
2.10 to 2 decimal places. [H+] = 10(−pH) = 10(−2.10) = 7.943 × 10−3 mol dm−3 (to 4 significant figures)
The new concentration of HCl after dilution = 7.943 × 10−3 mol dm−3
32.0 × 0.0420
Initial moles of HCl added = = 1.344 × 10−3 mol
TIP 1000
1.344 × 10−3 117
The volume of water added may New concentration of HCl after dilution = 7.943 × 10−3 = × 1000
V
be calculated by subtracting the where V represents the new total volume of solution in cm3.
initial volume of solution used
from the final volume calculated, Rearranging the expression to calculate V,
in this example 169.21 − 32.0 = V= 1.344 × 10−3
× 1000 = 169 cm3 (to 3 significant figures)
137.21 cm3. 7.943 × 10−3

807701_C06_AQA_Chemistry_2_100-134.indd 117 13/06/15 9:02 am

 Neutralisations
In a neutralisation question, a volume of a certain concentration of a
strong acid is added to a volume of a certain concentration of a strong base.
Either the base or the acid may be in excess.
It is the amount, in moles of the acid or base in excess together with
the new total volume of the solution which is used to calculate the new
concentration of either the acid or the base.

MATHS MATHS
Rearranging an expression The units of volume are important as there are several that could be
to change the subject is an used. It is a good idea to always put appropriate units after a number,
important skill. If you are unsure even mol after an amount, in moles.
that you have done it correctly,
substitute in simple values such
as different whole numbers to
see what the subject equals EXAMPLE 22
before rearrangement. Then 25.0 cm3 of 0.214 mol dm−3 sodium hydroxide solution is added to 25.0 cm3
use this with other values to see of 0.258 mol dm−3 hydrochloric acid. Calculate the pH of the resulting
if you obtain the value for the solution. Give your answer to 2 decimal places.
new subject when you use your
rearranged expression. Answer
This style of question is all about the number of moles of a reactant which
are left over.
NaOH + HCl → NaCl + H2O
NaOH and HCl react in a 1:1 ratio.
25.0 × 0.214
Initial moles of NaOH = = 0.00535 mol
1000
25.0 × 0.258
Initial moles of HCl = = 0.00645 mol
1000
The equation for the neutralisation is:
6    ACIDS AND BASES

NaOH + HCl → NaCl + H2O

TIP 0.00535 mol of NaOH reacts with 0.00535 mol of HCl so
In the reaction the ratio of the
(0.00645 − 0.00535) = 0.00110 mol of HCl remaining.
acid to base is 1 : 1, but if sulfuric
acid is used (it is assumed to be New total volume of solution
completely dissociated) then the = 25.0 + 25.0 = 50 cm3
ratio of a base to sulfuric acid is
New concentration of reactant in excess
often 2 : 1.
moles of reactant in excess
= × 1000
new total volume of solution
118
New concentration of reactant (HCl) in excess
0.00110
= × 1000 = 0.0220 mol dm−3
50.0
As HCl is strong monobasic acid, [H+] = 0.0220 mol dm−3
pH = −log10[H+] = −log10(0.0220) = 1.66 (to 2 decimal places)

807701_C06_AQA_Chemistry_2_100-134.indd 118 13/06/15 9:02 am

 Dilutions and neutralisations
EXAMPLE 23
Close to the end point of a titration 24.9 cm3 of 1.00 mol dm−3 potassium
hydroxide solution have been added to 25.0 cm3 of 0.500 mol dm−3 sulfuric
acid. Calculate the pH of the solution formed. Assume that the sulfuric
acid is fully dissociated. Give your answer to 2 decimal places.

Answer
25.0 × 0.500
Initial moles of H2SO4 = = 0.0125 mol
1000
24.9 × 1.00
Initial moles of KOH = = 0.0249 mol
1000
The equation for this neutralisation is:

2KOH + H2SO4 → K2SO4 + 2H2O

From the equation, 2 mol of KOH reacts with 1 mol of H2SO4.
0.0249 mol of KOH reacts with 0.01245 mol of H2SO4. This leaves
(0.0125 − 0.01245) = 5 × 10−5 mol of H2SO4.
If you are unsure above which reactant is used up (limiting reactant) and
which is left over (reactant in excess), follow the method below:
Using the equation for the reaction, write the amount, in moles, you have
been told below the equation in a line called ‘moles you have’.

2KOH + H2SO4  →  K2SO4 + 2H2O

moles you have: 0.0249 0.0125

Using either one of the moles below the reactants, calculate the moles of the
other reactant which is needed to react with that number of moles of the first
reactant. The ratio in the equation is used here. In this example the moles of
KOH is divided by 2 as 2KOH reacts with H2SO4.

2KOH + H2SO4    →  K2SO4 + 2H2O

moles you have: 0.0249 0.0125

moles you need: 0.01245

÷2
For H2SO4, you have more moles than needed so the H2SO4 is in excess and
the KOH is the limiting reactant (it is all used up).
You can now calculate the amount, in moles, of H2SO4 left over
(0.0125 − 0.01245) = 5 × 10−5 mol.
H2SO4 is the reactant in excess.
Moles of H2SO4 in excess = 5 × 10−5 mol
New total volume of solution = 25.0 + 24.9 = 49.9 cm3 119
New concentration of reactant in excess = moles of reactant in excess × 1000
new total volume of solution
5 × 10−5
New concentration of reactant (H2SO4) in excess = × 1000
49.9
= 1.002 × 10−3 mol dm−3 (to 4 significant figures)
[H+] = 2 × [H2SO4] so [H+] = 2 × 1.002 × 10−3 = 2.004 × 10−3 mol dm−3
pH = −log10[H+] = −log10(2.004 × 10−3) = 2.6981 (to 4 decimal places)
pH = 2.70 (to 2 decimal places)

807701_C06_AQA_Chemistry_2_100-134.indd 119 13/06/15 9:02 am

 TIP EXAMPLE 24
A weak acid and a strong base Calculate the pH of the solution
can be used in a neutralisation formed when 20.0 cm3 of TIP
question as long as the strong 0.150 mol dm−3 of aqueous As Kw is given in this
base is in excess. If the weak sodium hydroxide are added neutralisation question, it is likely
acid is in excess, the solution to 10.0 cm3 of 0.180 mol dm−3 that the base (sodium hydroxide)
formed is a buffer. Buffers will be ethanoic acid at 25 °C. At is in excess and so the pH of the
examined later in this topic. 25 °C, Kw has a value of 1.00 × solution will be greater than 7.
10−14 mol2 dm−6. Give your answer
to 2 decimal places.

Answer
Moles of NaOH = 20.0 × 0.150 = 0.00300 mol
1000
Moles of CH3COOH = 10.0 × 0.180 = 0.00180 mol
1000
The equation for the neutralisation is:
NaOH + CH3COOH → CH3COONa + H2O
1 mol of NaOH reacts with 1 mol of CH3COOH
0.00180 mol of CH3COOH reacts with 0.00180 mol of NaOH so
(0.003 − 0.0018) = 0.00120 mol of NaOH remaining.
New total volume of solution = 20.0 + 10.0 = 30.0 cm3
New concentration of reactant in excess = moles of reactant in excess × 1000
new total volume of solution
New concentration of reactant (NaOH) in excess = 0.00120 × 1000 =
30.0
0.0400 mol dm−3
As 1 mol of NaOH contains 1 mol of OH−, [OH−] = 0.0400 mol dm−3
Kw = [H+][OH−]
Kw 1.00 × 10−14
[H+] = − = = 2.50 × 10−13 mol dm−3
[OH ] 0.0400
pH = −log10[H+] = −log10(2.50 × 10−13) = 12.6021 (to 4 decimal places)
pH = 12.60 (to 2 decimal places)
6    ACIDS AND BASES

TEST YOURSELF 5
1 Calculate the pH of the solution formed when 25.0 cm3 of
0.350 mol dm−3 hydrochloric acid is added to 175.0 cm3 of water. Give
your answer to 2 decimal places.
2 Calculate the pH of the solution formed when 20.0 cm3 of
0.120 mol dm−3 aqueous sodium hydroxide solution is added to 150 cm3
120
of water at 25 °C. Kw = 1.00 × 10 −14 mol 2 dm−6 at 25 °C. Give your
answer to 2 decimal places.
3 Calculate the pH of the solution formed when 20.0 cm3 of
0.250 mol dm−3 aqueous hydrochloric acid is added to 15.0 cm3 of
0.300 mol dm−3 aqueous sodium hydroxide. Give your answer to 2
decimal places.
4 Calculate the pH of the solution formed when 17.5 cm3 of
0.100 mol dm−3 aqueous sulfuric acid is added 12.5 cm3 of
0.120 mol dm−3 aqueous potassium hydroxide. Give your answer to 2
decimal places.

807701_C06_AQA_Chemistry_2_100-134.indd 120 13/06/15 9:02 am

 ●● Titration curves

Titration curves
A titration curve is a graph of pH against volume of the base or acid added.
To plot a titration curve, carry out an acid–base titration, adding the base in
5 cm3 portions, and in smaller portions near the end point. Record the pH
after each addition.
A typical curve shows the initial pH of the acid or base and the point when
neutralisation occurs.
The shape of the curve shows the type of titration.
The inflection in a curve is where the curve goes vertically showing a rapid
change in pH.
The inflection in the curve occurs at the equivalence point in a titration.
Most titration curves show a base added to an acid but the reverse is also
possible.

Equivalence points

13 Titration 13 Titration 13 Titration 13 Titration

11 curve 1 11 curve 2 11 curve 3 11 curve 4

9 Strong acid- 9 Weak acid- 9 9

strong base strong base
7 titration 7 titration 7 7
pH

pH

pH

pH
Strong acid- Weak acid-
5 5 5 weak base 5 weak base
titration titration
3 3 3 3
1 1 1 1
0 0 0 0
0 25.0 0 25.0 0 25.0 0 25.0
Volume of base added/cm3 Volume of base added/cm3 Volume of base added/cm3 Volume of base added/cm3

There are four different of titration curves and the equivalence points
(points where there is a rapid change in pH and show a vertical inflection in
the curve) are different.
For titration curve 1 the inflection occurs between pH 3 and pH 10. This is
indicative of a strong acid–strong base titration. The initial pH of the acid is
1 which would suggest a strong acid.
For titration curve 2 the inflection occurs between pH 6 and 10. This is
indicative of a weak acid–strong base titration. The initial pH of the acid is
almost 3 which would suggest a weak acid.
For titration curve 3 the inflection occurs between pH 3 and 8. This is
indicative of a strong acid–weak base titration. The initial pH of the acid is
1 which would suggest a strong acid. 121

For titration curve 4 there is no major inflection. This is indicative of a

weak acid-weak base titration. The initial pH of the acid is between 3 and 4
which would suggest a weak acid.

Understanding titration curves

When examining or choosing a titration curve, the following four features
should be considered.

807701_C06_AQA_Chemistry_2_100-134.indd 121 13/06/15 9:02 am

 Base added to acid or acid added to base.
The initial pH is the main clue to this if the horizontal axis is not labelled. If the
titration curve has an acidic pH below 7 at 0 cm3, the base is being added to the
acid. If the initial pH is greater than 7, the acid is being added to the base.

Initial pH
An initial calculation for the pH of the strong or weak acid – this is the
starting pH for the curve where the volume of base added is equal to 0 cm3.

Shape of the curve

The names of the acid and base used – this will determine the shape of
the titration curve including the length of the inflection at the equivalence
point. The information on the shapes of the curves is important as the
TIP shape of the curve depends on the type (strong or weak) acid or base used
A sketch of a titration curve is in the titration.
just that – a rough sketch of
the shape – so when analysing Volume at which the equivalence point occurs
curves use the (rough) guidelines
as to where the inflection (vertical The concentrations of the acid and base used – the volume at which
section) occurs, i.e. between the equivalence point occurs can be calculated from the volume of base
approximate pH values. required to neutralise the acid.

Key features of a titration curve

In a titration, 0.200 mol dm−3 sodium hydroxide solution is added to
25.0 cm3 of 0.100 mol dm−3 hydrochloric acid.
Considering the four features can help to identify a titration curve from a
selection of curves.

Acid added to base or base added to acid

In this titration you are told that the base (sodium hydroxide) is added to
the acid so the titration curve will start at an acidic pH.

Initial pH
6    ACIDS AND BASES

HCl is a monobasic acid so [H+] = 0.100 mol dm−3

Initial pH = −log10(0.100) = 1.00

Shape of the curve

Strong acid (hydrochloric acid)–strong base (sodium hydroxide) titration so
curve shaped like curve 1.
The equivalence point occurs with a change in pH between 3 and 10
approximately.
122
Volume at which equivalence point occurs
Amount, in moles, of HCl present, n = v × c = 25.0 × 0.100 = 0.00250 mol
TIP 1000 1000
These types of calculations were NaOH + HCl → NaCl + H2O
first encountered in Amount of
Substance in AS Chemistry. You 1 mol of NaOH reacts with 1 mol of HCl
should refresh your knowledge
0.0025 mol HCl reacts with 0.00250 mol NaOH
of this section to ensure you can
0.00250 × 1000
carry out these calculations. Volume of NaOH = n × 1000 = = 12.5 cm3
c 0.200

807701_C06_AQA_Chemistry_2_100-134.indd 122 13/06/15 9:02 am

 The titration curve for this neutralisation looks like this, taking into account
TIP the four features of the curve.

Titration curves
The titration curve may be for 14
a volume of acid added to a
12
volume of base. This is less
10 Shape of
common. Work out the initial pH curve
of the strong base – this is the 8 indicates

pH
initial pH; the volume required strong
6 acid-
for neutralisation is determined strong
4
in the same way; the shape of Initial base
curve is the same but reflected, pH of I 2 titration
starting at a pH above 7 and Base 0
added 0 5 10 15 20 25
coming down. to acid Volume of NaOH/cm3
12.5 cm3 of 0.2 mol dm–3
NaOH solution required for
neutralisation

EXAMPLE 25
In a titration, 0.500 mol dm−3 aqueous ammonia is added 2 mol of NH3 reacts with 1 mol of H2SO4
to 25.0 cm3 of 0.250 mol dm−3 aqueous sulfuric acid.
0.00625 mol H2SO4 reacts with 0.0125 mol NH3
Identify the following key features of the titration curve.
n × 1000 0.0125 × 1000
Volume of NH3 = = = 25.0 cm3
Acid added to base or base added to acid c 0.500
The titration curve for this neutralisation looks like
In this titration you are told that the base (aqueous am-
this:
monia) is added to sulfuric acid so the titration curve
will start at an acidic pH. 14
12
Shape of
Initial pH 10 curve
H2SO4 is a diprotic acid so [H+] = 0.500 mol dm−3 indicates
8 strong
pH

acid-
Initial pH = −log10(0.500) = 0.3010 (to 4 significant 6
weak
figures) 4 base
Initial pH titration
= 0.30 (2 decimal places) of 0.30 2
0
Shape of the curve Base
0 10 20 30 40 50
added to Volume of NH3 (cm3)
Strong acid (hydrochloric acid)–weak base (ammonia) acid as
titration so curve shaped like curve 3. starts at 25.0 cm3 of 0.500 mol
acidic pH dm–3 NH3 solution required
for neutralisation
The equivalence point occurs with a change in pH
between 3 and 8 approximately.

Volume at which equivalence point occurs

123
Amount, in moles, of H2SO4 present,
25.0 × 0.250
n= v×c = = 0.00625 mol
1000 1000

2NH3 + H2SO4 → (NH4)2SO4

807701_C06_AQA_Chemistry_2_100-134.indd 123 13/06/15 9:02 am

 Indicators for titrations
The choice of an indicator for an acid–base titration depends on the pH
range in which the indicator changes colour.
The colour change pH range of the indicator must be in the inflection range
of the titration curve (the pH range of the equivalence point).
The indicator must change colour with one drop of the substance being
added so the rapid change in pH must be in the range of the colour change
of the indicator.
The end point in a titration is when the indicator changes colour which
occurs at the equivalence point when there is a rapid change in pH. This
changes the colour of the indicator.

Some indicators and their colour change pH ranges

pH range of Colour in lower Colour in upper
Indicator colour change pH range pH range
Thymol blue 1.20–2.80 Red Yellow
Methyl orange 3.10–4.40 Red Yellow
Methyl red 4.40–6.20 Red Yellow
Bromothymol blue 6.00–7.60 Yellow Blue
Phenolphthalein 8.30–10.00 Colourless Pink
TIP
The colour change observed
● For a strong acid–strong base titration the inflection occurs between pH
in the titration is based on the 3 and 10 so any of the indicators except thymol blue would work.
first point of the analysis of the ● For a strong acid–weak base titration, the inflection occurs between pH
titration curves. Phenolphthalein 3 and 8 so any indicator in this range would work (i.e. methyl orange,
is colourless in acid and neutral methyl red and bromothymol blue).
solution but pink in alkaline ● For a weak acid–strong base titration, the inflection occurs between pH 6
solution so a rapid change from 3 and 10 so any indicator in this range would work (i.e. bromothymol blue
to 10 would change the colour of or phenolphthalein).
phenolphthalein from colourless ● Methyl orange and phenolphthalein are the main indicators of choice.
to pink. If the pH changed from Both may be used for strong acid–strong base titrations. Methyl orange
10 to 3 or 10 or 6 the colour of is used for strong acid–weak base titrations. Phenolphthalein is used
phenolphthalein would change
6    ACIDS AND BASES

for weak acid–strong base titrations. A pH meter must be used for weak
from pink to colourless.
acid–weak base titrations as there is no inflection point.

TEST YOURSELF 6
1 Calculate the volume of 0.250 mol dm−3 sodium hydroxide solution
required to react with 20.0 cm3 of 0.150 mol dm−3 sulfuric acid.
2 From the list below:
124 sodium hydroxide ethanoic acid ammonia
hydrochloric acid nitric acid potassium hydroxide
a) Name one strong acid.
b) Name one weak base.
c) Name one weak acid.
3 The pH colour change of phenolphthalein is between pH 8.3 and 10.0.
Explain why phenolphthalein cannot be used for a titration between
hydrochloric acid and ammonia.

807701_C06_AQA_Chemistry_2_100-134.indd 124 13/06/15 9:02 am

 Buffers
REQUIRED PRACTICAL 9
Investigating the change in pH when c) The pH curve for this titration is shown below.
methanoic acid reacts with sodium hydroxide Calculate the value of the concentration in
mol dm−3 of the aqueous sodium hydroxide.
As early as the 15th century, naturalists were aware
that ant hills gave off an acidic vapour. In 1671, the 14.00

English naturalist John Ray isolated the active 12.00

10.00
ingredient. To do this he collected and distilled 8.00

pH
a large number of dead ants, and the acid he 6.00
discovered later became known as formic acid from 4.00

the Latin word for ant, formica. Its proper IUPAC 2.00
0.00
name is now methanoic acid. 0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Volume NaOH/cm3
Woodland ants are the largest native ant species of
Figure 6.7 A titration curve for the titration of
the UK and are known to be aggressively territorial.
methanoic acid with NaOH
They squirt methanoic acid from their abdomens as
a form of protection when provoked. The acid has
a strong, penetrating odour and is used to ward off d) The pH ranges in which the colour changes for
hungry birds such as woodpeckers and jays. three acid–base indicators are shown below.
Explain which of the three indicators is suitable
1 Methanoic acid is a weak acid. In an experiment, for this titration.
a calibrated pH meter was used to measure the
pH of methanoic acid solution. At 20 ºC the pH of a Indicator pH range
0.100 mol dm 3 solution was 2.37. Metacresol purple 7.40–9.00
a) Explain why a pH meter should be calibrated 2,4,6-trinitrotoluene 11.50–13.00
before use. Ethyl orange 2.4–4.8
b) Write an equation for the dissociation of
methanoic acid and explain what is meant by
weak acid.
c) Write an expression for the equilibrium
constant, Ka, for the dissociation of methanoic
acid in aqueous solution. TIP
d) Use your answer from (c) to calculate the value of For a weak acid–strong
Ka for this dissociation at 20 ºC. Give your answer base titration the pH at half
to the appropriate precision. Show your working. neutralisation (pH at half the
volume where the equivalence
2 A student used aqueous sodium hydroxide to
point occurs) is equal to the pKa.
determine the titration curve for the reaction of
This can be used as a method of
methanoic acid and sodium hydroxide. 25.0 cm3 of
determining Ka of a weak acid
1.50 × 10 −2 mol dm−3 methanoic acid was placed in
from a titration curve. At this
a conical flask at 25 °C. The sodium hydroxide was
point of half neutralisation, the
added in 2 cm3 portions and the pH of the reaction
acid concentration is equal to the
mixture was measured using a pH meter.
salt concentration so they cancel
a) Write a balanced symbol equation for the
out and pH = pKa.
reaction between HCOOH and NaOH.
b) Why was the reaction mixture stirred with
a glass rod after the addition of each 2 cm3 125
portion of sodium hydroxide?

●● Buffers
Buffers are solutions that can resist changes in pH when small quantities of
acid or base are added. An interesting application of buffers is their use in
skin creams. Anti-ageing creams are buffered at pH values lower than 5.5.
The low pH irritates the skin, causing it to swell hiding wrinkles.

807701_C06_AQA_Chemistry_2_100-134.indd 125 13/06/15 9:02 am

 There are two main types of buffer:
1 an acidic buffer
2 a basic buffer.

Acidic buffers
An acidic buffer is a solution formed from a weak acid and its salt.
The buffering action is represented by the general equation:
HA ⇋ H+ + A−
where HA is the undissociated acid, A− is the anion and H+ are hydrogen ions.
Ethanoic acid and sodium ethanoate may be mixed to form an acidic buffer.
Alternatively, the salt may be formed indirectly from the reaction of sodium
hydroxide with an excess of ethanoic acid. This leaves a solution containing
the excess ethanoic acid and sodium ethanoate formed from the reaction
with ethanoic acid.
The equation for this buffering action is:

CH3COOH ⇋ CH3COO− + H+

Explanation of buffering action

When small quantities of acid or base are added, the pH of a buffer remains
almost constant.
You can be asked to explain how an acidic buffer resists the change in pH.

Addition of dilute acid

The following points are used to explain how a buffer maintains an almost
constant pH when a small amount of a dilute acid is added:
● When a small amount of an acid is added, extra hydrogen ions, H+, are
added.
The position of equilibrium in the equilibrium HA ⇋ H+ + A− moves to
6    ACIDS AND BASES

●
the left to remove the added H+ ions.
● This keeps the pH almost constant.
If the weak acid and its salt are named then use the correct anion and weak
acid. For example, if the buffer is made from ethanoic acid and ethanoate
ions, the equation should read CH3COOH ⇋ CH3COO− + H+ and the
position of equilibrium will move to the left to remove the added H+ ions.

Addition of base
126 The following points are used to explain how a buffer maintains an almost
constant pH when a small amount of a base is added:
● When a small amount of a base is added, extra hydroxide ions, OH−, are
added.
● The hydroxide ions react with the hydrogen ions in the buffer, removing
some H+ ions.
● The position of equilibrium in the equilibrium HA ⇋ H+ + A− moves to
the right to replace the H+ which reacted with the OH− ions.
● This keeps the pH almost constant

807701_C06_AQA_Chemistry_2_100-134.indd 126 13/06/15 9:02 am

 Again if the weak acid and its salt are named then use the correct weak acid and
TIP anion. For example if the buffer is made from hydrocyanic acid and cyanide

Buffers
The equation for the reaction of ions, the equation should read HCN ⇋ H+ + CN− to explain the buffering
hydroxide ions, OH−, with a buffer action. When OH− is added, they react with H+ ions in the buffer and the
may be represented by position of equilibrium moves to the right to replace the H+ that were removed.
HA + OH− → A− + H2O Basic buffers
to show how the buffer removed A basic buffer is a solution formed from a weak base and its salt. The most
the hydroxide ions which were common example involves ammonia in solution with an ammonium salt.
added.
The buffering action of a basic buffer can be explained using the equation:
NH3 + H+ ⇋ NH 4+
When small amounts of acid are added, the added hydrogen ions, H+, are
removed as they react with the ammonia in the solution to form ammonium
ions. The position of equilibrium moves from left to right.
When small amounts of an alkali are added, the hydroxide ions,
OH−, react with some of the hydrogen ions in the buffer to form water:
H+ + OH− → H2O.
The position of equilibrium moves from right to left to replace the H+ ions.

TIP Preparation of an acidic buffer

Organic bases such as amines There are several methods which may be used to prepare a buffer. All of the
can also act as buffers in solution. methods result in a solution containing a weak acid and the anion of its salt.
The basic nature of amines is
examined in Chapter 13. No 1 Addition of a solid salt of the weak acid to a solution of the weak acid.
calculation work on the pH of
basic buffers is expected.
2 Addition of a solution of the salt of a weak acid to a solution of the weak
acid.
3 Addition of sodium hydroxide solution to an excess of the weak acid.
Method 3 is the most often used.

Calculating pH of an acidic buffer

To determine the pH of an acidic buffer you must determine the amount,
in moles, of the anion A− (this equals the amount, in moles, of the salt) and
the amount in moles of the weak acid, HA, from the information given in
the method used to prepare the buffer.
+ −
In the Ka expression for a weak acid, Ka = [H ] [A ]
[HA]
The [H+] is determined from the Ka expression and pH is then calculated
in the usual way. As both HA and A− are in the same volume of solution,
the amount in moles of HA and A− may be used in the calculation instead
127
of concentration. It will be shown that the calculations using moles and
concentrations give the same pH values for the buffers.

807701_C06_AQA_Chemistry_2_100-134.indd 127 13/06/15 9:02 am

 Method 1: Addition of a solid salt of the weak acid to a solution
of the weak acid
In this method the concentration of the acid remains unchanged as there is
no other solution or water added to dilute it.
The amount in moles of the anion is given or in other examples it may be
determined from the mass of the solid salt added.

TIP
If a mass of the salt is given, simply divided the mass, in g, by the Mr of
the salt to determine the amount in moles of salt added. The rest of the
calculation follows the method shown.

EXAMPLE 26
A buffer solution was prepared by dissolving 0.012 mol salt, CH3COONa, by the volume of the solution and
of sodium ethanoate in 100 cm3 of 0.0520 mol dm−3 multiplying by 1000 to convert to moles per 1 dm3
ethanoic acid. The dissociation constant, Ka, for (1000 cm3).
ethanoic acid has the value
Concentration of the salt: [CH3COONa] = [CH3COO−]
1.74 × 10−5 mol dm−3 at 25 °C.
0.012
[CH3COO−] = × 1000 = 0.12 mol dm−3
Calculate the pH of this buffer solution. Give your 100
answer to 2 decimal places. Concentration of anion [CH3COO−] = 0.12 mol dm−3
[H+] [CH3COO−]
Answer Ka = = 1.74 × 10−5 mol dm−3
[CH3COOH]
Moles of CH3COO− = 0.012 K × [CH3COOH] 1.74 × 10−5 × 0.0520
[H+] = a =
Moles of CH3COOH = 100 × 0.0520 = 5.20 × 10−3 [CH3COO−] 0.12
1000 −6
= 7.54 × 10 mol dm −3
[H +] [CH COO−]
Ka = 3 = 1.74 × 10−5 mol dm−3
[CH3COOH] pH = −log10[H+] = −log10(7.54 × 10−6) = 5.1226 (to 4
Ka × [CH3COOH] 1.74 × 10−5 × 5.20 × 10−3 decimal places)
[H+] = =
[CH3COO−] 0.012 pH = 5.12 (to 2 decimal places)
6    ACIDS AND BASES

= 7.54 × 10−6 mol dm−3

pH = −log10[H+] = −log10(7.54 × 10−6) = 5.1226
(to 4 decimal places) TIP
All these calculations will give the
pH = 5.12 (to 2 decimal places) same answer if concentrations
of HA and A− are determined and
Using concentrations used in the calculation of pH but
To show how this works using concentrations: the amount in moles method
Concentration of weak acid [CH3COOH] = is shorter and fewer steps
0.052 mol dm−3 means fewer potential errors in
128
calculations.
The concentration of the anion, in mol dm−3, is
determined by dividing the amount (in moles) of the

807701_C06_AQA_Chemistry_2_100-134.indd 128 13/06/15 9:02 am

 Method 2: Addition of a solution of the salt of a weak acid to a solution
of the weak acid

Buffers
In this method a certain volume of the solution of the salt (most often a
solution of the sodium salt) is added to a certain volume of a solution of the
weak acid. Both solutions dilute each other so the concentrations of both
the salt and the weak acid change.

EXAMPLE 27
A buffer is prepared by mixing 50.0 cm3 of a Ka × [HX] 7.583 × 10−6 × 0.0153
[H+] = =
0.0417 mol dm−3 solution of the salt of a weak acid, [X−] 0.010425
NaX, with 150 cm3 of a 0.0204 mol dm−3 solution of the [H ] = 1.113 × 10 mol dm−3 (to 4 significant figures)
+ −5
weak acid, HX. The pKa for HX is 5.12 at 25 °C.
pH = −log10[H+] = −log10(1.113 × 10−5) = 4.9535 (to 4
Calculate the pH of this buffer solution. Give your decimal places)
answer to 2 decimal places
pH = 4.95 (to 2 decimal places)
Answer
50.0 × 0.0417 The same value for pH is obtained as the operation
Moles of NaX = = 2.085 × 10−3 mol of ×5 on both the amounts of the acid, HX, and the
1000
anion, X−, would cancel out.
Moles of HX = 50.0 × 0.0204 = 3.06 × 10−3 mol
1000 Henderson-Hasselbalch equation
The pKa is converted into a Ka using Ka = 10−pKa. The Henderson-Hasselbalch equation may also be
Ka = 10(−5.12) = 7.583 × 10−6 mol dm−3 (to 4 significant used to calculate the pH of a buffer.
figures) pH = pKa + log [H ] where [X−] is the concentration
−
+ [HX]
Ka = [H ] [X ] = 7.583 × 10−6 mol dm−3
−

[HX] of the anion and [HX] is the concentration of the

K 7.583 × 10−6 × 3.06 × 10−3
[H ] = a × −[HX] =
+ acid. Again, moles of X− and HX may be used in the
[X ] 2.085 × 10−3 calculation.
[H+] = 1.113 × 10−5 mol dm−3 (to 4 significant figures)
pKa = 5.12, the amount in moles of HX present
pH = −log10[H+] = −log10(1.113 × 10−5) = 4.9535 (to 4 is 3.06 × 10−3 and the amount of X− present is
decimal places) 2.085 × 10−3 mol.
pH = 4.95 (to 2 decimal places) 2.085 × 10−3
pH = 5.12 + log = 4.95
3.06 × 10−3
Using concentrations Using concentrations
The new total volume of the solution is 200 cm3 so For this example, the pKa = 5.12, [HA] was calculated
concentrations in mol dm−3 may be determined using to be 0.0153 mol dm−3 and [A−] was calculated to be
the amount of solute, in moles, in 200 cm3 converted 0.010425 mol dm−3
to 1 dm3 (1000 cm3) by dividing the amount, in moles, 0.010425
by 200 and multiplying by 1000 (this is the same as pH = 5.12 + log = 4.95
0.0153
multiplying by 5).
Concentration of NaX: [NaX] = [X−] = 2.085 × 10−3 × 5
= 0.010425 mol dm−3
129
Concentration of HX: [HX] = 3.06 × 10−3 × 5 TIP
= 0.0153 mol dm−3 Practise these styles of
The pKa is converted into a Ka using Ka = 10−pKa calculation on your calculator if
you are using the Henderson-
Ka = 10(−5.12) = 7.583 × 10−6 mol dm−3 (to 4 significant Hasselbalch equation to calculate
figures) the pH of an acidic buffer.
[H+] [X−]
Ka = = 7.583 × 10−6 mol dm−3
[HX]

807701_C06_AQA_Chemistry_2_100-134.indd 129 13/06/15 9:02 am

 Method 3: Addition of sodium hydroxide or potassium hydroxide
solution to an excess of the weak acid
In this buffer preparation, the sodium hydroxide (or potassium hydroxide)
reacts with the weak acid to form the salt in situ.
The weak acid must be in excess so no sodium hydroxide remains and the
resulting solution contains the weak acid and its salt.

TIP
Be careful with examples involving a weak acid reacting with a strong
base such as ethanoic acid with sodium hydroxide. If the sodium
hydroxide is in excess, it is a neutralisation example and NOT a buffer
example. Look for Kw being given as you will have to work out the pH of a
base. Buffer examples will usually use the word buffer.

EXAMPLE 28
100 cm3 of 0.0515 mol dm−3 nitrous acid (HNO2) was Ka × [HNO2] 7.20 × 10−4 × 3.01 × 10−3
mixed with 50.0 cm3 of 0.0428 mol dm−3 sodium [H+] = =
[NO2−] 2.14 × 10−3
hydroxide solution. The acid dissociation constant, [H ] = 1.0127 × 10 mol dm−3
+ −3
Ka, for nitrous acid is 7.20 × 10−4 mol dm−3 at 25 °C.
Calculate the pH of this buffer solution. Give your pH = −log10[H+] = −log10(1.0127 × 10−3) = 2.9945 (to 4
answer to 2 decimal places. decimal places).
pH = 2.99 (to 2 decimal places)
Answer
Again both solutions dilute each other and the sodium Using concentrations
hydroxide reacts with some of the nitrous acid to form Moles of HNO2 in 150 cm3 = 3.01 × 10−3 mol
the salt, sodium nitrite (NaNO2). Moles of NaNO2 in 150 cm3 = 2.14 × 10−3 mol

Moles of nitrous acid added (HNO2) = 100 × 0.0515 The total volume is 150 cm3 and this may be used to
1000 calculate the concentrations of the weak acid and its
= 5.15 × 10−3 mol salt in the solution.
6    ACIDS AND BASES

−3
Moles of sodium hydroxide added (NaOH) [HNO2] = 3.01 × 10 × 1000 = 0.02007 mol dm−3
50.0 × 0.0428 150
= = 2.14 × 10−3 mol −3
1000 [NaNO2] = [NO2−] 2.14 × 10 × 1000 =
The equation for the reaction between nitrous acid 150
−3
0.01427 mol dm (to 4 significant figures)
and sodium hydroxide solution is given below
HNO2 + NaOH → NaNO2 + H2O [H+]NO2−]
Ka = = 7.20 × 10−4 mol dm−3
[HNO2]
2.14 × 10−3 mol of NaOH will react with 2.14 × 10−3 mol −4
of HNO2 (leaving 5.15 × 10−3 − 2.14 × 10−3 = 3.01 × 10−3 [H+] = Ka × [HNO2] = 7.20 × 10 ×0.02007
−
[NO2 ] 0.01427
130 mol of HNO2) and forming 2.14 × 10−3 mol of NaNO2. [H+] = 1.0126 × 10−3 mol dm−3 (to 4 significant figures)
Moles of HNO2 in 150 cm3 = 3.01 × 10−3 mol pH = −log10[H+] = −log10(1.0126 × 10−3) = 2.9945 (to 4
Moles of NaNO2 in 150 cm3 = 2.14 × 10−3 mol decimal places).
All of the sodium hydroxide has been used up leaving pH = 2.96 (to 2 decimal places)
only some moles of the weak acid (HNO2) and some Note the very slight difference in the concentration
moles of the salt (NaNO2) in solution. The water of the H+ ion using concentration caused by the
formed is in the solution. rounding of the concentration of HNO2 and NaNO2 but
[H+]NO2−] the pH is the same.
Ka = = 7.20 × 10−4 mol dm−3
[HNO2]

807701_C06_AQA_Chemistry_2_100-134.indd 130 13/06/15 9:02 am

 Addition of acid or base to a buffer

Buffers
A buffer by definition maintains an almost constant pH when small
amounts of acid or base are added to it.
The pH of a buffer can be calculated after the addition of a small amount of
an acid or a base.
Addition of a small amount of an acid
● When an acid is added, the amount in moles of the acid should be
calculated if it is not given.
● The position of equilibrium for the equilibrium HA ⇋ H+ + A− moves to
the left to remove the added H+ ions.
● The amount, in moles, of HA increases by the number of moles of acid
added.
● The amount, in moles, of A− decreases by the number of moles of acid added.
● The new amounts in moles of H+ and A− and the Ka expression are used
to calculate [H+]. Then pH = −log10[H+] is used to calculate the pH of the
buffer after the addition of the acid.

EXAMPLE 29
A buffer is prepared by adding 0.0122 mol of salt, NaY The amount, in moles, of HA increases by 2.0 × 10−4
to 40.0 cm3 of a 0.210 mol dm−3 solution of the weak mol
acid, HY. The acid dissociation constant, Ka, for the Initial amount of HY = 40.0 ×0.210 = 8.40 × 10−3 mol
weak acid, HY, is 1.71 × 10−5 mol dm−3 at 25 °C. Give all 1000
pH answers in this question to 2 decimal places. New amount of HY = = 8.40 × 10−3 + 2.00 × 10−4 =
8.60 × 10−3 mol
1 Calculate the pH of the buffer formed. The amount, in moles, of A− decreases by 2.0 ×
2 A 2.00 × 10−4 sample of hydrochloric acid was added 10−4 mol
to this buffer solution. Calculate the pH of the buffer Initial amount of Y− = 0.0122 mol
solution after the hydrochloric acid was added. New amount of Y− = 0.0122 − 2.00 × 10−4 = 0.0120 mol
Answers + −
Ka = [H ][Y ] = = 1.71 × 10−5 mol dm−3
1 moles of A− added = 0.0122 [HY]
[H+] = Ka × −[HY] = 1.17 × 10 × 8.60 × 10
−5 −3
moles of HA = 40.0 × 0.210 = 8.40 × 10−3
1000 [Y ] 0.0120
[H +][Y−]
Ka = = 1.71 × 10−5 mol dm−3 [H+] = 1.226 × 10−5 mol dm−3 (to 4 significant figures)
[HY] pH = −log10[H+] = −log10(1.226 × 10−5) = 4.9115 (to 4
−5 −3
[H+] = Ka × −[HY] = 1.17 × 10 × 8.40 × 10 decimal places)
[Y ] 0.0122 pH = 4.91 (to 2 decimal places)
[H+] = 1.177 × 10−5 mol dm−3 (to 4 significant figures)
pH = −log10[H+] = −log10(1.177 × 10−5) = 4.9292 (to 4
decimal places) TIP
pH = 4.93 (to 2 decimal places) As can be seen, the pH of buffer
2 Adding 2.00 × 10−4 mol of HCl, adds 2.0 × 10−4 mol remains relatively constant even
of H+. with the addition of a small
The position of equilibrium for the equilibrium amount of acid. This is the basis 131
HA ⇋ H+ + A− moves to the left to remove the of the definition of a buffer.
added H+ ions.

Addition of a small amount of a base

● When a base is added, the amount in moles of the base should be
calculated if it is not given.
● The position of equilibrium for the equilibrium HA ⇋ H+ + A− moves to
the right to replace the H+ ions which were removed by the base.
● The amount, in moles, of A− increases by the number of moles of base added.
● The amount, in moles, of HA decreases by the number of moles of base
added.

807701_C06_AQA_Chemistry_2_100-134.indd 131 13/06/15 9:02 am

 EXAMPLE 30
The value of Ka for methanoic acid is 1.78 × The amount, in moles, of HA decreases by 6.00 ×
10−4 mol dm−3 at 25 °C. A buffer solution contains 10−4 mol
0.0150 mol of methanoic acid and 0.0120 mol of Initial amount of HA = 0.0150 mol
sodium methanoate in 500 cm3 of solution at 25 °C. New amount of HA = 0.0150 − 6.00 × 10−4 =
Give all pH values in this question to 2 decimal 0.0144 mol
places. The amount, in moles, of A− increases by 6.00 ×
10−4 mol
1 Calculate the pH of this buffer at 25 °C. Give your
Initial amount of A− = 0.0120 mol
answer to 2 decimal places.
New amount of A− = 0.0120 + 6.00 × 10−4 =
2 A 5.00 cm3 sample of 0.120 mol dm−3 sodium
0.0126 mol
hydroxide solution is added to the buffer. Calculate + −
the pH of the buffer solution after this addition. Ka = [H ][HCOO ] = 1.78 × 10−4 mol dm−3
[HCOOH]
Answer 1.78 × 10−4 ×0.0144
+ − [H+] = Ka × [HCOOH] =
1 Ka = [H ][HCOO ] = 1.78 × 10−4 mol dm−3 −
[HCOO ] 0.0126
[HCOOH] [H+] = 2.034 × 10−4 mol dm−3 (to 4 significant figures)
1.78 × 10−4 ×0.0150
[H+] = Ka × [HCOOH] = pH = −log10[H+] = −log10(2.034 × 10−4) = 3.6916 (to 4
[HCOO−] 0.01427 decimal places)
[H+] = 2.225 × 10−4 mol dm−3 pH = 3.69 (to 2 decimal places)
pH = −log10[H+] = −log10(2.225 × 10−4) = 3.6527 (to 4
decimal places)
pH = 3.65 (to 2 decimal places)
2 5.0 cm3 of 0.12 mol dm−3 NaOH added = 5.00 ×0.0120
TIP
1000 Any of the buffer questions above
= 6.00 × 10−4 mol
can be carried out by converting
Adding 6.00 × 10−4 mol of NaOH, adds 6.00 × to concentration of the weak acid
10−4 mol of OH−. and its salt but be careful as the
6.00 × 10−4 mol H+ ions in the buffer react with 6.00 total volume in the last calculation
× 10−4 mol of OH− ions is 505 cm3 as 5.00 cm3 of the
H+ + OH− → H2O sodium hydroxide solution was
The position of equilibrium for the equilibrium HA added to 500 cm3 of the buffer.
⇋ H+ + A− moves to the right to replace the H+ ions
that were removed by OH− ions.

TEST YOURSELF 7
6    ACIDS AND BASES

1 What is a buffer?
2 Explain why the pH of an acidic buffer solution remains almost
constant despite the addition of a small amount of hydrochloric acid.
3 The acid dissociation constant, Ka, for ethanoic acid is
1.74 × 10−5 mol dm−3 at 25 °C. Calculate the pH of a buffer formed when
0.00170 mol of sodium ethanoate is added to 75.0 cm3 of 0.0550 mol dm−3
ethanoic acid at 25 °C. Give your answer to 2 decimal places.
4 25.0 cm3 of 0.200 mol dm−3 sodium hydroxide solution was added to
50.0 cm3 of 0.250 mol dm−3 methanoic acid. Ka for methanoic acid at
132 25 °C is 1.78 × 10 −4 mol dm−3. Calculate the pH of the buffer solution
formed at 25 °C. Give your answer to 2 decimal places.
5 1.00 dm3 of a buffer solution contains 0.0880 mol of a weak acid HA and
0.0540 mol of the salt of the acid NaA. pKa for the weak acid HA is 4.52.
a) Calculate the pH of the buffer at 25 °C. Give your answer to 2
decimal places.
b) 4.00 cm3 of 0.150 mol dm−3 nitric acid is added to the buffer.
Calculate the pH of the buffer after this addition. Give your answer
to 2 decimal places.

807701_C06_AQA_Chemistry_2_100-134.indd 132 13/06/15 9:02 am

 Practice questions water. Give your answer to 2 decimal
places. (3)

Practice questions
1 Which of the following has units of mol dm−3? c) 15.0 cm3 of 0.124 mol dm−3 sulfuric acid
A Ka B Kw are mixed with 35.0 cm3 of deionised water.
Give your answer to 2 decimal places. (3)
C pH D pKa (1)
8 Calculate the pH of the solution formed when
2 What is the pH of a solution of 25.0 cm³ of 0.100 mol dm−3 hydrochloric acid
0.0154 mol dm−3 H2SO4? are reacted with 10.0 cm³ of 0.150 mol dm−3
A 1.00 B 1.51 sodium hydroxide solution. Give your answer
to 2 decimal places. (5)
C 1.81 D 2.11 (1)
9 A buffer is prepared by mixing 0.0271 mol
3 Write expressions for the following: of sodium ethanoate with 125 cm3 of
a) pH 0.325 mol dm−3 ethanoic acid. The acid
dissociation constant for ethanoic acid, Ka, is
b) Acid dissociation constant, Ka, for the weak 1.74 × 10−5 mol dm−3 at 25 °C.
acid HA
a) Explain why the pH of a buffer solution
c) Kw (3) remains almost constant despite the
4 The acid dissociation constant, Ka, for the weak addition of a small amount of an acid. (2)
acid HX is 2.45 × 10−4 mol dm−3 at 25 °C. b) Calculate the pH of the buffer formed. Give
Calculate the pH of a 0.215 mol dm−3 solution your answer to 2 decimal places. (4)
of the weak acid HX at 25 °C. (3) c) 5.00 cm3 of 0.200 mol dm−3 hydrochloric
5 The ionic product of water, Kw, is acid was added to the buffer solution.
5.48 × 10−14 mol2 dm−6 at 50 °C. Calculate the pH of the buffer solution after
the hydrochloric acid was added. Give your
a) Write an expression for Kw. (1) answer to 2 decimal places. (6)
b) Calculate the pH of pure water at 50 °C. 10 25.0 cm3 of a solution of 0.125 mol dm−3
Give your answer to 2 decimal places. (2) hydrochloric acid was placed in a conical
6 a) In the reaction: flask and sodium hydroxide solution added
+
from a burette. 22.7 cm3 of sodium hydroxide
CH3NH2 + H2O ⇋ CH3NH3 + OH− solution was required to reach the end point.
Explain whether water is acting as a a) Calculate the pH of the 0.125 mol dm−3
Brønsted-Lowry acid or base in this hydrochloric acid used in this titration. (2)
reaction. (2)
b) Write an equation for the reaction between
b) In the reaction: sodium hydroxide and hydrochloric acid.
+
H2SO4 + HNO3 ⇋ H2NO3 + HSO4
− (1)

State which of the reactants acts as a c) Calculate the concentration, in mol dm−3, of
Brønsted-Lowry base in this reaction. (1) the sodium hydroxide solution used. Give
your answer to 3 significant figures. (3)
7 Calculate the pH of the solutions produced in 133
the following way at 25 °C. d) Using your answer to (c), calculate the pH
Kw = 1.0 × 10−14 mol2 dm−6 at 25 °C. of this concentration of sodium hydroxide
solution at 25 °C. At 25 °C, Kw has the value
a) 50.0 cm3 of 0.200 mol dm−3 sodium 1.00 × 10−14 mol2 dm−6. If you did not get
hydroxide solution are diluted to 250 cm3 answer to (c), use 0.145 mol dm−3 as the
with deionised water. Give your answer to concentration of the sodium hydroxide
2 decimal places. (4) solution. This is not the correct answer to
b) 5.0 cm3 of 0.0520 mol dm−3 hydrochloric (c). Give your answer to 2 decimal places.
acid are mixed with 20.0 cm3 of deionised (3)

807701_C06_AQA_Chemistry_2_100-134.indd 133 13/06/15 9:02 am

 11 Titration curves 1 to 4 below were obtained i) Select from the table an indicator
for combinations of different solution of acids which could be used in the titration
and bases. which produces curve 1 but not in the
titration that produces curve 3. (1)
Curve 1 Curve 2
14 14
12 12
ii) Give the colour change at the end
10 10 point of the titration which produces
8 8 curve 4 when bromothymol blue is
pH

pH
7 7 used as the indicator. (1)
6 6
4 4 12 An acidic buffer solution is prepared by
2 2
0 0 mixing 25.0 cm3 of 0.180 mol dm−3 potassium
Volume/cm3 Volume/cm3 hydroxide solution with 50.0 cm3 of a
0.200 mol dm−3 solution of a weak acid HX.
Curve 3 Curve 4 Ka for the weak acid HX at 25 °C has the value
14 14 2.74 × 10−5 mol dm−3.
12 12
10 10 a) Explain why the pH of a buffer solution
8 8
remains almost constant despite the
pH

pH

7 7
6 6 addition of a small amount of a base. (2)
4 4
2 2 b) Calculate the pH of the buffer at 25 °C.
0 0 Give your answer to 2 decimal places. (6)
Volume/cm3 Volume/cm3
c) 0.00240 mol of sodium hydroxide was
a) From the curves 1, 2, 3 and 4, choose the added. Calculate the pH of the buffer
curve which would be produced by the solution after the addition of the sodium
addition of the following. hydroxide. Give your answer to 2 decimal
i) sodium hydroxide added to ethanoic places. (4)
acid (1)
Stretch and challenge
ii) hydrochloric acid added to potassium 13 An acidic buffer is formed by mixing 0.124
hydroxide (1) mol of ethanoic acid with x mol of sodium
iii) ammonia added to nitric acid (1) hydroxide in 1 dm3 of solution. The pH of the
buffer formed is 4.81. The Ka for ethanoic acid
b) The following indicators may be used in is 1.74 × 10−5 mol dm−3. Calculate a value for x.
6 ACIDS AND BASES

titrations. Give your answer to 3 significant figures. (5)

pH range
of colour Colour in Colour
Indicator change acid in alkali
Thymol blue 1.20–2.80 Red Blue
Methyl orange 3.10–4.40 Red Yellow
Methyl red 4.40–6.20 Red Yellow
Bromothymol
6.00–7.60 Yellow Blue
blue
134 Phenolphthalein 8.30–10.00 Colourless Pink

807701_C06_AQA_Chemistry_2_100-134.indd 134 13/06/15 9:02 am

 Properties of Period 3
7 elements and
their oxides
PRIOR KNOWLEDGE
● Elements in the Periodic Table are grouped into blocks which are the
s, p, d and f blocks.
● The position of an element in the Periodic Table is defined by its
atomic number (or proton number).
● From sodium to argon, the atomic radius decreases.
● From sodium to argon, first ionisation energy generally increases.
● From sodium to argon, the melting points of the elements increases
to silicon and then decreases (apart from a slight rise between
phosphorus and sulfur).
● Elements of Group 2 are known as the alkaline earth metals and
elements of Group 7 are known as the halogens.
● Group 2 elements show an increase in reactivity down the group whereas
Group 7 elements show a decrease in reactivity down the group.
● Group 2 elements react with water forming the metal hydroxide and
releasing hydrogen gas (the reaction of magnesium with water is
very slow).
● Acidified barium chloride solution is used to test for sulfate ions. A
positive test yields a white precipitate of barium sulfate.
● Acidified silver nitrate solution is used to test for halide ions. A white
precipitate indicates the presence of chloride ions, a cream precipitate
indicates bromide ions and a yellow precipitate indicates iodide ions.

TEST YOURSELF ON PRIOR KNOWLEDGE 1

1 From the following ten elements:
barium iron uranium chlorine sodium
magnesium neon bismuth silver vanadium
a) Name the s block elements.
b) Name the p block elements.
c) How many are d block elements?
d) How many are f block elements?
2 Write an equation for the reaction of barium with water.
3 State the colour of the precipitate observed when the following 135
solutions are mixed:
a) Potassium iodide solution and acidified silver nitrate solution
b) Acidified barium chloride solution and magnesium sulfate solution
c) Zinc chloride solution and acidified silver nitrate solution.
4 State the following trends:
a) Melting point across Period 3
b) Reactivity down Group 7
c) Atomic radius across Period 3
d) First ionisation energy down Group 2.

807701_C07_AQA_Chemistry_2_135-148.indd 135 13/06/15 9:02 am

 ●● Elements of Period 3
The elements of Period 3 include the metals sodium and magnesium which
reacts with water.

Reaction of sodium with water

Sodium metal reacts vigorously with water. A small piece of the metal is cut
and added to a trough of water.
Observations: sodium floats on the water, moves about the surface of the
water and there is fizzing. The metal melts to form a silvery ball. It eventually
disappears and the solution which remains is colourless.
The equation for the reaction is:
2Na + 2H2O → 2NaOH + H2
The solution which remains contains sodium ions and hydroxide ions and
it has an alkaline pH. The more sodium that is added, the higher the pH.
Sodium has a slightly lower density than water and so floats on the water.
The reaction is vigorous and very exothermic and this why the sodium
melts. The fizzing is caused by the production of hydrogen which also
7    PROPERTIES OF PERIOD 3 ELEMENTS AND THEIR OXIDES

propels the molten bead of sodium across the surface of the water.

Reaction of magnesium with water

Magnesium metal reacts very slowly with water. A piece of magnesium
ribbon will produce a small volume of hydrogen when left in contact with
water for several weeks. The equation for the reaction is:
Mg + 2H2O(l) → Mg(OH)2 + H2
The solution that remains contains magnesium ions and hydroxide ions and it
has a very slightly alkaline pH (just above 7).
Magnesium reacts vigorously with water vapour at temperatures above
100 °C (373 K) in the absence of air. This is often carried out using the
apparatus shown in Figure 7.1.

damp
mineral clamp
wool magnesium
delivery hydrogen
boiling tube
tube gas jar
trough
heat

136 beehive
water
shelf
Figure 7.1 The laboratory reaction of magnesium and steam.

Heating the damp mineral wool generates water vapour and drives the air
out the boiling tube.
Observations: The magnesium burns with a bright white light and a white
solid is formed.
Mg + H2O(g) → MgO + H2
The white solid formed is magnesium oxide.

807701_C07_AQA_Chemistry_2_135-148.indd 136 13/06/15 9:02 am

 ●● Oxides of elements in Period 3

Oxides of elements in Period 3

The oxides of elements in Period 3 will be examined in terms of their
formula, type of bonding, structure, acidic, basic or amphoteric nature of
the oxide and the reactions of the oxides with water.

TIP Metal oxides

You should know how to draw Sodium oxide
a representation of Figure 7.2
● Sodium oxide is an ionic, basic oxide.
with a limited number of ions as
discussed in the bonding chapter ● Its formula is Na2O and its bonding is ionic. Ionic bonding is the
in the Year 1 AS chemistry book. electrostatic attraction between the positive and negative ions.
● It is a white solid which has an ionic lattice structure.

Sodium ions, Na+

TIP Part of the ionic

Lithium oxide melts at 1438 °C lattice of sodium
or 1711 K. This is due to the oxide
smaller Li+ ion creating greater Oxide ions, O2–
electrostatic attractions between
the ions in lithium oxide.
Figure 7.2 The ionic lattice structure of sodium oxide.

Sodium oxide has a high melting point (1275 °C or 1548 K) as it consists

of an ionic lattice and there are strong forces of attraction between the ions
which require a large amount of energy to break.
Formation of sodium oxide
Sodium oxide can be formed from the reaction between sodium and oxygen.
4Na + O2 → 2Na2O
A yellow flame is observed and a white solid is formed.
Sodium metal reacts spontaneously when exposed to air. Sodium, like the
other alkali metals, is stored under oil to prevent it reacting with air. The
alkali metals are soft metals which can be cut with a knife exposing a shiny
surface. The shiny surface tarnishes (goes dull) rapidly.
During this reaction there will also be some sodium peroxide formed,
Na2O2 when sodium reacts with oxygen. Sodium peroxide contains the
peroxide ion, O2−2 . It is a highly reactive compound.

Reactions of sodium oxide

Sodium oxide reacts with water to produce a colourless solution of sodium
Figure 7.3 Combustion of sodium in a hydroxide which is alkaline (pH 12–14).
gas jar. This is an exothermic reaction
as seen by the bright flame. Na2O + H2O → 2NaOH 137
This can be written to show the ions formed:
Na2O+ H2O → 2Na+ + OH−
TIP Sodium oxide is basic so it also reacts with acids producing a salt and water.
You would not be expected to give Na2O + 2HCl → 2NaCl + H2O
the equation for the formation of
the peroxide when asked for an Na2O + H2SO4 → Na2SO4 + H2O
equation for sodium reacting with Sodium oxide dissolves in water and the oxide ion acts as a base and
oxygen in air but you should be accepts H+ ions from the water or the acid:
aware that some forms.
with water: O2− + H2O →2OH−
with acids: O2− + 2H+ → H2O

807701_C07_AQA_Chemistry_2_135-148.indd 137 13/06/15 9:02 am

 Magnesium oxide
● Magnesium oxide is an ionic, basic oxide.
● Its formula is MgO and its bonding is ionic. Ionic bonding is the
electrostatic attraction between the positive and negative ions
● It is a white solid which has an ionic lattice structure.

Magnesium
ions, Mg2+

Part of the ionic

lattice of
magnesium oxide
Oxide ions,
O2−

Figure 7.4 Magnesium oxide is a white

solid. Figure 7.5 Ionic lattice structure of magnesium oxide.

Magnesium oxide has a high melting point (2852 °C or 3125 K) as it consists

7    PROPERTIES OF PERIOD 3 ELEMENTS AND THEIR OXIDES

of an ionic lattice and there are strong forces of attraction between the
oppositely charged ions which require a large amount of energy to break.
The melting point of magnesium oxide is substantially higher than that of
sodium oxide as the Mg2+ ion is smaller and has a higher 2+ charge than the
single positive charge on the Na+ ion. The electrostatic forces of attraction
between the Mg2+ ions and the O2− ions are stronger than the attraction
between the Na+ ions and O2− ions in sodium oxide.

Formation of magnesium oxide

Magnesium oxide can be formed from the reaction between magnesium and
oxygen.
2Mg + O2 → 2MgO
Magnesium burns in air. A white light is observed and a white solid is formed.

Reactions of magnesium oxide

Magnesium oxide is sparingly soluble in water but some does react to form
magnesium hydroxide
MgO + H2O → Mg(OH)2
The pH of a solution of magnesium oxide is slightly alkaline, producing a
solution of around pH 9 due to some of the magnesium oxide reacting with
water. The slightly alkaline pH is due to the fact that magnesium oxide is
138 slightly soluble so only some of the oxide ions dissolve and react with the
water producing hydroxide ions. The enthalpy of solution of magnesium
oxide is not quoted in data books as it is so sparingly soluble in water.
Magnesium oxide is basic so it reacts with acids producing a salt and water.
MgO + 2HCl → MgCl2 + H2O
MgO + 2HNO3 → Mg(NO3)2 + H2O
The oxide ion accepts protons from the acid to form water:
O2− + 2H+ → H2O

807701_C07_AQA_Chemistry_2_135-148.indd 138 13/06/15 9:02 am

 Aluminium oxide

Oxides of elements in Period 3

● Aluminium oxide is an ionic, amphoteric oxide.
● Its formula is Al2O3 and its bonding is ionic.
● Ionic bonding is the electrostatic attraction between the positive and
negative ions.
● It is a white solid which has an ionic lattice structure similar to those
shown previously for sodium oxide and magnesium oxide.
Aluminium oxide melts at 2072 °C (2345 K). The high melting point is
caused by the strong electrostatic attraction between the Al3+ and O2− ions.

