Bylikin S., Horner G., Grant E.J., Tarcy D. - Oxford Resources For IB DP Chemistry - Course Book-Oxford University Press (2023)

Oxford Resources for IB
Diploma Programme
2 0 2 3 E D I T I O N
C H E M I S T RY
CO U R S E CO M PA N I O N
Sergey Bylikin
Gary Horner
Elisa Jimenez Grant
D avid Tarcy
Oxford Resources for IB
Diploma Programme
2 0 2 3 E D I T I O N
C H E M I ST RY
CO U R S E CO M PA N I O N
Sergey Bylikin
Gary Horner
Elisa Jimenez Grant
D avid Tarcy
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The authors have the following acknowledgements and thanks:

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Sergey Bylikin: I would like to thank Dr Natalia K alashnikova for her support and
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suggestions.
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Gary Horner: To my friends and colleagues for their support throughout my
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teaching c areer, my sister Susan for her unwavering friendship, c are and profes-
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sional advice, my inspirational parents Myrtle and Dennis: I dedic ate this book in
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their loving memory.
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Contents
Structure 1. Models of the particulate nature of matter 2
Structure 1.1
Structure 1.2
Structure 1.3
Structure 1.4
Structure 1.5
Structure 2. Models of bonding and structure 94
Structure 2.1
Structure 2.2
Structure 2.3
Structure 2.4
Structure 3. Classic ation of matter 228
Structure 3.1
Structure 3.2
Tools for chemistry 308
Tool 1:
Tool 2:
Tool 3:
Reactivity 1. What drives chemic al reactions? 386
Reactivity 1.1
Reactivity 1.2
Reactivity 1.3
Reactivity 1.4
Reactivity 2. How much, how fast and how far? 460
Reactivity 2.1
Reactivity 2.2
Reactivity 2.3
Reactivity 3. What are the mechanisms of chemic al change? 536
Reactivity 3.1
Reactivity 3.2
Reactivity 3.3
Reactivity 3.4
Cross-topic exam-style questions 652
The inquiry process (authored by Maria Muñiz Valcárcel) 655
The internal assessment (IA) (authored by Maria Muñiz Valcárcel) 668
Index 686
Periodic Table 708
Answers: www.oxfordsecondary.com/ib-science-support
iii
Introduction
The diploma programme (DP) chemistry course is aimed at students in the 16
to 19 age group. The curriculum seeks to develop a conceptual understanding
of the nature of science, working knowledge of fundamental principles of
chemistry and practic al skills that c an be applied in familiar and unfamiliar
contexts. As with all the components of the DP, this course fosters the IB learner
prole attributes (see page viii) in the members of the school community.
Nature of science
Nature of science (NOS) is concerned with methods, • F alsication
purposes and outcomes that are specic to science. Hypotheses c an be proved false using other
NOS is a central theme that is present across the evidence, but they c annot be proved to be
entire course. You will nd suggested NOS features denitely true. This has led to paradigm shis in
throughout the book and are encouraged to come up science throughout history.
with further examples of your own as you work through
• Models
the programme.
Scientists construct models as simplied
NOS c an be organized into the following eleven explanations of their observations. Models oen
aspects: contain assumptions or unrealistic simplic ations,
but the aim of science is to increase the complexity
• Observations and experiments
of the model, and to reduce its limitations.
Sometimes the observations in experiments are
unexpected and lead to serendipitous results. • Theories
A theory is a broad explanation that takes observed
• Measurements
patterns and hypotheses and uses them to generate
Measurements c an be qualitative or quantitative,
predictions. These predictions may conrm a
but all data are prone to error. It is important to
theory (within observable limitations) or may falsify
know the limitations of your data.
it.
• Evidence
• Science as a shared activity
Scientists learn to be sceptic al about their
Scientic activities are oen c arried out in
observations and they require their knowledge to
collaboration, such as peer review of work before
be fully supported by evidence.
public ation or agreement on a convention for clear
• Patterns and trends

communic ation.
Recognition of a pattern or trend forms an
• Global impact of science
important part of the scientist’s work whatever the
Scientists are responsible to society for the
science.
consequences of their work, whether ethic al,
• Hypotheses
environmental, economic or social. Scientic
Patterns lead to a possible explanation. The

knowledge must be shared with the public clearly
hypothesis is this provisional view and it requires

and fairly.
further veric ation.
iv
Syllabus structure
Topics are organized into two main concepts: structure and reactivity. This is shown in the syllabus roadmap
below. The skills in the study of chemistry are overarching experimental, technologic al, mathematic al and inquiry
skills that are integrated into the course. Chemistry is a practic al subject, so these skills will be developed through
experimental work, inquiries and investigations.
Skills in the study of chemistry
Structure Reactivity
Structure refers to the nature of matter Reactivity refers to how and why
from simple to more complex forms chemic al reactions occur
Structure determines reactivity, which in turn transforms structure
Structure 1. Structure 1.1 — Introduction to Reactivity 1. Reactivity 1.1 — Measuring
Models of the the particulate nature of matter What drives enthalpy changes
particulate nature chemic al

Structure 1.2 — The nuclear atom Reactivity 1.2 — Energy cycles in
of matter reactions?
reactions
Structure 1.3 — Electron Reactivity 1.3 — Energy from fuels
congurations
Structure 1.4 — Counting Reactivity 1.4 — Entropy and
particles by mass: The mole spontaneity (Additional higher
level)
Structure 1.5 — Ideal gases
Structure 2. Structure 2.1 — The ionic model Reactivity 2. Reactivity 2.1 — How much? The
Models of How much, amount of chemic al change
bonding and how fast and

Structure 2.2 — The covalent Reactivity 2.2 — How fast? The
structure how far?

model rate of chemic al change
Structure 2.3 — The metallic Reactivity 2.3 — How far? The
model extent of chemic al change
Structure 2.4 — From models to
materials
Structure 3. Structure 3.1 — The periodic Reactivity 3. Reactivity 3.1 — Proton transfer
Classic ation of table: Classic ation of elements What are the reactions
matter mechanisms
Reactivity 3.2 — Electron transfer
of chemic al
reactions
change?
Structure 3.2 — Functional Reactivity 3.3 — Electron sharing
groups: Classic ation of organic reactions
compounds
Reactivity 3.4 — Electron-pair
sharing reactions
Chemistry concepts are thoroughly interlinked. For example, as shown in the
roadmap above, “Structure determines reactivity, which in turn transforms structure”.
You are therefore encouraged to continuously reect on the connections between
new and prior knowledge as you progress through the course. Linking questions will
help you explore those connections. In assessment tasks, you will be expected to
identify and apply the links between dierent topics. On page 652, there are three
examples of DP-style exam questions that link several dierent topics in the course.
v
How to use this book
The aim of this book is to develop conceptual understanding, aid in skills
development and provide opportunities to cement knowledge and
understanding through practice.
Feature boxes and sections throughout the book are designed to support these
aims, by signposting content relating to particular ideas and concepts, as well as
opportunities for practice. This is an overview of these features:
Developing conceptual understanding
These boxes in the
Guiding questions
margin will direct you
to other parts of the
Each topic begins with a guiding question to get you thinking. When you
book where a concept
start studying a topic, you might not be able to answer these questions
is explored further or in
condently or fully, but by studying that topic, you will be able to answer
a dierent context. They
them with increasing depth. Hence, you should consider these as you work
may also direct you to
through the topic and come back to them when you revise your
prior knowledge or a skill
understanding.
you will need, or give
a dierent way to think
Linking questions
about something.
Linking questions within each topic highlight the connections between
content discussed there and other parts of the course.
Nature of science
These illustrate NOS using issues from both modern science and science
history, and show how the ways of doing science have evolved over the
centuries. There is a detailed description of what is meant by NOS and the
dierent aspects of NOS on the previous page. The headings of NOS feature
boxes show which of the eleven aspects they highlight.
Theory of knowledge
This is an important part of the IB Diploma course. It focuses on critic al
thinking and understanding how we arrive at our knowledge of the world.
The TOK features in this book pose questions for you that highlight these
issues.
Parts of the book have a coloured bar on the edge of the page or next to a
LHA
question. This indic ates that the material is for students studying at DP
Chemistry Higher Level. AHL means “additional higher level”.
vi
Developing skills
ATL Approaches to learning Chemistry skills
These ATL features give examples of how famous These contain ways to develop your mathematic al,
scientists have demonstrated the ATL skills of experimental or inquiry skills, especially through
communic ation, self-management, research, experiments and practic al work. Some of these
thinking and social skills, and prompt you to think c an be used as springboards for your Internal
about how to develop your own strategies. Assessment.
To o l s for c h e m i s t r y, the inquiry p r o c e ss and internal a ss e ss m e n t
These three section of the book are full of reference material for all the essential mathematic al and
experimental tools required for DP Chemistry, details on data analysis and modelling chemistry, as
well as guidance on how to use the inquiry process in the study of the subject and to work through
your Internal Assessment. Flick to this section as your working through the rest of the book for
more information. Links in the margin throughout the book will direct you towards it too.
Practicing
Worked examples Practice questions
These are step-by-step examples of how to answer
These are designed to give you further practice at
questions or how to complete c alculations. You
using your chemistry knowledge and to allow you to
should review these examples c arefully, preferably
check your own understanding and progress.
aer attempting the question yourself.
Data-based questions Activity
Part of your nal assessment requires you to answer questions that are based These give you an
on the interpretation of data. Use these questions to prepare for this. They opportunity to apply
are also designed to make you aware of the possibilities for data acquisition your chemistry
and analysis for day-to-day experiments and for your IA. knowledge and skills,
oen in a practic al way.
End-of-topic questions
Use these questions at the end of each topic to draw together concepts from that topic and to practise
answering exam-style questions.
vii
Course book denition The IB Learner Prole
The IB Diploma Programme course books are resource The aim of all IB programmes to develop internationally
materials designed to support students throughout minded people who work to create a better and
their two-year Diploma Programme course of study more peaceful world. The aim of the programme is to
in a particular subject. They will help students gain an develop this person through ten learner attributes, as
understanding of what is expected from the study of described below.
an IB Diploma Programme subject while presenting
Inquirers: They develop their natural curiosity. They
content in a way that illustrates the purpose and aims
acquire the skills necessary to conduct inquiry and
of the IB. They reect the philosophy and approach of
research and snow independence in learning. They
the IB and encourage a deep understanding of each
actively enjoy learning and this love of learning will be
subject by making connections to wider issues and
sustained throughout their lives.
providing opportunities for critic al thinking.
Knowledgeable: They explore concepts, ideas and
The books mirror the IB philosophy of viewing the
issues that have loc al and global signic ance. In so
curriculum in terms of a whole-course approach;
doing, they acquire in-depth knowledge and develop
the use of a wide range of resources, international
understanding across a broad and balanced range of
mindedness, the IB learner prole and the IB Diploma
disciplines.
Programme core requirements, theory of knowledge,
the extended essay, and creativity, activity, service

Thinkers: They exercise initiative in applying thinking
(CAS).
skills critic ally and creatively to recognize and approach
complex problems, and to make reasoned, ethic al
E ach book c an be used in conjunction with other
decisions.
materials and, indeed, students of the IB are required
and encouraged to draw conclusions from a variety

Communic ators: They understand and express
of resources. Suggestions for additional and further

ideas and information condently and creatively in
reading are given in each book and suggestions for

more than one language and in a variety of modes of
how to extend research are provided.

communic ation. They work eectively and willingly in
collaboration with others.
In addition, the course companions provide advice
and guidance on the specic course assessment

Principled: They act with integrity and honesty, with
requirements and on ac ademic honesty protocol.

a strong sense of fairness, justice and respect for the
They are distinctive and authoritative without being

dignity of the individual, groups and communities.
prescriptive.
They take responsibility for their own action and the
consequences that accompany them.
Open-minded: They understand and appreciate their
IB mission statement
own cultures and personal histories, and are open
The International Bacc alaureate aims to develop

to the perspectives, values and traditions of other
inquiring, knowledgeable and c aring young people

individuals and communities. They are accustomed to
who help to create a better and more peaceful world

seeking and evaluating a range of points of view, and
through intercultural understanding and respect.

are willing to grow from the experience.
To this end, the organization works with schools,

C aring: They show empathy, compassion and respect
governments and international organizations to

towards the needs and feelings of others. They have
develop challenging programmes of international

a personal commitment to service, and to act to make
educ ation and rigorous assessment.

a positive dierence to the lives of others and to the
environment.
These programmes encourage students across the
world to become active, compassionate and lifelong
learners who understand that other people, with their
dierences, c an also be right.
viii
Risk-takers: They approach unfamiliar situations and ‘Formal’ means that you should use one of the several
uncertainty with courage and forethought, and have accepted forms of presentation. This usually involves
the independence of spirit to explore new roles, separating the resources that you use into dierent
ideas and strategies. They are brave and articulate in c ategories (e.g. books, magazines, newspaper
defending their beliefs. articles, internet-based resources, and works of art)
and providing full information as to how a reader or
Balanced: They understand the importance of
viewer of your work c an nd the same information. A
intellectual, physic al and emotional ballance to achieve
bibliography is compulsory in the Extended Essay.
personal wellbeing for themselves and others.
What constitutes malpractice?
Reective: They give thoughtful consideration to their
M alpractice is behaviour that results in, or may result in,
own learning and experience. They are able to assess
you or any student gaining an unfair advantage in one
and understand their strengths and limitations in order
or more assessment component. M alpractice includes
to support their learning and personal development.
plagiarism and collusion.
Plagiarism is dened as the representation of the ideas
or work of another person as your own. The following
A note on ac ademic
are some of the ways to avoid plagiarism:
integrity
●
words and ideas of another person to support one’s
arguments must be acknowledged

It is of vital importance to acknowledge and
appropriately credit the owners of information when
●
passages that are quoted verbatim must
that information is used in your work. Aer all, owners
be enclosed within quotation marks and
of ideas (intellectual property) have property rights.
acknowledged
To have an authentic piece of work, it must be based
on your individual and original ideas with the work of

●
email messages, and any other electronic media
others fully acknowledged. Therefore, all assignments,

must be treated in the same way as books and
written or oral, completed for assessment must use your

journals
own language and expression. Where sources are used
●
the sources of all photographs, maps, illustrations,
or referred to, whether in the form of direct quotation
computer programs, data, graphs, audio-visual and

or paraphrase, such sources must be appropriately
similar material must be acknowledged if they are

acknowledged.
not your own work
●
when referring to works of art, whether music, lm
How do I acknowledge the work of

dance, theatre arts or visual arts and where the
others? creative use of a part of a work takes place, the
The way that you acknowledge that you have used the original artist must be acknowledged.
ideas of other people is through the use of footnotes
Collusion is dened as supporting malpractice by
and bibliographies.
another student. This includes:
Footnotes (placed at the bottom of a page) or endnotes

●
allowing your work to be copied or submitted for
(placed at the end of a document) are to be provided

assessment by another student
when you quote or paraphrase from another document
●
duplic ating work for dierent assessment
or closely summarize the information provided in
components and/or diploma requirements.

another document. You do not need to provide a
footnote for information that is part of a ‘body of

Other forms of malpractice include any action that gives
knowledge’. That is, denitions do not need to be

you an unfair advantage or aects the results of another
footnoted as they are part of the assumed knowledge.

student. Examples include, taking unauthorized
material into an examination room, misconduct during
Bibliographies should include a formal list of the
an examination and falsifying a CAS record.
resources that you used in your work.
ix
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xi
Structure 1
Models of the particulate
nature of m a tt e r
Structure 1.1 Introduction to the
particulate nature
of matter
How c an we model the particulate nature of matter?
The universally accepted idea that all matter is composed of
atoms came from experimental evidence that could only be
explained if matter were made of particles.
Early classical theory suggested that all matter was composed
of earth, air, re, and water. However, this theory lacked
predictive power and could not account for the great variety
of chemical compounds, so it was eventually abandoned.
The systematic study of chemical changes led to the
discovery of many chemical elements that could not be
broken down into simpler substances. The fact that these
elements could only combine with one another in xed
proportions suggested the existence of atoms. It was this

 Figure 1 In 2021, scientists at Cornell University c aptured the
way of processing knowledge through observation and most detailed picture of atoms to date. What do models show us that
experimentation which led to the modern atomic theory microscope images c annot?
Understandings
Structure 1.1.1 — Elements are the primary constituents Structure 1.1.2 — The kinetic molecular theory is a model
of matter, which c annot be chemic ally broken down into to explain physic al properties of matter (solids, liquids,
simpler substances. and gases) and changes of state.
Compounds consist of atoms of dierent elements Structure 1.1.3 — Temperature (in K) is a measure of
chemic ally bonded together in a xed ratio. average kinetic energy (E ) of particles.
k
Mixtures contain more than one element or compound
in no xed ratio, which are not chemic ally bonded and
so c an be separated by physic al methods.
The composition of matter (Structure 1.1.1)
M atter and energy
C h e mi s t r y is th e study of matt e r and its c o mp o s i t i o n . M a tte r is e ve r y w he re.
We a re made up of ma tte r, we c o n s u me i t, it s u r ro u n ds us, and we c an see
and touch m a ny fo r m s of ma tt e r. Air is a fo r m of ma tte r th a t we kn ow is t he re,
th o u g h we c annot see i t. The u n i ve rs e is made of m a tt e r and c he mi s tr y seeks
to ex pa n d our u n de rs t a n di n g of ma tte r and its pro pe r t i e s . The characteristics
of matter are shown in gure 2.
In contrast, energy is anything that exists but does not have these properties.
M atter and energy are closely associated with each other, and energy is oen
considered as a property of matter, such as the ability to perform work or
produce heat.
3
Structure 1 Models of the particulate nature of matter
Although mass and energy c an be converted into one another (for example, in
Chemic al reactions are introduced
nuclear reactors or inside stars), chemistry studies only those transformations of
in Reactivity 1.1.
matter where both mass and energy are conserved. In chemic al reactions, the
products have the same mass as starting materials, and the energy is transformed
from one form to another rather than created or destroyed.
made up of
particles –
atoms,
molecules,
or ions
u Figure 2 The characteristics of matter
particles are occupies a
in constant MATTER volume in
motion space
has a mass
ATL Thinking skills
The famous Einstein equation, E = mc , shows that mass (m) and energy
(E) are interconvertible. However, the energy released or absorbed in
chemic al reactions is relatively small while the speed of light (c) is very large
8 –1
(3.00 × 10 m s ). As a result, the loss or gain in mass c aused by chemic al
changes is negligible.
This example demonstrates the importance of approximation in science: if
the eect of a certain factor is minor, it c an oen be ignored in c alculations
without compromising the nal result.
What other examples of negligible eects have you encountered
inchemistry?
4
Structure 1.1 Introduction to the particulate nature of matter
The atomic theory
The law of conservation of mass and the observation that certain substances
always combine in denite proportions led to the idea that matter was composed
of elements. It was theorized that elements combined to form other substances
but could not be broken down chemic ally. Hydrogen and oxygen c an react to
form water, and experiments showed that the mass of hydrogen and oxygen
consumed equalled the mass of water formed. Other experiments showed that
1.0 g of c arbon would react with 1.33 g of oxygen through combustion to form
c arbon monoxide, and with 2.66 g of oxygen to form c arbon dioxide.
It was proposed that elements, such as hydrogen, oxygen or carbon, are the
The internal structure and
primary constituents of matter, and they cannot be chemically broken down into
characteristics of atoms will be
simpler substances. The idea of denite proportions suggested that particles of one
discussed in Structure 1.2
element, called atoms, would combine with atoms of another element in a xed,
simple ratio, and that atoms of one element have a dierent mass than atoms of a
dierent element. This, and other experimental evidence, led to the atomic theory.
The atomic theory states that all matter is composed of atoms. These atoms
c annot be created or destroyed, but they are rearranged during chemic al
reactions. Physic al and chemic al properties of matter depend on the bonding
and arrangement of these atoms.
Evidence
Ancie nt atomists, among them the In dian s age
Uddāl ak a Ā runi and the Gre ek philos ophers
Democ ritus and Leuci ppus, re a sone d that matte r
w as made up of tiny, indi visible pa rticl es. They
postu late d that chan ges in the natu ra l wor ld are due to
interactions betwe en these parti cles.
In 8th century BCE, Āruni proposed that “particles too
small to be seen mass together into the substances and
objects of experience”. He c alled the particles “kana”.
Similarly, in 5th century BCE, Democritus is said to have
observed that one could successively snap a seashell
into increasingly smaller parts until producing powder
composed of indivisible units, known as “atomos”, “not
splittable”, that could not be broken any further.
The next stage in the development of atomic theory, over
2000 years later, is credited to John D alton. D alton drew
from mass conservation experiments to propose that
atoms could be classied into dierent types known as
“elements”, based on their masses.
Scientic knowledge must be supported by veriable
evidence. What evidence was used to develop these
atomic theories? What is evidence? Is evidence shaped
 Figure 3 Top: Āruni lived in what is now modern day
by our perspective?
Northern India, by the Ganges river. Bottom: Democritus is
depicted in a Renaissance-era painting
5
Chemic al symbols
In modern chemistry, atoms and elements are represented by the same symbols,
which consist of one or two letters and are derived from the element names. For
example, the chemic al symbol for hydrogen is H (the rst letter of hydrogen), and
the chemic al symbol for iron is Fe (the rst two letters of the L atin ferrum “iron”).
Symbol Name
Common chemic al elements and their symbols are listed in table1; the full list is
given in the data booklet and in the periodic table at the end of this book.
H hydrogen
C c arbon
Atoms are the smallest units of matter that still possess certain chemic al
properties. While atoms c an exist individually, they tend to combine together

O oxygen
and form chemic al substances. Elementary substances contain atoms of a single
Na sodium
element, while chemic al compounds contain atoms of two or more elements
Mg magnesium
bound together by chemic al forces. For example, magnesium metal is an
S sulfur
elementary substance, as it contains only one type of atom, Mg. Similarly, sulfur
(S) is another elementary substance composed of sulfur atoms only. In contrast,

Cl chlorine
magnesium sulde (MgS) is a chemic al compound, as it consists of two dierent,
Fe iron
chemic ally bound atomic species, Mg and S (gure4). MgS is the chemic al
 Table 1 Common chemic al elements formula of magnesium sulde.
 Figure 4 M agnesium (le), sulfur (middle) and magnesium sulde (right)
Pure substances and mixtures
M atter c an be classied as a pure substance or a mixture, depending on the type
of particle arrangement (gure 5).
matter – any substance that
occupies space and has mass
pure substance – has a definite and mixture – a combination of two or more pure
uniform chemical composition substances that retain their indiidual properties
element – compound – composed homogeneous – has

heterogeneous – has
composed of one of two or more kinds of uniform composition

nonuniform composition
kind of atoms, e.g., atoms in a fixed ratio, and properties

and arying properties,
magnesium (Mg), e.g., magnesium sulfide throughout, e.g., sea

e.g., paint, salad dressing
sulfur (S) (MgS), water (H ) water, metal alloy


 Figure 5 How matter is classied according to the arrangement of particles
6
Pure substances cannot be separated into individual constituents without a chemical
reaction, which alters their physical properties. In contrast, mixtures can be separated
into individual components that retain their respective physical properties.
Data-based questions
A student had two pure substances, A and B. They were heated in separate crucibles and some qualitative and
quantitative observations were made and recorded in table 2.
 Substance B
 Substance A
 Appearance aer heating each of the two substances
M ass of crucible
M ass of crucible Change in Observations aer

Observations
and contents aer
Substance
and substance / g mass / g heating
before heating
heating / g
A Red colour 26.12 ± 0.02 26.62 ± 0.02 Black colour
B Green colour 27.05 ± 0.02 25.76 ± 0.02 Black colour
 Table 2 Results from heating substances A and B
1. C alculate the change in mass for substances A and B.
2. State a qualitative observation from the experiment performed on A and B.
3. Melting ice is a physic al change while rusting iron is a chemic al change. Explain, using the observations, whether
the changes to substances A and B represented a physic al change or a chemic al change.
4. A and B were both pure substances, not mixtures. Discuss whether the experiment shows that A and B are
elements.
5. Both A and B turned black on heating. C an it be concluded that the heating of these two substances produced the
same substance?
7
Melting point determination
Melting point data c an be used to a ss e ss the Method
purity of a s u b s t a n c e. Pure substances h av e sharp (Your teacher will provide specic instructions, depending
melting points, which me ans they melt at a specific on the identity of the solids being analysed.)
t e m p e ra t u r e that closely matches the the oretic al

1. Obtain samples of two organic solids (A and B) for
v a l u e. The presence of impurities in a substance

analysis.
l ow e rs its melting point and c auses melting to occur

2. Prepare samples of each solid in two separate
over a t e m p e ra t u r e ra n g e.
c apillary tubes.
3. Following your teacher ’s instructions, mix small

Relevant skills
amounts of the two solids together.

• Tool 1: Melting point determination
4. Prepare, in a third c apillary tube, a small sample of the

• Inquiry 2: Identify and record relevant qualitative
mixture of the two solids.

observations and sucient relevant quantitative data
5. Determine the melting point of your three samples
Materials
(A, B and the mixture).
• Melting point apparatus
Questions
• C apillary tubes
1. Record relevant qualitative and quantitative data in an
• S amples of two known organic solids, for example,
appropriate format.
aspirin and salol (phenyl 2-hydroxybenzoate)
2. Comment on the results, comparing the melting
S afety points of pure substances with impure substances.
• Wear eye protection. 3. Research the structural formulas of A and B and use
• Note that the melting point apparatus gets very hot. this information to explain the dierence in their
• You teacher will give you further safety prec autions, melting points.
depending on the identity of the solids being 4. To what extent could melting point data be used to
analysed (for example, salol and aspirin are irritants analyse the success of an organic synthesis?
and environmentally hazardous).
Mixtures contain more than one element or compound in no xed ratio, which
Methods for determining the
are not chemic ally bonded and so c an be separated by physic al methods.
melting point of a substance are
Mixtures c an be homogeneous, in which the particles are evenly distributed.
discussed in the Tools for chemistry
Air is a mixture of nitrogen, oxygen, and small amounts of other gases. Air is a
chapter.
homogeneous mixture, and its composition of roughly 80% nitrogen and 20%
oxygen is consistent regardless of where air is sampled.
If the particles are not evenly distributed, such as in a mixture of two solids, then
the mixture is referred to as heterogeneous. Natural milk will have the cream rise
to the top, which reveals that milk is a heterogeneous mixture.
E ach component of a mixture maintains its physic al and chemic al properties. For
The most common homogeneous

example, hydrogen, H , is explosive, and oxygen, O , supports combustion.
2 2
mixtures, aqueous solutions, will

When these substances are present in a mixture, their properties stay the same.
be discussed in Reactivity 3.1, and

In contrast, water, H O, is not a mixture of hydrogen and oxygen but a chemic al
2
the properties of metal alloys in

compound formed by bonding two hydrogen atoms with one oxygen atom.
Structure 2.4.
The new substance has none of the properties of hydrogen or oxygen. It is not a
gas, is not explosive, and it does not support combustion. It is a pure substance
with its own properties and the hydrogen and oxygen c annot be separated from
water without a chemic al reaction, which creates new substances.
8
Separating mixtures
Mixtures c an be separated by physic al means bec ause each component of the
mixture has unique properties. A mixture of iron and sulfur powders c an be
separated using a magnet. Iron is magnetic while sulfur is not. This dierence
in property is used to separate them. The compound iron(II) sulde, FeS, is not
magnetic and does not have a sulfurous smell. It maintains none of the properties
of the components as it is a new, individual pure substance.
Two solids c an usually be separated if we understand their intermolecular forces.
S and c an be separated from sugar bec ause sugar will dissolve in water, due to
the intermolecular attractions between sugar and water.
Th e solid m i x tu re of sand and s u ga r is placed in water and t he s u ga r
Intermolecular forces are discussed
di ss o l ve s . T he solution c an th e n be po u re d t h ro u g h fi l t e r paper placed i n s i de
in Structure 2.2
a funnel, a p ro c e ss c alled fil t ra t i on (fi gu re 6 ). T he l a rg e sand p a r ti c l e s will
not p a ss th ro u gh and re m a i n on th e fi l t e r p a p e r, w h e re a s the sugar d i ss o l ve d
in th e w a te r will p a ss t h ro u gh t he f i l te r p a p e r. Th e wet sand is dried, and th e
w a te r e v a p o ra te s l e av i n g behind th e pu re sand. Th e s u ga r c an be o bt a i n e d
by e v a p o ra t i n g th e w a te r f ro m the fil tra t e — the solution which pa ss e d
th ro u gh t he f i l te r pa p e r. S u ga r c r ys ta l s will fo r m in t hi s c r yst al li za t i on pro c e ss
(fi gu re 7 ).
filter paper
filter funnel
residue
(We define
a residue
as a substance
that remains
aer evaporation,
distillation,
filtration or any
similar process)
filtrate
 Figure 6 Filtration apparatus
evaporating sugar solution
basin
solution from
evaporating basin
leave for a few days

cold tile
t Figure 7 The crystallization
heat
for sugar to crystallize

process
9
Distillation can be used to separate miscible liquids with dierent boiling points,
such as ethanol and water. Ethanol has a lower boiling point and will evaporate rst.
Once the vapours rise up a cooling column, they can be condensed to a liquid. As
shown in gure 8, cold water surrounds the condenser and allows the vapours to
condense to liquid ethanol. The water remains mostly in the distillation ask.
thermometer
distillation
water out
u Figure 8 Distillation apparatus
flask
condenser
ethanol
water in
and water
distillate
heat (mostly ethanol)
Paper chromatography can be used to separate substances such as components
Paper chromatography will

in inks. A piece of chromatography paper is spotted with the mixture. The bottom
be discussed in more detail in

of the paper, below the spot, is placed in a suitable solvent as in gure 9(a).
Structure 2.2
The substances in the mixture have dierent anities for the solvent (the mobile
phase) and the paper (the stationary phase). The anity depends on the
intermolecular forces of attraction between the pure substances in the mixture
and the solvent or the paper. Figure 9(c) shows a mixture that was composed of
ve pure substances.
u Figure 9 The stages in 2D paper

(a) (b) (c)
chromatography
paper
some
some
hours
hours
later
later
drop of turn paper 90° clockwise

solvent
mixture and use a different solvent
Look at gure 9.
1. Which colour dot had the strongest anity for both solvent 1 and solvent 2?
2. Which colour dots had a stronger anity for solvent 1 than solvent 2?
3. Which had a stronger anity for solvent 2 than solvent 1?
10
Table 3 shows a summary of the separation techniques discussed.
Components
Technique Description
removed le
mixture is poured
ltration through a paper lter or liquid(s) solid(s)
other porous material
dissolution mixture is added to water soluble insoluble
(solvation) or an organic solvent substance(s) substance(s)
mixture is dissolved in
Activity
hot water or an organic
solvent, the solution more soluble less soluble

Suggest a suitable method for
crystallization
cools down, and the substance(s) substance(s)

separating each of the following
crystals formed are

mixtures:
isolated by ltration
a. salt and pepper
mixture is heated up solid(s) and/

b. several water-soluble dyes
evaporation or volatile
until one or more of its or non-volatile

c. sugar and water
distillation liquid(s)
components vaporize(s) liquid(s)

d. iron and copper lings
mixture is placed on For each mixture, describe the
less soluble
a piece of paper; one separation technique and outline
more soluble component(s)
paper side of the paper is how each component is isolated.
component(s) move(s) slower
chromatography submerged in water or
move(s) faster or stay(s) in
a solvent; components
place
move along the paper
 Ta b l e 3 Summary of separation techniques
 Figure 10 An advanced ltration technique c alled reverse osmosis extracts salt from seawater, providing fresh
water for millions of people. However, this process requires vast amounts of energy, most of which is currently
provided by fossil fuels. Why might it be important to consider alternative energy sources?
11
Planning experiments and risk assessments
Relevant skills
• Tool 1: Separation of mixtures
• Tool 1: Addressing safety of self, others and the environment
Instructions
1. Using the ideas in this chapter, devise a method that would allow you
to separate a mixture containing sand, salt, iron lings and powdered
c alcium c arbonate. In doing so, you must consider the physic al and
chemic al properties of each of these four substances.
2. Once you have decided on a method, identify the hazards and complete
a risk assessment protocol in which you:
• Identify the hazards
• Assess the level of risk
• Determine relevant control measures
• Identify suitable disposal methods aligned with your school’s health
and safety policies.
3. If you have time, try it out! Remember that your teacher should validate
your methodology and risk assessment beforehand.
Extension
You could evaluate the eectiveness of your method by comparing the mass
of each component (sand, salt, iron lings, and c alcium c arbonate) before and
aer the separation. Measure the mass of each component prior to mixing
them together. Then mix them together, c arry out your separation, make sure
the components are all dry, and measure the mass of each again. Compare
the masses before and aer to c alculate the percentage recovery of each
component.
Linking questions
What factors are considered in choosing a method to separate the
components of a mixture? (Tool 1)
How c an the products of a reaction be purified? (Tool 1)
How do intermolecular forces influence the type of mixture that forms
between two substances? (Structure 2.2)
Why are alloys generally considered to be mixtures, even though they often
contain metallic bonding? (Structure 2.3 and Structure 2.4)
12
States of matter (Structure 1.1.2)
Solids, liquids and gases
Matter is composed of particles. The types of interactions between these particles
determine the state of matter of a substance: solid, liquid or gas. All substances
can exist in these three states, depending on the temperature and pressure.
The states of matter of substances are shown by letters in brackets aer the
formula: (s) for solid, (l) for liquid and (g) for gas. For example:
• Water is a solid below 0 °C: H O(s)

2
• Water is a liquid between 0 and 100 °C: H O(l)

2
• Water is a gas above 100 °C: H O(g).

2
A special symbol, (aq), is used for molecules or other species in aqueous solutions.
For example, the expression “NaCl(aq)” tells us that sodium chloride is dissolved
in water while “NaCl(s)” refers to the pure compound (solid sodium chloride). The
properties of the three states of matter are summarized in gure 11.
solid liquid gas
• fixed volume • fixed volume • no fixed volume
• fixed shape • no fixed shape • no fixed shape
• c annot be • c annot be • c an be
compressed compressed compressed
• attractive forces • attractive forces • attractive forces
between particles between particles between particles
are strong are weaker than are negligible
• particles vibrate in those in solids • particles vibrate,
fixed positions but • particles vibrate, rotate, and move
do not move around rotate, and around faster than
move around in a liquid
 Figure 11 Steam, liquid water and ice are the three states of water
Changes of state
Substances change their states of matter as they absorb or release energy. Solid
ice will absorb energy as it is heated. The particles continue to vibrate in xed
positions, but more violently, until a temperature known as the melting point
is reached. At this point, the ice melts (changes its state from solid to liquid).
A further increase in temperature accelerates the movement of particles, and
eventually the water vaporizes and becomes a gas. The decrease in temperature
reverses these changes of state.
Under certain conditions, solid substances c an turn into gases directly, without
melting. This change of state, known as sublimation, is typic al for dry ice (solid
c arbon dioxide, CO (s), gure12), which is commonly used for refrigerating ice
2
cream and biologic al samples.  Figure 12 Sublimation of dry ice
13
The process opposite to sublimation is c alled deposition. At low temperatures,
water vapour in the air solidies and forms snowakes of various shapes and sizes
(gure13).
When a substance changes from a more condensed state to a less condensed
state, energy is absorbed by the particles from the surroundings. This happens
when a solid becomes a liquid or a gas, and when a liquid becomes a gas. These
are endothermic processes.
When a substance changes from a less condensed state to a more condensed
state, the particles lose energy to the surroundings and, for a molecular
substance, the intermolecular forces become stronger. This happens when a gas
becomes a liquid or a solid, and when a liquid becomes a solid. The process of
releasing energy to the surroundings is an exothermic process.
 Figure 13 A snowake, the product of
The changes of state occurring in these transformations are shown in gure 14.
deposition of water
Non-Newtonian uids
Some substances, known as non-Newtonian uids, 2. Slowly add water to the maize starch and mix.
do not behave like typic al liquids. The viscosity of non- Continue adding water until the mixture achieves
Newtonian uids varies depending on the force applied a thick consistency. Adjust by adding more maize
to them. You will make a non-Newtonian uid commonly starch or more water, as needed.
known as maize starch slime or “oobleck”, and explore its 3. Spend some time exploring the properties of
properties. your mixture. It should harden if tapped, and ow
smoothly if stirred slowly.
Relevant skills
Questions
• Inquiry 1: Identify dependent and independent
1. Describe the properties and identify the state of

variables
matter of each of the following:

• powdered maize starch

observations
• water
S afety
• the maize starch–water mixture.
Wear eye protection.
2. Suppose you were asked to develop a research
question relating to a maize starch–water mixture.

Materials
Consider possible independent and dependent

• Spoon or large spatula
3 variables.
• 250 cm beaker
3. Research non-Newtonian uids and identify other

• Powdered maize starch
examples of these substances.

• Water
4. How has this experience changed the way you think
Method
about states of matter and their properties? Reect on
1. Ad d t h re e or fo u r h e a pe d spoons of ma i z e
this, completing the following sentence starters:
s ta rc h to t he b e a ke r. N o te i ts a pp e a ra n c e and
• I used to think...
c o n s i s t e n c y.
• Now, I think...
Linking questions
Why are some substances solid while others are fluid under standard
conditions? (Structure 2.4)
Why are some changes of state endothermic and some exothermic?
(Structure 2, Reactivity 1.2)
14
gas (g)
freezing
melting
solid (s) liquid (l)
 Figure 15 Orange growers spray their fruit with water on cold nights.
 Figure 14 Endothermic and exothermic
Freezing of water is an exothermic process that releases energy (in the form of
changes of state
heat) to the fruit, protecting it against cold
Kelvin temperature sc ale (Structure 1.1.3)
As temperature rises, the energies of particles increase. Temperature is a
measure of the average kinetic energy of particles. As substances absorb energy,
particles of a solid vibrate in the lattice more, particles in a liquid vibrate more and
move faster, while in a gas they move faster.
When water is heated, there is no temperature change during the periods when
a solid changes to a liquid and when a liquid changes to a gas (gure 16). The
added energy is used to disrupt the solid lattice and overcome the intermolecular
forces between molecules in the liquid.
vaporization
steam
100
kg
C°
condensation
d
m
c
/
water + steam
erutarepmet
water
om
ice + water
melting
K
A
freezing
 Figure 17 The seven base SI units

ice
are kilogram (kg) for mass, meter (m) for
energy input length, second (s) for time, ampere (A) for
electric current, kelvin (K) for temperature,
 Figure 16 Graph of the heating curve for water
mole (mol) for amount of substance, and
c andela (cd) for luminous intensity. All units
There were many attempts to measure relative temperature, but the rst widely
of measurement c an be derived from these
accepted temperature sc ale was introduced by the Polish-born Dutch physicist
seven base units
D aniel Gabriel F ahrenheit.
You will learn more about the mole
The kelvin is the base unit of temperature measurement in the International
in Structure 1.4.
System of Units (SI). There are seven base units, and all other units of
measurements c an be derived from these (gure 17).
15
Measurement
3 –3
M aking, recording, and communic ating measurements volume (m ), density (kg m ), energy ( joule, J, where 1 J
2 –2
greatly benets from agreed upon sc ales. The = 1 kg m s ) and so on, are derived from the seven base
International Bureau of Weights and Measures (BIPM, units.
from the French Bureau international des poids et

The base units are dened according to seven constants,
mesures), established in the late 19th century, is an

including several that you will recognize, such as the
international organisation which seeks to set up and

Boltzmann constant, k; speed of light, c; the Avogadro
continuously rene measurement standards.

constant, N ; and the Plank constant, h
A
The International System of Units (SI, from the French

The use of universal and precisely dened units is very
Système international d’unités) is the most commonly

important, as it allows scientists from dierent countries
used system of measurement. Its building blocks are the

to understand one another and share the results of their
seven base units: length (metre, m), mass (kilogram, kg),

studies. What other advantages are there to internationally
time (second, s), electric current (ampere, A), temperature

shared and continuously updated measurement systems in
(kelvin, K), amount of substance (mole, mol) and luminous

the natural sciences? You might want to look up the Mars
intensity (c andela, cd). All other units, such as those of

Climate Orbiter.
ATL Thinking skills
Throughout history, several universal temperature sc ales have been
developed, each with dierent reference points. Some of these are
summarized in table 4.
Sc ale D ate Reference points
Newton 1700s H O freezing point = 0°

2
Human body temperature = 12°
F ahrenheit 1700s H O freezing point = 32°

2
H O boiling point = 212°

2
Delisle 1700s H O freezing point = 150°

2
2
Celsius 1700s H O freezing point = 0°

2

2
Kelvin 1800s Absolute zero = 0
CGPM 1950s Triple point of water = 273.16 K
BIPM 2018 Kelvin dened in terms of the Boltzmann
constant, k.
 Table 4 Examples of v arious t e m p e ra t u r e sc ales
Temperature is related to thermal energy and as such it could be expressed
in the unit for energy, joules ( J), which are in turn dened in terms of the base
units kg, m and s. It has been decided to keep kelvin as an SI base unit “for
 Figure 18 A platinum–iridium cylinder historic al and practic al reasons”. What do you think some of these historic al
in the US was used to dene a kilogram of and practic al reasons could be?
mass. This standard bec ame obsolete in

Look c arefully at table 4 above. Identify one thing you see, one thing it makes
2019, when the kilogram and all other SI
you think about, and one thing it makes you wonder. Share your ideas with
units were redened as exact quantities
your class.
based on physic al constants
16
Kelvin temperature is proportional to the average kinetic energy of particles and
is considered an absolute sc ale.
Absolute zero (0 K) implies that at this temperature the particles c annot transfer
any kinetic energy on collisions. M atter at absolute zero c annot lose heat and
hence c annot get any colder. An increase in temperature of 1 kelvin is equivalent
to an increase in temperature of 1 degree Celsius. 0 °C is equal to 273.15 K.
Under normal pressure, water boils at 100 °C, so that makes the boiling point of
water 373.15 K. Absolute zero on the Celsius sc ale is –273.15 °C.
t Figure 19 The Celsius and Kelvin
sc ales for temperature (all values are
rounded to whole numbers)
400 K
water
100 °C
373 K
boils
350 K
50 °C
300 K
water
0 °C 273 K
freezes
40 °C
250 K
50 °C
You will learn more about the
200 K
dry ice
kinetic energy of particles in
78 °C
195 K
solid CO
2
Reactivity 2.2.
100 °C
150 K
150 °C
100 K
liquid
191 °C
82 K
air
200 °C
50 K
250 °C
absolute
273 °C 0 K
zero
Celsius Kelvin
Linking questions
What is the graphic al distribution of kinetic energy values of particles in a
sample at a fixed temperature? (Reactivity2.2)
What must happen to particles for a chemical reaction to occur? (Reactivity 2.2)
17
5. Which changes of state are opposite to each other?
Topic review
A. melting and condensation
1. Using your knowledge from the Structure 1.1 topic,
B. vaporization and deposition
answer the guiding question as fully as possible:
C. deposition and sublimation
How can we model the particulate nature of matter?

D. sublimation and freezing
6. Which of the following statements is incorrect?
Exam-style questions
A. solids and liquids are almost incompressible
Multiple-choice questions
B. particles in both solids and liquids are mobile
2. Which of the following are examples of homogeneous
C. liquids and gases have no xed shape
mixtures?
D. particles in solids, liquids and gases c an vibrate
I. Air
7. Which elements c an be separated from each other by
II. Steel
physic al methods?
III. Aqueous potassium manganate(VII),
A. oxygen and nitrogen in air
KMnO (aq).
4
B. hydrogen and oxygen in water
A. II only
C. c arbon and oxygen in dry ice
B. III only
D. magnesium and sulfur in magnesium sulde
C. I and II only
8. Which change in temperature on the Celsius sc ale is
D. I, II and III equivalent to the increase in temperature by 20 K?
A. decrease by 20 °C
3. What correctly describes the sublimation of dry ice
B. increase by 20 °C
(c arbon dioxide)?
C. decrease by 293.15 °C
Exothermic or Equation describing the

D. increase by 293.15 °C
endothermic? process
A exothermic CO (s) → CO (g) Extended-response questions

2 2
B exothermic CO (s) → C(g) + O (g) 9. Explain why the Kelvin temperature is directly
2 2
proportional to average kinetic energy but the
C endothermic CO (s) → CO (g)

2 2
Celsius temperature is not, even though a 1-degree
D endothermic CO (s) → C(g) + O (g)

2 2 temperature increment is the same in each sc ale? [2]
4. Which of the following methods could be used to

10. Ionic salts c an be broken down in electrolysis. The
obtain solid sodium chloride from a solution of sodium

unbalanced ionic equation for the electrolysis of molten
chloride in water?
lead(II) bromide is:
I. evaporation
2+
Pb + Br → Pb + X
II. ltration
a. One of the products is lead, Pb. State the

III. distillation
formula of product X. [1]
A. I only
b. Balance the equation. [1]
B. I and II only
c. The electrolysis of molten lead(II) bromide is
C. I and III only

c arriedout at 380 °C. With reference to melting
D. I, II and III point and boiling point data, deduce the state of
matter of each of the species in the equation at this
temperature. Write state symbols in the balanced
equation you gave in (b). [2]
18
11. The kinetic energy of particles is equal to half of their c. Once the excess copper(II) oxide had been
mass × the square of the velocity of the particles: removed, the student needed to gure out how
1 to obtain pure crystals of copper(II) sulfate from

2
E = mv . Determine how much the speed of

k
2 the solution. Describe a method the student
molecules in a pure gaseous substance will increase

couldfollow to obtain pure, dry copper(II)
when the Kelvin temperature is doubled. [2]

sulfatecrystals. [3]
12. Pure c aeine is a white powder with melting point

14. Study the gure below.
235 °C.
vaporization
a. State the melting point of c aeine in kelvin. [1]
100
C°
b. A chemist is investigating the ec acy of three
condensation
/
c aeine extraction methods. The theoretic al
erutarepmet
water + steam
yield in all three c ases is 0.960 g. She uses each

water
method once and collects the following data for the

ice + water
yield and melting point of the product:

melting
Method 1 Method 2 Method 3
freezing
ice
Mass of c aeine
0.229 0.094 0.380
energy input
obtained / g
Melting point of
190–220 229–233 188–201
caeine product / °C
a. Explain why, in spite of the increasing energy
input,the temperature of the sample remains

i. C alculate the mean and range of the mass
constant at 0 °C for a period of time. [2]

of c aeine obtained. [2]
ii. C alculate the percentage yield of Method 1.

A solution of 5.00 g of sodium chloride in 100.0 g of
Give your answer to an appropriate number

pure water (at standard atmospheric temperature and
of signic ant gures. [2]

pressure) has the following properties:
iii. Determine, giving a reason, which method
 melting point: –3 °C
gave the purest c aeine product. [1]
 boiling point: 101 °C
c. Suggest one way to minimize the random
b. Sketch a graph similar to the one in gure 16

error in this experiment. [1]
to show the heating curve for a sample of this
13. A student prepares a copper(II) sulfate solution by

sodiumchloride solution. [2]
reacting dilute sulfuric acid with excess copper(II) oxide.
15. Elemental iodine exists as diatomic molecules, I . At

2
Copper(II) oxide is insoluble in water.
room temperature and pressure, it is a lustrous purple-
black solid that readily forms violet fumes when heated

The word equation for this reaction is as follows:
gently. When cooled, gaseous iodine deposits on
sulfuric acid + copper(II) oxide → copper(II) sulfate + water

cold surfaces without condensing. Under increased
pressure, solid iodine melts at 114 °C to form a deep-
a. Write a balanced chemic al equation, including
violet liquid.
state symbols, for this reaction. [2]
a. Formulate equations that represent all changes of
b. The acid was heated, then copper(II) oxide
state mentioned above. [3]
powder was added until it was in excess and
b. State the melting point of iodine in kelvin. [1]

could be observed suspended in the solution,
quickly sinking to the bottom of the beaker. Suggest, c. Suggest how liquid iodine c an be obtained from
giving a reason, a method the student could gaseous iodine. [1]
use to remove the excess copper(II) oxide. [2]
19
Structure 1.2 The nuclear atom
Understandings
How do nuclei of atoms dier?
Structure 1.2.1 — Atoms contain a positively charged, dense
The answer to this question was obtained by over

nucleus composed of protons and neutrons (nucleons). Negatively
100 years of brilliant research. Sometimes, the

charged electrons occupy the space outside the nucleus
question of how we know is more fascinating than
Structure 1.2.2 — Isotopes are atoms of the same element with

the question of what is known
dierent numbers of neutrons.

In the late 1800s, the idea that matter was
LHA
composed of atoms that were indivisible and
Structure 1.2.3 — M ass spectra are used to determine
rearranged in chemic al reactions (known as
the relative atomic masses of elements from their isotopic
the atomic theory) was gaining popularity. The
composition.
discovery of electricity and radioactivity allowed
scientists to study the structure of the atom itself.
The structure of the atom (Structure 1.2.1)
An atom contains a positively charged nucleus, which itself contains protons
and neutrons (collectively known as nucleons). Atoms also contain electrons,
which occupy the vast region outside of the nucleus. The protons, neutrons and
electrons are known as subatomic particles.
The key factors of the nucleus are:
1. It is very small in comparison to the atom itself.
2. It is a highly dense structure containing virtually all the mass of the atom.
3. It has a positive charge.
In an experiment designed by Ernest Rutherford in 1911, positively charged
radioactive alpha particles were red toward a sheet of gold foil. The main
observations made are given in gure 1.
movable
beam of
Rutherford’s explanation
detector
alpha particles
+
Most alpha
+
alpha source particles are
undeflected
atom
gold Some alpha
vacuum
foil particles are
+
deflected
slightly
A few alpha
undeflected
particles
+
large slight
bounce
+
deflection deflection
off nucleus
 Figure 1 Rutherford’s gold foil experiment
20
F alsic ation
The gold foil experiment falsied the atomic model Scientic claims are falsiable. This means that they are
that preceded it, namely the “plum-pudding model”. vulnerable to evidence that contradicts them. A scientic
The plum-pudding model suggested that the atom was claim that stands up to severe testing is strong but c an
an amorphous positively charged blob with electrons never be proven true with absolute certainty. Scientic
present throughout. If this were the c ase, all alpha knowledge is therefore always accompanied by a
particles red at the gold foil would have gone through its degree of uncertainty. The provisional nature of scientic
atoms undeected. Rutherford’s results contradicted the knowledge means that further evidence c an steer it in
existing model, paving the way for the development of a new directions.
new model of the atom.

C an a single counterexample falsify a claim?
Activity
The lists below show the observations in the gold foil experiment and the
properties of the nucleus. Determine which observation is explained by
which property.
Observation Property
Nearly all the alpha particles went The nucleus has a positive charge.
straight through the gold foil.
Occ asionally, some of the alpha The nucleus is very small in
particles bounced straight back. comparison to the size of the atom.
The alpha particles are repelled The nucleus is very dense, containing
when closely approaching the virtually all the mass of the atom.
nucleus.
In 1911, Rutherford summarized the results of his experiments by proposing the
planetary model of the atom, also known as the Rutherford model (gure2).
In this model, negatively charged electrons orbit the positively charged atomic
nucleus in the same way as planets orbit the Sun. Just as the Sun contains 99.8%
of the solar system’s mass, the atomic nucleus contains over 99.9% of the mass of
the entire atom. However, instead of by gravity, the electrons are held around the
nucleus by electrostatic attraction.
– electron
+
– proton
– neutron
– nucleus
 Figure 2 The Rutherford model of the atom
21
Models
Scientists use models to represent natural phenomena. All Atoms themselves are extremely small. The diameter of
–10 –10
models have limitations, which should be identied and most atoms is in the range 1 × 10 to 5 × 10 m. The
understood. Consider the depiction of the atom in gure unit used to describe the dimensions of atoms is the
2. The size of the nucleus is exaggerated but it serves as a picometre, pm:
–12
useful model of the nuclear atom.
1 pm = 10 m
The vast space in the atom compared to the tiny size of

In X-ray crystallography a commonly used unit for atomic
the nucleus is hard to fully appreciate. Rutherford’s native

dimensions is the angstrom, symbol Å:
New Zealand is a great rugby-playing nation. Imagine –10
1 Å = 10 m
being at Eden Park stadium (gure 3) and looking down at
For example, the atomic radius of the uorine atom is
the centre of the pitch from the top row of seats. If a golf
–12
60 × 10 m (60 pm). To convert this toÅ we c an use
ball were placed at the centre of the eld, the distance
dimensional analysis, using the conversion factors
between you and the golf ball would represent the
given above:
distance between the electron and the nucleus.
–12
10 m 1 Å
–1
The relative volume of open space in the atom is vast, and 60 pm × × = 0.60 Å = 6.0 × 10 Å
–10
1 pm 10 m
our simple representation of Rutherford’s atomic model
In spite of its limitations, Rutherford’s work has formed the

in gure 2 is obviously unrealistic. The nucleus occupies
basis of much of our thinking on the structure of the atom.

a tiny volume of the atom and the diameter of an atom is
Rutherford is rumoured to have said to his students:

approximately 100 000 times the diameter of the nucleus.
All science is either physics or stamp collecting!
 Figure 3 Eden Park, Auckland, New Zealand. If the atom were the size of the stadium, the nucleus would look like a golf ball in the centre
of the eld
22
TOK
All the models we have discussed assume that atoms are real. However, it
could be argued that objects are only “real” when they c an be seen. In 1981
two physicists, Gerd Binnig and Heinrich Rohrer, working at IBM in Zurich,
Switzerland invented the sc anning tunnelling microscope (STM), an electron
microscope that generates three-dimensional images of surfaces at the atomic
level. This gave scientists the ability to observe individual atoms directly. The
Nobel Prize in Physics in 1986 was awarded to Binnig and Rohrer for their
groundbreaking work.
You c an nd an atomic sc ale lm created by IBM c alled A Boy and his Atom on
the internet.
 Figure 4 A still from A Boy and his Atom
Has technology extended human’s c apacity to make observations of the
natural world?
How important are material tools in the production or acquisition of
knowledge?
Other experiments have shown that the nucleus also contains a neutral subatomic
particle, the neutron, with nearly the same mass as the proton. The relative
masses and charges of the subatomic particles are shown in table 1.
t Table 1 Relative masses and charges for

Particle Relative mass Relative charge Loc ation
the proton, neutron and electron
proton 1 +1
nucleus
neutron 1 0
electron negligible –1 outside nucleus
The electric charge c arried by a single electron is known as the elementary
The actual masses and charges of

–19
charge (e) and it has a value of approximately 1.602 × 10 C. The charges of
these particles c an be found in the
subatomic particles are commonly expressed in elementary charge units. For
data booklet.
example, the charge of an electron c an be represented as –e, and the charge
of a proton as +e. The symbol e is oen omitted, so it is customary to say that
electrons and protons have charges of –1 and +1, respectively.
23
How small is small?
Relevant skills
• Tool 3: Apply and use SI prexes and units
• Tool 3: Use and interpret scientic notation
Instructions
1. A variety of small lengths are shown in table 2. Without looking at their
lengths, but rather based on what you know about each item, list these
objects in order of size, from smallest to largest.
Item Length
proton, charge radius 0.84 fm
sheet of paper, thickness 0.10 mm
onion cell, diameter 250 µm
iodine-iodine bond, length 267 pm
printed full stop, diameter 0.30 mm
c arbon atom, diameter 150 pm
C fullerene, diameter 0.71 nm

60
 Table 2 Lengths of various small items
2. Convert the length values into metres and state them in standard form to
two signicant gures. Refer to the following conversion factors:
–3
• milli, m: 10
–6
• micro, µ: 10
–9
• nano, n: 10
–12
• pico, p: 10
–15
• femto, f: 10
3. List the length values in table 2 in order of increasing size. Was the list you
gave for question 1 correct?
4. Conduct a web search to nd three more values to add to the list: one
smaller than the values given in table 2, one larger, and one intermediate.
5. Provide the full reference for your information sources in question 4,
ATL
following your school’s citing and referencing system.
Atomic number and the nuclear symbol
As of 2023, there are 118 known elements, given atomic numbers 1 to 118. The atomic
number of an element is also the number of protons in the nucleus of that atom. Gold,
atomic number 79, has 79 protons, while carbon, atomic number 6, has 6 protons. As
all the relative mass is in the nucleus, the dierence between the atomic number and
mass number is the number of neutrons in the element. Gold has atomic number 79 and
mass number 197. Therefore, it has 197 – 79 = 118 neutrons. Each element is neutral,
with no charge, so the number of electrons in a neutral atom must equal the number
ofprotons.
24
Activity
Determine the missing values from the table.
Atomic symbol Atomic number M ass number Protons Neutrons Electrons
O 8
13 27
85 37
80 35
27 32
120 80
Pb 207
69 100
Chemists frequently use nuclear symbol notation, X, to denote the number of
neutrons, protons and electrons in an atom. A represents the mass number of the
isotope, Z is the atomic number, and X is the chemic al symbol (gure 5). Gold,
for example, with mass number 197 and atomic number 79, would have a nuclear
197
symbol notation of Au.
79
mass number chemic al symbol
A = Z + N where for the element
N = number of neutrons
X
Z
atomic number =
number of protons
 Figure 5 The nuclear symbol notation
Atoms form compounds by sharing or transferring electrons. As a result, these
atoms sometimes are no longer neutral, having more or fewer electrons than
protons. For example, magnesium atoms react with oxygen atoms to produce
the ionic compound magnesium oxide. M agnesium loses two electrons to form
a magnesium ion with a 2+ charge, as the number of positively charged protons
in the nucleus (12) is two greater than the number of negatively charged electrons
remaining (10).
The resulting charge is also displayed in the nuclear symbol notation below:
+
mass number: 24 charge: 2+
24 2
(12 protons + 12 electrons) (12 protons – 10 electrons)
Mg
atomic number: 12
12 chemic al element: Mg
(12 protons) (magnesium)
The oxygen atom gains the two electrons lost by magnesium to produce an oxide
16
2–
ion with a 2– negative charge. The nuclear symbol for the oxide ion is O .
25
The overall chemical equation for the reaction between magnesium and oxygen is
1
2+ 2–
Mg + O → Mg + O
2
Ionic bonding is discussed further
2
in Structure 2.1 2+ 2–
Mg + O is more commonly written as MgO, as the opposite charges on the
two ions result in a force of attraction between them known as an ionic bond.
Ionic bonds hold the ions together to form solid magnesium oxide.
Activity
Linking questions
Deduce the nuclear symbol
What determines the different chemical properties of atoms? (Structure 1.3)

notation for an ion with 24
protons, 21 electrons, and 28

How does the atomic number relate to the position of an element in the
neutrons.
periodic table? (Structure 3.1)
Isotopes (Structure 1.2.2)
Isotopes are dierent atoms of the same element with a dierent number of neutrons.
As a result, they have dierent mass numbers, A, but the same atomic number, Z.
35
Chlorine, for example, has two isotopes: one with mass number 35, Cl, and one
17
37
with mass number 37, Cl. They have similar chemical properties, as they are both
17
chlorine atoms with the same number of electrons, but dierent physical properties,
such as density, because atoms of one isotope are heavier than atoms of the other.
Naturally occurring hydrogen consists of two stable isotopes, hydrogen-1
(protium) and hydrogen-2 (deuterium). The third isotope of hydrogen, tritium
(gure6), is radioactive, so it does not occur in nature in signic ant quantities.
Activity
Copy the table below and complete it by deducing the nuclear symbols and/
or composition of these isotopes.
Isotope Nuclear symbol Z N A
hydrogen-1 (protium)
H
1
hydrogen-2 (deuterium) 1
hydrogen-3 (tritium) 3
Atomic numbers of isotopes are oen omitted in nuclear symbol notation. For
37
example, the isotope of chlorine with mass number 37 c an be written as Cl.
‘Cl’ tells you the isotope is chlorine and therefore must have an atomic number of
17, so including the atomic number is not necessary. These isotopes c an also be
written with a hyphen, such as chlorine-37, or Cl-37. The relative atomic mass,
A , listed for each element on the periodic table is not a whole number bec ause it
r
is the weighted average of all isotopes of that element.
Natural abundance (NA) of an isotope is the percentage of its atoms among

 Figure 6 A portable tritium light source.
all atoms of the given element found on our planet. If we know the natural
The radioactive dec ay of tritium produces
abundances for all isotopes of an element, we c an c alculate the average A of that

high-energy electrons (beta particles).
r
These electrons hit a uorescent material element. The opposite task (c alculation of natural abundances from A ) is possible
r
and make it glow in the dark

only if the element is composed of two known isotopes.
26
Worked example 1
C alculate the A for iron using the values in the following table.
r
Isotope N atural abundance (NA)/ %
54
Fe 5.845
56
Fe 91.754
57
Fe 2.119
58
Fe 0.282
Solution
We know A = average of the natural abundance of each isotope multiplied by their mass numbers.
r
The natural abundance values add up to 100% so we divide by 100 to obtain the average.
Therefore:
54 × 5.845 + 56 × 91.754 + 57 × 2.119 + 58 × 0.282
A = = 55.91
r
100
Worked example 2
There are two stable isotopes of chlorine: Cl-35 and Cl-37. C alculate the natural
abundance (NA) of each isotope given that A for chlorine is 35.45.

r
Solution
(A of isotope 1 × NA of isotope 1) + (A of isotope 2 × NA of isotope 2)
A =
100
Therefore:
(35 × NA of Cl-35) + (37 × NA of Cl-37)
= 35.45
100
Let x = NA of Cl-35, then 100 x = NA of Cl-37.
Substituting in the above equation gives:
35x + 37(100 x)
= 35.45
100
Expanding the brackets and resolving the x terms gives:
3700 2x
= 35.45
100
Then rearrange in terms of x:
3700 3545
x =
x = 77.5 and 100 x = 22.5. Therefore, the natural abundance of Cl-35 is 77.5% and Cl-37 22.5%.
35 37
The actual natural abundances of Cl and Cl are 75.8 and 24.2%, respectively.
Average A values for all elements

r
The results of our calculations are slightly dierent because we used mass numbers,
are given in the data booklet and in

35 37
which are rounded values for the actual masses of the Cl and Cl atoms.
the periodic table at the end of this
book.
27
Density at Melting Boiling
Compound
–3
4 °C / g cm point / °C point / °C
H O 1.000 0.00 100.0

2
H O 1.106 3.82 101.4

2
 Table 3 Physic al properties of normal and heavy water
235 238
Naturally occurring uranium consists of two main isotopes, U and U. The
dierences in physic al properties of these isotopes are used for the enrichment
 Figure 7 A pellet of enriched uranium
235 238
(increase in the proportion of U over U) of nuclear fuel (gure7), as most

used as fuel in nuclear reactors
235
nuclear reactors require uranium with at least 3% of U, while natural uranium
contains only 0.72% of this isotope.
Enriching one type of isotope in a particular substance c an also make it possible
to track the mechanisms and progress of reactions. This is oen referred to as
isotope labelling.
Global impact of science
Developments in science and their applic ations may have ethic al,
environmental, politic al, social, cultural and economic consequences.
Nuclear ssion, which involves splitting up the nuclei of large atoms releasing
colossal amounts of energy, is one such development. It has led tothe
development of nuclear energy, as well as the atomic bomb.
Element 109, meitnerium (Mt), is named aer Lise Meitner, the second
woman in history to receive a physics doctorate from the University of Vienna
(gure8). Her work with Otto Frisch led to the discovery of nuclear ssion,
published in Nature in 1939. In later years, Meitner was invited to work on
atomic bomb technology being developed in the US. She declined, famously
stating “I will have nothing to do with a bomb!”
C an you think of other scientic developments that have had important
 Figure 8 Austrian-Swedish physicist
ethic alimplic ations?
Lise Meitner in 1906
28
LHA
Practice questions
Linking question
1. State the nuclear symbols for potassium-39 and copper-65. Deduce the
How c an isotope tracers

numbers of protons and neutrons in the nucleus of each isotope.
provide evidence for a reaction
2. Naturally occurring sulfur has four isotopes with the following natural
mechanism? (Reactivity 3.4)

32 33 34 36
abundances: S(95.02%), S(0.75%), S(4.21%) and S(0.02%).
C alculate the average A value for sulfur.

r
3. The actual A value of sulfur is 32.07. Suggest why your answer to the
r
previous question diers from this value.
M ass spectrometry (Structure 1.2.3)
The mass spectrometer (gure 9) is an instrument used to detect the relative
abundance of isotopes in a sample.
detector
(stage 5)
lightest particles
positive ions are

(deflected most)
accelerated in the electric
field (stage 3)
heating filament to vaporize
magnet (stage 4)
sample (stage 1)
inlet to inject heaviest particles
sample (deflected least)
electron beam to
ionize sample (stage 2)
 Figure 9 Schematic diagram of a mass spectrometer
The sample is injected into the instrument and vaporized (stage 1). The atoms
within the sample are then bombarded with high-energy electrons (stage 2). As
a result, the atoms lose some of their electrons to form positively charged ions,
known as c ations. For example, copper atoms c an be ionized as follows:
Cu(g) + e → Cu (g) + 2e
The resulting ions are then accelerated by an electric eld (stage 3) and deected by
a magnetic eld (stage 4). The degree of deection depends on the mass to charge
ratio (m/z ratio). Particles with no charge are not aected by the magnetic eld and
therefore never reach the detector. The species with the lowest m and highest z will
be deected the most. When ions hit the detector (stage 5), their m/z values are
determined and passed to a computer. The computer generates the mass spectrum
of the sample, in which relative abundances of all detected ions are plotted against
their m/z ratios(gure 10).
29
u Figure 10 M ass spectrum of a

LHA
sample of copper
100
80
ytisnetni
60
evitaler
40
20
0 60 62 64 66 68
m/z
The operational details of the mass spectrometer will not be assessed in
examination papers.
Worked example 3
Figure 11 shows a mass spectrum from a sample of boron. C alculate the relative atomic mass,
A , of boron from this mass spectrum.

r
100
80.1
ytisnetni
evitaler
50
19.9
0 2 4 6 8 10 12
m/z
 Figure 11 M ass spectrum of boron
Solution
First, we need to derive the information from graph. The peak at m/z = 10 represents an isotope with a mass
number of 10, which has a relative abundance of 19.9%. The peak at m/z = 11 represents an isotope with a
mass number of 11, which has a relative abundance of 80.1%.
We c an then c alculate A by finding the sum of the relative abundance of each isotope multiplied by its mass
r
number. The relative abundance values add up to 100%, so we divide the result by 100 to obtain the average.
11 × 80.1 + 10 × 19.9
= 10.8
100
30
LHA
1. Estimate the relative abundance of each isotope from gure 12. Use your estimates to c alculate the relative
atomic mass, A , for this element and identify the element.

r
t Figure 12 M ass spectrum
of unknown element
ytisnetni
4
evitaler
203 204 205 206 207 208 209
m/z
2. M ass spectrometry is used for discovering the presence of specic elements in geologic al samples,
including those of cosmic origin. For example, cobalt and nickel are common components of iron meteorites
(gure14).
Cobalt and nickel have similar properties and nearly identic al relative atomic masses. However, the isotopic
compositions of these two metals are very dierent, so they c an easily be distinguished by mass spectrometry
(gure13).
100 100
80
80
ytisnetni evitaler
ytisnetni evitaler
cobalt
nickel
60
60
40
40
20
20
0
0
0 58 60 62
0 58 60 62
m/z
m/z
 Figure 13 M ass spectra of cobalt (le) and nickel (right)
Estimate the relative abundance of each isotope for nickel. Use your estimates to c alculate its
relative atomic mass, A and hence deduce whether cobalt or nickel has the larger A
r r
3. The actual A value for nickel is 58.69. Suggest why your result in question 2 is dierent.
r
31
LHA
 Figure 14 Tamentit iron meteorite, found in 1864 in the S ahara Desert
Mass spectra
M ass spectra c an be found in various databases on the internet, giving you
a chance to practice c alculating average atomic mass values from authentic
data.
Relevant skills
• Tool 2: Identify and extract data from databases
• Tool 3: Percentages
Instructions
1. Using a database of your choice, search for the mass spectra of three
dierent elements.
2. From the mass spectra, c alculate the relative atomic mass of each
element.
3. Compare your c alculated relative atomic mass to that stated in the data
booklet. Comment on any dierences you observe.
Linking question
How does the fragmentation pattern of a compound in the mass spectrometer
help in the determination of its structure? (Structure 3.2)
32
5. Which of the following statements are correct?
Topic review
I. Nearly all mass of the atom is contained within
its nucleus.
II. The mass number shows the number of
How do nuclei of atoms dier?

protons in an atomic nucleus
III. Isotopes of the same element have equal
numbers of protons.
A. I and II only
63
2+ B. I and III only
2. What is correct for Cu ?
29
C. II and III only
Protons Neutrons Electrons

D. I, II and III
A 29 34 27
6. Which of the following species contain equal numbers
B 29 34 31
of neutrons in their nuclei?
C 34 63 31
A. cobalt-58 and nickel-58
D 34 29 27
B. cobalt-58 and nickel-59
1 2
C. cobalt-59 and nickel-58
3. Which values are the same for both H and H ?

2 2
D. cobalt-58 and cobalt-59
I. boiling point
II. ∆H of combustion Extended-response questions
III. number of protons

7. The gold foil experiment involved ring alpha particles
IV. density at gold foil. This experiment is depicted in gure 1 on
page 20.
A. I and III only
a. An alpha particle is a helium nucleus. State the
B. I and IV only
nuclear symbol for an alpha particle. [1]
C. II and III only
b. Suggest the results of the gold foil experiment
D. I, II and III
that would have been observed in each of the
4. The naturally occurring isotopes of lithium are Li and following alternative scenarios:
Li. Which shows the correct approximate percentage
i. Atoms are instead hard, dense, solid balls
abundances for lithium?
of positive charge. [1]
Percentage Percentage
ii. Atomic nuclei are instead negatively
6 7
abundance of Li abundance of Li
charged. [1]
A 75 25
LHA
39
8. There are two stable isotopes of potassium: K and
B 50 50
41
K. The A of potassium is 39.10. Use this information

r
C 35 65
to determine the relative abundances of the two
D 10 90 isotopes and sketch the mass spectrum of potassium
metal. [3]
9. “Dutch metal” is an alloy composed of 86% copper and
14% zinc. This alloy closely resembles gold, so it is
oen used for making costume jewellery. Explain how
Dutch metal c an be distinguished from gold using
mass spectrometry. [2]
33
Structure 1.3 Electron congurations
How c an we model the energy states of electrons in atoms?
This question is complex with many layers. What are electrons? How do we know they exist in energy states? What various
models about these energy states are there?
According to modern views, electrons are quantum objects that behave as both particles and waves. Although such
behaviour has no analogues in our everyday life, we c an visualize electrons in atoms as fuzzy clouds. The shapes and
sizes of these clouds depend on the energies of electrons, which c an have only certain, predened v alues.
Understandings
Structure 1.3.1 — Emission spectra are produced by Structure 1.3.5 — E ach orbital has a dened energy
atoms emitting photons when electrons in excited states state for a given electron conguration and chemic al
return to lower energy levels. environment, and c an hold two electrons of opposite
spin. Sublevels contain a xed number of orbitals, regions

Structure 1.3.2 — The line emission spectrum of
of space where there is a high probability of nding an

hydrogen provides evidence for the existence of
electron.
electrons in discrete energy levels, which converge at
LHA
higher energies.
Structure 1.3.6 — In an emission spectrum, the limit
Structure 1.3.3 — The main energy level is given an of convergence at higher frequency corresponds to
integer number, n, and c an hold a maximum of 2n ionization.
electrons.
Structure 1.3.7 — Successive ionization energy data
Structure 1.3.4 — A more detailed model of the atom

for an element give information about its electron
describes the division of the main energy level into s, p, d

conguration.
and f sublevels of successively higher energies.
Emission spectra (Structure 1.3.1)
Much of our understanding of electron congurations in atoms has come from
studies involving interaction with light. In the 1600s, Sir Isaac Newton showed
that sunlight c an be broken down into dierent coloured components using a
prism. This generates a continuous spectrum (gure 1a). This type of spectrum
contains light of all wavelengths, and appears as a continuous series of colours,
in which each colour merges into the next, and no gaps are visible. The classic
example of a continuous spectrum is the rainbow. The wavelength of visible light
ranges from 400 nm to 700 nm.
A pure gaseous element subjected to a high voltage under reduced pressure
will glow — in other words, it will emit light. When this light passes through a
prism, it produces a series of lines against a dark background. This is known
as an emission spectrum (gure 1b) In contrast, when a cold gas is placed
between the prism and a source of visible light of all wavelengths, a series of dark
lines within a continuous spectrum will appear. This is known as an absorption
spectrum (gure 1c)
34
continuous spectrum
emission spectrum
b
hot gas
c
cold gas
absorption spectrum
 Figure 1 The spectra generated from (a) visible light of all wavelengths (b) a heated gas (c) visible light of all wavelengths
passing through a cold gas
 Figure 2 The aurora borealis (Northern Lights) in Lapland, Sweden. Charged high-energy particles from the Sun are
drawn by the E arth’s magnetic eld to the polar regions, where they excite atoms and molecules of atmospheric gases,
c ausing them to emit light
35
Emission spectra
Emission spectra c an be observed through a simple Method
handheld spectroscope by holding it up to a light source. 1. Observe natural light through the spectroscope. Note
Discharge lamps contain low-pressure gases which are down the details of the spectrum you observe.
ionized when a voltage is applied. 2. O bs e r ve a r ti fi c i a l light f ro m a c o m pu te r s c re e n or
L E D. No te d ow n the details of th e s pe c tr u m yo u
Relevant skills
o bs e r ve.
• Tool 3: Construct graphs and draw lines of best t
3. Observe light from various discharge lamps. Note
down the details of the emission lines you observe,
observations and sucient relevant quantitative data.
including colours, wavelengths and number of lines.
• Inquiry 2: Identify and describe patterns, trends and
Q uestions
relationships
1. Sketch the spectra you observed.

• Inquiry 2: Assess accuracy
2. Describe each as a continuous, emission or
S afety
absorption spectrum.
• Wear eye protection.

3. Look up the emission spectra of the elements in
• The discharge lamps will get very hot. Handle them

the discharge lamps you observed. Compare the
with c are.
theoretic al and observed emission lines, commenting
• Further safety prec autions will be given by your

on the number, colours and positions of the
teacher, depending on the exact nature of the

emissionlines.
discharge lamps.
4. Next, you will compare the theoretic al and observed
wavelengths of the emission lines. Construct a graph

M aterials
of theoretic al wavelength vs observed wavelength.

• Discharge lamps
Draw a line of best t through your data.

• Handheld spectroscope
5. Comment on the relationship shown in your graph.
6. Comment on the accuracy of the observed
wavelength data.
E ach element has its own characteristic line spectrum, which c an be used
to identify the element. For example, excited sodium atoms emit yellow-
orange light with wavelengths of 589.0 and 589.6 nm (gure3, right). The
same yellow-orange colour appe ars in a ame test of any sodium-containing
substance. Like barcodes in a shop that c an be used to identify products, line
emission spectra c an be used to identify chemic al elements.
 Figure 3 Sodium streetlights (le) and the line emission spectrum of sodium (right)
36
Observations
Chemists oen generate data from observing the What is the dierence between observing a natural
properties of matter. Observations c an be made phenomenon directly and with the aid of an instrument?
directly through the human senses (oen sight), or with
instruments. Advancements in technology expand the
boundaries of our observations, revealing otherwise
imperceptible features or detail. Sodium vapour lamps
emit orange-yellow light. As seen in gure 3, observing
the light through a spectroscope reveals a strong
emission in the yellow region of the spectrum. The light
 Figure 4 Helium emission spectrum

from helium lamps is also orange to the naked eye but the
emission spectrum of helium is more complex (gure 4).
Flame tests
Flame testing is an analytical technique that can be used to Materials
identify the presence of some metals. The principle behind • Flame test wire (platinum or nichrome)
ame tests is atomic emission. Electrons are promoted • Small portion of dilute hydrochloric acid
to a higher energy level by the heat of the ame. When • Bunsen burner and heatproof mat
they fall back to a lower energy level, photons of certain • Small samples of various metal salts (e.g. LiCl, NaCl,
wavelengths are emitted. Some of these photons are in the KCl, C aCl , SrCl , CuCl )
2 2 2
visible region of the spectrum.
Method
1. Clean the end of the ame test wire by dipping it into
the HCl solution and placing it in a non-luminous Bunsen
burner ame. Repeat until no ame colour is observed.
2. Dip the end of the ame test wire into one of the salt
samples, and place it in the edge of the non-luminous
Bunsen burner ame, noting down the identity of the
metal in the salt and the colour(s) you observe.
 Figure 5 Flame test colours for dierent elements
Relevant skills
observations
S afety
3. Clean the wire again and repeat with other salt samples.
• Take suitable prec autions around open ames.
4. Clear up as instructed by your teacher.
• Dilute hydrochloric acid is an irritant.
• A variety of dierent chloride salts will be used, some
Q uestions:
of which are irritants — avoid contact with the skin.
1. Look up the emission spectra of the metals you tested.
• Dispose of all substances appropriately.
Compare these to the colours you observed. Comment
• Further safety prec autions will be given by your
on any similarities and dierences.
teacher, depending on the identity of the salts being
2. Explain why the dierent metals show dierent
analysed.
amecolours.
37
TOK
One of the ways knowledge is developed is through reasoning. Reasoning c an be deductive or inductive.
Inductive reasoning involves drawing conclusions from experimental observations. Inductive arguments are “bottom
up”: they take specic observations and build general principles from them.
inductive reasoning (“bottom-up” approach):
4. theory
3. hypothesis
2. pattern
1. observation
For example, you might make the following observations about lithium salts:
Lithium chloride gives a red ame test.
Lithium sulfate gives a red ame test.
Lithium iodide gives a red ame test.
From these observations, you c an make the conclusion that all lithium salts give red ame tests.
Deductive arguments are “top down”: they infer specic conclusions from general premises. You do this all the time
when asked to apply your scientic knowledge in a new context.
deductive reasoning (“top-down” approach):
1. theory
2. hypothesis
3. pattern
4. observation
For example, suppose your scientic knowledge includes the following existing premises:
Lithium bromide is a lithium salt.
Lithium salts give red ame tests.
From this, you could propose that lithium bromide gives a red ame test.
What are the advantages and disadvantages of each type of reasoning?
C an reasoning always be neatly classied into these two types?
On what grounds might we doubt a claim reached through inductive reasoning?
On what grounds might we doubt a claim reached through deductive reasoning?
Visible light is one type of electromagnetic (EM) radiation. In addition to visible
light, microwaves, infrared radiation (IR), ultraviolet (UV), X-rays and gamma rays
are all part of the electromagnetic spectrum.
The energy of the radiation is inversely proportional to the wavelength, λ:
E ∝
λ
38
Electromagnetic waves all travel at the speed of light, c, in a vacuum. The speed
8 –1
of light is approximately equal to 3.00 × 10 m s . Wavelength is related to the
frequency of the radiation, f, by the following equation:
c = f × λ
High energy EM waves, such as gamma rays, have short wavelengths and high
frequencies while low energy waves, such as microwaves, have long wavelengths
and low frequencies.
f λm
1
10
4
10
gamma rays
14
10

10
(γ rays)
1 λnm
10
0
10
400
10
X-rays 10
1
10

ultraviolet
10 00
1
10
elbisiv
(UV)
ygrene

10
14
10
infrared
00
(IR)
4
10
1
10

10
Activity
microwaves
10
10
00
0 Compare the colours red and

10

10
green in gure 6. Determine which
 colour has:
10

10 radio waves
a. the highest wavelength
4
10
4
10 b. the highest frequency
 Figure 6 The wavelength (λ) of electromagnetic radiation is inversely c. the highest energy
proportional to both frequency and energy of that radiation
Look at the spectra below. Explain how we know that stars are partly composed of hydrogen.
3900 7600
4000 4500 5000 5500 6000 6500 7000 7500
 Figure 7 The hydrogen emission spectrum (top) and the absorption spectrum generated from the Sun (bottom)
39
The line emission spectrum of hydrogen
(Structure 1.3.2 and 1.3.3)
E ach line in the emission spectrum of an element has a specic wavelength,
which corresponds to a specic amount of energy. This is c alled quantization:
the idea that electromagnetic radiation comes in discrete packets, or quanta.
A photon is a quantum of energy, which is proportional to the frequency of the
radiation as follows:
E = h × f
Where E = the specic energy possessed by the photon, expressed in joules, J
–34
h = Planck’s constant, 6.63 × 10 J s
f = frequency of the radiation, expressed in hertz, Hz, or inverse
–1
seconds, s
In 1913, Niels Bohr proposed a model of the hydrogen atom based on its
emission spectra. The main postulates of his theory were:
1. The electron c an exist only in certain stationary orbits around the nucleus.
These orbits are associated with discrete energy levels
2. When an electron in the orbit with the lowest energy level absorbs a photon
of the right amount of energy, it moves to a higher energy level and remains
at that level for a short time.
3. When the electron returns to a lower energy level, it emits a photon of light.
This photon represents the energy dierence between the two levels.
Bohr ’s theory was the rst attempt to overcome the main problem of the
Rutherford model of the atom (Structure 1.2). Classic al electrodynamics predicted
that orbiting electrons would radiate energy and quickly fall into the nucleus,
making any prolonged existence of atoms impossible. Bohr postulated that
electrons did not radiate energy when staying in stationary orbits.
Since electrons in the Bohr model of the atom could have only certain, well-
dened energies, their transitions between stationary orbits could absorb or emit
photons of specic wavelengths, producing characteristic lines in the atomic
spectra. By measuring the wavelengths of these lines, it was possible to c alculate
the energies of electrons in stationary orbits.
For a hydrogen atom, the electron energy (E ) in joules could be related to the
n
energy level number (n) by a simple equation:
E = –R
n H 2
–18
where R ≈ 2.18 × 10 J is the Rydberg constant. This equation clearly represents

H
the quantum nature of the atom, where the energy of an electron c an have
only discrete, quantized values. These values are characterized by integer or
half-integer parameters, known as quantum numbers. The principal quantum
number (n) c an take only positive integer values (1, 2, 3, …), where greater
numbers mean higher energy.
40
The most stable state of the hydrogen atom is the state at n = 1, where the
electron has the lowest possible energy. This energy level is known as the
ground state of the atom. In contrast, the energy levels with n = 2, 3, … are
c alled excited states. Atoms in excited states are unstable and spontaneously
return to the ground state by emitting photons of specic wavelengths (gure8).
+energy
e e
+ + +
p p p
excitation dec ay
hf
 Figure 8 Electrons returning to lower energy levels emit a photon of light, hf
Energy levels in atoms resemble ladders with varying distances between the
rungs. Electrons c annot exist between energy levels, much like how you c annot
stand between the rungs of a ladder. Jumping up each rung or level requires a
specic, discrete amount of energy, and jumping down a rung or level releases
the same amount of energy.
An electron c an be excited to any energy level, n, and return to any lower
energy level. Electrons returning to n = 2 will produce distinct lines in the visible
spectrum of hydrogen (gure 9).
Note that the red line has a longer wavelength and lower frequency than the violet
line. The energy of the photon released is lower when an electron falls from n = 3 to
n = 2, than from n = 6 to n = 2. In both cases, it represents the dierence between
two of the allowable energy states of the electron in the hydrogen atom.
colour violet blue cyan red
wavelength / nm 410 434 486 656
transition from n = 6 n = 5 n = 4 n = 3
n = 6
n = 5
n = 4
n = 3
n = 2
n = 1
◂ Figure 9 The visible lines in the
emission spectrum of hydrogen
show electrons returning from higher
energy levels to energy level n = 2
41
n = 7
Electron transitions to the ground state, n = 1, release higher energy, shorter
n = 6
wavelength ultraviolet light, while electrons returning to n = 3 produce lines in
n = 5
the infrared region of the electromagnetic spectrum (gure 10).
n = 4
It is important to note that electrons will absorb or rele ase only the exact energy
n = 3
required to move between allowable energy states. Any excess will not be
IR radiation
absorbed, and if an insucient amount of energy is supplied the electrons will
not move.
n = 2
visible light
Energy levels closer to the nucleus hold fewer electrons. The maximum number
of electrons in any energy level, n, is 2n . For example, the energy level with n = 1
holds up to two electrons, at n = 2 there could be a maximum of eight electrons,
n = 3 has a maximum of 18 electrons, and n = 4 has a maximum of 32 electrons.
n = 1
UV radiation
 Figure 10 Electron transitions for the
ATL Communic ation skills
hydrogen atom. Notice how the allowable
energy levels get closer together when
When explaining concepts, we sometimes use diagrams, graphs or images to
the electron moves further away from the
help us convey our ideas more clearly.
nucleus. The energy dierence between
Prepare a written explanation of atomic emission that does not include

n = 3 and n = 2 is much smaller than that
any diagrams. Exchange it with a partner. Give each other feedback,

between n = 2 and n = 1
concentrating on:
• Use of scientic voc abulary
• Order in which ideas are given
• Whether any important concepts are missing from the explanation.
When you have shared each other ’s feedback, spend some time using the
feedback to make improvements to your work. Finally, choose a graph, image
or diagram to accompany your explanation. Discuss why you chose it and
whether or not it adds to the explanation.
Linking questions
What qualitative and quantitative data c an be collected from instruments
such as gas discharge tubes and prisms in the study of emission spectra
from gaseous elements and from light? (Inquiry 2)
How do emission spectra provide evidence for the existence of
different elements? (Structure 1.2)
How does an element’s highest occupied main energy level relate to its
period number in the periodic table? (Structure 3.1)
42
The quantum mechanic al model
of the atom (Structure 1.3.4)
The Bohr model was an attempt to explain the energy states of electrons in
atoms. It was based on quantization: the idea that electrons existed in discrete
energy levels. According to Bohr, the emission spectra of hydrogen consisted
of narrow lines bec ause the wavelengths of these lines corresponded to the
dierences in allowable energy levels. However, this model was limited by
several problems and incorrect assumptions:
1. The model could not predict the emission spectra of elements containing
more than one electron. It was only successful with the hydrogen atom.
2. It assumed the electron was a subatomic particle in a xed orbit about the
nucleus.
3. It could not account for the eect of electric and magnetic elds on the
spectral lines of atoms and ions.
4. It could not explain molecular bonding and geometry.
The principles behind molecular
5. Heisenberg’s uncertainty principle states that it is impossible to precisely
bonding and geometry are
know the loc ation and momentum of an electron simultaneously. Bohr ’s
explained in Structure 2.2
model stated that electrons exhibited xed momentum in specic
circularorbits.
Bec ause of these limitations, the Bohr theory has been eventually superseded by
the modern quantum mechanic al model of the atom.
TOK
The modern quantum mechanics combines the idea of momentum and the tendency to be absorbed or released
quantization with the following key principles. as discrete entities suggest their particulate nature.
However, photons, electrons, and even whole atoms and

Heisenberg’s uncertainty principle states that it is
small molecules, are c apable of interference (combination

impossible to determine accurately both the momentum
of waveforms), diraction (bending around obstacles) and

and the position of a particle simultaneously. This means
tunnelling (passing through obstacles), all of which are

that the more we know about the position of an electron,
characteristic to waves.
the less we know about its momentum, and vice versa.
Although it is not possible to pinpoint the loc ation or We have two contradictory pictures of reality;
predict the trajectory of an electron in an atom, we c an separately neither of them fully explains the
c alculate the probability of nding an electron in each phenomena of light, but together they do.
region of space.
Albert Einstein (1879–1955)
One aim of the physical sciences has been to give an

The wave–particle duality of the electron is quantitatively
exact picture of the material world. One achievement …

described by the Schrödinger equation, which was
has been to prove that this aim is unattainable.

formulated in 1926 by the Austrian physicist Erwin
Jacob Bronowski (1908–1974) Schrödinger (1887–1961). Solutions to the Schrödinger
equation give a series of three-dimensional mathematic al

What are the implic ations of this uncertainty principle on
functions, known as wave functions, which describe the

the boundaries of knowledge?
possible states and energies of electrons in atoms.

What are the limits of human knowledge?
The concept of wave–particle duality illustrates the fact

Wave–particle duality is the ability of electrons and other
that objects of study do not always fall neatly into the

subatomic species to behave as both particles and waves.
discrete c ategories we have developed. What is the role

Certain characteristics of these species, such as mass,
of c ategorisation in the construction of knowledge?
43
Schrödinger ’s wave functions describe the electrons in atoms in terms of their
probability density, using Heisenberg’s idea that the momentum and position of
electrons are uncertain. Instead of saying that electrons follow a dened travel
path, this theory gives the probability that an electron will be found in a specic
region of space at a certain distance from the nucleus. An atomic orbital is a
region in space where there is a high probability of nding an electron.
There are several types of atomic orbitals, and each orbital c an hold a maximum
of two electrons. E ach orbital has a characteristic shape and energy. The rst
four atomic orbitals, in order of increasing energy are labelled s, p, d, and f.
Subsequent orbitals are theoretic al, and these are labelled alphabetic ally
(g, h, i, k and so on).
The principal quantum number, n, introduced by the Bohr model represents the
main energy levels. These energy levels are split into sublevels comprised of
 Figure 11 An s orbital is spheric al. The
atomic orbitals. For example, for n = 1, 2 and 3, the s atomic orbitals are 1s, 2s
sphere represents the boundary space
and 3s. As n increases, the s orbitals are further distanced from the nucleus.
where there is a 99% probability of nding
an electron. The s orbital c an hold two
Figure 12 shows that, for 1s, there is a high probability of nding electrons close
electrons
to the nucleus and this probability never reaches zero when we move further
away from the nucleus. For 2s, the highest probability is somewhat further away,
although there is a small probability that an electron could be found closer to the
nucleus. There is zero probability of nding the electron between the two peaks.
The same is true for 3s, with the highest probability at an even greater distance
from the nucleus and two regions of zero probability.
1s
0 50
pm
2s
0 50 100
pm
average radius
3s
0 50 100 150
pm
 Figure 12 The plots of the wavefunctions for the rst three s orbitals
44
Imagine that you are a student waiting for your DP chemistry lesson to begin at
8.00am. At 8.15am, there is still no sign of your teacher, so you wonder where
they could be. Some students from your class suggest that the teacher:
• is possibly in the sta room, the chemistry laboratory, or the library
• could be in the school principal’s oce or in the school c ar park
• may be at their house in the town centre
• might perhaps be at the airport
• might even have gone to the North Pole!
Although the exact loc ation of the teacher is unknown, it is possible to draw a
three-dimensional cluster of dots showing areas where there is a high probability
of nding the teacher. A boundary surface could be drawn around this cluster
to dene a region of space where there is a 99% chance of nding them. This
might be the school perimeter, or the town where your school is loc ated, or a
certain region around the town that includes the airport. Similarly, an atomic
orbital represents the region of space with a high probability of nding an
electron (gure13).
t Figure 13 Representation of a 1s atomic orbital as
y y
a cluster of dots (le) and a sphere that encloses 99%
of the dots (right)
x
x
z
z
A p orbital is dumbbell shaped There are three p orbitals, each described with
orientations parallel to the x, y and z axes (gure 14). These are labelled p , p and
x y
p . These shapes all describe boundaries with the highest probability of nding
z
electrons in these orbitals.
t Figure 14 The three p atomic orbitals
are dumbbell shaped, aligned along the

z
z
z
x, y and z axes. There is zero probability
of nding the electron at the intersection
of the axes between the two lobes of the
x x x
dumbbell. E ach of the p orbitals c an hold
two electrons
y
y
p orbital p orbital
x y p orbital
z
45
Theories and models
Current atomic theory evolved from previous models, each superseding the one that c ame
before. Theories are comprehensive systems of ideas that model and explain an aspect of
the natural world. Contrary to the use of the word “theory” in everyday language, scientic
theories are substantiated by vast amounts of observations and tested hypotheses, which
are amassed, documented and communic ated by a large number of scientists.
+
+
+
+ + +
800–400 BCE 1897 1913 1930
Āruņi’s kana Thomson’s “plum ohr model uantum mechanic al
Democritus’ atomos pudding” model model
1803 1912 1926
D alton’s “billiard ball” Rutherford’s model Heisenberg’s uncertaint
model and regions of probabilit
model
 Figure 15 The atomic theory has seen the idea of atoms evolve from indestructible spheres to the quantum mechanic al
model where electrons have specic energies and are found in regions of high probability
What other examples of theories c an you think of ?
Linking question
What is the relationship between energy sublevels and the block nature of the
periodic table? (Structure 3.1)
46
Electron congurations (Structure 1.3.5)
E ach atomic orbital type has a characteristic shape and energy. The s orbital is
spheric al and it has the lowest possible energy. There are three p orbitals, each
oriented dierently. There are ve d orbitals and seven f orbitals, and these are
higher in energy than s or p.
x
s
z z z
y y y
x x x
p p p
–1 0 1
z z z z z
y y y y y
x x x x x
d d d d d
–2 –1 0 1 2
z z z z z z z
y y y y y y y
x x x x x x x
f f f f f f f
–3 –2 –1 0 1 2 3
 Figure 16 The shapes of the s, p, d and f orbitals. Only the shapes of s and p orbitals need to be known
E ach energy level dened by the principal quantum number, n, c an hold n types
of orbitals (table 1). For n = 1, only the s orbital exists. For n = 2, there are two
types of orbital: s and p. For n = 3, there are three types: s, p, and d. For n = 4,
there are four types: s, p, d, and f.
Total number M aximum
Principal Number
Type of of orbitals number of
quantum of orbitals
sublevel per energy electrons within
number (n) per type

2 2
level (n ) energy level (2n )
1 s 1 1 2
s 1
2 4 8
p 3
s 1
3 p 3 9 18
t Table 1 Each energy level, dened by
2
d 5
n, c an hold 2n electrons. The number of
sublevels, or atomic orbital types, is equal

s 1
to n. For n = 4 there are four types of orbitals
p 3
(s, p, d, and f ) with 16 atomic orbitals in total
4 16 32
d 5 occupied by a maximum of 2(4) = 32 total
electrons
f 7
47
Activity
State the following for the energy level with n = 5:
a. the sublevel types
b. the number of atomic orbitals in each sublevel
c. the total number of atomic orbitals
d. the maximum number of electrons at that energy level.
Orbital diagrams
For convention, an “arrow in box” notation c alled an orbital diagram is used
to represent how electrons are arranged in atomic orbitals (gure 17). The
arrangement of electrons in orbitals is c alled electron conguration
u Figure 17 In orbital diagrams, each box

s sublevel (one box representing an s orbital)
represents an orbital. This diagram shows
the number of orbitals for each sublevel.
Arrows are drawn in the boxes to represent
electrons. A maximum of two electrons
c an occupy each orbital, so each box has a
maximum of two “arrows”
p sublevel (three boxes representing the three p orbitals p , p , and p )

x y z
d sublevel (five boxes representing the five d orbitals)
f sublevel (seven boxes representing the seven f orbitals)
Atomic orbitals are regions of space where there is a high probability of nding
electrons. Electrons are charged negatively, and like charges repel each other, so
two electrons should not be able to occupy the same region of space. Quantum
mechanics solves this problem by using a ± spin notation for each electron. A
pair of electrons with opposite spins behave like magnets facing in opposite
directions. Hence each orbital box is shown with an upwards half-arrow, , and
one downwards half-arrow, (gure 18). This is known as the Pauli exclusion
principle:
Only two electrons c an occupy the same atomic orbital and those electrons
must have opposite spins.
48
t Figure 18 Electron spin is represented

N S
by an arrow pointing up (positive spin) or
down (negative spin)
S N
N S
magnet analogy
S N
half-arrows representing
3d
electrons of opposite spin
in an orbital
degenerate
3p
TOK ygrene
degenerate
3s
Electron spin is oen interpreted as the rotation of the electron around its
own axis. However, this interpretation has no physic al basis: electrons in
2p
atoms behave like waves, and a wave c annot rotate. Unfortunately, neither
the spin nor the wave-like behaviour of electrons c an be visualized in any way,
2s
as they have no analogues in our everyday life and c an be expressed only in
degenerate
mathematic al form. This lack of visualization does not undermine the quantum
1s
theory but rather shows the limits of human perception and, at the same time,
the power of mathematics as the language of science.
1 2 3
To what extent does mathematics support knowledge development in the
natural sciences?
 Figure 19 The three 2p orbitals are
degenerate as they have the same energy.
E ach of the atomic orbitals of the same type in one sublevel are of equal energy. These three degenerate atomic orbitals
Orbitals with the same energy are referred to as degenerate orbitals (gure 19). have lower energy than the three 3p orbitals
49
An atom of boron (B) has ve electrons, and its orbital diagram is drawn as follows:
1
2p
2
2s
boron
(B)
2
1s
The single 2p electron in boron c an occupy any of the three orbitals, as they have
equal energies. The degenerate 2p orbitals are represented by boxes joined
together to show their energy equivalence. Traditionally, the half-arrow is drawn
in the lemost box, although it is a matter of personal preference.
Hund’s rule states that every degenerate orbital in a sublevel is singly
occupied before any orbital is doubly occupied and that all electrons in singly
occupied orbitals have the same spin. This means that the three p orbitals must
have one electron with the same spin in each of them before any orbital c an
become doubly occupied with an electron of opposite spin (gure 20).
Practice questions
1. Look at gure 20. The 1s and 2s orbitals are fully occupied by electrons.
Why do you think the 1s and 2s orbitals are lled before the 2p orbitals?
2. State which of the diagrams below represents a correct electron
conguration based on Hund’s rule and the Pauli exclusion principle.
State the reason for the four incorrect diagrams being wrong.
A.
1s 2s 2p
B.
1s 2s 2p
C.
1s 2s 2p
1s 2s 2p
D.
1s 2s 2p
1s 2s 2p
 Figure 20 The electrons are evenly
E.
distributed across the three degenerate
2p orbitals in nitrogen before an orbital is
1s 2s 2p
doubly occupied
The Aufbau principle states that as electrons are added to atoms, the lowest
available energy orbitals ll before higher energy orbitals do. The third and
fourth energy levels contain d and f orbitals (gure 21). These orbitals are typically
lled aer the s orbitals of the following levels because they are higher in energy.
As shown in gure 21, the 3d sublevel has a higher energy than 4s but lower than
4p, so 4s is lled with electrons rst, followed by 3d and nally 4p. For the same
reason, 4d orbitals are lled aer 5s, and 4f orbitals are lled only aer 6s.
50
t Figure 21 The 4s sublevel has a lower
energy and will ll before the 3d sublevel
4f
6s
5p
4d
5s
4p
ygrene
3d
4s
3p
3s
2p
2s
1s
This is consistent with experimental data that show that potassium, K, and
c alcium, Ca have electrons in the 4s sublevel, not in 3d.
t Figure 22 Potassium orbital lling diagram showing the outermost
4p
electron in the 4s orbital bec ause 3d orbitals are higher in energy
3d
4s
3p
3s
ygrene
2p
2s
1s
Generally, the following order is observed:
Activity
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p …
Copy the orbital diagram from
In the IB Diploma Programme, only the electron congurations of atoms and ions
gure21 and complete it for the
up to Z=36 will be assessed. Electrons in these species can ll sublevels up to 4p.
following elements in their ground
states:
Electron sharing and transfer are fundamental to understanding chemic al
a. aluminium, Al
reactions, so it is important to know the electron conguration of an atom or an
b. chlorine, Cl
ion. There are three ways to show the electron conguration:
c. iron, Fe
1. Full electron conguration

Refer to the periodic table at the
back of this book to deduce the
2. Condensed electron conguration
number of electrons in each atom.
3. Orbital lling diagram (“arrows in boxes” notation)
The orbital lling diagram for potassium is given in gure 22.
51
Full electron congurations
To write a full electron conguration, we use the periodic table, and “build up”
the electrons in successive orbitals according to the Aufbau principle, Hund’s
Rule and the Pauli exclusion principle.
Worked example 1
Determine the full electron conguration for the c alcium atom.
Solution
The Aufbau principle states that as electrons are added to atoms, the lowest
available energy orbitals ll before higher energy orbitals do. From the Pauli
exclusion principle, we know that each orbital will have a maximum of two
electrons.
The atomic number of calcium is 20. Let’s split the 20 electrons evenly across
each orbital, starting with the lowest energy rst. When writing electron
congurations, the number of electrons within each sublevel is given in
superscript, next to the sublevel:
• The 1s orbital has two electrons: 1s
• The 2s orbital also has two electrons: 2s
• The three 2p orbitals have two electrons each, six in total: 2p
• The 3s orbital has two electrons: 3s
• The three 3p orbitals have three electrons each, six in total: 3p
Practice question
This brings us up to 18 electrons, with two le over to go into the orbital with
3. Determine the full electron

2
the next lowest energy, 4s: 4s
conguration for the phosphorus

2 2 6 2 6 2
So, for c alcium, the full electron conguration is 1s 2s 2p 3s 3p 4s
atom.
Condensed electron congurations
As the atomic number of an element increases, the full electron conguration
gets longer and it c an be time-consuming to write. The chemistry of atoms and
ions is mostly determined by their valence electrons, that is, the outermost
electrons, rather than the inner core electrons. A more convenient way of writing
electron congurations is to highlight the valence electrons and represent the
inner core electrons as having the same electron conguration as the previous
group 18 (known as the noble gases) element in the periodic table:
Condensed electron conguration = [previous noble gas] + valence electrons
Table 2 shows some more examples of full and condensed electron congurations.
u Table 2 Examples of full and condensed
Condensed
electron congurations for selected Atomic
Element Full electron conguration electron

elements
number
conguration
2 2 4 2 4
O 8 1s 2s 2p [He] 2s 2p
2 2 6
Ne 10 1s 2s 2p [Ne]
2 2 6 2 6 2 5 2 5
Mn 25 1s 2s 2p 3s 3p 4s 3d [Ar] 4s 3d
2 2 6 2 6 2 10 5 2 10 5
Br 35 1s 2s 2p 3s 3p 4s 3d 4p [Ar] 4s 3d 4p
52
Worked example 2 Practice question
Determine the condensed electron conguration for the c alcium atom.

4. Determine the condensed
electron conguration for the
Solution
phosphorus atom.
In worked example 1, we determined the full electron conguration of
2 2 6 2 6 2
c alcium to be 1s 2s 2p 3s 3p 4s .
The previous noble gas in the periodic table is argon, which has an atomic
2 2 6 2 6
number of 18. Argon has an electron conguration of 1s 2s 2p 3s 3p , and we
can therefore write the condensed electron conguration of calcium as [Ar] 4s .
Orbital diagrams c an also sometimes be shortened by using a condensed
The periodic table is structured
electron conguration. The condensed orbital diagrams for oxygen and
according to the type of sublevel
manganese are shown below.
that valence electrons of elements
appear in. This is discussed further
oxygen: [He]
in Structure 3.1.
2s 2p
manganese: [Ar]
4s 3d
ATL Self-management skills
The ideas in this topic span a range of concepts and skills: from the quantum
mechanic al model of the atom, to how to write electron congurations.
Write a chapter summary, no longer than a sheet of A4 paper.
Write three key takeaways from the chapter.
List the key voc abulary you should know from this chapter.
Write ve brief questions that test your understanding of the ideas in this
chapter. M ake an answer key, then try them out on one of your peers.
Exceptions to the Aufbau principle
The Aufbau principle correctly predicts the order of lling of atomic orbitals for
most elements. However, when atoms lose electrons to form ions, the electrons
in the sublevel with the highest principal quantum number ( n) are lost rst.
2 5
So, for Mn, with electron conguration [Ar] 4s 3d , the 4s electrons will be lost
2+ 5
rst. This gives the manganese ion, Mn , with electron conguration [Ar] 3d ,
2 3
not [Ar] 4s 3d .
All elements with 3d valence electrons tend to lose two 4s electrons to form 2+
ions. These are known as the 3d transition elements, or transition metals. If
you look at the periodic table at the back of this book, these elements are from
sc andium (Sc) to copper (Cu). These transition metals c an also have variable
oxidation states in compounds.
There are some exceptions. With only one electron in its 3d orbital, sc andium
3+
readily forms only Sc ions, by losing this 3d electron and the two 4s electrons.
53
The ground state congurations of copper and chromium are also dierent from
Ionization and oxidation are
those predicted by Aufbau principle.
covered in Structure 2.1 and
2 9
Structure 3.1
The predicted electron conguration of copper is [Ar]4s 3d , as the Aufbau principle
suggests that the lower-energy 4s orbital should be lled rst. However, the observed
1 10
ground-state electron conguration for copper is [Ar]4s 3d (gure 23). For
2 4 1 5
chromium, the predicted conguration is [Ar]4s 3d and the observed is [Ar]4s 3d
Activity
(gure 23). In each case, promoting a 4s electron to a 3d level leads to a more stable
electron conguration. In the case of copper, this gives a full d sublevel, and in the
Deduce the electron conguration
case of chromium, there are no paired electrons but rather six half-occupied orbitals,
2+
of the Cu c ation.
each containing an electron with the same spin.
u Figure 23 The expected

Cu (Z = 29) Cr ( Z = 24)
and observed electron
expected
congurations of copper and [Ar] [Ar]
configuration
chromium
9 2 4 2
3d 4s 3d 4s
observed
[Ar] [Ar]
configuration
10 1 5 1
3d 4s 3d 4s
The electron congurations of chromium (Cr) and copper (Cu) are the only
two exceptions that you need to know. In all other elements up to Z=36, the
sublevels are lled with electrons according to the general order.

LHA
Ionization energy (Structure 1.3.6 and 1.3.7)
The quantum mechanic al model of the atom helps to explain the trends and
discontinuities in the rst ionization energies (IE) of elements. Ionization energy
is the minimum energy required to eject an electron out of a neutral atom or
molecule in itsground state.
X(g) + energy → X (g) + e
Ionization energy and periodic

The columns in the periodic table are known as groups, and the rows are known
table trends are discussed further in

as periods. Going across the periodic table, the groups are numbered from 1 to
Structure 3.1
18. The periodic table c an be shown as four blocks corresponding to the four
sublevels s, p, d, and f (gure 24). The sublevels holding the outermost valence
electrons for each element are also shown.
First ionization energy (IE ) generally decreases down the groups of the periodic
1
table and increases across the periods.
Going down a group, the number of sublevels increases. The outermost
electrons are shielded from the pull of the nucleus by the electrons in the lower
energy sublevels (so-c alled “inner electrons”). The more sublevels, the greater
the shielding and therefore less energy is required to remove electrons from the
outermost sublevel.
Going ac ross a period, the number of protons in the nucleus inc re ases, so
the outermost ele ctrons are held closer to the nucleus by the inc re ase d
nucle ar charge. At the s ame time, the shielding ee ct remains ne arly
constantbe c ause the number of inner ele ctrons does not change.
54
LHA
s-block
1 18
transition elements
1s 1s
2 13 14 15 16 17
2s 2p
d-block
3s 3p
3 4 5 6 7 8 9 10 11 12
4s 3d 4p
5s 4d
6s 5d 6p
7s 6d 7p
4f
f-block
5f
 Figure 24 The blocks of the periodic table correspond to the sublevels s, p, d and f
Therefore, more energy is re quire d to remove outermost ele ctrons, so
ionization energy inc re ases ac ross the period.
The general trend of decreasing ionization energy down a group and increasing
across a period is shown in gure 25:
Period 2 Period 3 Period 4 Period 5
2500
He
1
Ne
lo
2000


gree
Ar
1500
N
Kr
 o i a  i  o i
O Xe
H
1000
Be
sriF
500 Al
Li
Na
K Rb
2 10 18 36 54
Aoi ber
 Figure 25 Plot of rst ionization energy against atomic number for the elements from hydrogen to xenon
55
LHA
There are two clear discontinuities across the period:
1. Between the group 2 and group 3 elements
2 2 1
The valence electron conguration of beryllium is 2s while for boron it is 2s 2p .
The paired 2s electrons shield the single 2p electron in boron from the nucleus,
making the electron slightly easier to remove.
+
Be Be
0 0
2p 2p
2 1
2s 2s
+
B B
1 0
2p 2p
2 2
2s 2s
Patterns and trends
Scientists look out for patterns and

The s ame trend c an be observe d in comparing group 2 to group 3 elements
2 1
trends in the data they collect.
in any period. For example, the 3s ele ctrons shield the lone 3p ele ctron in
The presence of discrepancies

aluminium, so the rst ionization energy of aluminium is lower than that of
— results that do not t the

magnesium.
overall pattern — allows further
Suppose you have a two-story building and you need to remove one oor to meet
conclusions to be drawn.
new height regulations. Which oor would you remove? Obviously, it will be the
What can be inferred from the
top oor, as the building would collapse otherwise! The same reasoning can be
patterns in successive ionization
applied to the ionization of atoms — electrons are removed rst from the highest
energies?
occupied energy level, and from the highest energy sublevel within that level.
2. Between the group 15 and 16 elements
From group 15 to 16 there is also a drop in ionization energy. The electron
2 2 3 2 2 4
conguration of nitrogen is 1s 2s 2p while for oxygen it is 1s 2s 2p
Nitrogen has a more stable electron conguration than oxygen as it has a half-
lled p sublevel, and therefore more energy is required to remove an electron
from nitrogen (gure 26). This is bec ause the paired electrons in oxygen occupy
the same region of space and have increased repulsion. However, in nitrogen,
the three electrons in the 2p orbitals do not come into close proximity.
u Figure 26 A half-lled p sublevel is

+
N N
more stable than p sublevels with 2 or 4 3 2

2p 2p
2 2
electrons 2s 2s
+
O O
4 3
2p 2p
2 2
2s 2s
56
LHA
The most stable p orbital conguration is p , a completely lled p sublevel,
followed by p , a half-lled sublevel. This is generally true for other sublevels. For
10 5
example, d and d electron congurations are also stable, which partly explains
why chromium and copper do not obey the Aufbau principle (gure 23).
C alculating ionization energy from spectral data
As the principal quantum number of energy levels increases, the distance
between the levels converges to a continuum. This c an be observed by spectral
lines converging in the hydrogen emission spectrum, shown in gure 27.
t Figure 27 Ultraviolet and visible light

level ∞
level 5 transitions in hydrogen and the resulting
level 4
emission spectrum
level 3
level 2
level 1
high energy low energy
ultraviolet light visible light
–8
The spectral lines in the hydrogen emission spectrum converge at 9.12 × 10 m, or
912 Å (gure 28). This represents the wavelength of light at which the hydrogen
atom is ionized.
This wavelength c an be used to c alculate the rst ionization energy of hydrogen.
t Figure 28 Hydrogen is ionized at

912 Å
the wavelength where the spectral lines
converge in the emission spectrum
900 950 1000 1050 1100 1150 1200 1250
Wavelength / Å
57
LHA
Worked example 3
Spectral lines converge at 9.12 × 10 m in the emission spectrum of the
hydrogen atom. C alculate the rst ionization energy of hydrogen in kJ mol
Solution
First, c alculate the frequency of radiation using c = f × λ, where c is the speed
8 1
of light, approximately equal to 3.00 × 10 m s
8 1 8
3.00 × 10 m s = f × 9.12 × 10 m
15 1
f = 3.29 × 10 Hz (s )
Then, c alculate the energy using Planck’s constant and the equation E = h × f
34 15 1
E = 6.63 × 10 J s × 3.29 × 10 s
18
= 2.18 × 10 J
Alternatively, these two steps c an be merged into one by using the
The values of the speed of light,
h × c
equation E =
Planck’s constant and Avogadro’s

λ
constant are given in the data This represents the energy of a single photon of light which would be
booklet. The mole and Avogadro’s absorbed in exciting the electron in a hydrogen atom to the convergence
constant are discussed further in level, or removing one electron from the atom.
Structure 1.4. Ionization energies are usually given in kJ mol . You c an convert the ionization
energy value to kJ mol using Avogadro’s constant (N , the number of atoms

A
in 1mol) and the following equation:
The ionization energy in kJ mol
(energy needed to remove one electron from an atom) × N

A
1000
–18 23 –1
2.18 × 10 J × 6.02 × 10 mol
1000
3 1
= 1.31 × 10 kJ mol
Worked example 4
The rst ionization energy of Na is 496 kJ mol as given by the IB data
booklet. C alculate the wavelength of convergence for the sodium atom
spectrum in Å.
Practice questions
Solution
5. In the emission spectrum of
First, nd the energy of ionization for one atom by converting the given value
the helium atom, the spectral
from kJ to J and dividing it by Avogadro’s constant.
–8
lines converge at 5.05 × 10 m. 1 23 1 19
496 000 J mol / 6.02 × 10 mol = 8.24 × 10 J
C alculate the rst ionization

h × c
Then c alculate the wavelength of light using E =

–1
energy, in kJ mol , of helium.

λ
–34 8 –1
6.63 × 10 J s × 3.00 × 10 m s
19
6. The rst ionization energy of 8.24 × 10 J =
λ
–1
c alcium is 590 kJ mol . C alculate

7
λ = 2.41 × 10 m
the wavelength of convergence,
= 2410 Å.
in Å, for the c alcium atomic
This corresponds to the UV region in the electromagnetic spectrum.

spectrum.
Successive ionization energies
It requires more energy to remove the second and successive electrons from an
atom bec ause the number of protons exceeds the number of remaining electrons
while the electron–electron repulsion decreases.
58
Structure 1.3 Electron congurations
LHA
As a result, electron clouds are pulled closer to the nucleus and held tighter by
the increased electrostatic attraction. Once all the valence electrons are removed
so that only the stable noble gas conguration remains, the energy required to
remove the next electron increases sharply, as shown in gure 29.
t Figure 29 Removing 10 electrons

ygrene
from magnesium gives the noble-gas
conguration 1s or [He]. There is a

)
1–
lom Jk(
considerable increase in energy required to

n o it a z i n o I
remove the 11th electron
1 2 3 4 5 6 7 8 9 10 11 12
Numer o eletron remoe
Worked example 5
The rst ve successive ionization energies for an unknown element X have
the following values: 403, 2633, 3860, 5080 and 6850 kJ mol . Deduce
Practice question
the group of the periodic table in which element X is likely to be found.
7. The rst ve successive ionization
energies of an unknown element

Solution
have the following values:

1
The largest increase in energy occurs from the rst ionization (403 kJ mol ) to
801, 2427, 3660, 25 026 and

1
the second (2633 kJ mol ). This means that the second electron is likely to be
–1
32 827 kJ mol . Deduce the
removed from a stable noble gas conguration of the atom. Therefore, the
group of the periodic table in
outermost energy level of the element contains one electron, so the element
which this element is likely to
belongs to group 1 of the periodic table.
befound.
Data-based question
Using gure 30 and the periodic table, explain the two large jumps in the
successive ionization energies for sodium.
6.0
5.5
5.0
EI
4.5
gol
4.0
3.5
3.0
2.5
1 2 3 4 5 6 7 8 9 10 11
number of electrons removed
 Figure 30 Successive ionization energies for sodium
59
LHA
Ionization energy data
Relevant skills Part 3: Graphing the logarithm of the ionization
• Tool 2: Extract data from databases energies
• Tool 2: Use spreadsheets to manipulate data and 6. Title the third column in your spreadsheet “log
represent data in graphic al form (ionization energy)” as shown below:
• Tool 3: Construct and interpret graphs
A B C
Instructions
Part 1: Data collection

1 element name:
1. Identify a database that contains successive
ionization energy data for the elements (for example,
ionization log
WebElements).
energy/ (ionization
2. Choose one of the following elements: sulfur,
–1
3 ionization kJ mol energy)

chlorine, argon, potassium or c alcium.
3. Collect successive ionization energy data in a

4 1
spreadsheet, labelling the columns as follows:

5 2
6 etc
A B
7. Compute the logarithm of each ionization energy
1 element name:
using the spreadsheet LOG (or LOG10) function.
2
8. Construct a graph showing the logs of successive
ionization energies by plotting log (ionization energy)

ionization
vs ionization number.
energy/
9. Answer the following questions:

–1
3 ionization kJ mol
a. Identify the large increases in ionization energy
4 1
that indic ate a change in main energy level.
5 2
b. Why is it useful to plot the logs of the ionization
6 etc energies?
Part 4: Evidence for the existence of sublevels
10. Construct a graph that will allow you to closely

Part 2: Graphing successive ionization energies
examine the electrons in energy level n = 2. Enlarge

4. Plot a line graph of ionization energy vs ionization.
the graph and “zoom in” to inspect the increases

M ake sure that you present your graph suitably, with
closely.
axis labels, suitable sc ales and a descriptive title.
11. C an you see any unusually large increases in

5. Answer the following questions:
ionization energy? Explain how they relate to the

a. Identify the IE values that correspond to the
existence of sublevels.
innermost and outermost electrons.
KOT
12. Experimental data is oen organized into tables
b. Explain why ionization energy increases with each
and later transformed into graphic al forms. What

successive electron.
is the role of graphic al representations in the

c. Explain how the graph provides evidence for the
advancement of scientic knowledge? Are graphic al

existence of main energy levels in the atom.
representations employed in other subject areas?
Linking questions
How does the trend in IE values across a period and down a group explain the trends
in properties of metals and non-metals? (Structure 3.1)
Why are log scales useful when discussing [H ] and ionization energies? (Tool 3, Reactivity 3.1)
LHA
How do patterns of successive ionization energies of transition elements help to explain
the variable oxidation states of these elements? (Structure 3.1)
60
Structure 1.3 Electron congurations
5. What is the maximum possible number of electrons in
Topic review
the third energy level?

A. 3
B. 6
How can we model the energy states of electrons

C. 9
inatoms?
D. 18
6. What is the electron conguration of chromium (Z = 24)

in the ground state?
7
A. [Ar] 3d
2. Which row is correct for the following regions of the

2 4
B. [Ar] 4s 3d
electromagnetic spectrum?
1 5
C. [Ar] 4s 3d
1 5
Ultraviolet (UV) Infrared (IR)
D. [Ar] 4s 4p
high short low energy low
LHA
A. 7. Which of the following is correct?
energy wavelength frequency
A. IE > IE
3 4
high low low energy long
B.
B. Molar ionization energies are measured in kJ.
energy frequency wavelength
C. The third ionization energy of the atom X represents
high short high long
C.
the process:
frequency wavelength energy wavelength
2+ 3+ –
X (g) → X (g) + e
high long low low energy
D.
D. Ionization energies decrease across a period going
frequency wavelength frequency
from le to right.
3. Which of the following sources of light will produce a
8. Which statement about the rst ionization energies of
line spectrum when placed behind a prism?
nitrogen and oxygen atoms is correct?
I. a gas discharge tube
A. IE (N) < IE (O) bec ause oxygen has two paired

1 1
II. an inc andescent lamp
electrons in its partly lled sublevel
III. an alkali metal salt placed in a Bunsen burner
B. IE (N) > IE (O) bec ause oxygen has two paired

1 1
ame
electrons in its partly lled sublevel
A. I and II only
C. IE (N) < IE (O) bec ause oxygen loses an electron

1 1
B. I and III only

from a higher sublevel than nitrogen
C. II and III only

D. IE (N) > IE (O) bec ause oxygen loses an electron
1 1
from a higher sublevel than nitrogen

D. I, II and III
9. The rst ve successive ionization energies for an

4. An electron transition between energy levels n = 4 and
unknown element are 578, 1817, 2745, 11 577 and

n = 2 in an isolated atom produces a line in the visible
–1
14 842 kJ mol . In which group of the periodic table is

spectrum. Which electron transition in the same atom is
this element is likely to be found?

likely to produce a line in the UV spectrum?
A. 1
A. from n = 4 to n = 1
B. 2
B. from n = 4 to n = 3
C. 13
C. from n = 3 to n = 2
D. 14
D. from n = 5 to n = 3
61
16. Sketch an orbital lling diagram for Al and deduce the

Extended-response questions
number of unpaired electrons. [2]
10. Explain, in your own words, why gaseous atoms
3+
produce line spectra instead of continuous spectra. [3] 17. A transition element ion, X , has the electron
conguration [Ar] 3d . Determine the atomic number of
11. State the full and condensed electron congurations for
element X. [1]
the following species in their ground states:
18. Sketch the condensed orbital lling diagram for

a. titanium atom [1]
germanium and deduce the total number of p orbitals
b. selenium atom [1]
containing one or more electrons. [2]
c. silicon atom [1]
LHA
3+
19. Describe, in your own words, how the rst ionization
d. Ti c ation [1]
energy of an atom c an be determined from its emission

2–
e. S anion [1]
spectrum. [2]
12. Determine which of the congurations below is
20. Using the data booklet, explore the rst ionization
impossible. Explain why it c annot exist. [2]
energies of the period 3 elements, from sodium to
2 2 7 2 5
1s 2s 2p 3s 3p
argon. Explain the general trend and discontinuities in
2 2 6 2 6
1s 2s 2p 3s 3p
these energies. [3]
13. Deduce and explain, which of the following electron

21. The rst four successive ionization energies for an
congurations represents a ground state. [2]

unknown element X are given in table3. Deduce the
2 2 6 2 6 2 10 5 1
group of the periodic table in which element X is likely
1s 2s 2p 3s 3p 4s 3d 4p 5s
2 2 6 2 6 2 10 6 1 to be found. [1]
1s 2s 2p 3s 3p 4s 3d 4p 5s
14. Sketch the shape of an s orbital. [1]
–1
n IE / kJ mol
n
15. The diagram below (not to sc ale) represents some of the
1 738
electron energy levels in the hydrogen atom.
2 1451
n = 7
3 7733
n = 6
4 10543
n = 5
 Table 3 Successive ionization energies for element X
n = 4
n = 3
n = 2
n = 1
Draw an arrow on the diagram to represent the lowest
energy transition in the visible region of the emission
spectrum of hydrogen. [1]
62
Structure 1.4 Counting particles
by mass: the mole
How do we quantify matter on the atomic sc ale?
Atoms are extremely small, so any physic al object comfortably with large numbers of very small particles. At
contains a huge number of these particles. There are the same time, the concepts of molar, relative atomic and
more atoms in a glass of water than glasses of water relative molecular masses allow the use of small numbers
in all of the oce ans combined. The unit of the amount for expressing masses of atomic species.
of substance, the mole, enables chemists to de al
Understandings
Structure 1.4.1 — The mole (mol) is the SI unit of amount Structure 1.4.4 — The empiric al formula of a compound
of substance. One mole contains exactly the number of gives the simplest ratio of atoms of each element present
elementary entities given by the Avogadro constant. in that compound. The molecular formula gives the actual
number of atoms of each element present in a molecule.

Structure 1.4.2 — M asses of atoms are compared on a
12
sc ale relative to C and are expressed as relative atomic Structure 1.4.5 — The molar concentration is determined
mass (A ) and relative formula mass (M ). by the amount of solute and the volume of solution.
r r
–1
Structure 1.4.3 — Molar mass (M) has the unitsg mol Structure 1.4.6 — Avogadro’s law states that equal
volumes of all gases measured under the same conditions
of temperature and pressure contain equal numbers
ofmolecules.
The mole (Structure 1.4.1)
Atoms and molecules are so small that their masses c annot be measured directly.
Even a million atoms of lead, Pb, the heaviest stable element, would have a mass
–16
of only 3.4 × 10 g. This is too small to be weighed even on the most sensitive
analytic al balance. At the same time, the number of Pb atoms in 1 g of lead is
21
huge, about 2.9 × 10 , which is hard to imagine, let alone count. Therefore,
chemists need a unit that allows them to work comfortably with both very small
masses and very large numbers of atoms. This unit, the mole, was devised in the
19th century and quickly bec ame one of the most useful concepts in chemistry.
The mole (with the unit “mol”) is the SI unit of amount of substance that contains
23
6.02214076 × 10 elementary entities of that substance. An elementary entity
c an be an atom, a molecule, an electron or any other species. In this book, we
23
will use the rounded value of the mole: 1mol = 6.02 × 10

 Figure 1 One mole quantities
of dierent substances (le to right):
aluminium, water, copper, sucrose and
sodium chloride
63
Avogadro’s constant (N ) is the conversion factor linking the number of particles

A
Prex Symbol F actor
–1
and amount of substance in moles. It has the unit of mol :
–12
pico p 10
23 –1
–9 N = 6.02 × 10 mol
nano n 10 A
–6
micro µ 10
In chemic al c alculations, Avogadro’s constant is used in the same way as any
–3
other conversion factor (table1). For example, to convert kilograms into grams,
milli m 10
we need to multiply the mass in kg by 1,000. Similarly, to convert the amount of

–2
centi c 10
substance (n) into the number of atoms or any other structural units (N), we need
–1
deci d 10
to multiply that amount by N :

A
kilo k 10
N = n×N
6
A
mega M 10
9
In chemistry texts, the term “amount of substance” is oen abbreviated to just
giga G 10
“amount”.
 Table 1 Decimal prexes
Worked example 1
C alculate the amount of lead (Pb), in mol and mmol, in a sample containing
21
2.9 × 10 atoms of this element.
Solution
To nd n, we c an rearrange the equation N = n × N as follows:

A
n =
N
A
21
2.9 × 10
3
Therefore, n(Pb) = ≈ 4.8 × 10 mol

23
6.02 × 10
3 3
According to table1, 1 mmol = 10 mol, so 4.8 × 10 mol = 4.8 mmol.
3
The use of correct signic ant
In this example, both answers (4.8 × 10 mol and 4.8 mmol) have been
gures is discussed in the Tools for

rounded to two signicant gures, the same as in the least precise value used in
21
chemistry chapter.
the division (2.9 × 10 ).
ATL Research skills
The mole is a huge number, and it is useful for counting particles bec ause they
are so small. Measuring amounts of everyday objects in moles c an help use to
convey just how large this number is.
Activity
Choose one of the following and conduct the necessary research to reach an
C alculate: approximate answer.
a. the number of atoms in • How many moles of grains of sand are in a desert of your choice?
2.5 mol of copper metal • How many moles of water molecules are in a large sea or ocean of your
choice?
b. the number of molecules in
• One mole of human cells represents roughly how many people?
0.25 mol of water
• What is the age of the universe, in moles of seconds?
c. the number of atoms in • How tall is a stack of one mole of sheets of paper?
0.25 mol of water • How many moles of air are in your school building?
64
Structure 1.4 Counting particles by mass: the mole
Relative molecular mass and molar mass
(Structure 1.4.2 and 1.4.3)
In Structure 1.2, we introduced the concept of relative atomic mass, A , which

r
is the ratio of the mass of a certain atom to one-twelh of the mass of a c arbon-12
atom. Similarly, relative molecular mass, M , is the ratio of the mass of a molecule
r
or other multiatomic species to one-twelh of the mass of a c arbon-12 atom. Both
A and M are ratios, so they have no units.

r r
To nd the M of a molecule, we need to add together the A values for all atoms
r r
in that molecule.
Worked example 2
C alculate the M for a molecule of water.

r
Solution
Water, H O, is composed of two hydrogen atoms (A = 1.01) and one oxygen

2 r
atom (A = 16.00). Therefore M (H O) = 2 × 1.01 + 16.00 = 18.02.

r r 2
You should always use the actual (not rounded) values of A , which are given
r
in the data booklet and the periodic table at the end of this book. Similarly,
keep all signic ant gures in c alculated M values and never round them to the
r
nearest integer number.
If a substance is composed of ions instead of molecules, the M for that substance

r
is c alculated using the smallest formula unit. For example, c alcium chloride
2+
(C aCl ) is an ionic compound that consists of many c alcium c ations (C a ) and

2
2+
twice as many chloride anions (Cl ). Its smallest formula unit contains one Ca
and two Cl ions. The ions have approximately the same masses as neutral atoms The composition and structure of
bec ause the masses of electrons are negligible. ionic compounds will be discussed
in Structure 2.1.
Therefore, M (C aCl ) = A (C a) + 2×A (Cl) = 40.08 + (2×35.45) = 110.98.

r 2 r r
M any ionic compounds form hydrates: compounds in which water molecules
form coordination bonds (Structure 2.2) with the ions. One of the most common
hydrates is copper(II) sulfate pentahydrate, CuSO •5H O. Copper(II) sulfate

4 2
Activity
pentahydrate forms large, clear, deep-blue crystals (gure2). The stoichiometric
coecient “5” before “H O” means that one formula unit of copper(II) sulfate is
2
C alculate the M values for the
r
bound with ve molecules of water. Therefore, the M value for this hydrate c an
r
following species:
be c alculated as follows:
a. ammonia, NH
3
M (CuSO •5H O) = A (Cu) + A (S) + 4×A (O) + 5×M (H O)

r 4 2 r r r r 2 b. sulfuric acid, H SO
2 4
= 63.55 + 32.07 + (4 × 16.00) + (5×18.02) c. sodium sulfate dec ahydrate,
Na SO •10H O
2 4 2
= 249.72
65
 Figure 2 Crystals of copper(II) sulfate pentahydrate, CuSO •5H O

4 2
Molar mass, M, of a chemic al substance is the mass of 1 mol of that substance.
Molar mass is numeric ally equal to relative molecular mass (for substances with
molecular and ionic structures) or relative atomic mass (for substances with atomic
–1 –1
structure). For example, M(Na) = 22.99 g mol and M(H O) = 18.02 g mol
2
Science as a shared endeavour
A shared understanding of common terminology helps scientists to
communic ate eectively. This terminology is constantly being updated.
Hi s to r i c a l l y, th e mo l e was defined as th e amount of substance t ha t
c o n ta i n e d as ma ny e l e me n ta r y entities (a to ms , mo l e c u l e s , ions, e l e c tro n s
or o t he r pa r t i c l e s) as t h e re w e re a to ms in 0.0 12 k g (o r 12 g ) of c a r b o n -1 2 .
23
How e ve r, t he n u me r i c a l v alue of th e mo l e ( a p prox i m a t e l y 6 .0 2  ×  10 ) had
to be re v i s e d f re qu e n tl y, as th e i m prove me n ts in i n s t r u me n t a t i o n a l l ow e d
s c i e n ti s t s to m e a s u re m a ss with gre a te r pre c i s i o n .
On 16 November 2018, scientists from more than 60 countries met at the
General Conference on Weights and Measures in Versailles, France. It was
agreed here that all SI base units, including the mole, were dened in terms of
physic al constants instead of physic al objects. Following these changes, one
23
mole of a substance is now dened exactly as 6.02214076 × 10 elementary
entities of that substance.
The 2018 redenition of the mole me ans that the mass of 1 mol of c arbon-12
no longer equals 12 g exactly. As a result, the numeric al v alues of M (dened
through two exact SI quantities, the kilogram and the mole) no longer
match the numeric al v alues of their respective A or M (dened through

r r
the experimentally determined mass of a c arbon-12 atom). However, the
dierences between these numeric al v alues are so small (approximately
–8
4 × 10 %) that they c an be ignored for all practic al purposes.
Why are constants and values continuously being revised and updated?
How do scientists achieve a shared understanding of changes made to
existing denitions?
66
The amount (n), mass (m) and molar mass (M) of any substance are related as
follows:
n =
This is probably the most common expression in chemistry, as it is used in almost
all stoichiometric c alculations. Although the base SI unit of mass is the kilogram,
the masses of chemic al substances are traditionally expressed in grams, and
–1
molar masses in g mol
Worked example 3
Table sugar is oen sold in the form of cubes that are made almost entirely
of sucrose. Sucrose is an organic compound with the molecular formula
C H O . C alculate:
12 22 11
a. the molar mass of sucrose
b. the amount of sucrose in one cube (2.80 g) of sugar
c. the number of oxygen atoms in one cube of sugar
Solution
a. M (C H O ) = 12 × 12.01 + 22 × 1.01 + 11 × 16.00 = 342.34

r 12 22 11
M(C H O ) = 342.34 g mol

12 22 11
Activity
b. n =
M
C alculate:
2.80 g
n(C H O ) = ≈ 0.00818 mol

12 22 11 a. the molar mass of sulfuric acid,
1
342.34 g mol
H SO
2 4
c. One mole of sucrose contains 11 mol of oxygen atoms, so
b. the amount of substance in
n(O) = 11 × n(C H O )
12 22 11
1.00 g of sulfuric acid
= 11 × 0.00818 mol ≈ 0.0900 mol
c. the number of hydrogen
23 –1 22
N(O) = n(O) × N = 0.0900mol × 6.02 × 10 mol ≈ 5.42 × 10 atoms in 1.00 g of sulfuric acid
19
 Figure 3 There are more oxygen atoms in one sugar cube than the estimated total insect population on Earth (10 ) and total grains of
21
sand on Earth’s beaches (10 )
67
Empiric al formula, molecular formula and
chemic al analysis (Structure 1.4.4)
The composition of a chemic al substance with a molecular structure c an be
represented by a molecular formula, which shows the actual number of atoms
of each element in the molecule of that substance. In contrast, the empiric al
formula shows the simplest ratio of atoms of the dierent elements that are
present in the substance. The molecular and empiric al formulas of the same
substance c an be identic al or dierent (table2). For ionic compounds, the
empiric al formula is the same as the formula unit, which represents the simplest
ratio of ions in the compound (gure4).
Substance Molecular formula Empiric al formula
oxygen O O
2
ozone O O
3
water H O H O
2 2
hydrogen peroxide H O HO
2 2
butane C H C H
4 10 2 5
glucose C H O CH O
6 12 6 2
sucrose C H O C H O
12 22 11 12 22 11
 Table 2 Molecular and empiric al formulas of selected substances
 Figure 4 Sodium uoride is an ionic compound with the empiric al formula NaF. It
is used in some countries as a food supplement to prevent tooth dec ay
The number of atoms of a certain element is proportional to the amount of that
element in mol (N = n×N ). Therefore, the empiric al formula also shows the
A
mole ratio of elements in a chemic al compound. For example, one molecule of
water, H O, contains two atoms of hydrogen and one atom of oxygen, so the
2
atomic ratio of hydrogen to oxygen in water is 2:1. Similarly, one mole of water
68
contains two moles of hydrogen atoms and one mole of oxygen atoms, so the
mole ratio of hydrogen to oxygen in water is also 2:1.
The elemental composition of a compound is oen expressed in percent by
mass, which is commonly referred to as the percentage composition, ω. The
mole ratio c an be used to c alculate the percentage composition of a compound.
Worked example 4
C alculate the percentage composition of water.
Solution
Let n(H O) = 1 mol, then n(H) = 2 mol and n(O) = 1 mol. Using m = n × M:
2
m(H) = 2 mol × 1.01 g mol = 2.02 g
m(O) = 1 mol × 16.00 g mol = 16.00 g
m(H O) = 1 mol × 18.02 g mol = 18.02 g

2
2.02 g
ω (H) = × 100% ≈ 11.2%
18.02 g
ω (O) = 100% 11.2% = 88.8%
In practice, chemists more oen face the opposite problem of deducing
Practice question
the empiric al formula for a compound from its percentage composition or
other experimental data. The percentage composition c an be determined by

C alculate the percentage
destruction analysis, in which the compound is combusted or decomposed, and

composition of sulfuric acid, H SO
2 4
the masses of the combustion or decomposition products are measured.
The mass percentages of elements in a sample c an be determined by various
analytic al techniques, such as fully automated combustion elemental analysis.
In a typic al experiment, the sample is burned in excess oxygen, and the volatile
combustion products are trapped and weighed. These weights are then
converted into mass percentages of chemic al elements in the original sample.
Worked example 5
Iron and oxygen form several compounds (iron oxides). Deduce the empiric al
formula of an oxide that contains 72.36% of iron.
Solution
If ω (Fe) = 72.36%, then ω (O) = 100% 72.36% = 27.64%.
Let m(Fe O ) = 100 g, then m(Fe) = 72.36 g and m(O) = 27.64 g

x y
Use n = to determine the amount of each element:
72.36 g
n(Fe) = ≈ 1.296 mol
–1
55.85 g mol
27.64 g
n(O) = ≈ 1.728 mol
–1
16.00 g mol
The mole ratio x : y = 1.296 : 1.728 ≈ 1 : 1.333 ≈ 3 : 4
Therefore, the empiric al formula of the oxide is Fe O .

3 4
 Figure 5 Fe O is the main component of the mineral
3 4
magnetite, a common iron ore
69
Worked example 6
Hydroc arbons are organic compounds of c arbon and hydrogen. An
unknown hydroc arbon has undergone combustion in excess oxygen
to produce 26.41 g of c arbon dioxide, CO , and 13.52 g of water, H O.

2 2
Deduce the empiric al formula of the hydroc arbon.
Solution
M(CO ) = 12.01 + 2×16.00 = 44.01 g mol

2
26.41 g
n(CO ) = ≈ 0.6001 mol

2
–1
44.01 g mol
n(C) = n(CO ) = 0.6001 mol

2
M(H O) = 2×1.01 + 16.00 = 18.02 g mol

2
13.52 g
n(H O) = ≈ 0.7503 mol

2
–1
18.02 g mol
n(H) = 2 × n(H O) = 2×0.7503 mol≈1.501 mol

2
All c arbon and hydrogen atoms in the combustion products originate from
the hydroc arbon, C H , so:

x y
The mole ratio x:y = 0.6001 : 1.501 ≈ 1 : 2.5 = 2 : 5
Therefore, the empiric al formula of the hydroc arbon is C H

2 5
We express empiric al formulas as whole number ratios. Whole numbers are also
known as integers. In worked example 5, the ratio we initially c alculated was
comprised of two non-integer values: 1.296 and 1.728. To convert it to a whole
number ratio, you divide each term in the ratio by the smallest number in the
ratio. This gives a ratio of 1 : 1.333. Then, you c an use trial and error to determine
a factor by which you should multiply the ratio to obtain the whole number ratio.
Multiplying this ratio by 3, and then subsequently rounding the result, gives a
whole number ratio of 3 : 4.
The molecular formula of a compound can be deduced from the empirical formula
if we know the molar mass of the compound. For example, you might determine
experimentally that the molar mass of the hydrocarbon in worked example 6 is
–1
58.12 g mol . The molar mass of the empirical formula can be calculated:
–1
(12.01 × 2) + (1.01 × 5) = 29.07 g mol
The value of 29.07 is roughly half of 58.12, therefore the molecular formula must
have twice the number of atoms as the empiric al formula: C H

4 10
Determining the molar masses of
Table2 suggests that this hydroc arbon could be butane, C H . However, we

4 10
gaseous substances is discussed in
c annot be sure about it without further analysis, as there is another hydroc arbon,
Structure 1.5.
methylpropane, with the same molecular formula. Butane and methylpropane
c an be distinguished by measuring their boiling points ( Structure 1.1) or
comparing their infrared spectra (Structure 3.2).
Practice questions
1. Deduce the empiric al formulas of the following compounds:
a. an oxide of manganese that contains 36.81% of oxygen
b. a hydroc arbon that produces 5.501 g of c arbon dioxide and 2.253 g of
water upon complete combustion
2. Deduce the molecular formula of the hydroc arbon from 1b if its molar mass
–1
is 42.09 g mol
70
Experimental determination of empiric al formula
Relevant skills Instructions
• Tool 1: Measure mass 1. Weigh a clean, dry crucible.
• Tool 3: C arry out c alculations involving decimals

2. Obtain a piece of magnesium ribbon (between 0.3 g
andratios
and 1.0 g) from your teacher. Measure its exact mass.
• Tool 3: Use approximation and estimation

3. Twist the magnesium into a loose coil and place it

inside the crucible.
• Inquiry 3: Explain realistic and relevant improvements

4. Heat the crucible, with its lid on, over a roaring
to an investigation
Bunsen ame. Periodic ally li the crucible lid to allow
air to enter the crucible.

S afety
5. Continue heating until the magnesium no longer

lights up. Then, remove the heat source and allow the
• Take suitable prec autions around open ames.
crucible to cool for a few minutes.

• The equipment will get very hot. Take suitable
prec autions around it and do not touch it while it 6. When the crucible is cool, weigh it.
ishot. 7. Heat the crucible and its contents strongly for an
• M agnesium burns with a very bright light. Do not look additional minute. Allow to cool and re-weigh.
directly at it. Repeat this heating-cooling-weighing cycle until the
mass is constant.
M aterials
• crucible and lid Q uestions
• balance (±0.01 g) 1. Process the data to determine the empiric al formula
• pipeclay triangle of magnesium oxide.
• tripod
2. Compare your experimental empiric al formula to the
• heat-proof mat
actual one.
• tongs
3. Obtain mass data from other members of your class.
• magnesium ribbon
Plot a graph of mass of magnesium oxide vs mass of
• Bunsen burner
magnesium.
lid 4. Identify any anomalies (if applic able) and draw a best
t line on the graph.
5. Explain what the graph shows about the composition
crucible of magnesium oxide.
6. Explain why you repeatedly heated and weighed the
coiled magnesium
crucible until a constant mass was achieved.

ribbon
7. Identify and explain two major sources of error in this
procedure.
8. Suggest realistic improvements to the methodology
that could minimize the sources of error you have

Bunsen burner
identied.
9. Reect on the role of approximation and rounding in
empiric al formula c alculations. When is it suitable to
 Figure 6 The experimental set-up round to the nearest whole number? When is it not?
C an you come up with a rule of thumb of when to
round and when not to round?
71
Measurement
Atoms, molecules and ions are so small that counting them directly is virtually
impossible. The concept of the mole is powerful bec ause it relates number of
particles to mass, which c an be easily measured.
As with all measurements, mass has an uncertainty associated with it.
Consider the mass of a sample of c alcium c arbonate, C aCO , is found to be

3
3.500 g ± 0.001 g. This means the mass measurement c an be inaccurate by
up to 0.001 g in either direction. This is clearly a minuscule mass. How many
moles does it represent? How many particles does it represent? Do a quick
c alculation and nd out. You will see that in moles the uncertainty is tiny, but in
terms of particles, it is quite large.
Is a measurement uncertainty ever negligible? If so, when? Think about these
questions as you proceed through the DP chemistry course, particularly when
doing experiments that involve making measurements.
Solutions and concentration
(Structure 1.4.5)
M any chemic al reactions are c arried out in solutions. Solutions are easier to
handle and mix than solids or gases. Sometimes a solvent is used bec ause it c an
aect the properties of dissolved substances or participate in chemic al reactions.
Solutions are homogeneous mixtures of two or more components. E ach solution
consists of a solvent and one or more solutes. The solvent is usually the major
component of the solution, so the properties of the whole solution are similar
to the properties of the solvent. The other components of the solution are
c alled solutes. For example, a solution of sugar in water is more like water (clear
Homogeneous and heterogeneous
colourless liquid) than sugar (white crystalline powder), so water is the solvent
mixtures are discussed in
while sugar is the solute. In this topic, we will consider only aqueous solutions
Structure 1.1.
(from the L atin aqua meaning “water ”), in which the solvent is water.
solute
 Figure 7 How a solution is formed
In some c ases, the identity of the solvent is unclear: for example, if we mix
ethanol and water, each of these liquids c an be c alled a solvent. However, if
water is present in the mixture, it is traditionally regarded as the solvent, even if
it is not the major component. For example, we say “96% solution of ethanol in
water ” rather than “4% solution of water in ethanol”.
72
Solutions are oen classied according to the mass or mole ratio between the
solute and solvent. A concentrated solution contains a large proportion of
solute, and so has a high ratio of solute to solvent, while a dilute solution has a
small proportion of solute, and so has a low ratio of solute to solvent. Generally,
the term “concentrated” refers to solutions with much more than 10 g of the
solute per 100 g of the solvent, and the term “dilute” refers to solutions with
much less than 10 g of the solute per 100 g of the solvent.
TOK
Some words do not have precise denitions and their choice and
interpretation is context dependent. The terms “concentrated” and “dilute”
are not precisely dened and should be used with c are. For example, most
chemists would c all a solution of 5 g of sulfuric acid (H SO ) in 100 g of water

2 4
“dilute”, as much higher proportions of sulfuric acid to water are commonly
used in laboratories. At the same time, a solution of 5 g of potassium
permanganate (KMnO ) in 100 g of water would be considered very

4
concentrated by any medic al worker, as typic al concentrations of potassium
permanganate in antiseptic solutions are less than 0.1 g per 100 g of water.
The concentrations in the examples above could be expressed numeric ally.
To what extent does expressing a quantity numeric ally help or hinder the
communic ation of knowledge?
Quantitatively, the composition of solutions is expressed in terms of
concentration. Molar concentration, c, also known as molarity, is the ratio of the
amount of a solute to the volume of the solution:
n
solute
c =
solute
V
solution
–3
The most common units for molar concentration are mol dm (which is the same
–1 –3 –3
as mol L ). For very dilute solutions, smaller units (mmol dm or µmol dm ) c an
also be used:
–3 –3 –3
1 mmoldm = 1 × 10 mol dm
–3 –6 –3
1 µmoldm = 1 × 10 mol dm
–3
The units of molar concentrations are sometimes abbreviated as M (for mol dm )
–3
or mM (for mmol dm ). For example, the expression “2.5 MNaOH” means that
each dm of the solution contains 2.5 mol of sodium hydroxide.
Note that the term “molar concentration” refers to a specic substance, not the
whole solution. For example, it is incorrect to say that “the concentration of a
–3
sodium chloride solution is 1.0 mol dm ”, as it is not clear whether we are talking
about the concentration of sodium chloride or water. The correct statement
–3
would be “the concentration of sodium chloride in a solution is 1.0 mol dm ”.
Molar concentration is oen represented by square brackets around the solute
–3
formula. For example, the expression [NH ] = 0.5 M refers to a 0.5 mol dm
3
solution of ammonia. Similarly, the expression [Cl ] refers to the molar
concentration of chloride ions in a solution.
73
Worked example 7
–3
C alculate the molar concentration of sodium chloride, in mol dm , in
a solution prepared by dissolving 3.60 g of N aCl(s) in water to make
25.0 cm of the nal solution.
Solution
First, c alculate the molar mass of sodium chloride:
M(NaCl) = 22.99 + 35.45 = 58.44g mol
Then use n = to c alculate the amount of solute:
3.60 g
n(NaCl) = ≈ 0.0616 mol
–1
58.44 g mol
Convert the volume to dm by dividing by 1,000:
Activity
3 3
V(solution) = 25.0 cm =0.0250 dm
C alculate the mass of sulfuric acid, Use c = to c alculate the concentration:
H SO , in 50.0 cm of a solution
2 4 0.0616 mol
3
–3 c(NaCl) = ≈ 2.46 mol dm

where [H SO ] = 1.50 mol dm 3
2 4 0.0250 dm
The composition of a solution is sometimes expressed as the mass
concentration, ρ , of the solute, which is the ratio of the mass of the solute to
solute
the volume of the solution:
m
solute
ρ =
solute
V
solution
Worked example 8
C alculate the mass concentration of sodium chloride in the solution from
worked example 7.
Solution
If we know the mass of the solute and the volume of the solution, we c an
Activity
c alculate the mass concentration as follows:
3.60 g
3
ρ(NaCl) = = 144 g dm
C alculate the molar concentration 3
0.0250 dm
–3
of sulfuric acid, in mol dm Alternatively, the mass concentration of NaCl c an be found from its molar
in a solution with ρ(H SO ) = concentration and molar mass, using the relationship ρ = c × M :
2 4 solute solute solute
–3
0.150 g cm
3 1 3
ρ(NaCl) = c(NaCl)× M(NaCl) = 2.46 mol dm ×58.44 g mol ≈ 144 g dm
–3 –3
The most common units for mass concentration are g dm and g cm . M ass
concentration and molar concentration of the same solute are related by molar
mass, as follows:
ρ
solute
c =
solute
M
solute
74
Worked example 9
A standard solution was prepared by dissolving 6.624g of sodium c arbonate, Na CO , in deionized water
2 3
3 3
using a 250 cm volumetric ask. An analytic al pipette was used to transfer 10.0 cm sample of this solution to a
100cm volumetric ask, and the ask was topped up to the graduation mark with deionized water. C alculate the
–3
concentration, in moldm , of sodium c arbonate in the new solution.
Solution
First, we need to nd the concentration of sodium c arbonate in the standard solution:
M(Na CO ) = 2×22.99 + 12.01 + 3×16.00 = 105.99 g mol

2 3
6.624 g
n(Na CO ) = ≈ 0.06250 mol

2 3
–1
105.99 g mol
3 3
V = 250 cm = 0.250 dm
standard
Note that the accuracy of a typic al volumetric ask is three signic ant gures.
0.06250 mol
3
c (Na CO ) = = 0.250 mol dm

standard 2 3
3
0.250 dm
Then we need to c alculate the concentration of sodium c arbonate in the new solution.
First, c alculate the amount of Na CO in the sample. Remember to convert all volumes to dm
2 3
3 3
V = 10.0 cm = 0.0100 dm
sample
c (Na CO ) = c (Na CO ) = 0.250 mol dm

standard 2 3 sample 2 3
3 3
n (Na CO ) = 0.250 mol dm ×0.0100 dm = 0.00250 mol

sample 2 3
When the sample is diluted with deionized water to produce the new solution, the amount of solute does not change.
Therefore
n (Na CO ) = n (Na CO ) = 0.00250 mol

sample 2 3 new 2 3
Now you c an work out the concentration of Na CO in the new solution by dividing the amount of Na CO by the
2 3 2 3
volume of the new solution:
3 3
V = 100 cm = 0.100 dm
new
0.00250 mol
3
c (Na CO ) = = 0.0250 mol dm

new 2 3
3
0.100 dm
It is a common practice to store chemic als in the form of concentrated solutions
Practice question
(so-c alled stock solutions) and dilute them to the required concentration when
needed. Stock solutions with a known concentration of the solute are c alled 3. A standard solution was prepared
standard solutions. by dissolving 2.497 g of
copper(II) sulfate pentahydrate,
To determine the concentration of the standard solution in worked example 9,
CuSO • 5H O, in deionized
4 2
we did the following two c alculations:

3
water using a 100 cm volumetric
ask. A 5.00 cm sample of this

1. n = c × V
sample sample sample
solution was diluted to 250.0 cm .
n
new
C alculate the concentration, in

2. c =
new
V
–3
new
mol dm , of copper(II) sulfate in the
nal solution.
You know that n = n , so you c an substitute equation 1 into equation 2. This
sample new
gives the following expression:
c × V The process for preparing standard
sample sample
c =
new
solutions is discussed in the Tools
V
new
for chemistry chapter.
Therefore, to c alculate the concentration of a solute in a new solution, you just
need to know the original concentration of the solute, the volume of the original
solution, and the volume of the new solution. In summary:
c × V = c × V
1 1 2 2
75
C ase study: spectrophotometry and c alibration curves
Spectrophotometry is an analytic al technique based on the measurement of
the intensity of visible, ultraviolet and near-infrared radiation. This technique
is commonly used for determining concentrations of coloured substances in
solutions.
A spectrophotometer produces light of a certain wavelength, which passes
through a small sample of the studied solution. The photodetector measures the
intensity of the transmitted light and converts it into the absorbance. Absorbance
is a value describing the amount of light absorbed by the sample. Initially, several
standard solutions of the studied substance are prepared by serial dilution
(gure9), and their absorbances are measured. These absorbances are plotted
against concentrations, producing a c alibration curve (gure8). The c alibration
curve is then used for determining the unknown concentration of the coloured
substance in the studied solution.
In the general c ase, a c alibration curve relates a measurable property (such as
absorbance, pH or electric al conductivity) of the solution to the concentration of
the solute. The unknown concentration c an be found by measuring that property
and plotting the result of the measurement on the c alibration curve.
0.40
0.30
ecnabrosba
0.20
0.10
0 0.10 0.20 0.30 0.40 0.50
3
concentration/mmol dm
 Figure 8 A typic al c alibration curve
Data-based question
 Figure 9 A series of standard solutions of potassium permanganate
The calibration curve in gure8
Ideally, the calibration curve should be linear, pass through the origin and have a
was obtained using a series of
tilt of approximately 45°. If the curve does not meet any of these requirements, it
standard solutions of potassium
should be constructed again using a slightly dierent wavelength of light and/or
permanganate, KMnO . A solution

4
dierent set of standard solutions. Sometimes linearity can only be achieved within
with unknown concentration of
a narrow range of concentrations. In this case, the studied solution can be diluted,
KMnO has an absorbance of

4
so the concentration of the studied substance falls within the range of calibration
0.285. Determine the concentration
curve. In the last case, some additional calculations will be required to relate the
of KMnO in that solution.