Formation of aluminium oxide

Aluminium oxide can be formed from the reaction between powdered
aluminium and oxygen.
4Al + 3O2 → 2Al2O3
A white solid is formed. Aluminium powder reacts readily but aluminium
foil does not react as easily as it has a protective oxide layer that prevents
reaction. This layer also protects aluminium from reaction with water so
preventing corrosion.
TIP
If the general equations are Reactions of aluminium oxide
learnt, then it is simply a matter
Aluminium oxide does not dissolve in water or react with water. This is due
of including the negative ion for
the acid (e.g. Cl−) to complete the
to the strength of the ionic bonds between the oppositely charged, small ions.
equation, or including the positive A mixture of aluminium oxide and water has a pH of 7 as it does not react
metal ion for the hydroxide with water.
(e.g. Na+) to complete the base
equation. Aluminium oxide is amphoteric as it reacts with both acids and bases:
General equations:
With acid: Al2O3 + 6H+ → 2Al3+ + 3H2O
TIP With base: Al2O3 + 2OH− + 3H2O → 2Al(OH)−4
The basic properties of the
When aluminium oxide reacts with a base, the aluminate ion, Al(OH)−4, is
metallic oxides of Period 3
elements is due to the presence formed.
of the oxide ion, O2−, which Overall equations:
can act as a base and accept a
proton, H+. with hydrochloric acid: Al2O3+ 6HCl → 2AlCl3 + 3H2O
with sodium hydroxide: Al2O3+ 2NaOH + 3H2O → 2NaAl(OH)4

TEST YOURSELF 2
1 State the structure of sodium oxide. 139
2 State the type of bonding found in magnesium oxide.
3 Sodium oxide reacts with water.
a) Write an equation for the reaction showing the ions formed.
b) State the pH of the solution formed when sodium oxide reacts
with water.
4 Write an equation for the formation of aluminium oxide from
aluminium and oxygen.

807701_C07_AQA_Chemistry_2_135-148.indd 139 13/06/15 9:02 am

 5 Aluminium oxide reacts with both acids and bases.
a) Write an equation for the reaction of aluminium oxide with
sulfuric acid.
b) Write an equation for the reaction of aluminium oxide with
potassium hydroxide.
c) What term is used for an oxide which reacts with both acids
and bases?

Non-metal oxides
Silicon dioxide
● Silicon dioxide is a covalent, acidic oxide.
● Its formula is SiO2 and its bonding is covalent.
● Silicon dioxide is a white powder and its structure is macromolecular
and the bonding within it is covalent.
● The structural term macromolecular can sometimes be called giant covalent.

Silicon atom
7    PROPERTIES OF PERIOD 3 ELEMENTS AND THEIR OXIDES

Macromolecular (giant covalent)

structure of SiO2 Covalent bond
The arrangement of the atoms
is tetrahedral. Each silicon atom
is connected to 4 oxygen atoms by Oxygen atom
covalent bonds and each oxygen
atom is connected to two silicon
atoms again by covalent bonds

Figure 7.6 Macromolecular structure of silicon dioxide.

The melting point of silicon dioxide is 1610 °C (1883 K). The high melting
point is caused by the macromolecular (giant covalent) structure with many
covalent bonds which require a great deal of energy to break them.

Formation of silicon dioxide

Finely divided silicon reacts with oxygen when heated. Silicon dioxide is
formed.
Si + O2 → SiO2

Reactions of silicon dioxide

140 Silicon dioxide does not dissolve in or react with water as the water cannot
supply enough energy to break the strong covalent bonds in the macromolecular
structure. The pH of a mixture of silicon dioxide and water is 7. Silicon dioxide
is still referred to as an acidic oxide as it reacts with bases.
Silicon dioxide is an acidic oxide that will react with bases forming silicates.
The silicate ion is SiO32−. Silicon dioxide reacts with hot concentrated
sodium hydroxide sodium forming sodium silicate and water. The reaction
is slow at room temperature but alkalis will cause marks on glass containers.
SiO2 + 2NaOH → Na2SiO3 + H2O

807701_C07_AQA_Chemistry_2_135-148.indd 140 13/06/15 9:02 am

 Ionic equation:
TIP

Oxides of elements in Period 3

SiO2+ 2OH− → SiO32− + H2O
Remember again that all you
have to do is add the metal ion Reaction with sodium hydroxide
into both sides of the general SiO2+ 2NaOH → Na2SiO3 + H2O
equation to write an overall
equation. Na2SiO3 is sodium silicate.

Phosphorus(V) oxide
● Phosphorus(V) oxide (phosphorus pentoxide) is a covalent acidic
O
oxide and is a white solid.
● Its molecular formula is P4O10 and its bonding is covalent. The
P4O10 consists of simple O
P
O
empirical formula is P2O5 but each molecule has 4 P atoms and 10
molecules. The molecular
O
O atoms so it is usually written as P4O10.
formula is P4O10 but the P P ● Its structure is molecular covalent. It consists of simple molecules
empirical formula is P2O5 O O O
O
P
O
of P4O10. The structure can be called simple covalent.
O The melting point of P4O10 is 300 °C (573 K). This melting point
Figure 7.7 Structure of phosphorus(v) oxide. is lower than the metallic oxides as P4O10 is molecular covalent so
considerably less energy is required to break the weak intermolecular
forces of attraction between the P4O10 molecules.

Formation of phosphorus(V) oxide

Phosphorus burns spontaneously in air with a very bright white flame and
forms a white smoke which is a mixture of phosphorus(iii) oxide, P4O6 and
phosphorus(V) oxide, P4O10. In excess oxygen the product is almost all
phosphorus(V) oxide.
P4+ 5O2 → P4O10
Phosphorus is normally stored under water to prevent it coming into
contact with oxygen in the air.
Figure 7.8 Phosphorus oxide is a
white powder. The picture shows the Reactions of phosphorus(V) oxide
formation of phosphorus oxide from the P4O10 reacts with water producing phosphoric(V) acid, H3PO4
combustion of phosphorus in a flask.
The white solid is seen around the top P4O10 + 6H2O → 4H3PO4
half of the flask.
Phosphorus(V) oxide is an acidic oxide so will react with bases forming
phosphate salts. The phosphate ion is PO43−.
General equation:
12OH− + P4O10 → 4PO43− + 6H2O
Overall equation (add the metal ion to both sides of the general equation):
12NaOH + P4O10 → 4Na3PO4 + 6H2O
141
Basic oxides such as sodium oxide and magnesium oxide also react with
P4O10 forming phosphate salts. Na3PO4 is sodium phosphate(v) and
Mg3(PO4)2 is magnesium phosphate(v). They are often simply called
sodium phosphate and magnesium phosphate.
6Na2O + P4O10 → 4Na3PO4
6MgO + P4O10 → 2Mg3(PO4)2

807701_C07_AQA_Chemistry_2_135-148.indd 141 13/06/15 9:02 am

 Basic oxides also react with phosphoric(v) acid, H3PO4. The same
phosphate(v) salt is formed but water is also formed.
3Na2O + 2H3PO3 → 2Na3PO4 + 6H2O
3MgO + 2H3PO4 → Mg3(PO4)2 + 3H2O

ACTIVITY
1 Write a balanced symbol equation for the
combustion of white phosphorus.
2 What is observed when white phosphorus burns?
White phosphorus matches were replaced in the
early 1900s by ‘safety matches’. The heads of
these matches contained a mixture of phosphorus
sesquisulfide P4 S 3 and potassium chlorate(v)
KClO3. When the match is struck across a rough
surface the heat of friction is sufficient to ignite the
phosphorus sesquisulfide; the potassium chlorate(v)
decomposes to provide the oxygen needed for
7    PROPERTIES OF PERIOD 3 ELEMENTS AND THEIR OXIDES

combustion.
3 Write a balanced symbol equation for the occurs between these two substances when a
combustion of phosphorus sesquisulfide to
match head ignites.
produce phosphorus(v) oxide and sulfur dioxide.
6 The phosphorus(v) oxide produced when a
4 Write a balanced symbol equation for the safety match head ignites is covalently bonded.
decomposition of potassium chlorate(v) into
Magnesium oxide, another Period 3 oxide is an
potassium chloride and oxygen.
ionically bonded compound. Outline a simple
5 Using your answers to question 4 and 5, write a experiment that could be used to demonstrate that
single equation to show the overall reaction that magnesium oxide has ionic bonding.

Oxides of sulfur
● Sulfur forms two oxides, sulfur(iv) oxide (sulfur dioxide) and sulfur(vi)
oxide (sulfur trioxide). Both are covalent acidic oxides.
● Sulfur dioxide has the formula SO2 and sulfur trioxide has the formula
SO3. The bonding in both is covalent. The structure of both SO2 and SO3
TIP is molecular (simple covalent).
Some texts describe sulfur ● Sulfur dioxide is a colourless gas (melting point −73 °C or 200 K) with
trioxide as a colourless solid a pungent odour. It often appears as misty fumes in most air due to its
but this may relate more to the reaction with the moisture in the air.
temperature of the environment, ● Sulfur trioxide is a colourless liquid (melting point 17 °C or 290 K).
given that its melting point is
close to room temperature. The structure of both sulfur dioxide and sulfur trioxide is described as molecular
142 covalent. The SO2 molecule is bent and the SO3 molecule is trigonal planar.

TIP O
The bond angle for SO2 is 119°. The two
double bonds and lone pair take up a S S
trigonal planar arrangement and the lone O O O O
pair reduces the bond angle from 120° to bent shape of trigonal planar
SO2 shape of SO3
119°. The bond angle for SO3 is 120° due to
the equal repulsions of the three double bonds. Sulfur dioxide is polar but
sulfur trioxide is non-polar because of the symmetry of its shape.

807701_C07_AQA_Chemistry_2_135-148.indd 142 13/06/15 9:02 am

 Formation of the oxides of sulfur
Sulfur burns in air. The yellow solid sulfur melts to form a red liquid which

Oxides of elements in Period 3

burns with a blue flame forming misty fumes of a choking and pungent gas.
S + O2 → SO2
Sulfur dioxide can be converted to sulfur trioxide on reaction with more
oxygen in the presence of a vanadium(v) oxide catalyst under specific
conditions.
2SO2 + O2 → 2SO3
Figure 7.9 Sulfur burning in air, on a
combustion spoon. It has an intense Reactions of the oxides of sulfur
blue flame. Sulfur dioxide reacts with water producing sulfuric(iv) acid, H2SO3.
Sulfuric(iv) acid is also called sulfurous acid.
SO2 + H2O → H2SO3
The solution formed when sulfur dioxide reacts with water is weakly acidic.
This is due to the reaction being reversible and the position of equilibrium
being to the left-hand side.
SO2 + H2O ⇋ H+ + HSO3−
Sulfur trioxide, SO3, reacts very vigorously with water producing sulfuric
acid, H2SO4. Sulfuric acid is also called sulfuric(vi) acid.
SO3 + H2O → H2SO4
As both sulfur dioxide and sulfur trioxide are acidic oxides, they react
with bases. Sulfur dioxide reacts with bases forming sulfate(iv) ions. The
sulfate(iv) ion is SO32−. Sulfur trioxide reacts with bases forming sulfate(vi)
ions. The sulfate(vi) ion is SO42−.
The sulfate(iv) ion is also called the sulfite ion and the sulfate(vi) ion is
called the sulfate ion.
General equations:
SO2 + 2OH− → SO32− + H2O
SO3 + 2OH− → SO42− + H2O
Overall equations (adding the metal ion to the left and the right will
complete the equation and give you the balanced symbol equation):
SO2 + 2NaOH → Na2SO3 + H2O
SO3 + 2KOH → K2SO4 + H2O
TIP
Examples relating melting point P4O10 melts at 300 °C (573 K) whereas SO2 melts at −73 °C (200 K). SO3
to the structure are common in melts at 17 °C (290 K). All three of these substances are molecular covalent. 143
this section. Make sure you can P4O10 has a higher melting point than the others as it is a larger molecule
explain it fully based on either an with more electrons so the van der Waals’ forces between the molecules are
ionic lattice, a macromolecular greater and more energy is required to overcome these forces of attraction
(giant covalent) structure or the between the molecules. SO3 is a larger molecule than SO2 so the melting
forces of attraction between
point is higher, again due to larger van der Waals’ forces between the
molecules for molecular (simple)
covalent substances.
molecules of SO3 compared to SO2, even though SO2 is polar and SO3 is
non-polar.

807701_C07_AQA_Chemistry_2_135-148.indd 143 13/06/15 9:02 am

 Summary table of the reactions of oxides of elements
in Period 3 with water
Oxide Reaction with water pH of resulting solution
Na2O Na2O+ H2O → 2Na+ + OH− 14
MgO MgO+ H2O → Mg(OH)2 9
Al 2O 3 None –
SiO2 None –
P4 O10 P4 O10 + 6H2O → 4H3PO 4 0
SO2 SO2 + H2O ⇋ H+ + HSO 3− 3
SO 3 SO 3 + H2O → H2 SO 4 0

●● Trends in the melting points

of the Period 3 oxides
The table below gives the melting points of the highest oxidation state
oxides of elements of Period 3.
Oxide Melting point (°C)
7    PROPERTIES OF PERIOD 3 ELEMENTS AND THEIR OXIDES

Na2O 1438
MgO 2852
Al 2O 3 2072
SiO2 1610
P4 O10 300
SO 3 17

For the metal oxides (Na2O, MgO and Al2O3) it is important to remember
that, in general, the melting point increases as the charge on the metal ions
and as the size of the metal ion decreases. Ionic compounds with smaller ions
and higher charge ions have the highest melting points. This explains the
increase in melting point from sodium oxide to magnesium oxide. However,
the melting point of aluminium oxide is lower than that of magnesium oxide.
This is due to the fact that the aluminium ion has such a high charge density
that it polarises the electrons in the oxide ion and aluminium oxide has a
degree of covalent character. This reduces the melting point.
Silicon dioxide has a macromolecular (giant covalent structure) and so a large
amount of energy is required to break the many strong covalent bonds to melt it.
P4O10 and SO3 are molecular in structure. P4O10 has a higher Mr than SO3
so it has stronger van der Waals’ forces of attraction between the molecules.

144 ●● Structure of the acids and anions

When acidic oxides react with water they form oxyacids. These oxyacids are
covalent compounds which form ions in aqueous solution.

Phosphoric acid
Food-grade phosphoric acid is used to acidify foods and beverages such as
various colas. It provides a tangy and sour taste.
● When P4O10 reacts with water, phosphoric(v) acid, H3PO4, is formed. The (v)
refers to the oxidation state of the phosphorus atom which is +5 in H3PO4.

807701_C07_AQA_Chemistry_2_135-148.indd 144 13/06/15 9:02 am

 O ● The structure of phosphoric(v) acid is shown on the left.
Phosphoric(v) acid is often simply called phosphoric acid.

Structure of the acids and anions

●
P
OH ● Phosphorus atoms in H3PO4 promote electrons into the 3d sub-level to
HO
OH be able to form five covalent bonds.
phosphoric(V) acid ● The shape around the phosphorus atom is tetrahedral (bond angle is 109.5°)
(see structure, left).
The three hydrogen atoms are acidic hydrogen atoms as they are bonded to
electronegative oxygen atoms and so can be donated as H+ ions.
Phosphoric(v) acid is a triprotic acid. It forms three different anions as the
H+ leave the molecule on reaction with bases.
NaOH + H3PO4 → NaH2PO4 + H2O
NaH2PO4 is sodium dihydrogenphosphate(v). The H2PO24 ion is the
dihyrogenphosphate(v) ion.
TIP
All of the anions formed from 2NaOH + H3PO4 → Na2HPO4 + H2O
phosphoric acid may have the Na2HPO4 is sodium hydrogenphosphate(v). HPO4− is the
oxidation state left out after the
hydrogenphosphate(v) ion.
name of the salt. For example
the phosphate(v) ion is often 3NaOH + H3PO4 → Na3PO3 + 3H2O
called the phosphate ion and
the dihydrogenphosphate(v) Na3PO4 is sodium phosphate(v). PO3−
4   is the phosphate(v) ion.
ion is often called the The structures of the three ions are shown below.
dihydrogenphosphate ion.
All the ions shown above have a tetrahedral shape with a 109.5° bond angle.

O O O

P P P
O− O− − O−
HO HO O
OH O− O−
dihydrogenphosphate(V) hydrogenphosphate(V) phosphate(V) ion, PO 3−
4
ion, H2PO−4 ion, HPO42−

Sulfuric(iv) acid
● When SO2 reacts with water, sulfuric(iv) acid, H2SO3, is formed. The (iv)
refers to the oxidation state of the sulfur atom in H2SO3 which is +4.
● The structure of sulfuric(iv) acid is shown on the left.
S
O
OH ● Sulfuric(iv) acid is often called sulfurous acid.
OH ● Sulfur atoms in H2SO3 promote one electron into the 3d sub-level to be able
sulfuric(IV) acid to form four covalent bonds. The sulfur atom has a lone pair of electrons.
● The shape around the sulfur atom is pyramidal (bond angle 107.5°) (see
structure, left).
Sulfuric(iv) acid forms two different salts on removal of one or both of the 145
hydrogen atoms as H+ ions.
NaOH + H2SO3 → NaHSO3 + H2O
NaHSO3 is sodium hydrogensulfate(iv). The HSO3− ion is the
hydrogensulfate(iv) ion, which is often called the hydrogensulfite ion.
2NaOH + H2SO3 → Na2SO3 + H2O

807701_C07_AQA_Chemistry_2_135-148.indd 145 13/06/15 9:02 am

 Na2SO3 is sodium sulfate(iv). The SO32− ion is the sulfate(iv) ion, which is
often called the sulfite ion.
The structures of the two anions are given below.
TIP
The ions shown have a pyramidal
S S
shape with a bond angle of OH O−
O O
107.5°. This is a similar shape to O− O−
an ammonia molecule. hydrogensulfate(IV) ion, HSO−3 sulfate(IV) ion, SO32−

Sulfuric(vi) acid
● When SO3 reacts with water, sulfuric(vi) acid, H2SO4, is formed. The (vi)
refers to the oxidation state of the sulfur atom in H2SO4 which is +6.
● The structure of sulfuric(vi) acid is shown on the left.
O
● Sulfuric(vi) acid is often simply called sulfuric acid.
S ● Sulfur atoms in H2SO4 promote two electrons into the 3d sub-level to be
OH
O able to form six covalent bonds.
OH
● The shape around the sulfur atom is tetrahedral (bond angle 109.5°) (see
sulfuric(VI) acid
structure, left).
7    PROPERTIES OF PERIOD 3 ELEMENTS AND THEIR OXIDES

Sulfuric(vi) acid forms two different salts on removal of one or both of the
hydrogen atoms as H+ ions.
NaOH + H2SO4 → NaHSO4 + H2O
NaHSO4 is sodium hydrogensulfate(vi). The HSO4− ion is the
hydrogensulfate(vi) ion, which is often called the hydrogensulfate ion.
2NaOH + H2SO4 → Na2SO4 + H2O
Na2SO4 is sodium sulfate(vi). The SO42− ion is the sulfate(vi) ion, which is
often called the sulfate ion.
The structures of the two anions are given below.

TIP O O
Both anions have a tetrahedral
shape with a bond angle of 109.5°. S
OH
S
O−
O O
O− O−
hydrogensulfate(VI) ion, HSO−4 sulfate(VI) ion, SO42−

TEST YOURSELF 3
1 Sulfur dioxide and sulfur trioxide both reacts with 3 State what is observed when sulfur burns in air.
146
water. 4 Write the formula for the following salts of
a) Write an equation for the reaction of sulfur oxyacids.
dioxide with water. a) sodium hydrogensulfate(VI)
b) State the pH of the solution formed when sulfur b) magnesium phosphate(v)
trioxide reacts with water. c) potassium hydrogenphosphate(v)
c) Write an equation for the reaction of sulfur d) sodium hydrogensulfite
dioxide with excess sodium hydroxide. 5 Write an equation for the reaction of P4O10 with
2 P4O10 is an acidic oxide. sodium oxide.
a) Write an equation for the reaction of P4O10 with
water.
b) State the structure of P4O10.

807701_C07_AQA_Chemistry_2_135-148.indd 146 16/06/2015 17:09

 Practice questions 6 The melting points of the oxides of the Period
3 are given in the table below.

Practice questions
1 Which one of the following oxides reacts with
Oxide Na2O MgO Al2O3 SiO2 P4O10 SO2 SO3
water to form an alkaline solution?
Melting
A Al2O3 B Na2O point 1275 2852 2072 1610 300 −73 17
(°C)
C SiO2 D SO2 (1)
a) Explain why the melting points of Na2O,
2 What is the formula of iron(III) sulfate(IV)?
MgO and Al2O3 are high. (2)
A FeSO3 B Fe2(SO3)3
b) Explain the difference between the melting
C FeSO4 D Fe2(SO4)3 (1) points of SiO2 and P4O10. (3)
3 Which one of oxides of Period 3 elements c) Explain why SO3 has a higher melting
reacts with water to form a compound with an point than SO2. (3)
element in the +6 oxidation state?
7 P4O10 is phosphorus(v) oxide.
A Aluminium B Phosphorus
a) Write an equation for the reaction of P4O10
C Silicon D Sulfur (1) with water. (1)
4 Which one of the following oxides has a b) Write an equation for the reaction of P4O10
molecular structure? with magnesium oxide. (1)
A Na2O B MgO c) Calculate the mass of P4O10 required
to react with 500 cm3 of water to
C SiO2 D P4O10 (1)
create a solution of phosphoric acid of
5 The melting points of the Period 3 elements concentration 0.15 mol dm−3. (3)
are given below.
8 Sodium oxide and sulfur dioxide have very
Element Sodium Magnesium Aluminium Silicon different melting points.
Melting point 98 649 660 1410 Sodium oxide melts at 1274 °C whereas sulfur
(°C)
dioxide melts at −73 °C.
State at room Solid Solid Solid Solid
temperature a) State the structure of sodium oxide and
and pressure sulfur dioxide. (2)
Element Phosphorus Sulfur Chlorine Argon b) Explain the difference in the melting points
Melting point 44 114 −101 −189 of the two substances. (2)
(°C)
State at room Solid Solid Gas Gas c) State the pH of the solution formed if
temperature they are dissolved in separate samples
and pressure of water. (2)
a) Explain why the melting point of d) Write an equation for the reaction of
magnesium is greater than the melting sodium oxide with sulfur dioxide. (1)
point of sodium. (2)
9 The structures of two oxyacids of elements in
b) Explain why silicon has the highest melting Period 3 are shown below: 147
point of the Period 3 elements. (2) O O

c) Phosphorus, sulfur and chlorine exist as S P

OH OH
molecules. Write the formulae of O HO
OH OH
the molecules of each element. (2)
Acid A Acid B
d) Explain why the phosphorus and sulfur are
solids at room temperature and a) Give the oxidation state of sulfur in
pressure but chlorine is a gas. (3) Acid A. (1)

807701_C07_AQA_Chemistry_2_135-148.indd 147 13/06/15 9:02 am

 b) Give the oxidation state of phosphorus in Stretch and challenge
Acid B. (1) 10 Sodium reacts with water according to the
c) Give the names of both acids. (2) equation:
d) Write an equation for the formation of 2Na + 2H2O → 2NaOH + H2
acid A from an oxide of an element in Calculate the pH of the solution formed
Period 3. (1) when a sample of 0.0300 g of sodium
e) Write an equation for the reaction of Acid B is added to 1.00 dm3 of water.
with calcium oxide. (1) (Kw = 1.00 × 10−14 mol2 dm−6). Give
your answer to 2 decimal places. (4)
f) Explain why both acids cannot be oxidised
further. (1)
g) Write the formulae including the charge
of two anions formed from Acid A. Name
these anions. (2)
7 PROPERTIES OF PERIOD 3 ELEMENTS AND THEIR OXIDES

148

807701_C07_AQA_Chemistry_2_135-148.indd 148 16/06/2015 17:19

 8 Transition metals

PRIOR KNOWLEDGE
● Transitions metals are found in the block between Groups 2 and 3
called the d block as their outer shell electrons are located in the d
sub-level.
● The 4s sub-level fills before the 3d sub-level.
● The electronic configuration of chromium and copper are different
than expected.
● When transition metal atoms form ions they lose their 4s electrons
first.
● Coordinate bonds are formed when the shared pair of electrons is
donated from one atom.
● The compounds of transition metals are coloured.
● Transition metals form compounds with the transition metal in
different oxidation states.
● Oxidation and reduction reactions between these oxidation states
are common and there are changes in colour associated with these
changes.
● Transition metal compounds can be used in organic chemistry for
oxidation reactions.
● Know the shapes of molecules including octahedral, tetrahedral and
linear.

TEST YOURSELF ON PRIOR KNOWLEDGE 1

1 Write the electronic configuration of the following transition metals.
a) Sc
b) Cr
c) Ni
d) Cu
2 Write the electronic configuration of the following ions.
a) Ti2+
b) Fe2+
c) Co2+
d) Cu2+ 149
3 Explain how a coordinate bond forms.
4 State the shape of the following molecules:
a) CH4
b) BeCl 2
c) SF6

807701_C08_AQA_Chemistry_2_149-174.indd 149 13/06/15 9:03 am

 ●● General properties of transition elements
The general properties of transition elements are listed below.
● Their atoms or ions have an incomplete d sub-level.
● They form complexes.
● They have variable oxidation states.
● The metals and their compounds show catalytic activity.
● The form coloured ions.
Figure 8.1 Transition metal ion Incomplete d sub-level
solutions. From left to right these
strongly coloured metal solutions are: ● Transition elements are elements in the middle of the Periodic Table that
titanium(ii) (Ti2+), vanadium(iii) (V3+), have atoms or ions with an incomplete d sub-level.
vanadium(iv) (VO2+), chromium(iii) (Cr 3+), ● The first transition series runs from scandium to zinc (elements 21 to 30).
dichromate(vi) (Cr2O2− 7   ), manganese(ii) ● Scandium and zinc are not true transition elements as they do not
(Mn2+), manganate(vii) (MnO 4-), iron(iii) have variable oxidation states in their compounds and their ions, Zn2+
(Fe 3+), cobalt(ii) (Co2+), nickel(ii) (Ni2+)
and copper(ii) (Cu2+).
and Sc3+ do not have an incomplete d sub-level. Zn2+ is [Ar] 3d10, Sc3+
is [Ar].
● The term d block element is a better description if scandium and zinc
are to be included. However as these two elements are not mentioned in
this part of the specification which specifically addresses Ti to Cu, it is
appropriate to use the term transition elements.
● It is the incomplete d sub-level that gives transition metals the other
properties listed above.

Electronic configuration
The table below gives the electronic configuration of the atoms of
the transition elements from Ti to Cu. Also given are the electronic
configurations of the most common simple ions.

Transition
element Transition
atom Electronic configuration element ion Electronic configuration
Ti 1s2 2s2 2p6 3s2 3p6 3d2 4s2 Ti2+ 1s2 2s2 2p6 3s2 3p6 3d2
8    TRANSITION METALS

V 1s2 2s2 2p6 3s2 3p6 3d3 4s2 V 3+ 1s2 2s2 2p6 3s2 3p6 3d2
Cr 1s2 2s2 2p6 3s2 3p6 3d5 4s1 Cr3+ 1s2 2s2 2p6 3s2 3p6 3d3
Mn 1s2 2s2 2p6 3s2 3p6 3d5 4s2 Mn2+ 1s2 2s2 2p6 3s2 3p6 3d5
Fe 1s2 2s2 2p6 3s2 3p6 3d6 4s2 Fe3+ 1s2 2s2 2p6 3s2 3p6 3d5
Co 1s2 2s2 2p6 3s2 3p6 3d7 4s2 Co2+ 1s2 2s2 2p6 3s2 3p6 3d7
Ni 1s2 2s2 2p6 3s2 3p6 3d8 4s2 Ni2+ 1s2 2s2 2p6 3s2 3p6 3d8
Cu 1s2 2s2 2p6 3s2 3p6 3d10 4s1 Cu2+ 1s2 2s2 2p6 3s2 3p6 3d9
TIP
It is important to remember that Metallic nature
150 the first series of transition metal Transition metals are all hard and dense. They are good conductors of
atoms always lose their 4s
electricity and heat and possess good mechanical properties.
electrons first when forming ions.
Their melting and boiling temperatures and standard enthalpies of
melting are higher for most transition metal elements than those of s block
elements.
All the above properties give a measure of the strength of the metallic
bond. With d electrons as well as s electrons available to take part in
delocalisation, the metallic bond is strong in transition metals.

807701_C08_AQA_Chemistry_2_149-174.indd 150 13/06/15 9:03 am

 ●● Complex formation

Complex formation
Transition metals form complexes.
Ligands have at least one lone pair of electrons that can form a coordinate
bond to a metal atom or ion.
In transition metal complexes, lone pairs of electrons on the ligand form
A complex is a central metal atom or ion
surrounded by ligands
coordinate (dative covalent) bonds to the central metal atom or ion.
A ligand is an ion or molecule which forms The lone pairs on the ligand are donated into empty orbitals in the
coordinate bonds with the transition metal transition metal atom or ion.
atom or ion by donating a pair of electrons.
Hexaaqua cations
When simple ions of transition metals dissolve in water, they form complex
ions such as [Cu(H2O)6]2+, [Ni(H2O)6]2+ and [Fe(H2O)6]3+. These are called
hexaaqua cations as they have six water ligands coordinately bonded to the
metal ion.
Dissolving nickel(ii) sulfate in water would produce a green solution
containing the [Ni(H2O)6]2+ complex ion. The sulfate ion would also be
present in the solution.
Compounds of metal ions, other than transition metal ions, such as Mg2+,
Zn2+ and Al3+ can also form hexaaqua cations as long as they have available
TIP empty orbitals into which the lone pairs of electrons can be donated.
It is important to note that atoms
and ions of the first series of Mg2+, Zn2+ and Al3+ ions are not transition metal ions but they do form
transition metals have empty complexes.
orbitals (some 3d, 4s and 4p) into
which the lone pairs of electrons Writing complexes
may be placed to form the Complexes are written with the metal atom or ion and the ligands inside
coordinate bond from the ligand. square brackets. The charge on the complex ion (if there is one) is placed as
a superscript outside the square bracket.

EXAMPLE 1

+ Overall charge on
[Cu (H2O)6]2
the complex

Metal atom or Ligands

ion

This complex has six water ligands coordinately bonded to the Cu2+ ion.
When multiple ligands are present which contain more than one atom, 151
these are placed in a bracket with the number outside the bracket.
Water ligands are neutral (they have no charge).
As the water ligands are neutral, the overall charge of the complex is the
same as the charge of the metal ion (2+) or its oxidation number (+2).

807701_C08_AQA_Chemistry_2_149-174.indd 151 13/06/15 9:03 am

 EXAMPLE 2

– Overall charge on
[CoCl4]2
the complex

Metal atom or Ligands

ion

This complex has four chloride ion ligands coordinately bonded to the
Co2+ ion.
These four ligands do not need a bracket as they do not consist of more
than one atom.
Chloride ion ligands have a single negative charge, Cl−.
The overall charge on the complex is a total of the charge on the metal ion
(2+) or its oxidation state (+2) and the total charge of the ligands (4 × 1−).

Coordination number
The coordination number is the number of Some ligands can form only one coordinate bond to the metal atom or ion.
coordinate bonds to the metal atom or ion.
Some ligands can form more than one coordinate bond to the metal atom or
ion at the centre of the complex.
[Ni(H2O)6]2+ coordination number = 6

[CuCl4]2− coordination number = 4

[Fe(H2O)6]3+ coordination number = 6

[FeEDTA]− coordination number = 6

[Ag(NH3)2]+ coordination number = 2

8    TRANSITION METALS

Monodentate ligands
Ligands that form one coordinate bond to a metal atom or ion are called
monodentate ligands. Examples of monodentate ligands are NH3, H2O,
Cl−, OH−, CN−.

H H
All the above ligands have at least one lone pair of electrons but even if
H H they have more than one, they are still monodentate as the lone pairs are
N C C N on the same atom or adjacent atoms. This means that these ligands cannot
H H form more than one coordinate bond to the metal atom or ion as the bonds
H H
must be in a certain orientation around the metal ion. This will be discussed
1,2-diaminoethane
152 showing the lone pairs of when shapes of complexes are considered.
electrons

O O
Bidentate ligands
Ligands which form two coordinate bonds to a metal atom or ion are called
C C
bidentate ligands. Examples of a bidentate ligand are 1,2-diaminoethane
−O O− (H2NCH2CH2NH2) and ethanedioate (oxalate) ions, C2O42−.
ethanedioate ion
showing the lone pairs of
For a bidentate ligand, the lone pairs of electrons must be on different
electrons atoms to allow the ligand to form more than one coordinate bond.

807701_C08_AQA_Chemistry_2_149-174.indd 152 13/06/15 9:03 am

 This is important as the coordinate bonds must form in certain orientations
around the central ion.

Complex formation
2+
coordinate bonds to the
Co2+ ion must form in
Co the orientation shown,
forming an octahedral
shaped complex ion

So even though water, H2O, has two lone pairs of electrons, both
occur on the oxygen atom so it would be impossible for these two
Figure 8.2 Kidney stones, are formed lone pairs to form two coordinate bonds to the Co2+, whereas the two
when calcium ethanedioate (calcium lone pairs of 1,2-diaminoethane are separated and so it can acts as a
oxalate) accumulate on the inner bidentate ligand.
surfaces of the kidney. As they grow
they may block the flow of urine out of CH2
the kidney, causing extreme pain. CH 2
H2 O H2 N
2+ 2+
H2 N

Co Co

Even if the coordination number of a complex is 4 or 2, water can only

ever act as a monodentate ligand due to the position of the lone pairs of
electrons.

Multidentate ligands
Ligands that form many coordinate bonds to a metal atom or ion are
called multidentate ligands. An example of a multidentate ligand is
EDTA4−.
EDTA is an abbreviation for ethylenediaminetetraacetic acid. The structure
of EDTA is given below.

HOOC–H2C H H CH2–COOH

N C C N

HOOC–H2C H H CH2–COOH

EDTA is usually used in alkaline buffered solution to ensure it is the anion

form. All the acid COOH groups lose their hydrogen ions to form the anion
EDTA4−.
−OOC–H C H H The six lone pairs are shown
2 CH2–COO− on the diagram. These form
coordinate bonds with the
N C C N
central metal ion. This makes
153
−
OOC–H2C H H CH2–COO− EDTA multidentate and
hexadentate

Six lone pairs are shown on the diagram. EDTA4− can form six coordinate
bonds with the central metal ion and so as well as being described as
multidentate, it is also described as hexadentate.

807701_C08_AQA_Chemistry_2_149-174.indd 153 13/06/15 9:03 am

 Chelates
All multidentate ligands form complexes called chelates. The word chelate
comes from the Greek word ‘chel’, meaning a crab’s claw, and refers to the
pincer-like manner in which the metal is bound. Multidentate ligands
bind more tightly because of the chelate effect. The metal atom or ion is
completely surrounded by the chelating ligand such as EDTA4−.
2-

Co

Figure 8.3 A simplified form of the [CoEDTA]2− complex. A chelate as the EDTA 4−
Figure 8.4 Blood collection tubes are has surrounded the Co2+ ion. Note the overall charge on the complex ion is 2− as
pre-sprayed with EDTA on the inside. cobalt has an oxidation state of +2 and EDTA has a charge of 4 −. The white circles
The EDTA 4− removes calcium ions from represent the N atoms of EDTA 4− and the green circles represent the O − of COO −.
the blood and so prevents it clotting
during tests: [Ca(H2 O)6]2+ + EDTA 4− →
(CaEDTA)2− + 6H2 O. EDTA4− reacts with metal ions in a 1:1 ratio. EDTA4− can be used to titrate
metal ions in solution using a suitable indicator such as eriochrome black T
for the titration of Mg2+ ions and Ca2+ ions.

●● Ligand substitution
A ligand substitution reaction is one in which one ligand which is
coordinately bonded to a metal atom or ion in a complex ion is replaced by
another ligand.

Ligand substitution with no change in coordination

TIP
The reactions are often written
number
as equilibrium reaction as they In the following examples the coordination number of the complex does
8    TRANSITION METALS

can be reversed, but it is also not change.

common to see them written with
→ as in many of the reactions the
This is common with smaller ligands such as water and ammonia as they
equilibrium is displaced almost have a similar size and are both uncharged.
completely to the right-hand side. It also occurs when bidentate ligands replace monodentate ligand and
multidentate ligands replace either monodentate or bidentate ligands.
● Reaction of [Co(H2O)6]2+ with ammonia.
Adding ammonia solution to a solution containing [Co(H2O)6]2+ results
in the six water ligands being replaced by six ammonia ligands to give
154 [Co(NH3)6]2+.
The equation for this reaction is written as:
[Co(H2O)6]2+ + 6NH3 ⇋ [Co(NH3)6]2+ + 6H2O
● Reaction of [Cu(H2O)6]2+ with ammonia.
Adding ammonia solution to a solution containing [Cu(H2O)6]2+ results
in four of the six water ligands being replaced by ammonia ligands to
give [Cu(NH3)4(H2O)2]2+. The substitution is not complete but the
coordination number in both complexes is 6.
The equation for this reaction is written as:
[Cu(H2O)6]2+ + 4NH3 ⇋ [Cu(NH3)4(H2O)2]2+ + 4H2O

807701_C08_AQA_Chemistry_2_149-174.indd 154 13/06/15 9:03 am

 ● Reaction of [Co(NH3)6]2+ with 1,2-diaminoethane.
Adding 1,2-diaminoethane to the cobalt-ammonia complex results in the

Ligand substitution
ammonia ligands being replaced by 1,2-diaminoethane.
[Co(NH3)6]2+ + 3H2NCH2CH2NH2 ⇋ [Co(H2NCH2CH2NH2)3]2+ + 6NH3
The coordinate number in both complexes is 6. Only three
1,2-diaminoethane ligands are required as it is bidentate and each
forms two coordinate bonds to the Co2+ ion.
● Reaction of [Co(H2NCH2CH2NH2)3]2+ with EDTA4−
Adding a solution of EDTA4− to the cobalt-1,2-diaminoethane complex
results in another ligand substitution reaction.
[Co(H2NCH2CH2NH2)3]2+ + EDTA4− ⇋ [CoEDTA]2− + 3H2NCH2CH2NH2
Again the coordination number in both complexes is 6. EDTA4− is a
multidentate ligand and forms six coordinate bonds to the Co2+ ion so
only one EDTA4- is needed per Co2+ in the complex.

Ligand substitution with a change in the coordination

number
Larger charged ligands such as Cl− may cause a change in the coordination
number of the complex when a ligand substitution reaction occurs. Often the
coordination number is 4 as only four of these larger ligands will fit around
the metal atom or ion. Also the charges on the ligands repel each other.
● Reaction of [Cu(H2O)6]2+ with concentrated hydrochloric acid.
Adding concentrated hydrochloric acid to a solution containing
TIP [Cu(H2O)6]2+ results in the water ligands being replaced with Cl− ligands.
The same reactions occur with [Cu(H2O)6]2+ + 4Cl− ⇋ [CuCl4]2- + 6H2O
[Co(H2O)6]2+ and [Fe(H2O)6]3+ with The coordination number of the complex changes from 6 to 4.
concentrated hydrochloric acid.
Enthalpy and entropy considerations
The enthalpy change and entropy change in a ligand substitution reaction
determine whether or not the substitution reaction is feasible, but most
often it is the entropy change that is used to explain the process.
The enthalpy change is a balance of the energy required to break the
coordinate bonds between the ligands and the metal atom or ion and the
energy released when the bonds are formed between the new ligands and
the metal atom or ion.
● Some ligand substitution reactions show no change in the type of
coordinate bond or the coordination number of the complex, so the same
number and type of coordinate bonds would be formed as are broken.
Generally, in these reactions ΔH = 0. For example:
155
[Co(NH3)6]2+ + 3H2NCH2CH2NH2 → [Co(H2NCH2CH2NH2)3]2+ + 6NH3 ΔH = 0
● There will be change in enthalpy in ligand substitution reactions where
there is a change in the coordination number.
● If more coordinate bonds are broken than made, ΔH is positive. If fewer
coordinate bonds are broken than made, ΔH is negative. For example:
[Cu(H2O)6]2+ + 4Cl− → [CuCl4]2- + 6H2O ΔH >0
In this example, six coordinate bonds are broken in [Cu(H2O)6]2+ and
four are made in [CuCl4]2−.

807701_C08_AQA_Chemistry_2_149-174.indd 155 13/06/15 9:03 am

 ● If fewer coordinate bonds are broken than made, ΔH is negative. For
example:
[CuCl4]2− + EDTA4− → [CuEDTA]2− + 4Cl− ΔH <0
In this example four coordinate bonds are broken in [CuCl4]2− and six
are made in [CuEDTA]2−.
The entropy change is determined by the number of reacting particles in
solution and the number of product particles in solution.
● If the number of particles in solution increases, this would increase the
disorder in the solution which would increase the entropy. The entropy
change for the reaction would be positive (ΔS >0).
● The denticity of a ligand has a large effect on the stability of the
complexes which it forms.
● A bidentate ligand will form more stable complexes than a monodentate
ligand.
● A multidentate ligand, such as the hexadentate ligand EDTA4−, will form
TIP more stable complexes than a bidentate or monodentate ligand.
When asked about the chelate ● This is often called the chelate effect as bidentate and multidentate
effect, always state the total ligands form chelates with metal ions in solution, and these complexes
number of particles in solution are more stable than those formed with monodentate ligands.
on the left of the reaction and the
● Moving from a monodentate ligand to a bidentate or multidentate
right and use this to explain the
ligand causes an increase in the number of particles in solution and so
increase in entropy.
an increase in disorder (entropy). The chelate effect can be explained in
terms of increasing entropy of the substitution reaction.

EXAMPLE 3
Explain why the equilibrium is displaced almost completely to the right in
the following reaction.

[Co(NH3)6]2+ + 3H2NCH2CH2NH2 ⇋ [Co(H2NCH2CH2NH2)3]2+ + 6NH3

Answer
8    TRANSITION METALS

Both complexes have a coordination number of 6 so the same type and

the same number of coordinate bonds are broken and made. ΔH = 0.
In this example, three molecules of a bidentate ligand replace six
molecules of a monodentate ligand. This leads to an increase in
the number of particles in the solution, the solution becomes more
disordered which leads to higher entropy.

EXAMPLE 4
156
Explain why the equilibrium is displaced almost completely to the right in
the following reaction.
[Co(H2NCH2CH2NH2)3]2+ + EDTA4− ⇋ [CoEDTA]2− + 3H2NCH2CH2NH2

Answer
One molecule of a hexadentate ligand replaces three molecules of a
bidentate ligand. There is a change in the number of particles in solution
from 2 to 4. Again this increases disorder which increases entropy and so
the reaction is feasible.

807701_C08_AQA_Chemistry_2_149-174.indd 156 13/06/15 9:03 am

 Complex ion formation can be detected by elevation of boiling point or
depression of freezing point or by a decrease in electrical conductivity of a

Ligand substitution
solution as there are fewer free ions than would be expected.

Charge and oxidation number

The overall charge of a complex ion depends on the oxidation number of
the metal and the number and charge of the ligands.
With neutral ligands such as H2O and NH3 the oxidation number of the
metal is the same as the overall charge of the complex ion.
[Fe(H2O)6]3+ [Fe(H2O)5(SCN)]2+

Figure 8.5 A solution of [Fe(H2 O)6] 3+ is [Fe(H2O)6]3+   oxidation number of Fe = +3

shown on the left. When thiocyanate
[Co(NH3)6]2+   oxidation number of Co = +2
ions are added a blood red solution, as
shown on the right, is produced. It has With anionic ligands, the negative charge of the ligands contributes to the
formula [Fe(H2 O) 5 SCN]2+. This ligand
overall charge of the complex ion.
substitution reaction is used as a test
for iron(iii) ions in solution. ● [CuCl4]2−: as there are four Cl− ligands; the overall charge is 2− as the
oxidation number of the copper is +2.
● [Fe(H2O)5SCN]2+: the five neutral H2O ligands have no effect on the
overall charge; however, the thiocyano (SCN−) ligand does. As the overall
charge is 2+ and there is one SCN− ligand, the oxidation number of the
Fe = +3
● [Pt(NH3)Cl2]: the neutral NH3 ligands have no effect on the overall
charge; however, the Cl− ligands do. As the overall charge of the complex
is 0, the oxidation number of the Pt = +2

Haem and haemoglobin

Haem is a complex of an iron(ii) ion surrounded by a porphyrin ring. The
iron(ii) ion can accept 6 pairs of electrons from ligands. The porphyrin
ring contains 4 nitrogen atoms which can form 4 coordinate bonded to the
iron(ii) ion.
The porphyrin ring is a multidentate ligand. An amino acid residue in a
protein chain forms the fifth coordinate bond to the iron(ii) ion.
CH2
CH3

H3C

N N CH2

Fe

N N
157
H3C CH3

COOH COOH

Figure 8.6 Haem, which is a complex of Fe2+ and a porphyrin ring.

807701_C08_AQA_Chemistry_2_149-174.indd 157 13/06/15 9:03 am

 Haemoglobin is a protein structure containing four haem groups bonded to
four globular proteins, called α and β units.
Each Fe2+-containing haem complex can accept a pair of electrons and form
a coordinate bond from an oxygen molecule. This complex formed is called
oxyhaemoglobin. This is how haemoglobin transports oxygen in the blood.
Carbon monoxide also contains a lone pair of electrons on the oxygen atom,
and this can form a very stable complex with haemoglobin. Hence when
incomplete combustion of fuels occurs and carbon monoxide is produced,
people can be poisoned as the stable complex, carboxyhaemoglobin,
prevents oxygen being carried in the blood. This is the cause of death in
almost all house fires.

TEST YOURSELF 2
1 From the following complexes:
A [Cu(H2O)6]2+
B [CoCl 4]2-
C [Ni(H2NCH2CH2NH2)3]2+
D [Ag(NH3)2]+
a) In which complex does the transition metal have an oxidation state
of +1?
b) Which complex has a coordination number of 4?
c) Which complex contains a bidentate ligand?
2 Which ion is present in haemoglobin?
3 In the following ligand substitution reaction:
[Co(H2 O)6]2+ + 4Cl− → [CoCl 4]2− + 6H2 O
a) State the coordination number of the two complexes in this
reaction.
b) Explain, in terms of entropy, why this ligand substitution reaction
occurs.

●● Shapes of complex ions

8    TRANSITION METALS

The shape of complex ions is based mainly on the coordination number.

You should be familiar with working out the shapes of simple compounds
using electron pair repulsion theory. Complex ions have bonding pairs of
electrons around a central metal atom or ion and these repel each other
and create different shapes depending on the ligands and the coordination
number of the complex.

6-coordinated complex ions

158 TIP These are complex ions in which there are six coordinate bonds to the metal
The shapes of complexes can atom or ion from ligands. These ions have an octahedral shape.
be remembered using LOST.
These are the initial letters of Four of the ligands are in one plane, with the fifth one above the plane,
the shapes: Linear, Octahedral, and the sixth one below the plane. It does not matter what the ligands are.
Square planar, Tetrahedral. If you have six coordinate bonds, the shape will be octahedral. The bond
angle at the central metal atom or ion in an octahedral complex is 90°.

807701_C08_AQA_Chemistry_2_149-174.indd 158 13/06/15 9:03 am

 The diagram shows three examples of octahedral ions.

Shapes of complex ions

3+ 2+ 2+
H2O NH3 H2O
H2O OH2 H3N NH3 H3N NH3
Fe Co Cu
TIP H2O OH2 H3N NH3 H3N NH3
H2O NH3 H2O
Remember that the ligands
attached to a wedge-shaped bond
[Fe(H2O)6] 2+ [Co(NH3)6] 2+ [Cu(NH3)4(H2O)2] 2+
are coming out of the screen
or paper towards you. Those The 6-coordinated copper(ii) complexes are actually distorted octahedral
attached to a dashed bond are complexes as the top and bottom ligands are further away than the others.
behind the plane of the screen or These ligands are often not replaced when copper complexes undergo
paper. The two ligands attached
ligand replacements reactions.
to the solid bonds are above and
below the plane of the rest. 4-Coordinated complex ions
These are less common, and they can take up one of two different shapes.
2− −
Cl Cl
Tetrahedral complex
Cu Fe The [CuCl4]2−, [CoCl4]2− and [FeCl4]− complexes are tetrahedral in shape.
Cl
Cl
Cl Cl
Cl
Cl The bond angle at the central metal atom or ion in 109.5°.
The above two complexes may be formed by adding concentrated
[CuCl4] 2− [FeCl4] − hydrochloric acid to [Cu(H2O)6]2+, [Co(H2O)6]2+ and [Fe(H2O)6]3+.
[CuCl4]2− is yellow/green and [FeCl4]− is orange.

Square planar complex

Cl
Occasionally a 4-coordinated complex turns out to be square planar.
These are fewer in number than the tetrahedral 4-coordinated complexes.
H3N Pt Cl Usually a 4-coordinated complex that has no overall charge is square planar,
whereas those with a charge tend to be tetrahedral. Also, platinum tends to
NH3
form square planar complexes. The bond angle in a square planar complex
is 90°.
[Pt(NH3)2Cl2]
Cisplatin is such a square planar complex ion and is used as an anti-cancer
drug.
Cisplatin is a neutral complex, [Pt(NH3)2Cl2]. It is neutral because the
2+ charge of the platinum(ii) ion is exactly cancelled by the two negative
TIP charges supplied by the chloride ions.
If asked to draw a displayed The platinum, the two chlorides and the two nitrogen atoms are all in the
structure of cisplatin, the same plane.
coordinate bonds between the N
and H atoms in the NH3 ligand 2-coordinated complex ions
must be shown.
The most common 2-coordinated complex is the one formed between silver
159
ions, Ag+, and ammonia, [Ag(NH3)2]+.

H3N Ag NH3
+ It is a linear complex. The bond angle is 180°.
This is the complex used in organic chemistry as Tollens’ reagent to
distinguish between aldehydes and ketones. It is also the complex formed
when the white precipitate of silver chloride redissolves in dilute ammonia
solution and the cream precipitate of silver bromide redissolves in
concentrated ammonia solution.

807701_C08_AQA_Chemistry_2_149-174.indd 159 13/06/15 9:03 am

 Stereoisomerism in complex ions
Some complex ions can show either optical or geometric (E-Z) isomerism.
Cl NH3
Tetrahedral complexes can show E-Z isomerism.
H3N Pt Cl Cl Pt Cl
Octahedral complexes can show E-Z isomerism with monodentate ligands
NH3 NH3 or optical isomerism with bidentate ligands.
the ‘cis’ form the ‘trans’ form
E-Z isomerism in square planar complexes
Z isomer E isomer
This occurs in planar complexes like the Pt(NH3)2Cl2 as shown on the left.
There are two different ways in which the ammonia molecules and chloride
ions could arrange themselves around the central platinum ion:
The two structures drawn are isomers because they are non-
superimposable. This is the key feature with stereoisomers. There are two
forms which are non-superimposable due to the different three-dimensional
arrangement of the atoms.
The terms cis and trans are used in the same way as they are in organic
chemistry.
Trans implies ‘opposite’ – notice that the ammonia molecules are arranged
opposite each other in that version, and so are the chloride ions.
Cis implies ‘on the same side’ – in this instance that just means that the
Figure 8.7 The diagram shows a ammonia molecules and the chloride ions are next to each other.
molecular model of cisplatin. Atoms
are represented as spheres and are It is better to use the E-Z system of naming these isomers. E (entgegen,
colour-coded: platinum (grey), hydrogen meaning across) is equivalent to trans and Z (zusammen, meaning together)
(white), nitrogen (blue) and chlorine is equivalent to cis. The E-Z system includes many examples which cannot
(green). Which isomer is shown? be named using cis and trans.
Only the Z or cis isomer of the complex shows any anti-cancer activity. The
O
E or trans form is inactive against cancer. It is thought that cisplatin has its
chloride ligands replaced after entering the cell. This occurs because of the
O low intracellular chloride concentration which favours the replacement of
8    TRANSITION METALS

C
the chloride ions with water.
O O
The aquated complex is able to form links between bases in DNA in the
H3N Cl
Pt tumour cell. This halts the process of DNA replication in the tumour cells
H3N Cl and effectively stops the growth of the tumour. The drug is expensive due to
OH its platinum content and there are side effects such as potential death, organ
Figure 8.8 Clinical use of cisplatin is damage and hair loss.
limited as it may develop resistance,
earning it the nickname the ‘penicillin Cis-trans isomerism in octahedral complexes
of cancer’. Anchoring aspirin onto
cisplatin could create a cancer treatment For octahedral complexes of the type ML4A2 where M represents the metal
160 capable of overcoming drug resistance in atom or ion and L and A represent different ligands, there is a cis and a trans
cisplatin resistant cells. This new drug is isomer of this complex.
called Asplatin.
The isomers of [Co(NH3)4Cl2]+ are shown on page 161; the left-hand
isomer is the cis isomer as the two Cl− ligands are beside each other, i.e. at
90° to each other.
TIP The right-hand isomer is the trans isomer as the two Cl− ligands are
Trans isomers are sometimes opposite each other, i.e. at 180° to each other.
called E isomers and cis isomers
are sometimes called Z isomers.
The charge on the complex is + as the cobalt is in the +3 oxidation state and
the two Cl- ligand bring the overall charge on the complex to +.

807701_C08_AQA_Chemistry_2_149-174.indd 160 13/06/15 9:03 am

 + +
Cl Cl

Formation of coloured ions

H3N Cl H3N NH3
Co Co
H3N NH3 H3N NH3
NH3 Cl

cis isomer trans isomer

Optical isomerism in octahedral complexes

Optical isomers are non-superimposable and their optical activity allows
them to rotate the plane of plane polarised light. One isomer rotates the
plane to the left and is referred to as an l-isomer and one rotates the plane
TIP
You would not be expected to
to the right and is call the d-isomer. The ‘l’ is from laevorotatory (rotates to
be able to distinguish between the left) and ‘d’ is from dextrorotatory (rotates to the right).
the d and l forms based on a Octahedral complexes formed with a bidentate ligand form two optical
diagram. This would be carried isomers. It is the connection of the ligands by coordinate bonds within the
out practically by determining the
octahedral shape which gives the different isomers.
effect of each on plane polarised
light. A racemic mixture of both isomers shows no overall rotation as there would
be equal concentrations of both and the overall rotations would cancel each
other out.
3+ 3+
H2N H2N
H2N NH2 H2N NH2 The diagram on the left shows the two optical isomers formed when
Co Co 1,2-diaminoethane forms a complex with Co3+ ions. The ligands are
H2N NH2 H2N NH2 represented by H2N—NH2. The two optical isomers have a different three-
H2N H2N
dimensional spatial arrangement of the ligands around the central metal ion.

TEST YOURSELF 3
1 For the following complexes:
A [CuCl 4]2−
B [NiEDTA]2−
C [Ag(NH3)2]+
D [Co(H2O)6]3+
E [Co(H2NCH2CH2NH2)3]2+
F [Pt(NH3)2Cl 2]
a) State the shape of all the complexes.
b) State the coordination number of all the complexes.
c) State the oxidation state of the transition metal in all of the
complexes.
d) Which one of the complexes would exhibit cis–trans isomerism?
e) Which one of the complexes would exhibit optical isomerism?

●● Formation of coloured ions 161

Transition metal ions show distinct colours that can aid in their
identification. The main colours of the some common ions are:
● Copper(ii) compounds are mainly blue in colour.
● Iron(ii) compounds are pale green in colour.
● Cobalt(ii) compounds are pink in colour.
In solution these ions become hexaaqua cations, for example [Cu(H2O)6]2+.

807701_C08_AQA_Chemistry_2_149-174.indd 161 13/06/15 9:03 am

 The electromagnetic spectrum
For an examination of coloured compounds, the different colours of visible
light needs to be examined. Visible light is part of the electromagnetic spectrum.
The electromagnetic spectrum consists of many bands of electromagnetic
radiation which differ in the wavelength (λ), frequency (ν) and energy (E).
The main types of electromagnetic radiation are given in the diagram below.
Visible light is split into seven different colours that have different
wavelengths and frequencies.

Frequency/Hz

Long-wave radio 103 Expanded visible spectrum

106
Short-wave radio Frequency Wavelength
( × 1014 Hz) ( × 10–9 m)
100
109 Microwaves
4.7–4.3 Red 640−700

Millimeter waves 10–3 5.3−4.7 Orange 570−640

Wavelength/m
1012
Infrared light 5.6−5.3 Yellow 535−570
10–6
Visible light 6.1−5.6 Green 495−535
1015
Ultraviolet light
6.7−6.1 Blue 450−495
10–9
1018 X rays
7.1−6.7 Indigo 425−450

Gamma rays 10–12 7.5−7.1 Violet 400−425

1021

Visible spectrum
Higher Lower
frequency frequency
8    TRANSITION METALS

UV IR

400 500 600 700

Wavelength in nanometers

Colour in transition metal compounds and complexes

The presence of a transition metal ion in a compound or a complex gives
colour to the compound and to the complexes they form in solution.
● In these coloured compounds and complexes the d sub-level must be
162
partially filled.
● In complexes the d sub-level is split into two distinct sets of orbitals that
have a difference in energy between them (ΔE).

Excited
state
Energy

ΔE

Unsplit 3d subshell Ground

present in gaseous state
ions Split d orbitals present
in complexes

807701_C08_AQA_Chemistry_2_149-174.indd 162 13/06/15 9:03 am

 ● Energy in the visible region of the spectrum causes d electron transition
between the ground state of the split d orbitals and electrons become

Formation of coloured ions

excited and are promoted to the higher energy orbitals (excited state).
● Some frequencies of visible light are absorbed and the complementary
TIP colour (the colours not absorbed) are observed as they are reflected or
This table only serves to act as a transmitted.
guide but in general the colour ● The table below shows the wavelength of visible light in nm, the colour
you see is the colour that is not observed when certain colours are absorbed from the visible region of the
absorbed. electromagnetic spectrum.

Wavelength/nm Colour absorbed Colour observed

400–430 Violet Yellow–green
430–460 Blue–violet Yellow
460–490 Blue Orange
490–510 Blue–green Red
510–530 Green Purple
530–560 Yellow–green Violet
560–590 Yellow Blue–violet
590–610 Orange Blue
610–700 Red Blue–green

TIP
Changes in identity of the metal, ● Different metal ions and different charges of the ions (oxidation states) of
oxidation state of the metal/ the same metal and different ligands cause different splitting of the d sub-
charge on the ion, identity of the level, and so different frequencies of visible light are observed.
ligands, coordination number ● The shape of the complex and its coordination number also causes
of the complex and shape of the differences in the splitting of the d sub-shell and so the colour of the
complex all have an effect on ΔE, complexes.
and change the light absorbed
and so the visible colour Calculating energy, frequency and wavelength
observed.
There is an equation that links the energy difference (ΔE) between the
ground state and the excited state of the d electrons with the frequency (and
wavelength) of the light absorbed:
TIP ΔE = hν
ν is written like a v in italics.
It is the Greek letter nu and where ΔE is the difference in energy measured in joules (J), h is the Planck
represents frequency. f is also constant (6.63 × 10−34 J s) and ν is the frequency measured in hertz (Hz) or s−1.
sometimes used for frequency.
The wavelength of the light absorbed may also be used to calculate ΔE or
the wavelength may be calculated in metres (m) or nanometres (nm).
λ (nm) The equation relating wavelength to frequency is:
c = νλ
×10–9
163
where c is the speed of light (usually taken as 3.0 × 108 m s−1), ν is the
frequency of light in Hz and λ is the wavelength in m.
λ (m)
hc The equations may be combined to give:
c ∆E =
n= λ
λ hc
∆E =
λ
n (Hz) ∆E(J)
∆E = hn
The diagram on the left shows how the calculations are carried out.