4
concentrations of the studied substance in the diluted and original solutions.
76
Another technique, colorimetry, is based on the same principles as
spectrophotometry but limited to visible light. The terms “colorimetry” and
“spectrophotometry” are oen used interchangeably, which is not entirely
correct but very common.
Concentration uncertainty of a standard solution
A standard solution is a solution of known concentration. M aterials
In this activity, you will prepare two standard solutions • Wash bottle containing distilled water
of copper(II) sulfate, each by using dierent equipment. • Weighing boats (2)
By propagating the measurement uncertainties, you will • 100 cm beakers (2)
assess the precision of the concentration values. You • Stirring rods (2)
will determine the actual concentration of your solutions • Funnels (2)
using a colorimeter. This will then allow you to assess the • Pipettes
accuracy of the concentrations. • Spatula
• Reagent bottles (2)
Relevant skills
• Blank labels
• Tool 1: Measuring volume and mass
• Colorimeter
• Tool 1: Standard solution preparation
• Cuvettes
• Tool 3: C alculate and interpret percentage error and
• C alibration curve relating concentration of copper(II)
percentage uncertainty
sulfate and absorbance
• Tool 3: Express quantities and uncertainties to an
• Copper(II) sulfate pentahydrate, CuSO •5H O

4 2
appropriate number of signic ant gures
• Tool 3: Record measurement uncertainties

Additional equipment for solution 1:
3
• Tool 3: Propagate uncertainties
• 100 cm volumetric ask
• Inquiry 2: Assess accuracy and precision

• Milligram balance (three decimal places)
S afety
Additional equipment for solution 2:
3
• 100 cm measuring cylinder
• Solid copper(II) sulfate is an irritant and toxic to

• Centigram balance (two decimal places)
the environment
Instructions
• Dispose of all solutions appropriately.
1. Use the equipment provided to prepare two
copper(II) sulfate standard solutions, both with
–3
concentration 0.020 mol dm . When preparing
solution 1, you should use the volumetric ask and
milligram balance. For solution 2, use the measuring
meniscus of the solution
cylinder and centigram balance.
2. Record the measurements you make along the way,
etched line indic ating

including their uncertainties.
3
volume, e.g. 250 cm
3. Following your teacher ’s instructions on how to use
the colorimeter, measure the absorbance of your
solutions.
4. Refer to the c alibration curve to determine the actual
concentration of your solutions.

volumetric flask contains
a fixed volume of solution Q uestions
when the meniscus is on 1. Determine the uncertainty of the concentrations of
the etched line, solutions 1 and 2.
3
e.g. 250 cm 2. C alculate the percentage error of the concentrations
of solutions 1 and 2.
3. Assess the precision and accuracy of the
concentrations of solutions 1 and 2.
77
5. The construction of c alibration curves involves

4. Consider the way you have presented your
ATL
preparing samples of solutions that cover a range of

c alculations for the questions above. Do you
concentrations. Instead of measuring and dissolving

think they convey your thinking? Do you think
a certain mass of solute the way you have done

a reader would be able to easily follow your
here, chemists oen start with a stock solution and

thought process? How could you improve
perform a serial dilution. Discuss the advantages

the presentation of your c alculations? You
and disadvantages of using a serial dilution in the

may want to look through some of the
preparation of samples for a c alibration curve.

worked examples in this textbook for ideas.
Avogadro’s law (Structure 1.4.6)
In 1811, Amedeo Avogadro suggested that equal volumes of any two gases
at the same temperature and pressure contain equal numbers of molecules.
This hypothesis has been conrmed in many experiments and is now known as
Avogadro’s law
Since the amount of a substance and the number of particles are proportional
to each other, the amount of a gas is proportional to its volume. Therefore, the
volumes of two reacting gaseous species measured under the same conditions
are proportional to the amounts of these species:
n V
1 1
n V
2 2
In turn, the amounts of reactants and products are proportional to their
stoichiometric coecients in a balanced chemic al equation. As a result, if we
know the volume of any gas consumed or produced in the reaction, the volumes
of other gaseous substances c an be found without c alculating their amounts.
Worked example 10
The combustion of hydrogen sulde, H S, proceeds as follows:

2
2H S(g) + 3O (g) → 2H O(l) + 2SO (g)

2 2 2 2
C alculate the volumes of oxygen, O (g), consumed and sulfur dioxide,

2
SO (g), produced if the volume of hydrogen sulde combusted was

2
0.908 dm . All volumes are measured under the same conditions.
Solution
Practice question
The ratio of the stoichiometric coecients of H S and O is 2 : 3. Therefore,

2 2
3
4. Incomplete combustion of
you c an multiply the volume of combusted H S by to nd the volume of
2
2
hydrogen sulde produces

combusted O :
2
elemental sulfur instead of sulfur

3 3 3 3
V(O ) = V(H S) = × 0.908 dm ≈ 1.36 dm

2 2
dioxide: 2 2
The ratio of the stoichiometric coecients of H S and SO is 1 : 1. Therefore,

2 2
2H S(g) + O (g) → 2H O(l) + 2S(s)

2 2 2
the volume of combusted H S is the same as the volume of produced SO :

2 2
C alculate the volume of 3
V(SO ) = V(H S) = 0.908 dm

2 2
combusted hydrogen sulde if the
Note that the volume of liquid water c annot be found in the same manner, as
volume of oxygen consumed in
Avogadro’s law applies to gases only.

3
this reaction was 1.25 dm
Linking question
Avogadro’s law applies to ideal gases. Under what conditions might the
behaviour of a real gas deviate most from an ideal gas? (Structure 1.5)
78
C alculate:
Topic review
a. The molar mass of potassium alum,

KAl(SO ) •12H O. [1]
4 2 2
b. The amount of substance, in mol, in 1.00 g of
How do we quantify matter on the atomic scale?

potassium alum. [1]
c. The total number of atoms in 1.00 g of
potassium alum. [1]
d. The amount of water, in mol, that c an be produced
2. What is the number of oxygen atoms in 0.400 mol of by complete decomposition of 1.00 g of
copper(II) sulfate pentahydrate, CuSO •5H O? potassiumalum. [1]

4 2
24
A. 3.60 C. 2.16 × 10 e. The percentage composition, by mass, of
24 potassium alum. [2]

B. 9 D. 5.40 × 10
8. To visualize the mole, a chemistry student decided to

3. A sample containing 0.70 g of c alcium nitrate,
23
3 pile up 6.02 × 10 grains of sand. Estimate the time

C a(NO ) , is dissolved in water to a volume of 200 cm .
3 2
– needed to complete this project if an average grain

What is the concentration of NO ions in this solution?
3
ofsand weighs 5 mg, and the student c an shovel

–3 –3
A. 3.5 g dm C. 0.021 mol dm
50 kg of sand per minute. [3]
–3 –3
B. 7.0 g dm D. 0.043 mol dm
9. Deduce the empiric al formulas for the following
4. For which molecule is the empiric al formula the same as
compounds:
the molecular formula?
a. an oxide of sulfur that contains 59.95% of oxygen [1]
A. CH CH CH OH C. CH CH CH CH
3 2 2 3 2 2 3
b. an oxygen-containing organic compound, 5.00 g of
B. CH COOCH CH D. CH COOH
3 2 3 3
which produces 9.55 g of carbon dioxide and 5.87 g
–3
of water upon complete combustion. [2]
5. Which volume of a 5.0 mol dm sulfuric acid (H SO )
2 4
stock solution is required to prepare 0.50 dm of a
10. A standard solution of potassium sulfate, K SO , was

2 4
solution whose concentration of hydrogen ions is 3
prepared from 8.714 g of the solid salt using a 250 cm
–3
0.10 mol dm ?
volumetric ask. C alculate the mass concentration, in
3 3
–3 –3
A. 0.010 cm C. 5.0 cm
g dm , and the molar concentration, in mol dm , of
3 3
potassium sulfate in the nal solution. [2]
B. 0.0050 cm D. 10 cm
11. The c alibration curve in gure7 was constructed using

6. A student obtained the following data during an
ve standard solutions, in which the concentration of

experimental determination of the empiric al formula of
potassium permanganate, KMnO , varied from 0.100

an oxide of tin:
4
–3
to 0.500 mmol dm . Describe how you would prepare
 M ass of tin before heating = 1.78 g
these solutions using serial dilution. [3]
 M ass of oxide of tin aer heating to a constant
12. C arbon monoxide, CO, is a toxic gas. Its combustion

mass= 2.26 g
produces c arbon dioxide, CO (g).

2
According to these data, what is the correct formula of
a. Deduce the balanced equation for the combustion
the oxide of tin?
of c arbon monoxide. [1]
A. SnO C. SnO
3
3
b. C alculate the volumes, in dm , of consumed c arbon
B. SnO D. SnO
2 5
monoxide and oxygen if the combustion produced
2.00 dm of c arbon dioxide. All volumes are
measured under the same conditions. [2]
7. Alums are salt hydrates of the general formula
XAl(SO ) •12H O, where X is an alkali metal or other

4 2 2
singly-charged c ation. When heated, most alums
decompose as follows:
XAl(SO ) •12H O(s) → XAl(SO ) (s) + 12H O(l)

4 2 2 4 2 2
79
Structure 1.5 Ideal gases
How does the model of ideal gas behaviour help us to predict the behaviour of real gases?
As with any theoretic al model, the concept of an ideal gas at low temperatures and high pressures the behaviour of
is a simplic ation that has its advantages and limitations. In real gases deviates signic antly from the prediction, so the
many c ases, it predicts the properties of real gases with a ideal gas model c annot be used under these conditions.
precision sucient for most practic al purposes. However,
Understandings
Structure 1.5.1 — An ideal gas consists of moving particles with negligible volume and no intermolecular forces. All
collisions between particles are considered elastic.
Structure 1.5.2 — Real gases deviate from the ideal gas model, particularly at low temperature and high pressure.
Structure 1.5.3 — The molar volume of an ideal gas is a constant at a specic temperature and pressure.
Structure 1.5.4 — The relationship between the pressure, volume, temperature and amount of an ideal gas is shown in
p V p V
1 1 2 2
the ideal gas equation pV = nRT and the combined gas law =
T T
1 2
Assumptions of the ideal gas
model (Structure 1.5.1)
The ideal gas model states that an ideal gas conforms to the following ve
assumptions:
1. Molecules of a gas are in constant random motion
This means that gas molecules are not stationary. They move in straight lines
until they collide with another gas molecule or the side of a container.
2. Collisions between molecules are perfectly elastic
In inelastic collisions of larger objects, energy c an be transferred as heat
or sound. However, the collisions between molecules in an ideal gas are
perfectly elastic and no energy is lost from the system.
3. The volume occupied by gas molecules is negligible compared to the
volume of the container they occupy
Vaporized water occupies 1600 times the volume of liquid water at 273.15K
(0 °C) and 100 kPa pressure (standard temperature and pressure, STP).
Nitrogen gas occupies about 650 times the volume of liquid nitrogen under
the same conditions. In both c ases, the number of molecules in liquid and
gaseous phase is the same and the size of individual molecules has not
changed, but the volume of the gas is >99.9% empty space. This is the
space in which the gas molecules are free to move.
4. There are no intermolecular forces between gas particles
Intermolecular forces are studied in
For an ideal gas, the intermolecular forces are negligible compared to the kinetic
Structure 2.2.
energy of the molecules. As such, an ideal gas will not condense into a liquid.
80
5. The kinetic energy of the molecules is directly proportional to Kelvin
temperature
This relationship is studied in Reactivity 2.2
Pressure–volume relationships
Robert Boyle (1627–1691) established that, at constant temperature, the
pressure of a given amount of a gas is inversely proportional to its volume. This
relationship, now known as Boyle’s law, c an be expressed as follows:
 Figure 1 An ideal gas consists of
1
particles that collide elastic ally, have no
p ∝ or pV = k (a constant) or p V =p V
1 1 2 2
V
intermolecular forces and occupy negligible
In gure 1, the molecules of a gas are constantly striking and bouncing o volume when compared to the volume of
the walls of the container. The force of these impacts produces a measurable the gas (the container)
pressure. If the volume is halved, there are twice as many molecules in each unit
of space, so every second there are twice as many impacts with the container
walls, so the pressure is doubled (gure 2).
volume halved
pressure doubled
 Figure 2 Halving the volume of a container doubles the pressure

p
p
,erusserp
,erusserp
TOK
Models are simplied
representations of natural
phenomena. The ideal gas model is
volume, V reciproc al volume, 1/V
built on certain assumptions related
 Figure 3 Graphs showing the inverse relationship between pressure and

to the behaviour of ideal gases.
volume of an ideal gas
What is the role of assumptions
in the development of scientic
–2 –3
models?
The SI unit of pressure is the pasc al (Pa), where 1 Pa = 1 N m = 1 J m . M any
other units of pressure are commonly used in dierent countries, including the What are the implic ations of
atmosphere (atm), millimetres of mercury (mm Hg), bar, and pounds per square not acknowledging a model’s
inch (psi). Standard temperature and pressure conditions (STP) are frequently limitations?
found in databases for comparative purposes. STP for gases is 0 °C or 273.15 K
temperature and 100.0 kPa pressure.
81
Worked example 1
A weather balloon lled with 32.0 dm of helium at a pressure of 100.0 kPa
is released at sea level. The balloon reaches an altitude of 4500 m, where
the atmospheric pressure is 57.7 kPa. C alculate the volume, in dm , of the
balloon at that altitude. Assume that the temperature and the amount of
helium in the balloon remain constant.
Solution
V × p
1 1
From Boyle’s law, it follows that V = , so:

2
p
2
32.0 dm × 100 kPa

3
V = ≈ 55.5 dm
2
57.7 kPa
Practice question
1. At a certain altitude, a weather balloon has a temperature of –35.0 °C and
a volume of 0.250 m . C alculate the pressure, in kPa, inside the balloon if
contains 16.0 g of helium, He(g).
Real gases vs ideal gases (Structure 1.5.2)
When the volume of a real gas decreases signic antly, the molecules may
begin to occupy a large proportion of the container. With so little space to
move, intermolecular forces become signic ant. This decreases the number
of collisions, reducing the pressure. This means that, for a real gas, the inverse
relationship between pressure and volume no longer applies. Figure 4 shows a
graph of pressure against volume for a real gas and an ideal gas. For the real gas,
doubling the pressure no longer halves the volume.
real gas
ideal gas
p
erusserp
0.5p
V 2V
volume
0
Figure 4 Doubling the pressure halves the volume for
an ideal gas but not for a real gas
82
For a gas to deviate from ideal gas behaviour, there must be detectable
intermolecular forces and/or a signic ant volume of the gas must be occupied by
the molecules themselves. This commonly occurs at a low temperature and high
pressure.
Low temperature: At low temperature, the kinetic energy of the gas molecules
is reduced. As they collide with one another, intermolecular forces of attraction
form and molecules may not necessarily rebound elastic ally.
High pressure: At high pressure, there are more molecules in a reduced space.
The volume of the molecules becomes a signic ant part of the volume of the gas.
As molecules themselves c annot be compressed, only the space between them,
the relationship between pressure and volume is no longer inverse, so the gas is
not considered to be an ideal gas.
Ideal gas conditions keep molecules far apart and prevent interaction between
them. The conditions for an ideal gas behaviour are low pressure and high
temperature. At low pressure, there are very few molecules per unit of volume
in the container, so the space occupied by the molecules themselves is
negligible. At high temperature, the molecules are moving too fast to allow for
intermolecular forces of attraction to form.
Activity
1. Outline the main assumptions behind the ideal gasmodel.
2. Discuss what conditions of pressure and temperature are likely to lead to
deviations from ideal behaviour.
3. Consider how each of the following might affect the validity of the ideal
gasmodel:
a. Strong intermolecular forces
b. L arge molecular volume
4. For each of the following pairs, predict which is more likely to exhibit
ideal behaviour and give a reason:
a. gas at low pressure
or
gas at high pressure
b. gas at low temperature
or
gas at high temperature
c. hydrogen fluoride, HF(g)
or
hydrogen bromide, HBr(g)
d. methane, CH (g)
4
or
dec ane, C H (g)

10 22
e. propanone, CH COCH (g)

3 3
or
butane, C H (g)
4 10
83
Real gases
Gases that deviate from the ideal gas model are known as
n 2
real gases.
V – nb
( ) ( )
p + a = nRT
V
Relevant skills
measured
• Tool 2: Use spreadsheets to manipulate data.
pressure
correction
• Inquiry 1: Select sufficient and relevant sources of

correction for for volume
information.
forces between of molecules
molecules
• Inquiry 1: Demonstrate creativity in the designing,
measured
implementation or presentation of the investigation.
volume
Instructions
Parameter a corrects for intermolecular force strength and
The relationship between pressure, volume, amount and

parameter b corrects for molecular volume. Values of a
temperature of real gases is modelled by the van der

and b for various gases are shown in table 1.
Waals equation:
–1 6 –2 –3 3 –1
Substance a / × 10 Pa m mol b / × 10 m mol
ammonia, NH 4.225 0.0371

3
argon, Ar 1.355 0.0320
butane, C H 13.89 0.1164

4 10
butan-1-ol, C H OH 20.94 0.1326

4 9
chloromethane, CH Cl 7.566 0.0648

3
ethane, C H 5.580 0.0651

2 6
ethanol, C H OH 12.56 0.0871

2 5
helium, He 0.0346 0.0238
hydrogen bromide, HBr 4.500 0.0442
hydrogen chloride, HCl 3.700 0.0406
hydrogen uoride, HF 9.565 0.0739
krypton, Kr 5.193 0.0106
methane, CH 2.303 0.0431

4
methanol, CH OH 9.476 0.0659

3
neon, Ne 0.208 0.0167
pentane, C H 19.09 0.1449

5 12
pentan-1-ol, C H OH 25.88 0.1568

5 11
propane, C H 9.39 0.0905

3 8
propan-1-ol, C H OH 16.26 0.1079

3 7
water, H O 5.537 0.0305

2
xenon, Xe 4.192 0.0516
Table 1 Van der Waals parameters, a and b, for a selection of gases
84
1. Use a selection of the data in table 1 to explore some You will need to decide how much data to select, and
of the factors affecting the values of a and b. For how to analyse it. Depending on which option you
instance, you could look at: choose to explore, you may need to perform c alculations
and/or look up additional data.
• intermolecular force strength and the value of a
• molar mass and the value of b

2. Consider how you could present your data
ATL
graphic ally. Prepare a one-page summary of

• the effect of volume on the deviation from ideal
your exploration to share with your class.

gas behaviour.
Linking question
Under comparable conditions, why do some gases deviate more from ideal
behaviour than others? (Structure 2.2)
The molar volume of an ideal gas Avogadro’s law is covered in
Structure 1.4.
(Structure 1.5.3)
Avogadro’s law states that equal volumes of any two gases at the same
temperature and pressure contain equal numbers of particles. The molar volume
of an ideal gas is a constant at specied temperature and pressure. For example,
3 –1
at STP, the molar volume of an ideal gas, V , is equal to 22.7dm mol .

m
28.3 cm
H He CH O Cl
2 4 2 2
3
V = 22.7 dm
Figure 5 Molar volume of an ideal gas
1 1 1 1 1
2.02 g mol 4.00 g mol 16.05 g mol 32.00 g mol 70.90 g mol
compared with a soccer ball
Figure 6 Molar volume of any gas is identic al at a given temperature and pressure
Worked example 2
A 2.00 dm sample of an unknown gas at STP has a mass of 2.47 g.
Determine the molar mass, in g mol , of the gas.
Solution
V 2.00 dm
n = = = 0.0881 mol
3 1
V
22.7dm mol
m
m 2.47 g
1
M = = = 28.0 g mol
n
0.0881 mol
Practice question
–1
2. Determine the molar mass, in g mol , of an elemental gaseous substance
–3
that has a density of 3.12 g dm at STP. Identify the substance if its molecules
are diatomic.
85
Hypotheses
Amedeo Avogadro postulated that equal volumes of dierent gases would
contain equal numbers of particles under the same conditions of temperature
and pressure. This bec ame known as Avogadro’s hypothesis.
A hypothesis is a tentative and falsiable explanation or description of a natural
phenomenon, from which predictions c an be deduced. Predictions c an then
be used to test the hypothesis.
What predictions might be derived from Avogadro’s hypothesis?
Experimental determination of the molar mass of a gas
The ideal gas equation c an be used to determine the Instructions
molar mass of a gas by collecting a known volume of it
1. Measure ambient pressure with a barometer.
under known conditions of temperature and pressure. In
Alternatively, you c an search loc al weather data for
this practic al you will experimentally determine the molar
atmospheric pressure in your geographic loc ation on
mass of butane found in disposable plastic lighters.
the day you do the experiment.
Relevant skills
2. Half-fill the plastic trough with water. Measure the
• Tool 3: Record uncertainties in measurements as a temperature of the water.
range to an appropriate precision and propagate
3. Fill the measuring cylinder to the brim with water
uncertainties in processed data.
andinvert it in the trough so that its mouth is under
• Tool 3: C alculate and interpret percentage error.
water. If done correctly, the measuring cylinder
• Inquiry 2: Assess accuracy and precision.

should be full of water. Hold it in this position with a
• Inquiry 3: Identify and discuss sources and impacts of

clamp (figure 7).
systematic and random error.
4. Submerge the lighter in water, then take it out again
• Inquiry 3: Evaluate the implic ations of methodologic al
and dry it thoroughly with a paper towel. Weigh the
weaknesses, limitations and assumptions on
lighter.
conclusions.
5. Hold the lighter under water and press the button

on the lighter to release the gas so that it bubbles up

to an investigation.
inside the measuring cylinder (figure 7). Continue until
S afety 3
you have collected around 100 cm of gas. Record the
exact volume.
• Butane gas is flammable. Keep away from open flames

6. Release the gas in a well-ventilated area.
and sparks.
7. Dry the lighter as thoroughly as possible and
Materials
reweighit.
• Disposable plastic lighter

8. If you have time, repeat to get three sets of results.
• L arge container, for example a large plastic trough
• Balance (±0.01 g)
• Clamp and stand

3
100 cm measuring
• Thermometer
cylinder
• Barometer (if available)
water
Figure 7 Experiment apparatus
86
Questions
1. Design a suitable results table for your data. 8. Suggest realistic improvements to this method for
determining the molar mass of a gas.
2. Process your data to obtain an experimental value for
the molar mass of butane. 9. The pressure inside the measuring cylinder is in fact
the sum of the vapour pressure of water and the
3. Propagate the uncertainties.
partial pressure of the butane. How could you
4. Compare your experimental value to the theoretic al

adjust your data processing to account for this?
value by c alculating the percentage error.

What additional data and information do you
need to research?
5. Assess the accuracy and precision of your data.
10. Consider alternative methods for determining the

6. Discuss the relative impacts of systematic and random
molar mass of a gas that could be done in a school

errors on your results.
laboratory. If you have time, show your ideas to your
7. Comment on at least two major sources of

teacher and try them out.
experimental error.
Linking question
Graphs c an be presented as sketches or as accurately plotted
data points. What are the advantages and limitations of each
representation? (Tools 2 and 3, Reactivity 2.2)
Pressure, volume, temperature and amount
of an ideal gas (Structure 1.5.4)
There are four variables of an ideal gas that aect each other:
1. The pressure exerted by the gas, p
2. The volume the gas occupies, V
3. The absolute temperature of the gas, T
4. The amount of the gas, n
The eect of any two of these variables on each other c an be investigated by
keeping the other two constant. This is what Robert Boyle did when he c ame
up with Boyle’s law: he performed an experiment where the amount and the
temperature of a gas were kept constant, but the volume of the container was
changed. He observed that the pressure and volume of the gas were inversely
proportional.
87
Graphing the gas laws
Online simulations allow you to easily explore the 3. Using the simulation, vary the temperature at a
relationships between pressure and volume, volume and constant pressure and record the resulting volume
temperature, and pressure and temperature for a fixed for a certain amount of gas. Collect data for at least
amount of gas. In this task, you will collect data from an five different temperatures in a suitable table in your
ideal gas simulation, which will allow you to practice spreadsheet.
spreadsheet data analysis skills, as well as reinforce ideas
4. Compute the temperature values in both °C and K.
about direct and inverse proportionality.
5. Construct two graphs of V vs T; one with T in °C and
Relevant skills
the other with T in K.
• Tool 2: Generate data from simulations.
6. Using the simulation, vary the volume at a constant
• Tool 2: Use spreadsheets to manipulate data.

temperature and record the resulting pressure for
• Tool 3: Understand direct and inverse proportionality. a certain amount of gas. Collect data for at least
five different volumes in a suitable table in your

• Inquiry 1: Identify dependent, independent and
spreadsheet.
controlled variables.
7. Construct a graph of p vs V
Materials
8. Use your spreadsheet to compute values for .

• Simulation that allows you to change pressure,
1
volume and temperature for an ideal gas. It must have
9. Construct a graph of p vs
V
an option to hold one variable constant and vary the
Questions
other two.
1. What were your dependent and independent

• Spreadsheet software
variables in each c ase? Which variables were
Instructions
controlled?
1. Using the simulation, vary the temperature at a
2. Describe the relationship shown in each graph
constant volume and record the resulting pressure
as direct proportionality, inverse proportionality,
for a certain amount of gas. Collect data for at least
orother.
five different temperatures in a suitable table in your
3. When studying gases, it is important to convert all

spreadsheet.
temperature values into SI units (kelvin). Discuss why
2. Construct a graph of p vs T.
this is the c ase for temperature, whereas pressure and
volume units c an vary depending on the source.
The combined gas law
We have seen that pressure is inversely proportional to volume and directly
proportional to absolute temperature.
p ∝ ; p ∝ T
Combining the two relationships gives:
pV
pV ∝ T or = k (a constant) or
p V p V
1 1 2 2
=
T T
1 2
This equation is known as the combined gas law
88
Experiments
The gas laws arose from experiments in which certain
variables were controlled, while others were c arefully
manipulated. Inspect the apparatus shown in gure8.
pressure gauge
thermometer
What might be explored with this set-up? What
is the independent variable? What variables must
250 mL round-bottomed flask
be controlled? What is the purpose of each of the
containing air
itemsdepicted?
water bath
uFigure 8 Apparatus for conducting an
experiment into the behaviour of a gas
Worked example 3
A weather balloon lled with 32.0 dm of helium at 25 °C and a pressure
of 100.0 kPa is released at sea level. The balloon eventually reaches an
altitude of 35,000 m, where the pressure is 475 Pa and the temperature is
–50 °C. C alculate the volume, in m , of the gas in the balloon under these
conditions.
Solution
List the conditions of the gas in the weather balloon.
p = 100.0 kPa
1
V = 32.0 dm
1
Remember to convert temperature to kelvin:
T = 25 + 273.15 = 298.15 K
1
Then, list the conditions of the gas in the weather balloon at 35,000 m.
Remember to make sure the units are consistent with the initial conditions of
the balloon.
p = 0.475kPa
2
V = unknown
2
T = –50 + 273.15 = 223.15 K

2
Substitute the numbers into the combined gas law:
p V p V
1 1 2 2
T T
1 2 Practice question
3
0.475kPa × V
100.0 kPa × 32.0 dm
2
= 3. A sample of an ideal gas has
298.15 K 223.15 K 3
a volume of 1.00 dm at STP.
3
Rearranging the expression in terms of V gives:
C alculate the volume, in dm ,
2
3 3 3
of that sample at 50.0 °C and
V ≈ 5.04 × 10 dm = 5.04 m
2
50.0 kPa.
89
TOK
Throughout this chapter you have explored models related to the particulate nature of matter. M any of these concepts
were developed through observations of the natural world or obtained through experimentation: from the interaction
of alpha particles with gold atoms, to the manipulation of gases in the gas laws, to explorations of subatomic particles
atCERN.
Figure 9 The set-up used by Joseph Louis Gay-Lussac to investigate the thermal expansion of gases (le)
The ATLAS detector at CERN used to investigate elementary particles (right)
How do scientists investigate the behaviour of particles that are too small to be observed directly? How have advances in
technology inuenced scientic research into what matter is made up of ?
Ideal gas equation
The combined gas law suggests that for any given gas, the change in one of
the three parameters, p, V or T, aects the other two in such a way that the
pV
expression remains constant. The exact value of that constant must be
proportional to the amount of the gas, n:
pV pV
∝ n or = nR
T T
where R is the universal gas constant, or simply gas constant. The last expression
is known as the ideal gas equation, which is traditionally written as follows:
pV = nRT
The value and units of R depend on the units of p, V, T and n. If all four parameters
are expressed in standard SI units (p in Pa, V in m , T in K and n in mol), then
–1 –1
R ≈ 8.31 J K mol .
The same value and units of R c an be used if pressure is expressed in kPa and
3 3 –3 3
volume in dm , as the two conversion factors (10 for kPa to Pa and 10 for dm to
m ) c ancel each other out.
Linking question
How c an the ideal gas law be used to c alculate the molar mass of a gas from
experimental data? (Tool 1, Inquiry 2)
90
Worked example 4
A 3.30 g sample of an unknown organic compound was vaporized at T =150 °C and p =101.3 kPa to produce
3 3
1.91 dm of a gas. The gas was combusted in excess oxygen to produce 3.96 g of water, 2.49 dm of c arbon dioxide
and 1.25 dm of nitrogen at STP.
Determine the following for the compound:
a. molar mass
b. empiric al formula
c. molecular formula
Solution
a. To determine the molar mass, we need to nd out the amount of the compound using the ideal gas equation:
pV
n =
RT
T = 150 + 273.15 = 423.15 K
101.3 kPa × 1.91 dm
n = ≈ 0.0550 mol
–1 –1
8.31 J K mol × 423.15 K
3.30 g
–1
Therefore, M = = 60.0 g mol
0.0550 mol
b. All c arbon, hydrogen and nitrogen atoms in the combustion products originate from the organic compound, so the
amounts of these elements in c arbon dioxide, water and nitrogen are the same as those in the original sample:
m 3.96 g
n(H O) = = ≈ 0.220 mol

2
–1
M
18.02 g mol
n(H) = 2 × n(H O) = 2 × 0.220 mol = 0.440 mol

2
V 2.49 dm
n(CO ) = = ≈ 0.110 mol

2
3 –1
V 22.7 dm mol
M
n(C) = n(CO ) = 0.110 mol

2
3
V
1.25 dm
n(N ) = = ≈ 0.0551 mol

2
3 –1
V
22.7 dm mol
M
n(N) = 2 × n(N ) = 2 × 0.0551 = 0.110 mol

2
The original compound could also contain oxygen. To check this, we need to compare the total mass
of the three elements (hydrogen, c arbon and nitrogen) with the mass of the original sample:
–1
m(H) = 0.440 mol × 1.01 g mol ≈ 0.444 g
–1
m(C) = 0.110 mol × 12.01 g mol ≈ 1.32 g
–1
m(N) = 0.110 mol × 14.01 g mol ≈ 1.54 g
m(total) = 0.444 g + 1.32 g + 1.54 g ≈ 3.30 g
Therefore, the organic compound did not contain oxygen, so its formula c an be represented as C H N .
x y z
x : y : z = 0.110 : 0.440 : 0.110 = 1 : 4 : 1
The empiric al formula of the compound is CH N.

4
–1 –1
c. M(CH N) = 12.01 + 4 + 1.01 + 14.01 = 30.06 g mol . This value is half the experimental value (60.0 g mol ),
4
so the molecular formula of the compound will have twice the number of atoms of each element: C H N .
2 8 2
91
0.58 × 8.31 × 373
Topic review B.
3 6
100 × 10 × 250 × 10

3 6
0.58 × 100 × 10 × 250 × 10
C.
8.31 × 100
3 6
How does the model of ideal gas behaviour help us to
0.58 × 100 × 10 × 250 × 10
D.
predict the behaviour of real gases?
8.31 × 373
Exam-style questions 6 Which graph correctly shows the relationship between
the pressure and volume of an ideal gas, at constant
Multiple-choice questions temperature?
2. Which of the following are assumptions of the ideal gas

A. B.
model?
P P
I. The volume occupied by the gas particles is
negligible
V V
II. There are no intermolecular forces between
gas particles
C. D.
III. Zero particle movement
P P
A. I and II only
B. I and III only
1 1
C. II and III only
V V
D. I, II and III
7. Which of the following balloons contains the largest
3. The temperature of an ideal gas is 27 °C. What is the
number of hydrogen atoms, at constant temperature
temperature of the gas aer the pressure is doubled and
and pressure?
the volume is tripled?
A. 162 °C
B. 450 °C
C. 1527 °C
D. 1800 °C
4. A gas syringe contains 40 cm of an ideal gas at 27 °C.
H (g) NH (g) CH (g) HF(g)

2 3 4
What will the volume of the gas be aer it is warmed to

3 3 3 3
2 dm 2 dm 1 dm 4 dm
57 °C at constant pressure?
8. What are the conditions for the ideal gas behaviour of

3
A. 1.9 cm
real gases?
3
B. 3.6 cm
3
A. Low temperature and low pressure.
C. 44 cm
3
B. Low temperature and high pressure.
D. 84 cm
C. High temperature and low pressure.
5. A 0.58 g sample of an ideal gas at 100 kPa and 100 °C
D. High temperature and high pressure.

3
has a volume of 250 cm . Which of the following
expressions is equal to the molar mass of the gas?
0.58 × 8.31 × 100
A.
3 6
100 × 10 × 250 × 10
92
9. Which of the following statements about an ideal gas 14. C arbon forms several gaseous compounds with uorine.
are correct? Deduce the empiric al and molecular formulas for these
compounds using the data from the table below. [3]

p
I. At constant temperature, = constant
C arbon / M ass of 1.00 dm

p
Compound
II. At constant volume, = constant
mass % at STP / g
T
X 13.65 3.88
V
III. At constant pressure, = constant
T Y 24.02 4.41
A. I and II only
Z 17.40 6.08
B. I and III only
15. An organic compound A contains 54.5% of c arbon,
C. II and III only

9.1% of hydrogen and 36.4% of oxygen by mass. A
vaporized sample of A with a mass of 0.230g occupies

D. I, II and III
a volume of 0.0785 dm at T=95 °C and p=102 kPa.
a. Determine the empiric al formula of A. [2]
10. Explain, in your own words, why real gases deviate

b. Determine the relative molecular mass of A. [1]
from ideal behaviour at low temperatures and high
c. Using your answers to parts a and b, determine the
pressures. [2]
molecular formula of A. [1]
11. A c ar tyre inated to 2.50 bar (250 kPa) at 10 °C contains
16. A closed steel cylinder contains 0.32 mol of hydrogen

3
12.0 dm of compressed air. Aer a long journey, the
gas and 0.16 mol of oxygen gas. The volume of the
tyre temperature increases to 25 °C and the pressure

3
cylinder is 25 dm and the initial temperature of the gas
to 261 kPa. Determine the tyre volume under these
mixture is 25 °C.
conditions. Assume that there was no air loss during the
journey. [2] a. C alculate the initial pressure, in kPa, of the gas
mixture in the cylinder. [1]
12. Ammonium c arbonate, (NH ) CO (s), decomposes

4 2 3
b. When the gas mixture is ignited, both reactants are
readily when heated:
consumed completely and the temperature inside
(NH ) CO (s) → 2NH (g) + CO (g) + H O(l) the cylinder rises to 800 °C. C alculate the pressure
4 2 3 3 2 2
inside the cylinder at that moment. [2]
Determine the volumes, in dm at STP, of the individual
–3
gases produced on decomposition of 2.25 g of 17. An unknown gas X has a density of 2.82 g dm at STP. A
ammonium c arbonate. [2] 4.00 g sample of X was combusted in excess oxygen to
produce 2.50 g of hydrogen uoride and 2.84 dm of
13. The gases produced in question12 were transferred to a
c arbon dioxide at STP.
sealed vessel with a volume of 1.50 dm , and the vessel
Determine the following for X:

was heated up to 200 °C. C alculate the pressure in the
vessel at that temperature. Assume that the gases do not

a. molar mass [1]
react with each other. [2]
b. empiric al formula [2]
c. molecular formula [1]
93
Structure 2
Models of bonding
and structure
Structure 2.1 The ionic model
What determines the ionic nature and properties of a compound?
Ionic compounds are characterized by the presence the strong electrostatic attractions between oppositely
of positive and negative ions, which attract each other charged ions. Once liquid, however, ionic compounds are
electrostatically. In solid ionic compounds, these ions electrical conductors due to the presence of mobile ions.
are arranged in rigid crystalline lattices. Melting these Due to their charge, ions interact strongly with polar water
solids requires a large amount of thermal energy due to molecules, so ionic compounds are oen water-soluble.
Understandings
Structure 2.1.1 — When metal atoms lose electrons, they Structure 2.1.3 — Ionic compounds exist as three-
form positive ions c alled c ations. When non-metal atoms dimensional lattice structures, represented by empiric al
gain electrons, they form negative ions c alled anions. formulas.
Structure 2.1.2 — The ionic bond is formed by
electrostatic attractions between oppositely charged ions.
Binary ionic compounds are named with the c ation rst,
followed by the anion. The anion adopts the sux “ide”.
Introduction to bonds and structure
Atoms rarely exist in isolation. They are connected together in several dierent
ways. Atoms c an be bonded to atoms of the same type, or to atoms of dierent
elements. The varying arrangements of atoms and features of the bonds between
them give rise to certain dierent properties. For example, 78% of the air around
us is nitrogen, N . However, in agriculture, nitrogen fertilizers are added to soils

2
to help crops grow. This is bec ause the structure and bonding of nitrogen in air
are dierent to that of the nitrogenous compounds found in fertilizers.
Atoms are held together by chemical bonds. This chapter discusses three dierent
bonding models: ionic, covalent and metallic. These lead to four types of structure:
ionic, molecular covalent, covalent network and metallic. You may be wondering
why there are four types of structure, given that there are only three types of bonds.
This is because covalent substances can be found in two arrangements: a continuous
3D network, or discrete groups of atoms known as molecules.
types of
ionic covalent metallic
bond
types of molecular covalent
ionic metallic
structure covalent network
metal ion
deloc alised
electron
tFigure 1 There are three types of
bonds and four types of structure
95
Structure 2 Models of bonding and structure
Chemic al bonds
Models
Chemic al bonds are strong forces of attraction that hold atoms or ions together
Structure 2 .1 , 2.2 and 2.3 d i s c u ss in a substance. All chemic al bonds occur due to electrostatic attractions between
models of bonding and s t r u c t u r e. positively charged species and negatively charged species. The type of bonding
Scientific models simplify and depends on which species are involved (table 1).
represent c o m p l ex phenomena.
Sometimes models help us to
visualize things that we c annot The electrostatic attraction between…
observe d i r e c t l y. This is one of Type of bonding

Positively charged Negatively charged
the re asons bonding models are

species species
so useful.
ionic c ations anions
All models have limitations.
covalent atomic nuclei shared pair of electrons
This does not necessarily make
metallic c ations deloc alized electrons

the models inadequate, but it
is important to understand the
Table 1 All bonding types involve a positively charged species and a negatively charged
weaknesses of a model. As you

species that are electrostatic ally attracted to each other
work through these sections,
identify some of the strengths and
limitations of the various bonding
models.
Ions (Structure 2.1.1)
Sodium chloride and copper(II) sulfate are examples of ionic compounds. They
are crystalline and brittle, which are properties characteristic of ionic compounds.
Ionic compounds are also poor electric al conductors when solid, but good
electric al conductors when molten or dissolved. The reactions and properties of
these ionic compounds are very dierent to those of their constituent elements.
For instance, sodium chloride, the main ingredient in table salt, is water-soluble.
However, elemental sodium is a so metal that reacts violently with water, and
chlorine is a poisonous gas.
Figure 3 Sodium chloride crystals on a tree branch and copper(II) sulfate crystals.
Sodium chloride and copper(II) sulfate are ionic compounds
Figure 2 Oshore oil platform in
C alifornia, USA. What examples of structure

Before discussing ionic bonds and the characteristics of ionic structures, we will
and bonding are present in the photo? rst look into what ions are.
96
a b
C ations and anions
Sodium chloride contains sodium ions, not sodium atoms. Sodium atoms and
sodium ions have dierent numbers of electrons, and therefore behave dierently.
Na
Na
You will notice three dierences between Na and Na :
1. number of electrons
Figure 4 (a) sodium atom (b) sodium ion
2. electron arrangement
3. charge.
Sodium atoms are neutral. Sodium ions have a 1+ charge, indic ated by a
superscript + sign next to the symbol: Na .
Worked example 1
Determine the number of subatomic particles to show that
a. sodium atoms are neutral
b. sodium ions have a 1+ charge.
Solution
In Structure 1.2, you learned
a. In a sodium atom there are:
that protons have a 1+ charge
11 protons (charge = 11+)
and electrons have a 1– charge.
11 electrons (charge = 11 )
You c an ignore neutrons in ionic
O verall charge is 11 11 = 0
charge c alculations as these are
b. In a sodium ion there are: uncharged.
11 protons (charge = 11+)
10 electrons (charge = 10 )
O verall charge is 11 10 = 1+
Worked example 2
Deduce the electron conguration of a sodium atom and a sodium ion.
a b
2–
Solution
2 2 6 1
Na: 1s 2s 2p 3s
S S
+ 2 2 6
Na : 1s 2s 2p
C ations are ions with more protons than electrons. This means that c ations are
Figure 5 (a) sulfur atom (b) sulde ion

positively charged, as the combined positive charge of protons is greater than
the combined negative charge of electrons. As sodium ions have 11 protons and
10 electrons, the overall charge is 1+
Activity
Anions are negatively charged ions. They contain a greater number of electrons
than protons. Figure 5 shows a sulfur atom and a sulde ion. The sulde ion has a
Show that the sulfur atom is neutral
2 charge, denoted by the superscript in the symbol S . Note that anions adopt
and the sulde ion has a charge
a slightly dierent name: the rst part corresponds to the name of their parent
of 2– by counting their subatomic
atom. This is followed by the sux ide.

particles. Determine the electron
conguration of the sulfur atom
For now, we will only consider monatomic ions. You will look at charged groups
and sulde ion.
of atoms (c alled polyatomic ions) in a later section.
97
Predicting the charge of an ion
The main group elements are in periodic table groups 1, 2, 13, 14, 15, 16, 17 and
18. The electron congurations for some main group element atoms and their
corresponding c ations are shown below:
1e
Na Na
2 2 6 1 2 2 6
1s 2s 2p 3s 1s 2s 2p
Na has the same electron conguration as neon, Ne. Two dierent species with
same electron conguration are c alled isoelectronic. Therefore, Na and Ne are
isoelectronic.
1e 2e
+ 2+
Li Li Ca Ca
2 1 2 2 2 6 2 6 2 2 2 6 2 6
1s 2s 1s 1s 2s 2p 3s 3p 4s 1s 2s 2p 3s 3p
2+
+
Li is isoelectronic with helium, He. Ca is isoelectronic with argon, Ar.
The resulting c ations all have noble gas congurations. Noble gases have full (or
“closed”) sublevels. When main group elements form ions, they oen achieve
this noble gas electron conguration. The atoms above have all done so by losing
their outermost valence electrons. As they have lost electrons, and electrons
are negatively charged, the resulting c ations are positively charged. C ation
formation is an example of oxidation bec ause it involves the loss of electrons.
Anions are formed when atoms gain electrons. Look at the examples below
where the parent atoms gain electrons in order to achieve a noble gas electron
conguration:
+1e +2e
Cl Cl O O
2 2 6 2 5 2 2 6 2 6 2 2 4 2 2 6
1s 2s 2p 3s 3p 1s 2s 2p 3s 3p 1s 2s 2p 1s 2s 2p
– 2–
Cl is isoelectronic with argon, Ar. O is isoelectronic with neon, Ne.
Atoms that gain electrons become anions. As reduction is the gain of electrons,
To obtain a noble gas conguration,

the formation of anions is a reduction process.
a chlorine atom gains an electron.
The formation of an ionic compound from its elements is a redox reaction.

Chlorine would also have a
Consider the formation of sodium chloride from its elements:

noble gas conguration if it lost
the seven outermost electrons.
2Na(s) + Cl (g) 2NaCl(s)

2
However, the removal of so many
electrons from the attractive pull Sodium chloride, NaCl, is made up of sodium c ations, Na , and chloride
of the positively charged nucleus anions, Cl . The half equations are shown below. The rst is an oxidation and the
requires a large amount of energy other is a reduction and therefore the formation of NaCl from its elements is a
while the addition of a single redoxreaction.
electron releases energy. This is

+
2Na 2Na + 2e Electron loss = oxidation
why chlorine instead will gain an
Cl + 2e 2Cl Electron gain = reduction
electron to become a chloride ion. 2
The energetics of these processes,

Once you have learned about oxidation states (Structure 3.1), you should also be
called ionization energy and

able to see that the sodium is undergoing oxidation bec ause its oxidation state
electron anity, are discussed in

increases (from 0 to +1) and the chlorine is reduced bec ause its oxidation state
Structure 3.1 and relevant in the

decreases (from 0 to 1).
construction of Born–Haber cycles
(Reactivity 1.2).
98
Atoms tend to achieve a noble gas electron conguration through gaining,
TOK
losing, or, as we will see in Structure 2.2, sharing electrons. This is oen referred
to as the octet rule. It is c alled the octet rule bec ause most noble gases have
General rules in chemistry (such

eight electrons in their outer shell.
as the octet rule) oen have
There exists a relationship between the charge of the ion formed by a main group exceptions. How many exceptions
element and its periodic table group. In general: have to exist for a rule to cease to
be useful?
• Elements in groups 1, 2 and 13 form 1+, 2+ and 3+ ions, respectively
• Elements in groups 15, 16 and 17 form 3–, 2– and 1– ions, respectively
The electron conguration of
2 2 2
• Elements in group 18 (noble gases) do not form ions
c arbon, 1s 2s 2p , suggests that
c arbon atoms could lose or gain
The relationship between periodic table group and ionic charge is illustrated in
four electrons in order to achieve
gure 6.
a noble gas conguration. This
would result in the formation
1 18
4+ 4–
of C or C ions, respectively.
Although this is possible, c arbon
2 13 14 15 16 17 more commonly forms compounds
through a process c alled covalent
+
Li 3 2
2
N O F bonding, which does not involve
ion formation. Covalent bonding is
+ 2+ 3+
Na Mg Al 3 2 discussed in Structure 2.2
3
P S Cl
+ 2+
K Ca 2
4
Se Br
+ 2+
Rb Sr 2
5
Te I
+ 2+
6 Cs Ba
Figure 6 The charges of some common ions
Hydrogen atoms have only one electron in the 1s sublevel. They form ions by
either losing that electron or gaining one. Electron loss leads to the formation of
H , which is simply a hydrogen nucleus: a proton with no electrons surrounding
it. The charge density of a H ion is therefore very high, so these c ations readily
combine with other species. One such example is the formation of acidic
hydronium ions, H O , formed when hydrogen c ations bond with water.

3
Hydrogen atoms c an also gain an electron to achieve a noble gas conguration,
Hydride anions are very strong

–
thus forming hydride anions, H .
bases. You will learn more about
bases in Reactivity 3.1
hydrogen
+
–
+
e ion, H
–1
+
+
1
e
hydride
hydrogen +
ion, H
atom
Figure 7 The formation of H and H
99
Practice questions
1. Determine the charge of the ion formed by each of the following elements.
a. lithium, Li
b. magnesium, Mg
c. aluminium, Al
d. uorine, F
e. nitrogen, N
f. selenium, Se
g. barium, Ba
2. State the name of ions d, e and f above.
3. Complete the table:
Number Number
Electron
Name Symbol of of Charge
conguration
protons electrons
beryllium 0
8 2
15 18
4. For each electron conguration given, identify three isoelectronic species:
2 2 6 2 6
a. 1s 2s 2p 3s 3p
b. 1s
5. Explain why noble gases do not form ions.
A transition element is an element with a partially lled d sublevel. In contrast
to main group elements, a transition element c an form multiple ions with
2+ 3+
dierent charges. For example, iron commonly forms Fe and Fe ions
(gure 8).
+
2
Fe : [Ar]
–
e
2
–
3d 4s
Fe: [Ar]
iron(II) ion
3d 4s
–
3
e –
iron atom +
3
Fe : [Ar]
3d 4s
iron(III) ion
Figure 8 Iron atoms c an form ions with a 2+ charge and ions with a 3+ charge
100
Consider the electron congurations of the rst-row transition elements.
As seen in chapter Structure 1.3,
2+
the 4s sublevel lls up before the
Most of them contain two 4s electrons, which are lost when the M ions
3d sublevel.
areformed. This helps to explain why most of these elements commonly form
2+c ations.
tTable 2 Electron congurations of the
Electron conguration
rst-row transition elements

Symbol Element
Atom 2+ ion
2 1 1
Sc sc andium [Ar] 4s 3d [Ar] 3d
2 2 2
Ti titanium [Ar] 4s 3d [Ar] 3d
2 3 3
V vanadium [Ar] 4s 3d [Ar] 3d
1 5 4
Cr chromium [Ar] 4s 3d [Ar] 3d
2 5 5
Mn manganese [Ar] 4s 3d [Ar] 3d
2 6 6
Fe iron [Ar] 4s 3d [Ar] 3d
2 7 7
Co cobalt [Ar] 4s 3d [Ar] 3d
2 8 8
Ni nickel [Ar] 4s 3d [Ar] 3d
1 10 9
Cu copper [Ar] 4s 3d [Ar] 3d
When the rst row transition elements are ionized, the 4s electrons are lost before
Practice questions
the 3d electrons. Further successive ionizations occur in many of these elements
6. Deduce the abbreviated electron

bec ause the 3d sublevel is similar in energy to the 4s sublevel.
conguration of each of the
Transition elements have variable oxidation states (Structure 3.1). This

following:
characteristic c an be explored by examining successive ionization energy data. 2+
a. Mn
Let’s focus on the transition elements in period 4. They have variable oxidation
3+
b. V
states bec ause the 4s and 3d sublevels are close together in energy, as shown
+
c. Cu
by successive ionization energy data (gure 9). It is important to realize that
2+
d. Cu
ionization rarely happens in isolation. Ionization absorbs energy, but this energy
7. Zinc only forms 2+ ions.

investment is usually oset by other processes that release energy, such as lattice
formation. If a certain ionization only requires a small amount of additional energy a. Deduce the full electron
2+
compared to the previous ionization, then it could be energetic ally favourable if it conguration of Zn .
leads to a subsequent exothermic process.

b. Explain why zinc is not a
transition element.
8. The ion of a transition metal

3
40
has mass number 55, electron
lom
conguration [Ar] 3d and a

Jk
charge of 2+.
3
30
01 / ygrene
a. Write its symbol using
nuclear notation.
20
b. Identify a 1+ ion that has the
same electron conguration

n o it a z i n o i
10
as the above.
0 2 4 6 8 10 12
number of electrons removed
Figure 9 D ata for the rst 12 ionization energies of iron. As you c an see, the 4s and
3d electrons are very close together in energy. The large jump between the 8th and 9th
electrons occurs bec ause the 9th electron is removed from the 3p energy level, which is
closer to the nucleus
101
You may have noticed that we c an refer to charge using dierent formats
depending on context. When using chemical symbols, charges appear as
3+
a superscript number followed by + or –, for example, Fe . In speech or
writing, we say “the ion has a 3+ charge”. Charge is related to oxidation state
(Structure 3.1), where the + or – sign is given rst followed by the magnitude.
For example, “oxygen has an oxidation state of –2”.
Roman numerals are also used to indic ate oxidation states in the names of
compounds (Structure 3.1 and Reactivity 3.2). For example, the symbol for a
2+
copper(II) ion is Cu , its charge is 2+, and its oxidation state is +2.
Write your own example to help you remember these distinct ways of
referring to ionic charge.
Linking questions
How does the position of an element in the periodic table relate to the
charge of its ion(s)? (Structure 3.1)
How does the trend in successive ionization energies of transition elements
explain their variable oxidation states? (Structure 1.3)
Ionic bonds (Structure 2.1.2)
C ations and anions are electrostatic ally attracted to each other bec ause of
their opposite charges. This attraction results in the formation of ionic bonds.
Therefore, if a given element forms c ations, and another forms anions, they c an
bond ionic ally to form an ionic compound.

ecnereffid
ionic
3.0
Electronegativity (χ)
greater
bonding
ionic
One way to estimate whether a bond between two given elements is ionic is to
character
look at the dierence in electronegativity between the two. Electronegativity

ytivitagenortcele
2.0
( χ) is a measure of the ability of an atom to attract a pair of covalently bonded
electrons. Within the periodic table, electronegativity increases across the
periods and up the groups. This means that uorine is the most electronegative
1.0
element, so it has a high tendency to attract pairs of covalently bonded electrons.
One of the electronegativity sc ales used by chemists is c alled the Pauling sc ale.
0
Values in the Pauling sc ale are dimensionless and range from 0.8 to 4.0. Fluorine
has an electronegativity value of 4.0. The electronegativity of c aesium, one of the

Figure 10 If two elements have an
least electronegative elements, is 0.8. Noble gases are generally not assigned
electronegativity dierence greater than 1.8,
electronegativity values.
the bonding between them will have a high
ionic character
The larger the dierence in electronegativity between two elements in a
compound, the greater the ionic character of the bond between them. Ionic
bonding is assumed to occur when the dierence in electronegativity is greater

Electronegativity and other
than 1.8 (gure 10). In reality, bonding occurs across a continuum, so above 1.8
periodic trends are discussed in
the main type of bonding in the compound is ionic, but there may be other types
greater detail in Structure 3.1
of bonding present.
102
Data-based question
Predict which of the compounds in table 3 will have ionic structure.
χ
Compound Dierence in electronegativity (∆ )
χ χ
sodium uoride, (Na) = 0.9 and ∆ (F) = 4.0
χ
NaF ∆ = 3.1
χ χ
sodium chloride, (Na) = 0.9 and (Cl) = 3.2
χ
NaCl ∆ = 2.3
χ χ
aluminium (Al) = 1.6 and (Cl) = 3.2
χ
chloride, AlCl ∆ = 1.6
3
Table 3 Electronegativity dierences for selected metal chlorides
Periodic table position
You c an qualitatively approximate how ionic a compound will be by looking
at the positions of its constituent elements in the periodic table. Elements with
large dierences in electronegativity are generally found at a greater horizontal
distance from each other.
Worked example 3
Compare the ionic character of bonding in the following pairs of compounds:
a. c aesium uoride, C sF, and c aesium iodide, C sI
b. magnesium oxide, MgO, and c arbon monoxide, CO
Solution
a. Qualitative comparison: b. Qualitative comparison:
Cs and F are a gre ater distance from e ach other In the periodic table, Mg and O are further away
than Cs and I are in the periodic table. Therefore, from e ach other than C and O are. Therefore, the
the dierence in electronegativity is larger between electronegativity dierence between Mg and O
Cs and F, me aning the bond between them is more must be larger than that between C and O, and the
ionic. bond between Mg and O must be more ionic.
Q uantitative comparison: Q uantitative comparison:
χ(C s) = 0.8 and χ(F) = 4.0 χ(Mg) = 1.3 and χ(O) = 3.4
∆χ(C sF) = 3.2 ∆χ (MgO) = 2.1
χ(C s) = 0.8 and χ(I) = 2.7 χ(C) = 2.6 and χ(O) = 3.4
∆χ(C sI) = 1.9 ∆χ(CO) = 0.8
Both ∆χ v alues are gre ater than 1.8, so the bonds Mg and O bond ionic ally bec ause ∆χ is gre ater
in both compounds are ionic. However, C sF has a than 1.8 for this compound. C and O do not bond
higher percentage ionic character than C sI. ionic ally bec ause ∆χ is lower than 1.8.
103
Activity
Determine whether the following pairs of elements are likely to bond ionic ally
using the following two methods:
i. look at their positions in the periodic table
ii. refer to their electronegativity values in the data booklet.
a. Li and F d. As and S
b. Rb and Ga e. P and Cl
c. C a and I f. Ag and Br
It is oen incorrectly said that only ionic bonds form when a metallic element and
a non-metallic element bond together. There are substances, such as aluminium
chloride, AlCl , that do not t this description. Aluminium is a metal and chlorine
3
is a non-metal, so you would expect them to bond ionic ally. But the compound
has properties that are characteristic of covalent compounds, such as a low
Figure 11 Polarized light micrograph
melting point and high volatility. The electronegativity dierence between these
of ammonium nitrate crystals. Ammonium
+
two elements (1.6) suggests they do not bond ionic ally.
nitrate contains two polyatomic ions: NH
4
and NO . Its uses include fertilizers and

3
Polyatomic ions
rocket propellants
Some ionic compounds contain more than two elements. For instance, NH Cl,
4
+ +
which is made up of NH c ations and Cl anions. Ammonium ions, NH , are

Name Formula 4 4
polyatomic ions. As their name suggests, polyatomic ions are ions that contain
+
ammonium NH
4
several atoms.
hydroxide OH
You are expected to know the names and formulas of the polyatomic ions shown
nitrate NO
3
in table 4.
hydrogenc arbonate HCO

3
2–
c arbonate CO
3
2–
sulfate SO
4
3–
phosphate PO
4
You will need to spend some time memorizing the names and formulas of the
polyatomic ions in table 4. Some students like to use ashc ards, others make
Table 4 Common polyatomic ions
up mnemonics. What strategies will you use? How will you make sure you
actively engage with them?
Naming ionic compounds

Name Formula
Consider the list of ionic compounds shown in table 5. C an you notice any
potassium uoride KF
patterns in their names?
magnesium uoride MgF

2
You should notice that, in the names of ionic compounds:

c alcium c arbonate C aCO
3
• the c ation name is given rst and is followed by the anion

barium hydroxide Ba(OH)
2
iron(III) oxide Fe O • c ations adopt the name of the parent atom and the name remains unchanged
2 3
silver(I) sulde Ag S
• monatomic anions adopt the rst part of the name of the parent atom,
2
followed by the sux -ide. If the anion is polyatomic, refer to table 4
Table 5 Names and formulas of some
ionic compounds • the name of the compound does not reect the number of ions in the formula.
104
Practice questions Anions are conjugate bases of
common acids. The strength of
9. State the name of each of the following compounds:
acids and stability of their anions
a. RbF d. Sr(OH)
2
c an be compared quantitatively
b. Al S e. BaCO
2 3 3
using their dissociation constants,
c. AlN f. NH HCO K , which will be introduced in

4 3
a
Reactivity 3.1
The formulas of ionic compounds
The name of an ionic compound tells you what elements it contains, but not the
ratio of the ions in it. The basis for working out the formula of an ionic compound
is remembering that the net charge of the compound is zero, so the positive
charges and negative charges must c ancel out. First, determine the charge of the
anion and the c ation, then work out how many of each ion you need to reach a
total charge of zero.
Worked example 4
Deduce the formulas of the following ionic compounds:
a. c alcium oxide b. c alcium nitride c. sodium c arbonate d. aluminium nitrate
Solution
a. To deduce the formula of c alcium oxide, work through The second method is the criss-cross rule. Swap
the following steps. the charges and turn them into the other ion’s
subscript, ignoring the sign:
Step 1: Determine the charges of the c ation and
the anion
Ca
C alcium has an electron conguration of
2 2 6 2 6 2
1s 2s 2p 3s 3p 4s . C alcium atoms have two outer
shell electrons, so they form ions with a 2+ charge.
2 2 4
Ca
Oxygen has an electron conguration of 1s 2s 2p .
Oxygen atoms have six outer shell electrons, so they
Then, simplify the ratio:

form ions with a 2 charge.
2+ 2
Therefore, calcium ions = Ca and oxide ions = O

Ca O
1 1
Step 2: Determine how many of each ion are needed

Step 3: Check that the net charge is zero
in order to achieve a net charge of zero
You check your working by adding up the charges of
There are two methods you can use for this step. The rst
e ach individual ion. If you did Step 2 correctly, the
is the bar diagram method. Write out the ions as blocks

charges will add to zero:
equal to the number of charges on each individual ion:
2+
Ca
+
2
Ca
Total positive charge = 2+
2 2–
O O
Total negative charge = 2
The bar diagram contains one c alcium ion and one
Net charge = 2 2 = 0
oxide ion, so the ratio of c alcium to oxide in the
compound is 1:1.
Step 4: Write the formula
This is a straightforward example where the

Ca O
1 1
magnitude of charge is equal for the c ation and
anion, and hence the formula is C aO.
105
b. C alcium nitride is a more complex example as the c. Sodium c arbonate contains a polyatomic ion. You
ions have dierent charges. Work through the steps must not split up or change the ratio of atoms in the
as before. polyatomic cluster. Treat it like an indivisible entity
and draw brackets around it if the formula contains
Step 1: Determine the charges of the cation and
more than one such ion.
the anion

2 2 6 2 6 2
C a: 1s 2s 2p 3s 3p 4s
the anion
C alcium atoms have two outer shell electrons, so

2 2 6 1
N a: 1s 2s 2p 3s
they form ions with a 2+ charge.
Sodium atoms have one outer shell electron, so

2 2 3
N: 1s 2s 2p
they form ions with a 1+ charge.
Nitrogen atoms have ve outer shell electrons, so 2
C arbonate ions, CO , have a 2 charge.

3
they form ions with a 3 charge.

+ 2
Sodium ions = Na and c arbonate ions = CO

3
2+ 3
C alcium ions = Ca and nitride ions = N
Step 2: Determine how many of each ion are
needed in order to achieve a net charge of zero

needed in order to achieve a net charge of zero Bar diagram method
Bar diagram method
+ +
Na Na
+ + +
2 2 2
Ca Ca Ca
2–
CO
3
3 3
N N
The bar diagram contains two sodium ions and one
c arbonate ion, so the ratio of sodium to c arbonate
in the compound is 2:1

The bar diagram contains three c alcium ions and
two nitride ions, so the ratio of c alcium to nitride

Na CO
2 3
ions in the compound is 3:2
Criss-cross rule
Ca N
3 2
Na CO
Criss-cross rule
3 1
Remember, you c an draw brackets around the
Ca N poly atomic ion to remind yourself that its formula
does not change. Again, there is no need to simplify
the ratio here.

There is no need to simplify the ratio here bec ause it
is alre ady in its simplest form.

Step 3: Check that the net charge is zero +
Na
+ CO
Na 3
2+
Ca
Total positive charge = 2+ Total negative charge = 2

2+ 3
Ca N
2+ 3
Ca N
Total positive charge = 6+ Total negative charge = 6 Step 4: Write the formula
The fo r mu l a is Na CO . Note th a t in th e fi n a l
2 3
a n sw e r the re a re no bra c ke ts a ro u n d th e
po l y a t o m i c ion be c a u s e t he fo r mu l a c o n ta i n s only
one c arbonate ion.

Step 4: Write the formula
Ca N
3 2
106
d. The nal example, aluminium nitrate, also contains a Criss-cross rule
polyatomic ion. Follow the same steps as before.
1
Al
the anion
2 2 6 2 1
Al: 1s 2s 2p 3s 3p
1 3
Aluminium atoms have three outer shell electrons,
so they form ions with a 3+ charge.
Again, there is no need to simplify the ratio here.
Nitrate ions, NO , have a 1 charge.

3
3+
Al ions = Al and nitrate ions = NO

3
NO
3
NO
3
If you do not remember the charge on a
3+ NO
Al 3
polyatomic ion, revise table 4. M ake sure that you
learn these formulas and charges o by heart.

Total positive charge = 3+ Total negative charge = 3
needed in order to achieve a net charge of zero Step 4: Write the formula
Bar diagram method The formula is Al(NO ) . Note that brackets are used
3 3
to indic ate the presence of more than one nitrate
+
3
Al
ion. The formula should not be written as AlN O
3 9
NO NO NO
3 3 3
The bar diagram contains one aluminium ion and
three nitrate ions, so the ratio of aluminium to nitrate
in the compound is 1:3.
Al (NO )
1 3 3
Practice questions
Names of ionic compounds that
contain transition elements have
10. Deduce the formula of each of the following compounds:
the oxidation number of the
a. magnesium oxide e. lithium nitrate
transition metal ion in brackets. This
b. strontium chloride f. barium hydrogenc arbonate

is covered in Structure 3.1
c. sodium sulde g. ammonium phosphate.
d. lithium nitride
Linking questions
Why is the formation of an ionic compound from its elements a redox
reaction? (Reactivity 3.2)

LHA
How is formal charge used to predict the preferred structure of
sulfate? (Structure 2.2)

LHA
Polyatomic anions are conjugate bases of common acids. What is
the relationship between their stability and the conjugate acid’s
dissociation constant, K ? (Reactivity 3.1)

a
107
Ionic lattices and properties of ionic
compounds (Structure 2.1.3)
L attices
Within ionic crystals, the ions are arranged in a lattice structure. L attices are
continuous, three-dimensional networks of repeating units of positive and
negative ions. The exact arrangement of ions in a lattice depends on the size and
charge ratio of the ions.
uFigure 12 Ionic compounds are made of
ions arranged in a lattice structure
Th e fo r mu l a of ionic c o mp o u n d s is an e mp i r i c a l fo r m u l a : it i n d i c a te s th e
ra ti o of e ach ty pe of ion in t he s tr u c tu re. A single g ra i n of sodium c h l o r i d e,
N aCl, c an e asily contain a qu a dr i l l i o n ions a r ra n ge d in a c o n ti n u o u s l a tti c e.
Th e fo r mu l a i n d i c a te s th a t t he Na and Cl ions a re p re s e n t in t he l a tt i c e in a
1:1 ra ti o.
ATL Thinking skills
Research oen involves nding information but also evaluating its usefulness
and reliability.
Consider the statement “each grain of NaCl can easily contain a quadrillion ions”.
• Does this sound reasonable to you?
• What information would you need to fact-check the statement?
+ – + – +
• How could you reliably nd this information?
• Come up with your own estimate of the number of ions in a grain of salt
– + – + –
and compare it to this one. How do they compare? Why might they be
dierent? Is the dierence between the two values signic ant?
+ – + – +
Ionic bonds are non-directional. This means that an ion will attract all oppositely
charged species surrounding it, with the attraction being equal in all directions.
– + – + –
Bec ause of this non-directional quality, each c ation in the ionic lattice attracts
the all the surrounding anions, and vice versa. This means the forces of attraction
Figure 13 Ionic bonding is non-
directional. Each ion attracts all oppositely

in an ionic lattice are very strong. Figure 13 shows a 2D representation of the
charged ions around it forces in an ionic lattice, but remember, actual lattices are 3D.
108
L attice enthalpy
L attice enthalpy values tell us how strong the ionic bonds are in particular ionic
lattice. L attice enthalpy, ∆ , is the standard enthalpy change that occurs on

lattice
the formation of gaseous ions from one mole of the solid lattice. It is a measure of
the strength of an ionic bond bec ause, in order for the ions to become gaseous,
all the electrostatic forces of attraction between c ations and anions in the lattice
need to be overcome. A general equation for the lattice dissociation process is
shown below:
+ 
MX(s) M (g) + X (g) ∆H > 0

lattice
The process is endothermic. Experimental values of lattice enthalpy at 298 K for
some compounds c an be found in the data booklet. L attice enthalpies are oen
quoted as negative values that represent the exothermic formation of the lattice
from gaseous ions — the opposite process to that shown in gure 14. However, in
this book we shall consider only the endothermic formation of gaseous ions from
a lattice, which is consistent with the denition given in the data booklet.
L attice enthalpy increases as the energy required to overcome the electrostatic
forces of attraction between ions increases. Two factors aecting lattice enthalpy
are ionic radius and ionic charge. The strength of the electrostatic attraction
between oppositely charged ions:
Figure 14 Lattice enthalpy is the energy
• increases with increasing ionic charge

required to overcome the electrostatic
forces of attraction holding ions together in
• decreases with increasing ionic radius.
the lattice
Look at the variations in lattice enthalpy of the compounds in table 6.
–12
Ionic radius/10 m Ionic charge

Ionic
 –1
∆H /kJ mol
lattice
compound
C ation Anion C ation Anion
KF 829 138 133 +1 –1
NaF 930 102 133 +1 –1
C aF 2651 100 133 +2 –1

2
Table 6 Lattice enthalpies of selected compounds
NaF has a greater lattice enthalpy than KF bec ause the c ations in NaF are smaller,
and therefore the electrostatic attraction between Na ions and F ions is greater.
The lattice enthalpy of C aF is considerably larger than that of KF. This is in part
2
2+ +
due to the smaller ionic radius of Ca compared to K . However, it is mainly due
2+
to the greater charge on the Ca c ation, which results in greater electrostatic
attraction between the c ations and anions in C aF

2
109
F actors aecting the lattice enthalpy of the group 1 chlorides
Charge density is a term used to describe charge per unit Part 3: Analysis
volume. In this task, you will explore the charge density
5. C alculate the volume of each c ation.
of the group 1 c ations and relate this to the trend in lattice
enthalpies of the group 1 chlorides. 6. C alculate the charge density of each c ation.
7. Plot two graphs: one graph showing the relationship

Relevant skills
between ionic radius and lattice enthalpy, and the
• Tool 2: Use spreadsheets to manipulate data
other, between charge density and lattice enthalpy.
• Tool 3: General mathematics
8. Describe and explain the trends shown in the
• Inquiry 1: State and explain predictions graphs.
9. Discuss the differences between the two

• Inquiry 2: Identify, describe and explain patterns,
graphs.
trends and relationships
10. Evaluate your prediction, including a comparison

Instructions
of the graphs you obtained in 7 and the sketched
Part 1: Prediction
graphs you obtained in 2.
1. For the group 1 c ations, predict the relationship
11. Consider possible extensions to this investigation:
between:
what other aspects of ionic radius, charge density and
a. ionic radius and lattice enthalpy of their chlorides
lattice enthalpy could you explore?

b. charge density and lattice enthalpy of their
chlorides.
2. Sketch the graphs you expect to obtain for the
relationships above.
3. Collect the following data for the group 1 chlorides:
ionic charge, ionic radius, lattice enthalpy. Possible
sources of information include the data booklet and
online databases. Cite each source appropriately.
4. Input your data into a spreadsheet and organize it into
a suitable table.
Practice questions
1. Write equations, including state symbols, that represent the lattice
enthalpies of KBr, C aO and MgCl

2
2. State and explain whether you expect KF or K O to have a lower lattice

2
enthalpy value.
3. State and explain which of the following ionic compounds you expect to
have the greatest lattice enthalpy value: NaCl, MgCl , Na O or MgO.

2 2
4. Describe and explain the trend in lattice enthalpy of the group 1 chlorides
down the group from LiCl to CsCl.
Properties of ionic compounds
The properties of ionic compounds are due to their structural features: they
contain c ations and anions held together by strong electrostatic attractive forces
in a lattice.
110
Volatility
Global impact
Volatility (from the Latin volare, to y) refers to the tendency of a substance to
of science
vaporize (turn into a gas). For an ionic compound to turn into a gas, the strong
electrostatic forces of attraction holding the ions together must be overcome.
Some ionic compounds have
The volatility of ionic compounds is therefore very low: they are said to be “non-
uncharacteristic ally low melting
volatile”. This also means they have high boiling points.
points and c an be used as
Ionic compounds typically have high melting points too. The melting point of solvents. Such ionic liquids c an
sodium chloride is approximately 1 075 K. Magnesium oxide, frequently used in be described as “green solvents”
furnaces due to its ability to withstand high temperatures, melts at around 3 098 K. bec ause they are non-volatile. This
means they c an be more easily
Electrical conductivity
contained and, oen, recycled.
This, however, does not necessarily

In order to conduct electricity, substances must contain charged particles that are
mean they are harmless. Their

able to move. Ionic compounds contain charged particles, cations and anions. In
manufacturing, disposal and

a solid ionic lattice, cations and anions can vibrate around a xed point, but they
transportation c an have signic ant

cannot change position. Solid ionic compounds do not conduct electricity because
environmental impacts.
ions in a solid lattice are not mobile. When molten or aqueous, both cations and
anions are free to move past one another, allowing them to conduct electricity
when a potential dierence is applied.
A solid ionic
compound
+ +
cannot conduct
– –
electricity
+ +
–
because the
– –
+ +
ions cannot
– –
move. They
+
+ +
Figure 15 These are waste separation
are fixed in the

– –
+ + bins in Jakarta, Indonesia. The lemost bin
regular
–
(red) is for batteries. Electrolytes in batteries
arrangement.
– –
+ + conduct electricity bec ause they contain
– –
mobile ions. Used batteries are frequently
+
separated from other types of waste to
heat dissolve in
prevent them from ending up in landll.
water
This is bec ause batteries contain valuable
metals and other substances, which c an
+ be recycled. Do you separate your used
+ +
+
batteries from other household waste?

+
+
+
+
+
+
+
+
+
+
water
+ + molecule
+
+
+ +
+
+
+
+
When an ionic compound is heated When an ionic compound is
strongly and melts, the ions can dissolved in water, it can conduct
move around and the molten electricity because its ions can
tFigure 16 Molten and aqueous ionic
compound conducts electricity. move among the water molecules.

compounds are electric al conductors
111
Solubility
Ionic compounds are typic ally soluble in polar solvents such as water, and
insoluble in non-polar solvents such as hexane.
Water is a polar solvent. The dierence in electronegativity between the oxygen
Polarity is discussed in greater

and hydrogen atoms, combined with the bent geometry of the water molecule,
detail in Structure 2.2.

result in the water molecule having a partial negative charge on the oxygen atom
and partial positive charges on the hydrogen atoms.
Imagine an ionic compound being added to water. The water molecules position
themselves so that their partial negative charges point towards the c ations, and
their partial positive charges point towards the anions. As a result, individual ions
are pulled out of the lattice and become surrounded by water molecules. In the
c ase of a non-polar solvent, there is no attraction between the ions of the ionic
compound and the solvent molecules, so the c ations and anions remain within
the lattice.
Activity
Draw a labelled diagram
δ+
explaining why ionic compounds δ‒
δ+ H H
O O
conduct electricity when molten or δ‒
dissolved, but not when solid. H H
δ+ δ+
Cl
δ+ δ+
H H
O H δ+ H O
δ‒ δ‒
δ+
H δ+
O δ+
δ‒
H δ‒
O
δ+ δ+
H
+
Cl
Cl
+ Na
δ+ Na
Cl Cl H H
+
δ+
Na
δ+ δ‒ δ‒ δ+
+
+ H H
Na O O
Na
+
Cl +
Na Cl
Na
Cl
+
Na
+ +
Cl Na Na Cl δ‒
δ‒
Cl + Cl
Na δ+ δ+
H
+ + O O
H
Na Na
+
Cl +
Na Na
Cl
H H
Cl
δ+ δ+
Figure 17 The dissolution of ionic compounds in water involves interactions between ions and water molecules
Not all ionic compounds dissolve in water. This is bec ause there are two
competing forces of attraction present:
• ionic bonds between c ations and anions in the lattice
• the association between the ions and the partial charges of water molecules
Ionic compounds are insoluble when the electrostatic attractions between the
c ations and anions in the lattice are stronger than the association between the
ions and water molecules. Examples of ionic compounds that are insoluble in
water include c alcium c arbonate and silver chloride.
112
ATL Research skills
H e av y metal ions, such as le ad and nickel, often form insoluble salts.
Some w a s t ew a t e r t re a t m e n t p ro c e ss e s take adv antage of this p ro p e r t y,
re m o v i n g h e av y metals out of industrial effluents t h ro u g h p re c i p i t a t i o n .
• Use the internet to re s e a rc h other ex a m p l e s of p re c i p i t a t i o n re a c t i o n s
and their uses.
• Describe and ex p l a i n the changes that a re o b s e r ve d when a
p re c i p i t a t e is forme d.
Linking questions
What experimental data demonstrate the physic al properties of ionic
compounds? (Tool 1, Inquiry 2)
How can lattice enthalpies and the bonding continuum explain the trend in Figure 18 Close-up photograph of the
formation of a lead(II) chromate precipitate

melting points of metal chlorides across period 3? (Structure 3.1)
in the reaction between aqueous solutions
of lead(II) nitrate and potassium chromate
Figure 19 S alt ats at S alar de Uyuni in Bolivia, which are mainly made of halite, the
mineral form of sodium chloride. The brine below the rock salt crust is rich in dissolved metal
ions, particularly lithium. Global demand for lithium is increasing due to its use in batteries.
Lithium-ion batteries c an be used to power mobile phones, laptops and electric vehicles
113
Solubility of ionic salts
The patterns in aqueous solubility of several common Instructions
ionic compounds are often referred to as solubility
Part 1: Solubility rules
rules. We c an use these differences in solubility to help
us deduce the identity of an unknown ionic compound.

General solubility rules c an be inferred from the data in
In this task you will mix different solutions of ionic

table 7. For example:
compounds and observe whether an insoluble product
• All nitrates are soluble.
(known as a precipitate) is produced.
• Sulfates are generally insoluble, except group 1
Relevant skills
sulfates and ammonium sulfate.
• Tool 1: Recognize and address relevant safety and
Study table 7 and infer at least three more general
environmental issues in an investigation
solubility rules.
• Inquiry 2: Interpret qualitative data
Part 2: Identification of ionic compounds
S afety
You will be provided with samples of solutions labelled

A, B, C, and D. These solutions are potassium c arbonate,
sodium chloride, silver nitrate and c alcium nitrate, but you
• Dilute c alcium nitrate and silver nitrate solutions are
do not know which is which. Your job is to identify each
irritants.
solution, using the materials listed and the solubility rules.
• You should take c are when handling all solutions

You may also draw from your knowledge of other areas
bec ause you do not know exactly which is which.

of chemistry.
They are all potential irritants.
Note you do not have to mix the solutions inside test
• Collect and retain any precipitates formed.

tubes. You c an prepare small-sc ale mixtures of solutions
by mixing a drop of each on a plastic sheet. If a precipitate

• Dispose of waste solutions and precipitates according
is formed, the solution will become opaque. This will be

to your school’s guidelines.
easily observable, particularly if you lay the sheet on a
Materials
black background.
• Clear plastic sheet on a black background
Devise a method, present it clearly, and show it to your
teacher. If they approve it and if you have time, try it out!

• Pipettes
• Small piece of copper wire (~0.5 cm long)
• Dilute acid solution
• S amples of solutions labelled A, B, C and D
C ations
group 1 c ations ammonium, barium, lead,

2+ +
c alcium, C a silver, Ag
+ + + + 2+ 2+
(Li , Na , K ) NH Ba Pb
4
nitrate, NO soluble soluble soluble soluble soluble soluble

3
ethanoate,
soluble soluble soluble soluble soluble soluble

–
CH COO
3
chloride, Cl soluble soluble soluble soluble insoluble insoluble

Anions
hydroxide, OH soluble soluble soluble slightly soluble insoluble insoluble
2–
sulfate, SO soluble soluble insoluble slightly soluble slightly soluble insoluble

4
2–
c arbonate, CO soluble soluble insoluble insoluble insoluble insoluble

3
Table 7 Aqueous solubility of common ionic compounds
114
7. What is the formula of sodium nitrate?
Topic review
A. NaNO
2
answer the guiding question as fully as possible: B. NaNO

3
What determines the ionic nature and properties of a C. Na N

3
compound?
D. S N
3 2
2. Explain why ionic substances are always compounds.
8. Which compound has the largest value of lattice
enthalpy?
A. C aS
B. C aO
3. The elements in group 17 generally form ions with
C. K S
which charge? 2
D. K O
A. 7+ 2
9. Which statement is correct?

B. 1+
A. L attice enthalpy increases when the radii of the

C. 1–
component ions increase.
D. 7–
B. Lattice enthalpy represents the energy needed to
4. The ion of element X has a 2 + charge and contains 20

transfer an electron from a c ation to an anion.
protons. Give the full electron conguration of this ion.
C. L attice enthalpy decreases when the charge of the
2 2 6 2 6
A. 1s 2s 2p 3s 3p
component ions increases.
2 2 6 2 6 2
B. 1s 2s 2p 3s 3p 4s
D. L attice enthalpy increases when the charge density
2 2 6 2 6 2
of the component ions increases.
C. 1s 2s 2p 3s 3p 3d
2 2 6 2 6 2 2
10. Which equation correctly represents the lattice enthalpy
D. 1s 2s 2p 3s 3p 4s 3d
of potassium oxide?
5. Which statement about ionic compounds is correct?
+ 2–
A. K O(s) → 2K (g) + O (g)

2
A. Ionic bonding results from the electrostatic
B. K O(s) → 2K(s) + ½O (g)

attraction between c ations and anions.
2 2
2+ 2–
C. K O(s) → K (g) + O (g)

B. C alcium uoride is made up of C aF molecules.
2 2
2
D. K O(s) → 2K(g) + ½O (g)

C. Ionic structures contain deloc alized electrons when
2 2
molten or dissolved, but not when solid.

11. List the lithium halides in order of increasing lattice
enthalpy.
D. Ions are held together bec ause anions transfer
electrons to c ations.
A. LiF, LiCl, LiBr, LiI
6. What is the name of C aSO ?

4 B. LiF, LiBr, LiCl, LiI
A. c arbon sulte
C. LiI, LiBr, LiCl, LiF
B. c alcium sulte
D. LiI, LiCl, LiBr, LiF
C. c arbon sulfate
D. c alcium sulfate
115
12. Which substance has an ionic structure?
Electric al Electric al
Melting Solubility
conductivity conductivity
point / °C in water
when molten when solid
A 36 high none none
B 186 low none none
C 1083 high good none
D 1710 low good good
13. C alcium uoride has applic ations in the eld of optics. c. Deduce the charge of the dichromate(VI) ion. [1]
a. Deduce the formula for c alcium uoride. [1] d. Potassium dichromate(VI) contains chromium.
Chromium is a transition element that commonly
b. Describe the structure and bonding in solid

2+ 3+
forms form Cr ions and Cr ions among others.
c alcium uoride. [3]
i. Write the abbreviated electron conguration
c. Explain why solid c alcium uoride is a poor
of a chromium atom. [1]
electric al conductor, but molten c alcium uoride
c an conduct electricity. [2] ii. Copy the diagram below and draw
arrows in the boxes to represent the
d. The lattice enthalpy of c alcium uoride is
electronconguration in the 3d and 4s

1
2 651 kJ mol .
2+
orbitals of a Cr ion. [1]
i. Write an equation, including state symbols,
that shows the process associated with the
lattice enthalpy of c alcium uoride. [2]

4s 3d
ii. Explain why the process in part (i) is
iii. Write the full electron conguration of a
endothermic. [1]
3+
Cr ion. [1]
iii. The lattice enthalpy of c alcium oxide, C aO,
15. The equation below shows the formation of lithium
is3 401 kJ mol . Explain why the lattice
uoride from its elements under standard conditions.
enthalpy of c alcium oxide is greater than
Li(s) + F (g) → LiF(s)

that of c alcium uoride. [2]
2
a. Balance the equation. [1]

14. Certain types of breathalyser contain the bright orange
ionic compound potassium dichromate(VI), K Cr O

2 2 7 b. Identify the charge of the lithium ion. [1]
a. Write the full electron conguration of a

c. Identify the oxidized species and the reduced
potassium ion. [1]

species in this reaction. [1]
b. Explain why the dierence in mass between a

d. Sketch a diagram showing the structure of
potassium atom and a potassium ion is

lithiumuoride. [2]
negligible. [1]
116
Structure 2.2 The covalent model
What determines the covalent nature and properties of a substance?
Covalent bonds lead to a vast range of dierent substances. Substances with covalent network structures are also
From water to diamond to nitrogen gas, from oils to characterized by high melting points and boiling points,
plastics to polyatomic ions, these species contain atoms low volatility and poor solubility in water. Substances with
held together by strong covalent bonds. Covalent bonds molecular structures, on the other hand, generally have
lead to the formation of two dierent types of structure: low melting points and boiling points. Their solubility and
covalent network structures (also known as giant covalent volatility vary greatly depending on their intermolecular
structures) and molecular covalent structures forces.
In general, covalent substances are poor electric al

In Structure 2.2, you will learn what a covalent bond is,
conductors.
how we represent molecules as well as how we describe
and explain their shapes and intermolecular forces. You
will also learn about covalent network structures.
Understandings
Structure 2.2.1 — A covalent bond is formed by the London (dispersion) forces < dipole–dipole forces <
electrostatic attraction between a shared pair of electrons hydrogen bonding.
and the positively charged nuclei.

Structure 2.2.10 — Chromatography is a technique
The octet rule refers to the tendency of atoms to gain a used to separate the components of a mixture based on
valence shell with a total of 8 electrons. their relative attractions involving intermolecular forces to
mobile and stationary phases.

Structure 2.2.2 — Single, double and triple bonds
involve one, two and three shared pairs of electrons
LHA
Structure 2.2.11 — Resonance structures occur when
respectively.
there is more than one possible position for a double
Structure 2.2.3 — A coordination bond is a covalent
bond in a molecule.
bond in which both the electrons of the shared pair
Structure 2.2.12 — Benzene, C H , is an important

originate from the same atom.
6 6
example of a molecule that has resonance.
Structure 2.2.4 — The Valence Shell Electron
Structure 2.2.13 — Some atoms c an form molecules in

Pair Repulsion (VSEPR) model enables the
which they have an expanded octet of electrons.

shapes of molecules to be predicted from the repulsion of
electron domains around a central atom. Structure 2.2.14 — Formal charge values c an be
c alculated for each atom in a species and used to

Structure 2.2.5 — Bond polarity results from the
determine which of several possible Lewis formulas is

dierence in electronegativities of the bonded atoms.
preferred.
Structure 2.2.6 — Molecular polarity depends on both
Structure 2.2.15 — Sigma bonds (σ) form by the head-on

bond polarity and molecular geometry.
combination of atomic orbitals where the electron density
Structure 2.2.7 — C arbon and silicon form covalent
is concentrated along the bond axis.
network structures.
Pi bonds (π) form by the lateral combination of p orbitals
Structure 2.2.8 — The nature of the force that exists
where the electron density is concentrated on opposite
between molecules is determined by the size and polarity
sides of the bond axis.
of the molecules. Intermolecular forces include London
Structure 2.2.16 — Hybridization is the concept of

(dispersion), dipole–induced dipole, dipole–dipole and
mixing atomic orbitals to form new hybrid orbitals for

hydrogen bonding.
bonding.
Structure 2.2.9 — Given comparable molar mass, the
relative strengths of intermolecular forces are generally:
117
Covalent bonds and molecules
(Structure 2.2.1)
Covalent bonds are formed when atoms share pairs of valence electrons. A
covalent bond results from the electrostatic attraction between a shared pair of
electrons and the positively charged nuclei of the atoms involved in the bond.
Diatomic hydrogen, H , is the simplest covalent molecule. It consists of two

2
hydrogen atoms held together by a covalent bond made from one electron
from each hydrogen atom (gure 1). Atoms c an share one, two or three pairs
of electrons, forming single, double or triple bonds, respectively. Figure 1 also
shows the formation of the double covalent bond in diatomic oxygen, O .

2
A shared pair of
electrons gives both
H H H H
atoms a stable
arrangement and forms
Hydrogen atoms Hydrogen molecule a single covalent bond
This is a double
covalent bond (two
O O O O
shared pairs of electrons).
Only the electrons in the
highest energy level (outer
shell) are shown here
Oxygen atoms Oxygen molecule
Figure 1 Covalent bond formation in diatomic hydrogen, H , and diatomic oxygen, O

2 2
Figure 2 Examples of substances that contain covalent bonds: plastics, graphite (in pencil leads), zzy water, and the c arbon dioxide
bubbles in it
118
Activity
Draw a diagram to show the triple covalent bond in diatomic nitrogen, N

2
Electronegativity
Covalent bonds generally form between atoms of relatively high
electronegativity, typic ally non-metals. In Structure 2.1, we saw that ionic bonds
form when the electronegativity dierence between two atoms is greater than
1.8. When the dierence in electronegativity between the atoms is less than 1.8
(gure 3), the bond between them is predominantly covalent.

ecnereffid ytivitagenortcele
3.0
ionic greater ionic
bonding character
2.0
covalent greater covalent

1.0
bonding character
Figure 3 Electronegativity dierences
that are lower than 1.8 suggest that covalent
As discussed in Structure 2.1,

bonding is present
there is no sharp borderline
Unlike ionic substances, which are always compounds, covalent substances between ionic and covalent
c an be either elements or compounds. When two non-metal atoms of the same bonding. Bonding occurs along
element bond together, the electronegativity dierence is zero, so they form a a continuum, with greater ionic
covalent bond between them. character at one end and greater
covalent character at the other.
Electronegativity increases across periods and up groups. If two atoms of
Structure 2.4 addresses this
relatively high electronegativity are found close to each other in the periodic
continuum in more detail with the
table, the bonds they form are likely to be covalent. For example, oxygen and
bonding triangle
uorine form covalent bonds with each other.
Practice questions
1. Determine whether the following pairs of elements bond covalently or
ionic ally, by referring to their electronegativity values:
a. c arbon and oxygen
b. sodium and oxygen
c. c arbon and hydrogen
d. chlorine and oxygen
e. iodine and iodine
f. aluminium and uorine
119
Lewis formulas
Groups of atoms that are covalently bonded together are c alled molecules. The
way valence electrons are arranged in a molecule c an be shown using Lewis
formulas. In Lewis formulas, pairs of valence electrons are represented as dashes,
pairs of dots or pairs of crosses, or a combination of all three. Consider the
various Lewis formulas of uoroamine, NH F, in gure 4.

2
H H H
Here are the rules for drawing Lewis formulas regardless of whether dots, crosses
or dashes are used:

F
1. Only valence electrons are shown.
H H
2. Electrons are arranged in pairs.
Figure 4 These are all acceptable Lewis
3. Each pair of electrons shared between two atoms represents a covalent bond.
formulas of uoroamine, NH F
2
4. Electrons in a bond (termed bonding electrons) are positioned in the region
between the two atoms involved in the bond.
5. Non-bonding electrons (also referred to as lone pairs) are positioned away
from the region between the two atoms involved in the bond.
Atoms in Lewis formulas generally have noble gas electron congurations. This is
known as the octet rule because noble gases oen have eight valence electrons.
Noble gases already have full octets and do not readily gain, lose or share
electrons. Hence, they are usually found in an unbonded, monatomic form.
The octet rule is a useful rule of thumb, but it has limitations. It does not explain
why some noble gases form bonds in certain situations. Sometimes atoms c an
form stable molecules even with fewer than an octet of electrons. Conversely,
larger atoms c an form expanded octets (this is seen at AHL). Species with odd
numbers of valence electrons are also exceptions to the octet rule.
Following these steps will help you draw Lewis formulas in most c ases:
1. Work out the total number of the valence electrons for each atom in the
molecule.
F F
2. Divide the total number of valence electrons by two to work out how many
pairs of electrons there are.
3. Arrange the atoms by drawing their symbols on the page. The element with
the least number of atoms is usually found in the centre. Hydrogen atoms
always surround the central atom(s).

O O
4. Bond the central and peripheral atoms together by drawing single bonds
+ between them. E ach single bond represents an electron pair.

N
N
5. Assign non-bonding pairs of electrons to the peripheral atoms. Keep going
until they achieve noble-gas congurations.
N N
6. Assign any remaining electron pairs to the central atom(s).
Figure 5 By sharing a pair of electrons,
two uorine atoms c an obtain a full octet of

7. Check that the central atom has a full octet. If it does not, try the following
valence electrons. Oxygen atoms c an do

two methods:
this by sharing two pairs of electrons, and
• Reassign non-bonding pairs on the peripheral atoms to become

nitrogen atoms share three pairs
additional bonds to the central atom
• Check that the molecule you are looking at is not an exception to the
octet rule (see page 123 for examples)
120
Worked example 1
Draw the Lewis formulas of each of the following molecules:
a. water, H O b. nitrogen trichloride, NCl c. c arbon dioxide, CO

2 3 2
Solution
Follow the steps above for e ach molecule:
a. water, H O b. nitrogen trichloride, NCl c. c arbon dioxide, CO

2 3 2
Step 1 Count hydrogen: 1 × 2 = 2 nitrogen: 5 c arbon: 4
valence electrons oxygen: 6 chlorine: 7 × 3 = 21 oxygen: 6 × 2 = 12
Total: 2 + 6 = 8 Total: 5 + 21 = 26 Total: 4 + 12 = 16
Step 2 C alculate 8 26 16
= 4 pairs = 13 pairs = 8 pairs
the number of 2 2 2
electron pairs
Step 3 Arrange H O H Cl O C O
the atoms
Hydrogens on the periphery. There is only one c arbon, so it
Cl N Cl
There is only one oxygen, so it is likely to be in the centre.
is likely to be in the centre. There is only one nitrogen, so it
is likely to be in the centre.
Step 4 Draw the H Cl O
single bonds
2 pairs used so far... 2 pairs used so far...
Cl N Cl
3 pairs used so far...
Step 5 Put non- The peripheral hydrogen

Cl O
bonding pairs on atoms already have noble gas
The oxygen atoms now have
peripheral atoms congurations bec ause the

Cl N Cl
full octets.
rst energy level only holds up

The chlorine atoms now have
to two electrons. They do not
full octets.
need any more electrons.
Step 6 Put We have used all 8 available

H Cl
any remaining electron pairs. None are
The 2 remaining electron pairs

electron pairs on available for the central c arbon.
Cl N Cl
are assigned to the oxygen.

the central atom
The remaining electron pair is
assigned to the nitrogen.
!
Step 7 Check Oxygen has 4 electron pairs in Nitrogen has 4 electron pairs in
O
that the central the Lewis formula, therefore a the Lewis formula, therefore a
atom has a full full octet. full octet.

The c arbon atom has only
octet
2 electron pairs in this Lewis
formula.
We need to reassign two of the
non-bonding pairs on the oxygen
atoms to form double bonds:
Now the c arbon atom has 4
electron pairs and therefore a
full octet.
121
Polyatomic ions are charged groups of covalently bonded atoms. The
magnitude of the charge indic ates how many electrons have been lost or
gained. Lewis formulas of poly atomic ions are enclosed in square brackets, with
the charge indic ated with a superscript outside the brackets. When counting
the v alence electrons, you also need to factor in the charge: for every additional
negative charge, you add an electron, and for every additional positive charge,
you subtract an electron. This is illustrated in the next set of worked examples.
Worked example 2
Draw the Lewis formulas of the following ions:
– 2– +
a. hydroxide ion, OH b. c arbonate ion, CO c. hydronium ion, H O

3 3
Solution
Follow the steps above for e ach ion:
2– +
a hydroxide ion, OH b c arbonate ion, CO c hydronium ion, H O

3 3
Step 1 Count oxygen: 6 c arbon: 4 hydrogen: 1 × 3 = 3
valence hydrogen: 1 oxygen: 6 × 3 = 18 oxygen: 6
electrons This polyatomic ion has a This polyatomic ion has a This polyatomic ion has a
1 charge, meaning that it 2– charge, meaning that it 1+ charge, meaning that it
has one additional electron. has two additional electrons. has one fewer electron.
Total: 6 + 1 + 1 = 8 Total: 4 + 18 + 2 = 24 Total: 3 + 6 1 = 8
Step 2 8 24 8
C alculate the 2 2 2
number of
electron pairs
Step 3 Arrange O
H O H
the atoms
O H
O O
Step 4 Draw the O H
single bonds
1 pair used so far...
C H
O O
Step 5 Put non- The hydroxide ion has only two The peripheral hydrogen atoms
O
bonding pairs atoms in it, so you do not need have noble gas congurations
on peripheral to distinguish between central and therefore do not need any

C
atoms and peripheral atoms here. more electrons.

O O
Skip this step.
full octets.

H O H
any remaining electron pairs. None are
The remaining 3 electron pairs
electron pairs available for the central c arbon.
H
are assigned to the oxygen
on the central
atom. The hydrogen already The fourth electron pair is
atom
has a noble gas conguration. assigned to the oxygen atom.
122
2– +
a hydroxide ion, OH b c arbonate ion, CO c hydronium ion, H O

3 3
+
Step 7 Check
O
H
O H
that the central
!
atom has a full
C
All atoms have noble-gas
H
octet
O O
congurations.
All atoms have noble gas

Note the square brackets and
The c arbon atom has only
congurations. Brackets and

charge, which are used in the
3pairs in this Lewis formula.
charge are added to complete

Lewis formulas of polyatomic
We need to reassign one of the
the Lewis formula.

ions.
non-bonding pairs on the oxygen
atoms to form a double bond:
Now the c arbon atom has
4electron pairs and therefore a
full octet. Brackets and charge
are added to complete the
Lewis formula.
Sometimes molecules contain atoms that do not follow the octet rule. At SL,
you should be aware of Lewis formulas that contain atoms with fewer than eight
valence electrons. Consider the arrangement of the 12 electron pairs of boron
triuoride, BF in the Lewis formula shown in gure 6. Here, the boron atom has
B
3
only three pairs of electrons around it. The boron atom is electron decient.
F F
Similar to boron, many other elements of groups 2 and 13 form stable electron-
Figure 6 Lewis formula of boron

decient molecules. These include beryllium, magnesium and aluminium. In Lewis
triuoride
formulas of such molecules, group 2 elements (Be and Mg) have only two bonding
electron pairs while group 13 elements (B and Al) have three bonding electron pairs.
Practice questions
2. Draw the Lewis formula of each of the following:
a. BH b. BCl
3 3
c. BeCl d. AlCl
2 3
e. CH
3
a. HBr b. OF
2
c. O d. O
2 3
e. HCN f. CH Cl
3
g. CH O h. N H
2 2 4
a. NH b. NO
4 3
c. NO d. NO
2 2
e. OCl
123
Linking questions
What are some of the limitations of the octet rule?
Why do noble gases form covalent bonds less readily than other elements?
(Structure 1.3)
Why do ionic bonds only form between dierent elements while covalent
bonds c an form between atoms of the same element? (Structure 2.1)
Bond order (Structure 2.2.2)
The hydrogen molecule, H , shown in gure 7, contains a single bond. The

2
oxygen molecule, O , contains a double bond. Diatomic nitrogen, N , contains

2 2
a triple bond
Figure 7 Hydrogen, oxygen and nitrogen molecules with diering bond order
single double triple
increasing strength
increasing length
Figure 8 The relationship between bond order, bond length and bond strength
The number of bonded electron pairs between two atoms is referred to as bond
order. Single bonds (bond order 1), double bonds (bond order 2) and triple
bonds (bond order 3) dier in their strength and length. Double bonds are
stronger than single bonds, and triple bonds are stronger still. Triple bonds hold
atoms closer together than double bonds, and hence triple bonds are shorter
than double bonds. Double bonds are, in turn, shorter than single bonds. Figure
8 shows this pattern for c arbon–c arbon bonds.
Bond enthalpies are discussed in
Bond strength and length c an be quantied. The stronger a bond is, the larger its
Reactivity 1.2
bond enthalpy.
124
Bond length is dened as the average distance between two bonded nuclei. Table
1 shows bond enthalpy and bond length data for carbon–carbon single, double and
triple bonds. The carbon–carbon triple bond is the shortest but also the strongest.
tTable 1 Bond enthalpies and bond

–1 –12
Bond Bond enthalpy (at 298 K) / kJ mol Bond length / 10 m
lengths of c arbon–c arbon bonds
C–C 346 154
C=C 614 134
C≡C 839 120
Data-based question
The bond enthalpy of a carbon–nitrogen triple bond is 890 kJ mol and its bond
12
length is 116 × 10 m. Use these data and the information in table 1 to predict
the bond enthalpies and bond lengths of single and double carbon–nitrogen
bonds. Then compare your predictions with the values in the data booklet.
Graphs oen complement written explanations. The paragraph below
explains why a covalent bond forms between two hydrogen atoms by
describing the relationship between potential energy and the distance
between two hydrogen atoms. Read it and try to represent what it is
describing by sketching a graph of potential energy (y-axis) vs distance
between hydrogen nuclei (x-axis).
Two hydrogen atoms have no eect on each other if they are
separated by a suciently large distance. As the two atoms
approach each other, the electrostatic attraction between the
hydrogen nuclei and each other ’s electrons increases. This process
leads to a decrease in potential energy. As the atoms get closer,
they reach a point where the two nuclei attract the two electrons
in the pair, eectively sharing them. This arrangement occurs at a
potential energy minimum, meaning that the molecule is energetically
stable. If the atoms were to get any closer together, the resulting
repulsion between the two positively charged nuclei would outweigh
the attraction for the shared pair of electrons, leading to a rise in
potential energy.
When you have nished, compare your sketch graph to a potential energy
Linking question
curve. You c an nd one by typing “hydrogen molecule potential energy
curve” into a search engine. How does the presence of double
What c an graphic al representations add to explanations such as the one and triple bonds in molecules
above? To what extent is a graphic al representation better than a textual inuence their reactivity?
description? (Reactivity 2.2)
125
The formation of coordination Coordination bonds (Structure 2.2.3)
bonds is a feature of electron pair
We have seen that a covalent bond is formed when each of the two atoms in
sharing reactions, as discussed in
the bond contributes an electron to the bond. Sometimes both the electrons
Reactivity 3.4.
in the covalent bond come from the same atom. The resulting bonds are c alled
coordination bonds For example, when a hydrogen c ation encounters a
water molecule, a coordination bond is formed, leading to the formation of a
hydronium ion (gure 9). Coordination bonds are oen indic ated with an arrow
along the bond. The direction of the arrow shows which atom donated the
electron pair to the bond, and which atom accepted the electron pair.
uFigure 9 Dierent representations +
of the hydronium ion, showing the +

H
H O H
H O H
coordination bond
H
H
coordination bond
Coordination bonds help to explain how bonding occurs in certain molecules.
Once formed, coordination bonds are indistinguishable from any other
covalentbond.
Practice questions
5. Draw the Lewis formulas of the following molecules, indic ating the
coordination bonds clearly.
a. ammonium ion, NH
4
b. ozone, O
3
c. c arbon monoxide, CO
d. ammonia boron triuoride, NH BF

3 3
LHA
Coordination bonds in transition metal complexes

The properties of complex ions
and their reactions are discussed in Transition metals can form complex ions such as the one shown in Figure 10. These
Reactivity 3.4. complex ions contain coordination bonds, which hold together the central metal
cation and the surrounding atoms or groups of atoms, called ligands.
A common feature of all ligands is a lone pair of electrons, which c an be used to
form the coordination bond to the metal ion.

Linking question
Why do Lewis acid–base
reactions lead to the formation of
+
2
coordination bonds? (Reactivity 3.4) H O
2
H O OH
2 2
Cu
H O OH
2 2
H O
2
+
2
[Cu(H O) ]
2 6
Figure 10 Water molecules form coordination bonds with copper(II) c ations, leading to
the formation of a blue hexaaquacopper(II) complex ion
126
The valence shell electron pair repulsion
model (VSEPR) (Structure 2.2.4)
You might have come across a Lewis formula for water that shows the two
hydrogen atoms at an angle. Such formulas better illustrate the geometry of the
molecule. This c an also be shown by ball-and-stick and space-lling models
(gure 11).
Two-dimensional representations of molecules such as Lewis formulas do not
reect the three-dimensional arrangement of atoms in a molecule. The three-
dimensional shape of a molecule is termed molecular geometry, and it is an
essential feature of molecules which contributes to their properties. For example,
the molecular geometry within a structure known as a beta-lactam ring is key to its
Figure 11 Space-lling model of a water
antibiotic properties. This is shown in gure 12. molecule
Molecular geometry c an be explored using the VSEPR model: side chain
β-lactam ring
Valence Shell Electron Pair Repulsion

R
H
N
C
The VSEPR model is based on the following premises: S
CH
3
1. Electron pairs repel each other and therefore arrange themselves as far apart
O
from each other as possible. C N

CH
3
2. Non-bonding (or lone) electron pairs occupy more space than bonding pairs
O
(single bonds).
O
amide bond
3. Double and triple bonds occupy more space than single bonds.
HO
The term electron domain will be useful in these discussions. An electron
Figure 12 The beta-lactam ring (in red
domain is a region of high electron density due to the presence of electron pairs.
above) is a common feature of antibiotic
An electron domain c an be:
molecules such as penicillins. The geometry
of this structure is vital to its reactivity. The
• a non-bonding pair of electrons (known as a lone pair)
amide bond hydrolyses readily due to the
• a bonding pair of electrons (single bond)

strain c aused by the 90° bond angles.
This means that it c an attach to enzymes
• a double or triple bond (which involve multiple pairs of electrons).
responsible for building bacterial cell walls.
The Lewis formula in gure 13 illustrates this point: the central sulfur atom has
three electron domains, of which one is a non-bonding domain, and two are
bonding domains. One of the bonding domains is a double bond, the other is a
single bond.
one non-bonding domain
composed of a lone
pair of electrons
S
one bonding domain
composed of a
double bond
one bonding domain
tFigure 13 The sulfur atom in sulfur
composed of a single bond

dioxide has three electron domains
We will now explore geometries involving two, three and four electron domains
using VSEPR. Predicting the VSEPR shape of a molecule involves two steps:
1. Count the number of electron domains around a central atom to deduce the
electron domain geometry.
2. Determine how many of these are bonding domains and how many are non-
bonding domains.
127
Two domains: Linear geometry
If there are two electron domains, the electron pairs in those domains repel each
other. They therefore adopt positions at 180° (gure 14). The angle between
bonding pairs in a molecule is known as the bond angle. This electron domain
geometry is c alled linear to illustrate that the central atom and both domains are
on a straight line.
Molecules with this electron domain geometry also have a linear molecular
geometry. Examples include beryllium chloride, BeCl , c arbon dioxide, CO ,

2 2
and ethyne, C H . These are shown in gure 15.

2 2
Figure 14 Linear geometry has two
180°
electron domains at a 180° angle to each
180°
180°
other
Cl Be Cl O C O
H
Figure 15 Examples of linear molecules, in which the central atom has two electron
domains. Note that double and triple bonds count as one domain
Three domains: Trigonal planar geometry
If there are three bonding domains, the electron pairs adopt positions at 120°
from each other. This electron domain geometry is c alled trigonal planar.
Trigonal, bec ause the domains form a triangle, and planar, bec ause the atoms lie
at on a plane.
Figure 16 Trigonal planar geometry has A trigonal planar electron domain geometry c an have two possible molecular
three electron domains at 120° angles to geometries, depending on the presence of non-bonding domains:
each other
• When all three domains are bonding domains, the molecule has trigonal
planar geometry.
• When only two of the three domains are bonding domains, and one is a non-
bonding domain, the molecule has bent (or V-shaped) geometry.
Examples of each type are shown in gure 17.
(a) (b)
Cl
120°
Cl Cl O O
<120°
Figure 17 A trigonal planar electron domain geometry c an lead to (a) trigonal planar
molecular geometry if all three domains are bonding domains, or (b) bent (V-shaped)
molecular geometry if one of the domains is a lone pair of electrons
The bond angle in NO is smaller than the predicted 120°. This is bec ause the
2
non-bonding pair (or lone pair) exerts a stronger repulsion than the bonding
domains, and therefore takes up more space.
128
Four domains: Tetrahedral geometry
If there are four bonding domains, the electron pairs adopt positions at 109.5°
from each other. This electron domain geometry is c alled tetrahedral bec ause
the ends of the domains form the corners of a tetrahedron.
You might expect four electron domains to arrange themselves in a square
conguration. However, this would result in angles of 90° between the domains.
The domains arrange themselves tetrahedrally to maximize the bond angles and
Figure 18 Tetrahedral geometry has
distances between them.

four electron domains at 109.5° angles to
each other
A tetrahedral electron domain geometry gives rise to three possible molecular
geometries, depending on the presence of non-bonding domains:
• When all four domains are bonding domains, the molecule has tetrahedral
geometry.
• When three of the four domains are bonding domains and one is a non-
bonding domain, the molecule has trigonal pyramidal geometry.
• When only two of the four domains are bonding domains and two are non-
bonding domains, the molecule has bent (or V-shaped) geometry.
tFigure 20 A
F
tetrahedral electron
domain geometry Figure 19 Tetrahedral food packages
Si P S
leads to tetrahedral, are convenient bec ause they c an be easily
trigonal pyramidal lled, stacked and packed. Their invention
F F
or bent (V-shaped) revolutionized the food packaging industry
molecular geometries in the mid-20th century

tetrahedral trigonal pyramidal bent or V-shaped
Non-bonding pairs occupy more space than bonding domains, which leads to
decreased bond angles. Methane, CH , has no non-bonding pairs, and therefore

4
the bond angle corresponds to the predicted 109.5°. Ammonia, NH , has one
3
non-bonding pair, and therefore has a smaller bond angle (107°). Water, H O, has
2
two non-bonding pairs and therefore has an even smaller bond angle of 104.5°.
The angles and geometries are shown in gure 21. Note that some bonds are
represented using wedges ( ) and dashes ( ) to better convey their 3D
shape. Wedges represent bonds that are coming out of the plane of thepage at
an angle and dashes represent bonds that are going into the plane ofthe page.
C
N
O
H
H
H
H
H
H
H
109.5° H
107°
104.5°
tFigure 21 In methane, CH , ammonia,

4
NH , and water, H O, the bond angles are

3 2
all slightly dierent due to the stronger
repulsion exerted by the lone pairs
129
Multiple bonds
Multiple bonds (double and triple bonds) count as one domain. A double bond
represents one domain, but it contains two electron pairs. Similarly, a triple bond
is one domain composed of three electron pairs. Since multiple bonds contain
more than one pair of electrons, they exert a greater repulsion than single bonds.
The increased repulsion causes the bond angles in the molecule to deviate from
predicted values.
121.5°
H H
C C 117°
For example, each c arbon atom in ethene has three bonding electron domains
H H and hence its molecular geometry is trigonal planar. This would suggest 120°
bond angles. However, the H–C–H bond angle is 117° and the H–C =C bond
Figure 22 Multiple bonds generally
angle is 121.5°, as the greater repulsion exerted by the double C=C bond
exert a greater repulsion than single bonds
pushes away both C–H bonding domains. This is shown in gure 22.
Table 2 shows a summary of the geometry of molecules with two, three and four
electron domains.
Number
Number of
Electron domain Number of of non- Molecular Bond
bonding Examples
geometry domains bonding geometry angle
domains
domains
BeCl
2
linear
linear 2 2 0 180° CO
2
HCN
3 0 trigonal planar 120° BF , NO , SO

3 3 3
trigonal planar 3
2 1 bent (or V-shaped) <120° O , SO , NO

3 2 2
4 0 tetrahedral 109.5° CH , NH , ClO

4 4 4
tetrahedral 4 3 1 trigonal pyramidal <109.5° NH , H O , PBr

3 3 3
2 2 bent (or V-shaped) <109.5° H O, NH , SF

2 2 2
Table 2 Summary of the geometries for two, three and four electron domains
ATL Thinking skills
You can model electron
domains using balloons. If
you hold several balloons
at a central point by their
knots, they will arrange
themselves as far away from
each other as possible. The
central point where the
balloons meet represents
the central atom in the
molecule. How else might
you model electron
domains?
130
VSEPR
Unlike Lewis formulas, molecular models represent the 3. For each, write down the following:
3D geometry of molecules. You will explore the models
• electron domain geometry
in a VSEPR database to develop your understanding of
• molecular geometry
molecular geometry.
• molecular formula
Relevant skills
• Tool 1: Digital molecular models

• bond angle data (if available)
• Tool 2: Identify and extract data from a database

• 3D sketch of the molecule, including bonding and
non-bonding domains.
Instructions
1. Write a list of the molecular geometries that you need 4. Draw the Lewis formula of each. Then deduce the
to know. number of bonding domains and non-bonding
domains, and whether the molecule is polar or non-
2. Access a VSEPR database (such as those suggested
polar.
in the Tools for chemistry chapter) and extract two
examples of species belonging to each molecular 5. Organize your data into a suitable table.
geometry. If possible, rotate the images to get a sense
6. If bond angle data is available, search for examples
of their three-dimensional shape.
that illustrate:
• the effect of non-bonding domains on the bond
angle
• the effect of multiple bonds (e.g. double or triple
bonds) on bond angle.
Practice questions
6. Identify the electron domain geometry and molecular 8. Deduce the electron domain geometry and molecular
geometry given the following numbers of bonding and geometry of each of the following:
non-bonding domains.
a. NF b. CH Cl
3 2 2
a. four bonding domains

c. BF d. BeH
3 2
b. two bonding domains and one non-bonding

e. HCN f. SO
3
domain
g. SF h. NO
2 2
c. two bonding domains only
9. Predict the bond angles in each of the species in
d. two bonding domains and two non-bonding
question 8.
domains
10. Methanal is an organic compound with the molecular
e. three bonding domains and one non-bonding
formula CH O.
2
domain.
a. Draw the Lewis formula for methanal.
7. Identify the number of bonding and non-bonding

b. Deduce the molecular geometry of methanal.
domains around atoms with the following molecular

c. Suggest values for the bond angles in methanal.
geometries.
Explain your reasoning.
a. linear
b. trigonal pyramidal
c. tetrahedral
d. trigonal planar
e. bent (there are two possible answers here).
131
Linking question
How useful is the VSEPR model at predicting molecular geometry?
Bond polarity (Structure 2.2.5)
Polarity is related to the way electrons are distributed within bonds and
molecules. The shared pair of electrons in a covalent bond is not necessarily
shared equally between the two atoms in the bond. Bond polarity results from
the dierence in the electronegativities of the bonded atoms.
In the c ase of identic al atoms, such as the two uorine atoms in F , there is an
2
equal sharing of the electrons in the bonding pair. This is not the c ase, however,
in HF. The uorine atom has a much greater electronegativity than the hydrogen
atom, so it pulls the shared electron pair more strongly than hydrogen does. This
F
leads to what we describe as a polar covalent bond, with one atom (uorine)
adopting a partial negative charge, δ–, and the other atom (hydrogen) adopting
a partial positive charge, δ+.
The separation of charge between two non-identic al bonded atoms is c alled a
dipole moment. The dipole moment c an be represented by a vector (gure23).
This vector is shown as an arrow along the bond. The arrow starts as a plus sign
at the less electronegative atom in the bond, and points towards the more
electronegative atom in the bond.
H F
The shared pair of electrons is shied towards the more electronegative atom in
+ the covalent bond. The greater the dierence in electronegativity between the
δ δ
two atoms, the greater this shi.
Figure 23 Representation of the
If the two atoms involved in the formation of the covalent bond are identic al, the
molecular electrostatic potential of the polar
covalent bond in HF. Note that the bond bond is said to be a pure covalent bond. The charge is distributed evenly about
dipole in HF c an be represented as a vector the covalent bond, meaning that it is non-polar and has no dipole moment.
(arrow)
Practice questions
As seen in Structure 2.1, if the
dierence of electronegativity
11. R ank the following bonds in order of increasing polarity:
between the two atoms is very
C–H, C–C, C–F, C–O
large (greater than 1.8), then the
12. Explain why Br is non-polar, whereas HBr is polar.

2
bonding pair of electrons is shied
almost entirely towards the more
electronegative atom. Such bonds
Linking question
are considered ionic because
electrons are transferred, not
What properties of ionic compounds might be expected in compounds with
shared.
polar covalent bonding? (Structure 2.1)
132
Molecular polarity (Structure 2.2.6)
Molecular polarity is similar to bond polarity, but it describes the electron
distribution throughout the whole molecule. A molecule is polar when the
electron distribution leads to a partial negative charge on one end of the
molecule, and a partial positive charge on the other. This results in a dipole
moment, μ. The value of the dipole moment is oen reported in the unit
debye, D. Polarity is an important trait of molecules bec ause it gives rise to many
characteristic properties such as volatility, solubility and boiling point.
Molecular polarity depends on both bond polarity and molecular geometry.
Some examples are given in table 3.
Dipole
Molecule Lewis formula Polarity
moment / D
water, H O bond dipole bond dipole polar 1.85

2 O
net dipole
trichloromethane, H polar 1.01
CHCl
3
bond dipole
Cl Cl
Cl
net dipole
boron triuoride, non- 0

F
BF polar
3 bond dipole
F F
c arbon dioxide, bond dipole non- 0
CO polar
2
ethane, H H non- 0
C H polar
2 6
H C C H
H H
Table 3 Examples of polar and non-polar molecules
133
Molecules are polar when their bond dipoles do not c ancel each other out.
This may occur due to the geometry of the molecule, or bec ause the bonds have
dierent polarities. Both water and trichloromethane (table 3) are polar bec ause
they contain polar bonds that do not c ancel out. This results in a net dipole across
the molecule.
Molecules are non-polar when their bond dipoles c ancel each other out.
This happens when the bond dipoles are equal and their arrangement results
in no net dipole. Examples include boron triuoride and c arbon dioxide. Both
molecules contain polar bonds bec ause of the dierence in electronegativity of
the atoms involved. These polar bonds are positioned in such a way that they
c ancel each other out. This means that boron triuoride and c arbon dioxide are
both non-polar, despite the presence of polar bonds.
Molecules are non-polar when all their bonds are non-polar. Hydroc arbons
(compounds of hydrogen and c arbon) such as ethane contain two types of
Practice questions
bonds: c arbon–c arbon bonds and c arbon–hydrogen bonds. The c arbon–c arbon
13. Determine whether each of the

bonds are non-polar bec ause both atoms have the same electronegativity.
following molecules is polar or

The c arbon–hydrogen bonds are virtually non-polar bec ause of the small
non-polar:
electronegativity dierence between the two atoms. In addition, the tetrahedral
a methane, CH geometry around each c arbon atom results in a net dipole of zero, or very close
4
to zero. Therefore, hydroc arbons are generally non-polar.

b ammonia, NH
3
c hydrogen cyanide, HCN
So far, we have only discussed small molecules. Long molecules c an have a polar
d hexane, C H
6 14 region and a non-polar region, leading to many interesting applic ations including
14. Explain why CO is non-polar.

emulsiers, soaps and detergents, as well as the phospholipid bilayer in cell
2
15. State and explain whether PH is membranes. Figure 24 shows a typic al detergent molecule. C an you identify the
3
polar or non-polar. polar and non-polar regions in the molecule?
H H
O H H H H H H H H H H H H
C C
+ –
Na O S C C C C C C C C
O H H H H H H H H H H
H H
hydrophilic hydrophobic tail
head
Figure 24 A diagram of a synthetic detergent molecule, showing the hydrophobic and
hydrophilic regions
Linking question
LHA
What features of a molecule make it “infrared (IR) active”?
(Structure 3.2)
134
Covalent network structures Chemists talk about two types of
stability: kinetic (Reactivity 2.2)

(Structure 2.2.7)
and thermodynamic (Reactivity
Covalent bonds give rise to two dierent types of structure: molecular and
1), and diamond illustrates the
covalent network (also known as giant covalent). The atoms in both cases are
dierence well. At high pressures,
joined by covalent bonds, but the two structures are very dierent in terms of their
such as those occurring deep
properties. Molecular substances consist of discrete groups of covalently bonded
inside the Earth’s crust, diamond
atoms called molecules. By contrast, covalent network structures contain atoms
is the most stable allotrope.
that are held together by covalent bonds in a continuous three-dimensional
At standard temperature and
lattice. Examples of covalent network structures include silicon, silicon dioxide,
pressure, graphite is the most
and most of the allotropes of carbon, such as diamond and graphite.
thermodynamically stable allotrope
of carbon. Under these conditions,
Allotropes of c arbon
the transformation of diamond
Some elements have dierent structural forms known as allotropes. C arbon is

into graphite is thermodynamically
one such element, and its allotropes include diamond, graphite, graphene, and
spontaneous, but is so slow that
a group of substances known as fullerenes. They are all composed of c arbon

diamonds eectively last forever.
atoms but have dierent chemic al and physic al properties due to their dierent
Diamond is kinetically stable but
structural arrangements.
thermodynamically unstable (we
describe it as being metastable).
(a) (b)
You can read more about
spontaneity in Reactivity 1.4
(e)
(c) (d)
Figure 25 The allotropes of c arbon: (a) diamond, (b) graphite, (c) graphene, (d) c arbon nanotubes and (e) buckminsterfullerene, C
60
135
In diamond, each c arbon atom is bonded to four other atoms in a tetrahedral
arrangement. It is one of the hardest substances known. For this reason, it is
oen used in heavy-duty cutting tools such as saws, polishing tools and dental
drills. Diamond’s high refractive index and durability mean that it is also used to
make jewelry. Diamond is a poor electric al conductor bec ause it has no mobile
charged particles — the electrons are all loc alized in the bonds. It is however an
excellent thermal conductor: vibrational energy c arriers c alled phonons travel
well through the highly regular lattice and strong covalent bonds.
uFigure 26 The Big Hole:
a former diamond mine in
Kimberley, South Afric a
Graphite is composed of layers of sheets made of carbon atoms. Each carbon
atom is bonded to three other carbon atoms in a hexagonal arrangement where
the geometry around each carbon atom is trigonal planar. The carbon atoms in
graphite are bonded such that one electron per carbon atom is delocalized. These
delocalized electrons are free to move in the planes above and below each sheet
and therefore graphite is a good electrical conductor. While the covalent bonds
between the carbon atoms within the sheets are strong, the forces of attraction
(called London (dispersion) forces) between the sheets are weak. This means that
the sheets can be separated easily, making graphite a good lubricant, as well as an
ideal material for pencil leads. When you use a pencil to write, the force applied
causes parts of the graphite sheets to come o, leaving a mark on the paper.
Graphene is essentially a single sheet of graphite. Graphene is thus one-atom
thick and is therefore said to be two-dimensional. Like graphite, it is an excellent
electric al conductor. It is also exible, lightweight, transparent and, at the same
time, extraordinarily strong. First isolated in 2004, graphene is a promising new
material, with a vast range of potential applic ations, from desalination technology
Figure 27 A microscope image of a

to bendable electronic displays.
dentist’s drill showing the diamond chips
Fullerenes are a group of c arbon allotropes with atoms arranged in interlinking
hexagonal and pentagonal rings. Some fullerenes form long hollow cylinders:
these are known as c arbon nanotubes. Due to their size, c arbon nanotubes
are utilized in nanotechnology. Nanotechnology involves the use of atoms,
molecules and objects with dimensions of less than 100 nm (about 1000 atoms or
less across).
C arbon nanotubes are used to reinforce composite materials. Their exceptional
strength is due to the strong covalent bonds holding the c arbon atoms together.
C arbon nanotubes have potential applic ations in electronics bec ause, like
graphite and graphene, the presence of deloc alized electrons means that they
are good electric al conductors.
136
Buckminsterfullerenes, or buckyballs, have a covalent molecular structure. With
Silicon and c arbon are found in
the formula C , the atoms in buckminsterfullerene are arranged in hexagons and

60
group 14 hence they have some
pentagons to suggest a very familiar shape: a football. Along with other spheric al
similar properties. Other patterns in
fullerenes, buckyballs could have exciting new roles in medicine as drug c arriers.
the periodic table are explored in
Bec ause of its molecular structure, C has a low boiling point: overcoming the
60
Structure 3.1.
weak intermolecular forces of attraction does not require much thermal energy.
Silicon and silicon dioxide
Silicon forms a three-dimensional lattice where each silicon atom is bonded to
four other silicon atoms in a tetrahedral arrangement. This arrangement is similar
to that of the c arbon atoms in diamond.
The extensive cov alent bonds in the lattice result in high strength, as well as
high melting point and boiling point. Table 4 contrasts some of the fe atures of
c arbon and silicon. The Si–Si bond is we aker than its C–C counterpart as silicon
has a larger atomic radius. Therefore, the Si–Si bond is more re active than the
C–C bond. This dierence in strength also helps to explain the dierent melting
and boiling points.
C (graphite) Si
–12
Atomic radius / 10 m 75 114
–1
X–X bond enthalpy / kJ mol 346 226
Melting point / °C 3500 1414
Boiling point / °C 4827 3265
–1
First ionization energy / kJ mol 1086 787
X–O bond enthalpy 358 466
Table 4 A selection of features of c arbon and silicon, where X = Si or C
Interestingly, despite belonging to the same periodic table group, the properties
of c arbon and silicon are not as similar as one might anticipate. For example,
c arbon is a non-metal, while silicon is a metalloid. Diamond is a poor electric al
conductor, while silicon is a semiconductor. Double and triple bonds are
common between c arbon atoms but unusual between silicon atoms.
Comparing the Si–O and C–O bond strengths (table 4) shows that single bonds
between Si and O are very strong. Silicon is one of the most abundant elements
in the E arth’s crust and much of it is found in species containing Si–O bonds.
Silic a, or silicon dioxide, is a mineral that forms a covalent network containing
Si and O in a 1:2 ratio, hence the formula SiO . E ach silicon atom is bonded
2
Figure 28 Structure (le) and crystals of
covalently to four oxygen atoms and each oxygen atom is bonded covalently
silicon dioxide, SiO , known as quartz. The

2
to two silicon atoms. The crystalline form of silicon dioxide is quartz (gure 28).
photograph also contains crystals of iron
Other forms of silic a include sand and glass.
disulde, FeS , commonly known as

2
“fool’s gold”
The properties of silicon dioxide are those we associate with sand: it is hard,
insoluble in water and has a high melting point. In its solid crystalline form,
quartz, it is a poor conductor of heat and electricity.
Linking question
Practice questions
Why are silicon–silicon bonds
16. Explain why graphite and graphene conduct electricity, but diamond generally weaker than c arbon–
does not. c arbon bonds? (Structure 3.1)
17. Explain why diamond and silicon dioxide have high melting and
boiling points.
137
Activity
Summarize the properties of some of the covalent substances using a table like the one below.
Diamond Graphite Graphene C fullerene Silicon dioxide

60
Element(s)
Arrangement of atoms
Electric al conductivity
Intermolecular forces (Structure 2.2.8)
So far, we have been discussing forces of attraction that hold atoms and ions
together, which are collectively referred to as bonding. We will now turn our
attention to the forces of attraction between molecules, known as intermolecular
forces. As their name suggests, intermolecular forces apply to molecular
substances. The type and strength of intermolecular forces depend on the size
and polarity of the molecules. Types of intermolecular forces include London
(dispersion) forces, dipole–induced dipole forces, dipole–dipole forces and
hydrogen bonding. Collectively the rst three intermolecular forces are termed
van der Waals forces
Consider a glass of water. You know that the water molecules contain two
hydrogen atoms each, bonded to a central oxygen atom through strong
covalent bonds. But what forces c ause the water molecules to stay close to
one another? How about the water molecules inside ice cubes? What exactly
is being overcome when some of the water molecules in ice break away from
the cube and join the liquid water surrounding it? The answer in each c ase is
Figure 29 Intermolecular forces hold intermolecular forces. Intermolecular forces are weaker than chemic al bonds,
the molecules together in water and inside but they aect physic al properties such as volatility, solubility and boiling point of
the ice cubes

molecular substances.
Intermolecular forces are weak electrostatic forces of attraction that occur
between molecules. Figure 30 highlights the dierence between intermolecular
and intramolecular forces.
+ +
δ δ δ δ
▸ Figure 30 Intramolecular forces, such
as covalent bonds, occur within molecules.
Intermolecular forces occur between

polar
molecules
covalent bond
intermolecular
force of attraction
138
When molecular substances melt, boil or sublime, the intermolecular forces weak intermolecular interactions
between the molecules are overcome. Therefore, melting and boiling points are between I molecules break
2
oen used as indic ators of intermolecular force strength. The covalent bonds in on changing state
the molecule do not break during phase changes (gure31).
In Structure 1.5, we discussed the ideal gas law, which c arries the assumption
that no intermolecular forces are present in the gas. This is generally true at low
pressures and high temperatures, for which the ideal gas equation c an frequently
be used. When a gas deviates from ideal behaviour, we must correct for the
presence of intermolecular forces using a real gas model. Real gas models
also take into account the actual volume of gas particles, which is considered
negligible in the ideal gas model.
200 K strong covalent bonds between
atoms in I molecule do not

2
500 K
break on changing state
Figure 31 Intermolecular forces of
2 attraction are overcome when a molecular
substance changes state, but the covalent
bonds remain intact

pV
1000 K
RT
ideal gas
300 600 900
p (atm)
Figure 32 Gases deviate more from ideal gas behaviour at lower temperatures. The
horizontal black line represents an ideal gas. The curves show the deviations from ideal gas
behaviour at dierent temperatures for a real gas
London (dispersion) forces (LDFs)
All molecules experience London (dispersion) forces (or LDFs), which are
intermolecular forces resulting from temporary instantaneous dipoles. A
molecule has a dipole when one side c arries a partial positive charge, and the
other a partial negative charge. London (dispersion) forces involve induced
dipoles, which means that one molecule c auses (or induces) a temporary dipole
in another molecule. These induced dipoles occur due to the random movement
of electrons around the molecule.

Figure 33 Intermolecular forces of
attraction are overcome when iodine
sublimes, and are formed when iodine is
deposited on a surface
139
In a simple non-polar molecule such as hydrogen, H , the electron distribution

2
is on average symmetric al (gure 34). However, electrons are constantly moving
around within the molecule. If we could somehow freeze time and take a photo
of electrons in a molecule, the electron distribution would very unlikely be
perfectly symmetric al. Instead, we would see a somewhat unequal electron
density, with one region of the molecule having more electrons, rendering it
slightly negative (δ–). There would also be a region of lower electron density
elsewhere in the molecule with a positive partial charge (δ+).
H H H H
Figure 34 On average, the electron distribution in H is symmetric al

2
This temporary dipole then induces further temporary dipoles in the molecules
around it. Due to electrostatic repulsion, a region of partial negative charge
(δ–) on one molecule will repel the electrons in neighbouring molecules.
This temporarily creates regions of partial positive charge (δ+). The resulting
electrostatic attraction between the δ– region on one molecule and the δ+ region
on the next is termed a London dispersion force. However, this arrangement
is temporary. In the next moment of time a dierent pattern of induced dipoles
willemerge.
+ +
δ δ δ δ
H H H H
London dispersion force
Figure 35 At any given moment in time, a temporary dipole is present in a molecule,
inducing a dipole in another. A weak London dispersion force forms between the opposite
partial charges
+ – – + +
δ δ δ δ δ δ δ
+
+
δ
δ
δ
+ δ
δ
–
δ
+ +
– δ δ
δ
δ
δ
– +
δ + δ
δ
+
δ δ
–
+
– δ +
δ
δ δ
δ +
+
δ
δ
+
δ δ
–
δ
– + δ
δ δ +
δ
+
δ
+
δ
+
δ
Figure 36 Dierent arrangements of LDFs between molecules, which result from interactions between an
instantaneous dipole on one molecule and an induced dipole on an adjacent molecule
140
There are two main factors that increase the strength of LDFs: the number of
electrons and the molecular shape. They aect the polarizability of the molecule:
how easily the electron distribution is distorted by an electric eld. The greater
the polarizability, the stronger the dispersion forces.
Consider the group 17 elements, all of which form non-polar diatomic molecules.
The number of electrons increases going down the group. As a result, the
electron clouds become larger and less attracted to the nuclei. This means that
the electrons become more easily polarized and the strength of LDFs increases,
leading to higher boiling points as you descend the group (table 5).
Substance Boiling point / °C
uorine, F –188.1
2
chlorine, Cl –34.04
2
bromine, Br 58.78
2
Increasing
iodine, I 184.4
2
LDF strength
Table 5 Boiling point increases down group 17 due to an increasing number of
electrons, resulting in stronger LDFs
more energy
larger higher
more greater stronger needed to
molecular boiling
electrons polarizability LDFs overcome
size point
IMFs
Figure 37 The eect of molecular size on LDF strength and boiling point
The boiling point also increases for successive members of a homologous series
Homologous series and isomers of
of organic compounds: each molecule has one more CH than the one before
2
organic compounds are discussed
it, hence greater molecular size and a larger number of electrons. Molecular size
in Structure 3.2.
c an be quantied in terms of mass, so we oen refer to molecular mass when
comparing molecules in terms of their LDFs.
Patterns and trends
Scientists look for patterns and try to understand relationships between
variables. For example, we oen say LDF strength increases with increasing
molecular mass, due to an increasing number of electrons. This may
seem contradictory bec ause electrons have negligible mass. But here
the relationship between molecular mass and the number of electrons is
not c ausal. R ather, the greater mass of larger molecules is accompanied
by a greater number of electrons. The greater number of protons and
neutrons is responsible for the increase in molecular mass. However,
each proton requires an electron to maintain the overall neutrality of the
molecule. Therefore, any increase in the number of protons always leads to a
proportional increase in the number of electrons.
141
Compare the boiling points of the two isomers of C H : pentane,

5 12
CH CH CH CH CH and 2,2-dimethylpropane (CH ) C (table 6 and gure 38).

3 2 2 2 3 3 4
uFigure 38 Space-lling models show
that pentane (top) has a greater area of
contact for LDFs than 2,2-dimethylpropane
(bottom)
Both isomers contain the same number of electrons and are non-polar. The
Boiling
Isomer dierence is in their shapes. Pentane molecules are long and are therefore able
point / °C
to interact with each other across the full length of the molecule; that is, there is
pentane 36.1
a large area of interaction bec ause of the better contact between molecules of
2,2-dimethylpropane 9.5 pentane. As a result, pentane has a relatively high boiling point and is a liquid at
room temperature. Molecules of 2,2-dimethylpropane are rounder and more
Table 6 Boiling points of the two
compact, so they pack together less eciently. As the interaction between the
isomers of pentane
molecules is limited, the LDFs in 2,2-dimethylpropane are weaker, so it is a gas at
room temperature.
1. Boiling point data for the rst four alkanes are shown below. Describe
and explain the boiling point trend you observe.
Alkane Boiling point / °C
methane, CH 161
4
ethane, C H 88
2 6
propane, C H 42.1
3 8
butane, C H 0.5
4 10
2. The boiling points of 2,2-dimethylpropane and pentane are 9.5 °C
and 36.1 °C, respectively. Predict a value for the boiling point of
2-methylbutane, CH CH CH(CH ) . Explain your answer.

3 2 3 2
LDFs occur between all types of molecules bec ause all molecules contain
electrons. If we have a substance made up of only non-polar molecules, only
LDFs will occur.
Dipole–induced dipole forces
LDFs are forces of attraction between temporary, or instantaneous, dipoles.
Activity Dipole–induced dipole forces are a type of related intermolecular force
occurring between a polar molecule and a nearby non-polar molecule. The
Compare and contrast London

presence of a permanent dipole in the polar molecule induces the formation of a
(dispersion) forces and dipole-

temporary dipole in the neighbouring non-polar molecule. For example, this type
induced dipole forces.

of intermolecular force attracts non-polar oxygen molecules, O , to polar water
2
molecules. Dipole–induced dipole forces are weak, which explains why the
aqueous solubility of oxygen is relatively low.
142
Dipole–dipole forces
+ +
Dipole–dipole forces involve permanent dipoles, whereas LDFs result from δ δ δ δ
H Cl H Cl
temporary dipoles. When a molecule is polar, it has a permanent dipole and
therefore experiences dipole–dipole forces of attraction with neighbouring polar

Figure 39 Hydrogen chloride, HCl,
molecules (gure 39).

molecules are polar and attract each other
due to dipole–dipole forces
Hydrogen chloride, HCl, and diatomic uorine, F , have similar sizes and
2
comparable molecular masses (table 7). They both therefore experience LDFs of a
similar strength. However, HCl molecules are polar and therefore experience dipole–
dipole forces in addition to LDFs. The intermolecular forces between HCl molecules
are stronger than those between F molecules, so HCl has a higher boiling point.
2
Molecule Molecular mass Boiling point / °C Intermolecular forces
F 38.00 –188.1 London (dispersion)

2
HCl 36.46 –85.05 London (dispersion)
and dipole–dipole
 Table 7 Diatomic uorine and hydrogen chloride have similar molecular masses but
dierent boiling points
Practice questions
18. Which of the following species experience dipole–dipole forces?
A. oxygen, O
2
B. c arbon dioxide, CO
2
C. c arbon monoxide, CO
2–
D. c arbonate ion, CO
3
19. The molecular masses of ICl and Br are very similar, while their boiling
2
points are 97.4 °C and 58.8 °C, respectively. Explain this dierence.
20. Draw a diagram to show how propanone molecules, CH COCH , might

3 3
arrange themselves when near one another. Label any dipole–dipole forces
that occur.
Hydrogen bonding
Hydrogen bonds are strong intermolecular forces that form when a molecule
contains a strong dipole involving hydrogen. When a hydrogen atom is
covalently bonded to a highly electronegative atom such as oxygen, nitrogen or
uorine, the bond between them is very polar. The electrons in the covalent bond
are drawn towards the more electronegative atom, resulting in a considerable
partial positive charge (δ+) on the hydrogen. This hydrogen atom c an then
form a strong electrostatic interaction — a hydrogen bond — with the electrons of
another electronegative atom. This is usually found on a dierent molecule, but
intramolecular hydrogen bonds c an also exist in certain situations.
tFigure 40 Hydrogen bonds

covalent bond hydrogen bond
form between the hydrogen in a
very polar bond and electrons on

electronegative electronegative
hydrogen
a highly electronegative atom
atom atom
atom
(e.g. F, O, N) (e.g. F, O, N)
δ+
lone electron pair
143
Hydrogen bonds occur, for example, between:
1. water molecules
2. ammonia (NH ) molecules

3
3. hydrogen uoride (HF) molecules
4. water molecules and dimethyl ether molecules, (CH ) O

3 2
These hydrogen bonds are depicted with blue dashes in gure 41.
H H
H
O
O N
F
H
H H H
N F
O CH
3
O H
H H
uFigure 41 Hydrogen bonds c an form
H C
H H H 3
between a variety of dierent molecules
Despite the name suggesting otherwise, hydrogen bonds are not chemic al
bonds: they are intermolecular forces. They are generally stronger than other
types of intermolecular force, but much weaker than covalent bonds.
Bond or intermolecular force type Typic al bond or intermolecular
–1
force enthalpy / kJ mol
Hydrogen bond 20–40
u Table 8 Enthalpies of hydrogen bonds
Single covalent bonds 150–600
and single covalent bonds compared
A good way to remember that hydrogen bonds are weaker than chemic al bonds
is to look at what happens when water boils. At 100 °C, the energy available
is sucient to overcome the hydrogen bonds between water molecules
(~20 kJ mol ), but not the covalent bonds between oxygen and hydrogen atoms
in the water molecules themselves (463 kJ mol ).
Practice questions
21. Which two of the following substances c an form hydrogen bonds between
their molecules?
A. hydrogen uoride, HF
B. uorine, F
2
C. methanol, CH OH
3
D. uoromethane, CH F
3
22. Draw a diagram to show a hydrogen bond between two methanol
molecules, CH OH.
3
23. Draw a diagram to show a hydrogen bond between a water molecule and a
methanamine molecule, CH NH
3 2
24. Draw a diagram to show a hydrogen bond between a water molecule and a
methanal molecule, CH O.
2
144
150
H O
2
100
50
HF
C° / t n i o p
H Te
2
period
0
nber
1 2 3 4 SbH 6
3
g n i l i ob
H Se
2
H
H S
2
NH
–50 3
SnH
4
H
3
Hr
PH
3
HCl GeH
4
–100
SiH
4
–150
CH
4
t Figure 42 The boiling points of the
group 14 to 17 hydrides show the eect of
–200
hydrogen bonding
How do the boiling points of the group 14 hydrides (CH , SiH , GeH and SnH )
4 4 4 4
change as you go down the group? The molecular mass increases down the
group, increasing the number of electrons and polarizability of the electron
cloud. Descending the group, there are stronger LDFs, and therefore an
increasing boiling point is expected. This is precisely what the data show in the
H
bottom curve of gure 42.
O
O
Now look at the trend of the group 15 hydrides, NH , PH , AsH and SbH , in
3 3 3 3
H
H H
the next curve up. We see the expected rise in boiling point from phosphine,
PH , to stibane, SbH , due to increasing molecular mass. Extrapolating the trend

O
3 3
O
to ammonia predicts a boiling point of around 130 °C, when in fact it is 100 °C
H
H
H H
higher, approximately 30 °C. The higher-than-expected boiling point is due to
the presence of hydrogen bonds between ammonia molecules.

O
H H
The trends in the group 16 and group 17 hydrides are similar to that of group 15:
H
H
the period 2 hydrides, water, H O, and hydrogen uoride, HF, have very high
O
2 O
boiling points. Again, this is due to the presence of hydrogen bonds between
their molecules.
H
H
A single water molecule c an form up to four hydrogen bonds (gure 43) and
Figure 43 Water molecules c an form up
therefore the boiling point of water is very high: 100 °C.

to four hydrogen bonds each
145
Hydrogen bonds give water its notable properties. Most substances have
higher densities when solid than when liquid. Solid water (ice) oats on liquid
water bec ause it is less dense than liquid water. This unusual property leads to
the formation of layers of ice on lake surfaces during the winter. Insulation from
this ice layer prevents lakes freezing into solid blocks of ice, allowing aquatic
ecosystems to survive.
The hydrogen bonding in ice results in the formation of a regular, very ordered
open-c avity network of molecules (gure 44). In the liquid phase, the hydrogen
bonding is more random, which results in a higher density compared to ice.
Note that O–H covalent bonds in water are shorter than H - - - O hydrogen bonds
between water molecules.
(a)
(b)
Figure 44 (a) The open-c avity structure of ice c auses it to be less dense than water (b) Ice oats on water bec ause of this
 Figure 45 The hexagonal arrangement of water molecules in  Figure 46 Extensive hydrogen bonding is responsible for
the ice lattice leads to the characteristic shape of snowakes the high surface tension of water, which allows small insects to
walk on the surface without sinking or becoming even partly
submerged
146
TOK
DNA (deoxyribonucleic acid) molecules store genetic information. A highly
accurate DNA-copying mechanism is essential for this information to be
passed along between generations. DNA has a double-helix structure
composed of two strands of organic molecules held together by hydrogen
bonds. DNA replic ation involves breaking these hydrogen bonds to “unzip”
the two strands, allowing copies to be made.
two new DNA

G
C
molecules form
T
A
C
G
A
T
A
T
C
A
T
G
G
A T
G
C
A T
double helix
“unzips” into two

A T
different strands
G C
C G
base pairs
A T
Figure 47 The DNA double helix is held together by hydrogen bonds, which are
broken during replic ation. Hydrogen bonds are shown by black dashes
What other types of information storage systems exist in the natural world, in
science and in other areas of knowledge?
In summary, intermolecular forces are electrostatic attractions that keep
molecules together. We have discussed the four types of intermolecular forces,
summarised in table 9.
Type of intermolecular force Where does it occur?
London (dispersion) forces (LDFs) between all molecules
van der Waals
dipole–induced dipole forces between a polar molecule and a non-polar molecule
forces increasing
dipole–dipole forces between polar molecules

strength
between a highly electronegative atom (F, O or N)
hydrogen bonding and a hydrogen covalently bonded to another highly
electronegative atom
 Table 9 Summary of types of intermolecular forces
147
Figure 48 shows the overall method for determining the strongest intermolecular
force present in a substance.
Do the molecules contain a
hydrogen directly bonded to
a very electronegative atom
(F, O, N)?
yes no
Are the molecules
hydrogen bonding
polar?
some molecules
are polar and some
yes no
are non-polar
London (dispersion) dipole–induced
dipole–dipole forces
forces dipole forces
Figure 48 Figuring out the strongest intermolecular force present between a pair of interacting molecules
Worked example 3
For each of the following substances, determine the intermolecular forces
that attract the molecules to each other.
a. butane, CH CH CH CH
3 2 2 3
b. ethoxyethane, CH CH OCH CH
3 2 2 3
c. c arbon tetrauoride, CF
4
d. ethanamine, CH CH NH
3 2 2
e. uoroethane, CH CH F
3 2
f. chloromethane, CH Cl, and methane, CH

3 4
g. water, H O, and hydrogen uoride, HF

2
Solution
All the substances in this worked example form London (dispersion) forces.
a. Butane is non-polar, so it only forms London (dispersion) forces.
b. Ethoxyethane is polar, so it forms dipole–dipole forces.
c. Carbon tetrauoride is non-polar, so it only forms LDFs.
d. Ethanamine c an form hydrogen bonds bec ause it contains a hydrogen
atom directly bonded to nitrogen, which is a very electronegative atom. It
is also polar, so it forms dipole–dipole forces.
e. Fluoroethane is polar, so it forms dipole–dipole forces. Note that it does not
form hydrogen bonds. The structural formula might suggest that uorine is
directly bonded to hydrogen, but this is not the case. If you draw the Lewis
formula, you will see that uorine is bonded to a carbon atom.
f. Chloromethane is polar while methane is non-polar. They would therefore
form dipole–induced dipole forces.
g. Hydrogen bonds are formed between water and hydrogen uoride
molecules bec ause they both contain a highly electronegative atom
that is directly bonded to a hydrogen. They are both polar, so they also
experience dipole–dipole forces.
148
Practice questions
25. For each of the following substances, determine the intermolecular forces
that attract molecules to each other:
a. propane, CH CH CH
3 2 3
b. hydrogen bromide, HBr
c. hydrogen uoride, HF
d. buckminsterfullerene, C
60
e. ammonia, NH , and diatomic oxygen, O

3 2
f. ethanal, CH CHO
3
26. State and explain which of the following species c an form hydrogen bonds
with water molecules:
a. ammonia, NH
3
b. propane, CH CH CH
3 2 3
c. ethanoic acid, CH COOH

3
Linking questions
To what extent c an intermolecular forces explain the deviation of real gases
from ideal behaviour? (Structure 1.5)
How do the terms “bonds” and “forces” compare?
(Structure 1.1, Structure 2.1, Structure 2.3)
How c an advances in technology lead to changes in scientic
denitions, e.g. the updated International Union of Pure and
Applied Chemistry (IUPAC) denition of the hydrogen bond?
The properties of covalent substances
(Structure 2.2.9)
Relative strength of intermolecular forces
Given comparable molar mass, the relative strengths of intermolecular forces are
generally:
London (dispersion) forces < dipole–dipole forces < hydrogen bonding.
Table 10 shows typic al enthalpy ranges associated with overcoming each of
these forces. The trend in enthalpy reects the trend in strength. The strength of
dipole–induced dipole forces lies somewhere in-between London (dispersion)
and dipole–dipole forces.
–1
Intermolecular force type Typic al enthalpy / kJ mol
London (dispersion) forces 1 to 5
sipole–dipole forces 3 to 25
hydrogen bonds 20 to 40
 Table 10 Comparison of the strength of various intermolecular forces
149
The relative strengths of intermole cular forces are best illustrate d by comparing mole cules that have similar
mole cular masses. Table 11 shows mole cules with mole cular masses in the range of 44.0 to 46.1 and wildly dierent
boiling points.
Intermolecular forces
Name and Molecular Boiling
Molecular
molecular Structural formula dipole point

London Dipole– Hydrogen
mass
formula moment / D / °C
(dispersion) dipole bond
propane H H H 44.11 0.084 –42.1 yes no no
C H
3 8
H C C C H
H H H
methoxymethane H H 46.08 1.30 –24.8 yes yes no

O
C H O
2 6
C C
H H H H
ethanal 44.06 2.69 20.2 yes yes no

O
C H O
2 4
H
C
C H
H H
ethanol H H 46.08 1.69 78.2 yes yes yes
C H O
2 6
H C C O
H H
methanoic acid 46.03 1.41 100.7 yes yes yes

O
CH O
2 2
H O H
Table 11 Polarity, boiling point and intermolecular force data for organic compounds of similar molecular masses
Interpreting and explaining data are important skills in science. What do the data in table 11 suggest? For example, they
show that all molecules experience London (dispersion) forces bec ause they all contain electrons that move around,
c ausing temporary dipoles that then induce further temporary dipoles in the surroundingmolecules.
Write down four more statements describing the relationship between molecular structure and intermolecular forces
that are shown by the data in table 11. Attempt to explain each statement using your knowledge from this topic.
150
Physic al properties of covalent substances
There are two types of covalent structures: covalent network and molecular
covalent. These two structures have very dierent properties. Most of the
properties of molecular substances are governed by intermolecular forces.
Substances with a covalent network structure are not comprised of molecules, so
their properties are dictated by their lattice features.
We will look at physic al properties of covalent substances including volatility,
electric al conductivity and solubility.
Volatility
Figure 49 Molecular covalent
substances vaporize when the

Substances with a covalent network structure are solids at room temperature and
intermolecular forces are overcome
pressure. Vaporizing them requires a lot of energy bec ause of the strong covalent
bonds holding the structure together. They are therefore non-volatile and have
very high melting and boiling points. Practice questions
27. Identify which species in each

In order to vaporize molecular substances, the intermolecular forces between the
pair has the highest boiling point.

molecules need to be overcome. Since intermolecular forces are relatively weak,
the energy required to overcome them is low and therefore molecular substances a. He or Kr
are generally volatile.

b. CH or NH
4 3
28. The boiling point of c arbon
Due to the variety of sizes and intermolecular forces, there is, however, a
tetrachloride, CCl , is
4
large variation in the volatility of molecular substances. M any of the molecular
76.7 °C. The boiling point
substances we have considered in this chapter consist of small molecules, for
of uoromethane, CH F, is
3
example, N , CO , H O and some hydroc arbons. M any of these are gases or
2 2 2
–78.2 °C. Comment on this
liquids at room temperature.
dierence using your knowledge
However, substances that consist of much larger molecules have lower volatility of intermolecular forces.
and higher melting and boiling points. This is bec ause larger molecules have
stronger LDFs between each other. Examples include buckminsterfullerene (C ),

60
which sublimes at 500–600 °C, and a component of c andle wax, tetracosane
(C H ), which boils at 391 °C.