807701_C08_AQA_Chemistry_2_149-174.indd 163 13/06/15 9:03 am

 MATHS EXAMPLE 5
The use of units such as nm [Cu(H2O)6]2+ absorbs red light (700 nm) and the solution appears blue.
and m and their interconversion
is key in this type of question. 1 Calculate a value for the energy, in J, associated with this wavelength
1 nm = 10−9 m. Rearranging even of light. The Planck constant, h = 6.63 × 10−34 J s and c = 3 × 108 m s−1
a simple expression can allow 2 When a solution containing [Cu(H2O)6]2+ is mixed with concentrated
other quantities in the expression hydrochloric acid the solution changed from blue to yellow–green and
to be calculated. All the absorbs violet light (400 nm).
calculations in the above diagram a) Explain whether the energy change, ΔE, between the ground state
can be reversed. and excited state of the d electrons is bigger, smaller or the same for
a solution which forms a yellow-green solution compared to a blue
solution.
b) State two different features of a transition metal complex which
causes a change in the value of ΔE

Answers
1 λ = 700 nm
λ = 700 × 10−9 m
hc
∆E = λ
hc 6.63 × 10−34 × 3 × 108 1.989 × 10−52
∆E = λ = 700 × 10−9 = 700 × 10−9 = 2.84 × 10−19J
2 a) Bigger
b) Identity of the metal; type of ligands which are present; coordination
number; oxidation state of the metal or charge on the ion; shape of
the complex

EXAMPLE 6
A d electron in a transition metal ion is excited by visible light from its
ground state to an excited state. ΔE for this change is 3.81 × 10−19 J.
1 Give the equation which relates the energy change (ΔE) to the frequency
8    TRANSITION METALS

of the visible light.

2 Calculate a value for the frequency of the visible light and state its
units.
3 Explain why a solution of this transition metal ion is coloured based on
the electronic transition.

Answers
1 ΔE = hν
ΔE 3.81 × 10−19
2 ν= = = 5.75 × 1014 Hz
h 6.63 × 10−34
3 Light is absorbed to excite electrons from ground state to excited state.
164 The complementary colour is the colour observed.

Colorimetry and spectrometry

Colorimetry is the measurement of colour intensity using an instrument
called a colorimeter. The intensity of colour in a solution is directly
proportional to the concentration of the coloured species.
A colorimeter works by passing a beam of light through the coloured
sample and comparing the light that was passed into the sample (incident
light) with the light that passes through the sample (transmitted light).

807701_C08_AQA_Chemistry_2_149-174.indd 164 13/06/15 9:03 am

 The absorbance is the ratio of the incident light to the absorbed light.
Absorbance is also proportional to the path length, which is the actual

Formation of coloured ions

length of solution through which the light must pass.
Cuvette
Filter containing
wheel sample

Light Incident Transmitted

Detector
light light
Source

The light from the light source is passed through a filter which changes the
light to a specific wavelength (i.e. colour) and the incident light then passes
into the sample. The choice of the incident light wavelength (colour) is
important. A blue solution is not absorbing blue light so a blue filter would
be useless. A red filter would be used to measure the absorbance of a blue
solution.
The sample is contained in a cuvette which is a 1 cm × 1 cm glass or plastic
vial.
The transmitted light is detected and the difference between the transmitted
light and the incident light is the absorbance.
The path length is the length through which the solution has to pass in
most cases 1 cm.
A simple equation relates absorbance to concentration and path length:
A = εcl
where c is the concentration in mol dm−3, l is path length in cm and ε is
the molar absorption coefficient (absorption by 1 mol dm−3 solution with a
path length of 1 cm). This equation is not required but an understanding of
the relationship between absorption and concentration and path length is
useful.
A graph of absorbance against concentration of the coloured species gives
a directly proportional line as shown. This type of graph is often used
to determine the concentration of an unknown sample of the coloured
substance from its absorbance.
Absorbance

Spectroscopy uses a spectrophotometer and it is the same process but

the wavelength can be varied over values in the ultraviolet region of the
spectrum, as well as in this visible region.
Many molecules and some complexes may appear white/colourless
Concentration of coloured substance
in solution as they do not absorb light in the visible region of the 165
electromagnetic spectrum, but they may have characteristic absorbance in
the ultraviolet region of the spectrum. This can be particularly useful in
organic chemistry.
The absorbance at a particular wavelength in the ultraviolet region of the
spectrum is still directly proportional to the concentration of the substance
under examination.

807701_C08_AQA_Chemistry_2_149-174.indd 165 13/06/15 9:03 am

 TEST YOURSELF 4
1 A solution of a complex ion absorbs light at a wavelength of 450 nm.
c = 3.0 × 108 m s−1. Calculate the energy, in J, associated with this
wavelength.
2 Suggest why a solution of [CoCl 4]2- is blue.
3 Calculate the wavelength of light, in nm, absorbed by a solution which
absorbs energy 3.617 × 10 −19 J. c = 3.0 × 10 8 m s−1.

●● Ions in aqueous solution

Transition metal compounds dissolve in water to form coloured complexes.
Other metal compounds also dissolve in water to form complex ions, for
example compounds of aluminium. The complexes are called hexaaqua
complexes and have the general formula [M(H2O)6]2+ where M is Fe or Cu
or [M(H2O)6]3+ where M is Al or Fe.
TIP
You should know the test for The reaction of these hexaaqua complexes with solutions of sodium
the anions covered in AS in hydroxide, ammonia and sodium carbonate can be used to identify them.
the chapters on the Halogens
and Group 2. You may be Sodium hydroxide solution, NaOH(aq)
asked to identify a transition Sodium hydroxide solution contains sodium ions and hydroxide ions. The
metal compound that involves hydroxide ions can cause the precipitation of insoluble metal hydroxides.
identifying the transition metal Sometimes the insoluble metal hydroxide may react with an excess of
cation and the anion. hydroxide ions and redissolve to form a hydroxo complex.

Ammonia solution, NH3(aq)

Ammonia, NH3, reacts with water reversibly to form a solution containing
NH3, NH4+ ions and OH− ions due to the reversible reaction:
NH3 + H2O ⇋ NH4+ + OH−
8    TRANSITION METALS

The presence of the hydroxide ions causes the precipitation of the insoluble
metal hydroxide. Sometimes the insoluble metal hydroxide may react with
excess ammonia and redissolve to form an ammine complex.

Sodium carbonate solution, Na2CO3(aq)

Sodium carbonate solution contains sodium ions and carbonate ions. For
2+ ions the carbonate ions may react to form an insoluble metal carbonate
precipitate. For 3+ ions the carbonate ions react with the solution to form a
hydroxide precipitate and carbon dioxide gas is evolved.

166 Acidity of [M(H2O)6]3+ solutions

The reaction of these complexes with sodium carbonate is because
complexes of the type [M(H2O)6]3+ form more acidic solutions than
complexes of the type [M(H2O)6]2+. The charge density of a 3+ ion is
generally greater than the charge density of the 2+ ion, but it does also
depend on the size of the ion. Water ligands bonded to a 3+ ion are
polarised and release H+ ions into the solution.
For example:
[Fe(H2O)6]3+ ⇋ [Fe(H2O)5OH]2+ + H+

807701_C08_AQA_Chemistry_2_149-174.indd 166 13/06/15 9:03 am

 This makes the solution acidic and the carbonate ions are broken down
TIP to CO2 and H2O by the H+ ions in the solution. H+ ions continue to be

Ions in aqueous solution

Sodium hydroxide solution or any released from the complex until a neutral insoluble complex is formed, i.e.
other solution may be referred Fe(OH)3(H2O)3. The reaction stops when either all the carbonate ions are
to as aqueous sodium hydroxide.
used up or all of the complex has been converted to the neutral complex.
Aqueous means dissolved in
water and often the two are used [M(H2O)6]2+
but mean the same thing.
For this type of complex, only Fe and Cu are considered.

[Fe(H2O)6]2+
When iron(ii) compounds dissolve in water, they form the hexaaquairon(ii)
complex, [Fe(H2O)6]2+. The solution formed is green due to the presence of
this complex.
When a solution of sodium hydroxide, ammonia or sodium carbonate is
added to a solution containing [Fe(H2O)6]2+ ions, precipitation reactions
occur.

TIP
A precipitate is a solid that
may be formed on mixing two
solutions. Often ppt is used an
abbreviation for precipitate. Figure 8.9 Iron(ii) hydroxide precipitate can be formed by adding sodium
hydroxide solution to a solution containing iron(ii) ions.

With sodium hydroxide solution

Observations: A green precipitate of iron(ii) hydroxide, Fe(OH)2(H2O)4, is
formed which slowly changes to a brown solid (caused by the oxidation of
iron(ii) hydroxide to iron(iii) hydroxide by oxygen in the air).
Equation:
[Fe(H2O)6]2+ + 2OH− → Fe(OH)2(H2O)4 + 2H2O
            green ppt

The precipitate of iron(ii) hydroxide does not redissolve on the addition of 167
more sodium hydroxide solution.

With ammonia solution

Equation:
TIP
Note that the observations and [Fe(H2O)6]2+ + 2OH− → Fe(OH)2(H2O)4 + 2H2O
the chemistry is essentially the             green ppt
same as both solutions contain
The precipitate of iron(ii) hydroxide does not redissolve on the addition of
hydroxide ions.
more ammonia solution.

807701_C08_AQA_Chemistry_2_149-174.indd 167 13/06/15 9:03 am

 With sodium carbonate solution
Observations: A green precipitate of iron(ii) carbonate, FeCO3, is formed.
Equation:
TIP
Make sure all the equations begin [Fe(H2O)6]2+ + CO32− → FeCO3 + 6H2O
with the hexaaqua complex, in       green ppt
this case [Fe(H2O)6]2+. Some
sources will show a simple
[Cu(H2O)6]2+
precipitation reaction as Fe2+ +
CO32− → FeCO3 but this is not When copper(ii) compounds dissolve in water, they form the
accepted by AQA as the equation hexaaquacopper(ii) complex, [Cu(H2O)6]2+. The solution formed is blue
must include the complex. due to the presence of this complex.
When a solution of sodium hydroxide, ammonia or sodium carbonate is
added to a solution containing [Cu(H2O)6]2+ ions, precipitation reactions
occur.

With sodium hydroxide solution

Observations: A blue precipitate of copper(ii) hydroxide, Cu(OH)2(H2O)4,
is formed.
Equation:
[Cu(H2O)6]2+ + 2OH− → Cu(OH)2(H2O)4 + 2H2O
            blue ppt

The precipitate of copper(ii) hydroxide does not redissolve on the addition

of more sodium hydroxide solution.

With ammonia solution

Observations: A blue precipitate of copper(ii) hydroxide, Cu(OH)2(H2O)4,
is formed.
Equation:
[Cu(H2O)6]2+ + 2OH− → Cu(OH)2(H2O)4 + 2H2O
8    TRANSITION METALS

            blue ppt

TIP
The deep blue solution may The precipitate of copper(ii) hydroxide redissolves on the addition of more
also be described as dark ammonia solution to form a deep blue solution.
blue or royal blue. It is a very
Equation
characteristic colour for this
reaction and helps identify Cu(OH)2(H2O)4 + 4NH3 → [Cu(NH3)4(H2O)2]2+ + 2H2O + 2OH−
copper(ii) ions.   deep blue solution

Figure 8.10 The test tube on the left

contains a solution of copper(ii) sulfate.
168 When a small amount of ammonia
solution is added (centre) a precipitate
of copper(ii) hydroxide is formed. Adding
more ammonia solution dissolves the
copper(ii) hydroxide (right) and forms a
deep blue solution.

807701_C08_AQA_Chemistry_2_149-174.indd 168 13/06/15 9:03 am

 With sodium carbonate solution
Observations: A green precipitate of copper(ii) carbonate, CuCO3, is formed.

Ions in aqueous solution

Equation:
[Cu(H2O)6]2+ + CO32− → CuCO3 + 6H2O
     green ppt

[M(H2O)6]3+
For this type of complex, only Fe and Al are considered.

[Fe(H2O)6]3+
When iron(iii) compounds dissolve in water, they form the hexaaquairon(iii)
complex, [Fe(H2O)6]3+. The solution formed is often yellow due to the
presence of this complex. The colour of the solution may vary depending
on the anion present in the compound. Some solutions of iron(iii)
compound may appear purple, brown, lilac or violet.
When a solution of sodium hydroxide, ammonia or sodium carbonate is
added to a solution containing [Fe(H2O)6]3+ ions, precipitation reactions
occur.

With sodium hydroxide solution

Observations: A brown precipitate of iron(iii) hydroxide, Fe(OH)3(H2O)3, is
formed.
Equation:
[Fe(H2O)6]3+ + 3OH− → Fe(OH)3(H2O)3 + 3H2O
TIP        brown ppt
The brown precipitate of iron(iii)
hydroxide may also be described The precipitate of iron(iii) hydroxide does not redissolve on the addition of
as rusty. more sodium hydroxide solution.

169

Figure 8.11 Iron(iii) hydroxide precipitate can be formed by

adding sodium hydroxide solution to a solution containing
iron(iii) ions.

With ammonia solution

Observations: A brown precipitate of iron(iii) hydroxide, Fe(OH)3(H2O)3, is
formed.

807701_C08_AQA_Chemistry_2_149-174.indd 169 13/06/15 9:03 am

 Equation:
[Fe(H2O)6]3+ + 3OH− → Fe(OH)3(H2O)3 + 3H2O
    brown ppt
The precipitate of iron(iii) hydroxide does not redissolve on the addition of
more ammonia solution.

With sodium carbonate solution

Observations: A brown precipitate of iron(iii) hydroxide, Fe(OH)3(H2O)3, is
TIP formed and bubbles of a gas are produced.
It is important to be aware of
the difference between the Equation:
reactions of solutions containing 2[Fe(H2O)6]3+ + 3CO32− → 2Fe(OH)3(H2O)3 + 3CO2 + 3H2O
iron(ii) compounds and iron(iii)       brown ppt
compounds with sodium
carbonate solution. Make sure
you can describe the observations
[Al(H2O)6]3+
and write the equations. When aluminium compounds dissolve in water, they form the
hexaaquaaluminium(iii) complex, [Al(H2O)6]3+. The solution formed is
colourless.
When a solution of sodium hydroxide, ammonia or sodium carbonate is added
to a solution containing [Al(H2O)6]3+ ions, precipitation reactions occur.

With sodium hydroxide solution

Observations: A white precipitate of aluminium hydroxide, Al(OH)3(H2O)3,
is formed.
Equation:
[Al(H2O)6]3+ + 3OH− → Al(OH)3(H2O)3 + 3H2O
      white ppt

The precipitate of aluminium hydroxide redissolves on the addition of more

sodium hydroxide solution to form a colourless solution.
8    TRANSITION METALS

Equation:
Al(OH)3(H2O)3 + OH− → [Al(OH)4(H2O)2]− + H2O
     colourless solution
As more sodium hydroxide solution is added more OH− ligands replace the
water ligands in the complex until [Al(OH)6]3− is formed. The equation can
be written with anywhere between 4 and 6 OH− present in the complex.
The equation below is very common:

Al(OH)3(H2O)3 + 3OH− → [Al(OH)6]3− + 3H2O

170 The solution formed is colourless irrespective of the number of OH- ligands
in the complex.

With ammonia solution

Observations: A white precipitate of aluminium hydroxide, Al(OH)3(H2O)3,
is formed.
Equation:
[Al(H2O)6]3+ + 3OH− → Al(OH)3(H2O)3 + 3H2O
        white ppt

807701_C08_AQA_Chemistry_2_149-174.indd 170 13/06/15 9:03 am

 The precipitate of aluminium hydroxide does not redissolve on the addition
of more ammonia solution.

Ions in aqueous solution

Figure 8.12 Aluminium hydroxide precipitate is formed by adding ammonia solution
to a solution containing aluminium ions.

With sodium carbonate solution

Observations: A white precipitate of aluminium hydroxide, Al(OH)3(H2O)3,
is formed and bubbles of a gas are produced.
Equation:
2[Al(H2O)6]3+ + 3CO32− → 2Al(OH)3(H2O)3 + 3CO2 + 3H2O
          white ppt
The table below summarises the observations and the formulae of the
complexes involved.

Hexaaqua complex [Fe(H2O)6]2+ [Cu(H2O)6]2+ [Fe(H2O)6]3+ [Al(H2O)6]3+

Colour Green Blue Yellow (or brown or Colourless
violet or purple or lilac)
Reaction with NaOH(aq) Green ppt Blue ppt Brown ppt White ppt
Complex formed Fe(OH)2(H2O)4 Cu(OH)2(H2O)4 Fe(OH)3(H2O)3 Al(OH)3(H2O)3
Does it redissolve in excess No No No Yes
NaOH(aq) and colour of Colourless
solution formed? solution formed
Complex formed [Al(OH)4 (H2O)2] − or
[Al(OH)6]3 −
Reaction with NH3(aq) Green ppt Blue ppt Brown ppt White ppt 171
Complex formed Fe(OH)2(H2O)4 Cu(OH)2(H2O)4 Fe(OH)3(H2O)3 Al(OH)3(H2O)3
Does it redissolve in excess No Yes No No
NH3(aq) and colour of Deep blue solution
solution formed? formed
Complex formed [Cu(NH3)4 (H2O)2]2+
Reaction with Na2CO 3(aq) Green ppt Green ppt Brown ppt White ppt
Bubbles of gas Bubbles of gas
released released
Compound or complex FeCO 3 CuCO 3 Fe(OH)3(H2O)3 Al(OH)3(H2O)3
formed

807701_C08_AQA_Chemistry_2_149-174.indd 171 13/06/15 9:03 am

 TEST YOURSELF 5 2 Consider the complex [Al(OH)4(H2O)2]−
1 Consider the following complexes: a) What is the coordination number of this complex?
A [Cu(H2O)6]2+ b) What is the oxidation state of aluminium in this
B [Al(H2O)6]3+ complex?
C [Fe(H2O)6]2+ c) Suggest the shape of this complex.
D [Cu(NH3)4(H2O)2]2+ d) Write an equation for the formation of this
a) Which complexes are blue? complex from Al(OH) 3(H2 O)3.
b) What is observed when aqueous sodium 3 A sample of iron(iii) chloride is dissolved in water.
carbonate is added to complex A? a) Write the formula of the iron complex formed
c) What is observed when aqueous sodium when iron(iii) chloride dissolves in water.
hydroxide is added to complex B until in b) What is observed when aqueous sodium
excess? carbonate is added to the solution containing
d) What is observed when aqueous ammonia the complex?
is added to complex C? c) Write an equation for the reaction of aqueous
sodium carbonate with this iron complex.

REQUIRED PRACTICAL II
Using test-tube reactions to identify ions in a polluted river. A forensic scientist may use a simple
solution chemical test, using an alkaline solution, to identify
components in a soil sample taken from a crime
Chemical tests are used by analytical chemists to scene and compare this with a soil sample taken
give an indication of the nature of substances that from a suspect’s shoes.
may be present in a sample. For example, a chemical
test may be used to determine the presence of a To determine the identity of a chemical salt A, the
particular metal ion in a sample of water taken from following tests were carried out and the observations
recorded.

Test Observation
1 Describe the appearance of A Blue crystals
2 Dissolve a spatula measure of A in approximately 50 cm3 of water Blue solution
3 Add a few drops of barium chloride solution to 2 cm3 of the solution of A White ppt
Blue solution remains
8    TRANSITION METALS

4 Add a few drops of silver nitrate solution to 2 cm3 of the solution of A Blue solution
5 Add sodium hydroxide solution to 2 cm3 of the solution of A, drop wise with Blue ppt
shaking, until in excess
6 In a fume cupboard, add concentrated ammonia solution drop wise, until Blue ppt which redissolves on
present in excess, to 2 cm3 of the solution of A excess to produce a deep blue solution
7 Add a few drops of sodium carbonate solution to cm 3 of the solution of A. Green ppt

1 Use the evidence in the table to suggest the metal 4 State the formula of the complex formed in test 5.
ion present in A. 5 Explain using two balanced symbol equations, the
2 Suggest the formula of the complex ion formed in reaction occurring in test 6.
172 test 2. Name the shape of this complex. 6 What is the name of the green ppt formed in test 7?
3 Using the results from tests 3 and 4, determine the 7 Suggest and explain what would be observed if the
anion present in A. State your reasons, giving an salt A was heated gently in a boiling tube.
ionic equation for any reaction which occurs. 8 Suggest a name for the salt A.

807701_C08_AQA_Chemistry_2_149-174.indd 172 13/06/15 9:03 am

 C iron(ii) bromide
Practice questions

Practice questions
D iron(iii) chloride (1)
1 Which of the following ions does not have an
electronic configuration of 1s2 2s2 2p6 3s2 3p6 5 [CuCl4]2− is green–yellow. It absorbs light
3d5? of wavelength 420 nm. The Planck constant,
h = 6.63 × 10−34 J s. The speed of light,
A Mn2+ c = 3.0 × 108 m s−1.
B Fe3+ a) Give the equation which relates the
C Cr+ energy change ΔE to the Planck constant
h and the wavelength of the visible
D Cr3+ (1) light, λ. (1)
2 In which of the following complexes does the b) Calculate a value for ΔE and state its
complex have a coordination number of 6 and units. (3)
transition metal have an oxidation state of +2?
c) Explain why the solution is coloured. (2)
A [CoCl4]2−
d) State three features of a transition metal
B [Fe(H2O)6]3+ complex which can cause a change in the
C [Pt(NH3)2Cl2] wavelength of light absorbed. (3)

D [CoEDTA]2− (1) 6 Some ligands are listed below. All of the

ligands are monodentate except the oxalate
3 Which one of the following is correct? ligand which is bidentate.
A On adding sodium hydroxide solution Ligands: thiocyano: SCN−; cyano: CN−;
to a solution of copper(ii) sulfate, a green aqua: H2O; hydroxo: OH−; oxalate: C2O42−;
precipitate is observed. ammine: NH3
B On adding sodium carbonate solution to a a) Explain the meaning of the term
solution of iron(ii) sulfate, a white precipitate bidentate. (1)
is observed.
b) Write the formula of the complex formed
C On adding ammonia solution to a solution between the nickel(ii) ion and the
of iron(iii) chloride, a brown precipitate is ammine ligand where the coordination
observed. number is 6. (1)
D On adding sodium carbonate solution c) Write the formula of the complex formed
to a solution of copper(II) sulfate, a blue between the chromium(iii) ions and the
precipitate is observed. (1) hydroxo ligand where the coordination
4 The following tests were carried out to a number is 6. (1)
solution of an unknown compound: d) Write the formula of the complex
Test 1: To a solution of the compound, sodium formed between the silver(i) ion and
carbonate solution was added and a brown the ammine ligand where the
precipitate and bubbles of a gas were observed. coordination number is 2. (1)
e) Suggest the shape of the complexes 173
Test 2: To a solution of the compound, nitric
acid and silver nitrate solution were added and a described in (b), (c) and (d). (3)
white precipitate was observed. 7 A ligand substitution reaction occurs when
Which one of the following is the most likely a solution containing EDTA4− is added to a
identity of the compound? solution containing [Ni(H2O)6]2+ ions.

A aluminium carbonate [Ni(H2O)6]2+ + EDTA4− → [NiEDTA]2− + 6H2O

B copper(ii) chloride

807701_C08_AQA_Chemistry_2_149-174.indd 173 13/06/15 9:03 am

 a) EDTA4− is a chelating agent. Explain this 10 Aqueous metal ions can be identified by test
term. (1) tube reactions.
b) Explain in terms of the chelate effect why For each of the following describe what you
this ligand substitution reaction occurs. (2) would observe.
c) What type of bond is formed between Write an equation or equations for any
EDTA4− and the nickel ion? (1) reactions that occur.
d) State the coordination number of the a) The addition of aqueous sodium carbonate
two complexes, [Ni(H2O)6]2+ and to solutions containing [Fe(H2O)6]2+ and
[NiEDTA]2−. (1) another solution containing [Fe(H2O)6]3+. (7)
8 Consider the following reaction scheme. All b) The addition of aqueous ammonia to a
the complexes are in aqueous solution. solution containing [Cu(H2O)6]2+. (4)
A Stretch and challenge
11 Iron rusts when exposed to air and moisture.
1
Rusting occurs in a series of reactions as
B
2
[Fe(H2O)6]3+
3
C shown below:
Reaction 1: Fe(s) → Fe2+(aq) + 2e−
a) In reaction 1, aqueous sodium hydroxide is
Reaction 2: O2 + 2H2O + 4e− → 4OH−
added to a solution of the complex. Write
an equation for the reaction. (2) Reaction 3: Fe2+(aq) + 2OH−(aq) → Fe(OH)2(s)
b) In reaction 2, ammonia solution is added Reaction 4:
to a solution of the complex. What is 4Fe(OH)2(s) + O2(g) → 2Fe2O3.H2O(s) + 2H2O(l)
observed? (1)
a) Write an overall equation for rusting by
c) In reaction 3, a solution of sodium combining the equations for reaction
carbonate is added to a solution of the 1 to 4 above. (3)
complex.
b) Which one of the reactions is not a redox
i) What is observed? (2) reaction? Explain your answer. (2)
ii) Write an equation for the reaction c) In the process of sacrificial protection of
8 TRANSITION METALS

which is occurring. (2) iron, blocks of magnesium are attached to

the iron.
9 Complexes of [Pt(NH3)2Cl2], [Co(NH3)4Cl2]+
and [Ni(H2NCH2CH2NH2)3]2+ exhibit different Mg2+(aq) + 2e− → Mg(s) E1 = −2.37 V
forms of stereoisomerism.
Fe2+(aq) + 2e− → Fe(s) E1 = −0.44 V
a) What is the coordination number and
i) Explain why the block of magnesium
shape of the complex [Pt(NH3)2Cl2]? (2)
is described as the negative electrode
b) State the type of stereoisomerism shown by (anode). (1)
the three complexes. (3)
ii) Write cell notation for the
174 c) What is a use of an isomer of the electrochemical cell in this redox
[Pt(NH3)2Cl2] complex. (1) reaction. (2)
d) Explain why the [Pt(NH3)2Cl2] complex iii) Calculate the emf of the cell. (1)
has no overall charge. (2)

807701_C08_AQA_Chemistry_2_149-174.indd 174 13/06/15 9:03 am

 Transition metals:
9 Variable oxidation
states
PRIOR KNOWLEDGE
● Transition metals form compounds with the transition metal in
different oxidation states.
● The oxidation states of transition metals vary from 0 (for the element)
to a maximum of +7.
● +2 is a common oxidation state of transition metals.
● Oxidation and reduction reactions between these oxidation states
are common and there are changes in colour associated with these
changes.
● Transition metal compounds can be used in organic chemistry for
oxidation reactions.
● Transitions metals and their compounds may be used as catalysts.
● Catalysts provide an alternative reaction pathway of lower activation
energy and so increase the rate of a chemical reaction.

TEST YOURSELF ON PRIOR KNOWLEDGE 1

1 Give the oxidation state of the transition metal in the following
compounds and ions.
a)
Fe2O3
b)
MnO−4
c)
Na2CrO4
d)
K 2Cr2O7
2 Calculate the value of x in the manganate(vi) ion, MnO2−
X.
3 Name the following compounds including the oxidation state of the
transition metal.
a) Na2Cr2O7
b) MnO2
c) Co2O3
4 Explain how a catalyst increases the rate of a chemical reaction.

●● Oxidation states of transition metals 175

Elements of the series of d block elements (Sc → Zn) excluding chromium

and copper have the general electronic configuration [Ar] 3dn, 4s2. The
removal of the 4s2 electrons creates the ubiquitous 2+ ion.
The oxidation states of the elements vary depending on the number of d
electrons available in the atom. The most common oxidation states of the d
block elements are as follows:
Sc +3; Ti +3, +4; V +4, +5; Cr +3, +6; Mn +2, +4, +7; Fe +2, +3;
Co +2; +3, Ni +2; Cu +2, Zn +2.

807701_C09_AQA_Chemistry_2_175-191.indd 175 13/06/15 9:03 am

 The stability of the +2 oxidation state relative to the +3 and higher states
increases from left to right across the series. This reflects the increasing
difficulty of removing a 3d electron as the nuclear charge increases.
The table below shows all oxidation states of the first series of d block
elements. The ones shown in bold are most common oxidation states of
the elements.

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
TIP Oxidation states +7
Scandium to zinc are the +6 +6 +6
elements in the first series of +5 +5 +5 +5
the d block, but scandium and +4 +4 +4 +4 +4 +4 +4
zinc are d block elements, not
+3 +3 +3 +3 +3 +3 +3 +3 +3
transition elements. Transition
+2 +2 +2 +2 +2 +2 +2 +2 +2 +2
elements form at least one ion
with an incomplete d subshell. +1 +1
Scandium and zinc form ions with
In general, the compounds of the higher oxidation states are found in covalent
empty or incomplete d subshells.
The first transition series runs compounds and molecular ions and they can act as oxidising agents as the
from titanium to copper. transition metal can gain electrons and be reduced to lower oxidation states.

Vanadium chemistry
9    TRANSITION METALS: VARIABLE OXIDATION STATES

Vanadium has 4 major oxidation states, +2, +3, +4 and +5. The molecular
and simple ions below show vanadium in these oxidation states with the
colour in aqueous solution.

TIP Oxidation Name of Colour in aqueous

You can remember the colours state molecular ion Formula of ion solution
of vanadium using ‘You Better +5 Dioxovanadium(v) ion VO +2 Yellow
Get Vanadium’. Y in you is yellow, Vanadate(v) ion VO −3
B in better is blue, G in get is +4 Oxovanadium(iv) ion VO2+ Blue
green and V in vanadium is violet. +3 Vanadium(iii) ion V 3+ Green
Try to create your own rhyme +2 Vanadium(ii) ion V 2+ Violet
(mnemonic) for this if you cannot
remember this one. These are a
good way to learn. An aqueous solution of vanadium in the +5 oxidation state (either
vanadate(v) or dioxovanadium(v)) can be reduced from +5 to +2 showing
all the oxidation states in between.

Figure 9.1 Test tubes containing

solutions of dissolved vanadium
compounds in different oxidation states.
Can you identify the oxidation states?

176

807701_C09_AQA_Chemistry_2_175-191.indd 176 13/06/15 9:04 am

 You must be able to write half equations for all these reduction reactions
(or oxidation reactions if going from +2 to +5). This is revision of writing

Oxidation states of transition metals

half equations from the oxidation, reduction and redox reactions section in
Book 1, AS level.
+5 to +4
Step 1: Write the species involved in the reduction.
 VO+2 → VO2+
Step 2: Check the oxidation numbers and add electrons as appropriate to
cause the reduction. (Remember electrons go on the left-hand side
of a reduction and they go on the right-hand side of an oxidation.)
 VO+2 + e− → VO2+
Step 3: Add H+ ions to one side and H2O to the other side to balance the
oxygen atoms. (Remember usually H+ go on the left-hand side in a
reduction and H+ go on the right-hand side in an oxidation.)
 VO+2 + 2H+ + e− → VO2+ + H2O
Step 4: Check the charge balance on each side
  Total charge on left = +2 Total charge on right = +2
Equation is balanced both with atoms and charges.
  Final equation: VO+2 + 2H+ + e− → VO2+ + H2O

+4 to +3
Step 1: Write the species involved in the reduction
 VO2+ → V3+
Step 2: Check the oxidation numbers and add electrons as appropriate to
cause the reduction
 VO2+ + e− → V3+
Step 3: Add H+ ions to one side and H2O to the other side to balance the
oxygen atoms.
 VO2+ + 2H+ + e− → V3+ + H2O
Step 4: Check the charge balance on each side
Total charge on left = +3 Total charge on right = +3
Equation is balanced both with atoms and charges.
  Final equation: VO2+ + 2H+ + e− → V3+ + H2O
177
+3 to +2
Step 1: Write the species involved in the reduction
TIP
You can revise writing half  V3+ → V2+
equations from the Oxidation,
Step 2: Check the oxidation numbers and add electrons as appropriate to
reduction and redox equations
cause the reduction
topic in AS Book 1.
 V3+ + e− → V2+
All charges balance
Final equation: V3+ + e− → V2+

807701_C09_AQA_Chemistry_2_175-191.indd 177 13/06/15 9:04 am

 Redox potentials
The reduction potentials for these reactions are given below.
VO+2 + 2H+ + e− → VO2+ + H2O +1.00 V
VO2+ + 2H+ + e− → V3+ + H2O +0.34 V
V3+ + e− → V2+ −0.26 V
Reduction of vanadium
Vanadium can be reduced from +5 to +2 using a reducing agent like zinc (in
the presence of acid).
Zn2+ + 2e− → Zn −0.76 V
When zinc reduces vanadium, the zinc becomes oxidised so the half
equation for the reaction of zinc is:
Zn → Zn2+ + 2e− +0.76 V
By combining this with each of the reduction half equations for the
vanadium reductions, we can see how far zinc can reduce vanadium.
The ionic equation for each overall reaction can be determined by
combining the oxidation and reduction half equations to cancel out
electrons on both sides.
9    TRANSITION METALS: VARIABLE OXIDATION STATES

The electromotive force (EMF) is determined by simply adding the

reduction potential and the oxidation potential together. Remember the
addition of redox potentials does not depend on the number of moles of
each substance reacting – it is simply a total.
The acid is present to provide H+ ions which are required in the redox reaction:
● A positive EMF means that the reaction is feasible.
● A negative EMF means that the reaction is not feasible.
VO+2 + 2H+ + e− → VO2+ + H2O +1.00 V (REDUCTION)
Zn → Zn2+ + 2e− +0.76 V (OXIDATION)
EMF =+1.76 V (FEASIBLE)
Ionic equation: 2VO+2 + 4H+ + Zn → 2VO+2 + 2H2O + Zn2+

VO2+ + 2H+ + e− → V3+ + H2O +0.34 V (REDUCTION)

Zn → Zn2+ + 2e− +0.76 V (OXIDATION)
EMF = +1.10 V (FEASIBLE)
Ionic equation: 2VO2+ + 4H+ + Zn → 2V3+ + 2H2O + Zn2+

V3+ + e− → V2+ −0.26 V (REDUCTION)

178 Zn → Zn2+ + 2e− +0.76 V (OXIDATION)
EMF = +0.50 V (FEASIBLE)
Ionic equation: 2V3+ + Zn → 2V2+ + Zn2+
Excess zinc, in acid solution, will reduce vanadium from +5 to +2. You
would observe a colour change to the solution from yellow to blue to
green to violet. You may see an intermediate green colour as the vanadium
changes oxidation state from +5 to +4 but this is simply caused by a
mixture of the yellow and blue colours of these oxidation states.

807701_C09_AQA_Chemistry_2_175-191.indd 178 13/06/15 9:04 am

 Some other substances may partially reduce vanadium. Sulfur dioxide will
reduce vanadium from +5 to +3 but not to +2.

Oxidation states of transition metals

SO42− + 4H+ + 2e− → SO2 + 2H2O +0.17 V
The sulfur dioxide will be oxidised so the half equation is rewritten as an
oxidation reaction and the sign of redox potential is changed.
SO2 + 2H2O → SO42− + 4H+ + 2e− −0.17 V
Examining each reaction separately:
VO+2 + 2H+ + e− → VO2+ + H2O +1.00 V (REDUCTION)
SO2 + 2H2O → SO42− + 4H+ + 2e− −0.17 V (OXIDATION)
EMF = +0.83 V (FEASIBLE)
Ionic equation: 2VO+2 + SO2 → 2VO2+ + SO42−

VO2+ + 2H+ + e− → V3+ + H2O +0.34 V (REDUCTION)

SO2 + 2H2O → SO42− + 4H+ + 2e− −0.17 V (OXIDATION)
EMF = +0.17 V (FEASIBLE)
Ionic equation: 2VO2+ + SO2 → 2V3+ + SO42−

V3+ + e− → V2+ −0.26 V (REDUCTION)

SO2 + 2H2O → SO42− + 4H+ + 2e− −0.17 V (OXIDATION)
EMF = −0.43 V (NOT FEASIBLE)
Sulfur dioxide can therefore reduce vanadium from +5 to +3. You would
observe the solution changing from yellow to blue to green.

Tollens’ reagent
Tollens’ reagent is an ammoniacal solution of silver nitrate. It contains
the complex [Ag(NH3)2]+. It can be used to test for the presence of an
aldehyde as it indicates the oxidation of an aldehyde. When warmed with
an aldehyde, the silver(i) ion in the complex is reduced to silver and a silver
mirror coats the inside of the test tube. Ketones cannot be oxidised so the
colourless solution of the complex remains colourless when warmed in the
presence of a ketone.

2[Ag(NH3)2]2+ + RCHO + 3OH− → 2Ag + RCOO− + 4NH3 + 2H2O

Tollens’ reagent    aldehyde    silver
                    mirror

Silver ions would not normally be reduced by the oxidation of an aldehyde,

but when the silver ions complex with ammonia and in alkaline conditions,
the redox potential changes so that the oxidation of an aldehyde is enough
to make the reduction of silver(i) ions in the complex feasible. 179

Manganate(vii) ions in acidic and alkaline solution

Manganate(vii) ions, MnO4−, are a strong reducing agent in acidic solution
but a weaker reducing agent in alkaline solution. pH has an effect on the
redox potential of the reduction of transition metal ions from higher to
lower oxidation state. In acidic solution, manganate(vii) ions, MnO4−, are
reduced to Mn2+ ions. In alkaline solution, manganate(vii) ions, MnO4−, are
reduced to manganate(vi) ions, MnO42−. In organic chemistry, manganate(vii)

807701_C09_AQA_Chemistry_2_175-191.indd 179 13/06/15 9:04 am

 ions in acidic solution are such a strong oxidising agent that they will break
TIP C – C bonds and completely oxidise the molecule. Manganate(vii) ions in
There is more detail on this in alkaline conditions are a weaker oxidising agent and can oxidise alkenes to
the electrode potentials and the corresponding diol.
electrochemical cells topic and in
aldehydes and ketones topic.
TEST YOURSELF 2
1 State the oxidation state and colour of the aqueous solutions of the
following compounds of vanadium.
a) VCl2 b) V2(SO4)3
c) NH4VO3 d) VO2SO4
2 Write a half equation representing the reduction of the
dioxovanadium(v) ion, VO+2, to the oxovanadium(iv) ion, VO2+.
3 Consider the half equations below:
VO2+ + 2H+ + e− → V 3+ + H2O +0.34 V
Zn2+ + 2e− → Zn −0.76 V
a) Write an ionic equation for the reaction between oxovanadium(iv),
VO2+, and zinc forming vanadium(iii) ions and zinc ions.
b) Calculate the EMF of this reaction.
c) What colour change would be observed in this solution?

●● Redox titrations
9    TRANSITION METALS: VARIABLE OXIDATION STATES

In this section you should revise all the detail of how to carry out a titration
from the Amount of Substance section in AS.
There are several types of redox titrations but the most common is the use
of a solution of potassium manganate(vii) to determine the amount in moles
of a reducing agent present in solution.
Potassium manganate(vii) (or potassium permanganate) has the formula
KMnO4 and is a purple solid and forms a purple solution. Manganate(vii)
ions are MnO−4 .
Purple potassium manganate(vii) is easily reduced to pale pink (virtually
colourless) manganese(ii) ions according to the equation:

MnO−4 + 8H+ + 5e− Mn2+ + 4H2O

Oxidation state Oxidation state

of Mn is +7 of Mn is +2

Acidified potassium manganate(vii) solution can be used to determine the

180 concentration of reducing agents in two ways:

Direct titration
1 25.0 cm3 of a solution of the reducing agent is placed in a conical flask.
2 The mixture is acidified using excess dilute sulfuric acid.
3 The standard solution of potassium manganate(vii) is added from the
burette until the solution changes from colourless to pink.

807701_C09_AQA_Chemistry_2_175-191.indd 180 13/06/15 9:04 am

 Titration with iron(ii) ions in solution produced from
reduction of iron(iii) ions

Redox titrations
1 A known amount (volume and concentration or mass) of a reducing
agent is added to a known volume and concentration of a solution
containing iron(iii) ions which are in excess.
The reducing agent reduces some of the iron(iii) to iron(ii)
2 Place a known volume (usually 25.0 cm3) of the reduced solution in a
conical flask
3 Acidify the solution with excess dilute sulfuric acid
4 The standard solution of potassium manganate(vii) is added from the
burette until the solution changes from colourless to pink
For all these titrations, as each drop of the potassium manganate(vii)
solution is added, the purple manganate(vii) is decolourised to colourless
manganese(ii); when the reducing agent is used up the last drop of
manganate(vii) is not decolourised so the last drop makes the solution pink.

Common examples of reducing agents

A reducing agent (or reductant) is an electron donor. It will donate electrons
to other species so that they gain electrons and become reduced. A reducing
agent becomes oxidised in a redox reaction.
● Iron(ii) ions, Fe2+, for example: iron(ii) sulfate, ammonium iron(ii)
sulfate.
● Oxalate ions, C2O2− 4, for example: sodium oxalate, potassium oxalate.

Oxalate ions are also called ethanedioate ions as they are the ion from
ethanedioc acid, (COOH)2

Iron(ii) ions
Manganate(vii) ions reduction:
MnO4− + 8H+ + 5e− → Mn2+ + 4H2O
Iron(ii) ions oxidation:
Fe2+ → Fe3+ + e−
Combining equations:
MnO4− + 8H+ + 5e− → Mn2+ + 4H2O
Fe2+ → Fe3+ + e− (×5 to cancel electrons)

MnO4− + 8H+ + 5e− → Mn2+ + 4H2O 181

5Fe2+ → 5Fe3+ +5e−
Ionic equation:
MnO4− + 8H+ + 5Fe2+ → Mn2+ + 4H2O + 5Fe3+
The most important part of the above equation is to realise that 1 mol of
manganate(vii) ions, MnO4−, react with 5 mol of iron(ii) ions, Fe2+.

807701_C09_AQA_Chemistry_2_175-191.indd 181 13/06/15 9:04 am

 Oxalate ions
Manganate(vii) ions reduction:
MnO4− + 8H+ + 5e− → Mn2+ + 4H2O
Oxalate ions oxidation:
C2O42− → 2CO2 + 2e−
Combining equations:
MnO4− + 8H+ + 5e− → Mn2+ + 4H2O (×2)
C2O42− → 2CO2 + 2e−(×5)
2MnO4− + 16H+ + 10e− → 2Mn2+ + 8H2O
5C2O42− → 10CO2 + 10e−
Ionic equation:
2MnO4− + 16H+ + 5C2O42− → 2Mn2+ + 10CO2 + 8H2O
TIP The most important thing here is to realise that 2 mol of manganate(vi) ions,
These are only two examples, but MnO4−, reacts with 5 mol of oxalate ions, C2O42−.
you can apply the techniques to
any titration with manganate(vii)
Overall ratios
ions. The most important thing
9    TRANSITION METALS: VARIABLE OXIDATION STATES

1 mol of MnO4−, reacts with 5 mol of Fe2+

is to determine the ratio of the
reducing agent to MnO4− ions. 2 mol of MnO4−, reacts with 5 mol of C2O42−

EXAMPLE 1
1.39 g of a sample of hydrated iron(ii) sulfate, Remember that this is the same as the number
FeSO4.xH2O were dissolved in dilute sulfuric acid of moles of manganate(vii) ions as 1 mol of KMnO4
and the volume made up using deionised water to contains 1 mol of manganate(vii) ions, MnO4−.
250.0 cm3 in a volumetric flask. A 25.0 cm3 sample
In the equation, ratio of MnO4− : Fe2+ = 1 : 5
of this solution was acidified and titrated against
0.005 mol dm−3 potassium manganate(vii) solution. The So moles of Fe2+ in 25.0 cm3 in conical flask =
average titre was found to be 20.0 cm3. 0.0001 × 5 = 0.0005 mol
Iron(ii) sulfate is usually dissolved in dilute sulfuric Moles of Fe2+ in 250 cm3 in volumetric flask =
acid as it is more soluble in it than in water; often 0.0005 × 10 = 0.005 mol
solutions are cloudy when just in water.
Moles of hydrated iron(ii) sulfate used = 0.005 mol
1 State the colour change observed at the end point in
Each mole of hydrated iron(ii) sulfate, FeSO4.xH2O
a manganate(vii) titration.
contains 1 mol of Fe2+ ions so the number of moles of
2 Calculate the value of x in FeSO4.xH2O.
FeSO4.xH2O = moles of Fe2+
182 Answer
20 × 0.005
Moles of potassium manganate(vii) used = =
0.0001 mol 1000

807701_C09_AQA_Chemistry_2_175-191.indd 182 13/06/15 9:04 am

 Redox titrations
TIP Add standard solution of
potassium manganate(VII)
A sketch of a titration is a good Place solution in from a burette
starting point so you know the volumetric flask and Take 25.0 cm3 sample
from solution and add
processes that are involved in the make up volume
20 cm3 of dilute
preparation of a solution and the using deionised water
to 250.0 cm3 sulfuric acid
titration.

Titrate until the

solution changes
A known mass of Sample is dissolved Iron(II) sulfate from colourless
hydrated iron(II) sulfate in dilute sulfuric acid solution to pink

There are two ways of finishing the calculation from here:

Method 1: Mr Method 2: ratios
mass 1.39 Mass of anhydrous FeSO4 in sample = 0.005 × 151.9
Mr of FeSO4.xH2O = = = 278
moles 0.005 = 0.7595 g
Mr of FeSO4 = 151.9
Mass of water in sample = 1.39 − 0.7595 = 0.6305 g
Total of the Mr due to xH2O = 278 151.9 = 126.1 mass 0.6305
121.6 Moles of water = = = 0.03503 mol
x= = 7 so the value of x in FeSO4.xH2O = 7 Mr 18
18 Ratio of anhydrous FeSO4 : H2O = 0.005 : 0.03503
= 1 : 7 so x = 7

EXAMPLE 2
Sulfate(iv) ions (also called sulphite ions) in natural moles of Fe2+ = 1.48 × 10−5 × 5 = 7.4 × 10−5 mol
seawater can reduce iron(iii) ions to iron(ii) ions. A 7.4 × 10−5
25.0 cm3 sample of seawater containing sulfate(iv) ions, moles of SO32− in 25.0 cm3 = = 3.7 ×10−4 mol
2
SO32−, is treated with 25.0 cm3 of 0.01 mol dm−3 iron(iii) concentration of SO32− in mol dm−3 = 3.7 ×10−4 × 40 =
chloride solution (an excess). 1.48 ×10−3 mol dm−3
SO32− + H2O + 2Fe3+ → SO42− + 2Fe2+ + 2H+
The resulting solution is placed in a conical flask and
an excess of dilute sulfuric acid is added. The solution TIP
is titrated with 0.001 mol dm−3 potassium manganate(vii) At this stage in the A-level
solution and 14.8 cm3 of this solution was required. course you would be expected to 183
recognise that dividing by 25 and
Calculate the concentration of sulfate(iv) ions in the multiplying by 1000 is the same
seawater in mol dm−3. process as multiplying by 40. This
Answer is common when converting from
14.8 × 0.001 an amount, in moles, in 25 cm3 to
moles of MnO4− used = = 1.48 × 10−5 mol a concentration in mol dm−3
1000
MnO4− + 8H+ + 5Fe2+ → Mn2+ + 5Fe3+ + 4H2O

807701_C09_AQA_Chemistry_2_175-191.indd 183 13/06/15 9:04 am

 EXAMPLE 3 The ratio of MnO4− : H2O2 in the ionic equation above is
Hydrogen peroxide is used in hair bleach. A sample of 2 : 5. This ratio is important in calculating the amount,
hair bleach (10.0 cm3) was added to a volumetric flask in moles, of hydrogen peroxide which reacted with the
and the volume made up to 250 cm3 of aqueous solution. manganate(vii) ions.
A 25.0 cm3 sample of this solution was acidified and it 17.25 × 0.0274
was found that it reacted completely with 17.25 cm3 of 2 moles of MnO4− = = 4.727 × 10−4 mol
1000
0.0274 mol dm−3 potassium manganate(vii) solution.
4.727 × 10−4
1 a) Write half equations for the reduction of moles of H2O2 in 25 cm3 = ×5=
1.182 × 10−3 mol 2
manganate(vii) ions in acidic solution and the
oxidation of hydrogen peroxide to oxygen gas. moles of H2O2 in 250 cm3 = moles of H2O2 in original
b) Write an ionic equation for the reaction of acidified 10 cm3 = 1.182 × 10−3 × 10 = 0.01182 mol
manganate(vii) ions with hydrogen peroxide.
0.01182
2 Calculate the concentration of hydrogen peroxide in concentration of original solution = × 1000 =
the hair bleach in mol dm−3. 1.182 mol dm −3 10

Answer
Each half equation is written using H2O and H+ to
balance the change in oxygen content and then the
electrons balance the charge on each side. TIP
When writing these equations
1 a) MnO4− + 8H+ + 5e− → Mn2+ + 4H2O make sure that the charges
H2O2 → O2 + 2H+ + 2e−
9    TRANSITION METALS: VARIABLE OXIDATION STATES

balance in every equation.

b) 2MnO4− + 6H+ + 5H2O2 → 2Mn2+ + 8H2O + 5O2

In the next example two ions in the solution can both react with the
manganate(vii) ions.

EXAMPLE 4
Iron(ii) ethanedioate dihydrate, FeC2O4.2H2O, reacts 4.011 × 10−4
moles of FeC2O4 in 25 cm3 = ×5=
with acidified potassium manganate(vii) solution. Both 3
6.685 × 10−4 mol
the iron(ii) ion and the ethanedioate ion are oxidised by
the manganate(vii) ions. moles of FeC2O4 in 250 cm3 = 6.685 × 10−4 × 10 =
5Fe2+ + MnO4− + 8H+ → 5Fe3+ + Mn2+ + 4H2O 6.685 × 10−3 mol
mass of original sample used = 6.685 × 10−3 × 179.8 =
5C2O2− − + 2+
4 + 2 MnO4 + 16H → 10CO2 + 2Mn + 8H2O 1.202 g
A sample of iron(ii) ethanedioate was dissolved in
excess dilute sulfuric acid and made up to 250 cm3
of solution. 25.0 cm3 of this solution decolourised TIP
21.45 cm3 of a 0.0187 mol dm−3 solution of potassium This can be worked out from the
manganate(vii). equations as if the equations were
combined 3 mol of MnO4− would react
1 Calculate the reacting ratio of moles of with 5 mol of Fe2+ and C2O42−.
manganate(vii) ions to moles of iron(ii) ethanedioate.
184 2 Calculate the mass of the sample of iron(ii)
ethanedioate dihydrate used.

Answer TIP
The ratio of ethanedioate ions to
1 5 mol of FeC2O4 in solution produces 5 mol of Fe2+ manganate(vii) is 5 : 2. The two ionic
and 5 mol of C2O42−. 5 mol of FeC2O4 will react with equations given in this example are
3 mol of MnO4− important and should be learnt as it
21.45 × 0.0187 can take time working them out from
2 moles of MnO4− = = 4.011 × 10−4 mol
1000 half equations.

807701_C09_AQA_Chemistry_2_175-191.indd 184 13/06/15 9:04 am

 Redox titrations
ACTIVITY
Finding the formula of Mohr’s salt Table 9.1 Results obtained in titration of Mohr’s salt
solution with potassium manganate(vii)
Crystalline ammonium iron(ii) sulfate is called
Mohr’s salt after the German chemist Karl Friedrich Rough Titration 1 Titration 2 Titration 3
Mohr, the son of a pharmacist who made many Final volume 21.10 20.05 21.40 20.00
important advances in titration methods in the 19th Initial volume 0.10 0.00 1.20 0.05
century, including an improved burette. Before this, Titre/cm3
chemists used equipment similar to a graduated
cylinder. 1 Why is 10 cm3 of sulfuric acid added to the conical
flask before titration?
Mohr’s salt is a common laboratory reagent that 2 Why is ethanoic acid not used?
is used for titrations. Due to the presence of 3 Why is ammonium iron(ii) sulfate less readily
ammonium ions it is less prone to oxidation by oxidised than iron(ii) sulfate solution?
air than many other compounds. The oxidation of 4 Complete the last row in Table 9.1 (Titre/cm3).
solutions of iron(ii) is very pH dependent, occurring
5 Calculate the mean titre and justify your answer.
much more readily at high pH.
6 State the colour change at the end point and
Mohr’s salt has the formula Fe(NH4)2(SO4)2.nH2O. explain why no indicator is added.
The symbol n represents the number of molecules of 7 The error in the titration value for this experiment
water of crystallisation. is ±0.25 cm3.Calculate the percentage error in this
To find the value of n, 25.0 cm3 of a solution of titration.
ammonium iron(ii) sulfate of concentration 31.4 g dm−3 8 Write the equation for the reaction of iron(ii) ions
were transferred to a conical flask; 10 cm3 of sulfuric with acidified permanganate ions (H+/MnO4−).
acid were added and the solution then titrated with a 9 Determine the concentration of Mohr’s salt
solution of potassium manganate(vii) of concentration solution and use it to find the molar mass of
at 0.0200 mol dm−3. A student obtained the results Mohr’s salt and deduce the value of n.
shown in Table 9.1.

TEST YOURSELF 3
1 A solution of iron(ii) sulfate was acidified. A 25.0 cm3 sample of the
solution was titrated with 0.0120 mol dm−3 potassium manganate(vii)
solution. 17.45 cm3 of the potassium manganate(vii) solution was
required for complete reaction.
a) Write an equation for the reaction between manganate(vii) ions and
iron(ii) ions.
b) Calculate the concentration of the iron(ii) sulfate solution in mol
dm−3. Give your answer to 3 significant figures.
2 A sample of iron(ii) ethanedioate, FeC2O4, was dissolved in excess
sulfuric acid and the volume made up to 250 cm3 in a volumetric flask.
A 25.0 cm3 portion of this solution was titrated with a 0.00200 mol dm−3
solution of potassium permanganate(vii). 24.75 cm3 were required 185
for complete reaction. Calculate the mass of the sample of iron(ii)
ethanedioate. Give your answer to 3 significant figures.
3 12.2 g of hydrated iron(ii) sulfate, FeSO4.xH2O, were dissolved in acidic
solution and the volume made up to 500 cm3. A 25.0 cm3 sample
of this solution was titrated against 0.0200 mol dm−3 potassium
manganate(vii). 21.95 cm3 of the solution were required. Calculate the
value of x in FeSO4.xH2O.

807701_C09_AQA_Chemistry_2_175-191.indd 185 13/06/15 9:04 am

 ●● Catalytic activity
Transition metals and their compounds are important catalysts.
A homogeneous catalyst is one in which the catalyst is in the same physical
state or phase as the reactants. Enzymes are homogeneous catalysts as they
are in the same physical state or phase as the reactants – all are aqueous.
A heterogeneous catalyst is one in which the catalyst is in a different physical
state or phase to the reactants. Iron is the catalyst in the Haber Process:
N2(g) + 3H2(g) ⇋ 2NH3(g)
The iron is described as a heterogeneous catalyst as it is in a different state
or phase to the reactants – the iron is a solid and the reactants are gases.
Heterogeneous catalysts work by chemisorption. You may be asked to
explain the process of chemisorption:
● reactants molecules are adsorbed onto active sites on the surface of the
catalyst
● the bonds in the reactants molecules are weakened
● the reactants molecules are held in a more favourable conformation for
reaction
the product molecules are desorbed from the surface of the catalyst.
9    TRANSITION METALS: VARIABLE OXIDATION STATES

Common heterogeneous catalysts

Haber Process:
N2(g) + 3H2(g) ⇋ 2NH3(g) Iron catalyst
Contact Process:
2SO2(g) + O2(g) ⇋ 2SO3(g) Vanadium(v) oxide catalyst
Hydrogenation of alkenes:
C2H4(g) + H2(g) ⇋ C2H6(g) Finely divided nickel catalyst
Figure 9.2 The catalyst found in a Catalysts in industrial processes
catalytic converter is usually platinum
or rhodium plated onto a ceramic ● In any industrial process, the manufacturers want to achieve the
honeycomb structure. The honeycomb maximum yield of product with the minimum of expense.
structure allows for a larger surface ● Often the use of a high temperature, a high pressure, and a catalyst can
area for the reactant gases to undergo increase the yield of their product.
chemisorption on the surface of the ● However, these factors can be expensive and a cost analysis must be
catalysts.
carried out to make sure there are significant benefits in terms of profit to
justify the expense.
● High pressure is expensive to apply as electrical pumping is needed and
186 valves and other equipment required for high pressures are also more
expensive than those which could be used at lower pressures. High
pressure is also expensive in terms of the containers needed and it is also
dangerous for staff working on the site though many questions ask you
not to focus on safety.
● The rate of a chemical reaction increases with temperature, so if a
manufacturer uses a lower temperature then the rate is lowered even if
more of the product is obtained (but in a much longer time period). A
compromise temperature is used which allows enough of the product to
be made in as short a time period as possible.

807701_C09_AQA_Chemistry_2_175-191.indd 186 13/06/15 9:04 am

 ● Development of more effective catalysts can increase the profit of an
industrial process. The best catalysts will give the lowest activation

Catalytic activity
energy but there must be a balance between the effectiveness of the
catalyst and its cost.
The platinum catalyst used to make hydrogen from the electrolysis of
water is a large part of the cost. A new catalyst made from molybdenum
and ground soybeans has just been discovered and it is around 1500 times
cheaper than platinum. This could make hydrogen a cheaper, clean fuel of
the future.
Figure 9.3 Soybeans.
Recognising a catalyst
A series of reactions may be given in which a substance reacts but is
reformed in later reactions. This substance is a catalyst as it meets the
description of a catalyst and increases the rate of the reaction and is not
used up during the reaction.

EXAMPLE 5
In the Contact process for the production of sulfuric acid, the following
reactions occur:
SO2 + V2O5 → SO3 + V2O4
The vanadium(v) oxide reacts with the sulfur(iv) oxide to form vanadium(iv)
oxide and sulfur(vi) oxide
The second reaction which occurs is:
2V2O4 + O2 → 2V2O5
The first step in combining a series of reactions into a single equation is
to increase the balancing numbers in one equation if necessary.
In this example there are 2 mol of V2O4 and 2 mol of V2O5 in the second
equation but only 1 mol of both V2O4 and V2O5 in the first equation. So the
first equation should be doubled, giving:
2SO2 + 2V2O5 → SO3 + 2V2O4
2V2O4 + O2 → 2V2O5
Write down all substances on the left of both equations then insert an
arrow and write out all substances on the right of both equations. Cancel
out substances that appear on both sides of the equation.
2SO2 + 2V2O5 + 2V2O4 + O2 → SO3 + 2V2O4 + 2V2O5
2V2O4 and 2V2O5 appear on both sides of the equation so they can be
cancelled out.
187
2SO2 + 2V2O5 + 2V2O4 + O2 → SO3 + 2V2O4 + 2V2O5
The equation simplifies to:
2SO2 + O2 → 2SO3
V2O5 is a catalyst as it takes part in the reaction but is reformed as it does
not appear in the overall equation for the reaction. It is not used up.

807701_C09_AQA_Chemistry_2_175-191.indd 187 13/06/15 9:04 am

 EXAMPLE 6
Hydrogen peroxide decomposes in the presence of This leaves:
potassium iodide. Making ‘elephant toothpaste’ is
2H2O2 → 2H2O + O2
a fun demonstration showing how the catalyst
potassium iodide causes the rapid decomposition of Potassium iodide is a catalyst as it takes part in the
hydrogen peroxide, generating a large volume of reaction but is reformed as it does not appear in the
oxygen, so the oxygen quickly pushes out of the overall equation.
container. The soapy water traps the oxygen, creating
bubbles, and turns into foam which looks like giant
toothpaste as shown in the photo.

The equations for the decomposition are:

H2O2 + KI → KIO + H2O
H2O2 + KIO → KI + H2O + O2
In the example the equation will balance out when
added together.
The overall added equation is:
2H2O2 + KI + KIO → KIO + KI + 2H2O + O2
9    TRANSITION METALS: VARIABLE OXIDATION STATES

Catalyst poisoning
A heterogeneous catalyst may be poisoned by impurities in the reaction
mixture. The heterogeneous catalyst can be coated by impurities that render
it passive and inactive. An example of this is the use of lead-containing
petrol in cars with a catalytic convertor that would normally take unleaded
petrol. The lead in the petrol coats the surface of the catalyst in the
convertor and makes it ineffective as a catalyst.
The catalyst is poisoned as the active sites on the surface of the catalyst
become blocked and therefore inactive. This has a cost implication as the
catalyst has to be replaced. Transition metals and their compounds are often
used as heterogeneous catalysts. These catalysts are expensive.

Homogeneous catalysis
The reaction between peroxodisulfate ions, S2O82−, and iodide ions, I− into
sulfate(vi) ions and iodine is an example of homogeneous catalysis.
The equation for this reaction is:
S2O82− + 2I− → 2SO42− + I2
188 The reaction between S2O82− ions and I− ions is slow (has a high activation
energy) as the two negative ions repel each other.
However, the reaction is catalysed by the either aqueous iron(ii) ions, Fe2+,
or aqueous iron(iii) ions, Fe3+.
The Fe2+ ions catalyse the reaction as shown below:
2Fe2+ + S2O82− → 2Fe3+ + 2SO42−
2Fe3+ + 2I− → 2Fe2+ + I2

807701_C09_AQA_Chemistry_2_175-191.indd 188 13/06/15 9:04 am

 Both iron(ii) ions and iron(iii) ions catalyse this reaction as the reactions above
TIP can occur in either order as both S2O82− and I− ions are present in the solution.

Catalytic activity
The iron(ii) or iron(iii) ions are
present in solution as are the
Homogeneous autocatalysis
reactant ions. This is an example Autocatalysis occurs when the product in a reaction acts as a catalyst for the
of homogeneous catalysis. reaction. A common example of this is:
Reaction of manganate(vii) ions, MnO4−, with ethanedioate ions, C2O42−.
The equation for the reaction is:
5C2O42− + 2MnO4− + 16H+ → 10CO2 + 2Mn2+ + 8H2O
The reaction between MnO4− ions and C2O42− ions is initially slow as the two
negative ions repel each other.
However, the reaction is catalysed by the manganese(ii) ions, Mn2+, formed
in the reaction. As these are formed the reaction rate increased dramatically.
The Mn2+ ions catalyse the reaction in two reactions:
4Mn2+ + MnO4− + 8H+ → 5Mn3+ + 4H2O
2Mn3+ + C2O42− → 2Mn2+ + 5CO2
Because the Mn2+ ion is positively charged it is attracted to the MnO4− ion,
therefore increasing the rate of the reaction.
The reaction can be monitored using a colorimeter as the MnO4− ion is
purple in solution.
A graph of absorbance or concentration of the MnO4− ion against time looks
like the one shown below. The graph has labels to explain the shape.

The gradient is low initially as the reaction is slow

as it has a high activation energy.

The gradient gets steeper as Mn2+ formed which

Concentration of
MnO4-/mol dm-3

is the autocatalyst.

The continued production of Mn2+ in the reaction

continues to maintain the increased rate of reaction.

As the MnO4− gets used up the gradient decreases

TIP as it approaches the axis.
Make sure that you can sketch
the shape of this curve or Time/s
explain it. This is an example of In both the examples above, the ions of manganese and iron are able to
homogeneous autocatalysis as act as catalysts as they have variable oxidation states. The ability to change
the catalyst and reactant ions are
oxidation state is important to their role as a catalysts. Group 1 and 2
all present in solution.
elements are not able to act as homogeneous catalysts as they do not have
variable oxidation states in their compounds. 189

TEST YOURSELF 4
1 Write two equations to show the role of V2O5 in the b) Which reaction(s) use a homogeneous catalyst?
contact process. c) Which reaction(s) use a heterogeneous
2 For the following reactions: catalyst?
A: N2(g) + 3H2(g) ⇋ 2NH3(g) d) Which reaction(s) show autocatalysis?
B: S2O82− + 2I− → 2SO42− + I2 3 Explain why Group 1 metal compounds are
C: 5C2O42− + 2MnO4− + 16H+ → 10CO2 + 2Mn2+ + 8H2O not able to act as homogeneous catalysts but
a) Name a catalyst for each reaction. transition metal compounds can.

807701_C09_AQA_Chemistry_2_175-191.indd 189 13/06/15 9:04 am

 Practice questions are required. In this reaction the hydrogen
peroxide is oxidised to oxygen gas.
1 Which one of the following is the correct a) Write an equation for the reaction between
colour for a solution of the compound acidified hydrogen peroxide and potassium
NH4VO3? manganate(vii).
A yellow b) Calculate the concentration of the hydrogen
B blue peroxide solution in mol dm−3. Give your
answer to 3 significant figures. (4)
C green
5 Manganate(vii) ions react with ethanedioate
D violet (1) ions.
2 Using the standard electrode potentials The half equations for the reactions are given
below, choose the oxidising agent capable below:
of oxidising vanadium from the +2 to
the +4 oxidation state but not to the C2O42− → 2CO2 + 2e−
+5 oxidation state. MnO4− + 8H+ + 5e− → Mn2+ + 4H2O
E1/V a) Write an equation for the reaction between
Cl2(aq) + 2e− ⇋ Cl−(aq) +1.36 ethanedioate ions and manganate(vii)
ions. (1)
I2(aq) + 2e− ⇋ 2I−(aq) +0.54
9 TRANSITION METALS: VARIABLE OXIDATION STATES

b) Explain why this reaction may be followed

SO42−(aq) + 2H+(aq) + 2e− ⇋ 2H2O(l) + SO2(g) +0.17 by colorimetry. (1)
VO2+(aq) + 2H+(aq) + e− ⇋ V3+(aq) + H2O(l) +0.32 c) Sketch a graph of the concentration of
VO+2 (aq) + 2H+(aq) + e− ⇋ VO2+(aq) + H2O(l) +1.00 manganate(vii) ions against time. Explain
the shape of the graph. (4)
V3+(aq) + e− ⇋ V2+(aq) −0.26
6 Vanadium(v) oxide, V2O5, is the catalyst used
Cu2+(aq) + 2e− ⇋ Cu(s) +0.34 in the contact process. The equations showing
A chlorine its mode of action are given below:

B Cu2+ ions SO2 + V2O5 → SO3 + V2O4

C iodine 2V2O4 + O2 → 2V2O5

D sulfate ions (1) a) Using these equations write an overall

reaction for the reaction V2O5 catalyses in
3 In which of the following lists are the contact process. (1)
the transition metals all in the +6 oxidation
state? b) Explain why V2O5 is a catalyst based on the
equations. (1)
A KMnO4 K2CrO4 K3CoO4
c) Explain why a compound of vanadium is
B K2Cr2O7 KVO3 K2MnO4 able to act as a catalyst in this reaction (1)
190 C K2MnO4 K2Cr2O7 K2FeO4 7 A sample of iron(ii) ethanedioate, FeC2O4,
was dissolved in an excess of sulfuric acid.
D K2CrO4 K3CoO4 KVO3 (1)
The volume was made up to 500 cm3 and a
4 25.0 cm3 of a solution of acidified hydrogen 25.0 cm3 sample of the solution titrated against
peroxide is titrated against 0.124 mol dm−3 0.0148 mol dm−3 potassium manganate(vii)
potassium managate(vii) solution. 17.55 cm3 solution. 25.25 cm3 of the potassium
of the potassium manganate(vii) solution manganate(vii) solution were required.

807701_C09_AQA_Chemistry_2_175-191.indd 190 13/06/15 9:04 am

 The half equations involved are: sulfuric acid and transferred to a volumetric

Practice questions
flask. The volume was made up to 250 cm3
MnO4− + 8H+ + 5e− → Mn2+ + 4H2O
and a 25.0 cm3 sample was titrated against
C2O42− → 2CO2 + 2e− 0.0127 mol dm−3 potassium manganate(vii)
solution.
Fe2+ → Fe3+ + e−
a) Write an equation for the reaction between
a) Write an equation for the reaction between
iron(ii) ions and manganate(vii) ions. (2)
manganate(vii) ions and ethanedioate
ions. (1) b) Calculate the volume of potassium
manganate(vii) solution required for
b) Write an equation for the reaction between
complete reaction. (4)
manganate(vii) ions and iron(ii) ions. (1)
c) Using the equations you have written in (a) Stretch and challenge
and (b) state the ratio of MnO4− : FeC2O4 (1) 10 Consider the half equations below and their
associated redox potentials:
d) Calculate the mass of iron(ii) ethanedioate
used. If you have been unable to VO+2 + e− + 2H+ → VO2+ + H2O +1.00 V
calculate a ratio in (c), use a ratio of 2
VO2++ e− + 2H+ → V3+ + H2O +0.34 V
MnO4− : 7FeC2O4. This is not the correct
ratio. (4) V3+ + e− → V2+ −0.26 V
8 The graph below shows how the concentration Zn2+ + 2e− → Zn −0.76 V
of manganate(vii) ions changes against time
SO2− + −
4 (aq) + 2H (aq) + 2e ⇋ 2H2O(l) + SO2(g) +0.17 V
during the reaction with ethanedioate ions,
C2O42−. a) Sulfur dioxide is mixed with a solution
A
containing VO+2 ions.
i) Explain using the redox potentials
B
which oxidation changes would
Concentration of
MnO4-/mol dm-3

occur. (4)
C
ii) Describe what would be observed. (1)
b) Zinc will reduce VO+2 ions to V2+ ions.
D
i) Explain using redox potentials why
Time/s zinc will reduce vanadium from VO+2
to V2+. (3)
a) At which point on the graph (A, B, C or D)
is the rate of the reaction fastest? (1) ii) Write a half equation showing the
overall reduction of vanadium from
b) Explain why the gradient of the graph is VO+2 to V2+. (2)
low at point A. (2)
iii) Write an ionic equation which shows
c) Explain why the gradient of the line begin the overall reaction between VO+2
to increase between A and B. (3) and zinc where V2+ is the vanadium
9 A sample of 4.483 g of hydrated iron(ii) reduction product. (2) 191
sulfate, FeSO4.7H2O, was dissolved in

807701_C09_AQA_Chemistry_2_175-191.indd 191 13/06/15 9:04 am

 10 Optical isomerism

PRIOR KNOWLEDGE
● Molecules which have the same molecular formula but a different
structural formula are known as structural isomers.
● Stereoisomers are molecules which have the same structural
formula but a different arrangement of atoms in space.
● E–Z isomers are stereoisomers, which exist due to restricted rotation
about a C=C.

COOH HOOC
TEST YOURSELF ON PRIOR KNOWLEDGE 1
1 The compound C4H10 exists as structural isomers.
a) What is meant by the term structural isomers?
b) How many structural isomers are there of C 4H10? Name these
isomers.
2 a) Draw and name a structural isomer of 1-chloropropane.
b) Draw and name the stereoisomers of CHCl CHCl.
C C
c) Draw and name the stereoisomers of C 4H8.
3 What is meant by the term stereoisomers?

OH HO
There are two types of stereoisomers, E–Z which you met in Book 1 and
H optical isomers.
H
Carvone is an organic compound with the molecular formula C10H14O.
It has two optical isomers, one that smells like caraway and the other that
smells like spearmint. Both isomers have the same structural formula but
CH3 H3C
are stereoisomers because they have a different arrangement of the atoms
in space.

●● Optical isomerism
Optical isomerism occurs in molecules that have a carbon atom with
four different atoms or groups attached to it tetrahedrally as shown
in Figure 10.1.
192
Such compounds exhibit optical isomerism because the tetrahedral molecule
is asymmetric, i.e. it has no centre, plane or axis of symmetry. As a result
two tetrahedral arrangements occur in space; one is the mirror image of
the other and they cannot be superimposed on each other. Figure 10.2
shows the optical isomers of 2-hyroxypropanoic acid. The mirror images are
non-superimposable. All molecules have a mirror image, but usually it is the
same molecule; non-superimposable mirror images and hence optical isomers
only occur with chiral molecules. The two mirror images are optical isomers,
and are often called enantiomers.

807701_C10_AQA_Chemistry_2_192-197.indd 192 13/06/15 9:04 am

 A molecule that is asymmetric and exhibits optical isomerism is said to be
chiral. The carbon atom, with four different atoms or groups attached to it

Optical isomerism
is called a chiral or asymmetric centre.

COOH HOOC

C C
OH HO
H H

CH3 H3C

Figure 10.2

When asked to draw optical isomers, a general method to follow is given below.
Figure 10.1 The carbon atom (black)
has four different atoms attached to ● Draw the displayed formula.
it tetrahedrally. The carbon atom is a ● Identify the chiral centre.
chiral centre. ● Draw the 3d tetrahedral structure based on the chiral centre and insert
the four different groups.
Mirror ● Draw a dotted line to represent a mirror, and draw the second isomer as
a mirror image.

EXAMPLE 1
Draw the optical isomers for 2-chlorobutane.
Cannot be Answer
Left hand Right hand superimposed
First draw the displayed formula.
Figure 10.3 Your left and right hands
are non-superimposable mirror H H H H
images. A molecule is chiral if,
like one of your hands, it cannot be H C C C C H
superimposed on its mirror image. The
H Cl H H
word ‘chiral’ comes from the Greek
word for hand.
Then identify the chiral centre. Looking closely at the molecule it is
clear that the two end carbon atoms have 3 H atoms attached and the
third carbon atom from the left has 2 H atoms so these cannot be chiral
centres. The second carbon atom has the following groups attached to it:
1 H 2 Cl 3 CH3 4 C2H5
These are four different groups so it is a chiral centre and is marked with
an asterisk as shown:
TIP
It is often useful to circle each H H H H
of the four groups on the chiral *
carbon, this helps you remember H C C* C C H CH3CHClCH2CH3 193
what groups to place around the
H Cl H H
tetrahedron.

807701_C10_AQA_Chemistry_2_192-197.indd 193 13/06/15 9:04 am

 Finally to draw the optical isomers, simply draw a 3 dimensional
tetrahedral arrangement and insert each of the four different groups at
different points on the tetrahedron. Then place a dotted line to represent
the mirror, and reflect the image as shown below.
These isomers cannot be superimposed H H
on each other. They have the same
molecular and structural formulae C C
but differ only in the arrangement of
H3C C2H5 H5C2 CH3
groups around the chiral centre. You Cl Cl
are expected to be able to draw optical
isomers for molecules which have a single chiral centre.

TIP
Remember when drawing 3d molecules a normal line represents
a bond in the plane of the paper, a dashed bond represents a bond
extending backwards ‘into’ the paper and a wedged line means
the bond protrudes forward, effectively ‘out’ of the paper.

EXAMPLE 2
H O H O
Nineteen out of the 20
amino acids used in protein H2N C C OH H2N C C OH
synthesis in the cells in your
H CH3
body are optically active – an
example is the amino acid glycine alanine
alanine. The one that is not
optically active is glycine. State why glycine is not optically active and
draw the optical isomers of alanine.

Answer
Glycine is not optically active as the central carbon atom does not have
10    OPTICAL ISOMERISM

four different atoms or groups attached to it – the carbon has two H

atoms attached.
Alanine has the following four groups attached to the central carbon atom.
1 H 2 CH3 3 NH2 4 COOH
The central carbon atom of H O
alanine is a chiral centre. *
H2N C* C OH H2NCH(CH3)COOH
The optical isomers can be
drawn as: CH3

H H
194
C C
TIP
Remember to correctly
H2N COOH HOOC NH2 attach the atoms – the COOH
CH3 H3C
must be drawn backwards in
the mirror image.

807701_C10_AQA_Chemistry_2_192-197.indd 194 19/06/2015 17:14

 TEST YOURSELF 1

Optical activity
1 Which of the following molecules have chiral centres?
a) CH3CH2CH2OH
b) CH3CH2CHCl CH2CH3
c) CH3CH(CH3)CO2H
d) CH3CH(OH)CO2CH3
e) CH3CH2CH2C(OH)2CH2CH2
f) CH3CH2CH2CHClCH3
2 Lactic acid, CH3CHOHCOOH, is a weak acid which builds up in
muscles during exercise. The molecule has an asymmetric centre.
a)Explain what is meant by the term asymmetric centre.
b)Draw the structures of the two optical isomers of lactic acid.
c)What is the bond angle around the central carbon?
d)State the IUPAC name for lactic acid.

●● Optical activity
A light beam consists of waves that vibrate in all planes at right angles to the
direction in which the beam is travelling. A polaroid filter only allows light
in one plane to pass through it, so when a light beam is passed through a
polarising filter all the waves are absorbed apart from the ones vibrating in
one particular plane. The light is said to be plane polarised.
An optically active substance is one that can rotate the plane of plane
Unpolarised Polariser Plane
polarised light. When a beam of plane polarised light is passed through a
light polarised solution of one optical isomer, the plane polarised light is rotated either to
light the left or to the right depending on which isomer is used.

H
Br Cl

The plane of plane polarised

light has been rotated clockwise
by one isomer, and anticlockwise
by the other

F
Cross section of light Polarising filter Cross section of
beam showing the plane polarised
H 195
vibrations in all light vibrating in Cl
directions one direction Br

Figure 10.4 The diagram shows how light is polarised and the plane polarised
light rotated in different directions by passing through the two optical isomers of
bromochlorofluoromethane.

Optical isomers each rotate the plane of plane polarised light in opposite
directions and hence they are optically active.
● If an optical isomer (enantiomer) rotates plane polarised light to the left,
it is given the prefix – or L (which stands for laevorotatory)

807701_C10_AQA_Chemistry_2_192-197.indd 195 13/06/15 9:04 am

 ● If an optical isomer (enantiomer) rotates plane polarised light to the
right, it is given the prefix + or D (which stands for dextrorotatory). You
will not be asked to assign a D or L prefix to an isomer simply from its
structure.
● Mixing equal amounts of the same concentration of two enantiomers
gives an optically inactive mixture which has no effect on plane
polarised light because the two opposite effects cancel out. This mixture
of equal amounts of each enantiomer is called a racemic mixture or
racemate.

A racemic mixture (racemate) is an

optically inactive mixture of equal amounts
of enantiomers of the same concentration. EXAMPLE 3
Plane polarised light is light in which all Explain how you could distinguish between a racemate of lactic acid and
the waves vibrate in the same plane. one of the enantiomers of lactic acid?
Optical isomers (enantiomers) are Answer
stereoisomers that occur as a result of
chirality in molecules. They exist as non- Plane polarised light will be rotated by the single enantiomer but it will
superimposable mirror images and differ in be unaffected by the racemate. The racemate is optically inactive as it
their effect on plane polarised light. contains equal amounts of each isomer, and one isomer rotates plane
polarised light to the right, the other to the left and the two opposite
An asymmetric carbon atom is chiral and
has four different atoms or groups attached. effects cancel out.

An optically active substance is one that

can rotate the plane of plane polarised light. When a chiral compound is synthesised in the laboratory, a mixture
Chiral: the structure and its image are non- of optical isomers is often formed. Many drugs have optical isomers,
superimposable. and often complicated separation techniques are needed to separate
the mixture. Separation is difficult because optical isomers have similar
physical properties. Ibuprofen is a drug that targets muscle and bone pain,
headaches and back pain. It is a chiral structure and has optical isomers.
You can read more of the use of optical isomers in the pharmaceutical
industry in Chapter 14.
10    OPTICAL ISOMERISM

TEST YOURSELF 2
1 How could you show that a solution of a drug was a racemate and not
a single enantiomer?
2 2-bromobutane is optically active.
a) Draw the displayed formula for 2-bromobutane.
b) Mark the chiral carbon atom with an asterisk (*).
c) Draw the two structures of 2-bromobutane that will form a
racemic mixture.
d) Explain why this racemic mixture will not rotate the plane of plane
polarised light.
196 3 What is plane polarised light?

807701_C10_AQA_Chemistry_2_192-197.indd 196 13/06/15 9:04 am

 Practice questions 4 There are a number of structural isomers

Practice questions
of C4H9OH. However, only one has an
1 Which one of the following does not contain asymmetric centre and can exist as optical
an asymmetric centre? isomers.
A CH3CH(CH3)CH2CH3 a) What is meant by the term asymmetric
centre? (1)
B CH3CH(OH)CH2CH3
b) Explain in terms of structure the meaning
C CH3CHClCH2CH3 of the term optical isomers. (1)
D CH3CH(NH2)CH2CH3 (1) c) Draw the displayed formula of the
2 Which one of the following displays optical structural isomer of C4H9OH which
isomerism? contains an asymmetric centre. (1)
A CH3CHOHCOOH d) Draw the two optical isomers of the
molecule identified in (c). (2)
B CH2OHCH2COOH
e) How can a solution of one optical isomer
C CH2OHCOOCH3 be distinguished from a solution of
D CH2OHCH2CHO (1) another? (2)
3 3-hydroxybutanal, CH3CH(OH)CH2CHO is f) Only one isomer of C4H9OH can be
optically active. oxidised to a ketone using acidified
potassium dichromate(VI). Draw the alcohol
a) Explain the term optically active. (1) and the corresponding ketone and state the
b) Draw the three-dimensional structures colour change that occurs. (4)
for the two optical isomers of
3-hydroxybutanal. (2)
c) 3-hydroxybutanal may be dehydrated to
form but-2-enal. Suggest a structure for
but-2-enal. (1)

197

807701_C10_AQA_Chemistry_2_192-197.indd 197 13/06/15 9:04 am

 11 The carbonyl group
PRIOR KNOWLEDGE
● A functional group is a group of atoms that is responsible for the
characteristic reactions of a molecule.
● A displayed formula shows how atoms are arranged and the bonds
between them. Ionic parts of the molecule are shown using charges.
● A structural formula shows the arrangement of atoms in a molecule,
carbon by carbon, with the attached hydrogens and functional groups.
● A skeletal formula shows the carbon skeleton with hydrogen atoms
removed and functional groups present.
● Be able to apply the IUPAC rules for nomenclature to name organic
compounds containing up to six carbon atoms.
● A homologous series is a series of compounds which have the same
general formula. Successive members differ from each other by
a –CH2 group. They have similar chemical reactions and show a
gradation in physical properties.
● Molecules which have the same molecular formula but a different
structural formula are known as structural isomers
● Primary alcohols can be oxidised to aldehydes and then to carboxylic
acids. Secondary alcohols can be oxidised to ketones, which are fairly
resistant to oxidation. Tertiary alcohols are not easily oxidised.

The carbonyl group is found in many organic compounds including

aldehydes, ketones, esters and acids. Benzaldehyde is an aldehyde that is
used to make almond essence, an ingredient in Bakewell tarts. It is also
added to give flavour to marzipan, which is commonly used on Christmas
cakes and Battenberg cakes.

TEST YOURSELF ON PRIOR KNOWLEDGE 1

1 Name the following compounds.
a) CH3CH(OH)CH2CH3
b) CH3CH2CH=CHCH2CH2CH3 f) CHBrClCHClCH3
c)
g) H H H Br

H C C C C Cl
d) H H H H
198
2 Choose one compound from
question 1 which is represented
as
e) H H H a) a skeletal formula.
b) a displayed formula.
H C C C H 3 Name the functional group
present in 1(a) and in (b)
H H
H C H
4 Draw the structure of an
isomer of the compound in 1(e).
H

807701_C11_AQA_Chemistry_2_198-232.indd 198 16/06/2015 17:20

 5 To use a disposable breathalyser, a motorist blows into a tube

The carbonyl group

containing crystals of acidified potassium dichromate(vi). Alcohol on
the motorist’s breath is detected by a colour change in the crystals.
a) What colour change occurs when acidified potassium
dichromate(vi) reacts with ethanol?
b) Write an equation for the oxidation of ethanol using [O] to represent
the acidified potassium dichromate(vi).
c) Name the organic product formed.
d) What class of alcohol is ethanol?

Chanel No. 5 was the first perfume made with synthetically produced
aldehydes and is one of the world’s most iconic perfumes. Perfume is
a mixture of fragrant compounds and solvents which together give a
pleasant smell. The earliest perfumes used natural ingredients such as
extracts from flowers, grasses, spices and fruit. Chanel No. 5, developed
in 1912 by Earnest Beaux, was the first perfume to use a synthetically
produced aldehyde, 2-methylundecanal, together with jasmine, rose and
lily scents to create its strong, pleasant smell. Today, perfumes contain
a mix of natural and synthetic chemicals, many of which are aldehydes,
ketones and esters that contain the carbonyl group. The carbonyl
group is the functional group in a range of organic molecules. In this
chapter you will study the aldehydes, ketones, carboxylic acids, esters,
acid anhydrides, acyl chlorides and amides. Some examples of these are
shown in Figure 11.1.

Figure 11.1 The carbonyl group, shown propanal butanone ethanoic acid
in red, is found in all of these different (aldehyde) (ketone) (carboxylic acid)
organic compounds.
H H O H O H H H O

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

H H H H H H H O H

CH3CH2CHO CH3COCH2CH3 CH3COOH

ethanoic anhydride ethyl ethanoate

(acid anhydride) (ester)
H O O H H O

H C C O C C H H C C H H

H H H O C C H

H H
CH3COOCOCH3 CH3COOCH2CH3 199

ethanoyl chloride propanamide

(acyl chloride) (amide)
H O H H O

H C C H C C C

H Cl H H NH2

CH3COCl CH3CH2CONH2

807701_C11_AQA_Chemistry_2_198-232.indd 199 13/06/15 9:04 am

 ●● Aldehydes and ketones
The carbonyl group
The carbonyl functional group is shown in Figure 11.2. It has a double
bond and, as expected for a double bond, undergoes addition reactions.
However the carbonyl double bond does not react in the same way as
δ− the carbon–carbon double bond in an alkene. This is because the C=O
O
bond is polar. Oxygen is more electronegative than carbon and draws the
C electrons in the covalent bond towards itself resulting in a δ+ charge on the
δ+
carbon and a δ− charge on the oxygen. The δ+ carbon is readily attacked by
Figure 11.2 The carbonyl functional nucleophiles (a nucleophile is a lone pair donor) and hence the carbonyl
group. group undergoes nucleophilic addition reactions.

Naming aldehydes
Aldehydes have the general formula CnH2nO. The table below gives the
names of the first four straight chain members of the aldehydes.

Name Structural formula Displayed formula

methanal HCHO O

H C

ethanal CH3CHO H O

H C C

H H

TIP propanal CH3CH2CHO H H O

When writing structural formula
always write the aldehyde as H C C C
–CHO. Writing –COH is incorrect H
and easily confused with alcohols. H H
Ethanal, for example, is written
11    THE CARBONYL GROUP

butanal CH3CH2CH2CHO H H H O
CH3CHO not CH3COH.
H C C C C

H H H H

Aldehydes are named according to IUPAC rules. The names are based on
the carbon skeleton with the ending changed from –ane to –anal.
Aldehydes do not need a positional number for the position of the carbonyl
group as it is always at the end of the chain and this is carbon number one, if
there are other substituents or groups on the chain.
200
EXAMPLE 1
The structure below shows an aldehyde which is present in coffee and
burnt cocoa. Name this structure
H
Figure 11.3 Benzaldehyde is an
aldehyde that is used to make almond
H HH C H O
essence, an ingredient in Bakewell
tarts. It is also added to give flavour to H 4
C 3
C 2
C 1
C
marzipan, which is commonly used on
Christmas cakes and Battenberg cakes. H H H H

807701_C11_AQA_Chemistry_2_198-232.indd 200 13/06/15 9:04 am

 Answer
TIP

Aldehydes and ketones

● Name the longest unbranched carbon chain in the molecule that
When naming organic compounds, includes the functional group – there are four carbons so the stem is but.
always put a dash between a ● The C=O is at the end of the chain, so the compound is an
number and a word, and a comma aldehyde – butanal
between two numbers, e.g. ● Number the carbon atoms in the carbon chain, with the carbon of the
2,2-dichloropentanal. carbonyl as carbon 1
● Name the side chains and/or substituents attached to the main carbon
chain and give their position – there is a methyl side chain on carbon
2 so it is 2-methyl
The name of the compound is 2-methylbutanal.

EXAMPLE 2
Name the molecule shown below.
H

H Cl H C HH H O
6 5 4 3 2 1
H C C C C C C

H H H Cl H H

Answer
● Name the longest unbranched carbon chain in the molecule that
includes the functional group – there are 6 carbons so the stem is hex.
● The C=O is at the end of the chain, so the compound is an
aldehyde – hexanal
TIP
● Number the carbon atoms in the carbon chain, with the carbon of the
When naming, the substituents
carbonyl as carbon 1
are written alphabetically.
● Name the side chains and/or substituents attached to the main carbon
However, the alphabetical rule
chain and give their position – there is a chloro side group on position 3
ignores ‘di’, ‘tri’ and ‘tetra’.
and on position 5 so this is 3,5-dichloro and a methyl side chain on carbon
1,2,3-trichloro-2 methylpentane
4 so this is 4-methyl
is a correct name as the chloro is
alphabetically before methyl and All substituent groups are written alphabetically
the ‘tri’ is ignored.
The name of the compound is 3,5-dichloro-4-methylhexanal
H H H O

H C C C C butanal
Aldehydes can have structural isomers, for example butanal is isomeric
with 2-methylpropanal. Both have the H same
H molecular
H H formula (C4H8O),
but each have a different structural formula.
H H H H CH3 O
O
butanal H C C C 2-methylpropanal
H C C C C
201
H H H H
H H H

Naming
H ketones
CH3 O
Ketones also have the general formula CnH2nO. The table below gives the
H C C C 2-methylpropanal
first two members of the ketones.
H H
In ketones, theH carbonyl group can be at any position on the chain, except
for the end, so the first member of the ketones is propanone.

807701_C11_AQA_Chemistry_2_198-232.indd 201 13/06/15 9:04 am

 Name Structural formula Displayed formula
TIP propanone CH3COCH3 H H
Remember in nomenclature
H C C C H
there is a difference in numbering
a molecule with a functional H O H
group rather than a substituted
alkane. In substituted alkanes the butanone CH3COCH2CH3 H H H
chain is numbered from the end
H C C C C H
that will give the lowest locant
numbers for the substituents BUT H O H H
when there is a functional group,
the position of the functional Ketones are named according to IUPAC rules. The names are based on the
group dictates the numbering in
carbon skeleton with the ending changed from –ane to –anone.
the chain.

EXAMPLE 3 ● Number the carbon atoms in the longest carbon

This molecule shown below is important in the chain.
manufacture of various herbicides and fungicides. ● The C=O is on carbon 3 and so the compound is a
Name the molecule. ketone, and the positon of the carbonyl group must
be given – pentan-3-one.
H H H H ● Name the side chains and/or substituents attached
5 4 3 2 1 to the main carbon chain and give their position
H C C C C C H
– there is one methyl side chain on carbon 2 so this
H H O CH3 H is 2-methyl, note that since the ketone group is on
carbon 3, the numbering could be from left to right –
Answer but this gives 4-methyl – the lower number is chosen
● Name the longest unbranched carbon chain in the – 2-methyl.
molecule that includes the functional group – there
The name of the compound is 2-methylpentan-3-one.
are 5 carbons so the stem is pent.
11    THE CARBONYL GROUP

Some ketones may have positional isomerism of the functional group; the
molecular formula is the same but the structural formula is different due
to the different positon of the carbonyl group. The pentanones are the first
ketones to exhibit positional isomerism of the functional group as pentan-2-
one and pentan-3-one exist.

H H H H

H C C C C C H pentan-2-one

H O H H H

202
H H H H

H C C C C C H pentan-3-one
Figure 11.4 This is the Ketostix test for
ketones, conducted on the urine of a
H H O H H
diabetic patient. Patients with diabetes
lack the hormone insulin, which
breaks down glucose in the blood.
The body uses fat as an alternative
energy source, leading to a build up of
ketones in the blood and urine that may
eventually cause a diabetic coma.

807701_C11_AQA_Chemistry_2_198-232.indd 202 13/06/15 9:04 am

 The same is true for hexanone. Hexan-2-one and hexan-3-one have
positional isomers.

Aldehydes and ketones

H H H H H

H C C C C C C H hexan-2-one

H O H H H H

H H H H H

H C C C C C C H hexan-3-one

H H O H H H

Aldehydes and ketones exhibit functional group isomerism. Propanone

and propanal are functional group isomers; they have different structural
formula but the same molecular formula.

H H H H O

H C C C H H C C C

H O H H H H

propanone propanal
C3H6O C3H6O

Physical properties of aldehydes and ketones

Boiling points
Van der Waals’ forces exist between one aldehyde molecule and another,
and in addition there are permanent dipole-permanent dipole attractions
between polar carbonyl groups on different molecules. The same is true of
ketones.
This means that the boiling points of aldehydes and ketones are higher than
that of alkanes with a similar relative molecular mass (Mr).
The table below shows the boiling points of three organic molecules with
similar Mr values.
Homologous series Molecule Mr Boiling point/°C
Alkane CH3CH2CH3 44 -42
(propane)
Aldehyde CH3CHO 44 +21
(ethanal)
Alcohol CH3CH2OH 46 +79 203
(ethanol)

● All three of these molecules have similar van der Waals’ forces between their
molecules, as there is a similar Mr and so a similar number of electrons.
● The boiling point of the aldehyde is much higher than the boiling point
of the alkane due to permanent dipole attractions between the carbonyl
groups on neighbouring aldehyde molecules.
● The boiling point of the alcohol is much higher than the boiling point
of the aldehyde due to hydrogen bonds between the hydroxyl groups on
neighbouring alcohol molecules.

807701_C11_AQA_Chemistry_2_198-232.indd 203 13/06/15 9:04 am

 The table below gives the boiling points of the first members of the
aldehydes and ketones.
Aldehyde Boiling point/°C Ketone Boiling point/°C
methanal −21 propanone 56
ethanal 21 butanone 80
propanal 49 pentan-3-one 102

As the length of the carbon chain increases, the boiling point of the aldehydes
increases. This is due to a greater number of electrons and hence stronger
van der Waals’ forces of attraction between the molecules. Methanal is a gas
but the other aldehydes shown here are liquids.
The boiling point of the ketones increases similarly, again due to an increase
in number of electrons.
Ketones tend to have a slightly higher boiling point than their isomeric
aldehydes (compare propanone and propanal). This is due to the position
of the carbonyl group. A carbonyl group at the end of the molecule (in
aldehydes) gives a longer non-polar section meaning there are more
effective van der Waals’ forces and less effective permanent dipole
attractions. The effect however is small and other factors play a part such as
the symmetry of the ketone structure.
Branched chain aldehydes and ketones have lower boiling points than their
straight chain isomers due to less effective permanent dipole attractions.
The branching allows less interaction between the molecules. For
example butanal (CH3CH2CH2CHO) has a boiling point of 74 °C whereas
2-methylpropanal ((CH3)2CHCHO) has a boiling point of 63 °C.
Solubility in water
All short chain aldehydes and ketones mix well with water because the polar
carbonyl groups are able to form hydrogen bonds with water molecules.
H
δ+ δ− H δ+ δ−
11    THE CARBONYL GROUP

H O C
δ− H O
H O H H δ+ δ−
C O H
δ+ H
H C C
hydrogen C
H hydrogen
H bond
H H bond
Figure 11.5 The hydrogen bond between ethanal and water and between propanone
and water.

Oxidation
You will recall that aldehydes and ketones are the products of the oxidation
204 of alcohols. The oxidising agent often used is a solution of potassium
dichromate(vi) dissolved in dilute sulfuric acid – this is commonly referred
to as acidified potassium dichromate(vi) and is represented in an equation
by [O].

807701_C11_AQA_Chemistry_2_198-232.indd 204 16/06/2015 19:03

 Aldehydes can be oxidised into carboxylic acids. Ketones can only be
oxidised by very strong oxidising agents, and they are not oxidised by the

Aldehydes and ketones

reagents used in A2 chemistry.

[O] [O]
primary alcohol aldehyde carboxylic acid

H O O

R C OH R C R C

H O H
H

Equation:
[O]
ethanal ethanoic acid
CH3CHO + [O] → CH3COOH
Condition: warm with acidified potassium dichromate(vi)
Observation: orange solution changes to green.
The aldehyde is oxidised to the carboxylic acid and the orange dichromate ion
is reduced to the green chromium(iii) ion, Cr3+ according to the ionic equation:
−
Cr2O27 + 14H+ +6e− → 2Cr3+ + 7H2O
orange             green

If an aldehyde is to be prepared from a primary alcohol it is important to

immediately distil it from the reaction mixture before it can be oxidised
further to the acid. Prolonged heating of a primary alcohol under reflux with
excess oxidising agent would cause complete oxidation to the carboxylic acid

[0]
secondary alcohol ketone no further oxidation
Equation:
[O]
propan-2-ol propanone
CH3C(OH)HCH3 + [O] → CH3COCH3 + H2O
Condition: warm with acidified potassium dichromate (vi)
Observation: orange solution changes to green.
Tertiary alcohols are not oxidised by acidified potassium dichromate(vi)
solution. The oxidising agent removes hydrogen from the primary and
secondary alcohols as shown below.
primary secondary tertiary

205
H [O] H [O] CH3 [O]

CH3 C O H CH3 C O H CH3 C O H

H CH3 CH3

There is no hydrogen attached

to this carbon for the oxygen
to remove

This enables the C=O bond to form. Tertiary alcohols do not have a hydrogen
atom attached to the carbon with the –OH and so cannot be easily oxidised.

807701_C11_AQA_Chemistry_2_198-232.indd 205 13/06/15 9:04 am

 Chemical test to distinguish between aldehydes and
ketones
Fehling’s solution and Tollens’ reagent are mild oxidising agents that are
used to distinguish between aldehydes and ketones. Aldehydes are oxidised
and ketones are not.
Fehling’s solution contains the copper(ii) complex ion in alkaline solution.
It is a blue solution.

Method
● Add a few drops of the unknown solution to 1 cm3 of freshly prepared
Fehling’s solution in a test tube.
● Warm in a hot water bath.
● If the unknown is an aldehyde an orange–red precipitate will be
produced, if it is a ketone, there is no reaction and the solution
remains blue.
Figure 11.6 Carrying out the Fehling’s The Cu2+ ions in the oxidising agent (Fehling’s solution) are reduced by the
solution test using a water bath: The aldehyde to form an orange–red precipitate of copper(i)oxide (Cu2O). The
orange-red precipitate identifies an aldehyde is oxidised to the carboxylic acid.
aldehyde.
2Cu2+ + H2O + 2e− → Cu2O + 2H+
The equation for the reduction may be simply written as:
TIP Cu2+ + e− → Cu+
If asked for a reagent to
distinguish between aldehydes Tollens’ reagent contains the complex ion, [Ag(NH3)2]+. It is formed by
and ketones, give the correct adding sodium hydroxide solution to silver nitrate solution to form a brown
name, e.g. Tollens’ reagent. precipitate of silver oxide and then adding ammonia solution drop wise
Writing [Ag(NH3)2]+ is incorrect as until the precipitate dissolves to form a colourless solution. Tollens’ reagent
it is not possible to have a reagent is often referred to as ammoniacal silver nitrate.
that only contains this ion; there
must be other ions present. Method
● Add a few drops of the unknown solution to 2 cm3 of freshly prepared
11    THE CARBONYL GROUP

Tollens’ reagent in a test tube.

● Warm in a hot water bath
● If the unknown is an aldehyde, a silver mirror will be produced on the
test tube, if it is a ketone, there is no reaction and the solution remains
colourless.
The silver ions in the oxidising agent (Tollens’ reagent) are reduced in this
reaction to produce silver
Ag+ + e− → Ag
The aldehyde is oxidised to the corresponding carboxylic acid.
206 Reduction
Aldehydes and ketones can be reduced to alcohols using the reducing agent
sodium tetrahydridoborate(iii) NaBH4.The structure of this compound is
shown below
H −

Na+ B
Figure 11.7 A silver mirror is deposited H H
H
on the test tube when an aldehyde is
warmed with Tollens’ reagent.

807701_C11_AQA_Chemistry_2_198-232.indd 206 13/06/15 9:05 am

 In equations a reducing agent is represented by [H].

Aldehydes and ketones

[H]
aldehyde primary alcohol
H H H H H
Equation: O

H C C C + 2[H] H C C C OH
CH3CH2CHO + 2[H]
[H]
→ CH3CH2CH2OH
H
aldehyde
H H
propanal primary
H
propan-1-ol Halcohol
H

propanal propan-1-ol
H H O H H H
aldehyde primary alcohol
H C C C + 2[H] H C C C OH

H H H H H H

propanal propan-1-ol
aldehyde primary alcohol

Condition: heat under reflux with sodium tetrahydridoborate(iii) in aqueous

ethanol followed by acidification with dilute sulfuric acid.
[H]
ketone secondary alcohol
[H]
ketone
Equation:
CH3
secondary Halcohol
CHC O + 2[H] CH3 H
C OH
3

CH3C O + 2[H] CH3 C

CH3 OH
CH3
propanone CH3
propan-2-ol
ketone secondary alcohol
propanone propan-2-ol
ketone secondary alcohol

Condition: heat under reflux with sodium tetrahydridoborate(iii) in aqueous

solution followed by acidification with dilute sulfuric acid.
Sodium tetrahydridoborate(iii) is a less reactive reducing agent than many
others, and so it could be used to selectively reduce only the carbonyl group
in a molecule which contained more than one functional group. It is widely
used today in the production of certain antibiotics.

TEST YOURSELF 2
1 Draw the structure of the following aldehydes and d) Which would show a reaction with acidified
ketones: potassium dichromate(vi) solution?
a) butanal    e) pentan-2-one e) Which would react with Tollens’ reagent. State
b) propanone   f) 2-methylbutanal the observation which would occur. 207
c) ethanal    g) 4-chloropentanal f) Which would be isomers of each other?
d) methanal 3 Write an equation for the reduction of methanal
2 From the following list of aldehydes and ketones: using [H] to represent the reducing agent.
ethanol, propanone, butanone, propanal 4 Write an equation for the oxidation of propan-2-ol
a) Which can undergo reduction? using [O] to represent the oxidising agent.
b) Which can undergo oxidation? 5 Write an equation for the oxidation of butanal using
c) Which have the same molecular formula? [O] to represent the oxidising agent.

807701_C11_AQA_Chemistry_2_198-232.indd 207 13/06/15 9:05 am

 6 Complete the table by placing a tick if a reaction A ethanal B propanone C ethanoic acid
occurs when the oxidising agent is warmed with
D propanal E butanone F butanoic acid
each of the substances shown. Place a cross if the
G propan-1-ol H propan-2-ol I methanol
reaction does not occur.
a) Which of the substances can be oxidised to
Oxidising Primary Secondary Tertiary
propanoic acid?
agent alcohol alcohol alcohol Aldehyde Ketone
b) Which of the substances can be reduced to
Acidified
ethanol?
potassium
dichromate c) Which of the substances has the empirical
Fehling’s formula C2H4O?
solution d) Which of the substances is a secondary
Tollens’ alcohol?
reagent e) State two substances which are isomeric.
f) Which of the substances produce a silver
7 From the following list of organic chemicals, mirror with Tollens’ reagent?
choose the correct answer for each question:

Reaction of aldehydes and ketones with hydrogen

cyanide
Hydrogen cyanide reacts with aldehydes and ketones to produce
compounds called hydroxynitriles.
H O CN

H C C + HCN CH3 C OH

H H H
TIP
ethanal hydrogen 2-hydroxypropanenitrile
When you name hydroxynitriles,
(aldehyde) cyanide (hydroxynitrile)
remember that the carbon with
the nitrogen attached is always The product of this reaction is a hydroxynitrile, with the functional
counted as the first carbon in group –CN. When naming this compound, the longest carbon–carbon
the chain. Also ensure that the
11    THE CARBONYL GROUP

chain must include the carbon in the –CN group, hence it is propanenitrile,
side group is called hydroxy not and the OH is a side group on carbon 2, named 2-hydroxy. The name is
hydroxyl, in the name.
2-hydroxypropanenitrile.
The product of the reaction of a ketone with hydrogen cyanide is also a
nitrile, with the functional group –CN. When naming this compound, the
longest carbon–carbon chain must include the carbon in the –CN group,
hence it is propanenitrile, and the OH is a side group on carbon 2, named
2-hydroxy. The name is 2-hydroxy-2-methylpropanenitrile.
CN
CH3

C O + HCN CH3 C OH
208
CH3 CH3

propanone hydrogen 2-hydroxy-2-methylpropanenitrile

(ketone) cyanide

The hazards of using KCN

The reactions of aldehydes and ketones with HCN are not usually carried
out using hydrogen cyanide as it is an extremely toxic and flammable gas.

807701_C11_AQA_Chemistry_2_198-232.indd 208 13/06/15 9:05 am

 Instead it is usual to generate hydrogen cyanide in the reaction mixture by
adding a dilute acid to an aqueous solution of potassium cyanide. Care

Aldehydes and ketones

must also be exercised when handling potassium cyanide as it is toxic when
ingested and forms hydrogen cyanide when in contact with acid.

Nucleophilic addition reactions

The carbonyl group is unsaturated and can undergo addition reactions. An
addition reaction is one in which the pi bond of the double bond is broken
and species are added across the double bond.
The carbonyl group is also polar and the carbon δ+ is susceptible to attack
by nucleophiles.
A nucleophile is a lone pair donor. It is an atom or group that is attracted
to an electron deficient centre, where it donates the lone pair to form a new
covalent bond.
Hence aldehydes and ketones take part in nucleophilic addition reactions.
There are two different nucleophilic addition mechanisms which you need
to be familiar with.

Nucleophilic addition mechanism for reduction reactions of aldehydes and

ketones with NaBH4
TIP The BH4− ion in NaBH4 is a source of hydride ions (H−). A hydride ion
−
When you write mechanisms is a negatively charged hydrogen ion with a lone pair of electrons, H: .
involving nucleophiles you The hydride ion acts as a nucleophile and attacks the carbon δ+. The lone
must show the lone pair. In this pair of electrons on the hydride ion is donated and forms a bond with the
example you must show both the carbon and at the same time the higher energy pi electrons in the carbonyl
lone pair and the negative sign on group move onto the oxygen, giving it a negative charge.
the hydride ion.
δ− −O
O
δ+
CH3 C CH3 C H
− H
TIP H H

Be very careful when drawing

curly arrows in a mechanism. When acid is added to complete the reaction the lone pair on the negative
Curly arrows represent the ion forms a covalent bond with a hydrogen ion of the acid, producing an
movement of electron pairs. The alcohol product.
formation of a covalent bond
is shown by a curly arrow that −O H+ (aq)
O H
starts from a lone electron
pair or from another covalent CH3 C H CH3 C H
bond. Similarly the breaking of a
covalent bond is shown by a curly H H
arrow starting from the bond. 209
This reaction is an addition reaction, because the C=O bond breaks and the
nucleophile adds across the C=O bond.

807701_C11_AQA_Chemistry_2_198-232.indd 209 13/06/15 9:05 am

 EXAMPLE 4
Name and outline a mechanism for the reaction of propanone with
NaBH4.

Answer
When answering questions on mechanisms it is sufficient to simply draw
the flow diagram, no words of explanation are necessary.
CH3 CH3 CH3
δ+ δ− −
C O CH3 C O H+(aq) CH3 C O H

CH3 −
H H H

Name: Nucleophilic addition

Nucleophilic addition mechanism for the reaction with KCN followed by

dilute acid
The cyanide ion acts as a nucleophile and attacks the carbon δ+. The lone
pair of electrons on the cyanide ion is donated and forms a bond with the
carbon and at the same time the higher energy pi electrons in the carbonyl
group move onto the oxygen, giving it a negative charge.
When acid is added to complete the reaction the lone pair on the negative
ion forms a covalent bond with a hydrogen ion of the acid, producing a
hydroxynitrile product.
The full mechanism for ethanal and potassium cyanide and dilute acid is
shown below

−O H+ OH
O
11    THE CARBONYL GROUP

H3C C H3C C H H3C C H

H CN CN
−
CN

All aldehydes and ketones undergo similar mechanisms with NaBH4 and
KCN. You must be able to draw the mechanism for any carbonyl compound
reacting with these reagents. Essentially all that changes is the structure of
the carbonyl compound and the final product.

Nucleophilic addition reactions of KCN followed by dilute acid

210
can produce a racemate
When potassium cyanide reacts with ethanal, 2-hydroxypropanenitrile is
formed. This compound exhibits optical isomerism as it has an asymmetric
centre with four different atoms or groups attached as shown below

CN

H3C C OH

807701_C11_AQA_Chemistry_2_198-232.indd 210 13/06/15 9:05 am

 In the reaction of ethanal with potassium cyanide, the product is
optically inactive. This is because a racemic mixture – a 50/50 mixture

Aldehydes and ketones

of the two optical isomers – is formed. The carbonyl bond is planar and
the cyanide ion could attack the carbon atom equally from either side.
As a result, the formation of each enantiomer is equally likely and so a
racemate is formed
cyanide can attack
here . . .
O

CH3 C
CH3 C O
H H

ethanal . . . or from this side

Figure 11.8 The nucleophile is equally likely to attack

from above or below.

H C
− CN
CN CH3
OH
C
CH3 O
H
−
CN
C
OH
CH3
CN

Figure 11.9 How a racemate is formed.

All aldeyhydes will produce a racemate.

Propanone, a symmetrical ketone, produces the product 2-hydroxy-2-
methylpropanenitrile which does not have an asymmetric carbon atom and the
product is optically inactive. Unsymmetrical ketones such as CH3COCH2CH3
will produce a racemate, because the product has an asymmetric carbon, and
the nucleophile is equally likely to attack it from either side.

TEST YOURSELF 3
1 a) Write the equation for the reaction of HCN with propanal.
b) Name the organic product.
c) Name the mechanism for this reaction.
d) Outline the mechanism for the reaction of KCN with propanal
followed by dilute acid.
e) Suggest why the product of this reaction is optically inactive.
2 Propanal can be reduced. 211
a) Name a reducing agent for this reaction.
b) Outline a mechanism for the reduction of propanal and name the
nucleophile.
c) Name the organic product.
3 Insects contain small organic molecules which they release to signal
alarm. One alarm chemical is hex-2-enal CH3CH2 CH=CHCHO.
a) Write an equation for the reaction of this compound with bromine
water.
b) Write an equation for the reaction of this compound with HCN.

807701_C11_AQA_Chemistry_2_198-232.indd 211 16/06/2015 17:07

 ●● Carboxylic acids
Structure and functional group
Carboxylic acids have the general structure:

R C

O H

The functional group is called the carboxyl group. It is drawn as

O H

and is written as –COOH.

The carboxyl group is a combination of a carbonyl group (C=O) and a
hydroxyl group (O–H).
Carboxylic acids are weak acids as they dissociate partially in solution; only
a small fraction of the molecules are ionised in solution.
Many carboxylic acids are found in nature. For example ant stings contain
methanoic acid, citrus fruits contain citric acid and the smell of goats and
other farmyard animals is caused by hexanoic acid. The leaves of rhubarb
contain ethanedioic (oxalic) acid. The level of acid in the leaves is so
high that it is dangerous to eat them – the acid can lower the calcium ion
concentration in the blood to dangerously low levels.

Naming carboxylic acids

Carboxylic acids are named according to IUPAC rules. The names are based on
the carbon skeleton with the ending changed from –ane to –anoic acid.
11    THE CARBONYL GROUP

The table gives the names, structural and displayed formulae of the first
four carboxylic acids.
Name of acid Structural formula Displayed formula
O

methanoic acid HCOOH H C

O H

H O

ethanoic acid CH3COOH H C C

212 O H
H

H H O

propanoic acid CH3CH2COOH H C C C

H H O H

H H H O

butanoic acid CH3CH2CH2COOH H C C C C

H H H O H

807701_C11_AQA_Chemistry_2_198-232.indd 212 13/06/15 9:05 am

 IUPAC nomenclature rules state that the carboxyl carbon in the COOH
functional group is always carbon number 1. Any substituents are

Carboxylic acids
numbered based on this.

EXAMPLE 5
The acid shown below is found in very smelly cheeses. ● It has a COOH functional group so it is an acid –
Name this structure. pentanoic acid.
H CH3 H H
● Number the carbon atoms with the carbon of the
O carboxyl group as carbon 1.
H 5
C 4
C 3
C 2
C 1
C ● Name the side chains and/or substituents attached
to the main carbon chain and give their position –
O H
H H H H there is a methyl side chain on carbon 4 – 4-methyl.
The name of the structure is 4-methylpentanoic acid.
Answer
● Name the longest unbranched carbon chain in the
molecule that includes the carbon of the functional
group – there are 5 carbons so the stem is pent.

Physical properties
Solubility in water
Short chain carboxylic acids are very soluble in water. This is because the
highly polar carbonyl and hydroxyl groups can form hydrogen bonds with
water. As the number of carbon atoms in the chain increases, the solubility
decreases due to the longer non-polar hydrocarbon chain.
δ−
δ− δ+
H O
O H δ+
δ+ H
H C C
δ+ δ+
δ− H
H O H O
δ+
H

hydrogen bonds

Boiling point
The boiling point of carboxylic acids is higher than corresponding alcohols.
Substance Formula Mr Boiling point/°C
propan-1-ol CH3CH2CH2OH 60.0 97.2
ethanoic acid CH3COOH 60.0 118.0
213
As shown in the table, propan-1-ol and ethanoic acid have the same relative
molecular mass and therefore the same number of electrons, resulting in
similar van der Waals’ forces between the molecules. Both have hydrogen
bonds between their molecules. The higher boiling point of the carboxylic
acid is because the hydrogen bonding occurs between two molecules of the
acid to form a dimer. This doubles the size of the molecule and increases the
van der Waals’ forces between the dimers resulting in a higher boiling point.

807701_C11_AQA_Chemistry_2_198-232.indd 213 19/06/2015 17:15

 δ− δ+
H O H O H
δ+ δ+
H C C C C H
δ+ δ−
O H O
H H

Hydrogen bonds

Salts of carboxylic acids

Like all acids, carboxylic acids can form salts in their reactions. The metal
salt of a carboxylic acid is called a carboxylate. The sodium salt of ethanoic
acid, sodium ethanoate, is formed by the reaction of ethanoic acid with
sodium hydroxide, and has the structure shown below.
H O O
TIP H C C H3C C
When writing the formula of a
O H O− Na+
salt you can put the charges in, H
stressing the ionic nature of the ethanoic acid sodium ethanoate
compound, e.g. CH3COO−Na+ (acid) (salt)
or you can leave them out, e.g.
CH3COONa. However, to put just When drawing this structure, do not place a line between the oxygen and
one charge in and omit the other the sodium – it is not a covalent bond, it is ionic.
is incorrect. The names of the first four carboxylic acid salts are shown below
Carboxylic acid Name of salt
methanoic methanoate
ethanoic ethanoate
propanoic propanoate
butanoic butanoate

Acid reactions of carboxylic acids

11    THE CARBONYL GROUP

All carboxylic acids in aqueous solution act as acids dissociating to form

H+(aq) (or H3O+(aq)) and the carboxylate ion. They are weak acids because
they are partially dissociated in solution.
For example:

CH3COOH(aq) ⇋ CH3COO−(aq) + H+(aq)

ethanoic acid     ethanoate ion    hydrogen ion

or

CH3COOH + H2O ⇋ CH3COO− + H3O+

214 ethanoic acid   water   ethanoate ion hydroxonium ion

Carboxylic acids take part in typical acid reactions – with carbonates,

metals and bases to form salts.

With carbonates
A carboxylic acid reacts with carbonates according to the general equation
acid + carbonate → salt + water + carbon dioxide

807701_C11_AQA_Chemistry_2_198-232.indd 214 16/06/2015 17:12

 For example:

Carboxylic acids
2CH3COOH + Na2CO3 → 2CH3COONa + CO2    +    H2O
ethanoic acid sodium carbonate sodium ethanoate carbon dioxide water

CH3COOH + NaHCO3 → CH3COONa + CO2 +    H2O

ethanoic acid
sodium hydrogen sodium ethanoate carbon dioxide water
carbonate

Observations: There will be effervescence and the solid sodium carbonate

will be used up, producing a colourless solution.

Test for a carboxylic acid

Despite being weak acids, carboxylic acids are stronger than carbonic
acid and release carbon dioxide when reacted with carbonates. This is the
reaction used to test for carboxylic acids.
● Add a spatula of sodium carbonate or sodium hydrogen carbonate to the
solution.
● If it is a carboxylic acid, effervescence is observed.
● The gas can be collected and bubbled into colourless limewater which
should turn cloudy, proving that the gas produced is carbon dioxide.

With metals
A carboxylic acid reacts with reactive metals according to the general
equation:

acid + metal → salt + hydrogen

For example:

2CH3COOH + Mg → (CH3COO)2Mg + H2
ethanoic acid magnesium magnesium ethanoate  hydrogen
Figure 11.10 Carboxylic acids react with
carbonates and produce effervescence. Observation: There will be effervescence and the solid magnesium will be
This is the test for a carboxylic acid. used up producing a colourless solution.

With bases
A carboxylic acid reacts with bases according to the general equation

acid + base → salt + water

For example:

CH3COOH + NaOH → CH3COONa + H2O

ethanoic acid sodium sodium ethanoate water 215
hydroxide

Observations: There is release of heat and the colourless solution remains.

With ammonia
CH3COOH + NH3 → CH3COONH4
ethanoic acid ammonia ammonium ethanoate

Observations: There is release of heat and the colourless solution remains.