24 50
Electrical conductivity
Covalent substances, both network and molecular, are usually not electric al
conductors. To conduct electricity, a substance needs to contain charged
particles that are free to move. Covalent substances generally do not contain
such particles, as their electrons are “locked up” in loc alized covalent bonds, and
they do not contain ions.
There are some notable exceptions, such as graphite, which is a good
electric al conductor due to the presence of deloc alized electrons. Silicon is a
semiconductor, meaning that its intermediate conductivity places it between
conductors and insulators.
Solar panels consist of photovoltaic cells, which convert solar energy into
electricity. The cells contain semiconductors, such as silicon.
 Figure 50 Solar panels containing
silicon provide this satellite with electric al
power
151
Solubility
When a substance dissolves, forces of attraction are formed between the
substance (known as the solute) and the solvent. Substances with covalent
network structures are insoluble in most solvents bec ause of the strong covalent
bonds holding their atoms together.
A molecular substance is likely to dissolve in a solvent if the intermolecular forces
between the solute and solvent are stronger than the attraction between the
solute molecules.
It is oen said in chemistry that “like dissolves like”. In other words, non-polar
solutes are likely to dissolve in non-polar solvents. Similarly, polar solutes are likely
to dissolve in polar solvents. Dissolving is unlikely to occur if the solute is polar
and the solvent is non-polar, or vice versa.
TOK
“Like dissolves like” is a useful rule of thumb, which is helpful in many cases
but not all, and it has no explanatory power. In a small group, discuss the
advantages and disadvantages of having rules like this. You may want to
consider: what are the alternatives? Do such rules have an “expiry date”? What
rules of thumb do you use in other areas of knowledge?
Iodine, I , is non-polar. It dissolves readily in non-polar solvents such as hexane.

2
H − O
−
Iodine is almost insoluble in water bec ause it c annot associate strongly with water
H
molecules. Substances that c an form hydrogen bonds, such as ethanol, are more
O − H likely to dissolve in water (gure 51). Ethanol and water are said to be miscible, as
−
they c an form a solution when mixed in any proportion.
H
(a) between water molecules
Methanol, ethanol and propan-1-ol readily dissolve in water. The solubility of
the primary alcohols, however, decreases with increasing c arbon chain length
(table12).
CH CH − O
3 2 −
Primary alcohol Structural formula Solubility g / 100 g of H O

2
O − H
ethanol CH CH OH miscible
− 3 2
CH CH
3 2
butan-1-ol CH (CH ) OH 6.8

3 2 3
(b) between ethanol molecules
nonan-1-ol CH (CH ) OH 0.014

3 2 8
 Table 12 The aqueous solubility of primary alcohols decreases with increasing
CH CH − O
3 2 −
hydroc arbon chain length
Hydroc arbon chains are non-polar and do not form hydrogen bonds with water.
O − H
F ats and oils are largely non-polar and therefore do not dissolve in water. This is
H
easily observable when vinegar (an aqueous solution of ethanoic acid) is mixed
(c) between ethanol and water with oil to make salad dressing. The two liquids form two layers and are said to be
immiscible, which means they do not mix, due to their diering polarities.
 Figure 51 Ethanol and water c an form
hydrogen bonds. Therefore, ethanol is
Long hydroc arbon chains, such as those in fats and oils, are said to be
water soluble
hydrophobic (water-hating). Soap and detergent molecules oen have a
hydrophobic tail and a hydrophilic (water-loving) head. They work bec ause
they associate with both water and the non-polar fats and oils frequently found in
greasy stains (gure 52). Molecules with a hydrophobic tail and hydrophilic head
are c alled surface-active agents, or surfactants
152
Water
Water
Water
Grease
Grease Surface of material
(a) Surface of material (b) Detergent 'heads' attracted by water (c) Grease washed aw ay by water
Figure 52 In a surfactant molecule, the hydrophilic (water-loving) head and a hydrophobic (water-hating) tail li greasy stains o materials
Morphine and its derivatives, known as opiates, are In diamorphine, also known as heroin, both hydroxyl
strong painkillers with a high potential for misuse and groups are substituted with ester groups, which greatly
addiction. The eect they have on the body depends on reduces the polarity of the molecule. Diamorphine is
two factors: soluble in lipids and c an easily cross the blood-brain
barrier. In the brain, diamorphine is quickly metabolized

1. their ability to cross the blood-brain barrier
into morphine, which binds to the opioid receptor.

2. their ability to bind to opioid receptors in the brain.
This mechanism of action makes diamorphine about ve

The blood-brain barrier consists of a series of cell
times more potent an analgesic than morphine. At the

membranes that coat the blood vessels in the brain and
same time, diamorphine has more severe side eects,

prevent polar molecules from entering the central nervous
including tolerance, addiction and central nervous system

system. These membranes are lipophilic, which means
depression. In most countries the use of diamorphine

they are permeable to lipid molecules. The presence
is either banned or restricted to terminally ill patients

of one amino and two hydroxyl groups in the morphine
with certain forms of c ancer or central nervous system

molecule (gure 53) makes it suciently polar to be
disorders.
soluble in water but at the same time reduces its solubility
in lipids and therefore limits its ability to reach the opioid
receptors in the brain.
(a) CH (b)
2 CH
2
OH
O CH
3
N H C N CH
H C CH
3 2 3 2
hydroxyl groups
(can be substituted in
O
O
tertiary morphine derivatives)
O
amino group
O
CH
3
OH
Figure 53 The structures of (a) morphine and (b) diamorphine (heroin)
153
Physical properties of ionic and covalent substances
You c an figure out the structure of a substance by testing you do not know which is which. Design a safe method
its physic al properties such as electric al conductivity, that could be used to identify A, B and C.
aqueous solubility and melting point.
Possible equipment and substances you could use
Relevant skills mightinclude:
• Tool 1: Recognize and address the relevant safety, spatulas, beakers, distilled water, pipettes, power pack,
ethic al or environmental issues in an investigation. leads, ammeter, lamp, conductivity probe, electrodes,
crucible, Bunsen burner, pipeclay triangle, heat-proof
• Inquiry 1: Demonstrate independent thinking,
mat, mortar and pestle, melting point apparatus, fume
initiative or insight.
hood, combustion spoon.
Complete a risk assessment and show this and your
observations.
proposed method to your teacher for approval. If you
Instructions
have time, try it out.
You are presented with three bottles labelled A, B and

Extension
C. E ach bottle contains a crystalline solid. One is sodium
What if the ionic substance were not water soluble? How
chloride, another is sugar, and the third is white sand, but
would you modify your method?
To summarize, substances with covalent network structures are typic ally:
• non-volatile bec ause they are held together by strong covalent bonds
between atoms
• poor electric al conductors (exceptions include graphite and graphene)
bec ause they do not contain mobile charged particles
Linking questions
• insoluble in all solvents bec ause their dissolution would require breaking the
strong covalent bonds.

What experimental data
demonstrate the physic al
Substances with molecular covalent structures are typic ally:
properties of covalent substances?
• volatile bec ause their molecules are held together by intermolecular forces,
(Tool 1, Inquiry 2)
which are weak

To what extent does a functional
group determine the nature • poor electric al conductors bec ause they do not contain mobile charged
of theintermolecular forces? particles
(Structure 3.2)
• of varying solubility, depending on the strength of the intermolecular forces
they form with solvent molecules.
Practice questions
29. Explain why covalent compounds are not electric al 33. Which two of the following substances are readily
conductors, except for graphite and graphene. soluble in water?
30. Describe and explain the relationship between A. ethanoic acid, CH COOH
3
volatility and boiling point.

B. octane, CH (CH ) CH
3 2 6 3
31. Explain why covalent network substances are non-

C. octan-1-ol, CH (CH ) CH OH
3 2 6 2
volatile, and molecular substances are volatile,

D. propanone, CH COCH
3 3
although they both contain covalent bonds.
34. Explain why ionic substances, such as sodium chloride,
32. Explain why ethanol, CH CH OH, is miscible

3 2 do not dissolve in oil.
with water.
35. Explain why diatomic bromine, Br , is more soluble in

2
hexane than in water.
154
Chromatography (Structure 2.2.10)
The components of a mixture c an oen be separated and identied using
chromatography. All forms of chromatography (gure 54) have the same
underlying principle: the existence of a mobile phase and a stationary phase.
In most forms of chromatography, the components of the mixture are separated
based on their dierent anities for each of the two phases. These anities
involve intermolecular forces.
The mobile phase moves through the stationary phase, c arrying the components
Methods for separating mixtures
of the mixture. The components all start at the same point but are transported
are discussed in Structure 1.1.
through the stationary phase at dierent rates due to their diering anities for
each of the two phases. The components are eventually separated.
(a) paper chromatography (b) liquid column chromatography
solvent solvent
paper clip
solvent front
sample
column
components
water (the solvent) packed
oran of the sample

ge e
lu
b with
move down the
adsorbent
column at
SiO
2
different rates,
forming bands
1 2 3
Sample is placed Solvent is Different components in the sample
on the top of the poured down become separated into bands and are
packed column the column collected at the bottom of the column
(c) gas–liquid chromatography
detector
heated
chamber
recorder
sample
injected
tFigure 54 All types of
here
column – c apillary tube chromatography involve a mobile
c arrier gas
with liquid-coated walls phase and a stationary phase
155
ATL Research skills
Chromatographic methods c an be classied into c ategories. They c an
be grouped according on their format (for example, planar vs column
chromatography), or the mechanism of separation (for example, partition,
adsorption, size exclusion or ion exchange chromatography). In this chapter,
we will focus on two types of planar chromatography: paper and thin-layer.
The former separates mixtures based on the principle of partition, whereas
the latter is based on adsorption. Research at least one other method of
chromatography (such as gas chromatography) and compare and contrast the
dierent methods. Organize your notes in a Venn diagram.
Paper chromatography
Separating mixtures of pigments is a simple way to demonstrate paper
chromatography (gure 55). The stationary phase is a rectangular piece of
chromatography paper (made of hydrated cellulose) and the mobile phase is a
suitable solvent. The mixture to be separated is dotted onto a start line near the
Figure 55 Simple paper
bottom of the paper. The paper is then placed in a chamber such as a beaker,
chromatography experiment using dierent
containing a small amount of solvent at the bottom. Placing a lid on top of the
inks. You c an see that the purple ink at the
beaker allows the atmosphere in the chamber to become saturated with the
right-hand side is a mixture containing red,
solvent vapour and prevents solvent loss through evaporation.
yellow and blue dyes
Before After
Spots of different Different components of
coloured ink are the inks rise up the paper to
dropped onto different extents and are
paper separated
chromatography
paper
solvent
The solvent is allowed to move up the paper until it reaches a point near the top.
The components of the mixture move dierent distances up the paper according
to their relative anities for the stationary and mobile phases. Components with
a greater anities for the solvent will dissolve more readily in it and are therefore
transported further up the paper. The results of a chromatography experiment are
known as chromatogram.
Chromatography paper is composed of hydrated cellulose, which contains many –OH
groups. These groups are very polar and attract water molecules tightly, saturating the
surface of cellulose with water. When coupled with a less polar organic solvent, this
technique can be used to investigate mixtures such as leaf pigments or amino acid
mixtures. The mixture components are partitioned between the water layer and the
solvent: less polar components dissolve in the solvent and get carried further up the
paper, whereas more polar components stay predominantly in the water layer. The
separation can be optimized by using dierent solvents, or mixtures of solvents.
156
Thin layer chromatography (TLC)
Thin layer chromatography (TLC) is more expensive than its paper counterpart, but
it oers greater sensitivity. In TLC, the stationary phase is a rectangular plate made of
glass or metal coated with silica (silicon dioxide, SiO ) or alumina (aluminium oxide,
2
Al O ). The silica or alumina surfaces are very polar and contain many hydroxyl
2 3
groups. The mixture is spotted onto the plate and placed into an eluting chamber
containing a non-polar organic solvent. The polar substances in the mixture travel
up the plate slowly because their tendency to adsorb onto the silica or alumina
surface is greater than their tendency to dissolve in the solvent. Conversely, non-
polar components dissolve in the solvent and travel further up the plate.
Experiments
Experimental techniques are adapted to suit dierent reacts with the spots to form coloured products. Other
purposes. Coloured substances are easily located on colourless compounds can be located in dierent ways.
a chromatogram. When a substance is colourless, an For example, some might show up under UV light. C an
additional step is needed. For example, when a mixture you think of any other examples of how existing scientic
contains amino acids, the chromatogram can be sprayed methods were adapted to solve a problem?
with a locating agent. A locating agent is a substance that
Retardation factor (R )
F
The results of a chromatography experiment c an be quantied by c alculating the
retardation factor ( R ). The R value for a spot on a chromatogram is the ratio of

F F
the distance travelled by the spot (b) to the distance travelled by the solvent (a):
R =
F
tFigure 56 Retardation factors,
R , are c alculated from the distances

solvent front
F
measured on a chromatogram
mixture on
baseline
b pencil baseline
Since the spots c annot travel further than the solvent that transports them, R
F
values are always in the range of 0 to 1. The distance travelled by a spot c an vary
depending on factors such as the composition of the solvent, temperature, pH
and type of paper used (in paper chromatography). R values are reproducible
F
and therefore c an be used to identify substances by comparing experimental
values to accepted values, provided that the conditions are the same.
157
Worked example 4
Consider the thin layer chromatogram shown in gure 57. Given that the stationary phase is silica and the solvent is a
Calculate the retardation factor for the red and blue spots. hydrocarbon, determine which component is more polar.
lid 8.0 cm
maximum
solvent
distance the
front 6.0 cm
solvent
distance
travelled
the spot
12.0 cm
travelled
2.0 cm
0.0 cm
solvent
mixture
solvent
baseline above the level of the solvent
Figure 57 The apparatus for thin layer chromatography (le) and the resulting chromatogram (right)
Solution
distance travelled by the blue spot
Figure 58 shows that the mixture contains three R (blue) =

F
distance travelled by the solvent
components, which appe ar as distinct spots at dierent
2.0 cm
distances from the baseline: at 8.0 cm (red), 6.0 cm
=
12.0 cm
(green) and 2.0 cm (blue). The distance between the
baseline and the solvent front is 12.0 cm.

= 0.17 (2 signic ant gures)
You c an c alculate the retardation factors (R ) for the red

R (red) is larger than R (blue). This me ans that the
F
F F
and blue spots (top and bottom) as follows:

component(s) of the red spot are more soluble in the
mobile phase (non-polar hydroc arbon solvent) and the

distance travelled by the red spot
R (red) =
F blue spot is composed of substances that have a gre ater
anity for the stationary phase. The stationary phase
8.0 cm
=
(silic a) is polar, so the blue spot contains substances that
12.0 cm
are more polar than the substances in the red spot.
= 0.67 (2 signic ant gures)
Chromatograms composed of clear dots are frequently shown in books. If you
do a chromatography experiment, you will oen obtain a chromatogram in
which each colour blends into the next. If you want a clearer separation between
substances in the mobile phase, you c an try using dierent solvents.
uFigure 58 This experimental
chromatogram has less clear separation
between substances than the previous
examples we looked at
158
Thin-layer chromatography of plant pigments
The pigments found in plants c an be separated by Part 2: Chromatography
chromatography, depending on their relative affinities to

3
4. Place a few cm of the chromatography solvent into
the mobile and stationary phases. The separation c an be
the tank. Place the lid on top, to ensure that the
optimized by changing the phases. In this investigation,
atmosphere in the chamber becomes saturated
you will compare the chromatograms obtained when the
with the solvent vapours. You c an place a paper

mobile and stationary phases are changed.
towel soaked in the solvent vertic ally inside the tank
Relevant skills
to speed up the process.
• Tool 1: Measuring length
5. Then, lower the TLC plate into the solvent, taking
• Tool 1: Paper or thin layer chromatography
c are to keep the solvent below the pigment spot
• Tool 3: Record uncertainties in measurements
on the starting line. Ensure the plate does not touch
• Tool 3: Propagate uncertainties in processed data
the sides of the beaker. Ifyou are using paper,
• Inquiry 3: Discuss the impact of uncertainties on the

you must make sure that it is upright in the tank by
conclusions
attaching it to the lid or to a splint placed across the
S afety top of the tank.
• Wear eye protection. 6. Remove the plate from the tank once the solvent
• Flammable solvents. Keep away from flames and is near the top. Q uickly draw a line in pencil over
other sources of ignition.

the solvent front before it evaporates. Draw circles
• Organic solvents are toxic to the environment. around the pigment spots that are visible in the
• Work in a well-ventilated space and dispense solvents chromatogram. Allow the plate to dry.
in a fume cupboard.
7. Measure the distance travelled by the solvent.
Materials
Measure the distance travelled by each pigment
from the base line to the centre of the spot.

• Pestle and mortar
• Chromatography spotter
8. Determine a reasonable uncertainty for the
• Chromatography paper
distances you have measured.
• TLC plate
9. C alculate the R value of each pigment, and the

F
• Pencil
uncertainty of each.
• Ruler
10. Compare your results to those of other members
• Chromatography tank or beaker
of your class. Compare your results to literature
• Lid or aluminium foil for the chromatography tank
values for the R values, if available. Search online

F
• Propanone
for information that will help you identify each of
• Fresh green leaves
thepigments.
• Chromatography solvents (9:1 petroleum
ether:propanone mixture) 11. Comment on the precision and, if possible,
accuracy, of your class’s results. Discuss the impact
Method
of measurement uncertainty on the validity of your

Part 1: Preparation of the chromatography plate
conclusions.
1. Grind the leaves with a few cm of propanone until
Part 3: Changing the phases

you have obtained a concentrated pigment extract.
12. Consider how the results would differ if you used

2. Handle the TLC plate c arefully by the edges. Draw
a different solvent system, or a different stationary

a line in pencil, across the plate, 1 to 2 cm from the
phase. Then, try it out.

bottom.
13. Clear up as instructed by your teacher, taking c are

3. Spot the plant pigment extract onto the starting
not to dispose of the solvents down the sink.

line, taking c are to create a small, concentrated
spot of pigment. Allow it to dry.
159
Practice questions
36. C alculate the retardation factor, R , for the green spot

F
at 6.0 cm in gure 58.
37. Suggest why the baseline in paper chromatograms is
drawn in pencil.
38. Chromatographic analysis of a mixture of dyes (A)
and three individual pigments (B, C and D) produced
the chromatogram on the right.
Identify and explain which pigments are present in A.
A B C D
Resonance (Structure 2.2.11)

LHA
Sometimes, a molecule c annot be described by a single Lewis formula. Instead,
there are two or more possible resonance structures that collectively represent
the molecule. Resonance oen happens when there is more than one position
for a double or triple bond in a molecule. For example, two Lewis formulas c an
be drawn for ozone, O (gure 59). Note that a double-headed arrow is used to
3
show alternative resonance structures.
O O
Figure 59 Ozone has two possible resonance structures
These structures might suggest that the two oxygen–oxygen bonds in ozone are
dierent: one single and one double. In reality, the ozone molecule is a hybrid of
these two resonance structures. Bond length and strength data (table 13) show
that the two bonds in ozone are:
• identic al to each other
• intermediate between a single O–O bond and a double O =O bond in terms
of bond strength and length
• have a bond order of 1.5, bec ause there are 3 bonding electron pairs
distributed across two domains.
Average bond
–12
Bond Length / 10 m Bond order

–1
enthalpy / kJ mol
O–O single bond 148 144 1
O O bond in ozone 128 362 1.5
O=O double bond 121 498 2
Table 13 Bond data for oxygen–oxygen bonds
160
LHA
Diatomic oxygen, O , and ozone, O , are oxygen UV-C and UV-B radiation c an c ause DNA mutations,
2 3
allotropes that absorb dierent wavelengths of resulting in skin c ancer (melanomas) and c ataracts.
electromagnetic radiation corresponding to the Ozone layer depletion c aused by chlorouoroc arbons
ultraviolet (UV) section of the spectrum. The double bond (CFC s) in the atmosphere means that more UV radiation
in O , with bond order 2, is stronger and therefore has a c an reach the E arth’s surface. International collaboration
2
higher bond enthalpy than the oxygen–oxygen bond in involving the 1987 Montreal Protocol and the banning
O , with bond order 1.5. Breaking the oxygen–oxygen of ozone-depleting substances has slowed down the
3
double bond requires higher energy. rate of depletion. Evidence in recent years suggests the
concentration of ozone in the stratosphere has increased,

The dissociation of the double oxygen–oxygen bond in O
2
resulting in the recovery of the ozone layer (gure 61).

c an be brought about by electromagnetic radiation with
wavelengths of 240 nm and below. The bonds in ozone
c an be broken by wavelengths of 330 nm and below.
These wavelengths correspond to the UV-C and UV-B
regions of the electromagnetic spectrum, respectively.
The presence of O in the stratosphere prevents nearly all

3
solar UV-C and UV-B radiation from reaching the E arth’s
surface (gure 60).
Figure 61 S atellite images of a hole in the ozone layer over
Antarctic a from 1979 to 2011. The largest ozone hole to date was
recorded in 2006. Since then, data suggests that the hole has
Figure 60 The ozone layer in the stratosphere absorbs
been getting smaller again
UV-C radiation and most UV-B radiation
tFigure 62 Former US president Barack
Obama presents the Presidential Medal
of Freedom to Mexic an chemist and
environmental scientist M ario Molina. Molina
helped to uncover the link between CFC s
and ozone layer depletion
161
LHA
Deloc alization
Resonance structures c an be described as a single structure using the concept
of deloc alization. In covalent bonds, two atoms share a pair of electrons, which
are loc alized between the two atoms. Deloc alization occurs when electrons
are shared by more than two atoms in a molecule or ion, as opposed to being
loc alized between a pair of atoms.
Consider the ion NO . It is represented by two resonance structures (gure63a).

2
The nitrogen–oxygen bond has bond order 1.5, and its length and strength are
between those of a single N–O bond and a double N =O bond. One pair of
electrons is deloc alized across the two N–O bonding domains. For this reason,
the ion c an be represented with a structure containing a dashed line that shows
Practice questions
the deloc alization (gure 63b).
39. Draw the structure of ozone that
shows the deloc alized electron (b)

(a)
pair.
40. Draw the deloc alized structure
N N N
2–
of the c arbonate ion, CO , and

3
O O
explain why the C–O bond order
in this ion is 1.33.
–
41. Compare the C–O bond lengths
Figure 63 (a) The ion NO c an be represented by two Lewis formulas (b) An alternative
2
and strengths in the c arbonate representation of the ion shows the deloc alized electron pair
ion to those in c arbon dioxide
and methanol, CH OH.

3
Note that the structure in Figure 63b is not a Lewis formula bec ause it does not
specify loc ations of bonding and non-bonding electron pairs.
Resonance does not involve the interconversion between the various resonance
structures through rotation or bond movement. Instead, resonance structures

Linking question
collectively describe a single molecule that c annot be represented by a single
Lewis formula due to the presence of electron deloc alization. Therefore, the
Why are oxygen and ozone
actual molecule is somewhere “in-between” the various resonance structures,

dissociated by different
which is best represented by the single deloc alized structure.

wavelengths of light?
(Structure1.3)
Benzene and resonance (Structure 2.2.12)
Benzene, C H , is an important example of a molecule that demonstrates

6 6
resonance.
 Figure 64 The ball-and-stick structure and electron cloud of benzene, C H

6 6
162
LHA
The Lewis formula for benzene contains a six-membered ring of c arbon atoms
connected through alternating single and double bonds. Two resonance
structures are possible (gure 65).
H H
H H H H
H H H H
t Figure 65 Resonance structures
H H
of benzene
Some of the electrons in the c arbon–c arbon bonds in benzene are deloc alized
In skeletal formulas, straight lines
around the ring. For this reason, these deloc alized electrons are oen
represent bonds. The ends and
represented with a circle:
vertices (corners) of the bonds
represent c arbon atoms, and
hydrogen atoms are not drawn.
Detailed instructions for drawing
skeletal formulas of molecules are
Benzene is an aromatic hydroc arbon. The term “aromatic” is used to describe given in Structure 3.2.
cyclic molecules that are planar and stabilized due to the presence of deloc alized
electrons. Benzene is the simplest aromatic hydroc arbon, and structures similar
to it c an be found in a large range of substances (gure 66).
Activity TOK
1. One of the resonance structures of 1,2-dichlorobenzene is shown below.

Skeletal formulas are an example
Draw the other resonance structure.

of “chemistry shorthand” that are
used extensively by chemists. To

Cl
what extent are chemic al symbols,
Cl formulas and equations like a
language? What is gained or lost
using chemic al notation?
2. Draw a structure of 1,2-dichlorobenzene that contains a circle to
represent the deloc alized electrons.
3. Research the structures of the following molecules and identify the
benzene rings in each:
(a) (b) (c)
curcumin Kevlar estradiol
Figure 66 (a) Curcumin, found in the yellow food spice turmeric (b) Kevlar is used
for making personal armour (c) Synthetic estradiol is used as medic ation in menopausal
hormone therapy
163
LHA
In ordinary conversation, the term “aromatic” c an be used to describe
something as having a pleasant smell. In chemistry, however, this term is
used to indic ate a benzene derivative or the presence of a benzene ring in
a compound. However, some aromatic compounds are non-benzenoids.
H H
For example, azulene — a component of some blue pigments found in
nature — contains alternating single and double

H
bonds in two planar rings that are joined
H H together:
C an you think of other examples of chemic al
H H terms that have dierent meanings in
C C
everydaylife?
H C C H
C C
H H
In benzene, one electron in each of the six c arbon atoms occupies a p orbital.
The six p orbitals overlap, forming a ring of electrondensity above and below the
Figure 67 The deloc alized
plane of the molecule. The electrons in this ring are deloc alized (gure 67). The
electrons in the p orbitals of benzene
c arbon atoms are sp hybridized (seeStructure 2.2.16).

form a ring of electron density above
and below the plane of the molecule
Physic al evidence for the structure of benzene
Once it was established that C H was the molecular formula for benzene,
6 6
the next step was to deduce its structure (gure 68). The 1:1 ratio of c arbon
to hydrogen suggested the presence of multiple bonds. Eventually a cyclic
arrangement of c arbon atoms with alternating single and double bonds was
proposed (gure 69). August Kekulé was credited with the structure, which is
said to have come to him in a dream. The structure proposed was a lop-sided
hexagon bec ause of the diering c arbon-c arbon bond lengths.
H CH CH
2
2
Figure 68 Some of the 19th century suggestions for the structure of benzene
(a) (b)
uFigure 69 (a) August Kekulé on
an E ast German postage stamp (b)
Kekulé’s suggestion for the structure of
benzene
164
LHA
X-ray diraction patterns later showed a regular hexagonal arrangement of
c arbon atoms in benzene where all c arbon–c arbon bonds had the same length,
suggesting they were all equivalent (gure 70).
The c arbon–c arbon bond length in benzene is intermediate between that of a
single and a double c arbon–c arbon bond (table 14). Bond enthalpy data shows
that they are also of intermediate strength.
0.140 nm
Average bond
–12
Bond Bond length / 10 m

–1
enthalpy / kJ mol
C–C single bond 154 346
C C in benzene 140 507
C=C double bond 134 614
Figure 70 A technique c alled X-ray

Table 14 Bond length and strength data for the c arbon–c arbon bond in benzene
diraction shows a contour map of

compared to single and double c arbon–c arbon bonds
the electron density in an individual
benzene molecule. E ach c arbon–
Chemic al evidence for the structure of benzene
c arbon bond length is 0.140 nm
The chemic al behaviour of benzene diers from what would normally be
expected from alkenes. Like alkenes, benzene is unsaturated, but unlike alkenes,
it does not readily undergo addition reactions. Alkenes undergo addition
reactions, where the double bond breaks and the c arbon atoms on either
end form bonds with new species. In benzene, addition would disrupt the
Addition and substitution reactions
stabilizing eect of the deloc alized electron ring, which would be energetic ally
are discussed in Reactivity 3.4
unfavourable. Instead, benzene tends to undergo substitution reactions.
Resonance energy of benzene
Resonance increases the stability of the benzene molecule. This is quantied
by a value c alled resonance energy. For benzene it is 152 kJ mol . This value is
established by comparing the thermochemistry data for benzene and those for
cyclic six-membered alkenes.
For example, cyclohexene contains one double bond. When we add hydrogen
to this double bond, the change in energy is 120 kJ mol .
1
ΔH = –120 kJ mol
+ H hyd
2
cyclohexene cyclohexane
This reaction is c alled a hydrogenation reaction, and the change in energy is
referred to as the enthalpy of hydrogenation, ∆H . 1,3-cyclohexadiene is

hyd
a similar molecule with two double bonds, so its enthalpy of hydrogenation is
nearly double: 232 kJ mol
1
ΔH = –232 kJ mol
+ 2H hyd
2
1,3-cyclohexadiene cyclohexane
165
LHA
The next molecule in the series matches Kekulé’s suggested structure and is the
Changes in energy across a
theoretic al molecule, 1,3,5-cyclohexatriene. 1,3,5-cyclohexatriene contains three
reaction are known as enthalpy
double bonds and its enthalpy of hydrogenation is predicted to be 120 × 3 =
changes. Enthalpy changes are

1 1
360 kJ mol (gure 71). However, the actual value for benzene is 208 kJ mol .
discussed in Reactivity 1.1. Naming
This is due to the added stability provided by resonance in the benzene ring. The
cyclic compounds is covered in

1
dierence between these enthalpy values is 152 kJ mol , which is the resonance
Structure 3.2.
energy.
lom Jk / yplahtne
152
360
208
uFigure 71 The resonance
–1
energy of benzene (152 kJ mol )
compared to the theoretic al
compound 1,3,5-cyclohexatriene
Hydrogenation of benzene is less exothermic than expected. This is bec ause the
reaction has an additional energetic cost to break the deloc alized electron rings.
1,2-disubstituted benzene compounds
Consider the Kekulé structure of benzene, containing alternating double
and single bonds. When chlorine, Cl , reacts with benzene to form

2
1,2-dichlorobenzene, you would expect that two possible isomers c an be
formed: one with the two chlorine atoms at either end of a c arbon–c arbon single
bond, whereas in the other isomer, the chlorines would be at either end of a
c arbon–c arbon double bond (gure 72a). However, bec ause all electrons are
evenly distributed, these two isomers represent the same molecule (gure 72b).
(a) (b)
Cl Cl Cl
Cl Cl Cl
Figure 72 (a) The two theoretic al isomers of 1,2-dichlorobenzene for the
Kekulé structure of benzene (b) The actual structure of 1,2-dichlorobenzene has
only one isomer bec ause the c arbon atoms are all chemic ally equivalent
166
LHA
Practice questions
42. Describe two pieces of evidence — one physic al and one chemic al — for the
structure of benzene.
43. How many deloc alized electrons does each of the c arbon atoms in a
benzene ring contribute to the deloc alized electron cloud?
44. State the bond angle in benzene and the molecular geometry around each
of the c arbon atoms.
Linking questions
How does the resonance energy in benzene explain its relative unreactivity?
(Reactivity 2.1, 2.2)
What are the structural features of benzene that favour it undergoing
electrophilic substitution reactions? (Reactivity 3.4)
(a)
F
P
F
Expanded octets (Structure 2.2.13)
F
Lewis formulas and VSEPR were discussed in the SL section of this chapter. At
HL you should also be familiar with molecules containing atoms with more
(b)
than eight valence electrons. This is known as an expanded octet. The central
Cl Cl
atoms in these molecules c an have ve or six pairs of electrons, amounting to
I
10 or 12 electrons, respectively. Examples of such species include phosphorus
Cl Cl
pentauoride, PF , and the tetrachloroiodide ion, ICl , shown in gure 73.
5 4
Drawing Lewis formulas for expanded octets

Figure 73 Two species with
expanded octets: PF and ICl , with

You c an follow the same steps used for drawing Lewis formulas at SL for
5 4
ve and six pairs of electrons around

molecules containing expanded octets. However, in this c ase, we omit the nal
the central atom, respectively

step — we do not check that the central atom has a full octet.
Worked example 5
Draw the Lewis formulas of each of the following species with expanded octets:
a. sulfur hexauoride, SF b. triiodide ion, I c. xenon trioxide, XeO

6 3 3
Solution
Follow the steps above for e ach molecule:
a sulfur hexauoride, SF b triiodide ion, I c xenon trioxide, XeO

6 3 3
Step 1 Count Sulfur: 6 Iodine: 7 × 3 = 21 Xenon: 8
valence Fluorine: 7 × 6 = 42 This polyatomic ion has a –1 Oxygen: 6 × 3 = 18
electrons Total: 6 + 42 = 48 charge meaning that it has an Total: 8 + 18 = 26
additional electron.
Total: 21 + 1 = 22
Step 2 48 22 26
C alculate the 2 2 2
number of
electron pairs
167
LHA
a sulfur hexauoride, SF b triiodide ion, I c xenon trioxide, XeO

6 3 3
Step 3 Arrange F O
the atoms
F F
S I I I Xe
F F O O
Step 4 Draw F
O
the single
F F
I I I
bonds
S
Xe
F F
O O
6 pairs used so far... 2 pairs used so far... 3 pairs used so far...
Step 5 Put non-

F I I I O
bonding pairs
F F
The peripheral iodine atoms
on peripheral
S now have noble gas Xe
atoms
F F congurations and therefore O O
do not need any more

F
electrons
The uorine atoms now have full octets.
full octets. 24 pairs used. 12 pairs used so far...

I I I O
any remaining electron pairs, so the structure
The remaining three pairs of
electron pairs above is nal. There are 6 pairs
electrons are assigned to the Xe
on the central of electrons around the central
central iodine atom. O O
atom sulfur atom. It has an expanded
We assign the nal electron

octet.
I I I
pair to the xenon atom.
All 13 available electron pairs

This species is an ion, so
have been used.

square brackets and the charge
are needed.
We can see that the central
iodine atom has an expanded
octet, with 5 pairs of electrons
around it.
In the structure deduced for XeO , each atom has L ater in this chapter, we will discuss the concept of
3
eight electrons and none have an expanded octet. formal charge: this will help us deduce the true
However, this structure is incorrect, and an exception structure of XeO and explain why it is considered
3
to the method we use for deducing Lewis formulas. to have an expanded octet.
Practice questions
a. PCl d. ICl
5 2
b. BrF e. ICl
3 2
c. IF f. SOF
5 4
168
LHA
Molecular geometry of expanded octets
In the SL section of this chapter, we discussed the geometries that arise when
atoms have two, three or four electron domains. Several additional geometries
occur for expanded octets containing ve or six electron pairs.
Five domains: trigonal bipyramidal geometry
If there are ve electron domains, the electrons in those domains repel each
other and therefore adopt positions at 120° and 90° from each other. This
electron domain geometry is c alled trigonal bipyramidal. The ve domains form
a shape consisting of two pyramids that share the same triangular base.
The electron domains in a trigonal bipyramidal molecule fall into two c ategories:
1. Equatorial: the bonds forming the triangular base of the pyramids, at 120° from
each other.
2. Axial: the bonds that form the axis of the molecule, at 90° from the plane of Figure 74 A balloon model of the
the triangular base. trigonal bipyramidal electron domain
geometry
A trigonal bipyramidal electron domain geometry gives rise to four possible
molecular geometries, depending on the presence of non-bonding domains:
• When all ve domains are bonding domains, the molecule has trigonal
bipyramidal geometry.
• When four of the ve domains are bonding domains, and one is a non-
bonding domain, the molecule has seesaw geometry.
• When three of the ve domains are bonding domains, and two are non-
bonding domains, the molecule has T-shaped geometry.
Figure 75 The four types of
• When only two of the ve domains are bonding domains, and three are
trigonal bipyramidal electron domain
non-bonding domains, the molecular has linear geometry.
geometry: (a) trigonal bipyramidal (b)
Examples of each type are shown in gure 75. seesaw (c) T-shaped (d) linear
(a) (b) (c) (d)

F
F
F
I
Cl
F
F
I
S
I
F
equatorial
position
B
B B a
a
a
B
a
B B
e e
120°
B A
less than 120°
B A A
e
e
B 180°
e B A
e
90°
B
B a
a
B
a
less than
less than 90°
B
a
90°
axial position
169
LHA
Like other geometries, the 120° and 90° bond angles in a trigonal bipyramidal
Practice question
shape are distorted by the presence of non-bonding pairs, due to their greater
46. Consider the seesaw and

repulsion.
T-shaped molecular geometries.
Six domains: octahedral geometry

Why do you think the non-
bonding domains are loc ated in
If there are six domains, the electron pairs in those domains adopt positions at
equatorial positions, not in axial
90° from each other. This electron domain geometry is c alled octahedral. This is
positions?
bec ause the domains form an octahedron, which is an eight-sided polyhedron
consisting of eight identic al equilateral triangles.
The electron domains in an octahedral molecule are all at 90° to each other, so
there is no need to distinguish between axial and equatorial domains.
An octahedral electron domain geometry gives rise to three common molecular
geometries, depending on the presence of non-bonding domains:
• When all six domains are bonding domains, the molecule has octahedral
geometry.
• When ve of the six domains are bonding domains, and one is a non-bonding
domain, the molecule has square pyramidal geometry.
• When four of the six domains are bonding domains, and two are non-bonding
domains, the molecule has square planar geometry.
Figure 76 A balloon model of the
The 90° bond angles in octahedral molecular geometries are distorted by the
octahedral electron domain geometry
presence of non-bonding pairs, due to their greater repulsion.
(a) (b) (c)

F F
S F
F
F
Br
Xe
F F
F F
B B B B
B B
A 90° A 90°
A <90°
B B B B
B B
Figure 77 The three types of octahedral electron domain geometry: (a) octahedral (b) square pyramidal
(c) square planar
170
LHA
Electron Number of
Number of Number of bonding Molecular Bond
domain non-bonding Example
domains domains geometry angle
geometry domains
trigonal 5 5 0 trigonal 90°, 120° PF

5
bipyramidal bipyramidal
4 1 seesaw <90°, SF
4
<120°
3 2 T-shaped <90° ClF

3
2 3 linear 180° I
3
octahedral 6 6 0 octahedral 90° SF

6
5 1 square <90° BrF

5
pyramidal
4 2 square planar 90° XeF

4
Table 15 Summary of molecular geometries with ve and six electron domains
Activity
1. Identify the electron domain geometry and molecular geometry of a
species with the following bonding and non-bonding domains:
a. six bonding domains
b. four bonding domains and one non-bonding domain
c. ve bonding domains
d. two bonding domains and three non-bonding domains
e. four bonding domains and two non-bonding domains
2. Identify the number of bonding and non-bonding domains around atoms
with the following molecular geometries:
a. trigonal bipyramidal
b. T-shaped
c. octahedral
d. square planar
e. seesaw
f. square pyramidal
g. linear (there are two possible answers here)
3. Deduce the electron domain geometry and molecular geometry of each
of the following:
a. PCl f. SOF
5 4
b. BrF g. SiF
3 6
c. IF h. IF
5 4
d. ICl j. SCl
2 4
e. ICl
2
4. Predict the bond angles in molecules a to j above.
Linking question
How does the ability of some atoms to expand their octet relate to their
position in the periodic table? (Structure 3.1)
171
LHA
Formal charge (Structure 2.2.14)
Formal charge is the charge an atom would have if all the bonding electrons
in the molecule were shared equally, and if its non-bonding electrons were not
shared at all. We c an assign formal charge to atoms in a molecule to select the
best Lewis formula when several are possible. Formal charge is c alculated by
looking at the electrons an atom has before and aer bonding:
Formal charge = number of electrons before bonding – number of
electrons aer bonding
FC = VE – (NBE + ½BE)
Where:
FC = formal charge
VE = number of valence electrons of the atom before bonding
NBE = number of non-bonding electrons assigned to the atom in the Lewis
formula
BE = number of bonding electrons assigned to the atom in the Lewis formula
The sum of the formal charges of all atoms in a molecule or ion should be equal to
the overall charge of that molecule or ion.
Worked example 6
Show that the overall charge of nitrogen trichloride, NCl , is zero by c alculating the formal charges of the atoms in the
3
molecule. The Lewis formula of NCl is shown below.

3
Cl
Cl N Cl
Solution
The formal charge of the nitrogen atom c an be The same process c an be repe ated to determine the
c alculated as follows: formal charge of e ach chlorine atom:
VE = 5 (bec ause nitrogen is in group 15) VE = 7 (bec ause chlorine is in group 17)
NBE = 2 (because in the Lewis formula the nitrogen NBE = 6 (bec ause in the Lewis formula each chlorine
atom has two non-bonding electrons) atom has six non-bonding electrons)
BE = 6 (bec ause in the Lewis formula the nitrogen BE = 2 (bec ause in the Lewis formula each chlorine
atom has three bonds, which are equivalent to six atom has one bond, therefore two bonding
bonding electrons) electrons)
FC(N) = 5 (2 + 0.5 × 6) = 0 FC(Cl) = 7 (6 + 0.5 × 2) = 0
Therefore, the formal charge of the nitrogen atom in this Therefore, the formal charge of e ach chlorine atom in
Lewis formula is zero. this Lewis formula is zero.
The sum of the formal charges is zero, which is also the
overall charge of the molecule.
172
LHA
The following conditions are generally favourable:
1. formal charges close to zero
2. a dierence in formal charges in the molecule close to zero
3. negative formal charge(s) assigned to the more electronegative atom(s).
When presented with alternative Lewis formulas, we look for the one that satises
these requirements most.
Worked example 7
2–
Assign formal charges to the atoms in the sulfate ion, SO , to deduce its Lewis formula.
4
Solution
2–
We start by drawing the Lewis formula of SO in a way We know that sulfur is prone to forming expanded
4
that follows the octet rule: octets, so the following Lewis formula is proposed:
2
2
O
O O
C alculating the formal charges of the sulfur and oxygen
atoms in this Lewis formula gives:

Now we c an c alculate the formal charges of the sulfur
and oxygen atoms based on this Lewis formula:

FC(S) = 6 (0 + 0.5 × 12) = 0
FC(S) = 6 (0 + 0.5 × 8) = +2
FC(O singly bonded) = 6 (6 + 0.5 × 2) = –1
FC(O) = 6 (6 + 0.5 × 2) = –1 (all the oxygen atoms

FC(O doubly bonded) = 6 (4 + 0.5 × 4) = 0
are equivalent in this Lewis formula and therefore each
The more electronegative oxygen has the negative
have the same formal charge of 1)
charge, same as that in the previously suggested
The formal charges in this Lewis formula are not close structure. However, the formal charge v alues in this
to zero, and the dierence between them is 3: these second Lewis formula are closer to zero and have
conditions are not favourable. a range of 1: these conditions are more favourable.
Therefore, the second Lewis formula is preferred.
In both c ases, the sums of the formal charges are 2,
which is equal to the charge of the poly atomic ion.
Practice questions
47. Determine the formal charge of every atom in each of the molecules below.
You will need to draw the Lewis formulas rst.
a. H O d. NO
2 3
b. CO e. SF
2 6
c. OH f. BH
3
173
LHA
Practice questions
48. Based on formal charge considerations, determine which Lewis formula is
preferred:
a.
Linking question b.
What are the dierent assumptions
made in the c alculation of formal
49. Determine the formal charge of each atom in the XeO molecule shown
3
charge and of oxidation states for
below and suggest an alternative Lewis formula in which the formal
atoms in a species? (Structure 3.1,
charges are all zero.
Reactivity 3.2)
Xe
50. Draw two alternative Lewis formulas for ClO . Determine, using formal
3
charge, which of the two is favourable.
Sigma bonds () and pi bonds (π)
(Structure 2.2.15 )
E arlier in this topic, we dened covalent bonding as the electrostatic
attraction between two nuclei and a shared pair of electrons. In this section,
we will delve deeper into how pairs of electrons occupying atomic orbitals
on neighbouring atoms are shared using valence bond theory. This is the
idea that valence electrons form bonds when orbitals in neighbouring atoms
overlap with each other, allowing the electrons to pair their spins
We know that bond strength increases with greater bond order. Consider the
average bond enthalpy for a single C C bond (346 kJ mol ) and contrast it
with that of a double C=C bond (614 kJ mol ). The average bond enthalpy for
the double bond is signic antly higher but not double that of the single bond.
This is bec ause the two bonds in the double bond are not the same: one is a
sigma bond () and the other is a pi bond (π). Pi bonds are generally weaker
than sigma bonds. This is why the strength of the double bond is not exactly
double the strength of the single bond.
In a triple c arbon–c arbon bond, one of the three bonds is a sigma bond and
the other two are pi bonds (gure 78).
σ π
σ
σ
π π
Figure 78 Single bonds are sigma bonds. Double bonds contain one sigma and one pi
bond. Triple bonds contain one sigma and two pi bonds
174
LHA
Sigma bonds ()
Imagine two hydrogen atoms approaching each other. They each have one
unpaired electron, in the 1s orbital. Eventually their 1s orbitals will overlap. When
they do so, the electrons will pair up forming a covalent bond.
s s s p p p
Imagine an invisible line between the nuclei of the two bonding atoms. This line
is known as the bond axis or internuclear axis. The two 1s orbitals will overlap
along this axis to form a sigma bond. This means that there is a region of high
electron density along the bond axis. Figure 79 shows that sigma bonds c an form
between pairs of orbitals of dierent types.
Figure 79 Sigma bonds are formed
Single bonds are always sigma bonds.
when orbitals overlap along the bond axis
ATL Thinking skills

The shapes of s and p orbitals are
discussed in Structure 1.3.
Sigma bonds get their name from the Greek letter , which is where the letter s
came from in the Latin alphabet. When you look directly along the bond axis, the
sigma bond looks spherical, like an s orbital.
Pi bonds get their name from the Greek letter π, which corresponds to the
letter p. When you look along the bond axis, the pi bond looks like a p orbital,
with lobes above and below the axis.
What other things in science are named aer things they resemble?
π bond
Pi bonds (π) p p
If p orbitals are present in two neighbouring atoms, they c an overlap sideways,
above and below the bond axis. This type of overlap forms a pi bond (gure80).
In pi bonds, the electron density is concentrated at opposite sides of the
overlap above and

bondaxis.
below bond axis
One pi bond consists of two lobes at opposite sides of the bond axis, as shown in
Figure 80 Pi bonds are formed when
gure 80. A pi bond contains two electrons, which occupy both lobes.
porbitals overlap above and below the
bond axis
Worked example 8
Determine the number of sigma and pi bonds in the molecule (NC) C=CH .
2 2
The structural formula is given below.
H H
Solution
First, count the sigma bonds in the structural formula. Remember that single
bonds are sigma bonds and each of the multiple bonds contains one sigma
bond. Therefore, there are 7 sigma bonds.
Then, count the pi bonds. E ach triple bond contains two pi bonds. E ach
double bond contains one pi bond. There are 5 pi bonds in total.
175
LHA
Worked example 9
Determine the number of sigma and pi bonds in the phosphate anion,
3–
PO . The Lewis formula is given below.

4
Practice questions
51. Compare and contrast sigma

Solution
bonds () and pi bonds (π).
The three single bonds and one of the bonds in the double bond are all sigma
52. Explain why two overlapping s

bonds, giving a total of 4 sigma bonds. There is one pi bond: the second bond in
orbitals c annot form a pi bond.

the double bond.
Activity
Look up the Lewis formula of each of the following molecules. Determine their
number of sigma and pi bonds.
a. ethanoic acid, CH COOH

3
b. propyne, CH CCH
3
c. ethanenitrile, CH CN
3
2–
d. c arbonate ion, CO
3
e. ammonium ion, NH
4
f. phosphorus trichloride, PCl

3
g. azide ion, N
3
h. methanoate ion, HCOO
Theories
While valence bond theory helps to explain molecular • Valence bond theory describes the strong, hexagonal
geometry, it fails to give information on electron energies sigma bond framework of benzene.
or properties such as magnetism. M any discussions
• Molecular orbital theory shows that deloc alization
of bonding amongst chemists are based on a more
gives benzene a distinct energetic advantage.
sophistic ated theory, molecular orbital theory. This
Molecular orbital theory draws heavily from quantum

theory assumes that electrons are spread across the entire
mechanics. C an you think of any other examples where

molecule rather than being loc alized in specic bonds.
we use the other sciences to enhance our understanding

Sometimes a phenomenon is best described using both
of chemistry?
theories. For example, the aromatic stability of benzene
c an be explained by two models:
Hybridization (Structure 2.2.16)
By now you should know that c arbon is tetravalent, meaning it c an form four
covalent bonds. If these bonds are single bonds, they are usually arranged in a
tetrahedral structure around the c arbon atom at approximately 109.5° angles
from one another. For example, methane, CH , has a tetrahedral structure.

4
176
2 2 2
LHA
However, the ground state electron conguration of c arbon, 1s 2s 2p ,
You c an deduce the electron
contradicts these observations. C arbon contains two unpaired 2p electrons
conguration of an element from its
(gure 81a) and therefore should form two bonds (one involving each unpaired
atomic number. This is covered in
electron), not four. Furthermore, the two occupied 2p orbitals are at 90° from
Structure 1.3.
one another, not 109.5°. This means that the atomic orbitals must undergo
certain changes when they form bonds.
Hybridization is the concept of mixing atomic orbitals to form new hybrid
orbitals for bonding. An example of this process is shown in gure 81 for the
c arbon atom. There are two steps:
1. Promotion: A 2s electron is promoted to one of the 2p orbitals.
2. Hybridization: The singly occupied 2s and 2p atomic orbitals are hybridized,
meaning they combine and give rise to orbitals of new shapes. The resulting
orbitals are called hybrid orbitals and they all have the same energy.
(b) (c)
(a)
2s 2p sp hybrid orbitals
2s 2p
Figure 81 (a) The ground state electron conguration of c arbon
(b) One of the 2s electrons is promoted to a 2p orbital
(c) The four atomic orbitals are hybridized to form four sp hybrid orbitals
of identic al energy
O verall, hybridization is energetic ally favourable. The promotion step absorbs
energy, but the energy released by the subsequent bond formation outweighs
this. Promotion does not require much energy bec ause it relieves the 2s electron
of the repulsion it experiences when paired.
sp hybrid orbitals
The number of resulting hybrid orbitals is equal to the number of atomic orbitals
combined to make them. If four atomic orbitals (one 2s and three 2p) are
combined in c arbon, four equivalent sp hybrid orbitals are produced. E ach of
these hybrid orbitals is a mixture composed of one part 2s and three parts 2p,
and therefore has 25% s character and 75% p character (gure 82).
central
109.5°
+ + + + + +
carbon atom
3
sp
3
2s 2p sp
Figure 82 One 2s and three 2p atomic orbitals combine to form four equivalent sp
H
hybrid orbitals
H 1s atomic
3
orbitals
The four sp hybrid orbitals arrange themselves tetrahedrally, leading to the
109.5° bond angles. In c arbon, these orbitals are each occupied by one electron 3
Figure 83 In methane, each c arbon sp
and therefore c an form four sigma bonds. For example, in methane, CH , each
orbital overlaps with a hydrogen 1s orbital.
4
of the sp hybrid orbitals overlaps with a 1s atomic orbital on a hydrogen atom, The geometry around the c arbon atom is
forming four covalent bonds (gure 83). tetrahedral
177
2
LHA
sp hybrid orbitals
p Carbon can also become sp hybridized. The combination of one 2s and two 2p
z
2 2
atomic orbitals produces three sp hybrid orbitals. These sp hybrid orbitals arrange
themselves in a trigonal planar fashion, at 120° from one another (gure 84).
2
sp
E ach hybridized orbital contains one electron, so they c an form sigma bonds.
The remaining unhybridized p orbital c an then go on to form a pi bond with a

2
z
sp
C
parallel p orbital on a dierent atom (gure 85).

z
2
sp 2 2
sp pi sp
H H
2 2 2
Figure 84 E ach of the three sp hybrid sp sp
orbitals (blue) contains one electron. The
unhybridized p atomic orbital (white) also C C

z
contains one electron
sigma
H H
2
2
sp sp
p p
z z
Figure 85 In ethene, C H , the two c arbon atoms each have three sp hybrid orbitals
2 4
(blue) which form sigma bonds with each other and two hydrogen atoms. The remaining
unhybridized p orbitals (white) overlap side-by-side and form a pi bond, resulting in a

z
c arbon–c arbon double bond
sp hybrid orbitals
The combination of one 2s and one 2p atomic orbital leads to the formation of
two sp hybrid orbitals. They adopt a linear arrangement, with 180° between
them (gure 86).
The hybrid orbitals can form sigma bonds. The remaining unhybridized p and
y
sp
C
sp
p orbitals can form two pi bonds with parallel p orbitals on a neighbouring atom
z
(gure 87).
p
y pi
p
z
sp sp
Figure 86 Each of the two sp hybrid
orbitals (blue) contains one electron. The

H
H
two unhybridized p and p atomic orbitals

y z
sigma
(white) also contain one electron each
pi
p p
y y
p p
z z
Figure 87 In ethyne, C H , the one sp–sp overlap and the two 1s–sp overlaps form three
2 2
sigma bonds. The four unhybridized p orbitals form two pi bonds, resulting in a c arbon–
c arbon triple bond
178
LHA
Hybridization in other atoms
Hybridization also occurs in atoms other than c arbon. The number of electrons
in the p orbitals will dier, but the general principles are the same. For example,
consider the oxygen atom in water, H O, which is sp hybridized: 2s

2
2p
2 2 4
• The oxygen atom’s ground state electron conguration is 1s 2s 2p .
• We c an distinguish between the three 2p orbitals to show that one of
them contains a pair of electrons and the other two are singly occupied:
2 2 2 1 1
1s 2s 2p 2p 2p
x y z
3 3
• The 2s and 2p orbitals hybridize to form four equivalent sp hybrid orbitals sp hybrid orbitals
containing six electrons in total (gure 88). Two of the sp hybrid orbitals
Figure 88 The 2s and 2p atomic orbitals
contain a pair of electrons each and therefore do not form bonds: they
3
in oxygen are hybridized to form four sp
constitute the two lone pairs on oxygen that you are familiar with. The
hybrid orbitals
remaining two hybrid orbitals are singly occupied and go on to form sigma
bonds with the s orbitals on hydrogen atoms.
Since the four hybrid orbitals are tetrahedrally arranged, the bond angles are
close to 109.5°. However, two of the hybrid orbitals are already full, so the
oxygen atom has two lone pairs. This corresponds to bent molecular geometry.
The fact that the bond angle is not exactly 109.5° but rather 104.5° suggests that
the hybridization is close to but not exactly sp
Practice questions
53. Draw orbital box diagrams to show the promotion 54. Describe the changes undergone by the atomic
and hybridization process for the oxygen atom in orbitals of nitrogen when it bonds to hydrogen to
water, described above. form ammonia, NH

3
Hybridization and geometry
Hybridization and sigma bonding are closely linked to electron domain
geometry. The number of hybrid orbitals formed by an atom is equal to the
number of its electron domains.
You will remember from the discussion of VSEPR that double and triple bonds
are treated as single additional electron domains when determining molecular
shape. This is bec ause pi bonds do not involve hybridized orbitals, so they do
not have a large eect on the geometry of a molecule.
Number Number Number of
Electron domain
Hybridization of hybrid of electron non-bonding Molecular geometry
geometry
orbitals domains domains
sp 4 4 tetrahedral 0 tetrahedral
1 trigonal pyramidal
2 bent
sp 3 3 trigonal planar 0 trigonal planar
1 bent
sp 2 2 linear 0 linear
Table 16 Hybridization, electron domain geometry and molecular geometry
179
LHA
Practice questions
55. State the hybridization of: 56. Consider the following species: CF , HCN, N H .
4 2 2
For each of the c arbon and nitrogen atoms in these

a. an atom with tetrahedral electron domain
species, deduce the following:

geometry
a. number of electron domains

b. the c arbon atom in ethene, C H
2 4
b. electron domain geometry

c. the oxygen atom in oxygen diuoride, OF
2
c. hybridization.
d. the nitrogen atom in molecular nitrogen, N
2
57. The Lewis formula of methyl propanoate is shown

e. an atom with trigonal pyramidal molecular
below. Deduce the hybridization, number of electron

geometry
domains, electron domain geometry and molecular

f. an atom with bent molecular geometry (two
geometry for atoms A, B and C.

answers are possible here).
H H O H
H C O H
H H H
B C
(a)
Hybridization and deloc alization
0.123 nm
Consider the ethanoate ion, CH COO . It forms when ethanoic acid loses a
3
H C C
3
hydrogen ion. By doing so, the c arbon–oxygen bond lengths change: the
0.133 nm bond orders change from 2 and 1 to 1.5 e ach. The electrons in the double
O H
bond become deloc alized across the two c arbon–oxygen domains. This is
shown in gure 89.
(b)
In the C=O bond of ethanoic acid, CH COOH, the c arbon and oxygen are both
3
O
2
0.128 nm
sp hybridized. The unhybridized 2p orbital electron in each atom forms the pi
bond between them. The other oxygen atom, in –OH, has sp hybridization.
C H C
3
0.128 nm
When the –OH hydrogen is lost to form ethanoate, the remaining oxygen
atom adopts an sp hy bridization. As a result, the oxygen atoms and the
Figure 89 When ethanoic acid loses

c arbon atom e ach have thre e ele ctron domains around them. Thre e ele ctron
a hydrogen ion, the C–O bonds become 2
domains correspond to sp hy bridization and one unhy bridize d 2p orbital
equivalent
e ach. The orbitals overlap allowing the p ele ctrons in them to be deloc alize d
as shown in figure 90.
Activity
ethanoate ion
Draw the two resonance structures
shown as
O
of the ethanoate ion.
C CH — C —
H C 3
3
Figure 90 The deloc alization of electrons due to resonance in the ethanoate anion
180
7. The hydronium ion is formed when a water molecule,
Topic review
+
H O, reacts with a hydrogen ion, H . Which type of

2

bond is formed in this reaction?
A. coordination bond
What determines the covalent nature and properties of a
B. ionic bond
substance?
C. hydrogen bond
2. Compare and contrast ionic bonding, covalent bonding
and intermolecularforces. D. intermolecular force
3. Compare and contrast molecular and covalent network 8. The electronegativities, χ, of four elements are:
substances.
Element H C O Cl
χ 2.2 2.6 3.4 3.2

Multiple-choice questions Which bond is the most polar?
4. Which of the following species is molecular? A. C–H
A. Na O B. O–H
2
B. KBr C. H–Cl
C. NH NO D. C–O
4 3
D. N O 9. Which of the following allotropes of c arbon is

2 4
molecular?
5. Which molecule has the shortest c arbon–oxygen bond?
A. graphite
A. CH CH OH
3 2
B. graphene
B. (CH ) O
3 2
C. buckminsterfullerene
C. (CH ) CO
3 2
D. diamond
D. CO
10. What are the intermolecular forces present between
6. What is the electron domain geometry, the molecular
molecules of CH F?
3
geometry and the Cl–P–Cl bond angle for the molecule
of phosphorus trichloride, PCl ? A. London (dispersion) forces

3
B. London (dispersion) forces and dipole–dipole forces

Electron domain Molecular Cl–P–Cl bond
geometry geometry angle / °

C. London (dispersion) forces, dipole–dipole forces
A. tetrahedral tetrahedral 109.5 and hydrogen bonding
B. tetrahedral trigonal 109.5

D. hydrogen bonding
pyramidal
LHA
11. What are the formal charges on P and O in the Lewis
C. tetrahedral trigonal 100.3
formula of the phosphate oxoanion?
pyramidal
3
A. P is 1 and O is 0
D. trigonal pyramidal trigonal 100.3
pyramidal
B. P is +5 and O is 2
C. P is 0 and O is 0 and 1
O
D. Both are 3
181
LHA
12. What is the electron domain geometry of the sulte 17. What is the hybridization of the oxygen atom in ethanol,
oxoanion, [SO ] ? CH CH OH?

3 3 2
A. trigonal planar A. sp
B. trigonal pyramidal B. sp
C. tetrahedral C. sp
D. bent (V-shaped) D. It is not hybridized.
13. What is the molecular geometry of BrF ? 18. What is the hybridization of the c arbon atom in
5
hydrogen cyanide, HCN?
A. octahedral
A. sp
B. square planar
B. sp
C. T-shaped
C. sp
D. square pyramidal
D. It is not hybridized.
14. What is the molecular geometry of [PF ] ?

6
19. How many sigma and pi bonds are present in a
A. trigonal planar
molecule of hydrogen cyanide, HCN?
B. trigonal bipyramidal
C. square pyramidal
sigma pi
D. octahedral A. 1 3
B. 2 1
15. Which of the following molecules is non-polar?

C. 2 2
A. SF D. 3 1
4
B. ClF
3
C. BrCl
5
20. Describe the meaning of the term covalent bond. [2]
D. SeF
6
21. The phosphonium ion, PH , is formed when a

4
hydrogen ion, H , reacts with a molecule of phosphine,

16. Which of the combinations of atomic orbitals shown
PH . For each species, phosphine and phosphonium:

below le results in a sigma bond? 3
a. Draw the Lewis formula. Identify any coordination

A. I and II only
bonds [3]
B. I and III only
b. Deduce the electron domain geometry and
C. II and III only

molecular geometry. [2]
D. I, II and III
c. Suggest the bond angle. [2]
+
I.
d. Deduce whether it is polar or non-polar.
Explain your reasoning. [2]
+
II.
22. Methane, CH , ammonia, NH , and water, H O, all
4 3 2
have tetrahedral electron domain geometry with bond
angles of 109.5°, 107° and 104.5°, respectively.
III. +
Explain these dierences in bond angle values. [2]
23. Diamond and graphite are allotropes of c arbon.
Describe and explain the electric al conductivity of
these two materials. [3]
182
24. Household vinegar is made from aqueous ethanoic 25. The following substances all have similar molar masses.
acid, CH COOH.
3
i ethanoic acid, CH COOH
3
a. Draw the Lewis formula of ethanoic acid. [2]

ii propan-1-ol, CH CH CH OH
3 2 2
b. Draw a diagram to represent the intermolecular

iii methoxyethane, CH CH OCH
3 2 3
interaction between a molecule of ethanoic acid
iv butane, CH CH CH CH
3 2 2 3
and a water molecule. [2]
a. Use your knowledge of intermolecular forces
c. Ethanoic acid molecules c an form dimers,
and structure to list these four substances in
particularly when gaseous or dissolved in a
order of increasing boiling point.
non-polar solvent. Dimerization means that two
ethanoic acid molecules c an associate as shown
below. b. Explain why, when comparing the strength of
dierent intermolecular forces, it is helpful to
O H O
compare substances that have similar molar
masses. [1]
H C C C CH
3 3
26. Explain why the boiling point of the group 17 elements
O H O increases down the group. [2]
27. Water is an excellent solvent.

i. C alculate the molar mass of an ethanoic
acid dimer. [1]

a. Oxygen dissolved in water bodies supports the
presence of aquatic organisms. Describe the type

ii. Suggest why ethanoic acid is more likely to
of intermolecular forces that occur between oxygen

form dimers when dissolved in non-polar
molecules, O , and water molecules, H O. [1]

solvents (such as hexane) than in polar 2 2
solvents (such as water). [2]

b. Ionic compounds oen dissolve in water but not
in organic solvents. Explain why ionic compounds

d. Ethanoic acid, CH COOH, dissolves readily in
3
do not readily dissolve in hydroc arbon solvents. [2]

water. The aqueous solubility of hexanoic acid,
CH CH CH CH CH COOH, is very low.

28. Morphine and diamorphine are strong painkillers
3 2 2 2 2
Explain this dierence in solubility. [2]

belonging to a group of substances known as opiates.
The esteric ation of morphine produces diamorphine

LHA
e. State the number of pi and sigma bonds in a
(heroin), as shown below:
molecule of ethanoic acid. [1]
a. Identify and explain which of these two opiates
has a higher aqueous solubility. [3]
f. Deduce the hybridization of the c arbon and
oxygen atoms in ethanoic acid. [2] b. The potency of opiates depends on their ability to
cross from the blood into the brain. The blood–
brain barrier is composed of lipids which are
non-polar. Identify and explain which of these
two opiates dissolves more readily in non-polar
environments. [1]
CH CH
2 2
OH
O CH
3
H C N CH H CH
3 2 3 2
O O CH O 2CH COOH
2H C 3 3
3
C C
O O
OH O
CH
3
morphine diamorphine (heroin)
183
LHA
29. A paper chromatogram for a mixture of amino acids is 31. The c arbonate ion contains deloc alized electrons.
obtained using a non-polar solvent.
a. Draw the three resonance structures of the
a. C alculate the retardation factor, R , for the spot c arbonate ion, CO . [2]
F 3
labelled X in the chromatogram. [2]
b. State the bond order of the c arbon–oxygen
b. Deduce which of the three components is likely bond in the c arbonate ion. [1]
to have the lowest polarity. [1]
32. Benzene, C H , contains deloc alized electrons and is

6 6
oen represented as follows.
4.90 cm
4.10 cm
5.40 cm
a. Explain, with reference to hybridization, why the
deloc alized electrons in benzene form a ring
above and below the plane of the molecule. [2]

1.70 cm
0.75 cm b. Outline how bond length data conrms the
structure of benzene. [1]
c. Describe one piece of chemic al evidence that
30. The diagram below is a chromatogram of an extract

further supports the structure of benzene shown
from a supermarket curry sauce (labelled S). Four

above. [2]
reference samples of food colourings have also been
run on the chromatogram. Outline three conclusions
33. Sulfur trioxide, SO , is an acidic gas. If present in the

3
that c an be derived from the information in the
atmosphere, sulfur trioxide c an dissolve in rainwater
chromatogram. [3]
leading to acid rain.
a. Draw two Lewis formulas for SO , one that follows

3
the octet rule, and one where the sulfur atom has
solvent front an expanded octet. [3]
b. Determine the formal charges of each of the
atoms in the Lewis formulas you drew in (a). [2]
c. Deduce, using the concept of formal charge,
which of the two Lewis formulas is preferred.
E102 E110 S E122 E124
184
LHA
34. Ethene, C H , belongs to a group of substances known 36. The condensed structural formula of phenylamine is
2 4
as the alkenes. C H NH . A molecular model of phenylamine is shown

6 5 2
below.
a. Draw the Lewis formula for ethene. [1]
H
b. Deduce the molecular geometry of each of the
c arbon atoms in ethene. [1]
c. Suggest values for the following bond angles in H
H N
ethene:
i. HCH
ii. HCC [2] C
d. State the number of sigma and pi bonds in a
molecule of ethene. [1] H
H
e. Deduce the hybridization of the c arbon atoms in
ethene. [1]
C
f. Explain why molecular rotation is restricted
C
around the c arbon c arbon bond in ethene. [2]
g. Identify the main type of intermolecular force
H
present between ethene molecules.
a. Deduce the electron domain geometry and
35. State the hybridization of the c arbon atoms in molecular geometry of the c arbon and nitrogen
diamond and in graphite. Using these data, explain the atoms in phenylamine. [2]
electric al conductivity of each of the two materials. [4]
b. State the hybridization of the c arbon and
nitrogen atoms in phenylamine. [2]
c. A theoretic al study of the electron structure of
phenylamine suggests that the H–N–H bond
angle in phenylamine should be 112.79°, which
is very close to the experimental value. Discuss
what you may conclude about the molecular
geometry around the nitrogen in the –NH group

2
in the structure of phenylamine, and deduce the
hybridization state of nitrogen on this basis. [3]
37. C arbon atoms c an form single, double or triple covalent
bonds with other c arbon atoms. Suggest why two
c arbon atoms are unlikely to form quadruple bonds
with each other. [2]
185
Structure 2.3 The metallic model
What determines the metallic nature and properties of an element?
A large proportion of the E arth’s crust is composed of The reduction of iron(II) from its ore is achieved with the
metallic elements, and humans have been using metals for addition of c arbon in a blast furnace. Higher reactivity
millennia. The ability of metals to be moulded into shapes, metals are reduced by electrolysis of their molten
drawn into wires, and conduct electricity and heat makes compounds.
them very useful and versatile. These properties are a result Metal extraction processes require large amounts of
of metallic bonding. energy, posing environmental risks. However, many metals
Some metals are found as elementary substances in c an be recycled, provided that metallic waste is collected
nature, but many are found in ores, in their oxidized state. and treated safely and correctly.
Understandings
LHA
Structure 2.3.1 — A metallic bond is the electrostatic Structure 2.3.3 — Transition elements have deloc alized
attraction between a lattice of c ations and deloc alized d-electrons.
electrons.
Structure 2.3.2 — The strength of a metallic bond depends
on the charge of the ions and the radius of the metal ion.
Metallic structures (Structure 2.3.1)
Nearly 100 of the 118 known elements are metals. Bonding in metals c an be
described as the electrostatic attraction between metal c ations and deloc alized
electrons. The degree of electron deloc alization in pure elements is inversely
related to their electronegativity, which generally increases across periods and
decreases down groups. Therefore, metallic properties of elements demonstrate
the opposite trend: they increase down groups and decrease across periods.
For example, the properties of period 3 elements, from sodium to argon, change
gradually from metallic to non-metallic (table 1).
Figure 1 Ancient copper aw l , a
piercing tool, discovere d in the Jordan
Va l l e y. It is estimated to be 6 ,0 0 0 y e a rs
old, and one of the oldest metal artefacts
k n ow n
186
Na Mg Al Si P S Cl Ar
Metal, metalloid, metal metal metal metalloid non-metal non-metal non-metal non-metal
or non-metal?
Structure metallic metallic metallic covalent molecular molecular molecular monatomic
network covalent covalent covalent
Electric al high high high semi- low low low low
conductivity conductor
Electronegativity 0.9 1.3 1.6 1.9 2.2 2.6 3.2 N/A
pTable 1 Properties of period 3 elements
ATL Thinking skills
Chemistry oen involves thinking about how microscopic behaviour aects
observable features of matter and materials. The connection between
structure and physic al properties is a central idea in this chapter. As you read,
make a conscious eort to connect each of the observable characteristics of
metals to the way their particles behave. When you have nished, compare
your notes to a peer ’s and see if there are any similarities and/or dierences.
The metallic–covalent bonding continuum is shown in gure 2. On the le,
there are elements with low electronegativity values that tend to form metallic
greater greater
bonds. On the right, there are highly electronegative non-metals that form
metallic covalent
covalent bonds. Metalloids are somewhere in the middle: they have both
character character
metallic and non-metallic properties.
The metallic bonding model
metallic covalent
When metallic atoms bond to other metallic atoms, their valence electrons
bonding bonding
become deloc alized. Deloc alized electrons are not attached to individual ions,
but rather move freely within the lattice of closely packed c ations. This creates a 1.0 2.0 3.0 4.0
negatively charged “sea” of electrons that surrounds the c ations.

mean electronegativity
Metallic bonding results from the electrostatic attraction between metal c ations pFigure 2 The metallic–cov alent
and the sea of deloc alized electrons around them (gure 3). bonding continuum
+ + +
+ + +
+ + +
+ + +
+ + +
+ + +
pFigure 3 Structure of a metal s h ow i n g an a r ray of positive ions (c a t i o n s) surrounde d
by a “s e a ” of deloc alized ele ctrons
187
+ –
The properties of metallic structures
+
−
−
The presence of deloc alized electrons gives rise to many characteristic properties
of metals. Metals are good electric al conductors, thermal conductors, and they
+ + +
are malleable and ductile.
− −
Substances c an conduct electricity when mobile charged particles are present.

+ + +
− Consider a sample of metal. It contains a lattice of c ations surrounded by

−
free-moving, negatively charged electrons. The deloc alized electrons move
randomly throughout the metallic structure. When a potential dierence is

pFigure 4 When a potential difference
applied, there is a net movement of electrons away from the negative terminal
is applied, the deloc alized ele ctrons are
donated by the negative terminal and and towards the positive terminal (gure 4).
move t ow a r d s the positive terminal
TOK
Metals are lustrous and reect light well, which is why they are used to make
mirrors. Reective surfaces have historic ally sparked human fascination
and curiosity. In some cultures, mirrors were believed to have magic al
properties. They have also been perceived as valuable, status-signalling
objects. Mirrors have appeared in literature, both as instruments of clarity and
misrepresentation. Nowadays, we know the deloc alized electrons in metals
reect incident light, and most household mirrors are made by applying a
layer of silver metal to a glass surface. These are examples of how dierent
areas of knowledge might approach the same topic.
Are some types of knowledge more open to interpretation than others?
pFigure 5 Anish K a p o o r ’s Cloud G ate in Millennium Park, C h i c a g o, refle cts the
p e o p l e, buildings and sky around it on its curved, s t a i n l e ss steel surface
188
One of the reasons metals are used to make cookware is their thermal
conductivity, meaning that they conduct heat well. The thermal energy of a
substance is related to the kinetic energy of its particles. When a substance
is heated, its particles gain kinetic energy, so their vibrations and movement
become more vigorous.
When a metal is heated, the vibrations of its c ations increase in magnitude.
These vibrations are easily passed along to other c ations bec ause of their
closely packed arrangement. The vibrating c ations also transfer energy to the
surrounding electrons through collisions. Since the electrons in metals are
mobile, they c an pass this increased kinetic energy to other parts of the lattice.
This explains why metals are good conductors of heat.
As thermal energy in metals increases, ions in the lattice vibrate more, so
there are more collisions between electrons and ions. Some kinetic energy is
converted to heat with each collision. These collisions are the c ause of electric al
resistance in metals, which increases with temperature (gure 6). Conversely,
a decrease in temperature reduces the frequency of collisions, so the electrons
move in a more direct path. In this c ase, the resistance decreases.
Figure 6 Re s i s t a n c e
400
inc re ases line arly with
t e m p e ra t u r e for most
300
Ω / e c n at s i s e r
metals
200
100
– – – –
+ + + +
–100
– –
0 300 600 900 1200
push
temperature / K + + + +
– – –
+ + + +
Superconductors are materials that oer no resistance to electric current below
a certain “critic al” temperature. At very low temperatures many metals and some
+ + + +
other materials exhibit this property.