807701_C11_AQA_Chemistry_2_198-232.indd 215 13/06/15 9:05 am

 TEST YOURSELF 4
1 a) Draw the structure of the following carboxylic acids:
i) 3-chloropentanoic acid
ii) 4-methylpent-2-enoic acid
iii) 2-hydroxypropanoic acid
iv) 3-hydroxypropanoic acid
b) Three of the acids in (a) can exist as stereoisomers. Which one
cannot?
c) Name the acid in (a) which can exist as E-Z isomers.
2 a) Complete the equation for the dissociation of ethanoic acid in solution.
CH3COOH ⇋
b) Name the anion formed in this reaction.
c) Would you expect ethanoic acid to be a good electrolyte? Explain
your answer.
3 Write equations for the formation of the following salts:
a) potassium ethanoate from potassium hydroxide
b) sodium ethanoate from sodium carbonate
c) magnesium propanoate from magnesium oxide
d) ammonium methanoate from ammonia
e) ammonium ethanoate may be dehydrated by heating. Write an
equation for this dehydration and name the organic compound
formed.
4 How would you test a substance and prove that it was a carboxylic acid?

Esters
Carboxylic acids react with alcohols in the presence of a strong acid catalyst,
to produce esters. Esters have the general structure:
R1 C O R2
11    THE CARBONYL GROUP

R1 is from the acid and R2 is from the alcohol.

The formation of the ester above can be represented by the equation:
O O

R1 C + R2OH R1 C + H2O

O H O R2

Water is eliminated from the reactants in this reaction, so the reaction can
be described as a condensation reaction. It is a reversible reaction.
216
The functional group of an ester is the –COO– group which is called simply
an ester group or an ester linkage.

Naming esters
The name of an ester is an alkyl carboxylate. When naming, the alcohol
provides the alkyl part of the name and the carboxylic acid provides the
carboxylate part of the name. For example the ester made from methanol
and propanoic acid is methyl propanoate.

807701_C11_AQA_Chemistry_2_198-232.indd 216 13/06/15 9:05 am

 The table below gives the names of some common esters and their parent
acids and alcohols.

Carboxylic acids
Carboxylic acid Alcohol Ester name Ester formula

ethanoic acid ethanol ethyl ethanoate CH3COOCH2CH3

TIP
ethanoic acid methanol methyl ethanoate CH3COOCH3
It is best when drawing the
structural formula of the ester propanoic acid ethanol ethyl propanoate CH3CH2COOCH2CH3
to start with the acid end of the
molecule. butanoic acid propan-1-ol propyl butanoate CH3CH2CH2COOCH2CH2CH3
Acid alkyl C O Alcohol alkyl
group group Esterification equations for formation of esters
O
Example 1:

CH3COOH + CH3CH2OH CH3COOCH2CH3 + H2O

ethanoic acid ethanol ethyl ethanoate water

H H H H H H
O

H C C H C C O H H C C O C C H + H2O

H O H H H H O H H

Condition: A catalyst of concentrated sulfuric acid is used and the mixture is

heated.
Example 2:

HCOOH + CH3CH2CH2OH HCOOCH2CH2CH3 + H2O

methanoic acid propan-1-ol propyl methanoate water

O H H H H H H

H C H C C C O H H C O C C C H

O H H H H O H H H

Questions can often be set which give the structure of the ester and
expect you to determine the structure of the acid and alcohol from
which they are formed

Uses of esters
Solvents
1 Esters are used as plasticisers, which are additives mixed into polymers
217
to improve their flexibility. For example, PVC is a rigid, strong polymer
used in drainpipes and window frames. If it is treated with up to 18% by
mass of a plasticiser made from an ester it becomes cling film, a much
more flexible polymer that is used to wrap non-fatty foods.
2 Esters are used as solvents for organic compounds. They are volatile
and so are easily separated from the solute. Ethyl ethanoate is a common
solvent due to its low cost and low toxicity. It is used in paints and nail
varnish remover.

807701_C11_AQA_Chemistry_2_198-232.indd 217 13/06/15 9:05 am

 Ester Aroma 3 Esters have pleasant smells and are used in perfumes, together with other
benzyl ethanoate jasmine compounds. The table on the left shows the smell of some different esters.
octyl ethanoate orange
4 Esters are used in food flavourings. Many artificial fruit flavourings
ethyl butanoate pineapple
contain esters, for example ethyl methanaote is used to give a raspberry
ethyl cinnamate cinnamon
flavour and pentyl pentanoate gives a pineapple flavour.

REQUIRED PRACTICAL 10
Preparation of an ester (an organic liquid)
The ester ethyl ethanoate was prepared from ethanol and ethanoic acid,
using the method given below.
● Mix equimolar volumes of ethanoic acid and ethanol in a pear-shaped
flask.
● Add 1 cm3 of concentrated sulfuric acid slowly with cooling and shaking.
● Assemble the apparatus for reflux, add some anti-bumping granules
and heat for 20 minutes.
● Distil off the ethyl ethanoate and collect the fraction between 74 and
79 °C.
● Place the crude ethyl ethanoate in a separating funnel and shake
with sodium carbonate solution. Invert the funnel and open the tap
occasionally.
● Allow the layers to separate and discard the lower aqueous layer.
● Add some calcium chloride solution to the ethyl ethanoate to remove
any ethanol impurities, shake, and run off the lower aqueous layer.
TIP ● Place ester in a boiling tube.
Reflux is the continuous boiling ● Add a spatula of anhydrous calcium chloride and stopper the boiling
and condensing of a reaction tube and shake. Repeat until the ester is clear.
mixture. Refer to Book 1 Chapter ● Filter to remove calcium chloride.
13 on Halogenoalkanes to ● Redistill to remove any remaining organic impurities, collecting the
refresh your memory on reflux, fraction at the boiling point.
distillation and the use of a
1 Why must the concentrated sulfuric acid be added slowly and with
11    THE CARBONYL GROUP

separating funnel.
cooling?
2 Why is concentrated sulfuric acid used in this reaction?
3 Write a balanced symbol
equation for the reaction to
prepare ethyl ethanoate.
Water out
4 What is the nature and purpose
of anti-bumping granules? Reflux
condenser
5 What is the function of the
sodium carbonate solution?
6 Why do you need to open the tap Water in
from time to time?
218 7 Why should the distillation flask
be clean and dry? Pear-shaped
flask containing
8 Why is anhydrous calcium all reactants and
chloride added until the ester is anti-bumping
clear? granules
Heat
9 Calculate the percentage yield if
the actual yield is 50.0 g of ethyl Figure 11.11 Apparatus for
ethanoate from 40.0 g of ethanol heating under reflux.
and 52.0 g of ethanoic acid.

807701_C11_AQA_Chemistry_2_198-232.indd 218 13/06/15 9:05 am

 Hydrolysis of esters

Carboxylic acids
Hydrolysis is the reverse of an esterification reaction. The ester is split (lysis)
by the action of water (hydro) into the carboxylic acid and alcohol.
The hydrolysis of an ester needs heat and can be catalysed by either a dilute
mineral acid such as hydrochloric acid or a solution of an alkali such as
sodium hydroxide. There is a difference in the products of acid hydrolysis
and alkaline hydrolysis.

Acid hydrolysis
In acidic conditions, esters are not completely hydrolysed – an equilibrium
TIP mixture is formed in which some ester is present.
It is important to remember that
H+
alkaline hydrolysis produces the ester + water ⇋ carboxylic acid + alcohol
sodium salt of the carboxylic acid
and the alcohol, whereas acid For example:
hydrolysis produces the carboxylic H+
acid and the alcohol. CH3COOC2H5 + H2O ⇋ CH3COOH + C2H5OH
ethyl ethanoate   water  ethanoic acid  ethanol

Condition: heat under reflux with dilute sulfuric or hydrochloric acid.

Alkaline hydrolysis
In alkaline conditions, esters undergo complete hydrolysis forming the
corresponding alcohol and the salt of the carboxylic acid. The reaction in
alkaline solution is quicker.

ester + water → carboxylic acid salt + alcohol

For example:

CH3COOC2H5 + NaOH → CH3COONa + C2H5OH

ethyl ethanoate sodium hydroxide sodium ethanoate ethanol

Condition: heat under reflux with aqueous sodium hydroxide.

In order to liberate the free acid from its salt in alkaline hydrolysis, a dilute
mineral acid such as dilute hydrochloric acid should be added.

CH3COONa + HCl → CH3COOH + NaCl

This reaction is sometimes called saponification and is the basis of soap
making.
Soap is manufactured today using a similar technique as in the 18th
century. Molten tallow (beef fat) or other fat is heated with sodium
hydroxide and saponified to glycerol and sodium salts of fatty acids. After
saponification, the water layer containing glycerol is drawn off and the 219
soap is boiled in water to remove excess sodium hydroxide and glycerol.
Additives such as pumice, dyes and perfumes are added and the soap
poured into a mould.

Vegetable oils and fats

Vegetable oils and animal fats are esters of propane-1,2,3-triol (a tri-
alcohol) and a long chain carboxylic acid called a fatty acid.

807701_C11_AQA_Chemistry_2_198-232.indd 219 13/06/15 9:05 am

 Propane-1,2,3-triol (also known as glycerol) has the structure shown.
H

H C O H

H C O H

H C O H

Fatty acids generally have the structure

O

R C O H

The R is hydrogen or an alkyl group.

Two common fatty acids are stearic acid, CH3(CH2)16COOH, a
saturated fatty acid containing 18 carbon atoms and oleic acid
CH3(CH2)7CH=CH(CH2)7COOH, an unsaturated fatty acid containing
18 carbon atoms.
The fats formed in the condensation reaction between fatty acids and
glycerol are triesters and are often referred to as triglycerides. Propane-
1,2,3-triol has three OH groups and so it reacts with three fatty acids to
form a triglyceride.
O O ester linkage
R1 C OH R1 C O CH2
O HO CH2 O

R2 C OH + HO CH R2 C O CH + 3H 2O
O
O HO CH2
R3 C O CH2
R3 C OH
11    THE CARBONYL GROUP

3 fatty acids glycerol triglyceride ester

A triglyceride is an ester of propane-

1,2,3-triol (glycerol) and three fatty acid It is important to note the triester linkage in the triglyceride. The three fatty
molecules. The fatty acids may or may not acids which form the lipid may be the same (e.g. three stearic acids) or they
all be the same. may be different. The triglyceride is a triester as it has three ester linkages.
Fatty acids are naturally occurring long
chain carboxylic acids. Hydrolysis of vegetable oils and fats
Fats and oils are esters and can be hydrolysed using hot alkali.
Saturated fatty acids do not have a double
bond in the hydrocarbon chain.
Saponification is the alkaline hydrolysis of fats into glycerol and the salts of
the fatty acids present in the fat.
Unsaturated fatty acids have at least one
220 O
C=C double bond in the hydrocarbon chain.
CH2 O C (CH2)16 CH3

CH2OH O
O
+ −
+ 3NaOH CHOH + 3 Na O C (CH2)16 CH3
CH O C (CH2)16 CH3

CH2OH
O

CH2 O C (CH2)16 CH3

Condition: heat under reflux with aqueous sodium hydroxide

807701_C11_AQA_Chemistry_2_198-232.indd 220 13/06/15 9:05 am

 The sodium or potassium salts of the fatty acids are called soaps. Soaps
generally contain C16 and C18 salts, but some also contain lower molecular

Carboxylic acids
mass carboxylates. Whenever soaps are manufactured, the glycerol produced
is a useful by-product used in the pharmaceutical and cosmetic industry.

Biodiesel
Biodiesel is a renewable fuel made from vegetable oils such as rapeseed oil,
palm oil and soybean oil. It can be used in normal diesel engines to power
cars and buses.
Biodiesel consists of a mixture of methyl esters of long chain carboxylic
acids (fatty acids).It is produced by heating vegetable oils (triglycerides)
with methanol in the presence of an acid catalyst. The process can be called
trans-esterification – reacting a ester with an alcohol to produce a different
ester and a different alcohol.
O
O
CH2 O C R1
CH3 O C R1 CH2 OH
O
O
+ 3 CH3OH + CH OH
CH O C R2
CH3 O C R2
CH2 OH
O O

CH2 O C R3 CH3 O C R3

triglyceride methanol mixture of methyl esters glycerol

of fatty acids (biodiesel)

The alkyl groups R1, R2 and R3 can be the same or different. The reaction is
reversible so an excess of methanol is used to drive the equilibrium to the right,
and under appropriate conditions this process can produce a 98% yield.
The glycerol produced is a by-product and can be used in pharmaceuticals
and cosmetics. It has moisturising properties because of the three hydroxyl
groups that can form hydrogen bonds with water and prevent its evaporation.
The use of biodiesel is increasing. However, there are concerns in some countries
that using land for growing crops for biodiesel is in competition with land use
for growing crops to produce food, and this could lead to food shortages.

TEST YOURSELF 5
1 Name the following esters:
a) CH3COOCH2CH3   c) CH3CH2OOCCH2CH3
b) HCOOCH3     d) HCOOCH2CH3 221
2 Write the equations for the formation of the following esters from
alcohols and carboxylic acids.
a) methyl ethanoate
b) ethyl pentanoate
c) propyl butanoate
3 State the name of the catalyst used in the preparation of an ester
from an alcohol and a carboxylic acid.

807701_C11_AQA_Chemistry_2_198-232.indd 221 13/06/15 9:05 am

 4 a) Write an equation for the hydrolysis of ethyl methanoate using
sodium hydroxide.
b) Write an equation for the hydrolysis of propyl methanoate using
hydrochloric acid.
5 State the IUPAC name of glycerol.
6 What is saponification?
7 Trilinolein (rape seed oil) may be
represented as: CH2OOC(CH2)7CH=CHCH2CH=CH(CH2)4CH3

a) Write an equation for the CHOOC(CH2)7CH=CHCH2CH=CH(CH2)4CH3

formation of trilinolein from
3 molecules of the fatty acid CH2OOC(CH2)7CH=CHCH2CH=CH(CH2)4CH3
linoleic acid and glycerol.
b) Explain why trilinolein is described as an unsaturated fat.
c) Rapeseed oil can be converted into biodiesel by reaction with
methanol. Draw the structure of this biodiesel molecule.

Carboxylic acid derivatives

Acid derivatives are compounds that are related to carboxylic acids; the
OH group has been replaced by something else.
Acyl chlorides (also known as acid chlorides) are derived from carboxylic
acids by replacing the OH group by a chlorine atom.
O O

H3C C H3C C

OH Cl

ethanoic acid ethanoyl chloride

(carboxylic acid) (acyl chloride)

Acid chlorides have the functional group:

O
11    THE CARBONYL GROUP

C
R Cl

and are named –anoyl chloride. For example, CH3CH2CH2COCl is butanoyl

chloride.
Acid anhydrides are formed when two molecules of a carboxylic acid join
together and water is eliminated.
O

H3C C O

O H H3C C
222
O
O H H3C C
H3C C O
O

2 molecules ethanoic acid ethanoic anhydride

(carboxylic acid) (acid anhydride)

The structure of ethanoic anhydride can be written as (CH3CO)2 O.

Anhydrides are derivatives of carboxylic acids as the –OH group is replaced
by the carboxylate (RCOO–) group.

807701_C11_AQA_Chemistry_2_198-232.indd 222 13/06/15 9:05 am

 Acid anhydrides have the functional group

Carboxylic acids
O O

C C
R O R

and are named –anoic anhydride. For example (CH3CH2CO)2O is

propanoic anhydride.
Amides are derived from carboxylic acids by replacing the –OH with a
–NH2 group.
O O

CH3 C CH3 C

OH NH2

ethanoic acid ethanamide

(carboxylic acid) (amide)

Amides contain the amide functional group

O

R NH2

and are named using –anamide. For example CH3CH2CH2CONH2 is

butanamide.

Acylation
An acyl functional group has the structure
O

R C

Acylation is the process of replacing a hydrogen atom in certain

molecules by an acyl group (RCO–). Acylation can be carried out
using acid derivatives such as acyl chlorides and acid anhydrides
which act as acylating agents. In general an acylating agent can be
represented by
O

R C

X
TIP
Notice that in these reactions where X = Cl in acid chlorides X = OCOR in anhydrides.
the organic product is the same. 223
The only difference is the other Acyl chlorides and acid anhydrides show similar reactions with water,
products formed, for example alcohol, ammonia and primary amines. Acyl chlorides react vigorously
acyl chlorides form HCl and acid with water, and so in these reactions, anhydrous conditions must be used
anhydrides form CH3COOH. to prevent hydrolysis of the acyl chloride. Acid anhydrides undergo slower
reactions than acyl chlorides.

807701_C11_AQA_Chemistry_2_198-232.indd 223 13/06/15 9:05 am

 1. With alcohol
Acyl chloride

CH3COCl + CH3CH2OH → CH3COOCH2CH3 + HCl

ethanoyl
    ethanol     ethyl ethanoate hydrogen
chloride chloride

Observation: A vigorous reaction which produces steamy fumes of HCl(g), heat

This is a suitable way of producing an ester from an alcohol because it
occurs at room temperature, is irreversible and the hydrogen chloride
is removed as a gas, forming pure ester. This method is not commonly
used in the laboratory due to the volatile and poisonous nature of the acid
chlorides. The normal laboratory preparation of an ester uses an alcohol
and a carboxylic acid and needs heat, a catalyst and is reversible so it is
difficult to get a high yield of ester.
Acid anhydride

(CH3CO)2O + CH3CH2OH → CH3COOCH2CH3 + CH3COOH

ethanoic ethanol ethyl ethanoic acid
anhydride    ethanoate

Observation: This is a slower and less vigorous reaction than that of an acid
chloride and water.
The reaction needs warming. An ester is produced in addition to ethanoic
acid.
Commercially, acid anhydrides are used preferentially to acyl chlorides in
acylation reactions, as the reactions are easier to control

2. With water
Acyl chloride
11    THE CARBONYL GROUP

R–COCl + H2O → R–COOH + HCl

CH3CH2COCl + H2O → CH3CH2COOH + HCl

propanoyl
     water propanoic acid hydrogen
chloride chloride
Observation: a vigorous reaction producing steamy fumes of hydrogen
chloride.
Acid anhydride

224 R1-COOCO-R2 + H2O → R1-COOH + R2-COOH

Figure 11.12 The pipetted addition
In this case two molecules of carboxylic acid are produced.
of ethanoyl chloride to the water in
the beaker has formed ethanoic acid
and fumes (white) of hydrochloric (CH3CH2CO)2O + H2O → 2CH3CH2COOH
acid, formed as hydrogen chloride      
propanoic anhydride water propanoic acid
(HCl) reacts with water in the air. An
ammonia-soaked glass rod tests
for HCl by forming white fumes of Observation: A slower reaction occurs at room temperature. Two colourless
ammonium chloride. solutions produce another colourless solution.

807701_C11_AQA_Chemistry_2_198-232.indd 224 13/06/15 9:05 am

 3. With ammonia
Acyl chloride

Carboxylic acids
The reaction happens in stages. First an amide and hydrogen chloride are
formed.
CH3COCl + NH3 → CH3CONH2 + HCl
However, because ammonia is basic it will react with the hydrogen chloride
to form an ammonium salt

NH3 + HCl → NH4Cl

As a result, two ammonia molecules react – this is usually shown in a
combined equation as below:

CH3COCl + 2NH3 → CH3CONH2 + NH4Cl

ethanoyl ammonia   ethanamide  ammonium
chloride chloride
Observation: a violent reaction producing white smoke that is a mixture of
solid ammonium chloride and ethanamide. Some of the mixture remains
dissolved in water as a colourless solution.
Acid anhydride
This reaction is similar and also occurs in two stages. First an amide and
hydrogen chloride are formed.
(CH3CO)2O + NH3 → CH3CONH2 + CH3COOH
However, because ammonia is basic it will react with the ethanoic acid to
form an ammonium salt
NH3 + CH3COOH → CH3COONH4
As a result, two ammonia molecules react – this is usually shown in a
combined equation as below:

(CH3CO)2O + 2NH3 → CH3CONH2 + CH3COONH4

ethanoic anhydride  ammonia     ethanamide    ammonium ethanoate

Observation: A slower reaction than that of ethanol and ethanoyl chloride.

Heating may be needed.

4. With primary amines

Acyl chloride
Ethanoyl chloride reacts with amines eliminating hydrogen chloride and
forming an N-substituted amide – this means that a methyl group has 225
substituted one of the hydrogen atoms of the NH2 group. The reaction
occurs in two stages:
For example:
H H O H H H H

H C C NH2 + C C H H C C N C C H + HCl

H H Cl H H H H O H

ethylamine ethanoyl chloride N-ethylethanamide

807701_C11_AQA_Chemistry_2_198-232.indd 225 13/06/15 9:05 am

 The amine is basic and reacts with the hydrogen chloride to form an
ammonium salt – methylammonium chloride

CH3NH2 + HCl → CH3NH3Cl

As a result, two ammonia molecules react – this is usually shown in a
combined equation as below:

CH3CH2COCl + 2CH3CH2NH2 → CH3CH2CONHCH3 + CH3CH2NH3Cl

propanoyl ethylammonium
chloride ethyl amine N-ethylethanamide chloride

Acid anhydride

(CH3CH2CO)2O + CH3NH2 → CH3CH2CONHCH3 + CH3COOH

propanoic
      methyl amine  N-methylpropanamide ethanoic acid
anhydride
The amine is basic and will react with the ethanoic acid formed to produce
a salt
CH3COOH + CH3NH2 → CH3COONH3CH3
The salt is called methylammonium ethanoate. It is just like ammonium
ethanoate, except that one of the hydrogens has been replaced by a methyl
group.
Again a combined equation is often used
(CH3CH2CO)2O + 2CH3NH2 → CH3CH2CONHCH3 + CH3COONH3CH3H
Nucleophile Products
Acyl chloride Water Carboxylic acid + hydrogen chloride
RCOCl HO-H RCOOH    + HCl
Acid anhydride Water Carboxylic acid
(RCO)2O HO-H 2RCOOH
Acyl chloride Alcohol Ester + hydrogen chloride
11    THE CARBONYL GROUP

RCOCl R1OH RCOOR1 + HCl

Acid anhydride Alcohol Ester + carboxylic acid
(RCO)2O R1OH RCOOR1 + RCOOH
Acyl chloride Ammonia Amide + hydrogen chloride
RCOCl H-NH2 RCONH2 + HCl
Then HCl + NH3 → NH4 Cl
Acid anhydride Ammonia Amide + carboxylic acid
(RCO)2O H-NH2 RCONH2 + RCOOH
Then RCOOH + NH3 → RCOONH4
Acyl chloride Primary amine N-substituted amide + hydrogen chloride
RCOCl R1NH-H RCONHR1        + HCl
Then HCl + RNH2 → RNH3Cl
226
Acid anhydride Primary amine N-substituted amide + carboxylic acid
(RCO)2O R1NH-H RCONHR1        + RCOOH
Then RCOOH + RNH2 → RCOONH3R

Nucleophilic addition–elimination reactions of acyl chlorides

Acyl chlorides are extremely reactive and react with nucleophiles such as
water, alcohols, ammonia and amines. The mechanism is nucleophilic
addition–elimination and occurs in two steps.

807701_C11_AQA_Chemistry_2_198-232.indd 226 13/06/15 9:05 am

 Addition: the δ+ carbon atom of the polar C=O bond attracts the lone pair
of a nucleophile. The lone pair forms a new bond to the carbon, and a pair

Carboxylic acids
of electrons in the C=O double bond are transferred to the oxygen leaving it
negatively charged. The nucleophile used below is H2O.
δ−
O
δ+ O−
CH3 C
δ− CH3 C Cl
Cl
H O+
H O
H
H

TIP Elimination: the pair of electrons on the oxygen atom reform the double bond
Remember, when asked to and the C–Cl bond of the acyl chloride breaks and releases a chloride ion, which
outline a mechanism you simply reacts with a hydrogen atom on the protonated hydroxyl group to form HCl.
show a flow diagram with the O−
correct curly arrows and lone O
pairs. CH3 C Cl CH3 C Cl
−

+
H O+ O H

H H

O O

CH3 C CH3 C + HCl

+
O H O H

H Cl
−

Often this elimination is shown in one step as in the examples shown below.
The following four mechanisms are all required.
Example 1: the reaction of ethanoyl chloride with water.
O
O−
CH3 C O
CH3 C Cl
Cl CH3 C + HCl
H O+ OH
H O
H
H

Example 2: the reaction of ethanoyl chloride with ethanol.

−
O 227
O O

CH3 C Cl CH3 C + HCl

CH3 C
+ OCH 2CH3
Cl CH3CH2 O H

CH3CH2OH

807701_C11_AQA_Chemistry_2_198-232.indd 227 13/06/15 9:05 am

 Example 3: the reaction of ethanoyl chloride with ammonia.
−
O
O O

CH3 C CH3 C Cl CH3C + HCl

Cl H
+
N H NH2

NH3 H

Remember that the HCl would react with another NH3 to form an
ammonium salt NH4Cl.
Example 4: the reaction of ethanoyl chloride with primary amines, e.g.
methyl amine.
TIP
The mechanism for nucleophilic O
−
O O
addition-elimination needs to
show 5 curly arrows as shown in CH3 C CH3 C Cl CH3 C + HCl
examples 1-4. Cl +
CH3 N H N H

CH3NH2 H CH3

Remember that the HCl would react with another amine to form an
ammonium salt.

Preparation of pure organic solids

Acylation reactions are used widely in the pharmaceutical industry. Two
of the most commonly used drugs, paracetamol and aspirin are both
manufactured using acylation reactions. Aspirin is manufactured by
acylating 2-hydroxybenzenecarboxylic acid. The –OH group is esterified to
form aspirin.
The industrial advantages of using ethanoic anhydride to acylate rather
than ethanoyl chloride include
11    THE CARBONYL GROUP

● it is less corrosive
● it is less vulnerable to hydrolysis
● it is less hazardous to use as it gives a less violent reaction
● it is cheaper than ethanoyl chloride
● it does not produce corrosive fumes of hydrogen chloride.
An equation for the preparation of aspirin from ethanoic anhydride and
2-hydroxybenzoic acid is shown below.
O

C
OH O CH3 O O
228 O
O
C C
CH3 C
OH OH + CH3 C
O
OH
CH3 C
O
ethanoic 2-hydrobenzoic acid aspirin
anhydride

807701_C11_AQA_Chemistry_2_198-232.indd 228 13/06/15 9:05 am

 Filter paper
Organic solids such as aspirin must be produced in as pure a state as possible.
Impurities can occur for many reasons; two of the most common are

Carboxylic acids
contamination with reactants due to an incomplete reaction and the presence of
Büchner
funnel
other compounds due to alternative competing reactions during the preparation.
Recrystallisation is a very important technique used to purify solids by
Suction removing unwanted by-products. The practical steps for the process of
recrystallisation are:
Side-arm ● Dissolve the impure crystals in the minimum volume of hot solvent.
conical flask
● Filter the hot solution by gravity filtration, using a hot funnel and fluted
Figure 11.13 Suction filtration apparatus. filter paper, to remove any insoluble impurities (filtering through hot filter
funnel and using fluted paper prevents precipitation of the solid).
● Allow the solution to cool and crystallise (the impurities will remain in solution).
● Filter off the crystals using suction filtration (suction filtration is faster than
gravity filtration and gives a drier solid).
● Dry between two sheets of filter paper.
A minimum volume of hot solvent is used to dissolve the solid, making
a saturated solution. The solution is cooled and the solubility of the
compound drops causing it to recrystallise from solution. Impurities remain
dissolved in the solution. A minimum volume of hot solvent is used to
ensure that as much of the solute is obtained as possible.

TIP Checking the purity of an organic solid

The melting point tube can be A pure substance has a fixed melting point while an impure substance melts
attached to a thermometer with over a wide range of temperatures and at a lower temperature than the pure
a rubber band and placed in an substance. The melting points of almost all substances are available in data
oil bath rather than in a melting tables. To check the purity of a solid, a melting point can be determined
point apparatus. Photos of both using the following method:
ways of finding a melting point
are found in Practical skills, ● Place some of the solid in a melting point tube.
Chapter 17. ● Place in melting point apparatus and heat slowly.
● Record the temperature at which the solid starts to melt and the
temperature at which it finishes melting.
● Repeat and average the temperatures.
● Compare the melting point with known values in a data book.
The melting point of a substance is not the exact point at which it melts but
rather the range of temperatures from when the sample starts to melt until
it has completely melted. The greater the range the more impurities are
present. A range of less than 2 °C indicates a fairly pure substance.

REQUIRED PRACTICAL 10
229
The preparation of aspirin (an organic solid) ● Place 20.0 g of 2-hydroxybenzoic acid in a
in the laboratory pear-shaped flask and add 40 cm3 of ethanoic
anhydride ((CH3CO)2 O).
Aspirin (2-ethanoylhydroxybenzenecarboxylic acid) is ● Safely add 5 cm3 of conc. phosphoric(v) acid and
an antipyretic drug (reduces fever by lowering body heat under reflux for 30 minutes.
temperature) and an analgesic (relieves pain). ● Add water to hydrolyse any unreacted ethanoic
Today, over one hundred companies hold patents anhydride to ethanoic acid, and pour the mixture
for processes that generate aspirin. Each is slightly into 400 g of crushed ice in a beaker.
different but all end with the same molecule. The ● The product is removed by suction filtration,
following method can be used to prepare aspirin in recrystallised from water and dried in a desiccator.
the laboratory. ● The melting point is then determined.

807701_C11_AQA_Chemistry_2_198-232.indd 229 13/06/15 9:05 am

 The reaction can be represented as follows. 6 Why is the mixture poured onto crushed ice?
HOOCC6H4OH + (CH3CO)2O → HOOCC6H4OCOCH3 + 7 Why is suction filtration used rather than gravity
filtration?
CH3COOH
8 Describe how the impure product is
1 Suggest the role of concentrated phosphoric(v) recrystallised.
acid in this preparation. 9 Calculate the atom economy for the preparation of
2 Explain how the concentrated phosphoric(v) acid aspirin by this method.
is added safely. 10 An alternative preparation, using ethanoyl
3 Draw a labelled diagram of the apparatus set up chloride rather than ethanoic anhydride, has a
for reflux. higher atom economy. Why is this reaction not
4 Assuming a 70% yield, calculate the mass of used in industry?
2-hydroxybenzoic acid required to form 5.0 g of 11 The melting point of aspirin was determined.
pure aspirin. From the result, state how you would determine if
5 Write an equation for the hydrolysis of ethanoic the aspirin was pure.
anhydride.

TEST YOURSELF 6
1 Name the following: c) propanoyl chloride and methylamine
a) CH3CH2COCl d) ethanoic anhydride and ethanol
b) CH3CH2CH2CONH2 3 Name the mechanism for the reaction between
c) (CH3CH2CO)2O ethanoyl chloride and water and state the name of
d) CH3COCl the organic product.
2 Write equations for the reaction of: 4 Name the method used to purify solids.
a) ethanoyl chloride and propanol 5 A pure sample of solid ethanamide is prepared in
b) butaonyl chloride and ammonia the laboratory. How would you test its purity?

Practice questions 3 Butan-1-ol was reacted with an excess of

propanoic acid in the presence of a small
11 THE CARBONYL GROUP

1 Which one of the following statements about amount of concentrated sulfuric acid. 6.0 g of
the formation of an ester from ethanoyl the alcohol produced 7.4 g of the ester. Which
chloride and propan-1-ol is correct? one of the following is the percentage yield of
the ester?
A Concentrated sulfuric acid is required.
A 57% B 70%
B Heat is required.
C 75% D 81% (1)
C The ester produced is called ethyl
propanoate. 4 The scheme below summarises the formation
and reactions of ethanoic acid.
D The reaction goes to completion. (1)
CH3CH2OH ethanal ethyl ethanoate
2 Which one of the following compounds is
230
optically active and incapable of reducing A B C
Fehling’s solution?
A CH3CH(CH3)CH2CHO CH3COOH

B CH3CH(C2H5)COCH3 D E

C CH3CHClCH2CHO CH3CH2OH CH3CH2CH2OOCCH3

D CH3CH(CH3)COCH3 (1)

807701_C11_AQA_Chemistry_2_198-232.indd 230 13/06/15 9:05 am

 a) Give suitable reagents and conditions for and explain one way in which the
each of the reactions A–E. (10) equilibrium yield of the ester could be

Practice questions
increased. (2)
b) Give the type of reaction occurring in the
reactions A–E. (5) ii) Draw and name two structural isomers
of ethyl methanoate. (4)
5 Nucleophiles react with carbonyl compounds
to form addition products. iii) Write an equation for the preparation
of ethyl methanoate from an acid
a) Define the term nucleophile. (1)
anhydride and an alcohol. (1)
b) Explain why the carbonyl group is
c) Fats may be produced by the equilibrium
susceptible to attack by a nucleophile. (2)
reaction between a fatty acid and glycerol.
c) Write an equation for the reaction of CH2OH CH2OOCR
propanal with HCN and name the
product. (2) CHOH + 3RCOOH CHOOCR + 3H2O

d) Outline a mechanism for the reaction of CH2OH CH2OOCR

propanal with HCN. (3)
i) State the IUPAC name for glycerol. (1)
e) Explain why the product is optically
inactive. (2) ii) The fat may alternatively be produced
by the reaction of acyl chlorides
f) Aldehydes can be distinguished from (RCOOCl) with glycerol. Write the
ketones using the following reagents. equation for the reaction. (4)
i) Complete the following table. (4) iii) The vegetable oil shown below reacts
with methanol in the presence of
Formula of Formula of
metal/ion metal/ion potassium hydroxide to form
Reagent before test after test biodiesel. Write the equation for this
Tollens’ reagent reaction. (1)
Fehling’s solution
CH2OOCC17H31
ii) Which reagent(s) will give a positive CHOOCC17H33
test for ethanal? (1) CH2OOCC17H29
6 Carboxylic acids, esters and fats are all found 7 Complete the diagram below by inserting the
in nature and contain the carbonyl group. organic product formed in each case. (3)
They have different functions in nature, for
example carboxylic acids are found in ant C2H5COOH
stings, esters flavour fruits, and fats are used
for energy storage. Na2CO3
NH3 NaBH4
a) i) Ethanoic acid has a boiling point of
119 °C and ethyl methanoate, an ester
has a boiling point of 56 °C. Explain
the difference in boiling points. (3) 8 Which one of the following would not be
affected by boiling with aqueous sodium 231
ii) Ethanoic acid reacts with solid
hydroxide?
potassium hydrogen carbonate. Write
an equation for this reaction and state A ethyl ethanoate
one observation. (2)
B glycerol
b) i) Ethanol reacts with methanoic acid
C olive oil
to form ethyl methanoate. Write an
equation for this equilibrium reaction D ethanoic acid (1)

807701_C11_AQA_Chemistry_2_198-232.indd 231 13/06/15 9:05 am

 9 a) Name and outline a mechanism for the in test tube reactions. For each pair, suggest
reaction of CH3CH2COCl with CH3NH2. (3) a suitable reagent or reagents that could be
added separately to each compound in order
b) Write an equation for the reaction of to distinguish between them. Describe what
CH3CH2COCl with ammonia. (1) you would observe with each compound.
10 The flow scheme below shows a series of a) methyl ethanoate and propanoic acid (3)
organic reactions.
b) butanone and propanoyl chloride (3)
H H
H H
reaction 1 c) butan-2-ol and 2-methylpropan-2-ol (3)
C C H C C Br
12 Dodecanoic acid, C11H23COOH, is an acid
H H H H found in coconut oil and human breast milk.
A B
It is a white solid at room temperature with
a melting point of 45 °C, and is insoluble in
reaction 2 water.
a) Explain why ethanoic acid is soluble
H H in water whereas dodecanoic acid is
insoluble. (2)
H C C C N
b) Describe a chemical test to prove that
H H
dodecanoic acid is an acid. (2)
C
c) Describe how you would experimentally
reaction 3 determine that a sample of solid
dodecanoic acid is pure. (3)
H H H H d) Dodecanoic acid can be reduced to the
O O
corresponding alcohol. Write an equation
H C C C H C C C for the reduction using [H] to represent
H H
Cl
H H
OH the reducing agent and name a suitable
reducing agent for the reaction. (2)
E D
e) The main constituent of coconut oil is
11 THE CARBONYL GROUP

a) Name compounds A to E. (5)

the triester formed from dodecanoic acid
b) State the type of reaction which is taking and glycerol. Write an equation for the
place in reactions 1 and 2. (2) formation of this triester. (1)
c) Name the mechanism by which reaction 1 Stretch and challenge
occurs. (2)
13 Propanone can be converted into
d) Name the mechanism by which reaction 2 2-bromopropane by a three-step synthesis
occurs. (2) as shown below. It is first reduced into
compound X. Deduce the structure and names
e) Name the reagents required for each of
of compounds X and Y and for each of the
reactions 1 and 2. (2)
three steps suggest a reagent that could be
232 11 The following compounds can be used and name the mechanism. (6)
distinguished by observing what happens
H H H Br H

H C C C H X Y H C C C H

H O H H H H

807701_C11_AQA_Chemistry_2_198-232.indd 232 16/06/2015 17:13

 12 Aromatic chemistry

PRIOR KNOWLEDGE
● Alkenes undergo addition reactions. The mechanism of these
reactions is electrophilic addition.
● Alkenes decolourise orange bromine water.
● Understand the terms structural formula, displayed formula,
molecular formula, empirical formula and skeletal formula

TEST YOURSELF ON PRIOR KNOWLEDGE 1

1 a) Write an equation for the reaction of bromine with ethene.
b) State the colour change in this reaction.
c) Name the product in this reaction.
2 Rubber is a polymer of isoprene. The structure CH3
of isoprene is shown below.
a) What is the molecular formula for isoprene? C CH2
H2C C
b) What is the empirical formula for isoprene? H
c) What is the skeletal formula for isoprene?
d) What is the IUPAC name for isoprene?
e) Isoprene reacts with excess bromine. Write an equation for this
reaction and name the product.
f) What is observed in the reaction of isoprene with bromine?

The word aromatic comes from the Latin word ‘aroma’ meaning fragrance.
Many of the first organic compounds produced from natural substances
such as cinnamon bark and vanilla beans, were found to give off pleasant
smells. When these compounds were analysed they were found to contain
benzene rings. Today’s definition of an aromatic compound is one which
contains a benzene ring. The smell generated by a compound has nothing
to do with the presence of a benzene ring and aromatic compounds do not
all have a pleasant smell!
Aromatic chemicals are very important in the production of synthetic
233
compounds such as drugs, dyes, explosives and plastics.

807701_C12_AQA_Chemistry_2_233-244.indd 233 13/06/15 9:05 am

 ●● The history of the structure of benzene
In 1825 Michael Faraday discovered benzene, a colourless, sweet smelling
liquid. It was found to have the empirical formula CH and relative molecular
mass 78.0 which gave a molecular formula of C6H6. He first extracted
benzene from whale oil, which was commonly used for lighting homes.
Scientists speculated over the structure of benzene for many years. Initially
H H it was suggested that it had a structure with several double bonds, like that
H C C C
shown in Figure 12.1.
C C C H However, experimental evidence showed that benzene was rather unreactive
for such an unsaturated molecule and this structure was rejected.
H H
Figure 12.1 A linear structure was In 1865 Friedrich August Kekulé proposed a hexagonal structure of six
initially suggested for benzene. carbon atoms joined by alternate single and double bonds as shown in
Figure 12.2 This was the first time that it was considered that carbon atoms
H could join together in rings rather than chains.

H C H Alkenes are reactive molecules due to their double bonds, and since
C C Kekulé’s structure contained double bonds, benzene was expected to react
or in a similar way to alkenes, and to decolourise bromine water. Benzene,
C C
H C H
however, did not decolourise bromine water and did not readily undergo
addition reactions. To account for this lack of reactivity, Kekulé proposed
H that his structure had two forms that existed in a rapid equilibrium. An
displayed formula skeletal formula approaching bromine molecule could not be attracted to a double bond
Figure 12.2 The Kekulé structure of before the structure changed, and so the bromine could not react with the
benzene. double bond. In this model, the structure of benzene is called a resonance
hybrid and it is often represented as shown below.
12    AROMATIC CHEMISTRY

The carbon–carbon bond lengths

The structure of benzene suggested by Kekulé had alternating single and double
bonds. In 1922 Kathleen Lonsdale used X-ray diffraction to measure the bond
lengths in benzene. She found all the carbon–carbon bonds were the same
length, at an intermediate value between that of a double and single carbon–
carbon bond. This suggested that the Kekulé structure of benzene was incorrect.
Bond Bond length
carbon–carbon bond in benzene 0.140 nm
C–C 0.153 nm
C=C 0.134 nm
234
Thermochemical data: enthalpy of hydrogenation
Enthalpy of hydrogenation is defined as When cyclohexene, with one carbon–carbon double bond is hydrogenated,
the change in enthalpy, which occurs when the enthalpy change of hydrogenation is −120 kJ mol−1.
1 mol of an unsaturated compound reacts
with an excess of hydrogen to become fully
saturated. + H2

cyclohexene cyclohexane

807701_C12_AQA_Chemistry_2_233-244.indd 234 13/06/15 9:05 am

 A sigma bond (δ) is formed by direct Kekulé’s benzene structure has three double bonds, so it would be expected
to have a enthalpy change of −360 kJ mol−1, three times that of cyclohexane

The history of the structure of benzene

overlap of two orbitals on adjacent carbons,
each providing one electron, so that the because three double bonds are hydrogenated. A theoretical cyclic
electron density is concentrated between compound with three double bonds is cyclohexa-1,3,5-triene.
the two nuclei.
A pi bond (π) is formed by the sideways
overlap of two p orbitals on adjacent carbon + 3H2
atoms, each providing one electron.

cyclohexa-1,3,5-triene cyclohexane

However, when benzene is hydrogenated the enthalpy change is only

−208 kJ mol−1, this is 152 kJ mol−1 less than expected. This means that the
actual structure of benzene is more stable than the Kekulé structure
(cyclohexa-1,3,5-triene)

The delocalised model of benzene

Today’s accepted structure for benzene is of a delocalised model which has
the following features:
Figure 12.3 Kekulé spent years studying ● it is a planar hexagonal molecule of six carbon atoms.
the nature of carbon–carbon bonds. He ● all carbon–carbon bond lengths are intermediate in length between that of a
said that he discovered the ring shape single C–C and a double C=C.
of the benzene molecule after having
a daydream of a snake seizing its own
● each carbon uses three of its outer electrons to form three sigma bonds
tail. This is an ancient symbol known as to two other carbon atoms, and one hydrogen atom. This leaves each
the ouroboras. carbon atom with one electron in a p orbital.

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

P orbitals overlap Sigma bond

sideways
Delocalised electrons above
and below the plane of the
carbon atoms

Figure 12.5 The formation of the delocalised electron structure of benzene.

● The lobes of the p orbitals do not pair up to form three carbon–carbon

double bonds as in the Kekulé structure, but overlap sideways to form a
ring of charge above and below the plane of the molecule. This overlap
produces a system of pi bonds. The six p electrons spread over the whole
ring – they delocalise and give regions of electron density above and 235
below the ring as shown in Figure 12.5.
● Delocalisation of p electrons makes benzene more stable than
the theoretical molecule cyclohexa-1,3,5-triene. The enthalpy of
hydrogenation is 152 kJ mol−1 less than expected due to the extra stability
of the delocalised electrons that are more spread out and so have fewer
Figure 12.4 Computer-generated model electron–electron repulsions.
of a molecule of benzene. It is a planar ● The delocalisation of electrons also accounts for the intermediate
molecule. carbon–carbon bond length.

807701_C12_AQA_Chemistry_2_233-244.indd 235 13/06/15 9:05 am

 ● The bond angles in the ring are 120°, meaning there is no strain in this
arrangement, another factor contributing to the stability of the molecule.
● A circle is used to represent the ring of delocalised electrons, as shown below.

Delocalised electrons are bonding

electrons that are not fixed between two
atoms, but shared by three or more atoms.

TEST YOURSELF 2
1 Explain why the bond lengths of the carbon–carbon bonds in benzene
prove that Kekulé’s structure is not correct.
2 State the shape of benzene and give the bond angle around a carbon
atom.
3 How does a delocalised ring of electrons form in benzene?

●● Benzene and addition and substitution

reactions
A substitution reaction is one in which an Benzene and alkenes are similar in that they have regions of high electron
atom or group of atoms is replaced with a density – the delocalised ring of pi electrons in benzene and the double
different atom or group of atoms. bond in alkenes. As a result of this they both react with electrophiles.
An addition reaction is one in which
a reactant is joined to an unsaturated
Alkenes undergo addition reactions but, as a result of its stability benzene
molecule to make a saturated molecule. is fairly resistant to addition reactions and instead substitution reactions tend
to occur. To undergo addition reactions, the electrons from the delocalised
system in benzene would need to bond with the atom or group being
added. The delocalised electron system would be broken, resulting in a loss
of stability. Instead benzene undergoes substitution reactions, where one or
more of the hydrogen atoms are replaced by another atom or group. The
12    AROMATIC CHEMISTRY

organic product formed retains the delocalised ring of electrons and hence
the stability of the benzene ring.
Bromine water is not decolourised by benzene, as it does not undergo an
addition reaction with bromine because the delocalised ring of electrons
would be broken.
Figure 12.6 Two test tubes containing
an organic layer floating on top of an Br
aqueous layer. The aqueous layer
+ Br Br
contains bromine water (orange). The
organic layer on the right (cyclohexene)
Br
decolourised the water because
236 cyclohexene contains a reactive
double bond which undergoes addition
reactions. The organic layer on the
left (benzene) did not decolourise the
bromine water because it does not
undergo addition reactions due to the
stable delocalised electron ring.

807701_C12_AQA_Chemistry_2_233-244.indd 236 13/06/15 9:07 am

 Naming compounds based on benzene

Benzene and addition and substitution reactions

If one of the hydrogen atoms on a benzene ring is replaced by an atom
or group then a benzene derivative is formed. Some common benzene
derivatives are shown below.

Cl Br NO2 CH3

chlorobenzene bromobenzene nitrobenzene methylbenzene

C6H5Cl C6H5Br C6H5NO2 C6H5CH3

If there is more than one atom or group on the benzene ring, the position of
the group must be given. Carbon atoms in the benzene are numbered 1–6
to give the smallest possible position of each group. For example,
CH3

Cl

could be 1-chloro-3-methylbenzene or 1-chloro-5-methylbenzene. The

correct name is 1-chloro-3-methylbenzene, using the smallest number for
the position of the methyl group.
Figure 12.7 shows three structural isomers of C7H7Br.

CH3 CH3 CH3

1 1 1
Br
2 2 2
6 6 6

3 3
5 3 5 5

4 4
Br 4

Br
1-bromo-2-methylbenzene 1-bromo-3-methylbenzene 1-bromo-4-methylbenzene
Figure 12.7 The structural isomers of C7H7Br.

Alkyl groups are formed by removing a hydrogen atom from an alkane, for
example a methyl group CH3 is formed from methane CH4 by removing a
hydrogen. Removing a hydrogen group from a benzene ring forms a phenyl
group C6H5. Some compounds containing a benzene ring have their name 237
based on phenyl. Some examples are shown below.

CH3 O
NH2 C CH CH2

phenylamine phenylethanone phenylethene

807701_C12_AQA_Chemistry_2_233-244.indd 237 13/06/15 9:07 am

 TEST YOURSELF 3
1 Name the following structures. 3 Why does benzene undergo substitution reactions
rather than addition reactions?
a) Cl b) CH3
4 Draw a possible structure for an aromatic
Cl compound which has the empirical formula C7H8.
5 Is this structure named 1-bromo-2-chlorobenzene
or is it 1-chloro-2-bromobenzene? Explain your
Cl
answer.

c) CH3 d) Br
Br
CH2CH3

Cl

Cl

2 a) Name a reagent that could be used to distinguish

between benzene and cyclohexene.
b) State what is observed when this reagent is
shaken with benzene and then with cyclohexene
in separate test tubes.

●● Electrophilic substitution
The region of high electron density above and below the plane of the
molecule results in benzene being attacked by electrophiles. Substitution
reactions occur rather than addition reactions as this preserves the
stability of the benzene ring. The mechanism is described as electrophilic
substitution.
12    AROMATIC CHEMISTRY

Mechanism of electrophilic substitution

A general mechanism for electrophilic substitution is shown in Figure 12.8.
TIP
If you need to outline the H E
mechanism, you simply need +
E
to draw a flow scheme with + E + H+
curly arrows as shown in
Figure 12.8 – words of explanation Figure 12.8 The mechanism of electrophilic substitution.
are not necessary.
● In the first step the high electron density of the delocalised ring of
238
electrons attracts the electrophile (E+) and a pair of electrons from the
ring of delocalised pi electrons form a bond with the electrophile (E+),
breaking the electron ring.
● This produces a highly unstable intermediate which has only a partially
delocalised electron system containing four delocalised electrons.
● A C–H bond breaks in the unstable intermediate and the two electrons
in the bond move back into the pi electron system, reforming the stable
delocalised electron ring. The hydrogen is lost as H+.

807701_C12_AQA_Chemistry_2_233-244.indd 238 13/06/15 9:07 am

 An electrophile is an electron pair acceptor. Benzene reacts with different types of electrophiles. Generally these
electrophilic substitution reactions employ heat, concentrated reagents and

Electrophilic substitution
It is usually is an atom or group of atoms that
is attracted to an electron rich centre where catalysts. This is because of the high stability and low reactivity of benzene.
it accepts a pair of electrons to form a new Two electrophilic substitution reactions which you must study in detail are
covalent bond.
nitration and acylation. Only monosubstitution, where one atom or group is
replaced is required.

Nitration
In nitration of benzene, a nitro group (NO2) replaces one of the hydrogen
atoms. To nitrate benzene a mixture of concentrated nitric and concentrated
sulfuric acid is used at 50 °C. The mixture of concentrated nitric and
concentrated sulfuric acid is often referred to as the nitrating mixture.

NO2

conc
H2SO4 catalyst
+ HNO3 + H2O
50°C

benzene nitrobenzene
C6H6 C6H5NO2

Condition: concentrated sulfuric acid and concentrated nitric acid at 50 °C.

TIP The concentrated sulfuric acid is a stronger acid than nitric acid and
The first curly arrow must come donates a proton to it, forming an intermediate H2NO3+ that decomposes to
from the delocalised ring to produce NO2+, the nitronium ion that is the electrophile.
the N or the + on the N of the
H2SO4 + HNO3 ⇋ HSO4− + H2NO3+
electrophile. In the intermediate
the broken electron ring must H2NO3+ → NO2+ + H2O
not extend beyond carbon 2 or
carbon 6. It must be approximately H2SO4 + H2O → HSO4− + H3O+
centred on carbon 1. The overall equation for the generation of the electrophile is
H
6 HNO3 + 2H2SO4 → NO2+ + 2HSO4− + H3O+
5 1
+ NO2
4 2 The mechanism for mononitration is shown in Figure 12.9.
3
The second curly arrow must H NO2
come from the middle of the bond +
NO2
into the hexagon. + NO2 + H+

Figure 12.9 The electrophilic substitution mechanism for the nitration of benzene.

The concentrated sulfuric acid acts as a catalyst in the reaction as it is

regenerated in the last step when H+ ion is released in the mechanism and 239
combines with HSO4− to reform sulfuric acid.
Uses of nitration
The nitration of benzene and other aromatic compounds is useful in
industry
1 In the manufacture of explosives. Many nitro compounds formed
by nitration are used in explosives – for example TNT 2-methyl-1,3,5-
trinitrobenzene otherwise known as 2,4,6-trinitrotoluene is a well-known

807701_C12_AQA_Chemistry_2_233-244.indd 239 16/06/2015 17:13

 explosive used to demolish buildings and to blast mines and quarries. It
is made by nitrating methyl benzene.
CH3

O2N NO2

NO2

TNT

The presence of the methyl group which is electron releasing makes the
benzene more susceptible to attack by electrophiles, so three nitro groups
substitute rather than just one.
2 In the formation of amines. Nitrobenzene can be reduced to
phenylamine (see Chapter 13) which is an important chemical in the
production of dyes.
3 In organic synthesis. In organic chemistry the synthesis of a particular
compound is often a multistage process. Often nitration is one of the steps
in synthesis. Organic synthesis will be looked at in detail in Chapter 15.

TEST YOURSELF 4
1 The first step in the nitration mechanism of benzene is shown below.
Both benzene and the intermediate structure formed have pi bonds.

H
+
NO2
+ NO2
12    AROMATIC CHEMISTRY

a) Name this mechanism.

b) What does the curly arrow represent?
c) State how many electrons are involved in the pi bonding in each
structure.
d) Describe in words what happens in the next step of this
mechanism.
e) Name two types of commercially important materials whose
manufacture involves the nitration of benzene.
f) State the conditions required for the nitration of benzene.

Acylation
240
Friedel-Crafts reactions were developed in 1877 by the French chemist
Acylation is the process of replacing a
hydrogen atom in certain molecules by an
Charles Friedel and the American chemist James Mason Craft. They are
acyl group (RCO–). electrophilic substitution reactions in which an acyl group is attached to
the ring, replacing a hydrogen atom. They are useful as the benzene forms a
O
bond with a carbon, producing a side chain.
R C
Benzene can be acylated using an acyl chloride, in the presence of a catalyst,
to form an aromatic ketone. The catalyst used is aluminium chloride, and
an acyl group
the conditions must be anhydrous to prevent its hydrolysis.

807701_C12_AQA_Chemistry_2_233-244.indd 240 13/06/15 9:07 am

 O

Electrophilic substitution
CH3 C

O
+ CH3 C + HCl

Cl

C6H6 CH3COCl C6H5COCH3

benzene ethanoyl chloride phenylethanone

TIP
Remember that phenylethanone is written C6H5COCH3. Writing
the formula as C6H5CH3CO is incorrect. The –one in the name
phenylethanone shows that it is a ketone and has a C=O in the chain, the
phenyl indicates that a C6H5 is attached.

+
The required electrophile is the acylium ion CH3 C O It is formed by
reaction between the ethanoyl chloride and the aluminium chloride catalyst.
The equation for the formation of the electrophile is
+
CH3COCl + AlCl3 → CH3CO + AlCl4−
The mechanism for acylation is shown in Figure 12.10.

H C CH3
+
C CH3 + C CH3 O
O + H+
O
Figure 12.10 The electrophilic substitution mechanism for the acylation of benzene.

The catalyst is regenerated:

H+ + AlCl4− → AlCl3 + HCl
When methyl benzene reacts with ethanoyl chloride in the presence of
aluminium chloride a similar electrophilic substitution reaction occurs
but the reaction is faster than the reaction of benzene. This is because the
methyl group increases the electron density on the benzene ring which
means the electrophile is attracted more, and so the reaction is faster.
An alternative acylation agent is ethanoic anhydride. Instead of HCl,
ethanoic acid is produced. 241

C6H6 + (CH3CO)2O → C6H5COOCH3 + CH3COOH

Importance of Friedel-Crafts acylation
Friedel-Crafts are important in synthesis of other organic compounds as
they allow carbon–carbon bonds to form. Acylation introduces a reactive
carbonyl functional group to the ring. This can undergo the reactions of
a carbonyl group and so act as an intermediate in the synthesis of other
compounds.

807701_C12_AQA_Chemistry_2_233-244.indd 241 13/06/15 9:07 am

 TEST YOURSELF 5
1 a) Write an equation for the reaction of butanoyl chloride with
benzene.
b) Explain why this reaction is an acylation.
c) Name the catalyst for this reaction and write an equation to show
how it reacts with butanoyl chloride molecules to produce an
electrophile.
d) At the end of this reaction the catalyst is regenerated. Write an
equation to show the regeneration of the catalyst.
e) Why must the reaction mixture be kept completely dry in this
reaction?
2 Phenylpropanone is used in the manufacture of the drug
amphetamine.
a) Draw the structural formula of phenylpropanone.
b) Write an equation to show how phenylpropanone is produced from
benzene and state the conditions and reagent used.
c) Write the empirical formula of phenylpropanone.
d) Name and draw the skeletal formula of a phenylaldehyde which is
an isomer of phenylpropanone.

REQUIRED PRACTICAL 10
Preparation of methyl 3-nitrobenzoate ● Pour the reaction mixture onto 25 g of crushed ice
(an organic solid) and stir until all the ice has melted and crystalline
methyl 3-nitrobenzoate is formed.
Dogs are extremely sensitive to smell and can ● Filter the crystals using Buchner filtration, wash
be trained to detect the smell of different types with cold water, recrystallise and obtain the
of chemicals. The drug cocaine hydrochloride melting point.
hydrolyses in moist air to give methyl benzoate.
Drug-sniffing dogs are trained to detect the smell of 1 Write an equation for the nitration of methyl
methyl benzoate. benzoate to produce methyl-3-nitrobenzoate.
12    AROMATIC CHEMISTRY

Nitrobenzene is not prepared in the laboratory due to 2 What homologous series does methyl benzoate
belong to?
the high toxicity of benzene. To illustrate nitration in
the laboratory methyl benzoate, a pleasant-smelling 3 What is the molecular and the empirical formula
organic compound of low toxicity is used. The of methyl benzoate?
procedure followed is detailed below. 4 What conditions were used during this preparation
to prevent further nitration of the product to the
● Weigh out 2.7 g of methyl benzoate in a small dinitro derivative?
conical flask and then dissolve in 5 cm3 of 5 How do the conditions for the nitration of methyl
concentrated sulfuric acid. When the solid has benzoate differ from those for the nitration of
dissolved cool the mixture in ice. benzene?
● Prepare the nitrating mixture by carefully adding 7 Why were the crystals washed with cold water?
2 cm3 of concentrated sulfuric acid to 2 cm3 of
242 6 Explain why recrystallisation was carried out.
concentrated nitric acid and then cool this mixture
in ice. 8 Calculate the theoretical yield of methyl
3-nitrobenzoate based on the mass of methyl
● Add the nitrating mixture drop by drop to the
benzoate used in this preparation.
solution of the methylbenzoate, stirring with a
thermometer and keeping the temperature below 9 If 2.1 g of methyl 3-nitrobenzoate are obtained,
10 °C. When the addition is complete allow the calculate the percentage yield.
mixture to stand at room temperature for 15
minutes.

807701_C12_AQA_Chemistry_2_233-244.indd 242 13/06/15 9:07 am

 Practice questions the aromatic ring in methylbenzene, resulting

Practice questions
in three possible structural isomers.
1 How many electrons are there in the a) Draw and name two of the structural
delocalised pi electron system in benzene? isomers. (4)
A 3 b) Explain why methylbenzene undergoes
B 6 substitution reactions rather than addition
reactions with bromine. (2)
C 9
6 a) Benzene may be converted to
D 12 (1) methylbenzene (toluene) by reaction
2 What is the total number of isomers of with chloromethane in the presence of
dichlorobenzene, C6H4Cl2? aluminium chloride. The mechanism is
similar to that for the nitration of benzene.
A 2
C6H6 + CH3Cl → C6H5CH3 + HCl
B 3
i) What is the function of the aluminium
C 4 chloride? (1)
D 5 (1) ii) Suggest the formula of the
3 Which one of the following statements about electrophile. (1)
benzene is incorrect? b) The explosive trinitrotoluene (TNT) is
A A total of six electrons per molecule are prepared by the nitration of methylbenzene
delocalised. (toluene).
CH3 CH3
B All of the carbon-carbon bonds are the
same length. O2N NO2

C The bond angles are all 120°.

D The empirical formula is C6H6. (1)
4 Cyclohexa-1,3,5-triene is a hypothetical NO2
molecule. It can be hydrogenated to form
Toluene TNT
cyclohexane
a) Write an equation for the hydrogenation of i) What is the IUPAC name for TNT? (1)
cyclohexa-1,3,5-triene. (1)
ii) TNT burns to form a mixture of carbon
b) Use the data below to state and explain dioxide, nitrogen and water. Write an
the stability of benzene compared with equation for the complete combustion
the hypothetical cyclohexa-1,3,5-triene of TNT. (2)
molecule. (2)
c) TNT is prepared from toluene by using the
Enthalpy of hydrogenation/kJ mol−1 same nitrating mixture as is used to nitrate
benzene.
cyclohexene −120 243
benzene −208 i) Name the reagents present in the
nitrating mixture. (2)
c) How would you experimentally distinguish
between a sample of benzene and a sample ii) Write an equation for the formation of
of cyclohexene? (2) the nitrating species. (1)
5 Methylbenzene C6H5CH3 is used to make iii) What name is given to the nitrating
artificial sweeteners, pharmaceuticals and species? (1)
explosives. Monobromination occurs when
one bromine atom substitutes a hydrogen in

807701_C12_AQA_Chemistry_2_233-244.indd 243 13/06/15 9:07 am

 d) The mechanism for nitrating toluene is f) How does the mechanism for this reaction
similar to that for nitrating benzene. show that the sulfuric acid is acting as a
catalyst. (1)
i) What name is given to this
mechanism? (1) Stretch and challenge
ii) Outline a mechanism for the 9 Benzene reacts with electrophiles. In a reaction
mononitration of toluene. (3) with an electrophile the compound Y, shown
below was formed.
iii) Name the organic product in the
mononitration of toluene. (3) O
7 Ethanoyl chloride reacts with benzene.
C CH2 CH3
a) Write an equation for this reaction and
name the organic product. (2)
Y
b) Name the catalyst for this reaction and
write an equation to show how the catalyst
reacts with ethanoyl chloride to produce a
a) Name the two substances that react to
reactive intermediate. (1)
generate the electrophile, and write an
c) Outline the mechanism for the reaction of equation to show the formation of this
benzene with the reactive intermediate. (1) electrophile. (3)
d) Name the mechanism. (1) b) Outline a mechanism for the reaction of
this electrophile with benzene to form
8 a) Draw a dot and cross diagram to show the
compound Y. (3)
bonding in the nitronium ion NO+2. (1)
c) What is observed when compound Y is
b) Explain why there is a positive charge on
warmed with Fehling’s solution? (1)
the nitronium ion. (1)
d) Another compound X is an isomer of Y. X
c) Explain if the nitronium ion is an
produces a silver mirror when warmed with
electrophile or nucleophile. (1)
the reagent Z. Compound X is optically
d) Write an equation for the generation of the active. Identify reagent Z and suggest a
12 AROMATIC CHEMISTRY

nitronium ion. (1) structure for X. (3)

e) The nitronium ion reacts with benzene.
Explain if this reaction is addition or
substitution. (2)

244

807701_C12_AQA_Chemistry_2_233-244.indd 244 13/06/15 9:07 am

 13 Amines
PRIOR KNOWLEDGE
● Ammonia has the formula NH3 and consists of a nitrogen atom
covalently bonded to three hydrogen atoms. The nitrogen atom has a
lone pair of electrons.
● Due to its lone pair ammonia can act as a nucleophile, an electron
pair donor.
● A Brønsted-Lowry base is a proton acceptor, ammonia is a weak base.
● Halogenoalkanes (e.g. chloromethane CH3Cl) have a polar
carbon–halogen bond due to the halogen atoms having a greater
electronegativity than carbon.
● Halogenoalkanes undergo substitution reactions with the nucleophile
NH3 to form amines.

TEST YOURSELF ON PRIOR KNOWLEDGE 1

1 Draw a dot and cross diagram to show the bonding in NH3 and label
the lone pair.
2 Why is ammonia a Brønsted-Lowry base?
3 Name the following structures:
a) H H H Br b) H H H

H C C C C H F C C C F

H Br Cl H H F H

c) H Cl H d) H CH3

H C C C H H C C Br

H H H H H
e) Br

4 Explain why ammonia is a nucleophile.

Amines are a group of nitrogen containing organic compounds that are

derived from ammonia. As with ammonia, they are characterised by a
distinctive unpleasant smell similar to rotting fish. 245

Amines play an important role in the survival of life – they are involved in
the creation of amino acids, the building blocks of proteins and they are
found in many chemicals in the body. Adrenaline, a hormone that helps the
body to deal with sudden stress, is an amine. Serotonin, a neurotransmitter
for the brain that controls the feeling of hunger and helps regulate sleeping
patterns is also an amine. Amines are classified as primary, secondary or
tertiary depending on the number of hydrogen atoms substituted.

807701_C13_AQA_Chemistry_2_245-260.indd 245 13/06/15 9:08 am

 OH H
NH2

HO

HO
N
OH

H
serotonin adrenaline
Figure 13.1 Serotonin and adrenaline are amines. Note the NH2 and NH groups.

The global demand for amines is increasing yearly and is expected to rise
to an average of 4501 kilo tonnes by 2020. This increase in demand for
amines reflects their wide ranging applications.
● Many analgesics (medicines that relieve pain) are amines. Morphine is
an example.
● Salbutamol, the active ingredient in asthma inhalers, is an amine.
● Many synthetic dyes are made from amines. Methyl orange is made from
an amine.
● Amines are used in anaesthetics such as Novocaine, which is a local
anaesthetic used in dentistry. It is an aromatic amine.

●● The structure of amines

Amines are compounds based on ammonia, where hydrogen atoms have
TIP been replaced by alkyl or aryl (C6H5–) groups. Primary amines contain
You came across the terms
primary, secondary and tertiary
the –NH2 functional group, which is called the amino group.
in Book 1 when you studied ● A primary amine contains one alkyl or aryl group attached to the
alcohols. Note that the terms do nitrogen atom as only one hydrogen atom in ammonia has been replaced.
not have the same meaning with This means there is only one carbon chain attached to the nitrogen.
amines. ● A secondary amine contains two alkyl or aryl groups attached to the
nitrogen atom as two hydrogen atoms in ammonia have been replaced.
● A tertiary amine contains three alkyl or aryl groups attached to the
nitrogen atom as three hydrogen atoms in ammonia have been replaced.
Figure 13.2 The structure of a primary, primary secondary tertiary
13    AMINES

secondary and tertiary amine. amine amine amine

H R′ R′

R N R N R N

H H R″
where R, R′ and R″ are alkyl or aryl groups

246 CH2CH3 CH3

CH3CH2NH2 CH3 N CH3 N

H CH3
ethylamine ethylmethylamine trimethylamine

807701_C13_AQA_Chemistry_2_245-260.indd 246 13/06/15 9:08 am

 Quaternary ammonium compounds
These are produced from tertiary amines when the nitrogen’s lone pair of

Naming amines
electrons forms a dative covalent bond to a fourth alkyl group. Hence a
TIP quaternary ammonium salt has four alkyl groups attached to the nitrogen atom.
Remember that the nitrogen
in ammonia can form a dative Like ammonium salts they are crystalline ionic solids.
covalent bond with another For example,
hydrogen producing a quaternary
ammonium salt. CH3

(CH3)4N+I− CH3 N+ CH3 l−

CH3

is tetramethylammonium iodide, a quaternary salt.

●● Naming amines
Amines are organic derivatives of ammonia. They are usually named
according to the alkyl or aryl chain followed by –amine. Naming amines
TIP can be confusing as there are many variations on the names. The following
The easiest way to recognise a examples will illustrate how to name different amines.
primary, secondary or tertiary
amine is to count the number of
H atoms on the N atom.
● 2 H atoms on N atom – primary
EXAMPLE 1
amine, e.g. C2H5NH2
● 1 H atom on N atom – Name the compound:
secondary amine, e.g. H H H H
(C2H5)2NH
● 0 H atoms on N atom – tertiary H C C C N
amine, e.g. (C2H5)3N] H
H H H

Answer
● Identify if it is a primary, secondary or tertiary amine – it is a primary
amine as it has only one alkyl group attached to the N.
● Name the alkyl chain – there are 3 carbons so the stem is propyl.
The compound is propylamine (you may also see this named as
1-aminopropane).

EXAMPLE 2
Name the compound: CH3 CH CH3 247

Answer NH2

● Identify if it is a primary, secondary or tertiary amine – it is a primary

TIP amine as it has only one alkyl group attached to the nitrogen.
When naming amines, if you ● Name the alkyl chain – there are 3 carbons so the stem is prop.
need to give the position of the ● In this case the amino group is attached to the second carbon so the
carbon to which the NH2 group is number must be included in the name.
attached, use the ‘amino’ form of
The compound is 2-aminopropane.
naming.

807701_C13_AQA_Chemistry_2_245-260.indd 247 13/06/15 9:08 am

 EXAMPLE 3
Name the compound: Answer
NH2 ● Identify if it is a primary,
secondary or tertiary amine – it
is a primary amine as it has
only one aryl group attached to
the nitrogen.
● Name the aryl group – phenyl.
The compound is phenylamine.

EXAMPLE 4
Name the compound (CH3)2NH: ● Name the longest alkyl chain –
H
it contains one carbon – methyl.
H ● Name the other alkyl chain – it
H C contains one carbon – methyl.
H ● The prefix di and tri are used
H C N
if there are two or three of the
H
H same alkyl group – there are
two methyls so it is named
Answer dimethyl.
● Identify if it is a primary,
The compound is dimethylamine.
secondary or tertiary amine – it
is a secondary amine as it has
two alkyl groups attached to
the nitrogen.

TIP EXAMPLE 5
The prefix N- is used to show that Name the compound: ● Name the longest alkyl chain –
the alkyl groups are attached to it contains three carbons –
the main chain via the nitrogen CH3CH2CH2
propyl.
13    AMINES

atom. N H ● Name the other alkyl chain – it

H3C contains one carbon – methyl.
This second alkyl chain is
Answer attached to the nitrogen, so a
● Identify if it is a primary, prefix N- is added to show this.
secondary or tertiary amine – it The compound is
248 is a secondary amine as it has N-methylpropylamine.
two alkyl groups attached to
the nitrogen.

807701_C13_AQA_Chemistry_2_245-260.indd 248 13/06/15 9:08 am

 TIP

Naming amines
EXAMPLE 6 CH3CH2CH2
The prefix diamino is used Name the compound: N CH2CH3
if a compound contains two
amino groups, for example Answer CH3CH2
1,2-diaminoethane is ● Identify if it is a primary, secondary or tertiary amine – it is a tertiary
H2NCH2CH2NH2. amine as it has three alkyl groups attached to the nitrogen.
● Name the longest alkyl chain – it contains three carbons – propyl.
● Name the other alkyl chain – it contains two carbons – ethyl. The
second alkyl chain is attached to the nitrogen, so a prefix N- is added
to show this.
● Name the third alkyl chain – it contains two carbons – ethyl and it also
is attached to the nitrogen – so the prefix N is added.
● The prefix di and tri are used if there are two or three of the same
alkyl group. There are two ethyl groups so it is N,N-diethyl.
The compound is N,N-diethylpropylamine.

Compounds that contain an amino group and other functional groups are
named based on the hierarchy in organic chemistry which states that the
order of priority from highest to lowest is as follows:
1 carboxyl (–COOH)
2 aldehyde (–CHO)
3 ketone (–CO–)
4 hydroxyl (–OH)
5 amines (–NH2, –RNH, –R2N)
6 alkene (–C=C–)
The following groups are always named as prefixes in alphabetical order:
alkyl (R–), phenyl (C6H5–), chloro (Cl–), bromo (Br–), iodo (I–), nitro (–
NO2).
For example:
TIP
2-aminoethanoic acid may be O H H
called aminoethanoic acid; the
H2NCH2COOH   C C N     
aminoethanoic acid
2 is not essential as the amino
group cannot be attached to any H O H (also known as glycine)
H
other carbon.
H

H2NC6H4OH   N O H   4-aminophenol 249

H

H H H O

H2NCH3CH2CHO N C C C     3-aminopropanal
H H H H

807701_C13_AQA_Chemistry_2_245-260.indd 249 13/06/15 9:08 am

 TEST YOURSELF 2
1 Name the following compounds
a) CH3CH2NH2 e) CH3CH(NH2) CH2CH3
b) C6H5NH2 f)  CH3 CH CH2 CH CH3
c) (CH3)2NH
NH2 NH2
d) H
H
H C g) CH3CH3CH2CH2NH2
H C N
H h)
H
OH
H C
H2N
H
H
O
2 Classify the amines in the table below as primary, secondary or
tertiary amines by placing a tick in the table below.

Amine Primary Secondary Tertiary

methylamine
ethylamine
dimethylamine
phenylamine
triethylamine

3 Isomers of CH3CH2CH2NH2 include another primary amine, a

secondary amine and a tertiary amine. Draw the structures of these
three isomers. Label each structure as primary, secondary or tertiary.

●● Preparation of primary amines

From halogenoalkanes
Halogenoalkanes react with ammonia to produce an amine.
R−X  +    2NH3 → R−NH2 + NH4X
halogenoalkane   ammonia   amine   ammonium halide
13    AMINES

For example:
CH3CH2Cl + 2NH3 → CH3CH2NH2 + NH4Cl
chloroethane    ammonia   ethylamine    ammonium chloride

Condition: heat in a sealed flask with excess ammonia in ethanol. A sealed

TIP glass tube is used because the ammonia would escape as a gas if reflux was
250
You have come across this implemented.
reaction and the mechanism
before in Book 1, and you will The ammonia has a lone pair of electrons and acts as a nucleophile
revise the mechanism later on in attacking the Cδ+ of the polar C–X bond. The mechanism is nucleophilic
this chapter. substitution
The amine produced also has a lone pair of electrons on the nitrogen
atom so it can act as a nucleophile. This can attack another molecule of
chloroethane, causing further substitution and so continuing the reaction.
CH3CH2Cl + CH3CH2NH2 → (CH3CH2)2NH + HCl

807701_C13_AQA_Chemistry_2_245-260.indd 250 13/06/15 9:08 am

 If excess ammonia is used then a primary amine is the major product. If
excess of the halogenoalkane is used then successive substitution is more

Preparation of aromatic amines

likely to occur and the reaction produces ethylamine, diethylamine and
triethylamine. We will look at this in more detail on page 255. Due to a mixture
of different types of amine being produced, this method is not generally used
for preparing primary amines. A better method is by reduction of a nitrile.

From nitriles by reduction

Amines can be formed by the reduction of nitriles using hydrogen in the
presence of a nickel catalyst or by using a reducing agent such as lithium
tetrahydridoaluminate(iii) (LiAlH4) in ether.
R − C ≡ N + 2H2 → R−CH2NH2
CH3CN + 2H2 → CH3CH2NH2
ethanenitrile       ethylamine

Condition: hydrogen in the presence of a nickel catalyst

R − C ≡ N + 4[H] → R − CH2NH2
or using a reducing agent of LiAIH4
CH3CH2CN + 4[H] → CH3CH2CH2NH2
propanenitrile      propylamine

Condition: [H] is lithium tetrahydridoaluminate(iii) in dry ether

The reduction reaction gives a better yield than the preparation of amines
from halogenoalkanes, and there are no other products.

●● Preparation of aromatic amines

By reduction of nitro compounds
Aromatic amines such as phenylamine are prepared by reduction of
nitrocompounds. Phenylamine is prepared by reduction of nitrobenzene
using tin and concentrated hydrochloric acid as reducing agent. Overall this
reduction can be written as:
RNO2 + 6[H] → RNH2 + 2H2O

NO2 + 6[H] NH2 + 2H2O

nitrobenzene phenylamine

Condition: heat under reflux with tin and excess concentrated hydrochloric 251
acid, followed by adding concentrated sodium hydroxide.
Since excess acid is used (rather than getting phenylamine directly), the
protonated form of phenylamine, i.e. the phenylammonium ion, is formed.

NH+3

phenylammonium ion

807701_C13_AQA_Chemistry_2_245-260.indd 251 13/06/15 9:08 am

 Concentrated sodium hydroxide is added to remove the hydrogen ion from
the NH3+ group. The addition of concentrated alkali liberates the free amine.

NH+
3 + OH
− NH2 + H2O

phenylammonium salt phenylamine

When writing an equation for this reaction, it is usual to write the equation
in one step:

NO2 + 6 [H] NH2 + 2H2O

nitrobenzene phenylamine

TIP
It is important to start trying to link your organic chemistry. A useful
scheme to remember is:
NO2 NH2

conc HNO3 / Sn/conc HCl/heat

conc H2SO4 /50°C NaOH solution

The nitrobenzene used to produce phenylamine is first produced by

nitration of benzene (see page 239).
Questions may often involve two nitro groups being reduced.

EXAMPLE 7 NO2 NH2

TIP Write a balanced equation for this reaction

13    AMINES

The command word ‘Identify’ using molecular formula and using [H]
allows the you to choose to use for the reducing agent. Identify a reducing
either the name or the formula agent for this conversion.
of a reagent in their answer.
Answer
NO2 NH2
The general equation for the reduction of a
252 nitro compound is:
RNO2 + 6[H] → RNH2 + 2H2O
Note that in this case there are two nitro groups hence the equation is:
C6H4N2O4 + 12[H] → C6H8N2 + 4H2O
The reducing agent is tin and concentrated hydrochloric acid

807701_C13_AQA_Chemistry_2_245-260.indd 252 13/06/15 9:08 am

 Use of aromatic amines

Basic properties of amines

Aromatic amines prepared by the reduction or nitro compounds are used
in the manufacture of dyes. These dyes, known as azo dyes were the first
synthetic dyes to be produced towards the end of the 19th century. Prior
to this, vegetable dyes, which easily faded were used. Azo dyes fade much
more slowly and are not removed by water or detergent. These dyes account
for about 60% of all the dyes used in food and textiles.

●● Basic properties of amines

Amines, like ammonia, are weak bases. A base is a proton (hydrogen ion)
acceptor. The lone pair of electrons on the nitrogen atom of ammonia and
amines can accept a proton as shown below. A dative covalent bond forms
between the lone pair of the nitrogen and the proton.
+
H H

H3C N + H+(aq) H3C N H

H H
Dative
methylamine proton methylammonium ion covalent
bond

Basic reactions of amines

With dilute mineral acids
In general, bases react with acids. Ammonia and amines are similar in their
reaction with acids:
ammonia + acid → ammonium salt
amine + acid → alkyl ammonium salt
With dilute hydrochloric acid:
CH3NH2 + HCl ⇋ CH3NH3+Cl−
methylamine    methylammonium chloride
TIP NH2 NH3Cl
Remember when writing the
formula of alkyl ammonium
salts you can put BOTH charges
in (as in the methylammonium + HCl
chloride example) to show the
ionic character, or you can
leave them both out (as in the phenylamine phenylammonium
chloride
phenylammonium chloride
253
example). Never put just one
With dilute sulfuric acid:
charge in – it is incorrect.
2CH3CH2NH2 + H2SO4 ⇋ (CH3CH2NH3)2SO4
    ethylamine      ethylammonium sulfate

These reactions with acids can be reversed using alkali. The amine can
be reproduced again from its salt using a dilute alkali such as sodium
hydroxide solution.

807701_C13_AQA_Chemistry_2_245-260.indd 253 13/06/15 9:08 am

 With water
When amines react with water, they accept a hydrogen ion from water to
produce an alkylammonium ion and hydroxide ions.
CH3NH2 + H2O ⇋ CH3NH3+ + OH−
methylamine      
methylammonium ion

The solution formed is weakly basic because the equilibrium lies to the left
as methylamine is only partly ionised, and as a result little of it has reacted
with the water resulting in a solution with low [OH−].

Comparison of base strength

The basicity of amines depends upon the availability of the lone pair on the
N atom, which is used to bond with the proton. Different types of amines
have different basic strengths as shown in the figure below:

Primary aliphatic amine

Basic strength
Ammonia decreases

Primary aromatic amine

Primary aliphatic amines are stronger bases than ammonia because of the
alkyl group attached to the nitrogen. The alkyl group is said to be electron
donating – it releases electrons meaning there is slightly more electron
density on the nitrogen atom. As a result, the lone pair is more available
and so has an increased ability to accept a proton. Aliphatic amines
generally increase in base strength as the number of alkyl groups attached
to the nitrogen atom increases.
The trend in basicity for the first three primary amines is shown in
Figure 13.3.

H H H H H H

H C > NH2 H C > C > NH2 H C > C > C > NH2

H H H H H H
13    AMINES

Increase in basicity
Figure 13.3 The diagram shows that as the size of the alkyl group increases
the electron donating ability increases, and so the lone pair is more available
resulting in an increase in basicity.

254
Primary aromatic amines such as phenylamine, are weaker bases than
ammonia because nitrogen’s lone pair of electrons can overlap with the
delocalised pi electrons in the benzene ring. The lone pair is delocalised
into the pi system, the electron density on the nitrogen is decreased and the
lone pair is less available for accepting a proton.
The relative strength of the primary amines can be compared by looking at
the pKa values in the table below. The pKa values given are for the conjugate
RNH3+. The stronger the base, the weaker the conjugate acid. As a result, the
stronger base will have a higher pKa value for its conjugate base – in this
table propylamine is the strongest base.

807701_C13_AQA_Chemistry_2_245-260.indd 254 13/06/15 9:08 am

 Name Formula pKa

Nucleophilic properties of amines

propylamine (primary aliphatic) CH3CH2CH2NH2 10.84
ethylamine (primary aliphatic) CH3CH2NH2 10.73 Decreasing
methylamine (primary aliphatic) CH3NH2 10.64 basicity
ammonia NH3 9.25
phenylamine (primary aromatic) C6H5NH2 4.62

TEST YOURSELF 3
1 Ammonia and ethylamine are examples of weak c) Explain how ethylamine reacts with water to
Brønsted–Lowry bases. form an alkaline solution using an equation.
a) State the meaning of the term Brønsted–Lowry d) Write an equation for the reaction of
base. methylamine with sulfuric acid.
b) i) Write an equation for the reaction of 3 For the flow scheme
ethylamine (CH3CH2NH2) with water to form
a weakly alkaline solution. NO2 NH2 NH3Cl

ii) In terms of this reaction, state why the

solution formed is weakly alkaline.
c) State which is the stronger base, ammonia or
ethylamine. Explain your answer.
2 a) Methylamine reacts with hydrochloric acid as A B C D
shown below.
CH3NH2 + HCl → CH3NH3Cl a) Name structures A–D
i) Name the product of this reaction. b) Name the reagents for each step in the
conversion
ii) Explain how the free amine may be liberated.
b) Place the following basic compounds in order of c) Name the mechanism for the conversion of A to
B
basicity from 1 (most basic) to 4 (least basic) by
placing the number in the table below. 4 Explain why X is a weaker base than Y.
NH2 NH2
Compound Basicity
ammonia
dimethylamine
methylamine X Y
phenylamine

●● Nucleophilic properties of amines

Nucleophiles are lone pair donors. All amines contain a lone pair of
electrons on the nitrogen atom, so they act as nucleophiles.
255
Nucleophilic substitution reaction with
halogenoalkanes
The reaction of a halogenoalkane with ammonia and amines forms primary,
secondary, tertiary amines and quaternary ammonium salts.
Making a primary amine
This reaction happens in two stages. Initially a salt is formed:
CH3CH2Br + NH3 → CH3CH2NH3Br
         ethylammonium bromide

807701_C13_AQA_Chemistry_2_245-260.indd 255 13/06/15 9:08 am

 Then the salt reacts with the excess ammonia in the mixture and removes a
hydrogen ion forming a primary amine.
CH3CH2NH3Br + NH3 ⇋ CH3CH2NH2 + NH4Br
             ethylamine
(primary amine)

Making a secondary amine

Further substitution reactions may occur. This is because the primary amine
produced has a lone pair so it can act as a nucleophile and continue to react
with any unused halogenoalkane, in the same stages as before.
CH3CH2Br + CH3CH2NH2 → (CH3CH2)2NH2Br

(CH3CH2)2NH2Br + NH3 ⇋ (CH3CH2)2NH + NH4Br

diethylammonium bromide   d
 iethylamine
(secondary amine)

This successive substitution results in the formation of a secondary amine.

Making a tertiary amine

The secondary amine produced also has a lone pair so it too can act as a
nucleophile and continue to react with any unused halogenoalkane, in the
same stages as before. This further substitution results in a tertiary amine.
CH3CH2Br + ( CH3CH2)2NH → (CH3CH2)3NHBr
(CH3CH2)3NHBr + NH3 ⇋ (CH3CH2)3N + NH4Br
             triethylamine
(tertiary amine)

Making a quaternary ammonium salt

Finally, the tertiary amine reacts with the halogenoalkane to form a quaternary
ammonium salt. There is no longer a lone pair on the nitrogen so the
quaternary ammonium salt cannot act as a nucleophile and the reaction stops.
CH3CH2Br + (CH3CH2)3N → (CH3CH2)4NBr
             quaternary ammonium salt
Choosing the conditions
In this reaction, due to the repeated nucleophilic substitution secondary amines,
tertiary amines and quaternary ammonium salts may all be present depending
13    AMINES

on the conditions. The product of each reaction is a better nucleophile than the
starting material as it contains more electron donating alkyl groups.

+
H H R R
RBr RBr RBr
R N R N R N R N R Br −
256
H R R R

primary secondary tertiary quaternary

Figure 13.4 The successive substitutions of an amine.

The initial conditions can be adjusted to favour production of a particular

type of amine.
● Excess ammonia favours the production of primary amines as it is less
likely that another halogenoalkane molecule will react with an amine,
when there is a large number of unreacted ammonia molecules available.

807701_C13_AQA_Chemistry_2_245-260.indd 256 13/06/15 9:08 am

 ● Excess halogenoalkane favours the production of the quaternary
ammonium salts as it ensures that each ammonia reacts with four

Nucleophilic properties of amines

halogenoalkanes molecules.

The use of quaternary ammonium salts

Quaternary ammonium salts are used in the production of cationic
surfactants that are found in detergents, fabric softeners and hair
conditioners. They coat the surface of the cloth or hair with positive
charges and reduce the static due to negatively charged electrons. A
quaternary ammonium salt found in detergent is shown in Figure 13.5.

CH3

N+ CH3 Cl−

CH3
Figure 13.5 Quaternary ammonium salts are found in fabric softener/water
repellents and hair conditioners.

Mechanism of the nucleophilic substitution

You have studied the mechanism of nucleophilic substitution in Book 1, for
the reaction of halogenoalkanes with ammonia.
CH3CH2Br + 2NH3 → CH3CH2NH2 + NH4Br
bromoethane + ammonia →    ethylamine   + ammonium bromide

H H H H H H H H

H C C Br H C C N+ H + Br− H C C N + NH4Br

H H H H H H H H
H H
N N
H H
H H

TIP
The balanced symbol equation for the overall reaction between ammonia
and a halogenoalkane contains two ammonia molecules. The first acts as
a nucleophile and substitutes the halogen. The second acts as a base and
accepts a proton, a hydrogen ion, from the reactive intermediate.

Further substitution is possible as the product, the primary amine, is also

a nucleophile. The mechanism below illustrates how further substituted 257
amines are formed.
H H H H H
+
N
H C C Br H C C N CH2CH3 + Br − H CH2CH3 + NH4Br
CH2CH3
H H H H H H
H
diethylamine
N CH2CH3
N H
H
H

807701_C13_AQA_Chemistry_2_245-260.indd 257 13/06/15 9:08 am

 The mechanism for the formation of a quaternary ammonium ion is shown
below.
H H CH2CH3
+
CH3 C Br CH3 C N CH2CH3 + Br−

H H CH2CH3
N (CH2CH3)3
quaternary
ammonium ion

Nucleophilic addition–elimination reactions of

ammonia and primary amines with acyl chlorides
and acid anhydrides
Primary amines and ammonia both react with acyl chlorides and acid
anhydrides to form substituted amides. You have already studied these reactions
on page 225 of this book. You must also be familiar with the nucleophilic
addition–elimination mechanism outlined for these reactions on page 227.

TEST YOURSELF 4
1 Draw the structural formula of the two compounds formed in the
reaction of CH3NH2 with ethanoic anhydride.
2 a) Write a equation for the reaction of CH3CH2NH2 with propanoyl
chloride.
b) Name the mechanism for this reaction.
c) Outline the mechanism for this reaction.
d) Name the product.
3 a) Name the compound (CH3)2NH.
b) (CH3)2NH can be formed by the reaction of an excess of CH3NH2
with CH3Br. Name and outline a mechanism for this reaction.
c) Name the type of compound produced when a large excess of
CH3Br reacts with CH3NH2.
d) Give a use for this type of compound.
13    AMINES

ACTIVITY
Paracetamol
Paracetamol and aspirin are the largest selling pain relief tablets
available without a prescription. Paracetamol can be made by reacting
4-aminophenol with ethanoyl chloride.
258 1 Suggest a structure for 4-aminophenol (4-aminohydroxybenzene).
2 Paracetamol has the IUPAC name 4-hydroxy-(N-
ethanoylaminobenzene).
a) Suggest a structure for paracetamol.
b) Write an equation for the reaction of 4-aminophenol with ethanoyl
chloride to produce paracetamol.
c) Name the mechanism for this reaction.
3 State two reasons why ethanoic anhydride is used in industry instead
of ethanoyl chloride.

807701_C13_AQA_Chemistry_2_245-260.indd 258 13/06/15 9:08 am

 Practice questions iii) Name the amine formed when

Practice questions
propanenitrile is converted to
1 Which one of the following gives the order an amine. (1)
of increasing basic strength for ammonia, iv) What type of reaction occurs when a
ethylamine and phenylamine? nitrile is converted to an amine? (1)
A ammonia, phenylamine, ethylamine v) Draw a structural equation showing
B ethylamine, ammonia, phenylamine all bonds for the reaction when
propanenitrile is converted to
C phenylamine, ammonia, ethylamine an amine. (1)
D phenylamine, ethylamine, ammonia (1) 5 a) i) Give the meaning of the term
2 The mechanism for the reaction of methyl Brønsted–Lowry base. (1)
amine with chloroethane is described as ii) State and explain which of ammonia
A electrophilic substitution or butylamine is the stronger base. (2)

B nucleophilic addition-elimination b) Draw the structure of the tertiary amine

which is an isomer of butylamine. (1)
C nucleophilic addition
c) i) Draw the structure of the
D nucleophilic substitution (1) species formed when the amine
3 Iodoethane may be converted to propylamine CH3(CH2)17NH2 reacts with an excess
by reaction with of CH3Br. (1)

A ammonia ii) Name the type of compound formed

in part (c) (i) and give a use for such
B ammonia followed by LiAlH4 compounds. (2)
C potassium cyanide followed by ammonia d) Name and outline a mechanism for the
D potassium cyanide followed by LiAlH4 (1) reaction in which N-methylethanamide is
formed from CH3NH2 and CH3COCl. (3)
4 Amines can be prepared from halogenoalkanes
or from nitriles. 6 Amines have characteristic properties and can
form hydrogen bonds due to the polarity of
a) 1-Bromobutane is heated with excess the N–H bond.
ammonia in a sealed tube.
a) Show the polarity of the N–H bond. (1)
i) Draw the structure and name the
amine formed in this reaction. (2) b) The table below gives the melting and
boiling points of some amines.
ii) Ammonia is a nucleophile and the
mechanism is described as nucleophilic Melting Boiling State at
substitution. What is a nucleophile? (1) Amine point/°C point/°C 25 °C
methylamine −93 −61.8
iii) Explain what is meant by a
ethylamine −81 17
substitution reaction. (1)
propylamine −83 49
b) Propanenitrile is formed from 259
dimethylamine −92 7
1-bromoethane by reaction of potassium trimethylamine −117 3
cyanide.
i) Complete the table giving the
i) Write an equation for the reaction of
physical state of each amine at room
1-bromoethane with potassium
temperature (25 °C). (5)
cyanide. (1)
ii) Explain why propylamine is miscible
ii) What reagent is used to convert
with water. (1)
propanenitrile to an amine? (1)

807701_C13_AQA_Chemistry_2_245-260.indd 259 16/06/2015 17:14

 c) i) Name the type of mechanism for the The second method involves starting from
reaction between phenylamine and CH3CH2CH2Br and involves just one step.
bromomethane. (1)
a) Name the intermediate compound in
ii) Name the type of substance formed method one and give the reagents and
when phenylamine reacts with a large conditions for all steps in the process. In
excess of bromomethane. (1) addition give the reagent and condition for
the second method. (6)
Stretch and challenge
b) State a disadvantage of each method of
7 Propylamine can be prepared in two different preparation of propylamine. (2)
ways.
One method involves starting with CH3CH3Br
and forms an intermediate before forming
propylamine.
13 AMINES

260

807701_C13_AQA_Chemistry_2_245-260.indd 260 13/06/15 9:08 am

 14 Polymers, amino acids
and DNA
PRIOR KNOWLEDGE
● Addition polymers are formed from alkenes in an addition reaction.

H H H H

n C C C C

H H H H
n
Figure 14.1 The equation for the formation of polythene from ethene.
Ethene is the monomer and poly(ethene) is the polymer, often called
polythene.

● Polythene chains only have van der Waals’ forces between chains so
are not good for forming fibres or weaving.
● The groups on the alkene may differ creating different polymers.
● If an H is replaced with a Cl, the monomer is chloroethene commonly
called vinyl chloride.
● The polymer formed is H Cl H Cl
called poly(chloroethene) or
n C C C C
polyvinylchloride (PVC).
● Two repeating units of the H H H H
polymer may be shown as: n

H Cl H Cl

C C C C

H H H H

● If the Cl is replaced with a benzene ring the monomer is called

phenylethene (commonly called styrene) and the polymer is
poly(phenylethene) or polystyrene.

TEST YOURSELF ON PRIOR KNOWLEDGE 1

1 Name the addition polymer formed from the following monomers
a) ethene 261
b) chloroethene
c) styrene
2 Using the following monomer: F F
a) Name the monomer.
b) Draw the structure of two repeating units of the polymer C C
formed from this monomer.
F F
c) Name the type of polymerisation.
d) The polymer is commonly called PTFE. Explain the name.

807701_C14_AQA_Chemistry_2_261-286.indd 261 13/06/15 9:11 am

 ●● Condensation polymerisation
Molecules which possess COOH groups and OH group or COOH groups
and NH2 groups can form condensation polymers. During the formation of
a condensation polymer, water or HCl is eliminated.
A condensation polymer is a polymer formed when monomers join together
and eliminate a small molecule such as water (or hydrogen chloride).
There are two types of condensation polymers considered here:
● polyesters
● polyamides.

Polyesters
A polyester is a condensation polymer formed between a diol and a
dicarboxylic acid (or between molecules of a single compound that contain
both a COOH group and an OH group). The reaction is described as
condensation polymerisation as it eliminates water.
This is in contrast to the addition polymerisation of ethene to form polythene.
One polyester is formed from the reaction between ethane-1,2-diol and
benzene-1,4-dicarboxylic acid (terephthalic acid). The polyester is called
poly(ethylene terephthalate) or PET (sometimes PETE).
PET is a polyester as it contains many ester (COO) groups.
H H O O O O H H

n HO C C OH + n C C O C C O C C + 2n H2O
14    POLYMERS, AMINO ACIDS AND DNA

H H HO OH H H n
ethane-1,2-diol benzene-1,4-dicarboxylic acid poly(ethylene terephthalate)
(terephthalic acid)

Two molecules of water are eliminated for the formation of one repeating
unit, as one repeating unit has two ester groups (COO) and the formation
of each one eliminates a molecule of water.
A polyester could be formed using an diacyl chloride (a molecule
containing two acid chloride groups) and an diol. In that case 2HCl would
be eliminated.
Most plastic bottles used for soft drinks are now made of PET (polyethylene
terephthalate), a plastic that is recyclable. At the start of the recycling
process, the bottles are compacted into bales, and then shredded. Discarded
plastic drinks bottles are compacted at a recycling facility. The plastic chips
formed are cleaned, and then sent to be used in new bottles.
262
Polyamides
Nylon is a condensation polymer formed from the reaction between
1,6-diaminohexane and adipic acid (hexane-1,6-dioic acid).
Nylon is a polyamide as it contains many amide groups (CONH).
O O

n H2N (CH2)6 NH2 + n C (CH2)4 C N C (CH2)4 C N (CH2)6 + 2n H2O

HO OH H O O H n

hexane-1,6,diamine hexane-1-6-dioic acid nylon

807701_C14_AQA_Chemistry_2_261-286.indd 262 13/06/15 9:11 am

 This form of nylon is often called nylon-6,6 as it is made from a diamine
containing 6 carbon atoms and a dioic acid containing 6 carbon atoms.

Condensation polymerisation
Nylon-6,10 also exists where the dioic acid contains 10 carbons.
Figure 14.2 The synthetic fibre,
nylon is made by the condensation
polymerisation of amine-containing
molecules and carboxylic acid-
containing molecules to form long
chains (polymers). Nylon is used to
make fabrics, and also ropes and some
medical prosthetics.

A diacyl chloride (molecule containing two acid chloride (COCl) groups

may be used in place of the dioic acid and the elimination product is HCl
rather than water.
O O

n H2N (CH2)6 NH2 + n C (CH2)4 C N C (CH2)4 C N (CH2)6 + 2n HCl

Cl Cl H O O H n
hexane-1,6,diamine hexanedioyl dichloride nylon

Hexanedioyl dichloride is often called adipoyl chloride from the

common name of the dioic acid. Sebacic acid is the common name
for decane-1,10-dioic acid and the acid chloride is called sebacoyl
chloride. Sebacoyl chloride is often used in the nylon rope trick
forming nylon from the boundary of two layers of sebacoyl chloride
and 1.6-diaminohexane.
Kevlar is a polyamide polymer formed from benzene-1,4-dicarboxylic acid
and benzene-1,6-diamine.

O O O O H H

n C C + n H2N NH2 C C N N + 2H2O

HO OH n

There are hydrogen bonds between the chains of polymers in polyamides

due to the presence of C=O bonds and N–H bonds. Polyesters have
permanent dipole–dipole attractions between the polymer chains due to
the presence of the polar C=O bonds. There are greater forces of attraction
between the polymer chains in polyamides and polyesters compared to 263
addition polymers, so polyamides like nylon and Kevlar and polyesters
like Terylene can be used to create clothing. The stronger forces of
TIP attraction between the polymer chains mean that the fibres can be woven
Make sure that you can draw together or knit together. Formula 1 racing drivers use helmets made of
the repeating unit in a polymer carbon fibre covered with a layer of Kevlar which gives protection, but is
based on the monomers or the still very light. Kevlar can also be spun into sheets which are five times
structures of the monomers from stronger than steel, and are used in bullet proof vests.
a section of the polymer.
Most addition polymers cannot be used to create clothing as there are only
weak van der Waals’ forces of attraction between the polymer chains.

807701_C14_AQA_Chemistry_2_261-286.indd 263 13/06/15 9:12 am

 EXAMPLE 1
Lactic acid, CH3CH(OH)COOH, can form a condensation polymer called
PLA, poly(lactic acid). Draw a section of PLA showing two repeating units.

Answer
The COOH and OH groups of the
single monomer allow it to form CH3 CH3
a condensation polymer. It is best O O
to draw the monomer with the HO C C HO C C
COOH and OH groups facing each
H OH H OH
other to be able to draw a section
of the polymer.
CH3 O CH3 O
The polymer is formed from the
reaction between the OH group and C C O C C O
the COOH group. The structure of the
H H
polymer showing two repeating units is:
This polyester condensation polymer shows two repeating units, but
you can start from anywhere in the polymer as long as two complete
repeating units are shown. The polymer could be drawn as shown below:
O CH3 O CH3
TIP
C O C C O C Examples will include being
H H
asked to draw a certain number
of repeating units of a polymer.
14    POLYMERS, AMINO ACIDS AND DNA

EXAMPLE 2
The structure below shows the repeating unit of a O O
polymer.
O C CH2 CH2 CH2 C O CH2 CH2
O O
3 Condensation polymer or polyester.
O C CH2 CH2 CH2 C O CH2 CH2

1 Give the IUPAC name for the carboxylic acid used to

form this polymer. TIP
2 Give the IUPAC name of the alcohol used to form In dioic acids the carbon atoms that are part of
this polymer. the carbon chain are counted as part of
3 Name the type of polymer formed. the chain, HOOC–COOH is ethanedioic acid.
HOOC–CH2–COOH is propanedioic acid.
Answers
1 Take the polymer and use the C=O groups to identify
the acid from which the polymer was formed.
264
O O TIP
Diols and triols require a number for the position
O C CH2 CH2 CH2 C O CH2 CH2 of the OH groups in the molecules. They also
require an extra ‘e’ in the name.
The acid is: HOOCCH2CH2CH2COOH. This acid is
pentanedioic acid.
2 The alcohol structure and name can be determined
by looking at the O atoms. They might be on different TIP
end of the polymer; one O atom in this polymer If this example had stated that the polymer is a
is on the left but the structure of the alcohol is condensation polymer, you would be expected to
HOCH2CH2OH. Its name is ethane-1,2-diol. give the type of polymer as a polyester.

807701_C14_AQA_Chemistry_2_261-286.indd 264 13/06/15 9:12 am

 ●● Biodegradability of polymers

Biodegradability of polymers
A biodegradable polymer is one that can be broken down in the environment
by the action of micro-organisms. Polyalkenes are chemically inert and non-
biodegradable because they are saturated and have no bond polarity.
Condensation polymers can be hydrolysed and so are now being used more
than addition polymers. This means that they are biodegradable in the
environment. Many drink bottles (especially water bottles) are now made
from PET.
Addition polymers, such as polythene, will remain for thousands of years
in the environment, but PET can be hydrolysed by micro-organisms in the
environment so it is biodegradable.
However, condensation polymers break down more quickly on a compost
heap than in landfill. There is less water available in landfill to hydrolyse the
polymer.
There is also less oxygen available in landfill and it is colder. There is less
UV light to assist breakdown of the polymers. A landfill site has fewer
bacteria than would be present in a compost heap.

Disposal of waste
A large proportion of household and industrial waste in the UK is plastic.
Plastic waste or polymer waste is particularly worrying as it does not
biodegrade and stays in the ecosystem for hundreds of years. Some 7% of
household waste is plastic as shown in the chart below.

Biodegradable waste
41% kitchen/garden/soil

Biodegradable & recyclable

24% 18% paper/cardboard
Recyclable waste
7% glass
3% 41%
7% plastic
7% 3% metal cans

7% Other waste e.g.

18% 5% wood, 5% whitegoods,
5% non-combustibles,
3% textiles, 2% nappies, etc.

Figure 14.3 Composition of UK household waste.

The methods of disposing of polymers are landfill and incineration. Both 265
have their advantages and disadvantages.

Landfill
Disadvantages
● Landfill wastes land and often pollutes the land with polymers which will
take hundreds of years to decompose.
● Some polymers can also leach compounds into the soil.
● Landfill sites are often an eyesore.
● Landfill releases methane, which is a very effective greenhouse gas.

807701_C14_AQA_Chemistry_2_261-286.indd 265 13/06/15 9:12 am

 Advantages
● Landfill is the most cost-effective method of waste disposal.

Incineration
Disadvantages
● Incineration releases greenhouse gases into the air and also some toxic
gases depending on the polymer being incinerated.
● Incineration can also produce gases that cause acid rain.
● Incineration still produces waste, which has to be sent to landfill, but this
is 90% less than waste sent directly to landfill.
● More expensive than landfill (but can be linked with energy recovery
where the heat of combustion is used to power an electricity generator).

Advantages
● Incineration saves money with regard to transport as waste can be
incinerated locally.
● Incineration prevents unsightly landfill sites.

The EU has guidelines about how to handle waste materials, including

polymers. EU policy ranks waste management strategies in the following
order:
1 Prevention of waste
2 Recycling and re-use of material
3 Safe disposal of waste that is not recyclable or re-useable – in this ranking
order:
a) Incineration with Energy Recovery
14    POLYMERS, AMINO ACIDS AND DNA

b) Incineration
c) Landfill

Reduce, re-use, recycle

Reduce, re-use and recycle are referred to as the 3Rs. Waste management
has become more and more important and we have been encouraged to

REUSE reduce the amount of waste we produce. Manufacturers must limit the
amount of packaging and as much packaging as possible must be able to be

REDUCE recycled. Reducing the amount of waste saves the Earth’s resources. We are
encouraged to re-use material such as carrier bags over and over again. At
RECYCLE the end of the lifetime of an item, then it should be recycled. All this saves
resources.

Strategies to reduce, control and manage polymer waste

Many strategies are already in place to reduce, control and manage polymer
266 waste.
● Reduction in the use of polymers in packaging.
● Reduction in use of carrier bags.
● Dedicated polymer recycling (blue bins).
● Use of biodegradable polymers.
● Businesses must recycle polymers.

807701_C14_AQA_Chemistry_2_261-286.indd 266 13/06/15 9:12 am

 TEST YOURSELF 2

Amino acids, proteins and DNA

1 Name the monomers used to make the following H H H H O H H O
condensation polymers:
O C C C C O C C C C
a) PET   b) Nylon-6,6   c) Kevlar
2 Draw the structure of the repeating unit formed H H H H H H
from condensation polymerisation between the
a) Name the diacyl chloride from which it is
following two monomers.
formed.
H2NCH2 CH2NH2 HOOCCH2 CH2 CH2 COOH
b) Name the diol from which it is formed.
3 The following polymer is a condensation polymer
c) Name the type of polymer.
formed from a diacyl chloride and a diol.

●● Amino acids, proteins and DNA

Proteins are compounds of the elements carbon, hydrogen, oxygen and
nitrogen and usually contain some sulfur as well. Proteins perform many
different roles within the body such as:
1 Enzymes are proteins.
2 Muscle fibres are made of several proteins.
3 Antibodies in the immune system are proteins.
4 Some hormones are proteins.
5 Bone is a matrix of protein and calcium phosphate.
6 Haemoglobin and chlorophyll are mainly protein.
There are many other roles of proteins within the body. In fact, the word
protein comes from the Greek word proteios meaning first. They are often
described as the fundamental material in living organisms.

Structure
The structure of proteins is the most complex all the nutrients and indeed
among the most complex of any molecule within any organism. Their
structure is divided into three levels:
1 Primary structure of a protein is concerned with the order in which
the amino acids are joined together in the molecule and corresponds to
the normal structural formulae that have been considered for simpler
molecules.
2 Secondary structure of a protein is concerned with the folding, coiling
and puckering of the chain of atoms of the protein molecule.
3 Tertiary structure of a protein is concerned with the final folding of the
267
protein molecule to form a globular protein as dictated by the interaction
between groups attached to the main body of the chain.

Primary structure
Proteins are often called natural polymers, but unlike synthetic ones, they
are made up from a selection of 20 different subunits called amino acids.
The sequence of these amino acids in the protein chain joined together by
peptide bonds makes up the primary structure of the protein molecule.

807701_C14_AQA_Chemistry_2_261-286.indd 267 13/06/15 9:12 am

 R Many amino acids are α-aminocarboxylic acids. Variation in the structure
of these monomers occurs in the side chain, denoted by R in the structure
H2N C COOH
on the left.
H Amino acids do not always behave like organic compounds. They have
melting points well in excess of 200 °C, whereas most organic compounds
of similar Mr are liquids at room temperature. Amino acids are soluble in
water and other polar solvents, but are insoluble in non-polar solvents such
as ether or benzene. They are less acidic than most carboxylic acids and less
basic than most amines.
The reason for the odd properties of amino acids is that they contain an
R
acidic carboxyl group and a basic amino group on the same molecule.
Amino acids undergo an internal acid–base reaction to yield a dipolar ion
+
H3N C COO− (called a zwitterion). In the solid state, an amino acid has the structure
shown on the left.
H
Solid amino acids contain ionic bonds, which leads to the higher than
expected melting point.
This zwitterion structure also explains the weakly acidic and basic properties
TIP
Read over the section on pH to
of an amino acid as it has the weakly basic COO− group and the weakly
make sure you understand this. acidic NH+3 group.
Proteins are polyamides. This is due to the
H H H H
condensation reaction which can occur between the
carboxyl group on one amino acid and the amino
N C C N C C N C C N C C group on the next. The bond linking these two
amino acids is called a peptide group or peptide link.
H R1 O H R2 O H R3 O H R4 O
14    POLYMERS, AMINO ACIDS AND DNA

Protein molecules would have the form shown on

the left.
This CONH bond is the The R1, R2, R3,  eptide groups are formed in a condensation
P
peptide link or group R4, etc. are the
that joins the amino amino acid
reaction (a reaction in which a small molecule
acids together side chains is eliminated, in this case water) between the
carboxyl end of one amino acid and the amino end
of another.
H H H H

H2N C COOH + H2N C COOH H2 N C C N C COOH + H2O

R1 R2 R1 O H R2

Amino acid 1 Amino acid 2 A dipeptide

Many amino acids joined in a chain creates a polypeptide and longer

268 polypeptides are called proteins.

Amino acids
TIP There are 20 naturally occurring amino acids. These vary in the R side
The structures of six amino acids
chain. The properties of the R side chain also vary and this allows a
are given in your Data Booklet.
convenient way of classifying the 20 amino acids in groups.
These groups are:
1 Non-polar aliphatic R group amino acids
2 Non-polar aromatic R groups amino acids

807701_C14_AQA_Chemistry_2_261-286.indd 268 13/06/15 9:12 am

 3 Polar uncharged R groups amino acids

Amino acids, proteins and DNA

4 Acidic R group amino acids
5 Basic R group amino acids.

Nonpolar, aliphatic R groups Nonpolar aromatic R groups

COOH COOH COOH COOH COOH COOH

NH2 C H NH2 C H NH2 C H NH2 C H NH2 C H NH2 C H

H CH3 CH CH2 CH2 CH2

CH3 CH3
C CH
Glycine Alanine Valine
NH
COOH COOH COOH

NH2 C H NH2 C H NH2 C H

OH
CH2 CH2 H C CH3
Phenylalanine Tyrosine Tryptophan
CH CH2 CH2
CH3 CH3 basic R groups
S CH3
COOH COOH COOH
CH3
Leucine Methionine Isoleucine NH2 C H NH2 C H NH2 C H

CH2 CH2 CH2

Polar, uncharged R groups

COOH COOH COOH CH2 CH2 C NH

CH2 CH2 CH
NH2 C H NH2 C H NH2 C H
C N
CH2OH H C OH CH2 CH2 NH H

CH3 SH NH2 C NH
Serine Threonine Cysteine
NH2
Lysine Arginine Histidine
COOH COOH COOH
H
C NH2 C H NH2 C H acidic R groups
NH CH2
CH2 CH2 COOH COOH
H2C CH2
C CH2 NH2 C H NH2 C H
H2N O
C CH2 CH2
H2N O
COOH CH2
Proline Asparagine Glutamine
269
COOH
Aspartic acid Glutamic acid

Figure 14.4 The 20 amino acids present in human proteins.

807701_C14_AQA_Chemistry_2_261-286.indd 269 16/06/2015 17:14

 TIP EXAMPLE 3
You do not need to remember Name the following amino acids: Answers
the structure of each amino acid
but make sure you can write the 1 H2NCH2COOH 1 aminoethanoic acid
correct IUPAC names for some 2 COOH 2 2-amino-3-methylpentanoic
common amino acids. acid
NH2 C H

H C CH3

CH2

CH3

Amino acids in acidic and alkaline solution

Amino acids contain the COOH group and the NH2 group. Both of these
groups are affected by changes in pH.
The COOH group at high pH deprotonates to form the COO− group. At low
TIP pH in an excess of H+ ions, the COOH group is protonated as COOH.
In a structure the + should be
shown on the N atom. The − The NH2 group can be protonated at low pH to form NH+3. At high pH the
charge on COO− should be shown NH2 group is deprotonated so NH2 is formed.
on the oxygen atom at the end of For amino acids that contain other COOH groups or NH2 group in the R group,
the single bond. these groups will also be protonated or deprotonated depending on the pH.

EXAMPLE 4
Alanine, leucine and lysine have the following structures: Answer
14    POLYMERS, AMINO ACIDS AND DNA

H2N CH COOH alanine 1 CH3

CH3 H2N C COO−

H
H2N CH COOH leucine At high pH the COOH group is deprotonated to form
COO-. The amino acid is negatively charged at high pH.
CH2 CH CH3
+
2 NH3
CH3
CH2

H2N CH COOH lysine CH2

CH2 CH2 CH2 CH2 NH2 CH2

CH2
1 Draw the structure of alanine at high pH.
270 2 Draw the structure of lysine at low pH. +
H3N C COOH
3 Give the IUPAC name for leucine.
H
At low pH the two NH2 groups in lysine are
both protonated. The amino acid is positively charged at
low pH.
3 2-amino-4-methylpentanoic acid

Amino acids from peptides

You may also be expected to extract the structure of an amino acid from a
section of a polypeptide or protein.

807701_C14_AQA_Chemistry_2_261-286.indd 270 13/06/15 9:12 am

 Amino acids, proteins and DNA
EXAMPLE 5
The tripeptide below shows three different amino 3
acids. O O−
C

H3C CH3 CH2

CH3 O H CH O H H O CH2

H2N C C N C C N C C H2N C COO−

H H CH2 OH
H

CH2 4
H O H H O
C
O OH H2N C C N C C
alanine valine glutamic acid OH
CH2 CH2
1 Draw the structure of the zwitterion formed by
CH2 CH2
alanine.
2 Give the IUPAC name for valine. C C
3 Draw the structure of species formed by glutamic O OH O OH
acid at high pH.
5 This is simply the ester formed from the COOH
4 Draw the structure of the dipeptide formed from two
group in valine with the OH group of ethanol.
glutamic acid molecules.
5 Valine reacts with ethanol in the presence of H3C CH3
concentrated sulfuric acid. Draw the structure of CH H H
the compound formed. +
H3N C C O C C H
Answers
H O H H
1
CH3

+
H3N C COO− TIP
As concentrated sulfuric acid is present it
H
would be expected that the NH2 group is
2 2-amino-3-methylbutanoic acid protonated as shown.

ACTIVITY
Lysine 1 Give the IUPAC name for lysine.
Today about 500 different amino acids are known, 2 What is meant by the term optically active?
of which nine are called ‘essential amino acids’ 3 Draw the two optical isomers of lysine, labelling 271
because they cannot be made by the human body, the asymmetric carbon with an asterisk (*).
and so must be taken in as food. Lysine is an 4 Explain why lysine has a relatively high
essential amino acid. Good dietary sources of lysine melting point.
include high protein foods such as eggs, meat, soy 5 What is meant by the term zwitterion?
beans, Parmesan cheese and salmon. 6 a) Draw the structure of the species formed by
lysine at low pH.
Lysine has the formula H2N(CH2)4CH(NH2)COOH. It is an
optically active molecule with a melting point of 196 °C. b) Write the formula of the organic ion present
when lysine is dissolved in an alkaline solution.

807701_C14_AQA_Chemistry_2_261-286.indd 271 13/06/15 9:12 am

 7 Draw the structure of a dimer formed when two
Element % composition
molecules of lysine react.
8 An amino acid was found to have the following N 10.5
composition by mass: C 36.1
H 5.3
O 48.1

Deduce the empirical formula for this amino acid.

Secondary structure
The secondary structure of a protein is the arrangement of the peptide-
linked backbone of the amino acid chain. It usually involved coiling of the
amino acid chain into one of two structures. This interaction between the
polar C=O groups and the N–H groups hold the amino acid backbone in
certain orientations. The two main secondary structure organisations of a
protein are α-helices and β-pleated sheets. These involve hydrogen bonding
between C=O and N–H groups.

α-Helix
The α-helix is a right-handed helix. It is the most common type of
secondary structure and forms when the amino acid R groups are small.
Keratin, a protein found in fur and feathers contains a high percentage of
α-helices. The structure of the helix is maintained by the hydrogen bonding
between the polar C=O and N–H groups of different peptide bonds in the
amino acid chain. Each turn of the helix contains 3.6 amino acid residues.
The hydrogen bond occurs for example from the C=O group in the peptide
bond after amino acid 1 in the chain to the N–H group in the peptide bond
14    POLYMERS, AMINO ACIDS AND DNA

after amino acid 4 in the chain. In fact due to the order of C=O and N–H in
the peptide chain, it is actually 3.6 amino acids away.

α helix
H
R R N H
H
R
H C C
R O C
C
H N H
C N H O C
H O O
N C C C
C N O
O R H H C N H
N C C H
H H H
H N R R N H
O C C O C
O R
C O C C
C C O N
272 N C H H R
H R H
H R

Hydrogen bonds between amino acids

at different locations in polypeptide chain
β-pleated sheet

R R R R
H H H H
O O O O
C C C C C
N N N N
C C N C C N C C N C C N
C C C C
O H O H O H O H
R R R R

807701_C14_AQA_Chemistry_2_261-286.indd 272 13/06/15 9:12 am

O
 R R N H
H
R
H C C
R O C
C
H N H
C N H O C
H O O
N C C C
C N O
O R H H C N H
N C C H
H H H
H R
β-Pleated sheet
C
N
O C
R N H
O C
O In a β-pleated R
sheet the amino acidOchain is Clined up side by side with

Amino acids, proteins and DNA

C C
C C O section of theN same chain and the hydrogen bonds occur again
another
N H
H groups on peptide R
H R H between theCC=O and N–H bonds which are facing each
other. The H protein
R found in silk (fibroin) contains a substantial proportion
of β-pleated sheet structure.
Hydrogen bonds between amino acids
at different locations in polypeptide chain
β-pleated sheet

R R R R
H H H H
O O O O
C C C C C
N N N N
C C N C C N C C N C C N
C C C C
O H O H O H O H
R R R R

H O H O H O O
H
R R R R
N C N C C C
N N
C C C C C C C
N N C C
C C C N C N
RH RH RH RH
O O O O

Tertiary structure
The tertiary structure of a protein is the way in which the coiled chain
of amino acids is folded. Many different interactions contribute to the
tertiary structure of a protein. These interactions usually involve amino
acid side chain group which are well separated in the amino acid sequence.
Interactions include:
1 Hydrogen bonding between polar side chain groups.
2 Disulfide bridges (–S–S–) between cysteine amino acid residues in the
protein chain.
3 Salt bridges (ionic interaction between RCOO− and RNH+3 side chain groups).
4 Hydrophobic and hydrophilic interactions. (Polar and non-polar side
chains localised in certain sections of the protein molecule depending on
its function.)
273
5 Side chains may be too large to be packed closely together. The folding of
the protein chain minimises steric hindrance.

807701_C14_AQA_Chemistry_2_261-286.indd 273 13/06/15 9:12 am

 The most stable tertiary structure is the one with the greatest number of
stabilising interactions. Given a particular primary structure, a protein
naturally assumes its most stable secondary and tertiary structure. For
example, every insulin protein synthesised in the body has the same
structure as it has the same amino acid sequence (primary structure).