– –
M alleability is the ability of a solid to be pressed or pounded into dierent shapes
electron ‘sea’
without breaking. This useful property is the reason why metallic objects have
such a wide array of shapes, ranging from sewing needles to aeroplanes to

– –
zippers to anchors.
+ + + +
– –
Metallic bonding is non-directional. When a force is applied to a metallic structure,
+ + + +
the layers of cations can slide past each other without breaking the electrostatic
– – –
attraction to the surrounding delocalized electrons. The cations can therefore

+ + + +
be rearranged, allowing the metal to take on a new shape (gure 7). Aluminium
foil, oen used to wrap food, demonstrates that the metal aluminium is readily
+ + + +
malleable.
– –
A related property, ductility, is the ability of a solid to be stretched into wires.

pFigure 7 Metallic bonding remains
Ductility and electric al conductivity are a very useful combination of properties intact even after a metal is hammere d
that allows electric al wires to be produced at the industrial sc ale. into a sheet or other shape
189
To summarize, metals are typic ally:
• good electrical conductors because they contain mobile delocalized electrons
• good thermal conductors bec ause they contain mobile deloc alized electrons
and closely packed c ations
• malleable and ductile, bec ause the layers of c ations c an slide past each other
without breaking the metallic bonds.
pFigure 8 Liquid iron metal f rom a blast furnace pFigure 9 Aluminium c ans in a re cycling plant. Like other
metals, aluminium retains its properties after being re cycle d
Database investigation of the properties of metals
In this skills task, you will use a database to explore the properties of metals.
Relevant skills
• Inquiry 1: Formulate research questions
• Inquiry 2: Collect and record sufficient relevant quantitative data
Instructions
Using at least one database of your choice, identify, extract and analyse data
that will allow you to investigate the trend relating to the properties of metals.
This may involve looking at electric al conductivity, melting point or thermal
conductivity of a number of metals across a period or down a group. (If you
are an AHL student, you may wish to explore a property of the transition
elements.)
State a research question that is addressed by your data collection and
processing.
Before starting this task, create a plan of the steps you think it will
ATL
require and estimate the time needed to complete each step. Then,
do the task and keep a log of the actual time you spent completing the
various steps.
When you have finished, compare the two sets of steps and times. How
do they compare? How can these observations help you plan extended
tasks in the future?
190
Practice questions
1. State the property (or properties) of metals that makes them suitable for
manufacturing:
a. kitchen pans
b. electric power c ables
c. radiators
d. c ars
e. articial hip joints
f. guitar strings.
2. Draw a labelled diagram to explain how bonding occurs in metals.
3. Draw labelled diagrams to explain why metals are:
a. malleable
b. good electric al conductors
c. good thermal conductors.
Linking questions
What experimental data demonstrate the physical properties of metals, and
trends in these properties, in the periodic table? (Tool 1, Inquiry 2, Structure 3.1)
What trends in reactivity of metals c an be predicted from the periodic table?
(Reactivity 3.2)
The strength of metallic bonds
(Structure 2.3.2)
The stronger the attractions between the c ations and deloc alized electrons, the
stronger the metallic bond.
Metallic bond strength decreases with greater ionic radius, and increases with
greater ionic charge
A third factor, related to ionic charge, is the electron density of the “sea” of
deloc alized electrons.
Melting point and boiling point data trends c an be used to compare the strength
of metallic bonding in dierent metals. Consider the melting and boiling points of
the group 1 metals lithium, sodium and potassium (table 2).
Table 2 Melting and boiling point
Element Charge of Ionic radius / Melting Boiling
data for group 1 metals

–12
the c ation 10 m point / °C point / °C
lithium 1+ 76 181 1342
sodium 1+ 102 98 883
potassium 1+ 138 63 759
The melting and boiling points decrease down the group as the ionic radius
increases. A greater ionic radius means a greater average distance between the
c ations and the deloc alized electrons. This weakens the electrostatic forces of
attraction between them.
191
Now compare sodium against two other period 3 metals, magnesium and
aluminium.
Table 3 Melting and boiling point
Element Charge of Ionic radius / Melting Boiling
data for period 3 metals

–12
the c ation 10 m point / °C point / °C
sodium 1+ 102 98 883
magnesium 2+ 72 650 1090
aluminium 3+ 54 660 2519
The melting and boiling points of sodium, magnesium and aluminium increase
across the period. The reasons for this are:
1. Decrease in ionic radius: this reduces the distance between the c ations and
electrons, increasing the electrostatic attraction between them
2. Increase in ionic charge: this increases the strength of the electrostatic
attraction between the c ations and deloc alized electrons
3. Greater number of deloc alized electrons per ion: E ach aluminium atom
contributes three valence electrons to the sea of electrons. Sodium atoms
have only one valence electron that becomes deloc alized.
Using trends in data to predict properties
In this skills task, you will examine the trends in group 1 melting points to
predict the properties of unknown elements.
Relevant skills
• Tool 3: Construct and interpret charts and graphs
• Tool 3: Extrapolate graphs
• Inquiry 2: C arry out relevant and accurate data processing
Instructions
1. Examine the melting point and boiling point data in table 2. Plot a graph
pFigure 10 Metallic bonding in sodium
of these data that will help you analyse the melting and boiling point
is relatively we ak. As a result, sodium is
trends down group 1.
a soft metal that c an e asily be cut with a
knife 2. Extrapolate your graph to predict the melting and boiling points of the
other metals in group 1 (rubidium and c aesium).
3. Look the values up in the chemistry data booklet and compare them to
your predicted values. C alculate the percentage errors.
4. Briefly evaluate the validity of the extrapolation.
5. Draw a second graph of these data, including Rb and Cs this time.
6. Reflect on how plotting data that covers a larger range affects the quality
of your second graph.
192
Practice questions
4. The melting points of potassium and c alcium are 63 °C and 842 °C,
respectively. State three reasons why the melting point of c alcium is higher
than that of potassium.
5. List these metals in order of increasing melting point.
A. Be, C a, Sr, Ba B. Be, Ba, C a, Sr
C. C a, Sr, Ba, Be D. Ba, Sr, C a, Be
6. Which of the following explains why aluminium has a higher melting point
than magnesium?
I. Al contains more deloc alized electrons per ion than magnesium
3+ 2+
II. The ionic radius of Al is smaller than that of Mg
III. The charge of an aluminium ion is greater than that of a magnesium
ion.
A. I only B. II only
C. II and III only D. I, II and III
Linking question
What are the features of metallic bonding that make it possible for metals to
form alloys? (Structure 2.4)
LHA
Bonding in transition elements The position of the d-block and
transition elements in the periodic

(Structure 2.3.3)
table are discussed in Structure 3.1.
Transition elements are found in the d-block in the periodic table, and they have
many properties typically associated with metals: hardness, strength and high
density. They exhibit variable oxidation states and, frequently, catalytic properties.
Transition elements are dened as those that have atoms, or give rise to ions, with
incomplete d sublevels. Most of the d-block elements are transition elements, but
there are some exceptions. For example, zinc is not a transition element because its
2+
3d sublevel is full, both when it is an atom and when it forms the only stable ion Zn
Observations
Scientists are observers, looking at E arth and all other parts of the universe,
to obtain data about natural phenomena. The name of the transition element
chromium alludes to the colourful compounds it forms. Chromium was
pFigure 11 C ar c atalytic c o nv e r t e r
discovered by French chemist Nicolas-Louis Vauquelin, who observed
made f rom platinum, rhodium and

and analysed a lead ore sample containing chromium from Siberia. Aer
palladium. Tra n s i t i o n metals often h av e
precipitating out the lead, Vauquelin noted the dierent colours and named
c atalytic properties due to their v ariable
this new element aer the Greek word for colour, chromos.
ox i d a t i o n states
193
LHA
In transition elements, the electrons in the d sublevel become deloc alized, as
well as the electrons of the outer level. The greater electron density strengthens
the electrostatic forces of attraction between the c ations and the electron sea
that surrounds them. This results in higher melting points for transition elements
compared to group 1 and group 2 metals.
The chemic al properties of

The large number of delocalized electrons in transition elements also allows for
transition elements are discussed

good electrical conductivity. This is because there are more delocalized electrons
in Reactivity 3.4.
that can move along the metal sample when a potential dierence is applied.
Figure 12 The g l ow i n g filament in
this inc andescent light bulb contains
tungsten. Tu n g s t e n ’s ex t ra o r d i n a r i l y
high melting point makes it suitable for
high t e m p e ra t u r e applic ations. It is also
exc e p t i o n a l l y strong and d e n s e. In fact,
its name derives f rom the Swedish for
h e av y stone: “ tung sten”
Practice questions
7. Which of the following properties of transition elements is a result of the
presence of deloc alized d electrons?
A. coloured compounds C. good electric al conductivity
B. high density D. c atalytic properties
8. Which of the following statements is incorrect?
A. Transition elements generally have high melting points and boiling
points due the presence of unpaired d electrons.
B. M any transition element compounds are coloured bec ause their ions
oen contain incomplete d sublevels.
C. Transition elements are good electric al conductors due to the
presence of deloc alized d electrons.
D. Transition elements oen have multiple oxidation states.
2+
9. Explain, with reference to the electron congurations of Zn and Zn , why
zinc is not a transition element.
ATL Thinking skills
As you know, there are various linking questions in this book that aim to
Linking question
interconnect the course content and encourage the development of a
networked understanding of chemistry. Write a linking question of your
Why is the trend in melting
own, that explores the connection between the content in this section and
points of metals across a period
at least one other part of the DP chemistry course. Share it with a partner and
less evident across the d-block?
compare answers.
(Structure 3.1)
194
Topic review
1. Using your knowledge from the Structure 2.3 topic, answer the guiding
question as fully as possible:
What determines the metallic nature and properties of an element?
2. Compare and contrast ionic, metallic and covalent bonding.
3. Compare and contrast ionic, metallic, covalent network, and molecular
structures.
4. Which statement best describes metallic bonding?
A. Electrostatic attractions between a lattice of positive ions and
deloc alized electrons.
B. Electrostatic attractions between a lattice of negative ions and
deloc alized protons.
C. Electrostatic attractions between protons and electrons.
D. Electrostatic attractions between oppositely charged ions.
5. Which substance has a metallic structure?
Melting Solubility in Electric al Electrical
point / °C water conductivity when conductivity
molten when solid
A 36 high low low
B 186 insoluble low low
C 1083 high high low
D 1710 insoluble high high
195
6. Metals have many useful properties including malleability and electric al
conductivity.
sodium, magnesium, aluminium, copper,
Element
Na Mg Al Cu
Electric al
conductivity / 2.1 2.3 3.8 5.9
7 –1
× 10 S m
a. Explain why metals are malleable. Include a labelled diagram in your
answer. [3]
b. The electric al conductivity of several elements is shown below:
i. Describe and explain the trend in the electric al conductivity of
sodium, magnesium and aluminium. [2]
ii. Explain why the electric al conductivity of metals decreases with
increasing temperature. [2]

LHA
iii. Suggest why the electrical conductivity of copper is signicantly higher
than that of the other three elements shown in the table. [1]
7. Boiling point data for the period 3 elements is shown below.
Element Sodium, M agnesium, Aluminium, Silicon, Phosphorus, Sulfur, Chlorine, Argon,
Na Mg Al Si P S Cl Ar
4 8 2
Boiling 883 1 090 2 519 3 265 281 445 –34 –186
point / °C
a. Identify the structure of each of the elements in period 3. [1]
b. Plot a graph of boiling point vs atomic number. [1]
c. Explain the trend in boiling point across the period. [3]
d. Describe and explain the trend in electric al conductivity across
the period. [3]
▴ Figure 13 The period 3 elements
8. Explain why melting point and boiling point are good indic ators
of metallic bond strength. [1]
196
Structure 2.4 From models to materials
What role do bonding and structure have in the design of materials?
So far in Structure 2, we have discussed how materials c an M aterials science is the study of the structure and
be classied according to their bonding: ionic, covalent properties of materials and their applic ation, and the
and metallic. M aterials c an also be classied according to development of new materials. It draws heavily from
their use, origin, and properties. chemistry, physics and engineering.
History has characterized civilizations by the materials Another way to classify materials involves grouping them
they use: Stone Age, Bronze Age, and Iron Age. Uses for into three types: metals, polymers and ceramics. Two of
materials were developed based on observations of their these c ategories are considered in Structure 2.4: metals
properties, before explanations for those properties had (specic ally, alloys) and polymers. Your knowledge of
been proposed. structure and bonding will help you understand the nature
of alloys and polymers. Alloys are predominantly metallic
From metals to nanotechnology, research into the uses of structures, while polymers are covalent compounds.
materials is sometimes deliberate, and sometimes their Polymers have molecular structure, although their
unique properties are discovered by chance. molecules are very large.
Understandings
Structure 2.4.1 — Bonding is best described as a continuum Structure 2.4.4 — Polymers are large molecules, or
between the ionic, covalent and metallic models, and can be macromolecules, made from repeating subunits c alled
represented by a bonding triangle. monomers.
Structure 2.4.2 — The position of a compound in the Structure 2.4.5 — Addition polymers form by the breaking
bonding triangle is determined by the relative contributions of a double bond in each monomer.
LHA
of the three bonding types to the overall bond.
Structure 2.4.6 — Condensation polymers form by the
Structure 2.4.3 — Alloys are mixtures of a metal and other reaction between functional groups in each monomer
metals or non-metals. They have enhanced properties. with the release of a small molecule.
pFigure 1 A 3D printer cre ating a model from a polymer material, and t ra d i t i o n a l J av a n e s e gamelan metallophones
197
The bonding continuum (Structure 2.4.1)
strongly ionic,
Some materials cannot be categorized easily into substances with metallic, ionic and
e.g. CsF
covalent bonding. We saw this in Structure 2.1, with compounds such as aluminium
chloride, AlCl , having a hybrid of covalent and ionic bonding. We also discussed
3
metalloids in Structure 2.3, which exhibit covalent and metallic properties.
Therefore, bonding is best described as a continuum between these models.
Dutch chemists Anton Eduard van Arkel and Jan Ketelaar constructed a triangular
diagram to represent the continuum of the three bonding types. The three
strongly
strongly
corners represent “pure” metallic, ionic and covalent bonding (gure 2). The
covalent,
metallic
sides of the triangle represent the intermediates between one bonding type and
e.g. F
e.g. Cs 2
another. For example, an Al–F bond c an be positioned roughly halfway along the
pFigure 2 The v an Arkel-Ketelaar

ionic–covalent continuum.
triangular bonding d i a g ra m
Patterns and trends
We use classic ation in science to organize objects, information and
concepts. This c an help us to recognize trends and patterns as well as
anomalies. M aterials c an be classied according to dierent criteria such as
use, origin, properties, structure, and bonding. What are the advantages and
disadvantages of each system?
The properties of materials with dierent bonding types
The solubility and volatility of a substance c an be explained in terms of
bond type, structure and, if applic able, intermolecular forces. The electric al
conductivity of a substance depends on the presence of mobile charged
particles. Table 1 summarizes these and other properties of substances with
dierent bonding types.
Property Bonding type
Metallic Ionic Molecular covalent Covalent network
melting point and varies high low high
boiling point
volatility low low high low
water soluble no varies varies no
electric al conductor yes no when solid no no (except for graphite
yes when liquid/ and graphene)
aqueous
thermal conductor yes no no varies
brittle no yes no, except some yes
polymers
susceptible to corrosion yes varies varies no
pTable 1 Ty p i c a l properties of metallic, cov alent and ionic substances. This table is me ant as a g e n e ra l guide and there are
exc e p t i o n s where substances do not ex h i b i t typic al b e h av i o u r
198
Brittleness is the opposite of malleability. Ionic crystals are brittle while metals are
malleable. Brittle substances snap and break when subjected to a force bec ause
they c annot be deformed easily. The atoms or ions within the substance are
unable to slide past each other.
Elastic materials will change shape when subjected to a force, and return to
their original shape aer the force is removed. In a metal spring, the metallic
bonding is responsible for the elasticity. In contrast, rubber is elastic due to its
long polymer chains being able to uncoil and coil up again. You c an observe this
property in an elastic band. The opposite property is plasticity, which means that
the material retains its deformed shape even aer the external force is removed.
Modelling clay is an example of a material with plasticity.
The term corrosion is oen used to describe the oxidation of a metal, such as
iron, in the presence of oxygen and water. Corrosion more generally refers to a
chemic al reaction between a material and its surrounding environment, which
damages the material in some way.
M any materials do not behave in a manner typic al of its bonding type. For
example, aluminium has a low density while mercury is volatile, despite the fact
that both substances are metals. Graphite and graphene are covalent network
solids that conduct electricity. Molecular covalent substances have variable
properties bec ause their molecular size and polarity vary widely. Waxes are
so molecular covalent substances, whereas some molecular covalent plastics
are hard. In some c ases, more than one bonding type c an contribute to the
properties of a substance. This helps to explain the variations of properties
observed within a given bonding c ategory.
pFigure 3 Rusting is a type of corrosion. Iron and steel rust in the presence of water
and ox y g e n
199
Worked example 1
Explain the trends in melting points for silver halides and potassium halides,
given that the bonds in silver halides have greater covalent character than
those in potassium halides. Use the data given in table 2 and table 3.
Melting
point (˚C)
point
AgCl 455
generally
AgBr 432
increases
AgI 558
pTable 2 Melting points of the silver halides
Melting
point (˚C)
point
KCl 773
decreases
KBr 734
KI 681
pTable 3 Melting points of the p o t a ss i u m halides
Solution
The partial covalent character of silver halides means that their melting points
depend on the strength of van der Waals forces. The increasing number
of electrons going down the group from AgF to AgI increases the strength
of the London (dispersion) forces, c ausing the melting point to increase
(table2).
The bonding in potassium halides is predominantly ionic, with minimal
covalent character. Therefore, the strength of the bonds depends on how well
the c ations and anions interact with one another. From KF to KI, the size of the
anion increases, so the electrostatic attraction between oppositely charged
ions decreases and therefore the melting point also decreases (table 3).
You c an try to loc ate these compounds in the triangular bonding diagram in
gure 2. The silver halides are all in the covalent region of the diagram, near the
ionic section. In contrast, the potassium halides are all rmly loc ated in the ionic
region of the triangle.
Plot a graph of the data given in tables 2 and 3. Compare your graph with the
tables and suggest which is a better method for illustrating the data.
200
Use of triangular bonding diagrams
(Structure 2.4.2)
O ver time, chemists have further developed van Arkel and Ketelaar ’s original
You rst encountered gure 4a
work. Eventually, electronegativity was incorporated in a way that merges the two
in Structure 2.2, and gure 4b in
continua in gures 4a and 4b.
Structure 2.3.
The resulting triangular bonding diagram (or “bonding triangle”) is shown in
gure 4c.
ecnereffid ytivitagenortcele
(a) (b) greater greater
3.0 metallic covalent

ionic greater ionic
character character
bonding character
2.0
metallic covalent
bonding bonding
covalent greater covalent

1.0
bonding character
1.0 2.0 3.0 4.0
mean electronegativity
0
%Covalent
(c)
%Ionic
3.5
Ionic
CsF
8 92
3.0
) 휒∆ (
ecnereffid
2.5
25 75
MgO
2.0
ytivitagenortcelE
50 50
1.5
AIN
75 25
1.0
OF
AILi
0.5
NO
Mg
100 0
0.0
1.0 1.5 2.0 2.5 3.0 3.5 .0
Mean electronegativity (휒
Metallic Covalent
pFigure 4 (a) The ionic–covalent bonding continuum (b) The metallic–covalent bonding continuum
(c) The resulting triangular bonding diagram. This diagram incorporates dierent bonding c ategories, the
mean electronegativity and the dierence in electronegativity. Examples of several substances are included
The position of a substance in the bonding triangle is determined by the relative
contributions of the three bonding types to the overall bond. To loc ate it, we
need to know the electronegativity values of the two elements involved in the
bond. We then need to work out two parameters:
• dierence in electronegativities, ∆χ, which is the ionic–covalent parameter
• mean electronegativity, χ, which is the metallic–covalent parameter.
201
We do not need to consider molecular formula or bond order. As a result, two or
more dierent bonds may have identic al parameters. For example, the double
c arbon–oxygen bond in c arbon dioxide is in the same place in the bonding
diagram as the triple c arbon–oxygen bond in c arbon monoxide.
Worked example 2
Determine the position of the following substances in the triangular bonding diagram:
a. c arbon tetrauoride, CF
4
b. pure silicon, Si
c. barium iodide, BaI

2
Solution
a. c arbon tetrauoride, CF b. pure silicon, Si

4
For this example, we need to look at the In this example, we consider the bond between
bond between C and F in CF . C arbon has an two Si atoms. In elemental substances like this, the
4
electronegativity of 2.6 and uorine is 4.0. From this, atoms are all the same type and thus have the same
we c an c alculate the electronegativity dierence, ∆χ: electronegativity. Therefore, the electronegative
dierence between two Si atoms is zero, and the

∆χ = 4.0 2.6
mean electronegativity is equal to the Pauling

= 1.4
electronegativity of one Si atom (1.9).
Then, c alculate the mean electronegativity, χ:
This places silicon in the region between metallic and
2.6 + 4.0
χ =
covalent in the bonding triangle (gure 5).
= 3.3 c. barium iodide, BaI

2
With these parameters, we c an loc ate the c arbon– The two atoms in the bond are barium ( χ = 0.9), and
uorine bond in the upper part of the covalent region iodine ( χ = 2.7).
of the triangle (gure 5). This means that the bond

∆χ = 2.7 0.9 = 1.8
between C and F is polar covalent.
2.7 + 0.9
χ = = 1.8
With these parameters, we c an loc ate the bond in the
ionic region of the diagram (gure 5).
%Covalent
%Ionic
3.5 Ionic
8 92
) 휒∆ (
3.0
ecnereffid
2.5
25 75
2.0
ytivitagenortcelE
Bal
50 50
1.5 CF
75 25
1.0
0.5
Si
100 0
0.0
1.0 1.5 2.0 2.5 3.0 3.5 4.0
Metallic ean electronegativity (휒 ) Covalent
pFigure 5 The loc ation of certain bonds in the triangular bonding d i a g ra m
202
Practice questions
1. Using electronegativity values, deduce the main type of bonding in each
of the following substances by determining their position in the bonding
triangle.
a. uorine, F
2
b. c aesium uoride, C sF
c. lithium oxide, Li O
2
d. brass, composed of Cu and Zn
e. aluminium chloride, AlCl

3
f. silicon dioxide, SiO

2
2. Qualitatively describe the relative contributions of the three dierent types
of bonding in each of the substances in the previous question.
3. Explain why nitrogen monoxide, NO, and nitrogen dioxide, NO , are

2
loc ated at the same point in the bonding diagram.
The properties of a substance c an be predicted by its position in the bonding
triangle. We have already discussed the typic al properties of pure ionic
(Structure 2.1), covalent (Structure 2.2), and metallic (Structure 2.3) substances.
Now we will look at a selection of substances with signic ant contributions from
more than one type of bonding.
Silicon: metallic and covalent character
Silicon is positioned between the metallic and covalent regions in the bonding
triangle. It is a metalloid, which means that it exhibits both covalent and metallic
properties. Silicon is lustrous (shiny) like a metal. On the other hand, it forms
a covalent network structure in which atoms share electrons. Like covalent
substances, silicon is brittle and forms a (weakly) acidic oxide. In terms of
electric al conductivity, it is an intermediate between conductors (like metals) and
insulators (like most covalent substances) and is classied as a semiconductor.
Semiconductors are generally poor electric al conductors, but their conductivity
increases when heated, illuminated, or in the presence of certain impurities.
Figure 6 A silicon wafer containing
hundre ds of t i ny mic rochips for use in
ele ctronics.
203
M agnesium iodide: ionic and covalent character

L attice enthalpy is discussed in
Structure 2.1, and in Reactivity 1.2

In magnesium iodide, ∆χ = 1.4 and χ = 2.0. The percentage ionic and covalent
at additional higher level.

character are both about 50%. As a result of this, magnesium iodide has an
unusually high lattice enthalpy.
You c an test the assumptions of a model by comparing predicted and
experimental values. For example, the theoretic al lattice enthalpy for an ionic
compound assumes completely ionic behaviour. However, if the bonds
between ions are partly covalent, the experimental lattice enthalpy tends to
be signic antly greater than the theoretic al prediction. This oen happens
with larger ions, particularly those with lower electronegativity values,
bec ause their electron clouds are more polarisable. This allows a certain
degree of electron sharing (covalent bonding) in addition to ionic bonding.
Table 4 shows the dierence between experimental and theoretic al values of
lattice enthalpy for sodium chloride and silver chloride.
Compound Experimental lattice Theoretical lattice
–1 –1
enthalpy / kJ mol enthalpy / kJ mol
sodium 790 750
chloride,
NaCl
silver 918 734
chloride,
AgCl
pTable 4 Comparison of ex p e r i m e n t a l and the oretic al l a tt i c e e n t h a l py
v alues for two compounds
Based on the dierences between theoretic al and experimental lattice
enthalpy values, assess and compare the ionic and covalent character of
bonding in each compound.
Aluminium chloride: ionic and covalent character
Cl Cl Cl
Another compound which is classied as ionic but has a signic ant covalent
contribution is aluminium chloride. Unlike magnesium iodide, aluminium chloride

Al Al
has an unusually low melting point, even though it appears in the same region of
Cl Cl Cl
the bonding triangle as magnesium iodide. This shows that the bonding triangle
c annot always be used to predict the properties of a substance. This is particularly
true if the bonding in that substance has a mixed character.

Cl Cl Cl
Al Al
In aluminium chloride, ∆χ = 1.6 and χ = 2.4. Therefore, aluminium chloride is
right at the boundary between ionic and polar covalent in the bonding triangle.
Cl Cl Cl
As a result, aluminium chloride exhibits both covalent and ionic properties. AlCl
3
pFigure 7 Tw o w ays of representing forms ionic lattices when solid. At high pressure, it melts into Al Cl dimers (gure
2 6
bonding in the aluminium chloride 7) at 190 °C, which is very low for an ionic compound. Also, unlike a typic al
d i m e r, Al Cl
2 6 ionic compound, aluminium chloride is soluble in non-polar solvents such as
trichloromethane.
204
Practice questions
Activity
4. Mean electronegativity and
Use your knowledge of the behaviour of compounds containing a hydrogen–
dierence in electronegativity
oxygen bond to predict where in the bonding triangle you expect to nd this
values for dierent bonds are
bond. Then c alculate the ∆χ and χ v alues to see if your predictions were
shown below. O utline the
close.
properties you would expect a
compound with these bonds to
have.
Linking question
a. χ = 2.9 and ∆χ = 1.4
b. χ = 1.9 and ∆χ = 0.3
Why do composites like reinforced concretes, which are made from ionic
c. χ = 2.3 and ∆χ = 1.9
and covalently bonded components and steel bars, have unique properties?
(Structure 2.1, 2.2, 2.3)
Alloys (Structure 2.4.3)

In Structure 2.3, we discussed
how metallic structures contain

Pure metallic elements c an be mixed with other elements, metallic or non-
a lattice of c ations in a sea of

metallic, to form alloys. Dierent atoms or ions c an be held within the structure,
deloc alized electrons, and the fact

while still maintaining the deloc alized sea of electrons throughout. Alloys
that bonding between the c ations

therefore retain many metallic characteristics such as electric al conductivity and
and electrons is non-directional.

lustre. However, the properties of alloys are dierent to those of pure metals.
This accounts for the malleability

Properties such as hardness, corrosion resistance and melting point, c an be
ofmetals.
enhanced by alloying a metal with other elements.
Alloys are mixtures. The ratio of the components in an alloy c an vary without
changing the identity of the substance. For example, the proportion of c arbon in
steel ranges from traces to about 2%. In addition, the components of alloys retain
many of their original properties. All these characteristics are typic al of mixtures.
Properties of alloys
In pure metals, all the c ations in the metallic lattice are the same size. When a
force is applied, the layers of c ations slide past each other easily.
While malleability is a useful property of metals, sometimes we require a metallic
structure to be stronger. Alloying involves the addition of atoms or ions with a
dierent radius to the cations of the pure metal, which disrupts the regular structure
of the lattice. When an alloy is struck with a force, the layers of cations do not slide
past each other as easily. Therefore, alloys are usually stronger than pure metals.
Figure 8 In pure metals, the ions

iron
alloy are packed in a re gular p a tt e r n ,
where as the addition of another
element to form an a l l oy disrupts this
a r ra n g e m e n t , re ducing the malle ability
205
Examples of alloys
NaK is a sodium–potassium alloy that has a lower melting point than its constituent
elements, so it is a liquid at room temperature. Because of this, NaK is used as a
nuclear reactor coolant, which is non-volatile and can be pumped as any other liquid.
Memory metals are alloys that return to their original shape upon heating. They
are used to make objects that are prone to being deformed through use, such as
spectacle frames.
Iron is an abundant metal in the E arth’s crust. Pure iron c an be deformed relatively
easily. This limitation c an be overcome by alloying it with c arbon to create steel.
Steels are harder and stronger than pure iron, making them ideal for a variety of
uses ranging from construction to tools. There are many varieties of steel, each
containing dierent amounts of c arbon and other elements.
Like iron, steel rusts in the presence of water and elemental oxygen, O . Rusting
2
is problematic bec ause it transforms iron into hydrated iron(III) oxide. This is an
ionic compound, so it does not have the valuable properties of metals. Rust also
akes o easily, lowering the volume of metal and exposing the iron underneath
to further corrosion.
The degradation of objects made from iron and steel has economic implic ations.
L arge steel-containing structures (for instance, ships and bridges) need to be
protected from rusting to preserve their physic al integrity. Rust protection
methods include barrier methods (such as painting and oiling) and sacricial
methods (such as galvanising).
Stainless steels are iron alloys that contain at least 11% chromium. The chromium
reacts with oxygen in the air or water to form a thin layer of chromium oxide on
the surface of the steel. This chromium oxide layer prevents rusting, and therefore
stainless steels have useful applications in cooking and medical-grade equipment.
(a) (b)
pFigure 9 (a) The Eiffel Tow e r in Paris, F ra n c e, is made of iron. It is painted every f ew y e a rs to p ro t e c t it f ro m rusting. The painting
process itself lasts several months (b) Adding chromium to steel cre ates stainless steel, a rust-resistant alloy suitable for kitchen equipment
206
How does the c arbon content aect the hardness of steel?
Steels that are made up of 0.3% to 0.6% c arbon by mass Relevant skills
are known as medium steels. The hardness of medium-
• Inquiry 1: Demonstrate independent thinking,
steel samples with varying c arbon contents were tested,
initiative or insight
giving the results shown in figure 10.
• Inquiry 1: Formulate research questions and
Hardness values (units: HV) were determined using a

hypotheses
method known as the Vickers hardness test. Harder

• Inquiry 2: Interpret graphs
materials have greater Vickers hardness values.
• Inquiry 3: Interpret processed data and analysis to
draw and justify conclusions
1600
Instructions
1400
1. Research how the Vickers hardness test is performed.

VH ,ssendraH
2. Based on the information given, compose a possible
1200
research question that would be answered by the
data shown above. M ake sure you include the:
1000
– variables
– range of the independent variable

800
– methodology
– specific system being studied (in this c ase,

600
0.25 0.30 0.25 0.40 0.45 0.50 0.55 0.60

medium c arbon steels).
Carbon content (wt. %)
3. Describe and explain the trend shown in the graph.
pFigure 10 G ra p h s h ow i n g the h a r d n e ss of c arbon-containing
4. Try to think of at least one alternative interpretation.

steels. Source of data: C alik, A., Akin, D. , S ahin, O. and U c a r, N.
(2010) “Effect of C arbon Content on the Mechanic al Properties

5. What do you think might happen to the hardness
of Medium C arbon Steels”, Z. Natur forsch. 65a, 4 6 8 – 472
in steels with c arbon content greater than 0.55%?
Outline your ideas.
6. O utline an experiment that could be done to explore
your answers to questions 4 and 5 above.
Bronze is an alloy of copper and tin. It is harder than pure copper and resistant to
corrosion. Before steel bec ame common, bronze was used in shipbuilding, tools
and various household artefacts including coins.
Brass is a highly malleable alloy of copper and zinc. It is used to make music al
instruments due to its acoustic properties. The copper in brass has antimicrobial
properties, which is why it is oen used to make door handles in public buildings
such as hospitals.
Figure 11 Old bronze
coins f rom China
pFigure 12 An 19th century theodolite
made of b ra ss . This instrument was used
for me asuring angles
207
ATL Research skills and social skills
The life cycle of a product involves the process and materials involved in its production, usage and disposal. The
substances present undergo various transformations throughout (figure 13). Structure, as well as chemic al and physic al
properties, determines many of the processes involved in a product life cycle.
crushing the ore
purifying the
mining the ore

mineral
crushed ore
pure mineral
rubbish to
recycle
end of
waste tip
waste metal
useful life
recycle
metal
scrap metal
in use
recycle
scrap metal
extracting
shaping the metal
the metal
manufacturing
metal ingot
products from
the metal
pFigure 13 The life cycle of a metal
In this task, you will work with a group to research the life 4. Consider
cycle of a particular product. You will also reflect on the

– if and how you will divide up the work within your
collaboration skills involved. Work with one or two other

team
people.
– how you and your team will share your findings
with each other.

1. Collaboratively, choose one of the following
substances and products to investigate:

5. C arry out your research.
– aluminium in an aircraft
6. Prepare a visual representation of your research,
– iron in a ship
depicting the life cycle of your product. Before
– c arbon in a plastic bottle.

you start, take a moment to reflect on how to take
everyone’s opinions into account when deciding how

2. Briefly reflect on how you collectively reached a choice.
to represent your work.
3. Plan to research the various stages of the product’s
7. Share your work with your class.

lifecycle:
a. extraction of raw materials

8. Individually, reflect on your role in your group,
b. manufacturing
and identify one IB learner profile attribute that you
c. use
developed during this task.
d. disposal.
208
Practice questions
5. Explain why alloys such as steel are harder than pure metals.
6. Suggest why the electric al conductivity of an alloy is oen lower than that
of a pure metal.
Linking question
Why are alloys more correctly described as mixtures rather than as
compounds? (Structure 1.1)
Polymers (Structure 2.4.4)
Polymers are a class of cov alently bonded materials characterized by their low
thermal and electric al conductivity, and low density compared to other types
of materials. Polymers are macromolecules, which are very large molecules.
Plastics and synthetic textiles such as nylon are examples of synthetic
polymers. N atural polymers include brous materials like lignin and silk, as
well as many of the biologic al molecules involved in life processes, such as
DNA, starch and proteins.
Long, covalently bonded polymer chains are made when small molecules
c alled monomers join end-to-end (gure 15), like beads strung together to
create a necklace. This process is c alled polymerization. There are two types of
polymerization: addition and condensation

pFigure 14 A digital model of
polyethene terephthalate (PET), a
sy n t h e t i c polymer
pFigure 15 In polymerization, m o n o m e rs join up to make a chain c alled
a p o l y m e r. Here the small be ads represent m o n o m e rs and the resulting
chain, the polymer
Repeating units
A repeating unit is a group of atoms that appears repeatedly along a polymer
chain. The exact lengths of polymers c an vary, so the best way to describe the
structure of a polymer is with the structural formula of the repeating unit. In the
formula, the repeating unit is shown enclosed in large brackets with bonds drawn
across the brackets, indic ating that the polymer chain continues on either side.
The subscript n aer the closing bracket represents the number of repeating units
in the polymer. A typic al polymer contains hundreds or thousands of repeating
units, so n represents a very large number.
209
Worked example 3
A section of the polypropene molecule is shown below.
Draw the repeating unit of polypropene.
CH H CH H CH H CH H
3 3 3 3
H H H H H H H H
Solution
Looking at the section, you c an see that there is a When drawing a repeating unit, make sure that the
repeating pattern every two c arbon atoms along the connecting bonds on both sides cross the brackets. If you
polymer chain. need to represent the whole polymer chain, do not forget
to include the subscript n to signify that the polymer is
Therefore the repeating unit is
composed of many repeating units:
CH H
3
CH H
3
H H
H H
n
Practice questions
7. Draw the repeating unit for each of the polymer sections shown.
a. b.
H H H H H H H H
H H H H H H
—
— C — C — C — C — C — C — C C C C
—
H Cl H Cl H Cl H C H H CH H C H H CH
2 5 3 2 5 3
c.
H OH CH OH H OH CH OH H OH
2
2
O O
H H H H
O O O
OH H H OH H H OH H
H
O
H H H H H
O O O
CH OH H OH CH OH H OH CH OH
2 2 2
8. The structure of poly(phenylethene), also known as polystyrene, is shown below.

—
— CH — CH —
2
Draw a section of the polymer showing three repeating units.
9. The structure of nylon-6,6 is shown below. Draw a section of the polymer showing two repeating units.
O O
NH (CH ) (CH ) C
2 6 2 4
210
The structure of the repeating unit originates from the monomer used to make the
polymer. As a result, some polymer names are monomer name in brackets, with
the prex poly-. However, many natural polymers have unique names that do not
refer to the monomer. Similarly, many synthetic polymers names are referred to by
their commercial brand names. C an you think of any examples?
Polymers can be classied according to their source (natural or synthetic), or type of
polymerization reaction undergone by the monomers (addition or condensation).
Some examples are shown in table 5.
Name Repeating unit Examples of Natural or Type of
uses synthetic? polymer
cis-1,4- balloons, elastic natural addition

CH CH
2 2
poly(isoprene) bands, c ar tyres
(natural rubber) (vulc anized
rubber)
H C H
3
polyethene H H c arrier bags, synthetic addition
packaging, c able
C C
insulation, toys
H H
cellulose OH cell walls, paper, natural condensation
cellophane
HO
OH
Kevlar H O sports synthetic condensation
equipment,
N N C C
personal armour
O
H
pTable 5 Examples of p o l y m e rs
Figure 16 Kev lar was f i rs t sy n t h e s i z e d by Po l i s h - A m e r i c a n
chemist Stephanie Kw o l e k . O ver 3 ,0 0 0 s av e d lives h av e been
dire ctly linked to the use of Kev lar in bulletproof vests and
anti-stab clothing. Kw o l e k remarke d, “I d o n ’t think t h e r e’s
a ny t h i n g like s av i n g s o m e o n e’s life to bring you satisfaction
and h a p p i n e s s .”
211
Properties of polymers
In general, polymers are strong, bec ause of their macromolecular nature. Like
most covalent materials, they do not contain moving charged particles, so their
thermal and electric al conductivities are also low.
Though molecular, polymers have relatively high melting points and boiling
points. This is due to the number of intermolecular forces that occur along
the length of the polymer molecules. The long polymer strands c an also wind
around each other and become entangled, requiring energy to disentangle and
separatethem.
The specic properties of a polymer depend on its chain length, the type of
forces holding the chains together, the type of monomers and the way these
monomers are arranged.
M any biologic al molecules, including proteins, c arbohydrates and nucleic acids,
are natural polymers. Some provide structure to living organisms, while others
support life processes. Starch is a natural polymer that acts as an energy store in
plants. Others include collagen, which gives our skin structure and elasticity, and
DNA, which houses an organism’s genetic information.
Cellulose is a c arbohydrate and a natural linear polymer of glucose. Plants make
glucose through photosynthesis. Cellulose is found in cell walls. It supports
brous structures such as cotton, as well as stalks and tree trunks. You c an see the
repeating unit of cellulose in table 5.
The presence of –OH groups (hydroxyl groups) in cellulose means that the
polymer chains c an form hydrogen bonds with one another. The resulting bres
are uniquely strong and insoluble in water as well as many common solvents. The
strength of cellulose makes it an important material for the structural integrity of
pFigure 17 Co tt o n , made up of
plants. Humans have taken advantage of these properties by using cellulose to
c e l l u l o s e, is a n a t u ra l polymer
make paper, textiles, and other polymer materials like cellophane.
Starch is the main energy store in plants and is also a glucose polymer, like
cellulose. However it has dierent properties: it is not as strong, so the chains c an
be broken down easily and digested by humans. The main dierence lies in the
way the monomers are connected: the polymer chains in starch have an irregular
OH branched structure. As a result, the polymer chains in starch c annot pack as
tightly as in cellulose and therefore form fewer hydrogen bonds with one another.
O
Synthetic polymers are humanmade. M any of them are petroleum-based, which
means that they are derived from crude oil. Examples include PET bottles, nylon
textiles, non-stick Teon coating on pans and synthetic rubber tyres. Semi-
OH
synthetic polymers are derived from renewable biologic al materials produced

O
HO
by plants and bacteria. These polymers provide a sustainable alternative to crude
pFigure 18 The repe ating unit of starch

oil-based polymers, and some have important biomedic al applic ations.
Practice questions
10. Explain why polymers have relatively high melting points.
11. Explain why polymers are generally electric al insulators.
212
Figure 19 This artificial t i ss u e was
c re ate d f rom a mixture of living cells and
s e m i - sy n t h e t i c p o l y m e r. T i ss u e s like this
c an be used in organ t ra n s p l a n t a t i o n
Plastics are synthetic polymers composed mainly of c arbon and hydrogen.
They are oen chemic ally unreactive, although they c an c atch re and sustain
combustion.
—
Poly(phenylethene), commonly known as polystyrene, is a widely used plastic
found in packing peanuts and food containers.
The structure of polystyrene is shown in gure 20. It is a non-polar hydroc arbon

CH — CH
2
and so it is insoluble in water. London dispersion forces (LDFs) hold the polymer
chains together. These LDFs c an be overcome by heating, so polystyrene c an

n
be melted down and reshaped easily. On cooling, new LDFs c an form between
pFigure 20 The structure of p o l ys t y r e n e
polystyrene molecules, so the polymer solidies again.
Polystyrene chains c annot rotate easily due to the bulky phenyl groups (C H ),
6 5
making it brittle. Polystyrene is a good thermal insulator, particularly in its
London dispersion forces (LDFs),
expanded form, so it is used to make coolers and insulating panels for the
and the other intermolecular forces
construction industry.
are discussed in Structure 2.2.
One of the reasons plastics are useful is that, due to their strong covalent bonds,
they are chemic ally inert and therefore durable. As a result, many plastics do
not typic ally biodegrade Biodegradation involves the breakdown of materials,
by microorganisms, into small molecules. Polymers rarely contain reactive
functional groups that could act as bacterial binding sites. In some plastics, the
polymer chains are covalently bonded together, which is known as crosslinking.
A dense covalent network formed by crosslinking provides very few entry points
for microorganisms.
Activity
Compare and contrast two of the polymers discussed in this topic.
213
Investigating hydrogels
Smart materials undergo a change in properties in Instructions
response to surrounding conditions (such as pH,
Part 1: The effect of pH variations on the hydrogel
temperature or magnetic fields). Hydrogels are smart
1. Prepare three clear shallow dishes, such as petri

materials used in a range of industrial and biomedic al
dishes, each containing one of the following:

applic ations. They are made up of crosslinked polymer
networks that c an absorb and hold water, c ausing the gel – contact lens buer solution
to swell. In this task, you will investigate the response of a

– weak acid solution
hydrogel to variations in the surrounding conditions.

– weak base solution
The hydrogel chains contain numerous c arboxyl groups. 2. Place the dishes on a white surface.
In acidic media, these –COOH groups form hydrogen

3. Place a contact lens in the rst dish and measure its
bonds with one another, c ausing the hydrogel to contract

diameter. (If it is dicult to see, it might be inside out.
(figure 21). In basic environments, they become ionized,

Reverse it and try again.)
forming c arboxylate ions, –COO . The negative charges
4. Place contact lenses in the other two dishes and note
on neighbouring c arboxylate groups repel each other,
any changes in diameter.
making the hydrogel swell.
5. Swap the contact lenses in the acidic and basic
Relevant skills solutions and observe what happens. Are the
changes reversible?
• Inquiry 1: Justify the range and quantity of
Part 2: The effect of salinity variations on the hydrogel

measurements
• Inquiry 2: Interpret qualitative and quantitative data

6. Repeat the Part 1 experiment, using these solutions
instead:
S afety
– contact lens buer solution
– distilled water
Materials
– saturated sodium chloride solution
• Commercially available soft contact lenses You c an reuse the Part 1 lenses, provided they are not
(manufactured from poly(2-hydroxyethyl damaged.
methacrylate-co-methacrylic acid))
7. Describe your results.
• Contact lens buffer solution
8. Propose a hypothesis to explain the observed results
• Sodium chloride
of the Part 2 experiment.
• Weak acid solution (for example, household vinegar)
9. Devise an experiment that you could do to test your
• Weak base solution (for example, sodium
hypothesis. Identify the independent, dependent
–3
hydrogenc arbonate 0.06 mol dm )
and control variables. What measurements would
• Distilled water
you make? Justify the range and quantity of these
• Standard laboratory equipment including petri

measurements.
dishes, beakers, pipettes and balances.
• Ruler
214
acid form base form
CO H COO
2 O
O
OH O
O
OH +
H
O
O
+
H
HO O O O
O
O
OH
O
COO
CO H
2
hydrogen bonds electrostatic repulsion
between carboxyl between carboxylate
groups cause groups causes hydrogel
hydrogel to contract to expand
pFigure 21 I n t e r c o nv e rs i o n between – CO O H groups and – CO O groups a ss o c i a t e d with the pH adjustments
Polymers and the environment
Aer reduction and reuse, recycling is the third approach for mitigating the
environmental impact of plastics. Plastic recycling poses several challenges.
The process is energy-intensive: plastic waste must be sorted and cleaned
beforehand. It then needs to be broken up and melted, which prevents some
plastic types from being recycled bec ause they release atmospheric pollutants
on heating. Unlike glass and aluminium, where the quality is largely unaected by
recycling, plastics oen deteriorate when they are recycled.

pFigure 22 D isc arde d plastics c an
end up in the oce an. The cold and dark
As a result, most plastic waste is not recycled and is instead incinerated or
oce an e nv i r o n m e n t s l ows d ow n plastic
disposed of in landlls. Much of disc arded plastic ends up in the oceans, where it
d e g ra d a t i o n
persists and poses a risk to wildlife.
Greenhouse gases are discussed

The challenge, and an area of growing interest, is designing plastic materials that
at AHL in Structure 3.2.

are durable enough to be used for a certain period of time but biodegradable
in the longer term. Work is also being done to nd ways to make existing
petroleum-based plastics more appetizing feedstock for microorganisms.
Biodegradable plastics facilitate bacterial action by having increased surface
area, shorter polymer chains, or functional groups that are attractive to bacteria
or light-sensitive. For example, plant-based hydro-biodegradable plastics
contain c arbohydrates that are broken down in a process c alled hydrolysis. C are
must be taken to dispose of them in conditions that provide enough oxygen for
bacterial action. In low oxygen environments found in landlls, decomposition
c an slow down or even produce environmentally harmful products, such as the
greenhouse gas methane.
pFigure 23 A sc anning ele ctron
m i c r o g ra p h of starch g ra n u l e s
embedded in a b i o d e g ra d a b l e plastic
c arrier bag. The starch absorbs water
and sw e l l s u p, providing gre ater surface
are a for bacterial action
215
The 12 green chemistry principles emphasize
the benets of non-hazardous chemic als and
solvents, ecient use of energy and reactants,
reduction of waste, choice of renewable materials,
use of biodegradable materials and prevention of
accidents. The philosophy of green chemistry has
been adopted by many educ ational and commercial
organisations and eventually passed into national and
internationallaws.
Plant-based biodegradable plastics, or bioplastics,
are aligned with two principles of green chemistry:
use of renewable feedstocks and designing materials
to be biodegradable. Most plastics are petroleum-
based, so their feedstock is non-renewable. The
raw materials for bioplastics are renewable, such as
maize. Even though plastic biodegradation releases
c arbon dioxide, plant-based polymers are sometimes
considered c arbon-neutral bec ause the same quantity
of c arbon dioxide is removed from the atmosphere by
the biosynthesis of monomers in plants.

pFigure 24 These bioplastic samples were made f rom
To evaluate the environmental impact of a product, household food waste such as banana peel, onion skins and even
you have to consider many factors. For example, p i n e a p p l e  c r ow n s
growing maize for plant-based plastics uses land that
could otherwise be used to grow other crops, which c an potentially c ause food shortages. Additionally, farming maize
may require fertilizers or pesticides, which have their own associated environmental implic ations.
Microplastics are very small fragments of plastic, broken down over time to sizes
Practice questions
under 5 mm. This process is not the same as biodegradation bec ause the plastics
12. Outline two challenges

remain chemic ally unchanged. Bec ause of their size, they c an enter the food
associated with recycling plastic

chain and nd their way into unexpected places. In 2022, microplastics of PET,
waste.
polystyrene and polyethene were discovered in human blood for the rst time.
13. Outline two structural features of Their health impact of microplastics is still unknown.
biodegradable plastics.
Figure 25 Ele ctron m i c r o g ra p h s h ow i n g
mic roplastic polyethene particles, k n ow n
as mic robe ads, on a single re d blood cell.
Mic robe ads are sometimes added to he alth
and be auty products, but this use is n ow
banned in m a ny countries
216
Addition polymers (Structure 2.4.5)
During polymerization, monomers combine together to form a polymer. One
way this c an happen is addition polymerization, which involves monomers that
contain a double bond. The double bond breaks and the two electrons form a
covalent bond with another monomer. Bec ause of the change in bond order, and
due to their extraordinary length, polymer molecules have quite dierent physic al
and chemic al properties than their corresponding monomers.
Ethene, C H , is the simplest alkene. It polymerizes to form polyethene. Consider

2 4
two ethene monomers:
H H H H
C C C C
1 2 3 4
H H
H H
The electrons in their double bonds open up…
H H H H
1 2 3 4
H H H H
… and these electrons are shared between c arbon-2 and c arbon-3 to form a
single bond, joining the monomers together:
H H H H
1 2 3 4
H H H H
Now imagine a similar process that involves a very large number of ethene
monomers:
H
H
H H
H
H
H
H
H
H H H
H H H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C
H H H H H H H H H H H H H H H H
217
We c an simplify the equation for the addition polymerization reaction using n to
convey that there are a very large number of monomers:
H H
H H
H
H
H H
n
We c an also use condensed structural formulas:
n H CH CH
2 2 2 2
Any monomer that contains a c arbon–c arbon double bond c an undergo addition
polymerization. Polyvinyl chloride, PVC, is a polymer made from chloroethene
molecules. Its IUPAC name is poly(chloroethene). Every other c arbon in the
resulting polymer has a chlorine substituent. The c arbon–chlorine bond is polar,
which results in dipole–dipole forces between the polymer chains, unlike in
non-polar polyethene where only London dispersion forces are present. PVC is
therefore the stronger of the two polymers.
(a) Cl (b) CH
H H
3
H Cl H CH
3
n n
H H
H H
H H H H
n n
pFigure 26 Ad d i t i o n polymerization re actions to form (a) p o l y (c h l o r o e t h e n e) and ( b) polypropene
TOK
Structure 2.4 illustrates the dierence between science and technology, and
the changing relationship between these two disciplines over time. Science is
concerned with observing and understanding the physic al and natural world.
The focus in technology is the practic al applic ation of scientic knowledge.
In the past, technologic al developments preceded scientic knowledge.
People used and developed materials for centuries before understanding the
underlying reasons behind the materials’ observable properties. Empiric al
observation of early technologies contributed to scientic understanding of
how and why they worked. Nowadays, the scientic research oen occurs
rst. Desirable properties for a particular applic ation are identied, and then
the required materials are engineered using scientic knowledge.
What is the role of empiric al observation in science and technology?
218
Practice questions
14. For each of the following monomers:
i. draw a section of the polymer containing three repeating units
ii. deduce the structure of the repeating unit of the polymer.
a. tetrauoroethene
F F
F F
b. acrylonitrile (prop-2-enenitrile)
H CN
C C
H H
c. but-2-ene
H H H H
—
—
H — C — C = C — C — H
—
H H
15. For each of the polymer sections shown:
i. deduce the structure of the repeating unit
ii. draw the structure of the monomer.
a.
CH CH CH CH
3 3 3 3
−
… …
− CH − CH − CH − CH− CH − CH− CH − CH −
2 2 2 2
b.
H H CH H C
3
Linking questions
C C C C What functional groups in
molecules c an enable them to
act as monomers for addition
H CH H H CH
3 3
reactions? (Structure 3.2)

C
Why is the atom economy 100%

3
for an addition polymerization
16. Compare and contrast ethene and polyethene in terms of their structure,
bonding, melting point and electric al conductivity.
219
LHA
Condensation polymers (Structure 2.4.6)
Condensation polymers, which include nylon and cellulose, are produced in a
reaction between monomers that have reactive functional groups on either end.
For every bond formed between two monomers, a small molecule is released (for
instance, water or HCl).
Figure 27 Slacklining is a p ra c t i c e
in balance that typic ally uses ny l o n
webbing tensioned between two anchor
points. Nylon is a condensation polymer
Esters are formed in a condensation reaction between an alcohol and
a c arboxylic acid (gure 28). In this reaction, the hydroxyl and c arboxyl
functional groups form an ester linkage, and a water molecule is released. This
condensation reaction is known as esteric ation
H O H H H O H H
−
conc. H SO
2 4
H−C−C−O−H + H−O−C−C−H H−C−C−O−C−C−H + H−O
−
−
heat
H O lost
2
H H H H H H H
ethanoic acid ethanol ethyl ethanoate water
pFigure 28 E t hy l e t h a n o a t e, an e s t e r, is formed in the condensation re action between ethanoic acid
and ethanol
The reactions used to make condensation polymers are similar to esteric ation:
The structure and properties of
two functional groups react to form a linkage, and a small molecule is released.
esters are discussed further in
However, in polymerization, the reacting monomers have two reactive functional
Structure 3.2.
groups, one at each end of the molecule, which allows a polymer chain to form.
We will look at two examples of how this c an happen.
220
Condensation between two dierent monomers
One monomer with the same functional group at either end c an react with
another monomer with a dierent functional group at either end. This creates
a polymer of alternating monomer structure: for example, if monomer A reacts
with monomer B, a polymer with the pattern ABABABAB is formed. The general
reaction between a dic arboxylic acid monomer and difunctional alcohol (diol)
monomer to form an ester linkage is shown in gure 29.
Figure 29 A condensation
O O
=
re action between two m o n o m e rs
HO − C C − OH H O− −
OH
to form an ester
Dic arboxylic acid Alcohol (diol)
O O
=
− − − − +
HO C C O OH H O
2
Ester linkage
LHA
The product molecule in gure 29 has two reactive ends that c an subsequently
react with more monomers (gure 30). This forms a long polymer chain with
an alternating pattern based on each monomer structure, with each monomer
joined by an ester linkage. The resulting polymer product is c alled a polyester.
Figure 30 A g e n e ra l i z e d condensation
O O
=
re action to make a p o l y e s t e r, where n is
− − + − −
n HO C C OH n H O OH
the number of monomer p a i rs i nv o l v e d and
the length of the resulting polymer chain
O O
=
− + 2n H O
−
C
− C− O− −
O
−
2
The polymer nylon-6,6 is produced in the condensation re action between
hexanedioic acid and hexane-1,6-diamine (gure 31). The product is known as a
poly amide due to the multiple amide linkages formed during the condensation
process.
−
−
=
=
−
O
=
O
=
H H
O H H O
N − (CH ) − N C − (CH ) − C N − (CH ) − N C − (CH ) − C

2 6 2 4 2 6 2 4
−
−
−
H H HO HO H H HO HO
−
H H H H
…
N − (CH ) − N (CH ) N − (CH ) − N (CH )
−
2 6 2 4 2 6 2 4
−
−
−
…
C C C C
=
O O O O
+ H O + H O + H O + H O
2 2 2 2
pFigure 31 The formation of ny l o n - 6 , 6 . The repe ating unit is s h ow n in gre en
221
LHA
Condensation of the same monomer
If there is a dierent functional group on each end of a monomer, then it c an
polymerize with itself by condensation. For example, 3-hydroxypentanoic
OH O
acid (gure 32) contains both a hydroxyl group and a c arboxyl group. Multiple
monomers of 3-hydroxypentanoic acid c an react with one another to form
apolymer.
OH
CH Proteins are biopolymers that play a central role in metabolic processes, transport
3
and sensory functions, structural integrity, and virtually all other molecular aspects
pFigure 32 The structure of the

of life. Proteins are polypeptides, which are polymers made up of monomers
3 - hy d r ox y p e n t a n o i c acid monomer
c alled 2-amino acids. There are 20 types of 2-amino acids used by living
organisms as building blocks of proteins. 2-amino acids have an –NH group

2
and a –COOH group, so they c an form amide linkages with each other through
condensation polymerization. In a polypeptide, the amide link is also known as a
peptide bond:
O
Figure 33 The formation of a

NH
NH
2
2
polypeptide chain
R C H
R C H 1
1
COOH
H O
2
H N
NH
2
C H C H
R R
2 2
COOH
H O
2
NH H N
2
C H C H
R R
3 3
COOH
H O
2
NH
2
C H C H
R R
4 4
COOH
H O
2
NH H N
2
C H C H
R R
5 5
COOH
H O
2
NH H N
2
C H
R C H
R
6 6
COOH COOH
amino acid molecules
polypeptide
(where R , R , R etc. represent
1 2 3
(part of)
any of the 20 or so groups
found in naturally occurring amino
acids)
222
LHA
Activity
Figure 34 shows the 3D structure of lysozyme, the natural antibacterial enzyme
contained in saliva, milk, mucus, tears and egg whites. The carbon atoms are
shown as white, the oxygen atoms are red and the nitrogen atoms are blue.
C an you nd any amide linkages?
pFigure 34 The 3D structure of l ys oz y m e
Practice questions
17. Draw the repeating unit of a condensation polymer made from
3-hydroxypentanoic acid (gure 32).
18. Outline two dierences between addition and condensation
polymerization.
19. Identify the type of polymer made and the small molecule released when
monomers containing these functional groups form polymers:
a. A hydroxyl group, –OH, and a c arboxyl group, –COOH
b. A c arboxyl group, –COOH, and an amino group, –NH

2
c. Two hydroxyl groups, –OH
d. An acyl chloride group, –COCl, and an amino group, NH

2
223
LHA
Hydrolysis
The reverse of condensation reactions is c alled hydrolysis, where the linkage
formed by condensation is split up by a molecule of water. All biologic al
macromolecules form by condensation reactions and break down by hydrolysis.
Figure 35 shows how monosaccharides are polymerized via condensation and
formed again by the reverse hydrolysis reaction. Note the two reactive ends of
monosaccharides are hydroxyl groups, which form polymers with a glycosidic
linkage. Polysaccharides make up c arbohydrates, which are used as energy
sources and energy reserves in living organisms.
CH OH CH OH
2 2
monosaccharides
e.g., glucose, fructose,
galactose
condensation hydrolysis
H O
2
(water removed) (water added)
CH OH CH OH
2 2
O O
H H
disaccharide
e.g., maltose, sucrose,
O
HO OH
lactose
glycosidic
bond
condensation hydrolysis
CH OH CH OH CH OH CH OH
2 2 2 2
O O O O
H H
polysaccharide
e.g., starch, glycogen
O O O
HO OH
pFigure 35 Condens ation and hy d r o l ys i s of monosaccharides, the p o l y m e rs that make up
c a r b o hy d ra t e s . Some —OH groups are o m i tt e d for clarity
Evidence
Water is oen referred to as the ‘molecule of life’ due to its vital role in
biologic al reactions. For this reason, NASA scientists have been searching
for water on M ars, as the presence of water is thought to be required for life
forms to exist.
Linking question
What functional groups in molecules c an enable them to act as monomers for
condensation reactions? (Structure 3.2)
224
LHA
6. Which of the following pairs of molecules will not
Topic review
react to form a polymer?

A.
OH O OH O
and
What role do bonding and structure have in the design
OH OH
ofmaterials?
CH CH
3 3
B.
H H
(CH )
2 6
2. C alculate the mean electronegativity, χ, and
H H
electronegativity dierence, ∆χ, for the bonds found in
lead(II) bromide, PbBr . and

2
O
O
 χ (Pb) = 1.8 and χ (Br) = 3.0.
(CH )
2 4
Mean Electronegativity
electronegativity, χ dierence, ∆χ
HO OH
A 4.2 2.6
C.
H
B 2.6 4.2
C 2.4 1.2
H N C COOH
2
D 1.2 2.4
CH
2
3. Which of the following substances has properties of
both ionic and covalent compounds? Refer to the
triangular bonding diagram and the electronegativity
values below.
Element Na K Cs F Zn S Ag Br
and
Electronegativity 0.9 0.8 0.8 4.0 1.6 2.6 1.9 3.0
A. NaK, a sodium-potassium alloy
B. C aesium uoride, C sF
H N C COOH
2
C. Zinc sulde, ZnS
CH
2
D. Bromine, Br
2
4. Which of the following mixtures is an alloy?

SH
A. sodium chloride and water
D. O
H H H
B. iron and vanadium
C. c arbon bre and a polymer

H C C H and H C
D. magnesium and chlorine
H H H
5. Which of these substances does not have the ability to
polymerize?
A. ethane, CH CH
3 3
B. tetrauoroethene, CF CF
2 2
C. propene, CH CHCH
2 3
D. propenenitrile, CH CHCN 225

2
7. Tin(II) chloride has a melting point of 247 °C while 10. Chloroethene c an react to form a polymer known as
lead(II) chloride has a melting point of 500 °C. Both are poly(chloroethene). The structure of chloroethene is
used in the production of aurene glass, an iridescent shown below.
artisan glassware. One of these two substances exists
H H
—
as discrete molecules in the vapour phase. Using
C= C
electronegativity tables and the triangular bonding
—
diagram, identify that substance and explain your
H Cl
reasoning. [3]
a. Identify the structural feature of chloroethene
8. Aluminium chloride, AlCl , forms white crystals with a

3
thatallows it to form a polymer. [1]
low melting point and boiling point.
b. State the name of this type of polymerization. [1]
a. i. C alculate the mean electronegativity and
c. Draw the repeating unit of the polymer. [2]

electronegativity dierence values for
aluminium chloride. [2]

The mean molecular mass of the polymer chains
in a sample of poly(chloroethene) is found to be

ii. Explain, with reference to the triangular
–1
69,000 g mol
bonding diagram, why aluminium chloride
displays characteristics of both covalent and
d. Deduce the mean number of repeating units
ionic substances. [1]
per polymer chain. State your answer to two
signic antgures. [2]

b. Draw the Lewis formula for aluminium chloride. [2]
e. The melting point of chloroethene is –154 °C,

c. Using your knowledge of VSEPR theory, deduce
whereas the melting point of poly(chloroethene)

the molecular geometry and bond angle of
is around 210 °C. Explain this dierence in

aluminium chloride. [2]
melting points. [2]
d. Aluminium chloride is oen found as the dimer
Al Cl . 11. Polylactic acid (PLA) is a bioplastic made from

2 6
renewable feedstocks such as sugarc ane and maize.
Cl Cl
It is broken down by microorganisms under high
Al
temperature and high humidity conditions.
Cl Cl
Al
nHO CH C OH
Cl Cl
CH
3
i. The dimer contains
two coordination bonds.

2-hydroxypropanoic (lactic) acid
Outline the meaning
of the term
coordination bond. [1]
ii. Determine the formal charges

LHA
O
of the atoms inthe aluminium
chloride dimer above. [2]

O + nH O
CH C 2
9. Explain why alloys are generally stronger than pure
CH
3
n
metals. Include a diagram in your answer. [3]
polylactic acid (PLA)
a. Deduce why PLA is more susceptible to bacterial
action than petroleum-based plastics such as
poly(propene). [2]
b. Outline two advantages and two disadvantages
of bioplastics such as PLA. [4]
226
LHA
LHA
12. Kevlar is a high tensile-strength polymer rst 13. The repeating units of polymers A and B are
synthesized in 1964 by chemist Stephanie Kwolek. shownbelow.
The structure of Kevlar is shown below.
… −
= O
C
−
CH — CH
2
n
−
polymer A
−
H
= C −
O N
−
H H H O H H O
C C C O C C C C O
−
−
N = O
− H H H H H
n
H C
−
polymer B
−
a. For each polymer, state whether it is an addition
−
H
= C −
or condensation polymer. [1]
O N
−
b. For each polymer, deduce and draw the structural
formulas of its monomer(s). [3]

−
14. Two condensation monomers are shown below:
−
N
−
…
H
O O
a. Identify the amide linkage in Kevlar. [1]

C C H N NH
2 2
b. Draw the structural formulas of the monomers

Cl Cl
from which Kevlar is made. [2]
a. Draw the repeating unit of the resulting polymer. [2]
c. State the formula of the other compound produced
b. Deduce the formula of the inorganic product

when Kevlar monomers polymerize and state the
formed in the polymerization process. [1]

name of this type of polymerization. [2]
d. Kevlar chains are attracted to one another through
hydrogen bonding. Identify which features of Kevlar
allow hydrogen bonding to occur. [1]
e. Draw a diagram showing hydrogen bonds
between two adjacent Kevlar polymer chains. [2]
227
Structure 3
C l a ss i f i c a t i o n of m a tt e r
Structure 3.1 The periodic table:
Classication of elements
How does the periodic table help us to predict patterns and trends in the properties of elements?
One of the ways we c an classify matter is based on what The increase and decrease of certain properties closely
we use it for. For example, motor oils c an be classied correlates with the position of elements across the periods
according to their viscosity, bec ause they are used for or down the groups of the periodic table. These patterns
dierent purposes depending on how thick they are. So, and trends in the periodic table c an be described visually
how c an we classify the elements? with graphs.
Understandings
Structure 3.1.1 — The periodic table consists of periods,
LHA
Structure 3.1.7 — Discontinuities occur in the trend of
groups and blocks.
increasing rst ionization energy across a period.
Structure 3.1.2 — The period number shows the outer
Structure 3.1.8 — Transition elements have incomplete
energy level that is occupied by electrons. Elements in a
d-sublevels that give them characteristic properties.
group have a common number of valence electrons.
Structure 3.1.9 — The formation of variable oxidation
Structure 3.1.3 — Periodicity refers to trends in properties
states in transition elements c an be explained by the
of elements across a period and down a group.
fact that their successive ionization energies are close
Structure 3.1.4 — Trends in properties of elements down a

in value.
group include the increasing metallic character of group 1
Structure 3.1.10 — Transition element complexes are
elements and decreasing non-metallic character of group
coloured due to the absorption of light when an electron
17 elements.
is promoted between the orbitals in the split d-sublevels.
Structure 3.1.5 — Metallic and non-metallic properties

The colour absorbed is complementary to the colour
show a continuum. This includes the trend from basic

observed.
metal oxides through amphoteric to acidic non-metal
oxides.
Structure 3.1.6 — The oxidation state is a number
assigned to an atom to show the number of electrons
transferred in forming a bond. It is the charge that atom
would have if the compound were composed of ions.
Periods, groups and blocks in the periodic
table (Structure 3.1.1 and Structure 3.1.2)
The periodic table consists of horizontal periods and vertical groups. The
periodic table is also divided into four blocks: s, p, d and f. Elements are
organized into these blocks according to the arrangement of their outermost
valence electrons. For example, elements in groups 1 and 2 have their outermost
valence electrons in the s sublevel, so these are in the s-block. The blocks are
shown in gure 1 on the next page.
We c an also classify elements in the periodic table as metals, non-metals and
You c an nd a detailed version of
metalloids. Metals generally have three or fewer valence electrons, which are
the periodic table at the back of
deloc alized and thus contribute to metallic bonding ( Structure 2.3). Non-metals
this book.
usually have four or more valence electrons which are not deloc alized.
229
Structure 3 Classic ation of matter
s-block
1 18
transition elements
1s 1s
2 13 14 15 16 17
2s 2p
d-block
3s 3p
3 4 5 6 7 8 9 10 11 12
4s 3d 4p
5s 4d
6s 5d 6p
7s 6d 7p
4f
f-block
5f
Figure 1 The s, p, d and f blocks of the periodic table
Metalloids show hybrid metallic and non-metallic behaviour. They c an form both
Group
Group name
ionic and covalent bonds. Elements considered to be metalloids are usually
number(s)
directly either side of the red zig-zag in gure 1. Metals are to the le of the
1 alkali metals
metalloids, and non-metals are on the right.
transition
3 – 11
Groups in the periodic table are numbered from 1 to 18. Elements in some
elements
groups are given a collective name, which are summarized in table 1.
17 halogens
18 noble gases Periods are numbered from 1 to 7. The period number corresponds to the
principal quantum number, n, of the outermost electron sublevels for elements
Table 1 Names of groups in the periodic
in this period. For example, elements in period 2 have n = 2, and their valence
table
electrons are found in the 2s or 2p sublevels.
Elements in the same group all have the same number of valence electrons. For
groups 1 and 2, the group number is equal to the number of valence electrons.
For example, elements in group 1, the alkali metals, all have one electron in their
valence sublevel. For groups 13 to 18, the last digit of the group number is equal
to the number of valence electrons. For example, elements in group 15 all have
ve valence electrons.
You c an use this information to deduce the electron congurations of elements.
This is straightforward for periods 2 and 3. Consider phosphorus: being in period
3 means that n = 3 for the valence sublevels, and being in group 15 means that
it has ve electrons in these sublevels. You c an use the symbol of the previous
noble gas to represent the inner electrons to give the condensed electron
conguration:
2 3
[Ne] 3s 3p
230
Structure 3.1 The periodic table: Classic ation of elements
With period 4, we need to take the 3d sublevel into account, which lls aer the
Remember that s, p, d and f
4s sublevel and before the 4p sublevel. The group number is equal to the total
sublevels all have a dierent
number of electrons occupying the 4s, 3d and 4p sublevels. Consider bromine:
maximum number of electrons.
being in group 17 means that 17 electrons ll the outer sublevels. Two go into 4s,
Detailed guidance on how to ll
ten go into 3d and the remaining ve go into 4p, so the electron conguration of
sublevels with electrons is given in

2 10 5
bromine is [Ar] 4s 3d 4p
Structure1.3
Patterns and trends
Imagine trying to learn chemistry without the periodic group 17 or a dierent loc ation altogether? A second
table. How many concepts are connected to this universal example is the ongoing discussion about which elements
way of organizing the elements? How oen do you refer belong to group 3: is it Sc, Y, La and Ac, or Sc, Y, Lu and
to it during a typic al chemistry lesson? Lr? Where in the periodic table do you think hydrogen
should be? Do you think it matters? What is the purpose of

Classifying things and exploring their similarities,
classic ation?
dierences and trends helps us to better understand
them. Without knowing the order and patterns depicted
in the periodic table, remembering and understanding
the properties of all the known elements would be very
dicult. By the mid to late 19th century, chemists had long
been classifying elements according to their properties.
Some had also put them in order of atomic mass and
found certain patterns. Russian chemist Dmitri Mendeleev
developed an early version of the periodic system based
on atomic masses of elements, which eventually led to the
periodic table as we know it today.
Organizing the elements like this not only helped
scientists understand the properties of the elements
known at the time, but the presence of gaps in
Mendeleev’s table also signalled the possible existence of
other undiscovered elements. G allium, for example, was
not known to Mendeleev, but he had assigned an element
with atomic mass of around 68 (near the scribbles at the
centre of gure 2) and predicted some of its properties.
When gallium was discovered, many of these properties
were close to Mendeleev’s predictions.
Classic ation of the elements is not always clear-cut.
For example, you may have questioned the loc ation of

Figure 2 Some of Mendeleev’s notes leading up to his 1869
hydrogen in the periodic table. Does it belong to group 1, periodic system
Linking question
Activity
For the element positions described in a, b and c, use the periodic table at How has the organization of
the back of this book to deduce the following information: elements in the periodic table
facilitated the discovery of new

i. name of the element
elements? (Structure 1.2)

ii. name of the group
iii. principal quantum number
iv. full electron conguration
v. condensed electron conguration
a. period 2, group 16 b. period 3, group 2 c. period 4, group 8
231
Periodicity: Trends in the periodic table
(Structure 3.1.3)
Elements are organized in the periodic table according to their electron
structure. As a result, you c an observe trends in the periodic table, which helps
you to make predictions about the chemic al reactivity of elements. The study
of trends in the periodic table is known as periodicity. Trends are observed
for various properties going across periods and down groups, such as atomic
radius, ionic radius, ionization energy, electron anity and electronegativity.
You c an graph these trends using the values for each property from sections 9
and 10 of the data booklet.
Atomic radius
Figure 3 shows the atomic radii of atoms with increasing atomic number.
250
200
m
21
01 / suidar
150
100
c i m ot a
50
0 10 20 30 40 50 60
atomic number
Figure 3 Plot of the atomic radius against atomic number. The alkali metals have data points highlighted in
red, the noble gases in blue, and the halogens in green
From the start to the end of each period (from red to blue), the atomic radius
decreases. This is bec ause each successive element has an additional proton,
and so a higher nuclear charge. The increased nuclear charge going across a
period means that there is greater attraction between the valence electrons and
the nucleus, c ausing the radius to become smaller with each additional proton.
As the electrons are added to the same energy level going across the period,
there is no increase in shielding by the inner electrons.
The atomic radius generally increases going down a group in the periodic table.
This is shown in gure 3 for the alkali metals (red dots). Although the number of
protons increases, and therefore the nuclear charge also increases, the valence
electrons are added to a higher energy level. This results in the outermost
electrons being shielded from the attractive electrostatic force of the nucleus by a
greater number of inner levels of electrons.
232
The diminished electrostatic force experienced by a shielded valence electron is
known as the eective nuclear charge, Z .

e
positively charged nucleus
valence electron
electrons between the
valence electron and
nucleus shield some of
the positive nuclear charge
Figure 4 The concept of eective nuclear charge based on electron shielding
Ionic radius
Ions with a positive charge are c alled c ations. To form a c ation, an atom loses
one or more of its valence electrons, resulting in more protons than electrons.
Therefore, the eective nuclear charge is greater for c ations, and the ionic radius
is smaller than the atomic radius. This eect increases with the charge magnitude,
so larger positive charges lead to smaller radii.
Groups 1, 2 and 13 tend to form c ations, with the charge equal to the number of
valence electrons. Therefore, these ions have noble gas electron congurations.
Similar to atomic radius, ionic radius decreases going from group 1 to group 2,
and from group 2 to group 13, as the nuclear charge increases. For example, Na
+ +
2 3
is larger than Mg , which is in turn larger than Al
Ions with a negative charge are c alled anions. To form an anion, an atom gains
electrons to ll its valence sublevel, resulting in more electrons than protons. The
force of attraction between the nucleus and these additional electrons is smaller,
and the ionic radius is greater than the atomic radius. The greater the magnitude
of negative charge, the larger the ionic radius.
Groups 15, 16 and 17 tend to form anions with the charge equal to the number of
valence electrons minus eight. Ionic radius decreases from group 15 to group 17,
3 2
as the nuclear charge increases. For example, N is larger than O , which in turn
is larger than F .
However, going down a group, ionic radius increases for both c ations and anions
due to the increasing number of electron energy levels and increased shielding
of the nucleus. This is similar to the trend for atomic radius.
233
Figure 5 shows atomic and ionic radii for c ations and anions.
+
Li +
2
Be
Li Be F F
45
76
60
99
130 133
+ +
2
Na Mg
+
3
Al
Na Mg Al Cl Cl
54
72
102 100
124
140
160 181
+
2
+ Ca
K
Data-based question
Ca Br Br
100
117
Use the values from the data booklet
138 196
174
to plot a graph of the ionic radii for 200
the period 2 and period 3 elements

I
I
12
values in 10 m
against their atomic number. Try to
136
explain the trends in your graph.
220
Figure 5 R adii of c ations are smaller than those of the parent atoms. R adii of anions are
larger than those of the parent atoms
+
2
Isoelectronic species have the same electron conguration. For example, Mg ,
+
2 2 2 6
Na , Ne, F and O all have the conguration 1s 2s 2p . Bec ause they are
formed from dierent elements, with a dierent number of protons, their size
varies depending on the ratio of protons to electrons (gure 6).
2 + 2+
O F Ne Na Mg
2 2 6
Figure 6 All of these species have the same electron conguration, 1s 2s 2p ,
but dierent sizes
Ionization energy
As discussed in Structure 1.3 (AHL ), ionization energy (IE) is the minimum energy
required to eject an electron out of a neutral atom or molecule in itsground state.
X(g) + IE → X (g) + e
The rst ionization energy (IE ) generally decreases down the groups of the
1
periodic table. This is bec ause the number of energy levels increases and the
shielding eect becomes greater, so less energy is required to ionize atoms.
Going across a period, the number of protons in the nucleus increases, so the
outermost electrons are held closer to the nucleus by the increased nuclear
charge. At the same time, the shielding eect remains nearly constant because the
number of inner electrons does not change. Therefore, more energy is required to
There are some discontinuities in
remove outermost electrons, so ionization energy increases across a period.

the trend of increasing ionization
energy across a period, which are
The general trend of decreasing ionization energy down a group and increasing
discussed in Structure 3.1.7 (AHL ).
across a period is shown in gure 7.
234
2500
He
Ne
1
2000
lo
  grene
Ar
1500
N
Kr
O Xe
H
n o it a  i n o i
1000
Be
B
tsrfi
500 Al
Li
Na
K Rb
2 10 18 36 54
atoi nber
Figure 7 Plot of rst ionization energy against atomic number for the elements from hydrogen to xenon
Electron anity
Electron anity (EA) is the energy released when an additional electron is
attached to a neutral atom or molecule.
X(g) + e → X (g) + EA
The more favourable this reaction is for a given element, the higher the electron
anity. The trend for rst electron anity (EA) in the periodic table going across
a period is similar to that of ionization energy: the nuclear charge increases and
so more energy is released when an electron is added. The general trend of
increasing electron anity across a period is shown in gure 8.
350 Cl
F
Br
300
1–
lo
250
k / ytiniffa
200
150
nortcele
O
Si
100
Li
Na P
50
Al
0 5 10 15 20 25 30 35 40
atoic ner
Figure 8 Plot of rst electron anity against atomic number for the elements from hydrogen to krypton
235
Going down a group, you would predict that less energy is released when an
TOK
atom gains an electron due to the increased shielding of the nucleus. However,
the data in gure 8 does not show a clear trend: this is true for group 1 elements,
US chemist Linus Pauling

but not for the other groups.
introduced the denition of
electronegativity described For some elements, adding an electron to an atom results in a less stable electron
here. Pauling was also the rst conguration, which will reduce the energy released. This explains the drop in
person to win Nobel Prizes in two electron anity between silicon and phosphorus, as phosphorus has a half-lled
dierent c ategories. In 1954, he 3p sublevel.
was awarded the Nobel Prize in
We do not always have accurate data for an element's electron anity. This is
Chemistry for his work on chemic al
usually the c ase in elements with full or half-lled sublevels, such as beryllium,
bonding and structure. Eight years
nitrogen, magnesium, manganese, zinc and the noble gases, where the process
later, he won the Nobel Peace Prize
of adding an electron is not favourable.
for his opposition to weapons of
mass destruction.
What role c an scientists play in the

Electronegativity
promotion of peace in the world
As dened in Structure 2.2, electronegativity is a measure of an atom’s ability to
today?
attract electrons from a chemic al bond to itself. Electronegativity decreases down
What are the ethic al responsibilities

a group, and increases across a period. This is bec ause smaller atoms with nearly
of scientists?
complete valence shells will attract electrons more easily than larger atoms with
fewer valence electrons.
Figure 9 shows a summary of the periodic trends discussed.
ionization energy
electronegativity
ygrene noitazinoi
suidar cimota
ytivitagenortcele
atomic radius
electron affinity
Figure 9 The direction of the arrow indic ates the direction of increasing value for each property
236
Activity
Identify the element with the greatest value for each property. The rst column has been done for you.
Property Strontium or iodine Mg or Ca C or Si Li or F Ba or Cl K or Br C or Pb C s or F
atomic radius Sr
ionic radius I
electron anity I
ionization energy I
electronegativity I
Periodic trends in atomic volume
In this task, you will follow some of the work done by Julius 3. C alculate the volume of a single atom of the other
Lothar Meyer, who explored the periodicity of the known elements by copying and pasting the formula down
chemic al elements in the 18th century. the column.
Relevant skills
4. C alculate the atomic volume of hydrogen. Atomic
volume is the volume taken up by one mole of an

3 1
element, in m mol . Again, copy and paste the
• Tool 2: Represent data in graphic al form

formula down the column to obtain data for the other
elements.
• Tool 3: Use and interpret scientific notation
5. Plot a graph of atomic volume vs atomic mass.