Primary protein structure

is sequence of a chain of amino acids joined
by peptide links
Amino acids

Alpha helix
Pleated
sheet Secondary protein structure
-helices and -pleated sheets held together
by hydrogen bonds

Pleated sheet
Tertiary protein structure
final folding of the protein chain caused by
several different types of interactions

Alpha helix

Figure 14.5 The primary, secondary and tertiary structure of a protein.

Fibrous and globular proteins

14    POLYMERS, AMINO ACIDS AND DNA

Proteins that have mainly secondary structure are fibrous in nature. Proteins
with a secondary and tertiary structure are globular.
Fibrous proteins (also called structural proteins) form skin, muscle, the
walls of the arteries and hair are composed of long thread-like molecules
that are tough and insoluble in water. They are also resistant to the action of
acid and alkali.
Globular proteins are small proteins, somewhat spherical in shape because
of the folding of the protein chains upon themselves. Globular proteins
are water soluble (due to the presence of hydrophilic side chains on the
surface) and perform various functions within the organism. For example,
haemoglobin transports oxygen to the cells; insulin aids in carbohydrate
metabolism; antibodies render foreign proteins inactive; fibrinogen (soluble)
can form insoluble fibres that results in blood clotting; and hormones carry
274 messages throughout the body.

Enzymes in our diet

Enzymes are proteins which act as biological catalysts. They are named
according to the reaction that they catalyse. In nutrition, enzymes are vitally
important as the three main food groups, fats, proteins and carbohydrates
are generally large insoluble molecules which need to be broken down to
give smaller soluble molecules which can then be absorbed into the blood
in the small intestine.

807701_C14_AQA_Chemistry_2_261-286.indd 274 13/06/15 9:12 am

 Mode of action of enzymes

Amino acids, proteins and DNA

The substrate is the reactant in the reaction that is catalysed by the enzyme.
The substrate fits into the active site in the enzyme and forms an enzyme–
substrate complex. The bonds in the substrate are strained by interaction
with the enzyme, and the enzyme–substrate complex becomes an enzyme–
product complex. The product is not the same shape as the substrate and
so the fit between the enzyme and the product is no longer perfect and this
causes the product to dissociate from the enzyme.
Most enzymes have an Mr of between 12,000 and 120,000 and sometimes
even higher. Most substrates, for example, an amino acid, are much smaller
molecules. The specific location on the enzyme where the substrate binds
is called the active site. The active site of the enzyme contains amino
acid residues which can interact with the substrate and hold it. There are
also residues within the active site which catalyse the reaction which the
substrate undergoes.
The shape of the active site matches exactly the shape of the substrate and
the mechanism for this is often described as a lock and key mechanism. The
key being the substrate, and the lock being the enzyme.
Figure 14.6a shows the substrate binding to the active site of the enzyme,
forming the enzyme–substrate complex, and then the products being
released from the enzyme.
The active site of an enzyme is stereospecific. If two enantiomers of a molecule
exist, the enzyme can only catalyse the reaction for one of the enantiomers.
Molecules can be designed that can fit into the active site and block it.
These molecules are called enzyme inhibitors and are useful as drugs in
metabolic and other diseases where it is important to block enzyme activity.
Computer modelling of the enzyme and its active site can be used to help
design enzyme inhibitors.

(a) Reaction

substrate
active site

enzyme

substrate molecule binds reaction occurs and

with active site of enzyme product molecules
molecule forming the are generated.
enzyme–substrate complex

(b) Inhibition

inhibitor 275
active site

enzyme

inhibitor molecule binds inhibitor molecule

with active site of prevents the binding of
enzyme molecule substrate molecules
Figure 14.6 The reaction and inhibition processes in enzymes.

807701_C14_AQA_Chemistry_2_261-286.indd 275 13/06/15 9:12 am

 Figure 14.7 Thalidomide is a sedative
drug, which was prescribed as the
racemate to treat nausea in pregnant
women in the early 1960s. It was later
found to cause foetal abnormalities
involving limb malformation, as shown
by the deformed hand and forearm of
the baby. Thalidomide is optically active:
the (+) isomer was an effective drug
but the (−) isomer caused deformation.
The drug was banned in 1962. Today,
the optical isomers of chiral drugs are
separated before testing.

Effect of temperature and pH on enzyme activity

Fibrous proteins are insoluble in water, resistant to dilute acid and dilute
alkali and are unaffected by moderate changes in temperature. Globular
proteins, on the other hand, are relatively soluble and are affected by
extremes of pH and temperature that disrupts the hydrogen bonding which
maintains their tertiary structure.
The specific action of enzymes is due to their tertiary structure, which is
maintained by hydrogen bonds. Consequently, enzymes are very sensitive to
14    POLYMERS, AMINO ACIDS AND DNA

changes in temperature and pH. All enzyme action is destroyed on boiling.

The optimum temperature range for the activity of an enzyme is between
35 °C and 40 °C.
In general, the optimum temperature for the activity of plant enzymes is
5 °C. Enzymes in warm-blooded animals have an optimum temperature of
37 °C. An increase in temperature usually leads to an increase in the rate of
a chemical reaction, but in the case of enzyme catalysed reactions, it will
eventually lead to inactivation of the enzyme.
Increasing enzyme activity

276

Optimum
temperature

0 10 20 30 40 50 60 70
Temperature (°C)

Enzyme activity is also dependent on the pH of the medium in which it

acts. Most enzymes operate in environments of pH 7. Some like pepsin
(a stomach protease enzyme) can only operate in acidic conditions.

807701_C14_AQA_Chemistry_2_261-286.indd 276 13/06/15 9:14 am

 Hydrolysis of proteins

Amino acids, proteins and DNA

Solvent Proteins can be hydrolysed to the constituent amino acids by boiling with

8
front a dilute mineral acid such as hydrochloric acid. The amino acids can be

3
E
analysed by thin-layer chromatography (TLC). The details of thin-layer

7
chromatography will be considered in Chapter 15.

6
D
Amino acids are colourless and can be located on the chromatogram by

2
5
staining with ninhydrin or using ultraviolet light. The retardation factor (Rf
C value) is determined by dividing the distance moved by a particular amino
4 3 acid by the distance moved by the solvent. Rf values for amino acids in TLC
Inches 1 with a particular solvent may be used to identify the amino acids present in
Centimeters
B
2

the protein.
A
1

The diagram shows a representation of a thin-layer chromatogram of five

Origin amino acids that was run in a solvent of propanone and water mixed in a
ratio of 1 : 3 and developed using ninhydrin.
The ruler allows the distance moved by the amino acids and the solvent to
be measured, and is used to calculate the Rf values:
● The solvent has moved 8.3 cm or 83 mm.
● The centre of spot A has moved 1.0 cm or 10 mm. The Rf value for the
amino acid at spot A is 10 = 0.120
83
● The centre of spot B has moved 2.1 cm or 21 mm. The Rf value for the
amino acid at spot B is 21 = 0.253 and so on.
83
Amino acids with low Rf values have been less soluble in the solvent
and have a greater affinity for the support on the TLC plate. This will be
examined in greater detail later.

TEST YOURSELF 3
1 The structure below is of isoleucine, an amino acid.
CH3

CH2

H3C CH

H2N C COOH

H
a) Identify any chiral centres in isoleucine and label each with an
asterisk (*).
b) Draw the structure of the species obtained from isoleucine at low
pH.
2 Name two feature of the secondary structure of a protein. 277
3 Explain how the Rf value is determined from a chromatogram.
4 Draw the structure of the zwitterion formed from alanine,
H2NCH(CH3)COOH.

807701_C14_AQA_Chemistry_2_261-286.indd 277 13/06/15 9:14 am

 ACTIVITY
Urea
Urea is a waste product of many living organisms, Urea is produced in industry from ammonia and
and is the major organic component of human urine. carbon dioxide. In this process ammonium carbamate
This is because it is produced at the end of a chain H2N–COONH4 forms and it then decomposes into
of reactions which break down the amino acids that urea and water. More than 90% of the world’s
make up proteins. The average person excretes about industrial production of urea – approximately 184
30 grams of urea a day, mostly through urine, but a million tonnes is used in nitrogen-release fertiliser.
small amount is also secreted in perspiration
Urea is an organic compound with the following
structural formula:

C
H2N NH2

Urea was first synthesised in 1828 by Friedrich Wohler

and this made urea the first organic compound to be
synthesised from wholly inorganic starting materials.
Urea can be prepared in the laboratory by reacting
lead(II) cyanate, Pb(CNO)2, with ammonia and water Figure 14.8 Urea has the highest nitrogen content of
to produce lead(ii) hydroxide and ammonium cyanate, all solid nitrogenous fertilisers in common use.
NH4CNO. The ammonium cyanate then rearranges 4 a) Write an equation for the reaction of ammonia
on heating to form urea, which has a melting point of and carbon dioxide to form ammonium
133 °C. carbamate.
b) Write an equation for the decomposition of
14    POLYMERS, AMINO ACIDS AND DNA

1 Write an equation for the reaction of lead(ii) cyanate

with ammonia and water. ammonium carbamate into urea and water.
2 Assuming an 80% yield, calculate the mass c) Calculate the percentage by mass of nitrogen in
of lead(ii) cyanate required to produce 420 g of urea.
ammonium cyanate. Urea is also used in the production of the polymer
3 a) The crude product in the preparation is purified urea-methanal which is a thermosetting plastic
by dissolving in the minimum volume of hot resin used as adhesive to glue wood and MDF. It is
ethanol, filtering to remove insoluble impurities, produced in the condensation reaction between urea
and cooling. What name is given to this and methanal in the presence of heat and a base.
purification process? Water is eliminated as the hydrogen atoms from one
b) What practical considerations determine the amino group on each of two urea molecules combine
choice of solvent used? with the oxygen atom from a methanal molecule. The
c) Why is the minimum amount of hot solvent remaining –CH2– group from the methanal molecule
used? then forms a bridge between two neighbouring urea
molecules. This process, repeated many thousands
d) How is the pure dry product obtained from the
of times, forms a long chain of urea-methanal.
filtrate?
278 e) Giving practical details, describe how you would 5 Write an equation to show the condensation
determine whether or not the crystals of urea reaction between methanal and urea, to produce
produced are pure. one unit of the polymer urea-methanal.

807701_C14_AQA_Chemistry_2_261-286.indd 278 13/06/15 9:15 am

 ●● DNA

DNA
DNA is deoxyribonucleic acid. It is a double-stranded polymer that is found
in the nucleus of cells and carries the genetic code in chemical form.
DNA is made up of a chain of 2-deoxyribose units connected by a
phosphate ion. Bases are bonded to the 2-deoxyribose and hydrogen bonds
between the bases hold the two strands together, forming a double-helix
structure.

Figure 14.9 The yellow pentagons

represent the 2-deoxyribose units
which are connected by small
phosphate ions. The two strands
(highlighted in red and green) are
often referred to as a sugar-phosphate
backbone in DNA. The strands are
connected by flat planar molecules
which are the bases. The entire
structure is a double helix arranged
around the same axis.

Components of DNA
The components which make up the backbone sugar–phosphate strand in
DNA are given below:

HOCH2 OH
O
OH
H H
−O
P O
H H
OH OH H

phosphate 2-deoxyribose

The carbon atoms in 2-deoxyribose are numbered as shown in the diagram

below. This numbering is very important as the other components are
bonded at specific carbon atoms. Ribose is a pentose sugar with the formula
C5H10O5 but 2-deoxyribose is C5H10O4. There is an oxygen atom removed
from carbon number 2 in deoxyribose compared to ribose. The structure of
ribose is also shown below.
279
5

HOCH2 OH HOCH2 OH
1
O O
H H H H
4
H H H H
3
OH H 2
OH OH

numbering of carbon ribose

atoms in 2-deoxyribose

807701_C14_AQA_Chemistry_2_261-286.indd 279 13/06/15 9:15 am

 OH A phosphate ion is bonded to 2-dexoyribose at carbon number 5 as shown
−O
on the left:
P O
The sugar-phosphate backbone is built from these units. The phosphate ion
OCH2 on carbon 5 bonds with carbon 3 on the next 2-deoxyribose unit.
OH
O
H H OH

H H −O P O
OH H
OCH2
OH
O
H H

H H
H
O

−O P O

OCH2
OH
O
H H

H H
OH H

This continues creating the sugar-phosphate backbone of the DNA polymer.

A base is bonded at carbon 1 on each 2-deoxyribose molecule of the sugar–
phosphate backbone. There are four bases in DNA. The structure of the
14    POLYMERS, AMINO ACIDS AND DNA

bases in DNA are shown below:

NH2 O

N N
N HN

N N H2N N N
H H

adenine guanine

NH2 O

H 3C
N NH

N O N O
280 H H
cytosine thymine

Adenine and guanine are purine bases and cytosine and thymine are
pyrimidine bases.
Adenine, guanine, cytosine and thymine are referred to as the bases as they
all contain amino groups.
The nitrogen atom, which bonds to carbon 1 of the 2-deoxyribose unit, is
circled in green on the molecules above. Water is eliminated in this reaction.

807701_C14_AQA_Chemistry_2_261-286.indd 280 13/06/15 9:16 am

 A single unit of a base bonded to a 2-deoxyribose at carbon 1 with a
phosphate ion bonded at carbon 5 is called a nucleotide.

DNA
There are four nucleotides, one for each of the bases. These nucleotides
are shown in Figure 14.10. The nucleotides are called adenosine
monophosphate, guanosine monophosphate, cytidine monophosphate and
thymidine monophosphate.

NH2 O
OH OH
N N
−O P O N −O P O N

OCH2 OCH2
N N N
O N NH2
O
H
H H H H

H H H H
OH H OH H

adenosine monophosphate guanosine monophosphate

NH2 O
OH OH
H3C
N −O NH
−O P O P O

OCH2 OCH2
N O N O
O O
H H H H

H H H H
OH H OH H

cytidine monophosphate thymidine monophosphate

Figure 14.10 Adenosine monophosphate, guanosine monophosphate, cytidine monophosphate and thymidine
monophosphate

TIP
Make sure that you are able to put together the components of DNA to
form the nucleotides or recognise the bases and other components of
DNA from a given structure.

DNA structure 281

The full structure of DNA is based on the connection of nucleotides to
form a sugar-phosphate-sugar-phosphate polymer chain. The nucleotides
are joined in a condensation reaction between the OH of the carbon 3 and
the OH of the phosphate ion group. Water is eliminated. Another chain
of nucleotides runs parallel and the bases are joined together by hydrogen
bonds. One chain runs from its carbon 5 end (often called 5′) to carbon 3
(often called 3′) and the other runs from 3′ to 5′.

807701_C14_AQA_Chemistry_2_261-286.indd 281 13/06/15 9:16 am

 O O
OH OH
N N
−O P O N −O P O N

OCH2 O N OCH2 O N
N NH2 N NH2
H H
H H H H
H H H H
NH2
OH H NH2 O H
N
OH −O P O + H2O
N
-O P O OCH2 O N O
OCH2 O N O
H H
H H H H
H H
OH H
OH H

two mononucleotides Dinucleotide

The condensation reaction continues forming a chain of nucleotides.

Thymine

Adenine

5' end O
O− NH2
O 3' end
P N OH
O HN
−O N N
N
O
N O
O
hydrogen bonds
O−
14    POLYMERS, AMINO ACIDS AND DNA

O
O NH2 O N P
O O
O
P
O N
−O N HN

O N N
O
O H2N

O−
O
O O H2N P
N O
O
P O

N
−O NH N

O N N
O
O

O−
282 O
H2N P
O O O
O
P N O
N
−O O NH N
O N
N O
NH2 O

Cytosine O−
O
Guanine
OH P
O
3' end
−O
5' end

807701_C14_AQA_Chemistry_2_261-286.indd 282 16/06/2015 17:15

 The bases are always in the same pairs. Adenine pairs up with thymine and
guanine pairs up with cytosine. So an adenosine monophosphate nucleotide

DNA
in one strand will be hydrogen bonded to a thymine monophosphate
nucleotide in the other strand. Similarly a guanosine monophosphate
nucleotide in one strand will be hydrogen bonded to a cytidine
monophosphate nucleotide in the other strand.
The pairing of the bases guanine and cytosine is often referred to as a GC
base pair and the pairing of the bases adenine and thymine is often referred
to as an AT base pair.
There are three hydrogen bonds between the bases guanine and cytosine
but only two hydrogen bonds between the bases adenine and thymine. This
can alter the properties of DNA. A section of DNA which is rich in GC base
pairs will require a higher temperature to separate the strands.
The diagram below shows the hydrogen bonds between thymine and
adenine and also between cytosine and guanine. The hydrogen bonds form
between a hydrogen atom bonded to a nitrogen atom in the base and a lone
pair of electrons on either a nitrogen atom or an oxygen atom.
H3C
O N
NH2

thymine NH adenine
NH N
NH
N

NH2 O N

N NH
HN
cytosine guanine
NH N
O
H2N

Short form of DNA

Often DNA may be represented as a double chain with G, C, A and T used
to represent the bases as shown below.

G T G A C A T A
C A C T G T A T

You may be given part of a section like this and be asked to complete the bases.
283

EXAMPLE 6
Complete the sequence of bases in this representation Answer
of a DNA molecule. This question is testing your knowledge of the base
pairs in DNA. It is important to remember that the
A G A C C G T C
base pairs are AT and GC.
T C

A G A C C G T C
T C T G G C A G

807701_C14_AQA_Chemistry_2_261-286.indd 283 16/06/2015 17:15

 Action of anti-cancer drugs
A cancerous cell is a cell in which cell division is not controlled and it
continues to divide to form a tumour. For the cell to divide, its DNA must
be replicated. This involves separating the DNA strands in the double helix,
and enzymes moving along the strand copying the DNA. The enzymes
catalyse the connection of the nucleotides forming two new double helices,
one formed from each of the original strands.
Figure 14.10 The helicase enzyme chromosome
DNA polymerase
unzips the DNA double helix and DNA free nucleotides
polymerase enzymes copy each strand.

helicase leading strand

original
lagging strand
(template)
DNA replication fork

Adenine
Thymine
Cytosine DNA polymerase original (template)
Guanine DNA strand

Some anti-cancer drugs inhibit the enzymes that are involved in the
synthesis of the nucleotides. Others inhibit enzymes which catalyse the
DNA replication process. Cisplatin is a platinum(ii) complex with 2 chloride
ions and 2 ammonia molecules. It was introduced in the chapter on
transition metals as a square planar complex which can cross-link DNA so
14    POLYMERS, AMINO ACIDS AND DNA

preventing replication.
Cisplatin acts by allowing a coordinate bond to form between a
Nitrogen atom which
O nitrogen atom in guanine and the platinum in cisplatin. Cisplatin can
bonds to Pt in cisplatin
also bond to other guanine residues in the same strand or between
N
HN the strands. DNA cannot be replicated.
In adults, most cells are no longer dividing. However, some cells like
H2N N NH sex cells, intestinal lining cells, hair and skin cells are still undergoing
guanine
cell division. The use of anti-cancer drugs destroys these dividing
cells as well. Patients taking these drugs lose their hair, have skin and
digestive problems and are often left unable to have children.
Doctors will advise patients of the potential adverse risks and benefits of the use
of anti-cancer drugs. Patients make the decision whether to take the treatment.

284
TEST YOURSELF 4
1 Name four bases in DNA.
2 Which two bases in DNA form three hydrogen bonds between them?
3 Describe the structure of a nucleotide.
4 Complete the sequence of bases in this section of DNA.

T C G A T A C G
A G

807701_C14_AQA_Chemistry_2_261-286.indd 284 13/06/15 9:16 am

 Practice questions g) Serine reacts with methanol in the presence

Practice questions
of concentrated sulfuric acid. Draw the
1 Which one of the following is the correct structure of the compound formed. (2)
formula of hexanedioic acid used in the 4 The IUPAC name for the amino acid,
production of nylon-6,6? threonine is 2-amino-3-hydroxybutanoic acid.
A CH3(CH2)4COOH a) Draw the structure of threonine.
B CH3(CH2)2CH(COOH)2 b) Draw the structure of the species formed
C HOOC(CH2)4COOH from threonine at low pH.

D HOOC(CH2)6COOH (1) c) Threonine reacts with ethanoic acid in

the presence of concentrated sulfuric
2 Which one of the following is not a acid. Draw the structure of the compound
condensation polymer? formed.
A Polyethylene terephthalate 5 The diagram below shows a representation of a
B Nylon-6,6 nucleotide.
O
C Polythene OH
H3C
D Kevlar (1) −O NH
P O
3 Three amino acids are given below:
OCH2
N O
COOH O
H H
H CH2 CH2OH
H H
H2N C COOH H2N C COOH H2N C COOH
OH H
H H H
thymidine monophosphate
glycine aspartic acid serine
a) i) Name the base in this nucleotide. (1)
COOH ii) Write the molecular formula for the
CH2 CH2OH
base. (1)
H

H2N C COOH H2N C COOH H2N C COOH

b) Name the sugar component of the
nucleotide. (1)
H H H
glycine aspartic acid serine c) i) With which base does this base
hydrogen bond? (1)
a) Which one of the amino acids is not ii) On the base show the point at which
optically active? Explain your answer. (2) hydrogen bonds form with the other
b) Draw the structure of a dipeptide formed base. (1)
from one aspartic acid molecule and one d) On the sugar show the point of attachment
serine molecule. (2) of the next nucleotide. (1) 285
c) Give the IUPAC name for aspartic acid. (1) 6 Cisplatin has the formula [Pt(NH3)2Cl2].
d) Give the IUPAC name for serine. (1) a) What is the oxidation state of platinum in
e) Draw the species formed from aspartic acid cisplatin? (1)
at high pH. (1) b) State the shape of the complex. (1)
f ) Draw the species form from serine at low c) Cisplatin is used as an anti-cancer drug.
pH. (1)

807701_C14_AQA_Chemistry_2_261-286.indd 285 13/06/15 9:16 am

 i) Explain how cisplatin acts as an anti- Stretch and challenge
cancer drug. (3) 9 Aspartame is an artificial sweetener used in
ii) State two adverse effects of the use of many products. Its structure is shown below. It
cisplatin. (2) is the methyl ester of a dipeptide.
7 Polyesters are formed from the reaction between CH3

polyhydric alcohols such as ethane-1,2-diol O

and dicarboxylic acids such as terephthalic acid
(benzene-1,4-dicarboxylic acid). C O

a) Draw the structural formula of the CH2 C H

following compounds:
N H
i) ethane-1,2-diol (1)
C O
ii) terephthalic acid (1)
HOOC CH2 C H
b) Give the polymer structure of the polyester
formed in this reaction showing two NH2
repeating units and circle an ester group. (3) a) Name the two amino acids present in
c) Name the type of polymer formed in this aspartame. (2)
polymerisation. (1) b) Draw the structure of the dipeptide at high
d) Polyesters may also be formed using diacyl pH. (1)
chlorides. c) Draw the structure of the dipeptide at low
i) Draw the structure of the diacyl chloride pH. (1)
formed from terephthalic acid. (1) d) Place an asterisk (*) at any chiral centres on
ii) Write an equation for the reaction of one the structure of aspartame. (1)
14 POLYMERS, AMINO ACIDS AND DNA

molecule of the diacyl chloride with two e) A sample of aspartame was hydrolysed
molecules of ethanol. (2) using dilute hydrochloric acid and thin-
e) Terephthalic acid is formed from the layer chromatography carried out on the
oxidation of 1,4-dimethylbenzene. Write products of hydrolysis. Ninhydrin was used
and equation for this oxidation using [O] to to develop the chromatogram. Two organic
represent the oxidising agent. (2) products were detected using ninhydrin.

8 The following polymer is a condensation i) Draw the structures of all the organic
polymer formed from a diacyl chloride and a products which would be formed on
diol. hydrolysis of aspartame using dilute
hydrochloric acid. (2)
O C2H5 O
ii) Which of these products are detected
C O C O C CH2 CH2 using ninhydrin? (1)
CH3

286 a) Draw the diacyl chloride from which it is

formed. (1)
b) Name the diol from which it is formed. (1)
c) Name the type of polymer. (1)

807701_C14_AQA_Chemistry_2_261-286.indd 286 13/06/15 9:16 am

 Organic synthesis,
15 NMR spectroscopy
and chromatography
PRIOR KNOWLEDGE
● A homologous series is a family of organic compounds containing the
same functional group.
● A functional group in an organic compound may be changed into
another functional group.
● Organic chemistry requires knowledge of the reagents used and
conditions required for a particular type of reaction.
● Infrared spectroscopy and mass spectrometry may be used to
analyse and identify an organic compound.
● Infrared spectroscopy may be used to determine the bonds present in
an organic compound and the fingerprint region used to identify the
compound.
● Mass spectrometry may be used to determine the molecular formula
of a compound.

TEST YOURSELF ON PRIOR KNOWLEDGE 1

1 Name the following aliphatic organic compounds and name the
homologous series to which they belong.
a)
CH3COOH
b)
CH3CH2 CN
c)
CH3CH2 CH2 COCH3
d)
CH3COOCH3
e)
CH3CH2 CHO
f)
CH2 =CHCH2 CH3
2 Which groups in an organic compound would absorb at the following
wavenumbers in an infrared spectrum?
a) 1680–1750 cm−1
b) 3230–3550 cm−1
c) 2220–2260 cm−1
3 Identify the alkene which has a peak, due to its molecular ion, at
m/z =42 in its mass spectrum.

●● Organic synthesis 287

Organic synthesis is a branch of chemistry concerned with producing

organic compounds by chemical reactions. The American chemist Robert
Burns Woodward is regarded as the father of modern organic synthesis
and was awarded the Nobel Prize in 1965 for synthesis of many natural
products such as cholesterol, chlorophyll, quinine and cortisone.

807701_C15_AQA_Chemistry_2_287-308.indd 287 13/06/15 9:20 am

 The synthesis of organic compounds requires functional groups to be
changed into other functional groups. The diagram below shows the
connections between different homologous series and the table gives the
details of reagents, conditions, mechanism and type of reaction for each
conversion.
Questions on synthesis focus on conversion between different organic
compounds, often as a one-step or a two-step process. However, synthetic
routes with up to four steps are possible.
A chemist will always try to limit the number of steps in a conversion
as there is loss at each step as the percentage yield is not 100% for each
reaction. There may also be waste in terms of atom economy.
Chemists try to avoid the use of auxiliary chemicals such as solvents if they
are not needed. Gas phase reactions are preferred as they do not require a
solvent. Water may be used where a solvent is required. Organic solvents
15    ORGANIC SYNTHESIS, NMR SPECTROSCOPY AND CHROMATOGRAPHY

such as chlorinated compounds and ether are volatile and it is hard to

control their escape into the atmosphere.
Chemists also try to minimise the use of hazardous starting materials. These
may be toxic, corrosive or flammable. Often the use of potassium cyanide is
avoided as it is toxic. Other synthetic routes will be used.

●● Summary of organic reactions

(The numbers on the arrows are references to the reaction details in
the table on pages 289–300.)
9
3° 3°
Halogenoalkane Alcohol
13
8 15 Ester
2° 2°
Halogenoalkane Alcohol Ketone
13 18
10 12 19 33
4
2 4
2 29 30
10 12
Hydroxynitrile 28
22
Acid
Alkene Sodium
31 anhydride
25 salt
19
10 4
2 16 Carboxylic
3 12 Aldehyde Acid
acid
1° 14 20 26 chloride
7 24
Dihaloalkane Halogenoalkane 17
1°
21
Alcohol 32
288 13 Ammonium
1 6
11 salt 27
Alkane
2° Amine
Nitrile

5
23 Amide
Phenylethanone

36
34 35 1° Amine
Benzene Nitrobenzene Phenylamine

807701_C15_AQA_Chemistry_2_287-308.indd 288 13/06/15 9:20 am

 No Example Reagents Conditions Mechanism Type of reaction

Summary of organic reactions

1 alkane → halogenoalkane Cl 2 UV light Free-radical Substitution
CH4 + Cl 2 → CH 3 Cl + HCl substitution
2 alkene → halogenoalkane HX N/A Electrophilic Addition
C2H 4 + HBr → C2H5Br addition
3 alkene → dihaloalkane Halogen, e.g. Br 2 N/A Electrophilic Addition
C2H 4 + Br 2 → CH2BrCH2Br addition
4 alkene → alcohol H2 O Concentrated H2 SO 4 Electrophilic Addition followed
C2H 4 + H2 O → C2H5 OH or concentrated addition by hydrolysis
1°, 2° and 3° alcohols can be H 3PO 4
produced depending on the position 300 ºC
of the C=C and the actual alkene 7 MPa
used
5 1° halogenoalkane → 1° amine Concentrated Excess NH 3 dissolved Nucleophilic Substitution
C2H5Br + NH 3 → C2H5NH2 + HBr NH 3 in ethanol substitution
6 1° halogenoalkane → 2° amine 1° amine Amine dissolved in Nucleophilic Substitution
C2H5Br + C2H5NH2 → (C2H5)2NH + ethanol substitution
HBr
7 1° halogenoalkane → 1° alcohol NaOH(aq) Heat under reflux Nucleophilic Substitution
C2H5Br + NaOH → C2H5 OH + NaBr substitution
8 2° halogenoalkane → 2° alcohol NaOH(aq) Heat under reflux Nucleophilic Substitution
CH3 CHBrCH 3 + NaOH → substitution
CH 3 CH(OH)CH 3 + NaBr
9 3° halogenoalkane → 3° alcohol NaOH(aq) Heat under reflux Nucleophilic Substitution
(CH3)3CBr + NaOH → (CH3)3C(OH) + substitution
NaBr
10 1° or 2° or 3° halogenoalkane → KOH (dissolved in Heat under reflux Elimination Elimination
alkene ethanol)
C2H5Br + KOH → C2H 4 + KBr + H2 O
The position of the halogen atom
and the actual halogenoalkane will
give different alkenes or even a
mixture
11 1° halogenoalkane → nitrile Potassium cyanide Nucleophilic Substitution
C2H5Br + KCN → C2H5 CN + KBr (dissolved in substitution
ethanol)
12 alcohol → alkene Concentrated 170 °C for acid Elimination Elimination
C2H5 OH → C2H 4 + H2 O H2 SO 4 or dehydration Dehydration
1° or 2° or 3° alcohols can undergo concentrated H 3PO 4
this reaction to form differing (or Al 2 O 3 catalyst)
alkenes or a mixture of alkenes
13 alcohol → halogenoalkane HX (prepared in situ Heat under reflux N/A Substitution
C2H5 OH + HX → C2H5 X + H2 O from NaX and conc
H2 SO 4)
14 1° alcohol → aldehyde Acidified potassium Heat and distil N/A Oxidation
C2H5 OH + [O] → CH 3 CHO + H2 O dichromate(vi)
solution
15 2° alcohol → ketone Acidified potassium Heat under reflux N/A Oxidation 289
CH3 CH(OH)CH 3 + [O] → CH3 COCH 3 dichromate(vi)
+ H2 O solution
16 aldehyde → carboxylic acid Acidified potassium Heat under reflux N/A Oxidation
CH3 CHO + [O] → CH 3 COOH dichromate(vi)
solution
17 aldehyde → 1° alcohol NaBH 4 Aqueous solution Nucleophilic Reduction
CH3 CH2 CHO + 2[H] → addition
CH 3 CH2 CH2 OH

807701_C15_AQA_Chemistry_2_287-308.indd 289 13/06/15 9:20 am

 No Example Reagents Conditions Mechanism Type of reaction
18 ketone → 2° alcohol NaBH 4 Aqueous solution Nucleophilic Reduction
CH3 COCH 3 + 2[H] → CH 3 CH(OH)CH 3 addition
19 aldehyde/ketone → hydroxynitrile KCN followed by N/A Nucleophilic Addition
CH3 CHO + HCN → CH 3 CH(OH)CN dilute acid addition
20 carboxylic acid → aldehyde LiAlH 4 In dry ether Nucleophilic Reduction
CH3 COOH + 2[H] → CH 3 CHO + H2 O addition
21 carboxylic acid → 1° alcohol LiAlH 4 In dry ether Nucleophilic Reduction
CH3 COOH + 4[H] → CH3 CH2 OH + addition
H2 O
22 carboxylic acid → ester Alcohol Concentrated sulfuric Nucleophilic Elimination or
CH3 COOH + C2H5 OH → acid addition– condensation
CH 3 COOC2H5 + H2 O elimination
23 nitrile → 1° amine Lithal/LiAlH 4 In dry ether Nucleophilic Reduction
C2H5 CN + 4[H] → C2H5 CH2NH2 addition
24 carboxylic acid → ammonium salt Ammonia solution Room temperature N/A Neutralisation
15    ORGANIC SYNTHESIS, NMR SPECTROSCOPY AND CHROMATOGRAPHY

CH3 COOH + NH 3 → CH 3 COONH 4

25 carboxylic acid → sodium salt NaOH(aq) Room temperature N/A Neutralisation
CH3 COOH + NaOH → CH 3 COONa or Na2 CO 3
+ H2 O
26 acid chloride → carboxylic acid H2 O Room temperature Nucleophilic Hydrolysis
CH3 COCl + H2 O → CH 3 COOH + HCl addition-
elimination
27 acid chloride → amide Ammonia Acid chloride added Nucleophilic Substitution
CH 3 COCl + NH 3 → CH 3 CONH2 + HCl to concentrated addition-
ammonia elimination
28 acid chloride → ester Alcohol added to Room temperature Nucleophilic Esterification or
CH3 COCl + C2H5 OH → CH 3 COOC2H5 acid chloride addition- elimination
+ HCl elimination
29 ester → carboxylic acid Dilute hydrochloric Heat under reflux N/A Acid hydrolysis
CH3 COOC2H5 + H2 O → CH 3 COOH + acid
C2H5 OH
30 ester → salt of carboxylic acid Sodium hydroxide Heat under reflux N/A Base hydrolysis
CH3 COOC2H5 + NaOH → solution (or any
CH 3 COONa + C2H5 OH alkali)
31 acid anhydride → carboxylic acid H2 O Room temperature N/A Hydrolysis
(CH3 CO)2 O + H2 O → 2CH 3 COOH
32 acid anhydride → amide Concentrated NH 3 Room temperature N/A N/A
(CH 3 CO)2 O + NH3 → CH 3 CONH2 +
3CH 3 COOH
33 acid anhydride → ester Alcohol Room temperature N/A Elimination or
(CH 3 CO)2 O + CH 3 CH2 OH → condensation
CH3 COOCH2 CH2 + CH 3 COOH
34 benzene → nitrobenzene Concentrated HNO 3 Low temperature Electrophilic Substitution
C 6H6 + HNO 3 → C 6H5NO 2 + H2 O Concentrated to prevent further substitution
H2 SO 4 nitration
290 35 nitrobenzene → phenylamine Sn Heat under reflux N/A Reduction
C 6H5NO 2 + 6[H] → C 6H5NH2 + 2H2 O HCl and add NaOH(aq)
to liberate the free
amine
36 benzene → phenylethanone CH 3 COCl or AlCl 3 catalyst with Electrophilic Substitution
C 6H6 + CH 3 COCl → C 6H5 COCH 3 + (CH 3 CO)2 O CH3 COCl substitution
HCl
C 6H6 + (CH 3 CO)2 O → C 6H5 COCH 3 +
CH 3 COOH

807701_C15_AQA_Chemistry_2_287-308.indd 290 13/06/15 9:20 am

 Summary of organic reactions
EXAMPLE 1
Ethanal may be converted into bromoethane using a
three-step synthesis.
TIP
Step 1: Ethanal is reduced to compound A. Knowing the type of reaction is
Step 2: Compound A is converted into compound B. important. It can give a clue to
Step 3: Compound B is converted into bromoethane. the synthetic route.
Give the names of compound A and B.
For each step, suggest a reagent which could be used Step 1: Ethanal is reduced to ethanol
and name the mechanism. Compound A is ethanol
Using reaction 17 in the table, the reagent
Answer required is NaBH4.
Firstly identify the homologous series to which each The mechanism for reduction is nucleophilic
named substance belongs: addition.
Step 2: Ethanol is converted into ethene (an alkene)
Ethanal is an aldehyde Compound B is ethene
Bromoethane is a 1° halogenoalkane Using reaction 12 in the table, the reagent
used in concentrated H2SO4.
Another clue to the route is the word ‘reduced’ The mechanism for the reaction is elimination.
in step 1. Aldehydes are reduced to 1° alcohols Step 3: Ethene is converted into bromoethane
(see reaction 17). Using reaction 2 in the table, the reagent is HBr.
Extracting a three-step route from the diagram that The mechanism for the reaction is
starts with an aldehyde being reduced to a 1° alcohol electrophilic addition.
could give the following:

Alkene TIP
1° This type of question is synoptic
2 12 Aldehyde
Alcohol as it uses all of your knowledge
17
of organic chemistry and the
1°
Halogenoalkane reactions you have met. It is a good
way to revise organic chemistry.

EXAMPLE 2
Compound C is synthesised in a three-step process
from propene as shown below.
OH
Step 1 Step 2 Step 3
propene compound A compound B CH3CH2C C N

H
compound C

Name compounds A, B and C. Propene is an alkene. 291

For each step, suggest a reagent which could be used Aldehydes are formed on oxidation of a 1° alcohol.
and any conditions required.
Alkenes can be converted to 1° alcohols.
Name the mechanism for step 3.
Hydroxynitrile
Answer Alkene
4
Compound C is a hydroxynitrile. Hydroxynitriles are 19
formed from aldehydes and ketones so compound B 1° 14
Aldehyde
must be the corresponding aldehyde. Alcohol

807701_C15_AQA_Chemistry_2_287-308.indd 291 13/06/15 9:20 am

 Step 1: Compound A is propan-1-ol. The reaction should be heated and the
Using reaction 4 in the table, possible product distilled off.
reagents are concentrated H2SO4 or Step 3: Compound C is 2-hydroxybutanenitrile.
concentrated H3PO4 at a temperature of Using reaction 19, the reagents are KCN
300 ºC and 7 MPa pressure. followed by dilute acid.
Step 2: Compound B is propanal. The mechanism is electrophilic addition.
Using reaction 14, the reagent is acidified
potassium dichromate(vi) solution.

TEST YOURSELF 2
1 Name the reagent used to carry out the following 3 1-Chloropropane can be converted into butylamine
reactions: in a two-step process.
15    ORGANIC SYNTHESIS, NMR SPECTROSCOPY AND CHROMATOGRAPHY

a) 1-bromobutane to butylamine a) Name the intermediate.

b) 1-bromobutane to pentanenitrile b) What are the reagents for each step?
c) nitrobenzene to phenylamine
d) ethanenitrile to ethylamine
2 a) What is the intermediate in the two-step
conversion of ethanoyl chloride to ethanal?
b) Name the reagents for each step.

●● Nuclear magnetic resonance spectroscopy

Nuclear magnetic resonance (NMR) spectroscopy is a method of examining
the 1H and 13C nuclei within an organic molecule. 1H and 13C nuclei are
The arrow represents referred to as spin-half nuclei and so they can act as a mini magnet.
+ the direction of the
magnetic moment If these nuclei are placed in a strong external magnetic field, they will align
themselves with the magnetic field as shown in the diagram.
If a strong magnetic field is applied to this hydrogen nucleus, there are two
possibilities. The magnetic moment can align with the external magnetic
field or against it.

external + + external
magnetic magnetic
field field
Lower Higher
energy energy

292 When the magnetic moments of the nuclei are aligned against the magnetic field,
this is the higher energy state of the nuclei. The amount of energy required to
flip the nuclei between the lower and the higher energy state is in the radio wave
region of the electromagnetic spectrum and the energy absorbed can tell us a
great deal about the environment in which the nuclei in the molecule are found.

Chemical shift
The chemical shift is a comparative measure of the energy required to flip
the spin of the nuclei and is often represented by the Greek letter δ and is
measured in parts per million (ppm). This forms the horizontal axis of the
NMR spectrum and unusually the scale increase from right to left; the 0

807701_C15_AQA_Chemistry_2_287-308.indd 292 13/06/15 9:20 am

 value being on the right-hand side. The chemical shift values are given in
the Data Booklet provided with your exam papers. These are given below:

Nuclear magnetic resonance spectroscopy

Table B Table C
1H NMR chemical shift data 13C NMR chemical shift data

Type of proton δ/ppm Type of carbon δ/ppm

ROH 0.5 – 5.0 5 – 40

C C
RCH3 0.7 – 1.2

RNH2 1.0 – 4.5

R C Cl or Br 10 – 70
R2CH2 1.2 – 1.4

R3CH 1.4 – 1.6

R C C 20 – 50
R C C 2.1 – 2.6
O
O H

R C N 25 – 60
R O C 3.1 – 3.9

H
alcohols,
RCH2Cl or Br 3.1 – 4.2 C O ethers or 50 – 90
esters

R C O C 3.7 – 4.1 90 – 150

C C
O H

R H R C N 110 – 125
4.5 – 6.0
C C
110 – 160
O
R C 9.0 – 10.0 esters or
CH3 R C
acids 160 – 185
H
O O
H3C Si CH3
aldehydes 190 – 220
R C 10.0 – 12.0 R C
or ketones
CH3
O H O
tetramethylsilane

These chemical shift give information about the environment in which the
1H and 13C nuclei are found in the molecule. Those nuclei in the same

environment appear at the same chemical shift on an NMR spectrum. A

higher chemical shift usually indicates that the 1H or 13C nuclei are closer to
an electronegative group or atom or an electron withdrawing group such as
a benzene ring.
All chemical shifts are measured relative to a standard. The standard used
in NMR spectroscopy is tetramethylsilane (TMS), (CH3)4Si, the structure of
which is shown on the left. 293

Due to the higher electronegativity of carbon compared to silicon, the

electrons in the four Si–C bonds are closer to the carbon atoms. This
causes a knock-on effect for the electrons in the C–H bonds and hence
the electrons are closer to any 13C and 1H nuclei than they would be in
any other organic molecule. The proximity of these electrons to the nuclei
shields the spinning particles in the nuclei.
Figure 15.1 A nuclear magnetic Other 1H and 13C nuclei in organic molecules are said to be deshielded
resonance (NMR) spectrometer compared to those in TMS, and as the chemical shift is higher they appear

807701_C15_AQA_Chemistry_2_287-308.indd 293 13/06/15 9:21 am

 to the left of the TMS peak in the NMR spectrum. The more electronegative
the groups bonded to the nuclei (or even those attached to a carbon
with hydrogen(s) attached) are, the more deshielded a hydrogen nucleus
becomes and the larger the chemical shift.
The solvent used for 1H NMR spectroscopy is tetrachloromethane or any
deuterated solvent such as CDCl3, CD2Cl2 or C2D6. These solvents do not
contain 1H nuclei which would give peaks on the spectrum.
1H NMR spectroscopy
H O The spectrum below shows the low resolution 1H NMR of ethanal,
CH3CHO. The three 1H nuclei in the CH3 group are all in the same
H C C
molecular environment in a molecule compared to a hydrogen nucleus
H H attached to an oxygen atom in an O–H bond. The spectrum shows these
ethanal peaks. The structure of ethanal is shown on the left:
15    ORGANIC SYNTHESIS, NMR SPECTROSCOPY AND CHROMATOGRAPHY

This is the absorbance peak for the 1H This is the absorbance peak
nucleus adjacent to the C=O group. It is for the 1H nuclei bonded to a
highly deshielded by the C=O group and carbon in a CH3 group. As it is
appears to the left in the spectrum at a adjacent to a C=O it would be
higher chemical shift value in the range expected its chemical shift is
9.0–10.0 in the range 2.1–2.6
Absorption

CH3
This is the absorbance
peak for the 1H nuclei
CHO TMS in the standard,
(Reference) tetramethylsilane, TMS
and appears at a
chemical shift of 0 ppm
10 8 6 4 2 0
c/ppm
The low resolution 1H NMR spectrum is often drawn more simply as a
series of spikes.
Sometimes the peak for TMS is omitted as shown to make it clearer how
many environments of 1H nuclei are present in the molecule.
12 10 8 6 4 2 0
δ/ppm The chemical shift for 1H nuclei in a CH3 group is not always the same, as
the other groups attached to the carbon may affect its degree of deshielding.
The above spectrum for ethanal shows the CH3 peak at 2.3 ppm as would
be expected for 1H adjacent to a C O in the range 2.1–2.6 from the table on
page 293. The chemical shift of 1H nuclei vary depending on the adjacent
groups. This is due to the oxygen atom attached to the carbon pulling the
electrons in the C–H bonds away from the 1H nuclei and so deshielding them
to a greater extent than would normally be expected. However, it is true to
say that the peaks at the lowest chemical shift in an aliphatic organic molecule
would normally be those of 1H nuclei in a CH3 group, if they are present.
294
Hydrogen atoms that appear at the same chemical shift on the spectra and
are therefore in the same environment within the molecule are said to be
chemically equivalent hydrogen atoms.
Chemically equivalent hydrogen atoms are not distinguishable on an
H O H NMR spectrum. In the ethanal spectrum, there are two distinct types of 1H
H C C C H
nuclei. The three CH3 1H nuclei are chemically equivalent and the single CHO
1H nucleus is another environment. Two CH groups may have all their 1H
3
H H nuclei in the same environment. for example in propanone, CH3COCH3, all 6
propanone 1H nuclei are in the same environment due to the symmetry of the molecule.

807701_C15_AQA_Chemistry_2_287-308.indd 294 13/06/15 9:21 am

 The 1H NMR spectrum of propanone is shown below:

Nuclear magnetic resonance spectroscopy

12 10 8 6 4 2 0

Peak integration
The ratio of the areas under the peaks in a 1H NMR spectrum indicates
the ratio of the numbers of chemically equivalent 1H nuclei or
equivalent protons. This is often given in a table with the chemical shift
value. For example for the spectrum of ethanal, the table would look
like the one below.
δ/ppm 2.3 9.8
Integration ratio 3 1
3
The ratio is calculated by integration of the area under the peaks as the
spectrum is produced. It can also be given as a trace over the spectrum
1
where the difference in the horizontal levels of the trace give the
integration ratio.
12 10 8 6 4 2 0
c/ppm The ratio of the difference in heights (measured using a ruler) can give the
Integration ratio integration ratio.

Spin-spin splitting patterns

Neighbouring 1H nuclei have an effect on each other, which can be seen in
a high resolution 1H NMR spectrum. Equivalent 1H nuclei will appear at the
same chemical shift value on the spectrum, but the peak for these 1H nuclei
will be split into a number of peaks depending on the number of non-
equivalent 1H nuclei bonded to the adjacent carbon atoms.
This splitting of the peaks into a set of peaks is called the spin-spin splitting
pattern. The splitting pattern follows the n+1 rule. If there are 5 peaks
(=n+1) on the spectrum, this is caused by 4 (=n) hydrogen nuclei on
adjacent carbon atoms. The table shows the names and the ratios of the
heights of the peaks in the various splits.
Number of hydrogen Number of peaks
nuclei on adjacent [n+1]
carbon atoms [n] (Ratio of peak heights) Name of pattern
0 1 Singlet 295
1 2 (1:1) Doublet
2 3 (1:2:1) Triplet
3 4 (1:3:3:1) Quartet
4 5 (1:4:6:4:1) Quintet
5 6 (1:5:10:10:5:1) Sextet

If there is one non-equivalent proton bonded adjacent carbon atoms, the

peak will be split into two peak of equal height. These peaks will be smaller,
as the number of peaks in the environment is unchanged so the integration
must be the same. These two peaks together are called a doublet.

807701_C15_AQA_Chemistry_2_287-308.indd 295 13/06/15 9:21 am

 The 1H nuclei bonded to the
carbon atoms in the peak on
the left have no hydrogen
nuclei (protons) bonded to
adjacent carbon atom(s) to
split them. However, on the
right the spectrum shows two
peaks of approximately equal
height (a doublet), which
indicates one proton bonded
to an adjacent carbon atom

A doublet is often shown more simply as two spikes of approximately equal

height.
If there are two equivalent 1H nuclei or protons bonded to the carbon
atom(s) adjacent to the carbon atom in question, the single peak we would
have expected is split into three peaks, the heights of which are in the ratio
15    ORGANIC SYNTHESIS, NMR SPECTROSCOPY AND CHROMATOGRAPHY

1 : 2: 1. Again the total area under the three peaks is the same as the total
area under the single unsplit peak so the peaks are smaller. The three peaks
together are called a triplet.
This splitting pattern is the result of the interactions of the spins of the
1H nuclei hence the name spin-spin coupling is used. It is the spin-spin
coupling which gives rise to the spin-spin splitting pattern observed in 1H
Triplet caused by The triplet is often NMR spectra.
2 non-equivalent shown like this as
protons bonded to a series of spikes 1H NMR spectroscopy is a powerful tool to help determine structure and is
adjacent carbon in the spectrum
atoms
often used with other analytical techniques such as infrared spectroscopy
and mass spectrometry.

EXAMPLE 3
The 1H NMR spectrum for chlorinated alkane is The peak is split into a triplet, which indicates that it
shown below: is split by 2 hydrogen nuclei (i.e. a neighbouring CH2).
The peak at a chemical shift value of 3.4 would be a
RCH2Cl or Br as it is in the range 3.1–4.2. This peak
is deshielded by the electronegative chlorine atom
attached to the carbon.
The integration ratio for this peak is 2 which could again
suggest a CH2 group.
The peak is split into a quartet which indicates that it
6 5 4 3 2 1 0
is split by 3 hydrogen nuclei (i.e. the CH3).
c/ppm
The evidence would suggest that the molecule is
296 The integration table is shown below: chloroethane.
δ/ppm 1.2 3.4
Integration ratio 3 2 These three protons are These two protons are
equivalent and split the equivalent and split the
The peak at a chemical shift value of 1.2 in the
CH2 protons signal for the CH2 protons
spectrum would suggest a CH3 group as it is within
the range 0.7–1.2.
CH3CH2Cl
The integration ratio for this peak is 3, which would
again suggest a CH3 group.

807701_C15_AQA_Chemistry_2_287-308.indd 296 13/06/15 9:21 am

 Nuclear magnetic resonance spectroscopy
EXAMPLE 4
The 1H NMR spectrum of a compound with molecular H H
formula C6H12O2 is given below.
H C C O

H H
d) δ = 2.2 and an integration of 3 would again suggest
a CH3 group.
The singlet would suggest that there are no protons
bonded to adjacent carbon atoms.
The chemical shift would suggest a C=O group
adjacent (2.1–2.6) which would explain the lack of
5 4 3 2 1 0
splitting.
c/ppm
The structural part here is:
H O
The integration gave the following data:
H C C
δ/ppm 1.2 2.2 2.6 3.5 3.8
Integration 3 3 2 2 2 H
ratio e) δ = 2.6 and an integration of 2 would suggest a CH2
Spin-spin triplet group.
splitting The triplet would suggest a CH2 group is adjacent.
The chemical shift of 2.6 would suggest the CH2
Use Table B shown on page 293 and the information
group is adjacent to a C=O group.
above to answer the following questions:
δ = 3.8 and an integration of 2 would suggest
a) Explain why this is not the spectrum of a carboxylic another CH2 group.
acid. The triplet would again suggest a CH2 group is
b) Complete the table giving the spin-spin splitting adjacent.
patter observed in the spectrum. The chemical shift would suggest an oxygen atom
c) Suggest which structural part of the molecule gives (3.1–3.9) or an ester group (3.7–4.1) adjacent.
rise to the peaks at δ = 1.2 and 3.5. However the rest of the structure would suggest it
d) Suggest which structural part of the molecule gives is not an ester so the CH2CH2 must come between
rise to the peak at δ = 2.2. the other parts so this structural part is:
e) Suggest which structural part of the molecule gives
O H H
rise to the peak at δ = 2.6 and 3.8.
f) Deduce the structure of this compound. C C C O

Answers H H
a) No peak at δ = 10.0–12.0 for a COOH. f) The entire compound has the structure:
b)
H O H H H H
δ/ppm 1.2 2.2 2.6 3.5 3.8
Integration ratio 3 3 2 2 2 H C C C C O C C H
Spin-spin triplet singlet triplet quartet triplet
splitting H H H H H

c) δ = 1.2 and an integration of 3 would suggest a CH3 297

group.
The triplet would suggest that there is a CH2 group TIP
adjacent. The absence of a peak in (a)
As the CH3 would cause the signal for the CH2 can be as much of a clue as its
group to be a quartet, it has to be the CH2 at δ = 3.5 presence. This compound must be
which is adjacent to the CH3. an ester or a molecule containing
The chemical shift of the CH2 would suggest it is a C=O and a C-O-C. It could also
adjacent to an oxygen atom (in the range 3.1–3.9). contain a C=C and two OH groups.
The structural part here is:

807701_C15_AQA_Chemistry_2_287-308.indd 297 13/06/15 9:21 am

 Analysis of a given molecule

EXAMPLE 5
In another type of question, you could be given the molecule with the
environments labelled and you have to match them to the peaks in the
spectrum, state the number of peak in the 1H NMR spectrum and/or
explain the chemical shift, peak integration or spin-spin splitting.
O

CH3 C O CH2 CH2 CH3

a b c d
1 Identify the protons which will have the highest chemical shift in the 1H
NMR spectrum.
2 Give the splitting pattern of the protons at d.
15    ORGANIC SYNTHESIS, NMR SPECTROSCOPY AND CHROMATOGRAPHY

3 Which protons would appear as a singlet on the spectrum?

Answers
1 Protons a and b are closest to the electronegative oxygen atoms.
a should give a chemical shift in the range 2.1–2.6.
b should give a chemical shift in the range 3.1–3.9
The answer is b.
2 The protons in d have 2 protons bonded to adjacent carbons (a CH2 on
one side). This means that the splitting for d is a triplet.
3 A singlet appears when protons have no protons bonded to adjacent
carbon atoms. The only protons for which this is the case is a, the CH3
with a C=O adjacent.

Figure 15.2 Nuclear magnetic resonance has been developed into the medical
298 scanning technique known as magnetic resonance image MRI. The photograph
shows a patient moving into a full body MRI scanning machine

13C NMR spectroscopy

13C NMR spectroscopy is much simpler than 1H NMR spectroscopy.
13C atoms occur as about 1% of all carbon atoms. 13C NMR spectroscopy
relies on the magnetic properties of the nuclei of these atoms.
TMS is again used as a standard for 13C NMR spectroscopy and the solvent
used is often CDCl3. CDCl3 will give a peak on a 13C NMR spectrum, but

807701_C15_AQA_Chemistry_2_287-308.indd 298 13/06/15 9:23 am

 this is easily identified and removed from the final spectrum. The peak at δ
= 0 ppm for TMS is often removed as well.

Nuclear magnetic resonance spectroscopy

There is no spin-spin splitting to worry about in 13C NMR spectroscopy
and you are simply looking for chemical shift and the number of types of
equivalent 13C nuclei in the molecule.
A spectrum is simply a number of peaks. Each peak corresponds to an
environment of equivalent 13C nuclei.
A 13C NMR spectrum for 1-chloropropan-2-ol is shown below.

100 75 50 25 0
c/ppm

There are three peaks in the spectrum which correspond to the three
13C nuclei.
H H H
The structure of 1-chloropropan-2-ol is shown below with the carbon
a b c
Cl C C C H atoms labelled a, b and c.
H OH H Using Table C from the Data Booklet (see page 293 of this chapter):
● The peak at δ = 20 is caused by c (range 5–40)
● The peak at δ = 51 is caused by a (range 10–70)
● The peak at δ = 67 is caused by b (range 50–90)
There may be some confusion with a and b as they are both in the range,
but the oxygen atom is more electronegative than the chlorine atom and so
it more likely that the CH(OH) 13C is the peak at 67.

Determining the number of peaks

The number of peaks expected in a 13C NMR spectrum is a common
question. This can be applied to aliphatic as well as aromatic molecules.
Again the environments are determined based on the structural symmetry
H O H
of the molecule.
H C C C H Two CH3 groups bonded to the same carbon in a symmetrical molecule
H H
such as propanone.
propanone The C in the two CH3 groups are equivalent and so propanone will show
two peaks on its 13C NMR spectrum.
Propanal is shown below:
H H
299
O

H C C C

H H H

There are three peaks in the 13C NMR spectrum of propanal. CH3, CH2 and
the CHO will all give individual peaks.
Benzene gives a single peak as all the 13C are in the same environment. The
same is true of cyclohexane.
Substituted benzene compounds are treated differently.

807701_C15_AQA_Chemistry_2_287-308.indd 299 13/06/15 9:23 am

 CH3 Methyl benzene (or toluene) shows 5 peaks in its 13C NMR spectrum. This
can be explained by examining the molecule.
The numbers represent the carbon atoms that are equivalent, i.e. both
labelled 3 are equivalent and both labelled 4 are equivalent. The CH3 group
breaks the symmetry of the benzene ring so 2 and 5 are no longer equivalent.
methylbenzene However, 1,4-dimethylbenzene (shown below) has 3 peaks on its 13C NMR
(toluene) spectrum. The carbon atoms are labelled as before. The presence of 2 CH3
groups gives the molecule more symmetry so the top and bottom carbon
1 atom in benzene are now equivalent and the other carbon atoms in the
CH3 benzene ring are all equivalent (being equally removed from the CH3 groups.
2 1,2-Dimethylbenzene (shown below) has 4 peaks in its 13C NMR spectrum.
3 3
1
CH3
4 4
2 1
15    ORGANIC SYNTHESIS, NMR SPECTROSCOPY AND CHROMATOGRAPHY

5
3 3 CH3
methylbenzene 1
2 CH3
3 3 3
2
2
4 3
CH3
1 4
1,4-dimethylbenzene 1,2-dimethylbenzene

EXAMPLE 6
Deduce the number of peaks in the 13C NMR spectrum Answers
of the following molecules. 1 5
1 1
CH3 CH3

3
4 2

5
3
CH3 4 1 CH3

2 2 Answer is 2 as every CH3 carbon atom is equivalent

CH3 and all the carbon atoms in benzene are equivalent.
3 5
H3C CH3 1
CH3

O2N 2 NO2
H3C CH3 3 3

CH3 4 4
300 3 5
CH3 NO2

O2N NO2
1 2 3 4
4 CH3COOCH(CH3)2 – the two carbon atoms in CH3
groups are equivalent. The answer is 4.

NO2

4 CH3COOCH(CH3)2

807701_C15_AQA_Chemistry_2_287-308.indd 300 13/06/15 9:24 am

 TEST YOURSELF 3

Chromatography
1 Name the standard reference used for NMR spectroscopy.
2 Describe the spin-spin splitting pattern for ethanol, CH3CH2OH in its
high resolution 1H NMR spectrum.
3 How many peaks would be present in the 13C NMR spectrum of
propan-2-ol CH3CH(OH)CH3?
4 For the following compounds:
CH3CH2 COCH3 CH3CH2 COCH2 CH3 CH3CH2 CH2 CHO
a) Name all the compounds.
b) Which one would give the least number of peaks in a 13C NMR
spectrum?

●● Chromatography
Chromatography is a method of separating soluble substances by their
partition between two different phases. This was also studied on page 277.
All types of chromatography have a mobile phase and a stationary phase.
The substances to be separated are initially in the mobile phase, but as
they move through the chromatogram they may partition themselves into a
liquid stationary phase or adsorb onto a solid stationary phase.
We will examine three different types of chromatography: thin-
layer chromatography (TLC), column chromatography (CC) and gas
chromatography (GC).
The three methods of chromatography we are looking at are described as
having a liquid mobile phase (TLC or CC) or a gas mobile phase (GC). The
stationary phase for paper and TLC and CC can be considered to be solid.
The stationary phase for GC is a liquid.
The time the substances stay in the stationary phase depends on:
1 Size/mass of the solute molecules/ions.
2 Solubility in the mobile phase vs solubility in liquid stationary phase
(partition)
3 Binding to the solid stationary phase (caused by adsorption).
● Particles that have a greater attraction to a solid stationary phase in TLC
and CC will adsorb more onto this phase and will move more slowly
through the chromatogram.
● Particles that are more soluble in the liquid stationary phase in GC will
301
partition themselves into this phase and move along the chromatogram
more slowly.
● Larger particles pass along a chromatogram more slowly too.
● Particles that are very soluble in the mobile phase compared to the liquid
stationary phase will move quickly through the chromatogram.

807701_C15_AQA_Chemistry_2_287-308.indd 301 13/06/15 9:24 am

 The mobile and stationary phases of the three types of chromatography are
shown in the table below.
Type of
chromatography Mobile phase Stationary phase
Thin-layer Liquid solvent Solid silica gel paste on
chromatography e.g. water or a microscope slide or
organic solvents plastic plate or solvent/
water in the gel
Column Liquid solvent Solid silica gel
chromatography e.g. water or
organic solvents
Gas Inert carrier gas, Microscopic film of liquid
chromatography e.g. N2, Ne on a solid support

Thin-layer chromatography (TLC)

15    ORGANIC SYNTHESIS, NMR SPECTROSCOPY AND CHROMATOGRAPHY

Thin-layer chromatography is carried out in almost an identical fashion to

paper chromatography. The thin-layer plates are prepared from silica gel. Silica
gel is a polymer form of silicic acid that has many –OH groups, making the
surface of the gel/paste very polar. This allows polar substances to be held by
the gel making their movement much slower than for non-polar substances.
1 Prepare a TLC plate using silica gel paste or use a commercial one.
2 M
 ark a fine pencil line about 0.5 cm from one end. Put a cross in the
centre of the line. This line is called the origin.
3 U
 sing a capillary tube, lift some of the sample dissolved in the
appropriate solvent and spot onto the cross.
4 P
 lace the thin-layer chromatogram in the same solvent (the end with the
spot just dipping in).
5 Allow to run for about 20–30 minutes as solvent moves up.
6 C
 heck every few minutes to ensure that the solvent has not run off the
top end of the chromatogram.
7 A
 s the solvent moves, the substances in the spot also move up and
separate.
8 O
 nce finished, draw a pencil line to show where the solvent has reached
on the chromatogram. This is the solvent front.
9 The distance the solvent has moved in centimetres is called the Rs value.
10 Rf = distance moved by spot (to centre of spot)
Figure 15.3 Thin-layer chromatography distance moved by solvent (Rs)
plate of black ink.  ithin a solvent system, a substance should always have the same Rf
11 W
302 value, hence allowing comparison.

Developing chromatograms
Most chromatograms are not visible unless they are developed. The
process of developing for amino acids with ninhydrin has been described
previously. Some spots on chromatograms are only visible under UV light
and can be marked with a pencil for viewing in normal light. Others require
a solution of iodine to mark aromatic compounds.

807701_C15_AQA_Chemistry_2_287-308.indd 302 13/06/15 9:24 am

 Column chromatography (CC)

Chromatography
In this method, a solid such as silica gel is placed in a glass column with
glass wool at the bottom to prevent the silica gel from blocking the column
or coming out of the bottom. Glass wool is used as it is non-absorbent.
The silica gel is a polar solid stationary phase for the column
chromatography. The solvent that will carry the substances to be separated
is chosen to minimise time. Often small-scale tests are carried with TLC as it
uses the same solid support to find the most appropriate solvent or mixture
of solvents.
The solvent is run through the silica gel and from this point the column
must not dry out.
The sample to be separated is dissolved in a solvent such as hexane. Hexane
is a non-polar solvent and so polar substances are more likely to stay in
the column longer as they will be more attracted to the polar silica gel.
Non-polar substances will move quickly through the column as they will
be more likely to remain in the non-polar solvent.
The eluent is the liquid that leaves the column at the bottom, and samples
of the eluent may be taken for further analysis. The amount of time that a
substance remains in the column is called the retention time.
The column is prepared and saturated with solvent. The mixture to be
separated is dissolved in the solvent and placed on the top of the column.
Fresh solvent is added to the column to stop it from drying out. The
solvent moves through the column and the substances in the mixture
separate based on their solubility in the solvent (mobile phase) and their
retention by the silica gel (stationary phase). The liquid leaving the column
is called the eluent. Substances are described as being eluted when they
leave the column.

Solvent Column packed

with silica gel
and saturated
with solvent

Glass wool is non-

absorbent and
prevents the silica
gel being lost
Figure 15.4 Two bands of a red/brown from the column
colour can be seen in the column. These
are different components of a mixture
If the samples being eluted from the column are coloured, it is easy to
that is being separated – the different
substances travel down the column of see them being eluted. However many substances being used are not
gel at different rates. The technique can coloured and separate containers are used to collect 1 cm3 or 5 cm3 303
be used to purify and isolate a required samples of eluent. The samples containing the separated substances may
product. be analysed using TLC and developed using chemical developing agents
or under UV light to determine which samples contained the individual
substances.

807701_C15_AQA_Chemistry_2_287-308.indd 303 13/06/15 9:24 am

 EXAMPLE 7
A sample of ethanol was contaminated with ethanal. The sample was
separated using column chromatography. The sample was dissolved in hexane
and added to the column. Hexane continued to be added to the column.
Explain why ethanal was found to be present in samples of eluent
collected first, whereas ethanol was collected later.

Answer
Ethanal is less polar than ethanol so it has a lower affinity for the polar
stationary phase than ethanol. Ethanol being more polar remained bonded
to the polar stationary phase longer and so stays longer in the column.
15    ORGANIC SYNTHESIS, NMR SPECTROSCOPY AND CHROMATOGRAPHY

REQUIRED PRACTICAL 12
Thin-layer chromatography of amino acids in myoglobin
Myoglobin and haemoglobin are globular proteins the distance it has travelled. Using the figure,
that serve to bind and deliver oxygen in the body. identify amino acid X on the chromatogram.
Haemoglobin is the primary oxygen-carrying protein
and is found in red blood cells. It consists of four Solvent front
connected polypeptide chains, each of which contains
a non-protein haem group, the site at which oxygen is
known to bind.
Myoglobin is the main oxygen-binding protein found
in muscle cells. Myoglobin is only found in the
6 cm
bloodstream after muscle injury. Myoglobin also
X
contains a haem group, but it consists of only one
3 cm
polypeptide chain containing 153 amino acid residues.
Myoglobin can be hydrolysed into its constituent
amino acids, using acid hydrolysis. Thin-layer
chromatography (TLC) can then be carried out on the
resulting mixture and the Rf value calculated for each Table 15.1 The Rf value of some amino acids
of the spots obtained on the chromatogram.
Amino acid Rf
1 Why is it necessary to wear plastic gloves when Alanine 0.38
holding a TLC plate? Arginine 0.20
2 Why is it necessary to draw a pencil base line Asparagine 0.50
1.5 cm from the bottom of the plate.
Glutamic acid 0.30
3 How is a very tiny concentrated drop of amino acid
Leucine 0.73
solution added to the TLC plate?
Lysine 0.14
4 Explain why the developing tank the solvent is at a
depth of only 1 cm. 9 Explain why different amino acids have different Rf
304 5 Explain why the developing tank is sealed with a lid values.
when the TLC plate is placed in it.
6 Explain why the TLC plate is allowed to dry in a High concentrations of myoglobin in muscle cells
fume cupboard. allow organisms to hold their breath for a longer
period of time. Diving mammals such as whales
7 The substance used to develop the spots on the
and seals have muscles with particularly high
chromatogram is ninhydrin. State one safety
abundance of myoglobin. Muscle cells use myoglobin
precaution specific to the use of this substance,
to accelerate oxygen diffusion and act as localised
apart from the use of goggles.
oxygen reserves for times of intense respiration.
8 The figure shows a developed chromatogram with
three spots. The dotted line through each spot
indicates its mid-point, which is used to measure

807701_C15_AQA_Chemistry_2_287-308.indd 304 13/06/15 9:24 am

 Gas chromatography (GC)

Chromatography
Gas chromatography (or sometimes called gas-liquid chromatography –
GLC) is carried out using a coiled tube containing a solid support that has a
coating of liquid on its surface. The coiled tube is contained within an oven,
which ensures that the sample when injected into the column will remain as
a gas.
This type of chromatography works by partition. The substances in the
gaseous mobile phase may dissolve in the stationary liquid phase and this
retards their progress through the column. The more soluble the substances
are in the liquid stationary phase, the more time they spend in the column.
The sample to be separated is heated to make it a gas and then mixed with
an inert carrier gas such as nitrogen or helium. The sample then enters into
the column and is allowed to pass through it.

sample detector waste

heater to
vaporise sample

inert carrier gas

computer
analysis
coiled
chromatography
oven column

The computer detects substances being eluted from the column. A substance
is eluted when it leaves the chromatography column. The time that each
substance spends in the column is called its retention time. The computer
analysis plots detector signal against retention time as shown below.
Detector signal

0 5 10 15 20
Retention time/minutes

There are five components to the above sample as there are five separate
peaks. The peaks at 5 and 7 minutes are close together so their properties
must be similar. The peak at 20 minutes represents a substance that was
very soluble in the liquid stationary phase as it was the last to elute from the
305
column and therefore had the highest retention time.
Figure 15.5 A gas chromatography GC is also useful as the area under the peak gives a measure of the
machine (left) connected to a mass relative amounts of each substance present in the sample. This allows
spectrometer (right) in a forensic
percentage composition of the mixture to be calculated. This can be useful
laboratory. This equipment is sensitive
enough to detect minute quantities of in monitoring an equilibrium reaction. The reaction can be sampled
illegal drugs in the hair of a suspect – and analysed using GC and the relative proportions of the reactants and
weeks after any drugs were taken. products calculated from the area under the peaks.

807701_C15_AQA_Chemistry_2_287-308.indd 305 13/06/15 9:25 am

 GC is usually linked with mass spectrometry which will enable each peak to
be identified. This combined technique is very powerful as it will identify each
component of a mixture and calculate how much of each component is present.
If a non-destructive detector is used, GC can be used to separate the
components of the mixture as they can be condensed.

EXAMPLE 8
The numbers above the peaks indicate the relative Answer
area under the peak which allows us to work out Total of all areas = 1.7 + 0.1 + 1.2 + 0.4 + 2.3 = 5.7
percentage composition.
Peak at 7 minutes percentage composition
= 1.7 × 100 = 29.8%
1.7
Detector signal

5.7
2.3 Peak at 9 minutes percentage composition
15 ORGANIC SYNTHESIS, NMR SPECTROSCOPY AND CHROMATOGRAPHY

1.2
= 0.1 × 100 = 1.8%
0.1 0.4 5.7
Peak at 14 minutes percentage composition
0 10 20 30 = 1.2 × 100 = 21.0%
5.7
Retention time/minutes
The total of the areas under the peaks should be Peak at 17 minutes percentage composition
calculated and then percentage composition can be = 0.4 × 100 = 7.0%
5.7
worked out.
Peak at 20 minutes percentage composition
= 2.3 × 100 = 40.4%
5.7

TEST YOURSELF 4
1 Name a common stationary phase used in column chromatography.
2 Which one of ethanol, ethanal and ethanoic acid would you expect to
be eluted first from silica gel column chromatography using a hexane
solvent?
3 Name one way in which a TLC plate may be developed.

Practice questions
1 Which one of the following does not react 3 Which one of the following is the correct
with KCN? splitting pattern in the 1H NMR spectrum
from lowest to highest chemical shift value for
A 1-bromopropane B propanal
propanoic acid?
306
C propanone D propanoic acid (1)
A quartet, triplet, singlet
2 Which one of the following has 2 peaks on
B singlet, quartet, triplet
its 13C NMR spectrum?
C triplet, quartet, singlet
A 1,2-dibromobenzene
D singlet, triplet, quartet (1)
B 1,3-dibromobenzene
C 1,2,3-tribromobenzene
D 1,3,5-tribromobenzene (1)

807701_C15_AQA_Chemistry_2_287-308.indd 306 13/06/15 9:25 am

 4 Methoxymethane (CH3OCH3) and ethanol 6 A ketone may be converted into a primary

Practice questions
(CH3CH2OH) are isomers. The 1H NMR alcohol by a four-step process.
spectrum are shown below.
Step 1: C4H8O is reduced to compound A.
Step 2: Compound A is converted into
compound B.
Step 3: Compound B is converted into
7 6 5 4 3 2 1 0 7 6 5 4 3 2 1 0
compound C.
Chemical shift c/ppm Chemical shift c/ppm
Spectrum A Spectrum B Step 4: Compound C is converted into a
primary alcohol, D.
a) Explain why spectrum A is the spectrum of
methoxymethane. (2) a) Give the structures and IUPAC name of A,
B, C and D.
b) Complete the table below giving the spin-
spin splitting for spectrum B. (2) b) Name the reagents required for each step.
(12)
δ/ppm 1.0 3.2 5.0
Integration ratio 3 3 1 7 The thin-layer chromatography plate shown
Spin-spin below shows the separation of a mixture of
splitting organic compounds. Silica gel is the support
and the solvent used was hexane. The mixture
c) Ethanol contains an ethyl group, CH3CH2.
contained propan-2-ol, propanone and ethyl
Explain this from spectrum B. (2)
propanoate.
5 4-Methylpentan-2-one has the structure:

9
CH3
a b Solvent

8
front

3
H3C C CH2 C CH3
3

7
H O

6
a) How many peaks are in the 13C NMR

2
5
spectrum of this compound? (1)
2 4
b) How many types of equivalent protons
are in the 1H NMR spectrum of this
3

1
Inches 1

spectrum? (1)
Centimeters
2

c) Give the IUPAC name for this compound.

1

(1) Origin
d) What is the spin-spin splitting pattern for
the protons labelled a? (1) a) Calculate the Rf values for spots 1, 2
e) What is the spin-spin splitting pattern for and 3. (3)
the protons labelled b? (1) b) Which spot represents which substances in
f) Draw the structure of the compound the mixture? (2) 307
formed on reaction of 4-methylpentan-2- c) Why is it important to wear gloves when
one with NaBH4. (1) preparing a TLC plate? (1)

807701_C15_AQA_Chemistry_2_287-308.indd 307 13/06/15 9:25 am

 8 The 1H NMR spectrum below is for an organic c) Which of the compounds would react with
compound which has the formula C4H8O2 is sodium hydroxide? (1)
shown below. The substance did not react with
d) Which one of the compounds has the
sodium carbonate. The integration ratios are
empirical formula CH3? (1)
given in the table below.
e) Which of the substances can be reduced
using NaBH4 or LiAlH4? (1)
f) CH3CH=CH2 can be converted to
CH3CH2CH2NH2 in a two-step process.
i) Give the IUPAC name for CH3CH=CH2
and CH3CH2CH2NH2. (2)
6 5 4 3 2 1 0 ii) Give the reagent required to convert
c/ppm CH2CH=CH2 into CH3CH2CH2NH2
in a two-step process. State any
15 ORGANIC SYNTHESIS, NMR SPECTROSCOPY AND CHROMATOGRAPHY

δ/ppm 0.9 2.4 3.8 conditions required and name the

Integration ratio 3 2 3 mechanism. (7)

a) Suggest a fragment of the molecule which Stretch and challenge

could be responsible for the peak at 10 There are several isomers with the molecular
δ = 3.8. (1) formula C5H10O.
b) Suggest a fragment of the molecule which a) Draw the structure of one isomer which
could be responsible for the peaks at exhibits optical isomerism. Give the IUPAC
δ = 0.9 and 2.4. (1) name of the compound and label the chiral
c) Draw a possible structure of the molecule. centre with an asterisk (*). (3)
(1) b) Draw the structure of one isomer which
d) Name a suitable solvent used in 1H NMR exhibits E-Z isomerism. Draw the structure
spectroscopy. (1) of the two stereoisomers and label them as
E and Z. (3)
9 For the following organic compounds:
c) Draw the structure of one isomer which
CH3CH2CH2OH CH3CH=CH2 CH3CH2COOH CH3CH(OH)CH3 would react with water forming pentane-
CH3CH2CH2Br CH3CH2CH3 CH3COCH3 CH3CH2CH2NH2 1,5-diol. (1)
a) Which one of the compounds would give 2 d) Give the IUPAC name for the isomer which
peaks on a 13C NMR spectrum? (1) could be oxidised to 3-methylbutanoic acid
using acidified potassium dichromate. (1)
b) Which of the compounds would react with
acidified potassium dichromate giving an
orange to green colour change? (1)

308

807701_C15_AQA_Chemistry_2_287-308.indd 308 13/06/15 9:25 am

 16 Maths for chemistry

PRIOR KNOWLEDGE
● In calculation work you must be able to use an appropriate number of
significant figures. If the raw data given is quoted to varying numbers
of significant figures, the calculated result can only be reported to the
limits of the least accurate measurement.
● Standard form expresses numbers in the form A × 10 n, where A is a
number between 1 and 10 and n is the number of places the decimal
point moves. When converting between numbers in ordinary and
standard form, the same number of significant figures must be kept.
● You must also be able to present your answers in calculations to a
number of decimal places and to state the correct units. Conversion
between units, e.g. cm3 to dm3 or kg to g, is also expected.
● The arithmetic mean is found by adding together all values and dividing
by the total number of values. Outliers must be identified and ignored
when calculating a mean.
● Per cent means ‘out of 100’ and is represented by the symbol %.
Percentage error is found using the equation
Percentage error = error × 100/quantity measured.
● To determine the percentage error when two burette readings are
used to calculate a titre value, the error must be multiplied by two.
● You must be able to rearrange the subject of an equation, for example
mass mass
moles = and so Mr = .
Mr moles
● The independent variable is the variable for which values are changed
by the investigator. The dependent variable is the variable of which the
value is measured for each change in the independent. The controlled
variable is one which must be kept constant, to prevent it affecting the
outcome of the investigation. When plotting graphs the independent
variable is placed on the x axis and the dependent variable is on the
y axis. Appropriate scales must be devised for the axis, making the
most effective use of the graph paper. Axes should be labelled with
the name of the variable followed by a solidus (/) and the unit of
measurement. A best-fit line or curve can be drawn by judging the
approximate positon of the line so that there are approximately the
same number of data points on each side of the line or curve. 309

●● Algebra
Changing the subject of an equation and substituting
values
Book 1 outlined how to change the subject of a simple equation; however,
you must now be able to change the subject of more complicated equations
involving rates and equilibrium.

807701_C16_AQA_Chemistry_2_309-320.indd 309 13/06/15 9:35 am

 EXAMPLE 1
Rearrange the rate equation rate = k[NO]2[O2] to make k the subject

Answer
Switch sides to get the new subject on the left:
k[NO]2[O2] = rate
You require k by itself on the left-hand side, hence [NO]2[O2] must be
moved to the right-hand side. Remember that k is multiplied by [NO]2[O2]
so when [NO]2[O2] moves to the right it is divided.
rate
k=
[NO]2 [O2 ]

EXAMPLE 2
Rearrange the equation to make [H+] the subject. ● To find [H+] simply substitute the values into this
equation. If Ka is 1.74 × 10−5 mol dm−3 and it is a
[H+ ]2
Ka = 0.20 mol dm−3 solution of ethanoic acid then:
[weak acid]
_5
[H+ ] = K a × [ weak acid] = 1.74 × 10 × 0.20
Answer
● Switch sides to get the new subject on the left. _6
+ 2
= 3.48 × 10
[H ]
= Ka
[weak acid] = 1.87 × 10−3 mol dm−3
● On the left-hand side [weak acid] is divided so
moving it to the right, it is multiplied, the inverse
operation TIP
[H+]2 = Ka × [weak acid] To rearrange an equation with a
squared power use the inverse
16    MATHS FOR CHEMISTRY

● To remove the power of two on the left-hand side, operation, which is a square root.
you must take the square root of the right-hand side. For example 32 = 9, 9 = 3. In
general a2 = b so a = b.
[H+ ] = K a × [ weak acid]

EXAMPLE 3
Rearrange the equilibrium expression to make [C] the Both [A] and [B]2 were divided, so when moved to the
subject. other side they are multiplied.
● Ifa quantity is multiplied on one side of the
[C]2[D]
Kc = expression, it will be divided on the other side when
310 [A][B]2 moved:
Answer Kc[A][B]2
[C]2 =
● Switch sides to get the new subject on the left: [D]

● To remove the power of two on the left-hand side,

[C]2[D]
= Kc you must take the square root of the right-hand
[A][B]2
side.
● If a quantity is divided on one side of the expression, Kc[A][B]2
[C] =
it will be multiplied on the other side when moved: [D]
[C]2[D] = Kc [A] [B]2

807701_C16_AQA_Chemistry_2_309-320.indd 310 13/06/15 9:35 am

 Units

Algebra
For A2 you must be able to work out units for rate constants and equilibrium
constants. To help with this it is useful to understand the laws of indices.
Multiplication
When multiplying numbers that have indices, add the powers:
x2 × x3 = x(2+3) = x5

EXAMPLE 4
mol dm−3 × mol dm−3
Remember mol is really mol1
mol × mol × dm−3 × dm−3 = mol(1+1) dm (−3 + −3) = mol2 dm−6
The units mol dm−3 are concentration units, so a simpler method is to
replace the unit mol dm−3 by the word concentration.
mol dm−3 × mol dm−3 = concentration × concentration
= (concentration)(1 + 1) = (concentration)2
This can then be converted back to units (mol dm−3)2 = mol2 dm−6

Division
When dividing numbers with indices, subtract the indices:
x4
= x(4-3) = x1 = x
x3
Remember when dividing it is possible to cancel terms if the same term is
on the top and bottom of the fraction.
x2 × x 4
= x4
x2

EXAMPLE 5
(mol dm–3 )2 (mol dm–3 )2 1
= = mol dm−3
(mol dm–3 ) (mol dm–3 )
mol dm−3 is on the top and bottom of the fraction so it cancels
Or alternatively this can be written:
(concentration)2
= concentration(2−1) = concentration = mol dm−3 311
concentration

807701_C16_AQA_Chemistry_2_309-320.indd 311 13/06/15 9:35 am

 EXAMPLE 6
(mol dm–3 )2 (mol dm–3 )2 no units
=
(mol dm–3 )2 (mol dm–3 )2
as the units top and bottom are the same, they cancel each other out.
(concentration]2
Units = = concentration(2−2) = concentration0 = no units
(concentration]2
Remember x0 = 1

Brackets
When taking the power of a number already raised to a power, multiply the
powers.
(x2)3 = x(2×3) = x6

EXAMPLE 7
(mol dm−3)2 = mol(1 x 2) × dm(−3 × 2) = mol2 dm−6

Reciprocal
1
x−1 = x

EXAMPLE 8
(mol dm−3 )2 (mol dm−3 )2 1
−3 4
= −3 4 2
= = (mol dm−3)−2 = mol−2 dm6
(mol dm ) (mol dm ) (mol dm−3 )2

EXAMPLE 9
16    MATHS FOR CHEMISTRY

mol dm−3s−1 mol dm−3s−1 s−1 s−1 s−1

−3 3
= −3 3 2
= −3 2
= (2×1) (− 3× 2)
=
(mol dm ) (mol dm ) (mol dm ) mol dm mol dm−6
2

= mol−2 dm6 s−1

Estimating results
TIP Sometimes changing different experimental conditions has an effect on
If the numerator (numbers on the measureable values. Using mathematics, it is possible to estimate this effect.
top) increases and denominator For example, temperature is the only factor that affects the value of Kc
(numbers on the bottom) for an equilibrium. This is because temperature affects the position of
312 decreases then Kc increases. equilibrium and the concentrations of reactants and products will change.
An increase in the concentration of the products (and decrease in the
concentration of the reactants) will increase the value of Kc. This is because
the numerator of the Kc expression gets larger and the denominator gets
smaller, giving a larger value of Kc.
For a reaction:
aA + bB ⇋ cC + dD
a decrease in the concentration of the products (and increase in the
concentration of the reactants) will decrease the value of Kc when
temperature is changed.

807701_C16_AQA_Chemistry_2_309-320.indd 312 13/06/15 9:35 am

 Graphs
EXAMPLE 10 If more ammonia is produced the numerator of
For the equilibrium: the fraction gets bigger, and the denominator gets
smaller, as there is a smaller concentration of
N2(g) + 3H2(g) ⇋ 2NH3(g) ΔH = −92 kJ mol−1 nitrogen and hydrogen, and so the value of Kc will
increase.
From your knowledge of Le Chatelier’s principle from
Book 1, the forward reaction is exothermic (ΔH is
negative) and so a decrease in temperature shifts the
equilibrium position right in the forward exothermic TIP
direction which means more ammonia is produced. Remember that the equilibrium
In the equation for Kc constant is affected in this way
by changes in temperature only;
[NH3 ]2 it does not change when the
Kc =
[N2 ][H2 ]3 pressure or concentration of the
system changes – see page 75.

●● Graphs
The equation of a straight line graph
Every straight line can be represented by an equation: y = mx + c. The
coordinates of every point on the line will solve the equation if you
substitute them in the equation for x and y.

y = mx + c

the gradient the y intercept

The y intercept is the point where the graph crosses the y-axis. It is the
value for y when x = 0.

EXAMPLE 11
For the graph shown below, the equation of the line is:

y = 2x + 1
6 y
5
4 y = 2x + 1 gradient intercept
3
2 313
1
x
–6 –5 –4 –3 –2 –1 0 1 2 3 4 5 6
–1
–2
–3
–4
–5
–6

807701_C16_AQA_Chemistry_2_309-320.indd 313 13/06/15 9:35 am

 Gradient
Gradient is another word for ‘slope’. The higher the gradient of a graph at a
point, the steeper the line is at that point. A positive gradient means the line
slopes up from left to right. A negative gradient means that the line slopes
downwards from left to right. A zero gradient graph is a horizontal line. For
a straight line graph the gradient is a constant value.
y y

x x

positive gradient negative gradient

lower left to top right. top left to lower right.

To find the gradient (m) of a straight line graph:

1 Choose any two points on the line.
2 At one end of the line chose a point and call it (x1, y1).
3 At the other end of the line chose another point and call it (x2,y2).
4 A more accurate answer is obtained when the points (x1, y1) and (x2,y2)
are as far apart as possible.
5 Substitute your values into the equation:
yz – y1
m=
x2 – x1
where the numerator represents the vertical distance between the two
points (the rise) and the denominator represents the horizontal distance
16    MATHS FOR CHEMISTRY

between two points (the run).

rise
A simpler equation to use may be gradient (m) = run
change in y
or even gradient (m) =
change in x

EXAMPLE 12
For this graph y = mx + c y

The y intercept(c) is 1 4
The gradient (m) is calculated as:
3
314
y − y1 3 − 1 2
m= 2 = = =2 (x1, y1) (x2, y2)
x2 − x1 1 − 0 1 (0, 1)
2 2 (1, 3)
or 1
1
rise 2
m= = =2 x
run 1 –1
0
1 2 3
–1
The equation for the line is:
y = 2x + 1

807701_C16_AQA_Chemistry_2_309-320.indd 314 13/06/15 9:35 am

 concentration/mol dm-3

Graphs
time/s

The rate equation for a zero order reaction is:

rate = k[A]0.
The graph above is a concentration against time graph for a zero order
reaction (see page 59) The gradient of this graph is equal to the rate
constant. Gradients can have units. For the concentration against time
graph the gradient does have units. This is because:
y2 − y1 concentration
Gradient (m) = =
x2 − x1 time

hence the units of the gradient of this graph are:

mol dm−3
= mol dm−3 s−1
s

Tangent
The word tangent means ‘touching’ in Latin. The tangent is a straight line
that just touches the curve at a given point and does not cross the curve.
To draw a tangent at a point (x,y):
1 Place your ruler through the point (x,y) on the curve.
2 Make sure your ruler does not touch the curve at any other point.
3 Draw a ruled pencil line passing through point (x,y).

(x, y)
The ruler passes through point
(x, y) on the curve, but no other
0
1
2 point 315
3
4
5
6
7

tangent

807701_C16_AQA_Chemistry_2_309-320.indd 315 13/06/15 9:35 am

 EXAMPLE 13 y2 − y 1 2 − 1 1
m= = = = 0.5
What is the gradient of the curve at point A? x2 − x1 3 − 1 2

y The gradient of the curve at point A is 1, or 0.5.

5 2
y rise
5 gradient =
4 run
= 1 = 0.5
4 2
3
tangent 3
2
C
A(2, 1.5) 2 C
1 A(2, 1.5)
B Rise = 2 − 1 = 1
1
x B Run = 3 − 1 = 2
0
0 1 2 3 4 5 6 x
0
0 1 2 3 4 5 6
Answer
To find the slope of the curve at any other point, you
Draw a tangent to the curve at point A. would need to draw a tangent line at that point and
then determine the slope of that tangent line. This is
B has coordinates (x1, y1) (1,1) and C has coordinates
the method used to find the order of a reaction using
(x2, y2) (3,2). The gradient of the curve at point A is
the initial rates methods, see page 58.
equal to the slope of the straight line BC.
Calculate the gradient of BC:

0.1
–0.027mol dm−3
At 100s, gradient =
0.08 110 s
0.027 mol dm−3
[HI]/mol dm−3

Rate = –0.00025 mol dm−3 s−1

0.06

0.04
16    MATHS FOR CHEMISTRY

110 s
0.02

0
0 50 100 150 200 250 300
Time/s

Figure 16.1 The graph shows how the rate of reaction at time 100 seconds is
calculated, by drawing a tangent to the curve and calculating the gradient of the
tangent.

●● Algebra
316
Logarithms
Large numbers are often complicated to deal with. By writing larger numbers
in terms of their power to base ten, a smaller scale, called a log scale is
generated which is often easier to comprehend. In chemistry, pH is defined in
terms of a logarithmic scale. Long before calculators were invented, logarithm
tables were used to simplify mathematical calculations. John Napier, a
Scottish mathematician published the first logarithm tables in 1641.
Logarithms, or ‘logs’, express one number in terms of a base number, that is
raised to a power.

807701_C16_AQA_Chemistry_2_309-320.indd 316 13/06/15 9:35 am

 TIP

Algebra
There are two different buttons to calculate logarithms on most
calculators. The ‘log’ button calculates logs to base ten and is the button
which you should use. The ‘ln’ button calculates natural logs; do not use
this button.

Don’t use
This is the this button
log button – it does not
you should calculate
use log10

For example, in the expression

100 = 102
10 is the base and 2 is the power or index. This expression can be written
in an alternative way. In terms of logs it is written
log10100 = 2
This can be read as the ‘log to base 10 of 100 is 2’. The relationship between
the two expressions is shown below.

Index or power

100 = 102 Log10100 = 2

Base

The base can be any positive number apart from 1, but in A-level Chemistry
we will be using logs to base 10. Logarithms to base 10, log10, will be
written simply as ‘log’, e.g. log100 = 2. You will use your calculator to
find logs.

317
EXAMPLE 14
Check that you can use your calculator correctly by verifying that:
log 93 is 1.97
log 0.03 is −1.52
log 1.1 × 103 is 3.04

807701_C16_AQA_Chemistry_2_309-320.indd 317 16/06/2015 17:07

 Two common equations involving logs which are used in chemistry are:
pH = −log[H+]
and
pKa = −logKa

EXAMPLE 15
If a solution has [H+] = 0.50 mol dm−3 find the pH of the solution using the
equation pH = −log[H+]

Answer
pH= −log (0.50)
To calculate this on your calculator, type in ‘−’, then ‘log’, then ‘0.50’.
This should give an answer of 0.30

EXAMPLE 16
The Ka for ethanoic acid
CH3COOH is 1.74 × 10−5 mol dm−3. Use the equation
pKa = −logKa
to find the value of pKa

Answer
pKa = −log(1.74 × 10−5)
Type in ‘−’, then ‘log’, then
‘1.74 × 10−5’.
The answer should be 4.76
16    MATHS FOR CHEMISTRY

You will find many examples of pH and pKa calculations in Chapter 6.

Antilogs
You must be able to use your calculator to find logs of any positive number.
In addition, sometimes you may be given the log of a number and must
work backwards to find the number itself. This is called finding the antilog
of the number. An antilog is the opposite of a log. To find the antilog on
most simple scientific calculators:
1 press the second function (2ndF) inverse (inv) or shift button, then
318
2 type in the number, then
3 press the log button. It might also be labelled the 10x button.

Press the shift

(or 2ndF) button
and then the log
button to access
the antilog function.
The antilog function
is 10x as shown

807701_C16_AQA_Chemistry_2_309-320.indd 318 13/06/15 9:35 am

 Algebra
EXAMPLE 17
If logx = 2.3 . What is x?

Answer
To find x you need to find the antilog of 2.3.

On your calculator type in ‘shift’ (or ‘inv’ or ‘2ndF’), then ‘log’, then ‘2.3’
The answer should be 199.5.

EXAMPLE 18
If logb = −0.2. what is b?

Answer
On your calculator find the antilog of −0.2. It should be 0.6 so b = 0.6

An antilog ‘undoes’ logs by raising the base to the log number.

For example:
log100 = 2, antilog2 = 100
In finding the antilog, the calculator is performing the calculation 102.

EXAMPLE 19 On your calculator, type in ‘shift’ (or ‘2ndF’ or ‘inv’),

Determine the concentration, in mol dm−3, of nitric acid then ‘log’, then ‘−0.65,
that has a pH of 0.65. This should give the value of [H+] = 0.22 mol dm−3

Answer An alternative way of answering this is to use the

equation:
pH = −log[H+]
[H+] = 10−pH
0.65 = −log[H+]
[H+] = 10−0.65
−0.65 = log[H+]
This is calculated in the same way on your calculator.

EXAMPLE 20 On your calculator, type in ‘shift’ (or ‘2ndF or ‘inv’),

then ‘log’. then ‘−2.89’. This should give the value of 319
Calculate the Ka of an acid which has a pKa value of
2.89 Ka of 1.29 × 10−3
An alternative way of answering this question is by
Answer using the equation:
pKa = −logKa Ka = 10−pKa
2.89 = −logKa Ka = 10−2.89
−2.89 = logKa

807701_C16_AQA_Chemistry_2_309-320.indd 319 13/06/15 9:35 am

 Logarithmic scales
Logs are a powerful way to reduce a set of numbers that range over many
orders of magnitude to a smaller more manageable scale. pH is a logarithmic
scale. The table below shows how taking the log of the hydrogen ion
concentration reduces the range of numbers being dealt with. If values for [H+]
range from 0.1 to 0.00000000000010 the pH can fit in the range 1 to 14!

pH 1 7 13 14
[H+]/mol dm−3 10 −1 10 −7 10 −13 10 −14

Presentation of data on a logarithmic scale can be helpful when drawing

graphs. Logarithmic scales are used when the data:
l covers a large range of values; the use of logs reduces a wide range to a
more manageable size which is easier to plot.
l may contain exponential or power laws since these will show up as
straight lines. For example, for a second order reaction rate = k[A]2, the
graph of rate against concentration would give a curve (see page 59). If
logs are taken of both sides, this gives:
log(rate) = logk + 2log[A]
This has the same form as a straight line graph y = mx + c. Consequently,
a plot of log rate against log[A] gives a straight line graph whose intercept
is the value for logk and the gradient is equal to the order of the reaction.
This treatment is valid for any order values. The gradient (slope) of the
graph line is always equal to the order.
Log(rate)
16    MATHS FOR CHEMISTRY

y = mx + c
log(rate) = 2log[A] + logk

log[A]

Sometimes you may be asked to plot a graph by calculating the log of some
values, and then plotting the logs. Simply calculate the log values on your
calculator and record them before plotting. An example of this type of
320 graph is included with the activity in the kinetics chapter on page 62.
The Richter scale is used to measure the strength of earthquakes by taking
the log of the amount of energy they release. It is a logarithmic scale. The
largest earthquake ever recorded was in 1960 in Chile and reached 9.5 on
the Richter scale.

807701_C16_AQA_Chemistry_2_309-320.indd 320 13/06/15 9:35 am

 Index
A testing for 179, 206
alkalis 100, 103
acylation of 240–1
electrophilic substitution
absolute entropy values alkenes, hydrogenation of 186 mechanism 238–9
(standard entropy values) 27 alpha (α)-helix structure 272 naming of derivatives 237
absorbance 165 aluminium compounds, nitration of 239–40
acid anhydrides 199, 222–3 hexaaquaaluminium(iii) reactions of 236
reaction with alcohols 224 complex 170–1 structure of 234–6
reaction with amines 226 aluminium oxide 139 beta (β)-pleated sheet structure 273
reaction with ammonia 225 melting point 144 bidentate ligands 152–3
reaction with water 224 amides 199, 223 biodegradability of polymers 265–6
acid–base titrations amines 245–6 biodiesel 221
indicators for 124 base strengths of 254–5 boiling, entropy changes 28–9
methanoic acid with sodium hydroxide basic reactions of 253–4 boiling points
125 naming of 247–9 aldehydes and ketones 203–4
titration curves 121–3 nucleophilic substitution reactions carboxylic acids 213–14
acid chlorides see acyl chlorides 255–8 bond dissociation enthalpy
acid dissociation equations 104–5 preparation of aromatic amines (bond enthalpy) 6–7, 11, 16
acidic buffers 126 251–2 Born–Haber cycles 9–11
pH determination 127, 128–30 preparation of primary amines 250–1 calculations from 11–13
preparation of 127, 128–30 structure of 246–7 enthalpy changes 16–17
acidic oxides 140 amino acids 268–9 for metal with oxidation
acids 100 effect of pH changes 270 state +2 13–16
Brønsted–Lowry theory 101, 105 lysine 271–2 bromothymol blue 124
dilutions 115–17 optical isomerism 194 Brønsted–Lowry theory 101, 105
Ka 112–14 ammeters 83–4 buffers 125–6
neutralisations 118–20 ammonia 104, 245 acidic 126
phosphoric 144–5 production of 39–40 addition of acid 131
reactions with amines 253 ammonia solution, reaction with addition of base 131–2
strong and weak 101–3 hexaaqua complexes 166, 167, basic 127
sulfuric 145–6 168, 169–71 mechanism of action 126–7
see also carboxylic acids ammonium nitrate, enthalpy of preparation of 127, 128–30
activation energy, Arrhenius equation solution 21–2
52–4 amphoteric oxides 139 C
active sites 275 anode 80
acylation 223 calibration curves 56
anti-cancer drugs 284 carbon–carbon bond lengths 234
of benzene 240–1 see also cisplatin
use in drug manufacturing 228 carbon monoxide poisoning 158
antilogs 318–19 carbonyl group 199–200
acyl chlorides (acid chlorides) 199, 222 arithmetic mean 309
nucleophilic addition–elimination nucleophilic addition
aromatic compounds 233 reactions 209–11
reactions 226–8 amines 251–3
reaction with alcohols 224 see also acid anhydrides; acyl
13C NMR 299–300
reaction with amines 225–6 chlorides; aldehydes; amides;
see also benzene carboxylic acids; esters; ketones
reaction with ammonia 225 Arrhenius equation 52–4
reaction with water 224 carboxylic acid derivatives 222–3
aspirin, preparation of 228–30 carboxylic acids 199, 212
adenine 280 atomisation, enthalpy of 5–6, 16
adrenaline 245–6 acid reactions 214–15
autocatalysis 189 naming of 212–13
alcohols 198 321
physical properties 213–14
oxidation of 205 B salts of 214
aldehydes 199
naming of 200–1 bases 100, 103 testing for 215
nucleophilic addition amines 253–5 catalyst poisoning 188
reactions 209–11 Brønsted–Lowry theory 101, 105 catalysts 43, 186
oxidation of 204–5 dilutions 115–17 autocatalysis 189
physical properties 203–4 neutralisations 118–20 effect on rate of a reaction 53
preparation of 205 strong and weak 103–4 homogeneous catalysis 188–9
reaction with hydrogen cyanide 208 bases in DNA 280 recognition of 187–8
reduction of 206–7 basic buffers 127 use in industrial processes 186–7
structural isomerism 201 benzene catalytic converters 186

807701_Index_AQA_Chemistry_2_321-325.indd 321 13/06/15 9:29 am

 cathode 80 dihydrogenphosphate ion 145 in ligand substitution 156
cell notation 86 dilution factors 117 prediction of 31–2
cells 79–80, 90–1 dilutions of acids and bases 115–17 enzymes 274–5
conventions 82 diprotic acids 102 effect of temperature and pH 276
electromotive force (EMF) 83 d-isomers 161, 196 mode of action 275
fuel cells 94–6 displayed formulae 198 equations, changing the subject of 309–10
non-rechargeable 91–2 DNA (deoxyribonucleic acid) 279 equilibrium 68
rechargeable 92–4 components of 279–81 Ka 112–15
silver cell investigation 90 replication of 284 Kc 68, 312–13
use of ammeters 83–4 short form of 283 Kp 71–6
changes in state structure of 281–3 redox reactions 79–80
entropy values 28–31 doublets, NMR 295–6 equivalence points 121
and Gibbs free energy 35–7 drugs 228–9 esters 199, 216
charge aspirin 228–30 biodiesel 221
of complex ions 157 and optical isomerism 196 hydrolysis of 219
effect on lattice enthalpy 17 paracetamol 258 naming of 216–17
chelate effect 156 thalidomide 276 preparation of 217, 218, 224
chelates 154 dynamic equilibrium 68 uses of 217–18
chemical shift 292–3 vegetable oils and fats 219–20
chiral (asymmetric) centres 194 E estimating results 312–13
chromatography 301–2 EDTA (ethylenediaminetetraacetic ethanoic acid 102–3
column 303–4 acid) 153–4 ethanol fuel cells 94–6
gas 305–6 electrochemical cells see cells E-Z isomerism, complex ions 160
thin-layer 302 electrode potentials 81–2
cisplatin 159, 160, 284 silver cell investigation 90 F
cis-trans isomerism, complex ions 160 electromagnetic spectrum 162 fatty acids 220
13C NMR 298–300
electromotive force (EMF) 83, 178 feasibility of reactions 27, 32–4
colorimetry 56–7, 164–5 determination from standard electrode influencing factors 34–5
coloured ions, transition metals 161–3 potentials 86–9 redox reactions 84–5, 87–8
column chromatography (CC) 302, 303–4 and feasibility of reactions 84–5 reduction of vanadium 178–9
combustion, enthalpy change of 1 electron affinity 8, 16 Fehling’s solution 206
complex formation, transition electronic configuration, of transition fibrous proteins 274
metals 151–4 metals 150 first ionisation enthalpy 7, 16
complex ions electrophilic substitution first order reactions
charge and oxidation number 157 acylation of benzene 240–1 concentration against time graphs 60
detection of 157 mechanism of 238–9 rate against concentration graphs 59
haem and haemoglobin 157–8 nitration of benzene 239–40 fluoroantimonic acid 101
ligand substitution 154–7 enantiomers 192 formation, enthalpy of 1, 4–5
notation 151–2 endothermic reactions, feasible Friedel–Crafts reactions 240–1
shapes of 158–9 reactions 27 fuel cells 94–6
stereoisomerism 160–1 end point of a titration 124 functional group isomerism, aldehydes
concentration, effect on rate of a energy changes, transition metal and ketones 203
reaction 45 ions 163–4 functional groups 198
concentration against time graphs enthalpy changes 1 carbonyl group 199
59–61 of atomisation 5–6
condensation polymerisation 262–4 bond dissociation enthalpy G
INDEX

Contact process 186, 187 (bond enthalpy) 6–7 gas chromatography (gas–liquid
continuous rate monitoring 59–60 of formation 4–5 chromatography) 302, 305–6
by colorimetry 57 of hydration 19–21 gases
by titration 58 of hydrogenation 234 entropy values 29
322 coordination numbers 152–3 ionic compounds 2–3 volume measurement 55
copper(ii) compounds, hexaaquacopper(ii) ionisation enthalpies 7–8 gas syringes 55
complex 168–9 of lattice dissociation 3 Gibbs free energy 32–4
covalent compounds, ionic character 18 of lattice formation 3 graphical calculations 38
curly arrows 209 in ligand substitution 155–6 and physical changes 35–7
cytosine 280 of solution 19–20, 21–2 and production of ammonia 39–40
see also Born–Haber cycles
D enthalpy profiles 3
globular proteins 274
glycerol (propane-1,2,3-triol) 220, 221
d block elements 150 entropy 27 gradient of a graph 314–16
see also transition metals entropy changes graphs 313–16
delocalised model, benzene 235–6 calculation of 29–31 guanine 280
2-deoxyribose 279–80 and changes of state 28–9

807701_Index_AQA_Chemistry_2_321-325.indd 322 13/06/15 9:29 am

 H ionic product of water 108–9
calculation of 111
M

Index
Haber process 39–40, 186 ionisation enthalpies 7–8, 16 macromolecular substances
haem and haemoglobin 157–8 ions, identification of 172 entropy values 28
half cells 79 hexaaqua cations 171 silicon dioxide 140
halide ions ion size, effect on lattice enthalpy 17 magnesium, reaction with water 136
enthalpy of hydration 20–1 iron(ii) compounds, hexaaquairon magnesium chloride, Born–Haber
test for 135 complex 167–8, 171 cycle 13–15
halogenoalkanes 245 iron(iii) compounds, hexaaquairon(iii) magnesium oxide 138
preparation of amines 250–1, 255–7 complex 169–70, 171 Born–Haber cycle 15–16
Hess’s law 1 iron(ii) ions, as a reducing agent 181, magnetic resonance imaging (MRI) 298
heterogeneous catalysts 186 182–3 manganate(vii) ions 179–80
catalyst poisoning 188 isomerism reaction with ethanedioate ions 189
hexaaquaaluminium(iii) complex 170–1 complex ions 160–1 mass, measurement of changes in 55
hexaaqua cations 151 see also optical isomerism mass spectrometry 287
acidity of 166–7 Maxwell–Boltzmann distributions 43
identification of 166 K mean bond enthalpy 1
hexaaquacopper(ii) complex 168–9, 171 mechanisms of reactions
hexaaquairon(ii) complex 167–8, 171 Ka 112–13 electrophilic substitution 238–9
hexaaquairon(iii) complex 169–70, 171 calculation of 115 link to order of a reactant 63–5
hexadentate ligands 153 Kc 68, 312–13 nucleophilic addition–elimination
high-resistance voltmeter 80 Kekulé, Friedrich 234 reactions 226–8
1H NMR 293–8 ketones 199 nucleophilic addition
homogeneous catalysts 186, 188–9 naming of 201–2 reactions 209–11
homogeneous equilibrium 68 nucleophilic addition reactions nucleophilic substitution
homologous series 198 209–11 reactions 257–8
hydration, enthalpy of 19–21 oxidation of 204 melting, entropy changes 28–9
hydrochloric acid 102 physical properties 203–4 melting points
hydrogen, production of 187 positional isomerism 202–3 checking the purity of a solid 229
hydrogenation of alkenes 186 reaction with hydrogen cyanide 208 of oxides of Period 3 elements 137–44
hydrogen bonding reduction of 206–7 metallic substances, entropy values 28
and boiling points 203, 213 testing for 206 metal oxides 137–9
in DNA 281–3 Kevlar 263 methanoic acid, reaction with sodium
in proteins 272–4 Kp 71 hydroxide 125
and solubility in water 204, 213 calculating total pressure 75 methanol fuel cells 96
hydrogen cyanide, reaction with calculation of 71–3 methyl 3-nitrobenzoate, preparation
aldehydes and ketones 208 effects of changes in temperature and of 242
hydrogen fuel cells 94–5 other factors 75–6 methyl orange 124
hydrogen ion concentration, calculation use in calculations 73–4 methyl red 124
of pH 106 mobile phases, chromatography 302
hydrogen peroxide, decomposition of L Mohr’s salt 185
188 lattice enthalpy 3–4, 16–17 molecular compounds, entropy
hydrogenphosphate ion 145 and the perfect ionic model 18 values 28
hydrogensulfate ion 146 lead-acid cells 93 mole fractions 69
hydrolysis of esters 219, 220 Le Chatelier’s Principle 68 monodentate ligands 152
hydroxynitriles 208 ligands 151 monoprotic acids 102, 103
coordination numbers 152–3 multidentate ligands 153
I ligand substitution chelates 154
indicators with a change in coordination number
for titrations 124 155 N
universal indicator 107 enthalpy and entropy considerations n+1 rule, NMR 295
155–6 323
indices, laws of 311–12 neutralisations 118–20
infrared spectroscopy 287 with no change in coordination see also acid–base titrations
initial rate monitoring 55–6, 58–9 number 154–5 nickel-cadmium cells 92–3
by colorimetry 57 linear complex ions 159 nitration of benzene 239–40
l-isomers 161, 195–6
by titration 58 nitriles, reduction of 251
integration ratio, NMR 295 lithium ion cells 93–4 non-metal oxides 140–3
ionic compounds lithium oxide 137 non-rechargeable cells 91–2
entropy values 28 logarithmic scales 320 nuclear magnetic resonance
perfect ionic model 18 logarithms (logs) 316–19 spectroscopy (NMR) 292
lysine 271–2

807701_Index_AQA_Chemistry_2_321-325.indd 323 13/06/15 9:29 am

 R
1H
NMR 293–8 Period 3 elements
13C
NMR 298–300 acids and anions 144–6
chemical shift 292–3 oxides of 137–44 racemic mixtures (racemates) 196,
peak integration 295 reactions with water 136 210–11
spin-spin splitting patterns 295–6 Periodic Table 135 rate against concentration
nucleophiles 209 peroxodisulfate ions, reaction with iodide graphs 59, 61
nucleophilic addition–elimination ions 188–9 rate constant 44
reactions 226–8 pH 100, 105–6 Arrhenius equation 52–4
nucleophilic addition reactions 209–11 calculation from hydrogen ion determination of 49–51
nucleophilic substitution concentration 106 effect of temperature 52
reactions 250, 255–7 determination of concentration of an units of 45
mechanism of 257–8 acid 107–8 rate-determining step 64–5
nucleotides 281 determination of the concentration of rate equations 44–5
nylon 262–3 a base 111 deducing and using orders of
dilutions of acids and bases 115–17 reaction 46–9
O effect on enzyme activity 276 determination of the rate
of strong acids 106–7 constant 49–51
octahedral complex ions 158–9 rate of a reaction 43–4
cis-trans isomerism 160–1 of strong bases 109–10
of water 108–9 continuous rate monitoring 59–60
optical isomerism 161 initial rate monitoring 58–9
optical isomerism 192–4, 210–11 of weak acids 112–14
phenolphthalein 124 measurement of 54–8
octahedral complexes 161 reactivity series 87–8
thalidomide 276 phenylamine, preparation of 251–2
phenyl group 237 rechargeable cells 92–4
optically active substances 195–6 recrystallisation technique 229
optically inactive mixtures 196 pH meters 116
pH monitoring 58 recycling 266
orders of reaction 44 redox equilibria 79–80
concentration against time graphs phosphate ion 145
phosphoric acid 144–5 redox potentials, reduction of
60–1 vanadium 178
deduction and use of 46–9 phosphorus(v) oxide 141–2
pKa 114 redox reactions 78–9
link to mechanism of a reaction 63–5 feasibility of 84–5, 87–8
rate against concentration graphs 59 pKw 111–12
plane polarised light, rotation of 195–6 of vanadium 177–9
required practical 62 redox titrations 180–1
and units of rate constant 45 pOH 112
polyamides 262–3 examples 182–4
organic reactions, summary of 288–90 Mohr’s salt 185
organic synthesis 287–8 polyesters 262
poly(ethylene terephthalate) (PET) 262 reducing agents 181–2
examples 291–2 refractory materials 16
Ostwald, Wilhelm 44 polymers 261
biodegradability 265–6 retention time, gas chromatography 305
oxalate ions (ethanedioate ions), as a ribose 279
reducing agent 181, 184 condensation polymerisation 262–4
positional isomerism, ketones 202–3
oxidation 78
oxidation numbers, of complex ions 157 potassium fluoride, Born-Haber S
oxidation states 78 cycle 11 salt bridges 79–80
of transition metals 175–6 potassium manganate(vii), redox salts 100
oxides of Period 3 elements titrations 180–1, 184 sampling, measuring the rate of a
aluminium oxide 139 primary amines 246, 247, 248 reaction 57
magnesium oxide 138 preparation of 250–1, 255–6 saponification 219, 220
melting points 144 primary structure of proteins 267–8 saturated fatty acids 220
INDEX

phosphorus(v) oxide 141–2 proteins 267 secondary amines 246, 248

reactions with water 144 enzymes 274–6 preparation of 256
silicon dioxide 140–1 fibrous and globular 274 secondary structure of proteins 267,
sodium oxide 137 hydrolysis of 277 272–3
sulfur oxides 142–3 primary structure of 267–8 second ionisation enthalpy 7, 16
324
oxyacids 144–6 secondary structure of 272–3 second order reactions
tertiary structure of 273–4 concentration against time graphs 61
P proticity of acids 106 rate against concentration graphs 59
purity of a solid, checking for 229 serotonin 245–6
paracetamol 258 shapes of complex ions 158–9
partial pressure 70
Kp 71–6
Q significant figures 309
quartets, NMR 296 silicon dioxide 140–1
peak integration, NMR 295 melting point 144
percentage error 309 quaternary ammonium salts 247
preparation of 256, 258 silver fluoride, Born–Haber cycle 12
perfect ionic model 18 skeletal formulae 198
perfumes 199 uses of 257
quenching 57

807701_Index_AQA_Chemistry_2_321-325.indd 324 13/06/15 9:29 am

 soaps 219, 221 strong bases 103–4 coloured ions 161–5
sodium determination of concentration from complex formation 151–4

Index
combustion of 137 pH 111 general properties of 150
reaction with water 136 pH 109–10 oxidation states 175–6
sodium carbonate solution, reaction with structural formulae 198 see also complex ions; vanadium
hexaaqua complexes 166, 168, 169, structural isomerism, aldehydes 201 triglycerides 220
170, 171 sulfate ions 143, 146 triplets, NMR 296
sodium chloride test for 135
Born–Haber cycle 10 sulfur, combustion of 143 U
enthalpy of solution 19–20 sulfur dioxide, reduction of universal indicator 107
sodium hydroxide 103–4 vanadium 179 unsaturated fatty acids 220
determination of enthalpy of sulfuric acid 102, 145–6 urea 278
solution 21–2 Contact process 186, 187
reaction with hexaaqua complexes sulfur oxides 142–3 V
166, 167, 168, 169, 170
reaction with methanoic acid 125 T vanadium
oxidation states 176
sodium oxide 137 tangents to a curve 315–16 redox reactions 177–9
sodium tetrahydridoborate(iii) 206, 207 temperature variables 309
solubility in water effect on enzyme activity 276 visible spectrum 162
aldehydes and ketones 204 effect on Kp 75–6
carboxylic acids 213
solution, enthalpy of 19–22
effect on rate constant 52–3 W
tertiary amines 246, 249
spectroscopy 165, 287 waste disposal 265–6
preparation of 256
NMR 292–300 water
tertiary structure of proteins 267, 273–4
spin-spin splitting patterns, NMR 295–6 ionic product of 108–9
tetrahedral shape, complex ions 159
spontaneous reactions 33 pH of 108–9
tetramethylsilane (TMS) 293
square planar complex ions 159 reaction with oxides of Period 3
thalidomide 276
standard electrode potentials 81–2 elements 144
thin-layer chromatography (TLC) 302
and feasibility of reactions 84–5 reaction with Period 3 elements 136
third ionisation enthalpy 7
standard form 309 see also solubility in water
thymine 280
standard hydrogen electrode 81 weak acids 102–3
thymol blue 124
stationary phases, chromatography 302 pH 112–14
titration curves 121–3
stereoisomerism 192 weak bases 104
titrations
complex ions 160–1 Woodward, Robert Burns 287
acid–base 121–5
see also optical isomerism measuring the rate of a reaction 57–8
straight line, equation of 38 redox 180–1
Z
straight line graphs 313–15 Tollen’s reagent 159, 179, 206 zero order reactions
strong acids 101–2 total pressure, Kp calculations 75 concentration against time graphs 60
determination of concentration from trans-esterification 221 rate against concentration graphs 59
pH 107–8 transition metals 149 zinc, reduction of vanadium 178
pH 106–7 catalytic activity 186–9 zwitterion structure, amino acids 268

325

807701_Index_AQA_Chemistry_2_321-325.indd 325 13/06/15 9:29 am

 Free online resources
Answers for the following features found in this book are available online:
● Test yourself questions
● Activities
You’ll also find Practical skills sheets and Data sheets. Additionally there is
an Extended glossary to help you learn the key terms and formulae you’ll
need in your exam.
Scan the QR codes below for each chapter.
Alternatively, you can browse through all chapters at
www.hoddereducation.co.uk/AQAChemistry2

How to use the QR codes

To use the QR codes you will need a QR code reader for your
smartphone/tablet. There are many free readers available, depending
on the smartphone/tablet you are using. We have supplied some
suggestions below, but this is not an exhaustive list and you should only
download software compatible with your device and operating system.
We do not endorse any of the third-party products listed below and
downloading them is at your own risk.
● for iPhone/iPad, search the App store for Qrafter
● for Android, search the Play store for QR Droid
● for Blackberry, search Blackberry World for QR Scanner Pro
● for Windows/Symbian, search the Store for Upcode
Once you have downloaded a QR code reader, simply open the reader app
and use it to take a photo of the code. You will then see a menu of the free
resources available for that topic.

1 Thermodynamics: 4 Equilibrium constant

Born-Haber cycles Kpfor homogeneous
systems

2 Thermodynamics: 5 Electrode potentials

Gibbs free energy change, and cells
326 ΔG, and entropy change, ΔS

3 Rate equations 6 Acids and bases

807732_FOM_AQA_Chemistry_2__BM_326-327.indd 326 16/06/2015 17:20

 7 Properties of Period 3 13 Amines
elements and their oxides

Free online resources

8 Transition metals 14 Polymers, amino
acids and DNA

9 Transition metals: 15 Organic synthesis,

Variable oxidation states NMR spectroscopy and
chromatography

10 Optical isomerism 16 Maths for chemistry

11 The carbonyl group 17 Practical skills

12 Aromatic chemistry 18 Preparing for the

examination

327

807732_FOM_AQA_Chemistry_2__BM_326-327.indd 327 13/06/15 9:31 am