• Tool 3: Apply and use SI prefixes and units
6. Discuss the features of the graph that illustrate the

• Inquiry 2: Identify, describe and explain patterns,
phenomenon of periodicity.
trends and relationships
7. At the time, chemists described the pattern of similar

Method
properties every eighth element as the law of octaves.
1. In a spreadsheet, collect atomic mass and atomic

To what extent does the pattern in your graph support
radius data for the elements from hydrogen to

the law of octaves?
strontium (see example of table format below).
8. Are there any elements that do not fit the general
2. C alculate the volume of a single hydrogen atom,

trend?
using the equation for the volume of a sphere.
A B   E  
Atomic
Atomic Volume of a
volume
Atomic Atomic radius Atomic single atom
3 1
12 3
/m mol
number mass /×10 m radius/m /m
2 H 1
4 Li 3
237
TOK
You have now learnt about various interconnected Because uorine atoms have a higher nuclear charge than
concepts in DP chemistry that c an be used to construct carbon atoms, and both types of atoms have the same
explanations. It c an be interesting to see how far back you number of energy levels.
c an keep asking ‘why’. For example:

Why?
The C—F bond is highly polar.

Because uorine atoms contain nine protons each,
Why? whereas carbon atoms contain six. Fluorine and carbon
atoms have two electrons in the rst energy level, and their
Because the electrons in the bond are not distributed
valence electrons are in the second energy level.

equally between the two atoms.
Why?
Why?
Because the rst energy level holds up to two electrons.

Because the dierence in electronegativity is large.
Why?
Why?
Because the rst energy level only has one orbital.

Because uorine is more electronegative than carbon.
And so on. How did you acquire the knowledge that

Why?
you use to build explanations such as this? What makes a

Because uorine has a stronger tendency to attract a
good explanation?
bonded pair of electrons towards itself than carbon.
Think about the “explain” questions in your IB

Why?
examinations. How c an you know how detailed your
Because uorine has a smaller atomic radius than carbon.
explanations should be?
Why?
Metallic character and periodicity
(Structure 3.1.4)
Metallic character is not a quantitative property, that is, we do not assign a
value to it. However, the metallic character of an element is closely linked to
its ionization energy. Elements with high metallic character have deloc alized
electrons in their structure. Therefore, elements with lower ionization energies
are more likely to be metallic.
For example, the group 1 elements, known as the alkali metals, have decreasing
ionization energy and increasing metallic character going down the group. This
means that they are also more reactive going down the group, as they have a
greater tendency to donate their single valence electron in chemic al reactions.
The group 17 elements are known as the halogens. We describe the halogens
in terms of their non-metallic character — this property is the opposite to metallic
character and is linked to electronegativity. The non-metallic character and
electronegativity of the halogens decrease going down the group. Halogens
higher up the group are therefore more reactive, as they have a greater tendency
to accept an electron in chemic al reactions and ll their valence sublevel.
We c an illustrate these trends in the alkali metals and the halogens by looking at
some typic al chemic al reactions.
238
Reactions of alkali metals with water
A Brønsted–Lowry acid is a substance that donates protons, H . A Brønsted–
+ Brønsted–Lowry acids and bases,
Lowry base is a substance that accepts protons, H . The alkali metals all form
and the distinction between
aqueous Brønsted–Lowry bases when reacted with water. The general equation
alkaline and basic substances are
for the reaction of a group 1 metal with water is as follows:
covered in Reactivity 3.1.
M(s) + H O(l) → H (g) + MOH(aq)

2 2
For example, lithium reacts with water as follows:
Li(s) + H O(l) → H (g) + LiOH(aq)

2 2
Ionization energy decreases and the metallic character of the alkali metals increases
going down the group. As a result, reactivity increases and the reactions of alkali
metals with water occur faster and more vigorously going down the group.
Reactions of halide ions with halogens
Elemental halogens react with other species to gain electrons, and to achieve
a complete octet, becoming anions. The electronegativity and non-metallic
character of the halogens decrease going down the group, and hence their
Figure 10 Elemental sodium metal
reactivity also decreases going down the group.
reacts vigorously with water. This eect
increases going down group 1
We c an illustrate the reactivity of the halogens by looking at the reactions
between elemental halogens and the anions of other halogens. When elemental
uorine reacts with a chloride ion, elemental uorine gains an electron, forming a
uoride ion and elemental chlorine as follows:
In this reaction, chloride loses

1 1
F + Cl → F + Cl
2 2
electrons (undergoes oxidation)
2 2
and uorine gains electrons
The reverse reaction will not happen, however: chlorine c annot oxidize uoride
(undergoes reduction). Oxidation
ions. This is bec ause uorine is more electronegative than chlorine, so the
and reduction are discussed in
reaction is not favourable.
Reactivity 3.2.
The greater the electronegativity dierence between the two reacting species, the
more readily the reaction occurs. Hence, F will react faster with I than with Cl .
2
This is also the case for the reactions between halogens and alkali metals: F reacts
2
faster with K than with Li. The equation for the former reaction is shown below:
1
+
F + K → K + F
2
Activity
Complete the table to show which reactions c an occur between halogen species.
The rst row has been done for you.
F Cl Br I
F No reaction F + 2Cl → 2F + Cl F + 2Br → 2F + Br F + 2I → 2F + I

2 2 2 2 2 2 2
Cl No reaction
2
Br No reaction
2
I No reaction
2
239
Practice questions
1. Write the word and symbol equations for the reaction 3. Identify the most reactive pair of reactants in a to d
between potassium and water.

a. Li + I or Li + F
2 2
2. List the alkali metals from the most reactive to the least
b. Ba + I or Ba + Cl
2 2
reactive, in terms of their reactions with water.

c. K + Cl or Li + Cl
2 2
d. F + KCl or F + KI
2 2
Linking question ATL Thinking skills
The modern periodic table is a very useful way of organizing the elements.
Why are simulations and online
Conduct an online search for alternative representations of the periodic table.

reactions often used in exploring
An example is shown in gure 11.

the trends in chemic al reactivity of
group 1 and group 17 elements?
(Inquiry 2, Tool 2)
Figure 11 This periodic table has a “bicycle wheel” structure, with each group
being a spoke of the wheel
Select two or three alternative periodic tables and consider:
• What features of the elements are being highlighted in each c ase?
• To what extent are they essentially the same as the standard periodic table?
• What are the advantages and disadvantages of the dierent periodic tables?
240
Metal oxides and non-metal oxides
(Structure 3.1.5)
Another way to describe acids and bases is through their ability to accept or donate
a pair of electrons: a Lewis acid can accept an electron pair, and a Lewis base can
donate an electron pair. Many metal oxides are Lewis bases. They react with water
to form hydroxides, also bases, by donating an electron pair to hydrogen in water.
Reactions of alkali metal oxides with water have the general equation:
M O(s) + H O(l) → 2MOH(aq)

2 2
Here are some examples:
Na O(s) + H O(l) 2NaOH(aq)

2 2
sodium oxide sodium hydroxide
Li O(s) + H O(l) 2LiOH(aq)

2 2
lithium oxide lithium hydroxide
Group 2 oxides are also Lewis bases. They also react with water to form
hydroxides, with the following general equation:
MO(s) + H O(l) → M(OH) (aq)

2 2
MgO(s) + H O(l) Mg(OH) (s)

2 2
magnesium oxide magnesium hydroxide
BaO(s) + H O(l) Ba(OH) (aq)

2 2
barium oxide barium hydroxide
Non-metallic oxides are Lewis acids. They react with water to form other acids by
accepting an electron pair from oxygen in water. Here are some examples:
CO (g) + H O(l) H CO (aq)

2 2 2 3
c arbon dioxide c arbonic acid
SO (g) + H O(l) H SO (aq)

2 2 2 3
sulfur dioxide sulfurous acid
SO (l) + H O(l) H SO (aq)

3 2 2 4
sulfur trioxide sulfuric acid
P O (s) + 6H O(l) 4H PO (aq)

4 10 2 3 4
phosphorus(V) oxide phosphoric acid
Going across any period, the oxides of the elements become less basic and more
acidic. For example, Na O(s) forms a stronger base than MgO(s) in its reaction
2
with water and SO (l) forms a stronger acid than P O (s).

3 4 10
A chemic al species that behaves as both a Lewis acid and a Lewis base is termed
amphoteric. For example, aluminium oxide, Al O (s), is amphoteric: it c an accept

2 3
an electron pair or donate an electron pair depending on what it is reacting with.
241
For example, when reacting with aqueous sodium hydroxide, a base, aluminium
oxide acts as a Lewis acid:
Al O (s) + 2NaOH(aq) + 3H O(l) → 2Na[Al(OH) ](aq)

2 3 2 4
aluminium sodium sodium aluminate
oxide hydroxide
When reacting with hydrochloric acid, aluminium oxide acts as a Lewis base:
Al O (s) + 6HCl(aq) → 2AlCl (aq) + 3H O(l)

2 3 3 2
aluminium hydrochloric aluminium
oxide acid chloride
Both of these reactions are neutralization reactions: an acid and a base react with
each other to form a salt.
The acid–base properties of some period 3 elements are shown in table 2.
Formula of Na O(s) MgO(s) Al O (s) SiO (s) P O (s) SO (l) and

2 2 3 2 4 10 3
At the standard level of DP
oxide SO (g)
2
chemistry, you do not need to
know the denition of Lewis acids Acid or basic basic amphoteric acidic acidic acidic
and bases. Lewis acids and bases base?
are discussed in more detail in
Table 2 Trend in the acid–base properties of the oxides of some period 3 elements
Reactivity 3.4 (AHL )
Acid rain and ocean acidic ation
Pure water at 298 K has a pH of 7.0, which corresponds to a neutral solution: it
is neither acidic nor basic. R ainwater is naturally acidic due to the presence of
dissolved c arbon dioxide, which forms weak c arbonic acid:
CO (g) + H O(l) → H CO (aq)

2 2 2 3
A typic al pH value for rainwater is 5.6. We know that other oxides, such as
nitrogen oxides, NO and sulfur dioxide, SO , are more acidic than CO bec ause
2 2
x
nitrogen and sulfur are further to the right in the periodic table. If these gases
dissolve in rainwater, the ensuing rain is more acidic than normal, and is known as
acid rain, which has a pH of less than 5.6.
Sulfur dioxide and nitrogen oxides are produced naturally by volc anic eruptions
and decomposing vegetation. These pollutants c an also be released into the
atmosphere by industrial processes, such as the combustion of fossil fuels with
high levels of sulfur impurities.
You have seen the reaction of SO with water that produces sulfurous acid. The
2
reaction between water and nitrogen dioxide produces nitric acid and nitrous acid:
2NO (g) + H O(l) → HNO (aq) + HNO (aq)

2 2 3 2
nitrogen dioxide nitric acid nitrous acid
Linking question
Ultimately, nitrous acid and sulfurous acid are oxidized by atmospheric oxygen
to nitric acid and sulfuric acid, respectively:
How do differences in bonding
explain the differences in the 2HNO (aq) + O (g) → 2HNO (aq)

2 2 3
properties of metal and non-

2H SO (aq) + O (g) → 2H SO (aq)
2 3 2 2 4
metal oxides? (Structure 2.1 and
Oceans absorb a large proportion of the c arbon dioxide released into the
Structure 2.2)
atmosphere. As a result, c arbonic acid is formed in the ocean. Increased ocean
acidity c an aect the ability of coral reefs and shellsh to c alcify their skeletons.
242
Figure 12 Sulfur dioxide reacts with

reacts
water and oxygen in the atmosphere to
in the air
form sulfuric acid, c ausing acid rain
acid rain
sulfur dioxide sulfur trioxide
H SO
2 4
corrodes
volc anoes
metals
power
kills
burning erodes
stations
erodes
trees
coal and wet
acidifies
limestone
other surfaces
lakes
buildings
fuels
(fish die)
Oxidation states (Structure 3.1.6)
The bonding triangle introduced in Structure 2.4 shows that bonding is oen not
purely ionic or covalent, but rather occurs on a continuum with unequal sharing
of electrons. The concept of oxidation state, or oxidation number, is used to
represent the charge on an atom in a compound if it were composed of ions. It also
describes the number of electrons shared or transferred when forming a bond.

O
Water, for example, is a predominantly covalent molecule: H O. If it were an ionic

2
H H
+1 +1
compound, then oxygen would gain two electrons and each hydrogen atom would
lose one, as oxygen is more electronegative than hydrogen. Therefore, oxygen is Figure 13 The oxidation states of
assigned an oxidation state of –2 and each hydrogen has an oxidation state of +1. elements in water
Deducing oxidation states in compounds
In compounds, the more electronegative atoms are assigned negative oxidations
states and the less electronegative atoms are assigned positive oxidation states.
There are a number of useful rules for deducing the oxidation states of atoms:
Rule 1 The oxidation state of any free element is zero.
Rule 2 The sum of the oxidation states of all atoms in a neutral compound is zero.
Rule 3 The sum of the oxidation states of all atoms in a polyatomic ion is equal to
the charge of the ion.
Rule 4 The oxidation state of uorine is –1 in all compounds.
Rule 5 The oxidation state of the group 1 metals is always +1 and the oxidation
state of the group 2 metals is always +2.
Rule 6 The oxidation state of oxygen is –2 except in OF , where uorine is

2
more electronegative, so oxygen has an oxidation state of +2, and in
peroxides such as H O , where it is –1.

2 2
Rule 7 The oxidation state of hydrogen is +1 when it is combined with more
electronegative elements (most non-metals), and –1 when it is combined
with less electronegative elements (metals). Hydrogen in a –1 oxidation
state is c alled a hydride ion.
243
The rst rule states that the oxidation state of an element is always zero. This
is bec ause atoms of the same element have equal electronegativity, so the
electrons are shared evenly across bonds in elemental compounds. For
example, consider elemental oxygen, O : the molecule is symmetric al, and the
2
electronegativity of the atoms is identic al. Therefore, the oxidation state of each
atom is zero.
Worked example 1
Deduce the oxidation state of
a. Mn in KMnO
4
b. the atoms in H , Cu, Zn, Xe, and Au

2
3–
c. P in the phosphate ion, PO

4
d. all the elements in LiAlF

4
Solution
a. According to rule 2, as KMnO is a neutral compound, the sum of the

4
oxidation states of its atoms is equal to zero:
(oxidation state of K) + (oxidation state of Mn) + (oxidation state of O
× 4) = 0
We multiply the oxidation state value for oxygen by four, as there are four
oxygen atoms in the compound.
You c an assign oxidation states to O and K, and then nd the value for Mn
that would make the sum of the oxidation states zero.
According to rule 5, the oxidation state of potassium is +1. According to
rule 6, the oxidation state of oxygen is –2. Substituting these values into
the above equation above gives:
1 + (oxidation state of Mn) + (–2 × 4) = 0
oxidation state of Mn = +7
b. These are all elemental species, so each atom has an oxidation state of 0
(rule 1).
Practice questions
3
c. According to rule 3, as PO is a polyatomic ion, the sum of the oxidation

4
4. Assign oxidation states to states of its atoms is equal to the charge on the ion:
each atom in the following
(oxidation state of P) + (oxidation state of O × 4) = –3

compounds:
According to rule 6, the oxidation state of oxygen is –2. Substituting this

a. K Cr O
2 2 7
value into the above equation above gives:
b. CH
4
c. CO (oxidation state of P) + (–2 × 4) = –3

2
d. HClO oxidation state of P = +5

4
e. OF d. Using rule 2: (oxidation state of Li) + (oxidation state of Al) + (oxidation

2
2
state of F × 4) = 0
f. SO
3
According to rule 5, the oxidation state of lithium is +1. According to rule

g. NaH
4, the oxidation state of uorine is –1. Substituting these values into the
h. Fe O
2 3
above equation above gives:
j. CH OH
3
k. CH O 1 + (oxidation state of Al) + (–1 × 4) = 0

2
l. Na O oxidation state of Al = +3
2 2
244
Naming of oxyanions
Oxyanions are polyatomic anions that include oxygen atoms. When naming
oxyanions, you should include the oxidation state of the non-oxygen atom as
a Roman numeral at the end of the name. The Roman numerals are enclosed in
brackets with no space between the ion name and the bracket.
For example, consider the anion MnO . The anion is named manganate(VII),
4
as Mn has an oxidation state of +7. The neutral compound KMnO is c alled

4
potassium manganate(VII). This compound is also known under its traditional

Practice questions
name, potassium permanganate.
5. Write the chemic al formulas for
While the Roman numerals are oen used to refer to the oxidation state of a the following compounds:
transition metal, the non-oxygen atom in an oxyanion c an also be a non-metal.

a. hydrogen nitrate
KClO , for example, is c alled potassium chlorate(VII).

4
b. sodium phosphate(V)
c. magnesium bromate(III)
In practice, the Roman numeral is omitted for some common oxyanions. These
d. potassium sulte
are shown in table 3.
Ionic formula Common name Systematic name
Linking question
NO nitrite nitrate(III)
2
How c an oxidation states be

NO nitrate nitrate(V)
3
used to analyse redox reactions?

2
SO sulte sulfate(IV)
3
(Reactivity 3.2)
SO sulfate sulfate(VI)
4
Table 3 The common names and systematic names of some oxyanions. Both are
acceptable in examinations
Scientists have used symbols to identify dierent elements for a long time
(gure 14). Nowadays, we use the symbols in the periodic table, and the
nomenclature conventions encouraged by the International Union of Pure and
Applied Chemistry (IUPAC). Your study of chemistry will involve using symbols
as they are stated in the data booklet, writing chemic al formulas correctly
(including subscripts and brackets where necessary) and naming substances
according to IUPAC guidance.
Test your chemical communication skills by nding the error in each of the
following and writing the correct answer:
1. HCL 4. MgOH2
2. NE 5. cuprum(II) oxide
3. O3
Figure 14 The symbols used by alchemists for copper and
iron, respectively
245
LHA
Discontinuities in ionization energy trends
(Structure 3.1.7)
E arlier in this topic, you saw that there was a trend of increasing ionization energy
going across a period. You may have noticed two discontinuities from group 2 to
group 13, and from group 15 to group 16 (gure 15).
2

lom
2 2nd period
Ne
  grene
F

N
Ar
O
C
n o it a  i n o i
Cl
 Be
B
S 3rd period
P
Li Si
Mg

t s r if
Al
Na
atomic number, Z
Figure 15 The ionization energies of the second and third period elements
The rst discontinuity, between beryllium and boron, c an be explained by
looking at their electron congurations. The electron conguration of boron
2 2 2 2 1
is 1s 2s and the electron conguration of beryllium is 1s 2s 2p . Despite the
greater nuclear charge in boron, it is easier to remove an electron from this
element as the valence electron is in a higher energy sublevel, which is shielded
from the nucleus by the 2s sublevel. This drop in ionization energy therefore
provides evidence for the existence of s and p sublevels.
The second discontinuity, between nitrogen and oxygen, c an be explained by
2 2 3
electron repulsion in orbitals. The electron conguration of nitrogen is 1s 2s 2p
2 2 4
while for oxygen it is 1s 2s 2p . In nitrogen, the three electrons in the 2p orbitals
do not come into close proximity. The paired electrons in oxygen occupy the
same region of space and have increased repulsion. The higher-energy paired
electron is therefore easier to remove. This explains the drop in ionization energy
between the two groups.
+
N N
3 2
2p 2p
2 2
2s 2s
+
O O
4 3
2p 2p
2 2
2s 2s
Figure 16 A half-lled p sublevel is stable due to decreased
electron repulsion, as none of the electrons are paired
246
LHA
Properties of the transition elements
(Structure 3.1.8)
A transition element is dened as an element that has a partially lled d-sublevel
or c an form a stable c ation with an incomplete d-sublevel. Having an incomplete
d-sublevel gives the transition elements some characteristic properties.
For example, the d electrons have high energy and are deloc alized throughout
the metallic structure. The attraction between the deloc alized electrons and the
metal ions in transition elements is strong, so these elements have high melting
points. Most transition elements have unpaired d electrons, and as a result they
are paramagnetic. This is bec ause the spin of an unpaired d electron creates a
magnetic moment, which c an align with an external magnetic eld.
Zinc is not considered a transition element despite being in the d-block. This
is bec ause it does not form c ations with an incomplete d-sublevel. Its electron
2 10
conguration is [Ar] 4s 3d , so it readily loses its 4s electrons to form 2+ ions,
but the complete d-sublevel remains intact. All of the d electrons in elemental
zinc are also paired in its neutral state, which means that zinc is not magnetic.
A c atalyst is a species that reduces the activation energy required for a reaction
to occur, while not being used up in that reaction. Heterogeneous c atalysts
are a type of c atalyst that exist in a separate phase to the reactants. Transition
elements are oen used as heterogeneous c atalysts. Gas molecules adsorb onto
a solid surface of the transition element, and the molecules undergo chemic al
C atalysts and activation energy are

changes. The products then desorb (gure 17).
discussed further in Reactivity 2.2
Platinum, palladium and rhodium are transition elements used as heterogeneous
c atalysts in c atalytic converters. C atalytic converters adsorb c arbon monoxide
and oxygen molecules in the exhaust of vehicle, and desorb c arbon dioxide:
Linking question
2CO + O → 2CO
2 2
What are the arguments for and
against including scandium as a

t
c
u
transition element? (Structure 2.3)

d
heterogeneous catalyst
A
o
r
p
reactant A adsorbs
catalyst
onto surface of solid

product desorbs
catalyst at active site

from catalyst
tsylatac
tsylatac
A
tcudorp
reaction occurs
reactant B adsorbs onto surface
on catalyst catalyst
of solid catalyst at active site Figure 17 The action of heterogeneous
B c atalysts. Transition elements are oen

A
good heterogeneous c atalysts
247
LHA
This reduces the emission of the products of incomplete combustion created
when burning fuel. Platinum is also used as a heterogeneous c atalyst in hydrogen
fuel cells. In this process, H (g) and O (g) adsorb onto the c atalyst surface and
2 2
H O(l) desorbs.
2
Transition elements are also able to form compounds known as complex ions,
some of which have distinctive colours. The chemistry behind this phenomenon
is detailed later in this topic.
Variable oxidation states in transition
elements (Structure 3.1.9)
Deducing electron congurations of transition elements
As with any other element, if you know the position of a transition element on the
periodic table, you c an determine its electron conguration.
Worked example 2
Determine the condensed electron conguration of iron, Fe.
Solution
The condensed electron conguration starts with the previous noble gas in
square brackets, which in this c ase is argon: [Ar]
Then, identify the valence sublevels. Iron is in period 4, so its valence
sublevels are 4s and 3d. Remember, 3d comes aer 4s bec ause it is higher
inenergy.
Then, determine the number of valence electrons. This c an be deduced from
the group number. Iron is in group 8, so it has eight valence electrons. Two go
into the 4s sublevel, and the remaining six go into the 3d sublevel.
2 6
Therefore, the condensed electron conguration of iron is [Ar] 4s 3d . If you
need the full electron conguration, expand the electron conguration of
2 2 6 2 6 2 6
argon: 1s 2s 2p 3s 3p 4s 3d
The two exceptions to the method described in the worked example are
chromium and copper. In both c ases, a 4s electron is promoted into the 3d
sublevel to achieve a more stable electron conguration. Therefore, chromium is
1 5 1 10
[Ar] 4s 3d and copper is [Ar] 4s 3d .
Variable oxidation states
Another property of the transition elements is their ability to form a variety of
The common oxidation states of

stable ions in dierent oxidation states. These are known as variable oxidation
the transition elements are given in

states. Some of the most common oxidation states of transition elements are
the data booklet.

given in gure 18.
248
LHA
Sc Ti V Cr Mn Fe Co Ni Cu
6 6 6
oxidation
5 5 5 5 5
states
4 4 4 4 4 4 4
that occur
in
3 3 3 3 3 3 3 3 3
compounds
2 2 2 2 2 2 2 2 2
1 1 1 1 1 1 1 1
Figure 18 Common oxidation states of the period 4 transition elements,
sc andium to zinc. The most common oxidation states are shown in a larger font
From gure 18, you c an see that the most common oxidation states of
manganese are +2, +4 and +7. This means that it forms the following oxides:
manganese(II) oxide, manganese(IV) oxide, and manganese(VII) oxide.
The formation of variable oxidation states in transition elements c an be explained

Methods for drawing orbital
by the fact that their successive ionization energies are close in value. The
lling diagrams are described in
successive ionization energies of chromium and copper are shown in gure 19,
Structure 1.3
along with their orbital lling diagrams.
(a) chromium
40000
1–
35000
om
30000
k / ygrene
25000
20000
n o it a z i n o i
15000
10000
5000
0 2 4 6 8 10 12 14 [Ar] 4s 3d
ionization
(b) copper
40000
1–
35000
om
30000
k / ygrene
25000
20000
n o it a z i n o i
15000
10000
5000
[Ar] 4s 3d
0 2 4 6 8 10 12 14
ionization
Figure 19 The rst 13 successive ionization energies and orbital lling diagrams for (a) chromium (b) copper
249
1
LHA
Chromium forms ions with oxidation states ranging from +1 to +6, losing the 4s
+
3
electron rst and then the d electrons. The most common ions are Cr , which
3 2 2
has an electron conguration of [Ar] 3d , and CrO and Cr O , in which

4 2 7
chromium has an electron conguration of [Ar]. There is a very small increase in
energy between losing the rst electron through to the sixth electron, so all six
Activity
oxidation states are possible.
Find data for the rst 13 ionization

The increments between successive ionization energies for copper are larger
energies of the other period

than those for chromium, so it forms fewer stable ions. The common ions are Cu ,
+
10 2
4 transition elements and plot
which has an electron conguration of [Ar] 3d and Cu , which has an electron
9
a graph for each element.
conguration of [Ar] 3d . Cu(III) and Cu(IV) exist in some compounds, such as in
Using your graphs, look for

superconductors, but higher oxidation states are not stable.
connections between the electron
+
2 1 3
Sc andium has the electron conguration [Ar] 4s 3d . Sc was the only known
congurations, the dierence in
ion up until the 1920s, and it was not considered a transition element, as a
successive ionization energies,
transition element has to be able to form ions with partially lled d-sublevels.
and the common ions for each
However, sc andium c an also exist in the +2 oxidation state, having an electron

transition element.
conguration of [Ar] 3d . An example of a sc andium(II) compound is C sScCl

3
Practice questions
6. M anganese and iron both c an exist in +2 and +3 oxidation states. The
condensed orbital lling diagrams of these elements and their ions are
given here:
atom/ion electron structure
4s
3d
Mn [Ar]
2+
Mn [Ar]
3+
Mn [Ar]
Fe [Ar]
2+
Fe [Ar]
3+
Fe [Ar]
+ + +
2 3 2
Explain why Mn is more common than Mn and why Fe c an be easily
+
3
oxidized to Fe
7. Vanadium commonly forms compounds where it has a +5 oxidation state.
a. Determine the condensed electron conguration of elemental
vanadium.
b. Explain why the most common oxidation state of vanadium is +5.
250
LHA
Transition element complexes
(Structure 3.1.10)
Transition elements form coloured compounds known as complexes or complex
ions when bonded with ligands. Ligands are molecules or ions with a lone pair 3+
OH
2
of electrons that c an be donated to a transition element c ation. This results in a
coordination bond formed between the ligands and the central c ation
H O OH
2 2
(gure 20).
Cr
When ligands form coordination bonds with transition element c ations, the
OH
orbitals in the d-sublevel are split into two sets with dierent energies (gure H O 2
2
21). Normally, all ve d orbitals have the same energy: they are degenerate. The
OH
energy gap between the split orbitals corresponds to a wavelength within the 2
visible light region of the electromagnetic spectrum. +

3
Figure 20 The complex ion [Cr(H O) ]

2 6
has six coordination bonds from the lone
pairs on the H O molecules to the central

2
level
+
3
Cr ion. It is violet in colour

ygrene
The formation of complex ions is
detailed in Reactivity 3.4
(a) five d orbitals in an (b) five d orbitals in a
isolated gaseous ion complex ion — non-
— degenerate orbitals degenerate orbitals
Figure 21 The eect of ligands on the d orbitals of the transition element ion
The dierence in energy between the split orbitals allows electrons in the lower
orbitals to be promoted into the higher orbitals. This happens when the complex
absorbs light with a wavelength corresponding to the energy gap between the
non-degenerate orbitals. The colour observed is the complementary colour to
the colour absorbed. Complementary colours are opposites on the colour wheel
given in gure 22. The colour wheel is also shown in the data booklet.
647 nm 585 nm
orange
red yellow
700 nm
575 nm
400 nm
green
violet
blue
424 nm
491 nm
Figure 22 The colour wheel
251
+
3
LHA
For example, [Cr(H O) ] absorbs yellow light when electrons are promoted
2 6
between the split d orbitals. As a result, the complex appears violet, as this is the
opposite colour on the colour wheel.
The larger the splitting of the d orbitals, the greater the energy required to
promote an electron. Therefore, for a larger splitting, the light needs to have a
shorter wavelength and higher frequency. Remember the relationships between
wavelength, frequency and energy:
8 1 1
speed of light (3.00 × 10 m s ) = frequency (in s ) × wavelength (in m)
c = f × λ
34 1
energy (in J) = Planck constant (6.63 × 10 J s) × frequency (in s )
E = h × f
Worked example 3
The colour of [CuCl ] ions is equivalent to visible light with a wavelength of

4
647 nm. Calculate the energy gap of the split d orbitals in [CuCl ]
4
Solution
If the colour of the complex ion corresponds to the wavelength 647 nm, the
wavelength of light absorbed is opposite on the colour wheel (gure 22):
491 nm.
To determine the frequency of the light, use c = f × λ. Remember to convert
the wavelength to metres.
8 1 9
3 × 10 m s = 491 × 10 m × f
14 1
f = 6.11 × 10 s
Then use E = h × f to determine the energy gap between the orbitals:
34 14 1
E = 6.63 × 10 J s × 6.11 × 10 s
19
E = 4.05 × 10 J
The identities of the ligand and the transition element c ation are two factors that
aect the colour of the complex observed. The same ligand will c ause dierent
splitting in the d orbitals depending on the central metal c ation. Ligands that form
stronger coordination bonds with the central ion will produce a greater energy
gap between the split d orbitals (gure 23).
stronger greater higher energy smaller greater
greater ligand
coordination splitting of of light wavelength of wavelength of
strength
bonds orbitals absorbed light absorbed complex colour
Figure 23 The relationship between ligand strength and the colour of complexes
The third factor aecting the colour observed is the charge on the central transitional
+ +
3 2
element cation. A Cr complex will have a dierent splitting of d orbitals than a Cr
complex with the same ligands, and they will therefore be of dierent colours.
252
LHA
Practice question
+
2
8. A complex [Cu(H O) ] (aq) changes colour when excess Cl (aq) is added.

2 6
Chloride ions are considered to be weaker ligands than water. Explain the
colour change observed.
Colorimetric analysis of a solution of unknown concentration
In this task, you will determine the unknown concentration Method
of a transition metal in solution by interpolating a

1. Review the colorimetry section of the Skills chapter.
c alibration curve. You will need a colorimeter, or a mobile
2. Read through the procedure below and make a list of
phone app that c an measure RGB values.
the equipment you will need.
Relevant skills
Part 1: Calibration curve preparation
• Tool 1: Use and apply colorimetry
3. Prepare a standard solution of the ion you will be
• Tool 1: Prepare a standard solution

analysing, and perform a serial dilution to obtain five
solutions of different concentrations.

• Tool 1: C arry out dilutions
4. Depending on the colour of the solution, determine a

suitable wavelength of incident light.
• Tool 3: Interpolate graphs
5. C alibrate the colorimeter.
• Tool 3: Draw and interpret uncertainty bars
6. Determine the absorbances of the five standard
• Inquiry 1: C alibrate measuring apparatus, including

solutions.
sensors
7. Plot a c alibration curve that shows absorbance vs

concentration.
conclusions
8. Check for errors by verifying that your line of best fit
• Inquiry 1: Formulate research questions goes through the origin.
Possible transition metal solutions include 9. Propagate uncertainties and include error bars on
those containing manganate(VII) ions, MnO , your graph. Draw lines to determine the maximum
4
2+
hexaaquacopper(II) complex ions, [Cu(H O) ] , and minimum gradients.

2 6
and pentaaquathiocyanatoiron(III) complex ions,
Part 2: Analysis of solution of unknown concentration

2+
[Fe(H O) (SCN)] . Knowledge of complex ions is not

2 5
10. Obtain a small sample of the solution of unknown
necessary to use this important analytic al technique, so
concentration. Determine the absorbance of the
this task is also suitable for SL students.
analysed solution.
A simplied version of this task involves determining the
11. Use your c alibration curve to determine the
concentration of a complex in solution prepared by your
concentration of the analysed ion in the solution.
teacher or technician. You c an also use it to determine
12. Determine the absolute, relative and percentage

the concentration of a particular coloured component in
uncertainty of the concentration.

everyday substances.
Part 3: Developing a research question
13. Brainstorm possible research questions that could
involve using this analytic al technique.
Linking question
What is the nature of the reaction between transition element ions and
ligands in forming complex ions? (Reactivity 3.4)
How c an colorimetry or spectrophotometry be used to c alculate the
concentration of a solution of coloured ions? (Tool 1, Inquiry 2)
253
End of topic questions
A. –141
Topic review
23
B. –141 × 2 × 6.02 × 10
23
answer the guiding question as fully as possible: C. (–141 + 753) × 6.02 × 10
How does the periodic table help us to predict patterns D. –141 + 753
and trends in the properties of elements?
7. Which pair of elements would react most vigorously?
A. C s and F
Exam-style questions 2
B. Li and I
2
C. C s and I
2
2. Which of the following does not apply to zinc?
D. Li and F
2
A. metal
B. d-block element 8. Which statement about the halogens is correct?
C. transition element
A. Cl is a weaker reducing agent than F
2 2
D. element
B. I will oxidize Br
2
3. Which of the following oxides forms an acidic solution
C. I has a lower tendency to be reduced than Br

2 2
when added to water?
D. Cl will reduce I
2
I. SiO
2
9. Deduce the oxidation state of nitrogen in sodium
II. SO
2
nitrate.
III. SrO
A. +1 B. +2 C. +5 D. +6
A. II only
LHA
10. Which of the following is not a typic al property of
B. III only
transition elements?
C. I and II only
A. c atalytic properties
D. II and III only
B. variable oxidation states
4. Which of the following trends does not explain why
electronegativity increases across periods? C. low electric al conductivity
A. increasing number of valence electrons D. complex ion formation
B. atomic radius decreases

11. Which of the following statements explains why
C. nuclear charge increases transition metal compounds are coloured?
D. constant shielding
A. Electrons absorb energy when they move to a
higher-energy d-orbital
5. Which of the following shows a second ionization
energy?
B. Electrons release energy when they drop down to a
+
2
lower-energy level
A. X(g) → X (g) + 2e
2
C. Transition elements have variable oxidation states
B. X (g) + e → X (g)
+ +
2 3
D. Electrons are deloc alized in transition elements
C. X (g) → X (g) + e
+ +
2
12. What is the oxidation state of cobalt in the complex ion
D. X (g) → X (g) + e
[CoCl ] ?
4
6. Which of the following represents the total amount of
A. 2 B. 0 C. +2 D. +4
energy, in kJ, required to form one mole of oxide ions
from one mole of oxygen atoms?
(1st EA of oxygen = –141 kJ mol ; 2nd EA of oxygen =
1 23 1
753 kJ mol ; N = 6.02 x 10 mol )

A
254
LHA
13. What is the ligand in the complex 17. This question is about acid deposition.
[NH ] [Fe(H O) ][SO ] ?

4 2 2 6 4 2
a. Explain, using relevant chemic al equation(s),
+
2
A. Fe why rain is naturally acidic. [2]
B. [SO ] b. Explain why burning coal leads to the

4
production of acid rain. [2]
C. H O
2
c. Figure 12 on page 243 shows some of the

+
D. [NH ]
4
consequences of acid deposition.
14. [Ni(NH ) ] is a complex ion with nickel in the +2

3 6
i. List the ve consequences of acid deposition
oxidation state. What is the overall charge, x, of the
shown in gure 12. [1]
complex?
ii. Choose one of the consequences of acid
A. 0
rain. Suggest how it c an be oset. [2]
B. 1+
18. a. Sketch a graph showing the rst 10 ionization
C. 2+
energies of copper. [2]
D. 3+
b. State the abbreviated electron conguration of
copper. [1]
c. State the full electron conguration of a copper(II)
ion. [1]
15. This question is about the halogens. The halogens are in
group 17 of the periodic table.
LHA
19. Explain why aqueous copper(II) nitrate forms a coloured
solution, whereas aqueous zinc nitrate is colourless. [2]

a. Explain why the atomic radius of the halogens
increases down the group. [2]

20. When excess hydrochloric acid is added to aqueous
cobalt(II) ions, a ligand exchange reaction takes place,

b. Explain why uorine has a greater electronegativity
c ausing the colour of the solution to change from pink

than oxygen. [2]
to blue:
c. Explain why the chloride ion has a greater radius
+
2 2
[Co(H O) ] + 4Cl ⇌ [CoCl ] + 6H O

than the chlorine atom. [2] 2 6 4 2
pink blue
d. When chlorine gas is bubbled through aqueous
potassium bromide, an orange-brown liquid is 2

+
a. The pink [Co(H O) ] complex ion absorbs light

2 6
produced.
with a wavelength of approximately 540 nm.
C alculate the energy dierence between the

i. Write a balanced equation, including state
split d orbitals of cobalt in this complex ion. [2]

symbols, for the reaction described above. [2]
b. Explain how the colour change in this reaction

ii. Explain why this reaction occurs. [2]
shows that chloride ions are weaker ligands than
16. The alkali metals react vigorously with water.
water molecules. [2]
a. State the group number of the alkali metals. [1]
21. Explain, by referring to successive ionization energies,
b. Explain why the ionization energy of the why titanium c an exist in variable oxidation states, but
alkali metals decreases down the group. [2] c alcium only occurs in the +2 oxidation state. [2]
c. Phenolphthalein indic ator is added to a large
container full of water. Then, a small piece of
sodium is added to the water.
i. Describe and explain the change in the
colour of the indic ator. [1]
ii. Suggest a value for the pH of the solution in
the container once the reaction has ended. [1]
d. Write a balanced equation, including state
symbols, for the reaction of rubidium with water. [2]
255
Structure 3.2 Functional groups:
Classic ation of
organic compounds
How does the classication of organic molecules help us to predict their properties?
Classic ation is a common human approach utilized in many elds of science. Just as biology uses scientic taxonomy to
classify organisms on the basis of shared characteristics, chemists utilize a unique system of nomenclature to group and
name compounds that share important features of structure and reactivity.
Understandings
LHA
Structure 3.2.7 — Stereoisomers have the same
constitution (atom identities, connectivities and bond
multiplicities) but dierent spatial arrangements of atoms.
Structure 3.2.8 — M ass spectrometry (MS) of organic
compounds c an c ause fragmentation of molecules.
Structure 3.2.9 — Infrared (IR) spectra c an be used to
identify the type of bond present in a molecule.
Structure 3.2.10 — Proton nuclear magnetic resonance
spectroscopy ( H NMR) gives information on the dierent
chemic al environments of hydrogen atoms in a molecule.
Structure 3.2.11 — Individual signals c an be split into
clusters of peaks.
Structure 3.2.12 — D ata from dierent techniques are
oen combined in structural analysis.
256
Structure 3.2 Functional groups: Classic ation of organic compounds
Formulas of organic compounds
(Structure 3.2.1)
Introduction to organic chemistry
O rganic chemistry is the field of chemistry where c arbon-base d compounds
are studie d. C arbon atoms have four v alence ele ctrons, so they c an form
four bonds to other atoms. C arbon atoms c an undergo c atenation , which is
the process by which many identic al atoms are joine d together by cov alent
bonds. This produces straight-chain, branche d, or cyclic structures. This
spe cial fe ature of c arbon is the re ason why organic chemistry is such a wide
and v arie d field of study. O rganic compounds include fuels, paints, dyes,
alcohol, plastics, industrial solvents, drugs and me dicines, foods, pesticides
and fertilizers. Most biologic al mole cules, such as DNA, contain c arbon
atoms and are also considere d to be organic.
Types of formulas
You c an represent the structure of an organic compound in several ways by using
dierent types of formulas.
An empiric al formula represents the simplest ratio of atoms present in a
molecule. The molecular formula describes the actual number of atoms
present in the molecule. Both these types of formula oer you little or no
Empiric al and molecular formulas
information about the possible structures of larger, more complex molecules.

were introduced in Structure 1.4.
For example, a molecule of the c arbohydrate glucose has the molecular
formula C H O and an empiric al formula of CH O. From this information, the

6 12 6 2
structure of glucose c annot be deduced.
pFigure 1 G l u c o s e, C H O , is a simple s i x- c a r b o n sugar with hy d r ox y l functional

6 12 6
groups. The structure of the ring is not refle cte d by the molecular formula
257
Structural formulas, unlike molecular formulas, describe the structure of a
compound. There are three types of structural formula: full, condensed
and skeletal.
• Full structural formulas or displayed formulas are two-dimensional
representations showing all the atoms and bonds, and their positions relative
to one another in a compound.
• In a condensed structural formula, all the atoms and their relative positions
are shown, but some or all the bonds are omitted.
• A skeletal formula is the most basic representation of the structural formula,
where the c arbon and hydrogen atoms are not shown but the end of
each line and each vertex represents a c arbon atom. The atoms present in
functional groups are also included as shown in table 1.
Name Full structural Condensed Skeletal
formula structural formula formula
H H H
H C C C H
propane CH CH CH
3 2 3
H H H
H H H
H C C C H
OH
propan-2-ol CH CH(OH)CH
3 3
H O H
H H
O
O
H C C C
propanal CH CH CHO
3 2
H H
H O H
H C C C H
propanone CH C(O)CH
3 3
H H
CH CH=CH or
C C 3 2
H
propene
H
C CH CHCH
3 2
H
H
pTable 1 Full, condensed and skeletal formulas c an all be used to represent
structures of organic compounds
In structural formulas, a covalent bond between two atoms is represented by a
single line that describes two bonding electrons. For a double bond, two lines
are used, and for a triple bond, three lines are used.
258
Constructing 3D models of organic compounds is an excellent interactive
technique, enhancing your ability to visualize of molecules and mutual orientation
of individual atoms. Models c an enhance understanding of a variety of concepts,
from the naming of organic molecules and visualizing stereoisomers (including
optic al isomers) to complex reaction mechanisms.
Practice questions
1. Draw the full structural formula and skeletal formula for each of the following
organic compounds.
a. hexane, CH CH CH CH CH CH
3 2 2 2 2 3
b. butan-1-ol, CH CH CH CH OH
3 2 2 2
c. chloroethene, H C=CHCl
2
2. Which of these molecular formulas are also empiric al formulas?
I. C H O
2 6
II. C H O
2 4 2
III. C H
5 12
A. I and II only
B. I and III only
C. II and III only
D. I, II and III
3. Which of the following compounds has the same empiric al formula and
molecular formula?
–1
Empirical formula Molar mass / g mol
A CO H 90
2
B CH O 62
3
C C H O 88
2 4
D C H O 72
4 8
Linking question
What is unique about c arbon that enables it to form more compounds than
the sum of all the other elements’ compounds? (Structure 2.2)
What are the advantages and disadvantages of dierent depictions
of an organic compound (structural formula, stereochemic al formula,
skeletal formula, 3D models, etc.)? (Structure 2.2)
259
Models
Models are useful when direct observation is dicult. Two-dimensional
representations of molecules (such as structural formulas) do not represent
some of the more complex features that become clear in three-dimensional
physic al and computer models. You c an explore some of the dierent types of
3D models in the Skills chapter.
Functional groups (Structure 3.2.2)
A functional group is an atom, or a group of atoms, that gives organic
compounds their physic al and chemic al characteristics.
There are tens of millions of organic compounds, and this number is constantly
rising as new compounds are synthesized in pharmaceutic al companies,
industrial laboratories and research universities. Natural compounds found in
plants and animals are synthesized by living organisms.
O
O
ester
OH
H
H OH
alkoxy O
OMe
H
β D-glucose- O
OH
hydroxyl
pFigure 2 D igitalin is a c ardioactive steroid found n a t u ra l l y in the f oxg l o v e plant. It is used to tre at congestive he art failure and
irre gular he artbe ats or atrial fibrillation. It fe atures hy d r ox y l , a l k ox y and ester functional groups
All organic compounds are divided into classes of organic compounds
dependent on the specic functional group found in their molecules. Compounds
of the same class have similar chemical properties. Some functional groups and
their corresponding classes are given in table 2. R groups are used in table 2 to
symbolize any c arbon-containing groups. They are useful for writing general
formulas for classes of organic compounds. C arbon-containing groups with no
other functionalities are c alled alkyl groups
260
Functional group
Name Formula Sux Class Example
halogeno chloromethane
(uoro, chloro, bromo R X — halogenoalkanes

H C Cl
3
or iodo)
ethanol H
H C C OH
hydroxyl R OH -ol alcohols 3
ethanal
O O
R C H C C
c arbonyl -al aldehydes 3
H H
propanone
R R’ H C CH
3 3
C C
c arbonyl -one ketones
O O
ethanoic acid
O O
R C H C C
c arboxyl -oic acid c arboxylic acids 3
OH OH
methoxymethane
alkoxy R O R′ — ethers
H C O CH
3 3
ethanamine
H
amino R NH -amine primary amines H C C NH

2 3 2
ethanamide
O O
R C H C C
amido -amide amides 3
NH NH
2 2
methyl ethanoate
O O
R C H C C
ester -oate esters
3
O R’ O CH
3
methylbenzene
phenyl R — aromatics H C
3
pTable 2 S ummary of c l a ss e s of organic compounds and their functional groups
261
How c an you develop familiarity with the various functional groups, their
names, and structures? You may wish to create a ashc ard deck to help you
to build and maintain your uency. As you will see in Reactivity 3, recognizing
the various functional groups will help you to predict the chemic al behaviour
of various substances.
S aturated and unsaturated hydroc arbons
Organic compounds c an also be classied according to whether they are
saturated or unsaturated. In a saturated compound, all the c arbon c arbon
bonds are single. The simplest example of a saturated hydroc arbon is methane,
CH , a member of the alkane family. The primary c arbon chain in an unsaturated

4
hydroc arbon must contain one or more double or triple c arbon c arbon bonds.
Hydroc arbons with c arbon c arbon double bonds are c alled alkenes. The
simplest alkene is ethene, H C=CH . Alkanes and alkenes are both aliphatic.
2 2
This means their molecules contain no aromatic rings.
H H
H H
C C C H
H H
H H
pFigure 3 Ethene (left) with a c arbon c arbon double bond, is u n s a t u ra t e d , where as
ethane (right) is s a t u ra t e d
TOK
Terms such as natural, organic and chemical have precise meanings in
chemistry, which c an dier from their meanings in everyday language.
Consider organic. This word takes on a variety of meanings depending on its
context: organic food, organic chemistry and organic household waste all use
the word organic to signify a dierent thing.
What is the role of context in the choice and interpretation of language?
Linking questions
LHA
What is the nature of the reaction that occurs when two amino acids
form a dipeptide? (Structure 2.4)
How c an functional group reactivity be used to determine
a reaction pathway between compounds, e.g., converting
ethene into ethanoic acid? (Reactivity 3.2, 3.4)
262
Homologous series (Structure 3.2.3)
A homologous series is a family of compounds that c an be grouped together
based on similarities in their structure and reactivity. A homologous series has
the same general formula, which varies from one member to another by one CH
2
(methylene) group. If you know the general formula for each homologous series,
you c an identify which group a particular compound belongs to without drawing
its structure.
The alkane series has the general formula C H . Alkanes are hydroc arbons
n 2n+2
that contain c arbon and hydrogen atoms only. Table 3 shows the alkane
homologous series. You should be able to identify how the structural formula of
each successive member diers from the previous by a single CH group.

2
Molecular Condensed structural
Name Full structural formula
formula formula
C
methane CH CH
4 4
H H
H C C H
ethane C H CH CH
2 6 3 3
H H
H H H
H C C C H
propane C H CH CH CH
3 8 3 2 3
H H H
H H H H
H C C C C H
butane C H CH CH CH CH
4 10 3 2 2 3
H H H H
H H H H H
H C C C C C H
pentane C H CH CH CH CH CH
5 12 3 2 2 2 3
H H H H H
H H H H H H
H C C C C C C H
hexane C H CH CH CH CH CH CH
6 14 3 2 2 2 2 3
H H H H H H
pTable 3 The homologous series of alkanes
263
The alkenes are a homologous series of unsaturated hydroc arbons that contain a
You c an synthesize
c arbon–c arbon double bond. The alkene series has the general formula of C H .
n 2n
halogenoalkanes from alkanes
The alkyne family have c arbon–c arbon triple bonds, with the general formula
by a process known as radic al
C H . Halogenoalkanes are alkanes where one of the hydrogen atoms has

n 2n–2
substitution. This form of
been substituted with a halogen atom. They have the general formula C H X,
n 2n+1
substitution introduces a highly
where X is the halogen atom.
polar c arbon–halogen bond into
what was a relatively inert alkane
molecule. R adic al substitution is
detailed in Reactivity 3.3.
Homologous series alkenes alkynes halogenoalkanes
General formula C H C H C H X
n 2n n 2n–2 n 2n+1
H H
H H
C C C H H C C Cl
C
2
H H
ethyne
H H
ethene
chloroethane
H H H
H H
C C C CH H C C C Cl
3
C
3
H
CH
3
propyne
H H H
propene
1-chloropropane
H H H H
H H
C C C C CH H C C C C Cl
3 3
C
4
H C
3
CH
3
but-2-yne
H H H H
but-2-ene
1-chlorobutane
pTable 4 The homologous series of s t ra i g h t - c h a i n alkenes, alkynes and halogenoalkanes
Members of the homologous series of alcohols all contain the hydroxyl functional
group ( OH). They have a general formula of C H OH. Alcohols c an undergo

n 2n+1
combustion reactions (Reactivity 1.3) and oxidation reactions (Reactivity 3.2).
Another homologous series, the aldehydes, have a general formula of C H O.

n 2n
Aldehydes contain the c arbonyl functional group (C=O) in the terminal position
of the c arbon chain. Ketones have the same general formula and functional group
as aldehydes, but the c arbonyl group is found anywhere on the c arbon chain
except the ends. These homologous series are summarized in table 5.
264
Homologous
alcohols aldehydes ketones
series
General
C H OH C H O C H O
n 2n+1 n 2n n 2n
formula
H H H
H C C OH H C C
C no C ketones
2
2
H H H
ethanol ethanal
H H H H H H H
H C C C OH H C C C H C C C H
C
3
H H H H H H O H
propan-1-ol propanal propanone
H H H H H H H H H H
O
H C C C C OH H C C C C H C C C C H
C
4
H
H H H H H H H H O H H
butan-1-ol butanal butanone
H H H H H H H H H H H H H
O
H C C C C C OH H C C C C C H C C C C C H
C
5
H
H H H H H H H H H H H O H H
pentan-1-ol pentanal pentan-3-one
pTable 5 The homologous series of alcohols, a l d e hy d e s and ketones
C arboxylic acids have the general formula C H O , and have a c arboxyl group.
n 2n 2
Methanoic acid, HCOOH, where n = 1, is the simplest c arboxylic acid of this
homologous family.
Ethers have the general formula ROR’, where R and R’ represent alkyl groups.
The OR group is c alled an alkoxy group. The simplest alkoxy group has one
c arbon atom: OCH . This is known as a methoxy group. Here are some
3
examples of ethers:
H H CH
3 3 3 2 3
methoxymethane
methoxyethane
265
Members of the amine homologous series all have the general formula C H N.
n 2n+3
There are three types of amines: primary amines, secondary amines and tertiary
amines. In primary amines, the nitrogen atom is bonded to only one c arbon
atom. In secondary amines, the nitrogen is bonded to two c arbon atoms,
and in tertiary amines, it is bonded to three c arbon atoms. This is summarized
in table 6.
Esters have the general formula RCO R’. They are derived from c arboxylic
2
acids and have a variety of applic ations ranging from avouring agents and
medic ations to solvents and explosives.
Amides are also derived from c arboxylic acids and have a general formula of
C H NO. They contain the amido functional group, –C(O)NH .

n 2n+1 2
Type of amine Number of c arbon atoms bonded to nitrogen Example
H H H
H C C C NH
2
primary 1
H H H
propanamine
H H
H C N C H
secondary 2
H H H
dimethylamine
H H
H C N C H
tertiary 3 H H
H C H
trimethylamine
pTable 6 P r i m a r y, secondary and tertiary amines
Linking question
How useful are 3D models (real or virtual) to visualize the invisible? (Tool 2)
266
Practice questions
4. Which functional group is circled in this molecule? 7. Which of the following functional groups is present in
paracetamol?
A. hydroxyl
OH
B. c arboxyl
C
C. c arbonyl
D. ether
5. Which functional groups are present in this molecule?
H CO
3
CH N O
3
H C
CH
3
A. c arboxyl B. amino
C. alkene D. hydroxyl
8. G alantamine is a drug used to treat symptoms of
CN Alzheimer ’s disease. Its structure is shown below.
OH
CN
A. c arbonyl, ether, phenyl
O
B. c arbonyl, ester, phenyl
C. c arboxyl, ether, amino
CH O
3
D. c arboxyl, ester, amino
6. Which of the following functional groups are present
in the aspirin molecule?

N
I. ether II. c arboxyl III. ester
CH
3
O
Which of the following functional groups are present
H
H
C
in this molecule?
O C O
A. amido, hydroxyl, ester
C
H
B. amino, hydroxide, ether
C C C. amino, hydroxyl, ether

O
D. amido, hydroxide, ester
H C C H
C C
H H
A. I and II only B. I and III only
C. II and III only D. I, II and III
267
ATL Research skills
Our atmosphere is mostly made up of nitrogen, N , and

2
ammonia
oxygen, O . Organic compounds, which may have been water vapour

2
(NH )
3
electrode
the precursors of biomolecules, are thought to have methane (CH )
4
hydrogen
formed billions of years ago when the composition of the
(H )
2
atmosphere was very dierent. An attempt was made to
recreate these conditions in the mid-20th century, known
as the Miller Urey experiment.
condenser
Research two sources on the Miller Urey experiment
(or another theory of the origin of biomolecules), and
summarize your ndings in your own words, drawing
as many connections as possible to your knowledge of
cold
chemistry. Fully document the information sources, and

water in
evaluate their reliability.
cooled water containing
organic compounds
sample taken for
chemical analysis
pFigure 4 The a p p a ra t u s for the M i l l e r– U r e y ex p e r i m e n t
Physic al trends in homologous series
(Structure 3.2.4)
Members of the same homologous series have similar chemic al properties, as
they have the same functional group. The functional group is responsible for the
types of characteristic reactions the compound undergoes.
For a given homologous series, physic al properties such as melting and boiling
points change gradually with each successive member. This is bec ause the length
of the c arbon chain increases by CH each time, altering the intermolecular

2
forces and therefore the physic al properties.
The boiling points and melting points for the straight-chain alkanes are shown
in table 7. These values increase as the number of c arbon atoms increases.
As a consequence, boiling point and melting point increase with increasing
molarmass.
Name Formula Boiling point / °C Melting point / °C
methane CH 161 183

4
ethane C H 89 172
2 6
propane C H 42 188
3 8
butane C H 0.5 135

4 10
pentane C H 36 130
5 12
hexane C H 69 95
6 14
pTable 7 The melting and boiling points of the s t ra i g h t - c h a i n alkanes
268
The close correlation between c arbon chain length and boiling point enables you
to predict the properties of neighbouring members of the homologous series.
The trend in melting points is not as smooth as that of boiling points and would
have less certainty in terms of the prediction of properties.
You learned about distillation
You c an use simple distillation apparatus and a temperature probe to measure the
techniques in Structure 1.1.
boiling points for successive members of a homologous series.
temperature probe
condenser
water
to sink
water
from faucet distillate
pFigure 5 D istillation a p p a ra t u s i n c o r p o ra t i n g a t e m p e ra t u r e probe
The trend in increasing boiling point results from stronger London (dispersion)
London (dispersion) forces and
forces as the c arbon chain increases in length. London (dispersion) forces are
other intermolecular forces were
attractive forces between non-polar molecules (for example, hydrogen H ).

2
covered in Structure 2.2. Which of
They also exist between polar molecules (for example, HCl). Every molecule will
the homologous series discussed
experience London (dispersion) forces, whether it is non-polar or polar.
so far experience hydrogen
bonding?
300
250
200
150
C° / erutarepmet
100
50
number of
carbon atoms
1
2 3 5 6 7 8 9 10
50
100
alkane Figure 6 The boiling point
inc re ases with e ach s u c c e ss i v e

alkene
member of a homologous
150 alcohol
series as the c arbon chain

carboxlc ac
g r ows in length
200
269
Constructing a simple graphical model
In this task you will construct and test a simple graphic al Part 3: Graph
model of the boiling points of a homologous series of

7. Create a sc atter graph of the data.
your choice.
8. Using software, draw a line or curve of best fit that
describes the data well.
Relevant skills
9. Determine the R value and the equation of the line
• Inquiry 1: State and explain predictions using scientific
or curve.
understanding
• Tool 2: Identify and extract data from databases Part 4: Test the model

You have now created a simple graphical model of the
• Tool 2: Represent data in graphic al form relationship between boiling point and carbon chain length.
You can test your model by using it to make predictions and

• Tool 3: Sketch graphs to qualitatively describe trends
2 then checking the accuracy of these predictions.
• Tool 3: Apply the coefficient of determination ( R )
• Tool 3: Construct graphs and draw lines or curves of 10. Use the equation of the line or curve of best fit to
best fit predict the boiling point of the 7th, 10th, and if
possible, the 20th members of the homologous series.

11. Look up their actual boiling point values.

• Tool 3: C alculate and interpret percentage error
• Inquiry 2: Describe and explain patterns, trends and 12. C alculate the percentage errors of each of the
relationships predictions.
Instructions
Part 5: Interpret the results
Part 1: Prediction 13. Compare and contrast the percentage errors for the
three predictions. Consider the following questions:

1. List the first six members of a homologous series of
your choice. • How do their accuracies compare? Why might
this be?
2. Predict the relationship between boiling point and
c arbon chain length. Justify your prediction, referring • Does the accuracy of the predictions change for
to your knowledge of intermolecular forces and longer c arbon chain lengths?
functional groups.
• This is an example of extrapolation bec ause you
3. Sketch a graph that qualitatively describes the predicted a value that was outside the range of
relationship you have predicted. the data. How might the accuracy change if you
had interpolated the data instead?
14. Describe and explain the trend shown in the graph
4. Identify an online database that contains boiling point
you plotted.
data for a variety of substances (for instance, NIST
15. If uncertainties were reported along with the boiling
Chemistry Web Book).
point data, what impact did these have on your analysis?
5. Collect data on the boiling point for the six organic
16. Briefly evaluate your model, giving examples of its
compounds you have selected and enter the data into
specific strengths and weaknesses.
a spreadsheet.
17. How might the accuracy of this simple model be
6. Organize the data: enter the name, formula,
improved?
and number of c arbon atoms, and convert all
temperatures into a consistent unit.

Extension
Choose a different homologous series and repeat the
task. Compare and contrast the two sets of results.
270
The dierent boiling points of members of homologous series mean that dierent
members will condense at dierent temperatures. In the petrochemic al industry,
this principle is used as a separation technique. For example, crude oil is a
mixture of hydroc arbons that vary in the length of their c arbon chain. Fractional
distillation is a physic al separation process where crude oil is vaporized and
then passed through a column. As the vapour rises through the column, it cools.
Therefore, compounds will condense at dierent levels in the column depending
on the length of their c arbon chain. Compounds with a similar boiling point,
and therefore similar chain length, will condense at the same level. Long-chain
compounds will condense further down the column, as they have a higher
boiling point. Shorter-chain compounds have a lower boiling point, so will
condense further up the column, where it is cooler.
The density and viscosity of members of a homologous series also increase with
c arbon chain length.
Linking question
What is the inuence of the c arbon chain length, branching and the nature of
the functional groups on intermolecular forces? (Structure 2.2)
Naming organic compounds (Structure 3.2.5)
With the existence of millions of dierent chemic al substances, names help us to
dierentiate them. The name of an organic compound needs to provide enough
information to identify the class of the compound, the length of its longest c arbon
chain, and any substituents and functional groups present. A substituent is any
part of an organic compound that is not part of the longest c arbon chain. For
example, any alkyl group in an alkane compound that is not part of the main
chain is considered a substituent. An alkane with alkyl substituents is known as a
branched-chain alkane
The International Union of Pure and Applied Chemistry (IUPAC) has developed
a universal chemical naming system for both organic and inorganic compounds:
IUPAC nomenclature. IUPAC nomenclature rules helps chemists to avoid
confusion, eliminate language barriers, and freely communicate knowledge. An
overview of the IUPAC naming system for organic compounds is shown in gure 7:
the longest c arbon chain that
includes the principal group,
or the most complex cyclic suffix indic ating
or heterocyclic system the principal group
-ane
a b c principal (parent) chain -ene
-yne
prefixes suffixes indic ating
in alphabetic al order saturation or unsaturation
of the principal chain
pFigure 7 O utline of the nomenclature of organic compounds
271
Naming alkanes
Alkanes are saturated organic molecules that only contain In the example below, numbering from le to right results in the
carbon carbon single bonds. You can use the following methyl substituent being on carbon2. Numbering from right to
steps to deduce the IUPAC name of an alkane: le would incorrectly have the substituent on carbon 5.
1 Examine the structure of the compound and determine
H C H
the longest continuous c arbon chain. This provides the
H H H H H
root name for the alkane depending on the number of
c arbon atoms (table8). If an alkane is a straight-chain

H C C C C C C H
1 2 3 4 5 6
molecule, its name is the same as its root name. All
H H H H H H
alkanes have the same sux: -ane.
4. The name of the alkyl substituent goes before the root
Number of carbon atoms Name

name as a prex, and a hyphen is used to separate the
loc ant number and the prex. Therefore, the above

1 methane
compound is c alled 2-methylhexane.
2 ethane
5. If there are multiple dierent substituents, they are arranged
3 propane
in alphabetical order prior to the root name. For example,
4 butane
the below compound is called 3-ethyl-2-methylhexane.
5 pentane
H
ethyl
6 hexane
H C H substituent
pTable 8 I U PAC root names for the alkane series

H C H
H H H
2. If alkyl substituents are present in the compound, the
name of a substituent is determined by the number of

H C C C C C C H 3-ethyl-2-methylhexane
1 2 3 4 5 6
c arbon atoms, with the sux changing from “-ane” to
H H H H H
“-yl”. Some examples are shown in table 9.
H C H
methyl
H
methyl
substituent
H
substituent
H C H
6. If there are multiple identic al substituents, the number
H H H
of substituents is indic ated by a multiplier before the
C C C C substituent name, as summarized in table10.
H H H H
Number of identic al substituents Multiplier name
2 di
Number of carbon Substituent Condensed
3 tri
atoms in alkyl group name formula
4 tetra
1 methyl CH
3
5 penta
2 ethyl CH CH
2 3
3 propyl CH CH CH pTable 10 Numeric al m u l t i p l i e rs in the I U PAC nomenclature

2 2 3
4 butyl CH CH CH CH
2 2 2 3
The loc ants of each substituent are separated by a
comma. For example, the below compound is c alled
pTable 9 I U PAC names for the alkyl substituents
2,3-dimethylhexane.
3. You c an specify the position of a substituent by H
assigning numbers, known as loc ants, to the main
H C H
c arbon chain. The c arbon chain is numbered such that
H H H
the substituent is given the lowest value loc ant.
H C C C C C C H
H H H H H
H C H
272
Structural isomers are compounds that have the same molecular formula but
dierent structural formulas. Dierent isomers have unique physical and chemical
properties. In the following worked example, we will look at the structural isomers of
the hydrocarbon hexane, and practise using the rules above to name these isomers.
Worked example 1
Three dierent structural isomers of hexane, C H , are shown below. Using the IUPAC nomenclature,
6 12
name these isomers.
a. H H H H H b. H c.
H
H C C C C C H H C H
H C H
H
H
H H H H
H C H H C C C C H
H C C C C H
H H H H
H H H
H C H
H C H
H
H
Solution
a. First, count the number of c arbon atoms in the There are two methyl ( CH ) substituents, one
3
longest straight c arbon chain. There are ve c arbon bonded to c arbon 2 and one to c arbon 3.
atoms, so the parent chain is pentane
Since the two substituents are identic al, a numeric al
multiplier is required to indic ate the number of

Then, number the c arbon chain so that the
these substituents. In this c ase, di indic ates two

substituent has the lowest possible loc ant. The
substituents.
methyl ( CH ) substituent is bonded to c arbon 2.
3
The IUPAC name for this compound is

The IUPAC name for this compound is
2,3-dimethylbutane. Remember that commas are

2-methylpentane.
used between numbers, and hyphens are used
b. There are four c arbon atoms in the longest straight
between a number and a letter.
c arbon chain, and so the parent chain is butane
c. Like b, the parent chain is butane. Two methyl
In this c ase, the direction of numbering of the
( CH ) substituents are bonded to c arbon 2.

3
c arbon chain is irrelevant as the compound is
The IUPAC name for this compound is therefore
symmetric al, so both approaches would give the
2,2-dimethylbutane.
same loc ants for the substituents.
Practice questions
9. Applying IUPAC nomenclature rules, state the name of 10. Draw the structural formulas of the following
each of the following compounds: molecules:
a. CH CH CH CH
3 2 2 2 3 a. 2,2,3-trimethylpentane
CH b. 5-ethyl-4,4-dimethyloctane
3
CH
3
b. CH CH C CH
3 2 2 3
CH CH
3 3
CH CH
2 3
c. CH CH CH
3 2 3
CH
3 3
273
Naming alkenes
Alkenes are unsaturated organic molecules that contain a c arbon c arbon double
bond. The IUPAC nomenclature rules for the naming of alkene molecules are the
same as those for the alkane series. All alkene names end with the sux -ene,
instead of -ane used for alkanes.
The following compound has both a c arbon c arbon double bond, and an alkyl
side chain.
H CH CH CH
3 2 3
1 2 3 4 5 6
CH
3
When you number the longest c arbon chain, the position of the c arbon c arbon
double bond must have the lowest loc ant, taking priority over any substituents
present in the molecule. Numbering from right to le would incorrectly place the
c arbon c arbon double bond on c arbon-4. Therefore, numbering occurs from
le to right in this example.
With the methyl ( CH ) substituent at loc ant 4, the name of this molecule is
3
as follows:
double
substituent bond
name loc ant
4-methylhex-2-ene
methyl substituent parent suffix indic ates
loc ant chain unsaturation
Worked example 2
Using the IUPAC rules, name the following alkenes.
a. H H b. H
H
H C H
H C C C C
H H H H H
H
H H H H C C C C H
H H H
H C H
Solution
H
a. There are four c arbon atoms in the longest straight b. There are six c arbon atoms in the longest straight
c arbon chain, so the parent chain is butane. c arbon chain, so the parent chain is hexane.
The molecule contains a c arbon–c arbon double The molecule contains a c arbon-c arbon double bond,
bond, so the sux changes from -ane to -ene. so the sux changes from -ane to -ene.
Numbering the c arbon chain from right to le gives The double bond follows c arbon-2 in the longest
the unsaturated c arbon–c arbon double bond the c arbon chain. Two methyl (–CH ) substituents are
3
lowest possible loc ant. The double bond follows bonded to c arbon atoms number 4 and 5.
c arbon-1.
The IUPAC name for this molecule is
The IUPAC name for this compound is but-1-ene. 4,5-dimethylhex-2-ene.
274
Naming halogenoalkanes
When naming halogenoalkanes, the position of the halogen substituent is
H alogeno Substituent
identied by the loc ant on the parent chain. Table 11 lists the prexes used for
group name
each halogeno group.
F uoro
For derivatives of methane and ethane featuring only one halogeno group, all
loc ants for the substituent are equivalent, so they are omitted. Consider the
Cl chloro
following compound:
Br bromo
H H
I iodo
H C C Br
pTable 11 N ames of halogeno
substituents
H H
Moving the bromine atom to other positions will form the same molecule. The
IUPAC name for this molecule is bromoethane, not 1-bromoethane.
For a halogenoalkane with more than one halogeno group, list the halogens in
alphabetic al order. For example, the following compound is named 2-chloro-
1,1,1-triuoroethane.
F H
F C C H
F Cl
If a halogeno compound also features a c arbon c arbon double bond, the
double bond takes priority over the halogeno group in terms of assigning
loc ants. So the following molecule is 3-chlorobut-1-ene, not 2-chlorobut-3-ene.
H H H
H C C C
2
H Cl
Practice questions
11. Apply the IUPAC nomenclature rules to deduce the c.

Cl
names of the following compounds.
a. Br
H H H H
12. Deduce the structural formulas for the following
H C C C C H
compounds.
a. 2,3,4-tribromohexane
H Cl Cl H
b. 1,3-dibromo-2-chlorobutane
b. H H H H
H
c. 2-uorobut-2-ene
C C C C C H
l Cl H
275
Naming alcohols
All alcohols contain the hydroxyl ( OH) functional group. When naming alcohols,
you need to change the parent chain sux from -ane to -anol. The c arbon chain
is numbered such that the hydroxyl group has the lowest possible loc ant, taking
priority over other substituents or c arbon c arbon double bonds.
The simplest molecule in this homologous series is methanol. The rst two
members of this homologous series do not require loc ants. This is bec ause the
hydroxyl group in any position results in the same molecule, as seen in methanol
and ethanol below.
H H H
HO C H HO C C H
H H H
methanol ethanol
Alcohol compounds with three or more c arbon atoms require loc ants to specify
the position of the hydroxyl group. The loc ant comes before the -ol sux,
for example:
H H H H H H
1 2 3 1 2 3
HO C C C H H C C C H
H H H H OH H
propan-1-ol propan-2-ol
Naming compounds with c arbonyl groups
The c arbonyl group (C=O) is the functional group for two classes of compounds:
aldehydes and ketones. In aldehydes, the c arbonyl group is always positioned
at the end of the c arbon chain. This is known as the terminal position. There is
no need to number the c arbonyl group in aldehydes, as it always occurs at the
end of the chain. When the aldehyde includes a substituent, the numbering of
c arbon atoms begins at the c arbon attached to the c arbonyl group. For example,
aldehyde names have the sux -al, so ethane becomes ethanal.
When the c arbonyl functional group is not loc ated at the terminal position in the
primary c arbon chain, the compound is a ketone. In ketones, the c arbon chain
is numbered such that the c arbonyl group has the lowest possible loc ant, taking
priority over other substituents or c arbon–c arbon double bonds. Ketone names
have the sux -one, so propane becomes propanone.
276
Worked example 3
Using the IUPAC rules, name the following aldehydes. There are no substituents, so the IUPAC name is
methanal.
a. b. H CH H H
O 3
O b. The parent chain comes from the C alkane, pentane

5
and the sux becomes -al.

H C C C C C
The c arbon numbering starts from the c arbonyl
H H H H group, and therefore the methyl substituent is
c. attached to c arbon-4.
H F H
The IUPAC name is 4-methylpentanal.
H C C C C
c. This is an example of an aldehyde featuring a halogeno
H substituent. The parent chain comes from the C

4
H H H
alkane, butane, and the sux becomes -al.
Solution
The c arbon numbering starts from the c arbonyl
a. The parent chain comes from the C alkane, methane.

1
group, and therefore the uoro substituent is attached
to c arbon-3.
The molecule contains a c arbonyl group in the
terminal position, so the sux -ane becomes -al.

The IUPAC name is 3-uorobutanal.
Worked example 4
Using the IUPAC rules, name the following ketones.
a. b. c.
H H H H H H CH H H
3
H C C C H H C C C C H H C C C C C H
H O H H H O H H H H O H
Solution
a. The parent chain comes from the C alkane, propane. b. The parent chain comes from the C alkane, butane,
3 4
The molecule contains a c arbonyl group that is not in and the sux becomes -one. The loc ant is not
the terminal position, so the sux becomes -one. required, as this is the only four-c arbon ketone that
c an exist. So the nal IUPAC name will be butanone.
The IUPAC name is propanone. The loc ant is not
required bec ause propanone is the only three-c arbon c. The parent chain comes from the C alkane, pentane,
5
ketone that c an exist; if the c arbonyl group were and the sux becomes -one. The c arbon atoms are
at c arbon-1 or c arbon-3, it would be an aldehyde. numbered from right to le such that the c arbonyl
Therefore, all the information required to deduce the group has the lowest loc ant. The c arbonyl group is
structure is in the name ‘propanone’. at c arbon-2, and the methyl group is at c arbon-4.
Therefore, the IUPAC name is 4-methylpentan-2-one.
Naming c arboxylic acids
C arboxylic acids are a class of compound featuring a c arboxyl group (–COOH).
C arboxylic acids have the sux -oic acid. So a c arboxylic acid with an ethane
parent chain is c alled ethanoic acid.
277
In c arboxylic acids, c arbon chains are numbered starting with the functional
group, including the c arbon from the c arboxyl group in the chain. Like in
aldehydes, there is no need to assign loc ants to c arboxyl groups, as they are
always in the terminal position. Here are two examples of c arboxylic acids:
H H H CH H H
3
O O
Br C C C H C C C C C
OH OH
H H H H H H
3-bromopropanoic acid 4-methylpentanoic acid
Practice questions
13. Draw the structures of the following molecules based on the IUPAC name
given:
a. hexan-3-one b. 2-chloropropan-1-ol
c. 3,3-dimethylpentane d. 5-ethyl-2-methylhept-3-ene
e. 2-methylpentan-2-ol
14. Apply IUPAC nomenclature rules to name the following molecules:
a. CH CH CH=CHCH CH CH
3 2 2 2 3
b. c.
CH CH
3 3
CH CH CCH OH
3 3 3 2
CH CH
3 3
d. CH e. O
3
CH CCHCH CH H
3 2 3
pFigure 8 Methanoic acid, commonly
k n ow n as formic acid, o c c u rs n a t u ra l l y in
some ants
Scientists collaborate across the world, and agreed-upon terminology
facilitates unambiguous communic ation. The naming rules you have learnt
in this chapter enable you to communic ate chemic al compounds using both
structures and names. If you look at the ingredients listed on the label of a
bottle of a personal hygiene product such as shampoo, you will now be able
to recognize some of the naming stems and suxes.
The s tanda rdization of orga nic n omenc lature enc ourages the u se of
names that foll ow IUPAC guideline s, bu t cer tain non-systemati c names
are still u se d widel y. M any of th ese a llude to the us es an d cha ra cteri stics
of su bstan ces. Fo r example, me thano ic ac id is commonly known as
formi c aci d, after the L atin for ant: for mic a . If you spe ak Italian , Fren ch,
Por tugue se or Span ish, you will re co gnize this as the roo t of for mic a,
four m i, for miga and hor miga, respe ctively.
In some c ases, IUPAC names are far too long to be useful. For example, the
IUPAC name for the mild painkiller ibuprofen is (RS)-2-(4-(2-methylpropyl)
phenyl)propanoic acid.
278
Structural isomers (Structure 3.2.6)
Structural or constitutional isomers are compounds that have the same
molecular formula but dierent connectivity of the atoms. There are several types
of structural isomers.
Chain isomers
Chain isomers are structural isomers with dierent lengths of c arbon chains. For
example, butane and methylpropane both have the molecular formula C H .

4 10
Butane is a straight-chain molecule bec ause it has no substituents on the c arbon
chain. However, methylpropane is a branched-chain molecule, bec ause it has an
alkyl substituent.
Isomer butane methylpropane
Molecular formula C H
4 10
H H H
H H H H
H C C C H
H C C C C H
Full structural formula H H
H C H
H H H H
Condensed structural formula CH CH CH CH CH(CH )

3 2 2 3 3 3
Skeletal formula
pTable 12 Butane and m e t hy l p r o p a n e are chain i s o m e rs
Positional isomers
Positional isomers are structural isomers where the position of the functional
group changes. For example, bromopentane has three dierent positional
isomers, all with the molecular formula C H Br.

5 11
Isomer 1-bromopentane 2-bromopentane 3-bromopentane
Molecular
C H Br
5 11
formula
H H H H H H H H H H H H H H H
Full
H C C C C C H H C C C C C H H C C C C C H
structural
formula
H H H H Br H H Br H H
H H H Br H
Br
Skeletal
Br
formula
Br
pTable 13 Po s i t i o n a l i s o m e rs of bromopentane
279
Worked example 5
Draw the structural formulas of all possible structural isomers of a compound with
the molecular formula C H F. Name the isomers using IUPAC nomenclature.

4 9
Solution
First, draw the longest possible straight c arbon chain. For Having identied and named all the butane isomers,
this molecule, it is a four-c arbon chain. you need to look at possible chain isomers. Shorten the
longest chain by one c arbon, creating a propane chain.
C C C C
C C C
Next, number the c arbon chain and place the uorine
To share the same molecular formula as the isomers above,

substituent on the c arbon chain in as many positions as
you need to add a methyl group to the propane chain. For

possible, then add the hydrogen atoms. Remember that
this molecule, the only possible position is on the central

the numbering of the c arbon chain c an occur in either
c arbon in the chain, as adding the methyl group anywhere

direction.
else will create a four-c arbon butane chain.
H H H H
1 2 3 4
H C H
H C C C C H
F H H H
C C C
1-fluorobutane
H H H H
Then, position the uorine substituent on the c arbon chain
in as many ways as possible to create unique molecules.

1 2 3 4
H C C C C H
H H
H F H H
H C H H C H
2-fluorobutane
H H H H
3 2 1 3 2 1
H C C
C F H C C
3-uorobutane and 4-uorobutane are not possible
isomers: 3-uorobutane is equivalent to 2-uorobutane, H H H H F H
and 4-uorobutane is equivalent to 1-uorobutane, and
1-fluoro-2-methylpropane 2-fluoro-2-methylpropane
the lower loc ants are favoured.
Activity
Draw and name all the structural isomers of chloropentane, C H Cl.

5 11
280
Primary, secondary and tertiary compounds
Changing the position of the functional group on the parent c arbon chain aects
the chemic al properties of compounds. You c an classify compounds such as
alcohols, halogenoalkanes and amines as primary, secondary and tertiary,
depending on the position of the functional group.
In halogenoalkanes, a halogeno group is bonded to a c arbon atom. In order to
determine whether the compound is primary, secondary or tertiary, we count
the number of c arbon atoms bonded to this c arbon atom. A primary (1°) c arbon
atom is bonded to one other c arbon atom, a secondary (2°) c arbon atom is
bonded to two other c arbon atoms, and a tertiary (3°) c arbon atom is bonded to
three other c arbon atoms (gure 9).
H
3° c arbon
1° c arbon 2° c arbon H C H
H H H H H H H H
H C C C Cl H C C C H H C C C H
H H H H Cl H H Cl H
The reaction mechanisms

1-chloropropane 2-chloropropane 2-chloro-2-methylpropane
and conditions used to form
pFigure 9 Primary (1°), secondary (2°) and tertiary (3°) halogenoalkanes
primary, secondary and tertiary
halogenoalkanes are discussed in
Alcohols are classied in the same way as halogenoalkanes: the number of

Reactivity 3.3.
c arbon atoms attached to the c arbon atom next to the functional group indic ates
the class of the alcohol (gure 10).
1° c arbon 2° c arbon H C H 3° c arbon
H H H H H H H H
H C C C OH H C C C H H C C C H
Primary, secondary and tertiary

H H H H OH H H OH H
alcohols form dierent products
propan-1-ol propan-2-ol 2-methylpropan-2-ol

in oxidation reactions. This is
discussed in Reactivity 3.2.

pFigure 10 Primary (1°), secondary (2°) and tertiary (3°) alcohols
Classic ation of amines as primary, secondary or tertiary is slightly dierent to the
method used with alcohols and halogenoalkanes. Amine classic ation depends
on the number of alkyl groups bonded directly to the nitrogen atom of the
functional group, unlike halogenoalkanes and alcohols that consider the c arbon
atom next to the functional group.
281
When naming amines, the parent name loses the sux -e, which is replaced by
“amine”. When naming secondary and tertiary amines, N is used to signify that
the substituents are bonded to the nitrogen atom. In gure 11, the substituents
are methyl groups.
1° amine 2° amine 3° amine
H H H H H H H H H
H CH CH
3 3
H C C C N H C C C N H C C C N
H H CH
3
H H H H H H H H H
propan-1-amine N-methylpropan- N,N-dimethylpropan-
1-amine 1-amine
pFigure 11 Primary (1°), secondary (2°) and tertiary (3°) amines
Practice questions
15. Propan-2-ol is a useful organic solvent.
a. Draw the skeletal formula of propan-2-ol.
b. Classify propan-2-ol as a primary, secondary or tertiary alcohol, giving a reason.
16. Deduce which of the following is a secondary alcohol.
A. B.
OH
H C H
H H H OH H H
H C C C H H C C C C H
H H H H H CH H
3
C. D.
H H H H H CH H H
3
H C C C H C C C C H
H H H H OH H H
H C H
OH
282
Functional group isomers
Functional group isomers are structural isomers with the atoms arranged
dierently such that they have dierent functional groups.
Compounds with hydroxyl and alkoxy functional groups c an be structural isomers
of each other. For example, consider the molecular formula C H O. Functional

2 6
group isomers of this molecule include ethanol, an alcohol with a hydroxyl group,
and methoxymethane, an ether with an alkoxy group.
H H H H
H C C OH H C O C H
H H H H
ethanol methoxymethane
Aldehydes and ketones c an be functional group isomers of each other, as they
both have c arbonyl groups. Propanone, the simplest ketone, is a functional
group isomer of propanal. Both isomers have the molecular formula C H O.

3 6
H H H H
H C C C H C C C H
H H H O H
propanal propanone
Compounds with ester and c arboxyl groups c an also be functional group
isomers. The simplest ester, methyl methanoate C H O , is an isomer of the

2 4 2
c arboxylic acid, ethanoic acid.
O O
H C H C
C
O C H O H
methyl methanoate ethanoic acid
Molecular models
Propan-1-ol, propan-2-ol and methoxyethane all have the 3. Create digital models of the three isomers using
molecular formula C H O. In this task, you will reflect on online molecular visualization software (for example,
3 8
the information obtained from different types of formulas MolView). Explore the different visualization
and models of these substances. possibilities, including: ball and stick model, space-
filling model, molecular electrostatic potential
Relevant skills
(MEP)surface.
• Tool 1: Physic al and digital molecular modelling
4. Compare and contrast the strengths and uses of each
Instructions
of the various formulas and molecular models.
1. State the full structural formula, condense d
5. How does the molecular structure of these three
structural formula and skeletal formula for e ach of
compounds relate to their physic al properties and
the thre e isomers.
reactivity?
2. Using a molecular model kit, construct models of the
three isomers.
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Linking question ATL Thinking skills
In the Molecular models task, you gathered information about three

How does the fact that
LHA
compounds, including: types of formulas, types of models, discussion of

there are only three isomers
strengths and properties. Reect on how this information could be organized.

of dibromobenzene
Would you opt for a table, Venn diagram, concept map, or anything dierent?
support the current model
Do you have a preferred method? Why does eective organization of

of benzene’s structure?
information support learning?

(Structure 2.2)
Stereoisomers (Structure 3.2.7)
Another type of isomerism exhibited by some organic compounds is
stereoisomerism. A pair of stereoisomers have the same molecular formula,
connectivities and bond multiplicity. However, they have dierent spatial
arrangements of the atoms. Stereoisomers c an be subdivided into two major
classes: conformational isomers and congurational isomers (gure 12).
isomerism
H H
H
H H stereo- structural
H
isomerism isomerism
H H H H
staggered eclipsed
conformational configurational
isomerism isomerism
pFigure 13 The two c o n f o r m e rs
of e t h a n e, v i ew e d along the
c arbon–c arbon bond pFigure 12 Ty p e s of isomerism
If a molecule contains two groups bonded together by a single bond, these
groups c an rotate about the single bond to form dierent conformational
isomers. For example, in ethane, CH CH , the two CH groups c an rotate

3 3 3
about the c arbon c arbon bond resulting in two possible orientations, known as
conformational isomers or conformers (gure 13).
configurational
This process does not involve breaking any bonds, and it is virtually impossible to
isomerism
separate the individual conformers.
Congurational isomers c an only be interconverted by breaking and reforming
optic al
cis–trans bonds. Congurational isomers c an be subdivided into cis trans isomers and
isomerism
optic al isomers (gure 14).
pFigure 14 Ty p e s of c o n f i g u ra t i o n a l
isomerism
Cis–trans isomers
In aliphatic alkenes, groups bonded to the unsaturated c arbon atoms are not
able to rotate about the c arbon c arbon double bond. If these two groups are
dierent, two isomers c an exist: a cis isomer where two identic al substituents are
on the same side of the c arbon c arbon double bond, and a trans isomer where
two identic al substituents are on opposite sides of the double bond. In Latin, cis
means “this side of ” and trans means “the other side of ”.
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For example, the symmetric al molecule of but-2-ene has cis trans congurational
isomers about the double bond (gure 15). The horizontal axis of the double
bond is the reference plane: it is used to determine whether an isomer is cis or
trans, depending on which groups are either side of the plane.
H H H C H
3
reference
C C C C
plane
H C H
3 CH CH
3 3
cis-but-2-ene trans-but-2-ene
pFigure 15 The cis trans i s o m e rs of but-2-ene
In gure 15, the cis-isomer of but-2-ene has the two methyl substituents on the
same side of the reference plane, while the trans-isomer has the two methyl
substituents on opposite sides of the reference plane.
For an alkene to exhibit cis–trans isomerism, the two groups attached to
each unsaturated c arbon atom have to be dierent. For example, propene,
H C=CHCH , will not experience cis–trans isomerism bec ause one of the c arbon
2 3
atoms has two identic al groups (hydrogen atoms), so the potential isomers will
also be identic al (gure 16).
H H H
3
reference
C C C C
plane
H C H
3
propene also propene
pFigure 16 Propene does not ex h i b i t cis trans isomerism
Cis trans isomerism also occurs in disubstituted cycloalkane molecules. In this case,
the reference plane is the at face of the ring structure. For example, the compound
1,2-dimethylcyclobutane has cis trans congurational isomers (gure 17).
The cis-isomer has both methyl substituents on the same side of the plane of the ring.
The trans-isomer has methyl substituents on opposite sides of the plane of the ring.
Disubstituted three-carbon rings also experience cis trans isomerism (gure 18).
H CH H CH
2 3 2 3
H H CH CH
2 2
C C
H H H H
C C
2 2
C C C C
H H
CH CH
3 3
CH CH CH CH
3 3 3 3
cis trans cis trans
pFigure 17 The cis–trans i s o m e rs of pFigure 18 The cis–trans i s o m e rs of
1 , 2 - d i m e t hy l c y c l o b u t a n e 1 , 2 - d i m e t hy l c y c l o p r o p a n e
285
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Practice questions
17. Deduce and draw the cis- and trans-isomers of
hex-2-ene.
18. For each of the following molecules, state whether they exhibit cis trans
isomerism. For the molecules that do, deduce whether they are in the cis
or trans conguration. Name each molecule using IUPAC rules.
a. b.
H CH CH
2 3 H CH CH CH
2 2 3
C C
C C
H C H
3 H H
c. d.
H
CH CH H C
H CH C 2 3 3
3 2
C C
C C
H H C H
H 3
19. Draw the structural formula of the following compounds, and then deduce
if they c an form cis trans isomers.
a. 2-bromoprop-1-ene b. pent-2-ene
c. 1-bromo-2-chloroethene d. 1,1-dibromobut-1-ene
e. 1-ethyl-2-methylcyclopropane f. 2,3-dimethylpent-2-ene
Optic al isomers
A chiral c arbon is dened as a c arbon atom bonded to four dierent atoms
or groups of atoms. It is also known as a stereocentre or asymmetric centre.
Molecules with one or more chiral c arbon atoms exhibit a type of congurational
isomerism c alled optic al isomerism. A pair of optic al isomers are c alled
enantiomers.
H C NH
3 2
Chiral molecules have the ability to rotate plane-polarized light; this is known as
3 2 1
HS C C C
optic al activity.
OH
Penicillamine is a drug used in the treatment of rheumatoid arthritis. It has the

H C H
3
molecular formula C H NO S. Its structural formula is shown in gure 19.

5 11 2
pFigure 19 Pe n i c i l l a m i n e has the
C arbon-1 is only bonded to three atoms, so it is not chiral, or achiral. C arbon-2

I U PAC name 2 - a m i n o - 3 - m e t hy l -
3 - s u l f a ny l b u t a n o i c acid and c arbon-3 each have four bonded atoms or groups. However, two of the four
groups bonded to c arbon-3 are identic al (the two methyl groups), so c arbon-3 is
achiral. C arbon-2 is bonded to four dierent atoms or groups of atoms, and it is
therefore chiral. The presence of this chiral c arbon atom means that penicillamine
is optic ally active and c an exist as a pair of two dierent enantiomers. Enantiomers
are non-superimposable mirror images of each other, and they have no plane
ofsymmetry.
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Structural formulas, like the one in gure 19, provide information on how the
H
atoms and groups present in a molecule are connected. However, these formulas
*
N
do not allow you to dierentiate between enantiomers in a molecule with a chiral
centre. As a result, enantiomers are drawn as three-dimensional structures known

CH
3
N
as stereochemic al formulas (gure 20), where specic symbols are used to
designate the direction of a bond (table 14).
OH
Name Symbol Directionality
* NH
2
line bond C — aligned with the plane of paper
wedge bond c coming out of the plane (towards the viewer)
HO
dash bond c going behind the plane (away from the viewer)
OH
pTable 14 S ummary of dire ctional bonds used in stere ochemic al formulas
OH
You will rec all from Structure 2.2 that a central atom with four regions of electron
*
density adopts a tetrahedral arrangement with bond angles of 109.5°. For the
NH
2
tetrahedral arrangement around a chiral c arbon atom, two of the bonds are
I
I
usually drawn as line bonds, one as a wedge bond, and one as a dash bond.
Wedge and dash bonds are tapered, meaning that they start o narrow from the
HO O I
c arbon atom and widen.
To draw the enantiomer of a stereochemic al formula, you need to draw its

I
mirror image. For example, the stereochemic al formulas of the penicillamine
pFigure 20 All of these molecules h av e

enantiomers are shown in gure 21.
a c h i ra l c arbon atom, designated by *.
Nicotine ( t o p) is n a t u ra l l y sy n t h e s i z e d
mirror plane
by the tobacco plant, norepinephrine
H N NH
2 2
( m i d d l e) is a n e u r o t ra n s m i t t e r, and
t hy r ox i n e ( b o tt o m ) is a hormone f rom the
C C
t hy r o i d gland
HS(H C) C HOOC
3 2
COOH C(CH ) SH
3 2
H H
pFigure 21 E n a n t i o m e rs of penicillamine
Enantiomers, like those in gure 21, are non-superimposable. This means that if
you were to create 3D models of them using a molecular model kit, it would be
impossible to align the models such that the functional groups of the same type
point in the same direction. However, if you were to hold a mirror to one of the
enantiomers, the mirror image would show the structure of the other enantiomer.
Figure 22 Molecular models of the
e n a n t i o m e rs of 2 , 3 - d i hy d r ox y p r o p a n a l ,
HOCH C H (O H ) C H O. C an you identify

2
the c h i ra l c e n t r e s?
287
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Worked example 6
Draw the stereochemic al formulas of the two enantiomers of
2-aminopropanoic acid showing a tetrahedral arrangement around the
chiral c arbon atom.
Solution
First, draw the structural formula to deduce which c arbon atom is chiral.
H H
H C C C
OH
H NH
2
The chiral c arbon atom is marked with an asterisk. It is attached to four
dierent atoms or groups of atoms: a hydrogen atom and methyl, amino and
c arboxyl groups.
To draw the stereochemic al formula, arrange the atoms and groups around
the chiral c arbon atom such that one is projected out of the plane of the
paper (wedge bond), one is projected behind the plane of the paper (dash
bond), and two atoms or groups of atoms are in the plane of the paper (line
bonds). This gives you your rst enantiomer.
H C
3 COOH
NH
2
It does not matter which bond is assigned to which group for this rst
enantiomer, as the bonds in the tetrahedral structure are all equivalent. The
wedges and dashes are just used to give you a sense of the 3D structure.
Finally, to draw the other enantiomer, draw a dashed vertic al line to represent
a mirror and draw the reected image of your existing enantiomer.
H
H
C
C
H C
3 COOH HOOC CH
3
NH H N
2 2
M ake sure that the connectivities between the central atom and the groups
are correct. For example, the methyl group has been reversed (H C) in the
3
le-hand image to correctly show a c arbon to c arbon bond.
288
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E arlier, we discussed the cis trans isomerism of a cycloalkane,
mirror plane
1,2-dimethylcyclobutane. The trans-isomer of this molecule also exhibits optic al
H C CH
3 3
isomerism. This is bec ause its mirror images are non-superimposable (gure 23).
Dierent enantiomers of the same compound have dierent odours. Our
perceived taste c an also be aected by a specic enantiomer present in foods.
H C CH
3 3
The dierent chemic al properties of enantiomers are identic al in non-chiral
environments, but become dierent in the presence of other chiral compounds,

pFigure 23 The optic al isomerism of
such as biologic al molecules in the human body. t r a n s - 1 , 2 - d i m e t hy l c y c l o b u t a n e
A pair of enantiomers under the same conditions will rotate plane-polarized
light by the same angle, but in opposite directions (gure 24). One enantiomer
rotates the plane of polarization clockwise and is designated the (+) enantiomer.
The other enantiomer rotates the plane of polarization anti-clockwise and is
designated the ( ) enantiomer.
light
source
unpolarized
light
polarized light
polarizer
pure enantiomer
polarizer
viewer
pFigure 24 Ro t a t i o n of plane-polarized light by a pure enantiomer
A 50:50 mixture of two enantiomers is c alled a racemic mixture (or racemate),
and it does not rotate plane-polarized light.
Activity
For each of the following molecules, complete the tasks (a)-(c):
i. butan-2-ol, C H O
4 10
ii. 2-hydroxypropanoic acid, C H O

3 6 3
a. Identify and explain which c arbon atom is chiral.
b. Draw stereochemic al formulas showing the tetrahedral arrangement
around the chiral c arbon atom.
c. Construct 3D models for the pair of enantiomers.
289
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Rotation of plane-polarized light by optically active compounds
Optic ally active compounds rotate plane-polarized light. 5. Place the second polarizing filter above the tube.
Here you will explore this phenomenon using simple

6. Dim the lights and look at the light source through the
polarizing filters, and consider ways to develop the

second polarizing filter.
investigation further.
Relevant skills
polarizing filter
• Inquiry 1: Demonstrate independent thinking and
creativity in the design of an investigation
• Inquiry 1: Identify control variables
sample
• Inquiry 1: Design and explain a valid methodology
observations
polarizing filter
S afety
light source
7. Rotate the second polarizing filter and observe the
Your teacher will provide you with further safety
changes to the light intensity.
prec autions, depending on the identity of the substances
8. Repe at the experiment, this time placing one of

being analysed.
your prepare d solutions in the tube. Explore the
M aterials
effe ct of this solution on the rotation of plane-
• Two polarizing filters polarize d light.
• Light source, for example, a mobile phone flashlight

Q uestions
or torch
1. List some of the variables that you must keep constant
• Clear glass tube with a clear cover at one end, for

in order to explore the effect of different compounds
example, a measuring cylinder

on the rotation of plane-polarized light.
• Clamp and stand

2. Identify and explain the changes you would make
• S amples of optic ally active substances, such as to this method in order to do one or more of the
sucrose, glucose or fructose. following:
Instructions • measure the angle of rotation
1. Prepare aqueous solutions of the substance(s) you

• investigate the effect of concentration on the
wish to test. Set them aside.

rotation of plane-polarized light
2. Place the light source on a flat surface, pointing up.

• investigate the effect of path length on the
Place a polarizing filter over the light source.

rotation of plane-polarized light
3. Pour distilled water into the tube and clamp it in place

• investigate the effect of the composition of a
above the source of plane-polarized light.

mixture on the rotation of plane-polarized light.
4. Record the height of water in the tube.

3. Show your ideas to your teacher, and if you have time,
try them out.
Mass spectrometry (MS) (Structure 3.2.8)
M ass spectrometry (MS) is an analytic al technique that c an be used to break up
organic compounds into fragments, some of which will be ions. This is known
The operational details of the mass
as fragmentation. The molecular masses of these fragments will correspond to

spectrometer are discussed in
the masses of certain functional groups or parts of the c arbon chain. As a result,
Structure 1.2.
MS c an be used to obtain information about the functional groups and structural
fragments present in an organic compound.
The molecular masses of the dierent fragments are recorded in a graph c alled
a mass spectrum. The dierent peaks within a mass spectrum are known
290
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collectively as a fragmentation pattern. The peak with the highest mass to
charge ratio (m/z) in a mass spectrum corresponds to the parent compound. This
is known as the molecular ion peak.
Worked example 7
The mass spectrum for propan-1-ol is shown in gure 25.
100
80
ytisnetni
60
evitaler
40
20
12 15 20 25 30 35 40 45 50 55 60
m/z
pFigure 25 M a ss spectrum of p r o p a n -1 - o l
Use the mass spectrum to show that the fragmentation pattern corresponds
to the structure of propan-1-ol.
Solution
If you know the name of the analysed compound, begin by drawing its
structural formula. This will help you to gure out the possible fragmentation
patterns. When you have more than one option, draw the structural formulas
of all the expected molecules. In this c ase, there is only one possible
structural formula (propan-1-ol):
H H H
H C C C OH
H H H
Then, examine the spectrum and identify the peaks and their m/z values. Use
the m/z values to propose structures for each of the fragments:
m/z Molecular fragment Explanation
Molecular ion (the original molecule that

+
60 [CH CH CH OH]
3 2 2
has lost one electron)
31 [CH OH] Loss of CH CH from the m/z 60

2 3 2
29 [CH CH ] Loss of CH OH from the m/z 60

3 2 2
H H H
H C C C OH
H H H
M = 29 M = 31
r r
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D ata on specic MS fragments are provided in section 21 of the data booklet.
• A peak with m/z = 15 corresponds to a CH fragment

3
• A peak with m/z = 17 corresponds to an OH fragment
• A peak with m/z = 29 corresponds to a CHO or CH CH fragment

2 3
• A peak with m/z = 31 corresponds to a CH O or CH OH fragment

3 2
• A peak with m/z = 45 corresponds to a COOH fragment
Practice questions
20. A straight-chain ketone with the molecular formula C H O has two

5 10
structural isomers.
a. Deduce the structural formulas of the two possible isomers.
M ass spectra A and B of the two isomers are given.
b. Explain which spectrum is produced by each compound using section
22 of the data booklet.
57
100
ytisnetni
80
29
60
evitaler
40
86
20
0.0
0.0 20 40 60 80 100
m/z
43
100
ytisnetni
80
60
evitaler
40
86
20
0.0
0.0 20 40 60 80 100
m/z
292
LHA
Infrared (IR) spectroscopy (Structure 3.2.9)
Infrared (IR) spectroscopy is an analytic al technique that c an be used to identify
the types of bonds present in an organic compound, and therefore determine its
functional groups. IR spectroscopy exposes a sample of an organic compound
to IR radiation. Molecules absorb IR radiation, c ausing certain bonds to vibrate. IR
spectroscopy is a type of vibrational spectroscopy
There are two basic types of vibration that are possible in molecules: stretching/
compression and bending. The type of movement observed depends on whether
the molecule is diatomic or polyatomic. For example, the diatomic molecule of
hydrogen chloride can only undergo stretching and compression (gure 26).
H Cl
pFigure 26 Stretching and c o m p re ss i o n in HCl molecule
When a bond in a molecule absorbs IR radiation, the frequency of the resultant
vibration depends on the bond enthalpy and the masses of the atoms in the
bond. The higher the bond enthalpy, the stronger the bond. This will in turn result
in a shorter wavelength, and higher frequency of the vibration. The larger the
masses of the atoms, the lower the frequency of the vibration.
Hydrogen iodide contains a large iodine atom and has a relatively low bond
enthalpy, so its vibration occurs at a lower frequency when compared to the other
hydrogen halide molecules (table 15).
Bond Frequency of Wavenumber
Molecule
–1 11 –1 –1
enthalpy / kJ mol vibration / 10 s / cm
H Cl 431 8.66 2886
H Br 366 7.68 2559 As described in Structure
1.3, frequency (f ) is related to
H I 298 6.69 2230
wavelength (λ) via the relationship
pTable 15 Bond e n t h a l py and w av e n u m b e rs of halogen halide molecules

c
f = , where c is the speed of
light. This means that frequency

In IR spectra, the absorption is usually described in terms of its wavenumber,
ν,
is related to the wavenumber as

shown in the fourth column of table 14. The wavenumber is the reciproc al of the
follows:
ν = c × f.
1
wavelength:
ν =
293
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In polyatomic molecules, the stretching c an be symmetric or asymmetric.
Polyatomic molecules c an also undergo bending, a vibration where the
bond angle changes. Both water and c arbon dioxide molecules stretch and
bend when they absorb IR radiation (gure 27), so they c an be analysed by IR
spectroscopy. In other words, such molecules are IR-active.
O O O
H H H H H H
symmetric asymmetric bending
stretching stretching
Figure 27 Modes of v i b ra t i o n of water and
c arbon d i ox i d e molecules. All thre e modes of
v i b ra t i o n are IR active
C C C
For a compound to be IR active, the molecule must experience a change in
dipole moment during the vibration; otherwise, no peak will be observed in the
IR spectrum. Diatomic homonuclear molecules that do not have a permanent
dipole, such as hydrogen, H , oxygen, O , and chlorine, Cl , are IR inactive.

2 2 2
Diatomic heteronuclear molecules, such as hydrogen uoride, HF, are only
c apable of performing the stretching and compression vibrations. Bec ause there
is a change in the dipole moment, such molecules are IR active.
Plotting the wavenumbers of the molecular vibrations against their intensity gives a
graph known as an IR spectrum. Certain wavenumbers are characteristic of specic
functional groups, which are listed in section 20 of the data booklet. We can
therefore analyse the IR spectrum to determine the types of functional group present
in a molecule. For example, the IR spectrum of butanoic acid is shown in gure 28.
100
)% ( ecnattimsnart
50
4000 3000 2000 1500 1000 500
wavenumber / cm
pFigure 28 IR spectrum of butanoic acid
–1
There is a strong, very broad peak in the range 2500 3000 cm characteristic of
–1
the O H bond in c arboxylic acids. The strong peak in the range 1700 1750 cm
is characteristic of the C=O bond.
294
LHA
IR spectroscopy only provides information about the functional groups present
in a molecule, so this technique alone c annot be used to determine the structure
of an unknown molecule. Therefore, information gathered from IR spectroscopy
must be used in conjunction with information derived from other analytic al
techniques, such as mass spectroscopy, nuclear magnetic resonance (NMR)
spectroscopy or combustion analysis.
Worked example 8
An organic compound containing only c arbon, hydrogen and oxygen is
composed of 62.02% c arbon and 10.43% hydrogen by mass.
a. Determine the empiric al formula of the compound, showing your
working.
b. The infrared spectrum of the compound is shown below. Deduce the
functional group present in the molecule.
1.0
0.8
% / e c n at t i m s n a r t
0.6
0.4
0.2
0.0
3500 3000 2500 2000 1500 1000 500
1
wavenumber / cm
c. The mass spectrum of the compound is shown below. Deduce the
relative molecular mass of the compound, and hence determine the
molecular formula.
43
100
80
ytisnetni
60
evitaler
40
58
20
15
42
39
26 27 29 37
41
14
44 57
38
16 25 28 31 36 40
15 20 25 30 35 40 45 50 55 60
m/z
d. Through experimental analysis, it was determined that the compound
did not contain a terminal c arbonyl group. Deduce the structural
formula of the compound.
295
LHA
Solution
a. The method for determining an empiric al formula is shown below:
C H O
Step 1: Divide the
62.02 10.43 27.55

percentage by the
= 5.16 = 10.33 = 1.72
12.01 1.01 16.00

relative atomic mass
Step 2: Divide
each result by the
lowest value (1.72)

5.16 10.33 1.72
= 3.00 = 6.01 = 1.00

to determine the
1.72 1.72 1.72
whole number ratio,
rounding if necessary
The empiric al formula is therefore C H O.

3 6
b. A strong peak in the range of 1700 1750 cm shows the presence of
a c arbonyl group, C=O. Possible organic molecules include aldehydes,
ketones, c arboxylic acids and esters, but the question has asked you
to deduce the functional group of the compound, so the answer is
c arbonyl/C=O.
c. The relative molecular mass of the compound is represented by the
molecular ion peak: 58. If you add up the atomic masses of the empiric al
formula, this is also equal to 58, so the molecular formula is C H O.

3 6
d. The molecule is not an ester or c arboxylic acid, as there is only one
oxygen atom in the molecular formula. As the c arbonyl group is not in
the terminal position of the molecule, the c arbonyl group must be in the
middle of the c arbon chain, so the molecule is a ketone. Therefore, the
compound is propanone, and its structural formula is CH COCH .

3 3
Proton nuclear magnetic resonance
( H NMR) spectroscopy (Structure 3.2.10
and Structure 3.2.11)
Proton nuclear magnetic resonance ( H NMR) spectroscopy is perhaps
the most useful analytic al technique for structural determination of organic
molecules. The spectra produced by H NMR spectroscopy help you to
determine the number of dierent chemic al environments of hydrogen atoms
in the molecule. An atom's chemic al environment is dened by the other atoms
attached to it.
H NMR spectroscopy is an example of spin resonance spectroscopy. The
nucleus of a hydrogen atom H contains a single positively charged proton. This
pFigure 29 A nucle ar magnetic

nucleus has two possible spin orientations, as described by the nuclear spin
resonance (NMR) spe ctrometer quantum number (m ), with possible values of m = +½ or m = –½.
I I I
296
LHA
The hydrogen nucleus behaves as a spinning charged particle that c an act as
a small magnet. Similar to the electron spin, the two possible spin states of a
H nucleus are degenerate: they exist at the same energy level. When a strong
magnetic eld is applied to the sample containing H nuclei, the two spin states
become non-equivalent and split into two dierent energy levels (gure 30).
the magnetic field generated by
the higher energy spin state is
high energy
opposite to the applied external
1 magnetic field
spin = –
훥 E
1 1
spin = + spin = –
2 2
the magnetic field generated by
low energy
the lower energy spin state is
spin = +
aligned with the applied external
2
magnetic field
no magnetic field magnetic field applied
applied
CH
pFigure 30 The two spin states of the hy d r o g e n nucleus are different in energy when 3
a magnetic field is applied
H C Si CH
3 3
CH
3
The energy dierence, ΔE, between the spin states increases along with the
pFigure 31 T MS is the u n i v e rs a l l y
external magnetic eld strength. For the nucleus to be promoted from the lower
accepted reference standard used in
energy state to the higher energy state, it must be exposed to radio waves of 1
H NMR s p e c t r o s c o py
energy equal to the dierence between the two spin states. The exact energy
required for this process depends on the chemic al environment of hydrogen
atoms in the analysed molecule. So, hydrogen atoms in dierent chemic al
A summary of chemic al shi
environments absorb electromagnetic radiation of dierent frequencies.
values for dierent hydrogen
environments is given in section 21

The frequencies of radiation absorbed by dierent hydrogen environments
1
of the data booklet.
are displayed in a H NMR spectrum as signals. These signals are given in
terms of their chemic al shi, δ, expressed in units of parts per million (ppm).
Chemic al shi is measured using a relative sc ale, where the signal produced by a
tetramethylsilane (TMS) standard is assigned a chemic al shi of 0 ppm. TMS is a
symmetric al molecule with four equivalent methyl groups (gure 31).
Low-resolution H NMR
When examining a low resolution H NMR spectrum, the area under each signal
is proportional to the number of H nuclei generating this signal. The area under
a signal is small and dicult to measure, so an integration trace is added to the
spectrum to indic ate the relative number of H nuclei represented by each signal.
297
1
LHA
Consider the H NMR spectrum of chloroethane, shown in gure 32. There are
two signals in the spectrum indic ating two hydrogen environments, one with
a b
an integration trace of 2, and one with an integration trace of 3. These signals

Cl CH CH
2 3
a b therefore correspond to the CH and CH groups in chloroethane, respectively.

2 3
Figure 33 shows the H NMR spectrum of 2-bromopropane. There are three
groups with hydrogen atoms in the molecule, but only two signals in the
spectrum. This is bec ause the molecule is symmetric al, so the two methyl groups
are identic al and therefore form a single hydrogen environment. The signal with
2 3
an integration trace of 6 corresponds to these methyl groups, as they have six
4 3 2 1
hydrogen atoms. The other signal corresponds to the CH group.
chemical shift δ/ppm
Br
a a
a
1
pFigure 32 The H NMR spectrum of

CH CH CH
3 3
c h l o ro e t h a n e, C H Cl b
2 5
1 6
4 3 2 1
chemic al shift δ / ppm
pFigure 33 The H NMR spectrum of 2 - b ro m o p ro p a n e, C H Br

3 7
Sometimes integration traces are given as a ratio. For instance, imagine a H NMR
spectrum with two signals where the area under one signal is equal to 1, and the
area under the other is equal to 2. These correspond to the relative number of
hydrogen atoms in each environment, so the actual numbers of hydrogen atoms
in dierent environments could be 2 and 4, or 3 and 6, or any other values in a
1:2 ratio.
TOK
The interactions between particles and dierent types of electromagnetic
radiation underpin many of the spectroscopic methods we have looked at.
These interactions result in nuclear spin changes (NMR) or bond stretching
and bending (IR). When electromagnetic radiation of a certain wavelength
encounters a molecule, the radiation is sc attered.
Occ asionally, the wavelengths of incident and sc attered radiation are
not the same. This phenomenon is known as “R aman sc attering” aer Sir
Chandrasekhara Venkata R aman who was awarded the 1930 Nobel Physics
Prize for his work in this area.
The R aman sc attering eect formed the basis of R aman spectroscopy, which is
nowadays used to determine structural features of various materials. Evidence
for R aman sc attering was very dicult to obtain at rst. Eventually, with
ongoing experiments, R aman and his team arrived at conclusive evidence for
pFigure 34 C. V. R aman, picture d h e r e,
the existence of the eect.
discovere d the R aman effect with his
c ow o r k e r, Sir K ariamanikkam Sriniv asa
How much evidence is required in order to support a robust conclusion?
Krishnan
298
LHA
Worked example 9
Sketch the H NMR spectra for the following molecules:
a. propanone, CH C(O)CH
3 3
b. ethanoic acid, CH COOH

3
Solution
a. Propanone, CH C(O)CH , is a symmetric al ketone. b. Ethanoic acid, CH COOH, has a total of four protons
3 3 3
The structural formula shows a c arbonyl functional in two dierent chemic al environments.
group and two methyl groups. The chemic al
The proton of the c arboxy l group will produce
environment for all the hydrogen atoms is identic al:
a signal in the re gion of 9.0 13.0 ppm, and the
H O H
methy l group will produce a signal in the re gion of
2.0 2.5 ppm. The are as under the signals should
H C C C H refle ct the ratio of protons in the two environments,
which is 1:3. A sketch of the H NMR spe ctrum is
H H shown below:
identic al chemic al
environments
The equivalent protons in propanone will produce
one signal in the range of 2.2 2.7 ppm (data booklet,
section 21). Integration traces are not useful here
bec ause there is only one hydrogen environment. A
sketch of the H NMR spectrum is shown below:
12 10 8 6 4 2 0 –2
10 9 8 7 6 5 4 3 2 1 0
Practice questions
21. The structural formulas of two organic compounds are shown below.
a. b.
COOH CH COOH CH
3 3
H C H C
3 3
OH H H OH
Deduce the number of signals and the ratio of areas under the signals in the
H NMR spectra of these compounds.
299
1
LHA
High-resolution H NMR
Advances in technology have led to improvements in the accuracy of analytical
instruments like H NMR. There are distinct dierences between low resolution and
high resolution H NMR spectra and the information that you can extract from them.
We have already demonstrated that low resolution H NMR provides us with
information about the chemic al environment of hydrogen atoms in a molecule.
The number of signals corresponds to the number of dierent chemic al
environments, while the integration trace shows the number of hydrogen atoms
associated with each signal. In a high resolution H NMR spectrum, individual
signals are split into clusters of peaks. The splitting pattern of a signal provides us
with information about the number of hydrogen atoms attached to neighbouring
atoms in a molecule.
Consider 1,1,2-trichloroethane, which has two hydrogen environments: H and H :

a b
Cl Cl
H C C Cl
a
H H
a b
There are two signals in the spectrum of 1,1,2-trichloroethane (gure 35). The
signal for the H atoms is split into a cluster of two peaks and is referred to as a
a
doublet. The signal for the H atom is split into a cluster of three peaks and is
b
referred to as a triplet.
a
1
=
=
noitargetni
noitargetni
9 8 7 6 5 4 3 2 1 0
pFigure 35 The high resolution H NMR spectrum of
1 ,1 , 2 - t r i c h l o r o e t h a n e
The dierent splitting patterns of the signals for the hydrogen environments
are c aused by the spin spin interactions of neighbouring hydrogen nuclei. As
discussed previously, each proton has nuclear spin that c an either be aligned
with or against the external magnetic eld. If hydrogen atoms in a molecule are
in close proximity, the magnetic elds generated by their nuclei c an aect each
other, resulting in NMR signal splitting. This is known as spin spin coupling
The number of peaks in a cluster for an individual signal, known as multiplicity,
c an be c alculated by using the N + 1 rule:
If the proton H has N protons attached to its nearest neighbours,

x
the NMR signal of H will be split into N + 1 peaks.

x
300
LHA
Examples are given in table 16. The ratio of the heights of the peaks in a cluster,
the peak ratio, is deduced using Pasc al’s triangle.
Number of Number
neighbouring of peaks in Splitting pattern Peak ratio
hydrogen atoms (N) cluster (N + 1)
0 1 singlet (s) 1
1 2 doublet (d) 1:1
2 3 triplet (t) 1:2:1
3 4 quartet (q) 1:3:3:1
pTable 16 Splitting patterns due to neighbouring hydrogen atoms in H NMR spectra.
Splitting patterns of ve and more peaks are oen c alled “multiplets”
For example, in 1,1,2-trichloroethane, the spins of the nuclei in the H

a
environment will couple with the spins in the adjacent H environment.

b
The H environment has one proton, and therefore the H signal will be split into
b a
a doublet (d) as per the N + 1 rule. The heights of the two peaks will be equal.
The H environment has two protons, and therefore the H signal will be split into
a b
a triplet (t), and the peak ratio will be 1:2:1. The magnetic ally equivalent H nuclei
a
do not couple with each other.
TOK
The splitting patterns observed in high-resolution H NMR spectra correspond
to the numbers in a mathematic al pattern known as Pasc al’s triangle
(gure36). In each row of the triangle, adjacent numbers are added together
to form the new row. Evidence exists that this pattern was known by ancient
civilizations in dierent parts of the world including China and Persia.
What is the role of mathematics in scientic knowledge-building?
etc etc etc
pFigure 36 P a s c a l ’s triangle
301
LHA
Worked example 10
Show that the splitting patterns in the signals of the H NMR spectrum in
gure 37 correspond to the structure of butanone, H CC(O)CH CH

3 2 3
11 10 9 8 7 6 5 4 3 2 1 0
pFigure 37 High resolution H NMR spectrum of butanone
Solution
First, draw the structure of butanone and deduce the number of hydrogen
environments.
H C C CH CH
3 2 3
A B C
There are three dierent hydrogen environments, which correspond to the
three signals in the spectrum.
Hydrogen environment A is not adjacent to any other hydrogen
environments, so N = 0. According to the N + 1 rule, this environment
corresponds to the singlet in the spectrum.
Environment B is adjacent to environment C, which has three hydrogen
atoms. Therefore, environment B corresponds to the quartet. The signal
corresponding to environment C is split into a triplet by the two hydrogen
atoms in environment B.
The peak ratio in each cluster corresponds to that predicted by Pasc al’s
triangle. The chemic al shis of the signals for B and C also closely match the
predicted values from the data booklet. This is summarized in table 17:
Hydrogen Splitting Peak Predicted Actual
N + 1 rule
environment pattern ratio δ / ppm δ / ppm
N = 0
A singlet (s) 1 2.2–2.7 2.1
0 + 1 = 1
N = 3
B quartet (q) 1:3:3:1 2.2–2.7 2.4
3 + 1 = 4
N = 2
C triplet (t) 1:2:1 0.9–1.0 1.1
2 + 1 = 3
pTable 17 Yo u c an d i s p l ay data like this when matching the s t r u c t u ra l details of a
compound to signals in a H NMR spectrum
302
LHA
Combining analytic al techniques
(Structure 3.2.12)
To determine the structure of a molecule, you may be required to interpret a
wide variety of data. For example, dierent methods are needed to deduce
the types of functional group present and the arrangement of the c arbon atoms
in a molecule. It is the combination of data that will enable you to deduce the
unknown structure.
This data may include:
• combustion analysis data (to c alculate empiric al formula)
• mass spectroscopy (MS) data
• the infrared (IR) spectrum
• the H NMR spectrum
• information from the data booklet
• description of reactions that the compound c an undergo (covered in the
Reactivity section of DP chemistry).
Predict spectra from molecular models
In the skills task on page 283, you were asked to create molecular models of
propan-1-ol, propan-2-ol and methoxyethane. Now you will examine these
molecular models and consider the spectroscopic data of these substances.
Skills
Instructions
1. Create molecular models of propan-1-ol, propan-2-ol and methoxyethane
using a molecular model kit, if you have not done so already.
2. Examine the molecular models and determine the number of different
hydrogen environments in each molecule. Then, predict the H NMR
spectrum of each (consider the number of signals, area under each signal,
splitting patterns and chemic al shifts).
3. Predict the major IR spectrum signals expected for each compound.
4. For each compound, predict some of the peaks found in its mass spectrum.
5. Search for the spectra in a suitable database and see how the actual
spectra compare to your predictions. Examples of databases include the
AIST Spectral D atabase for Organic Compounds.
303
LHA
Worked example 11
Ethane reacts with chlorine to form product X. a. Determine the empiric al formula of product X.
Combustion analysis was used to determine that product

1
b. The mass and H NMR spectra of product X are shown
X has the following composition by mass: c arbon
below. Deduce, giving your reasons, its structural
24.27%, hydrogen 4.08%, chlorine 71.65%.
formula, and hence the name of the compound.
mass spectrum
1
H NMR spectrum
100
ytisnetni
80
60
evitaler
40
20
10 9 8 7 6 5 4 3 2 1 0
10 20 30 40 50 60 70 80 90 100 110

m/z
Solution
a. Divide the percentages by the relative atomic mass for From the mass spectrum, we c an deduce that the
each element. empiric al formula is identic al to the molecular formula
bec ause the average of the molecular ion peak m/z

24.27 4.08
c arbon: = 2.021 hydrogen: = 4.04

values is equal to the relative molecular mass of the
12.01 1.01
empiric al formula (99). We c an also deduce that the
71.65
chlorine: = 2.021
following structural elements occur in the molecule:
35.45
C H Cl and C H . Therefore, the structural formula of

2 4 2 4
The empiric al formula is therefore C H Cl

2 4 2
product X is likely to be CH CHCl . We c an conrm

3 2
b. When analysing mass spectra of compounds 1
this using H NMR spectroscopy.
containing chlorine, we need to consider that chlorine
The H NMR spectrum has two signals, indic ating two

has two abundant isotopes of dierent relative atomic
dierent hydrogen environments.

mass: chlorine-35 and chlorine-37. Therefore, the
fragment ions of product X will contain a mixture of

The integration trace shows a ratio of 3:1, indic ating
chlorine-35 and chlorine-37 atoms (table 18).

there are three times as many hydrogen atoms in one
environment than in the other.
Molecular
m/z Reason
fragment The signal at 2.0 ppm is a doublet (H ), indic ating

A
a neighbouring hydrogen environment with one

35 37 +
100 [C H Cl Cl] molecular ion containing

2 4
proton. At 5.8 ppm there is a quartet (H ), indic ating

B
chlorine-37 and chlorine-35
a neighbouring hydrogen environment with three
isotopes
protons. We c an therefore conclude that product X is
35 +
98 [C H Cl ] molecular ion containing two

2 4 2
1,1-dichloroethane:
chlorine-35 isotopes
H Cl
A
37 +
65 [C H Cl] loss of chlorine-35 atom from

2 4
molecular ion peak (m/z 100)
H C C H
A B
35 +
63 [C H Cl] loss of chlorine-35 atom from

2 4
molecular ion peak (m/z 98)

H Cl
A
27 [C H ] loss of HCl and Cl

2 3
pTable 18 F ra g m e n t ions of product X
304
LHA
4. Which of the following analytic al techniques would
Topic review
show the dierence between propan-2-ol,

CH CH(OH)CH , and propanal, CH CH CHO?
3 3 3 2
I. mass
How does the classication of organic molecules help us
II. infrared
to predict their properties?
III. H NMR
A. I and II only
B. I and III only
2. What is the name of the following compound, applying

C. II and III only
IUPAC rules?
D. I, II and III
CH
3
5. Which substance has the following H NMR spectrum?

H C
2
HC C
CH
H C 3
3
H
A. 4-methylhex-2-ene
B. 4-ethylpent-2-ene
C. 2-ethylpent-3-ene
5 4 3 2 1 0
D. 3-methylhex-4-ene PPM
3. Which of the following is in the same homologous

A. propane
series as CH OCH ?
3 3
B. propanal
A. CH COCH
3 3
C. ethyl ethanoate
B. CH COOCH
3 3
D. butanoic acid
C. CH CH CH OH
3 2 2
D. CH CH CH OCH
3 2 2 3
LHA
6. a. State, giving a reason, if but-1-ene exhibits cis–trans
isomerism. [1]
b. The reaction which occurs between but-1-ene and
hydrogen iodide at room temperature produces
the halogenoalkane, 2-iodobutane. State, giving
a reason, if the product of this reaction exhibits
stereoisomerism. [1]
305
LHA
7. Organic chemistry c an be used to synthesize a variety of products. Combustion
analysis of an unknown organic compound indic ated that it contained only c arbon,
hydrogen and oxygen.
a. Deduce two features of this molecule that c an be obtained from the mass
spectrum, namely m/z 58 and m/z 43. Use section 22 of the data booklet. [2]
120
43
100
ytisnetni evitaler
80
60
40
58
20
15
42
27
39
37 41
14 26 29
36 38 40 44
28 31 57
16 25
15 20 25 30 35 40 45 50 55
m/z
b. Identify the bond responsible for the absorption at A in the infrared spectrum.
Use section 20 of the data booklet. [1]
1.2
1.0
ecnattimsnart
0.8
0.6
0.4
0.2
0.0
3500 3000 2500 2000 1500 1000 500
1
wavenumber / cm
c. Deduce information from the H NMR and then identify the unknown compound
using the previous information, the H NMR spectrum and section 21 of the
databooklet. [3]
10 9 8 7 6 5 4 3 2 1 0
chemic al shi / ppm

306
LHA
8. a. Draw the stereoisomers of butan-2-ol using wedge-dash type
representations. [1]
b. Outline how two enantiomers c an be distinguished using a polarimeter. [2]
9. Compound A is in equilibrium with compound B
OH
O
A B
a. Identify the functional groups present in each molecule. [2]
b. Compound A and B are isomers. Draw two other structural isomers
with the same formula. [2]
LHA
c. The IR spectrum of one of the compounds is shown:
0.9
0.8
0.7
ecnattimsnart
0.6
0.5
0.4
0.3
0.2
0.1
0.0
4500 4000 3500 3000 2500 2000 1500 1000
1
wavenumber / cm
Deduce, giving a reason, the compound producing this spectrum. [1]
10. The mass spectrum of chlorine is shown.

ecnadnuba
evitaler
0 10 20 30 40 50 60 70
m/z
a. Outline the reason for the two peaks at m/z = 35 and 37. [1]
b. Explain the presence and relative abundance of the peak at m/z = 74. [2]
11. a. Draw the structural formula of ethoxyethane. [1]
b. Deduce the number of signals and chemical shis with splitting patterns in the
H NMR spectrum of ethoxyethane. Use section 21 of the data booklet. [3]
307
To o l s for Chemistry
Introduction
The purpose of this section is to provide you with a toolkit containing key experimental, technologic al and mathematic al
skills that support scientic inquiry in DP chemistry. You should refer to this section frequently throughout the course to
develop uency with these skills and practise applying them in a variety of contexts. Such contexts might include skills
tasks, practic al work, lab-based questions, the collaborative sciences project, and your scientic investigation for internal
assessment (IA).
 Figure 1 Al-R āzī (c. 860–930) was an Islamic Persian scholar, physician and alchemist
308
Tool 1: Experimental
techniques
S afety and respect of self, others and environment
Being principled is one of the learner prole attributes. This means that you act
with integrity and honesty, with a strong sense of fairness and justice, and that
you take responsibility for your actions and their consequences. In conducting
experimental work, being principled involves lab safety and ac ademic integrity.
S afety
Two of the twelve green chemistry principles relate to prevention: accident
prevention and waste prevention
Accident prevention is an integral and important part of labwork. It includes
wearing protective gear, conducting risk assessments, putting the correct safety
measures in place, and eliminating risks by opting for safer alternatives if possible.
S afety considerations must protect the experimenter, the environment, as well as
anybody else using the laboratory space.
Familiar personal protective equipment (PPE) includes safety goggles and lab coats
for the people present during the experiment. The use of PPE is commonplace in
schools and laboratories these days, but it has not always been the case. When
looking at historical photographs or images of science experiments, see if you can
identify any safety risks and discuss suitable control measures.
A risk assessment needs to be completed prior to c arrying out experiments.
Assessing risk involves identic ation of hazards, ways of minimizing risk, and what
to do if something goes wrong. The main parts of a risk assessment are:
• Hazards: substances or activities that have the potential to c ause harm (for
example, a hot crucible).
• Risks: evaluating the severity and likelihood of harm, including who could
get harmed and how (continuing with our example, the person doing the
experiment could burn themselves if they touch the crucible. This is likely to
happen if they need to measure the mass of the crucible and its contents).
• Control measures: what will be done to minimize the risk and, if possible,
remove the hazards (the experimenter should wait 5 minutes for the crucible
to cool before placing it on the balance, and pick it up using tongs. The
balance should be loc ated near the experimenter ’s lab bench).

 Figure 2 A selection of hazard symbols
that you are likely to see on reagent bottles
S afety is not only relevant during the experiment, but also aer its completion.
in a chemistry lab. Do you know what each
Chemists need to think about the products of their experiments and identify
of them means?
suitable disposal procedures. The disposal of chemic als needs to be done in
accordance with loc al rules and policies in order to protect the environment, as
well as people involved in the disposal process. If possible, le-over reagents
should be recovered for future use.
309
Tools for Chemistry
ATL Research skills
Research the 12 principles of green chemistry and try to complete the blanks in gure 3.
oday I’m interviewing Well, we use renewable feedstocks
It involves making chemic al

How do you do that?
r merald, who leads where possible. So our company
processes as sustainable
the way in green chemistry. makes polyester from corn
as possible.
So, r merald, ust what starch instead of crude oil.
is green chemistry ?
And I guess you try to

We reduce waste by ........................
es, of course. We do this by ............
How else do you make
make processes energy

.....................................................
.....................................................
processes sustainable?
efficient?
.....................................................
.....................................................
.....................................................
.....................................................
.....................................................
.....................................................
.....................................................
.....................................................
What about pollution? How do you In lots of ways es. We always aim to replace toic
Anything else you

reduce the waste that spews out wo of them are feedstocks with ones that do not
want to say?
into the atmosphere, water ................................. threaten human health
and the ground? ................................. or the environment.
.................................
.................................
, that’s
.................................
great. hanks
.................................
.................................
.................................
.................................
 Figure 3 This comic strip shows two people discussing green chemistry. Think of examples to ll in the blanks
310
Tool 1: Experimental techniques
Experiments should involve using the smallest possible amounts of reagents.
Doing so further minimizes the environmental and economic impact of
practic alwork.
Ac ademic integrity
Respecting others includes respecting their ideas and giving them credit by
citing information sources. You must clearly distinguish between your own words
and those of others using quotation marks followed by an appropriate citation.
In-text citations are also required when you paraphrase another person’s ideas.
Full references should then be included in a section at the end of the document
(usually titled bibliography, works cited or references). The IB does not mandate
a particular referencing style, but it is expected that the minimum information
included are the name of the author, date of public ation, title of source, page
numbers and URL, if applic able.
Practice questions
1. State which hazard symbols are you likely to nd on a bottle containing:
a. concentrated nitric acid
b. 0.10 mol dm sulfuric acid
c. solid copper(II) sulfate
d. solid sodium metal
e. cyclohexane.
2. Find out what referencing system is used at your school, then write a full
reference for this book.
 Figure 4 Bottles containing
3. What are some of the hazards associated with the two reagents in concentrated solutions of sulfuric acid and
gure4? hydrogen peroxide
Measuring variables 55 °C 55 °C
tr ue
Handling data is a vital skill of scientic research. Qualitative data include all
value
non-numeric al information not obtained from measurement, such as colour
changes or bubbling. Quantitative data are numeric al information obtained
from measurement. Measurement is a core aspect of science and is important to
50 °C 50 °C
scientists bec ause it provides quantitative data. One of the factors aecting data
quality is the type of instrument used to obtain these data, as well as whether it
was used correctly or not.
Accuracy and precision

45 °C 45 °C
precise accurate
Measured values (and processed values) c an be evaluated in terms of their
(but not accurate) (but not precise)
precision and accuracy (gure 5). Repeating measurements under the same
conditions allows us to assess their precision: precise values are close to each  Figure 5 Precise values are close to each
other. Therefore, if a high-precision instrument is used to determine a particular other. The mean of accurate values is close
to the true value

measurement several times, the measured values will occur over a small range.
Accuracy refers to how close a measured or processed value is to the true value.
311
Tools for Chemistry
low precision low precision high precision high precision
and low accuracy and high accuracy and low accuracy and high accuracy
 Figure 6 The dierence between accuracy and precision. The bullseye represents the true value
Data-based question
Aer performing a c alorimetry experiment, a group of How would you describe these results in terms of
students determined the enthalpy of combustion of accuracy and precision?
ethanol. Their results are shown below.
A. high accuracy, low precision
B. low accuracy, high precision

Trial 1 2 3 Mean
ΔH / kJ mol ± −705 −707 −701 −704

C. high precision, high accuracy
5 kJ mol
D. low precision, low accuracy
Ethanol’s standard enthalpy of combustion is reported in
the data booklet as −1 367 kJ mol .
Validity and reliability
ATL Thinking skills
The quality of measurements, and indeed of entire pieces of research, is oen
assessed in terms of validity and reliability.

In a c alorimetry experiment, for
example, the assumption that the
Validity is concerned with whether something measures what it is meant to
specic heat c apacity of a dilute
measure. Measuring pH with an improperly c alibrated pH probe will result in an
solution is equal to that of water
invalid measurement. A methodology or analysis is valid when it addresses the
does not invalidate the analysis
research question appropriately.
bec ause dilute solutions are mostly
composed of water (Reactivity 1.1).

Reliability is connected to whether doing the same investigation again produces
C an you think of other reasons why

the same results. Reliability c an be assessed in terms of repeatability: the
this is usually a valid assumption?

agreement of results when trials are repeated using identic al methods, c arried
C an you think of any situations in

out under the same conditions and by the same experimenter.
which this assumption would not
Repeating trials during an experiment is good practice. When you do a

be valid?
school practic al, you c an compare the results of dierent trials to assess their
repeatability. Conducting several trials allows you to c alculate a mean, assess
precision and identify any clear outliers. The more repeats, the more reliable the
results, but doing three trials is usually a good rule of thumb.
In some c ases (certain statistic al tests for example) greater numbers of replic ates
are required. In others (such as titrations), measurements should be repeated until
several concordant values are obtained. Concordance means that the values
agree with each other, and in titrations this generally means a range of less than
0.1 cm (although this value is not set in stone, and it is best to specify it when
writing up lab investigations).
312
Reproducibility is the consistency of results obtained by following the same
Practice questions
method and conditions but c arried out by dierent people, instruments and
reagent sources. Comparing the outcomes of an experiment to those obtained

4. Explain why measurements
by dierent research teams gives scientists insight into the reproducibility of their
taken with a pH probe are
results. One of the reasons scientists include detailed experimental methods

more precise than pH values
when reporting ndings is to allow other scientists to reproduce these ndings.

determined using pH paper.
5. C an experimental outcomes be
Next, we will consider several key types of measurements in chemistry: mass,
reliable but not valid?

volume, time, temperature, length, pH, electric current and electric potential
dierence.
M ass
Dierent balances have dierent levels of precision. In a chemistry lab, the
greater the precision of a balance, the greater the number of decimal places it
will measure mass to. When writing down a value, do not leave out any trailing
zeroes. For example, a mass recorded to four decimal places (e.g. 0.5000 g) was
measured with a more precise balance than a mass recorded to only one decimal
place (e.g. 0.5 g).
Gravimetric analyses involve the measurement of mass changes during a
chemic al reaction. For example, the reaction mixture that produces a gas will
decrease in mass over time bec ause the mass of the esc aped gas will be lost.
Another example is the mass increase that happens when magnesium burns
in air. The mass of the reaction mixture before and aer the reaction provides
information on how much gas was produced or absorbed. It is worth noting
that not all containers, however similar they may seem, have the same mass.
 Figure 7 A digital balance. Why is there a
Remember to record the mass of the empty container when conducting a number on the display even though there is
gravimetric analysis. nothing on top of the balance?
Data-based question
A student wishing to determine the enthalpy of hydration of copper(II) sulfate collected the following data. A mistake
was made when the mass was being measured. Identify the mistake and suggest what might have c aused it:
M ass / g ± 0.01 g
M ass of empty crucible 13.55
M ass of crucible and hydrated copper(II) sulfate 11.96
M ass of crucible and anhydrous copper(II) sulfate 11.60
Practice questions
6. Which of the following mass measurements was
obtained using the most precise balance?
A. 0.0007 g
B. 2.0 g
C. 2.030 g
D. 100.10 g
7. Is the feather shown in the photo really massless?
313
Tools for Chemistry
Volume
The suitability of a particular type of volume-measuring equipment depends on
its intended function and the desired level of precision. Measuring cylinders
designed to measure approximate volume are not very precise.
Volumetric analyses involve the measurement of volume changes during a
chemic al reaction. For volumetric analyses, a pipette, burette and/or volumetric
asks are needed. Beakers and conic al asks give an approximate measurement
of the volume and are designed for holding liquids, not measuring volume.
A B C D
 Figure 8 A liquid being released from a  Figure 9 Various volume-measurement devices. A – measuring cylinder, B – volumetric
volumetric pipette into a conic al ask pipette, C – burette, D – volumetric ask
M any liquids, including aqueous solutions, form a U-shaped meniscus inside
a narrow vessel, such as a burette or the neck of a volumetric ask. Volume
measurements should be read from the bottom of the meniscus (gure 10).
read from the bottom
of the meniscus
burette
tap
 Figure 10 Water and aqueous solutions  Figure 11 Mercury forms an upside-down meniscus,
form a U-shaped meniscus where the centre bulges upwards above the sides
314
Practice questions
8. Which of the following are appropriate for precise volume measurements?
• volumetric pipette
cm
• volumetric ask
100
• burette
90
80
• beaker
70
• conic al ask 60
60
• measuring cylinder
50
50
40
9. What glass container would you use to:
30
a. determine the volume of liquid added during a titration
20
b. prepare a standard solution from a solid reagent

10
c. c arry the acid you need for a pH experiment from the reagent bottle
to your lab bench
 Figure 12 The meniscus should be read
3
at eye-level
d. approximately measure 25 cm of liquid?
10. What is the volume of liquid contained in the measuring cylinder in gure12?
Time
The SI unit for time is the second (s). When measuring the rate of a chemic al
reaction, for example, you might use a stopwatch to record how long it takes, in
seconds, for a certain volume of gas to be produced. The uncertainty associated
with time measurements usually depends on the context in which time is being
measured. The uncertainty of the stopwatch itself is oen far smaller than the
uncertainty arising from the experimenter ’s reaction time.
For example, if you are recording how long it takes for a clock reaction to produce
a change in colour, there will be a short delay between the instant the colour
changes and your nger stopping the stopwatch (gure 13). The stopwatch display
might indicate a time of 16.45 seconds, which might suggest an uncertainty of
± 0.01 s indicated by the two-decimal-places display (gure 13). A more realistic
uncertainty, given your reaction time, would be around 0.5 to 1second.
ATL Thinking skills
Some experiments take place
over long periods of time, such
as hours, days, or even weeks. In
these c ases, is it always necessary
to record times to the nearest
second?
 Figure 13 In the “iodine clock” reaction, the clear and colourless reaction mixture
suddenly turns blue-black aer a certain period of time
315
Tools for Chemistry
Temperature
You c an use digital or analogue thermometers to measure temperature. The
required accuracy and precision of a temperature measurement is highly
dependent on the context of the experiment.
Continuous monitoring of temperature c an be achieved by connecting a
temperature probe to a data logger as shown in gure 14
interface
.pmet
time
temperature
sensor
ammonium chloride
dissolving in water
 Figure 14 Temperature sensors and data loggers c an be used to
monitor the temperature changes over time
Length
Length measurements usually involve rulers although other devices, such as
Signic ant gures are discussed in
c alipers, c an also be used. As with other analogue devices, reading the sc ale
detail in Tool 3: Mathematics.
usually involves estimating the last digit in the measurement, depending on its
loc ation between two sc ale divisions. Sc ale resolution will therefore have an
impact on the number of signic ant gures in the measurement (gure 15).
1 2 3 4
1 2 3 4
1.7 cm
1.75 cm
This ruler gives a reading to two significant figures This ruler gives a reading to three significant figures
 Figure 15 The relationship between sc ale resolution and signic ant gures
316
Practice questions
11. A student conducted three trials of an iodine clock reaction. The reagent
concentrations and temperatures were the same in all three trials. The
results obtained, in minutes, seconds and milliseconds (min:s.ms) are
shown below.
a. State the times to the nearest second.
b. Suggest a suitable uncertainty for the time measurements, in
seconds.
c. C alculate the mean time, in seconds.
Time taken for the colour change to occur
Trial
/ min:s.ms
/ s Mean / s
± 1 ms
1 01:15.120
2 01:10.400
3 01:12.985
12. Identify and explain the limitations of each of the following temperature
measurement scenarios and propose an alternative method.
a. A student heats 5 cm of water in a beaker and checks the
temperature by placing a thermometer in the water, with the bulb
touching the bottom of the beaker.
b. A student wishing to perform a reaction at 2 °C cools one of the
reagents down to this temperature in a beaker, removes the beaker
from the ice bath, and adds the second reagent.
c. In a study of an enzyme action at 40 °C, a student places a test tube
containing a sample of the enzyme solution into a 40 °C water bath. The
student then immediately adds the substrate to the enzyme solution.
13. What is the length of the orange bar?
11 12 13 14 15 16 17 18 19 20
14. Figure 16 shows a device c alled a c aliper. What chemistry-related
measurements might you obtain using a c aliper?
 Figure 16 A vernier c aliper
317
Tools for Chemistry
pH of solution
The pH of a solution is related to the concentration of hydrogen ions in that
solution. pH c an be estimated with indic ators, such as universal indic ator, or the
anthocyanins extracted from red c abbage. These indic ators vary in colour across
the entire pH sc ale. The colour shown is compared to a key, allowing a pH value
to be estimated (gure 17).
The pH of a solution c an be more reliably determined with a properly c alibrated
pH probe (gure 18).
 Figure 17 pH paper turns dierent
colours depending on the pH of the

substance being tested






 Figure 18 A pH probe reading compared to the colour of the universal indic ator
Using a natural acid–base indic ator
In this task, you will use the juice of red c abbage as a Materials
natural acid–base indic ator for determining the pH of • red c abbage
household products.
• two liquid household products, such as vinegar or
Red c abbage juice is rich in anthocyanins (HA), which are liquid detergent
amphiprotic organic compounds. In acidic solutions with
• two solid household products, such as baking soda or
low pH, anthocyanins accept protons and form c ations,
antacid tablets
+
H A . In basic solutions with high pH, anthocyanins lose

2
• five clear glasses

protons and form anions, A :
+ + • cloth or filter paper

H H
+
H A HA A
2
• standard laboratory glassware

+ +
+ H + H
cationic form neutral form anionic form
Method
(red) (blue) (green to yellow)
1. Prepare the indic ator by blending several leaves
All three forms (c ationic, neutral and anionic) of
of red c abbage with a glass of water and filter the
anthocyanins absorb visible light at different wavelengths
resulting mixture through cloth or paper.
(Structure 1.3), producing the characteristic colour
2. To test one of your liquid household products, pour

changes of red c abbage juice.
20–30 cm of the filtered c abbage juice into a clear
Relevant skills glass and add 2–3 cm of the analysed solution.
• Tool 1: Measuring variables
3. To test one of your solid household products, crush
• Inquiry 1: Designing the solid and dissolve it in water, before mixing with
the c abbage juice.
S afety
4. Compare the colours of your solutions with
• Wear gloves and eye protection
thoseshown in figure19 to determine their
• Do not use products with a corrosive safety warning approximate pH.
318
 Figure19 Red c abbage juice at pH 1 (le) to 10 (right)
Practice questions
15. What are the pH values of each of the substances tested in gures 17 and
18? What might a suitable uncertainty be in each c ase?
16. O utline one advantage and one disadvantage of
a. pH indic ators
b. pH probes.
circuit 1
switch
Electric current
Electric current is the rate of ow of electric al charge. It is measured in amperes A
(A), using an ammeter. To measure current, the ammeter must be connected in
series in the circuit. The simplest type of circuit is one where all the components
are connected one aer another, following a single path, with no branches.
solid to be tested
Current is the same throughout a series circuit, so the ammeter c an be placed
anywhere in the circuit.
circuit 2
switch
Figure 20 shows how to connect solid and liquid samples in a series
circuit powered by a battery pack. Inserting a solid into a circuit is usually
straightforward: you simply connect the leads to either end of the solid. Inserting
A
a conductive liquid or solution (collectively known as electrolytes) requires
electrodes made of inert materials, such as graphite or platinum. C are must be
taken to ensure that the electrodes do not touch each other.
beaker
Current depends on factors such as electrode surface area, distance between the
electrodes, voltage applied and the materials involved. These factors all aect the carbon
opposition to the ow of charge within the circuit, known as resistance. electrodes
solution
1 to be
Electric al conductivity, oen given in microsiemens per centimetre, µS cm ,
tested
is a related property, which is the ability to conduct charge and which c an be
measured directly with a probe. Electric al conductivity measurements c an

 Figure 20 Ammeters are connected in
be used to monitor the progress of a reaction in which ions are consumed or

series. Circuit 1 shows how to connect a
produced bec ause conductivity of a solution depends on the concentration and solid sample while circuit 2 shows how to
identity of mobile ions present. connect a solution
319
Tools for Chemistry
Electric potential dierence
Potential difference is the energy dierence per unit charge between two points
in a circuit. It is expressed in volts (V) and measured using a voltmeter. Voltmeters
measure the potential dierence across circuit components and are therefore
connected in parallel to the component being measured (gure 21).
4
6
2
8 In chemistry, you will most likely encounter potential dierence measurements

0
10
in the context of voltaic cells. The potential dierence between the anode and
c athode is known as cell potential. Measuring cell potential involves connecting
the voltmeter to the two half-cells and completing the circuit with a salt bridge as
 Figure 21 Voltmeters are connected

shown in gure 22.
in parallel to a component to measure
its potential dierence (in this c ase, the

V
potential dierence of the lamp is being
voltmeter
measured)
A B
salt bridge
Practice questions
17. O utline how current passes
through solid materials, such
as a copper wire or graphite
electrode.
18. O utline how current passes
through electrolytes, such as
solution containing solution containing
molten lead(II) bromide or

2+ 2+
A (aq) B (aq)
aqueous sodium chloride.
 Figure 22 The potential dierence across the two half-cells is measured by connecting a
voltmeter to the electrodes. A and B represent metals
Another term you might come across is electromotive force (emf ), which is the
maximum value of potential dierence across a cell when no current is owing.
This is the reason why high-resistance voltmeters are used to measure cell
potential. Their high resistance means that virtually no current ows through
them, hence the cell potential measured is close to the emf.
Practice questions
19. Explain why the following mixtures undergo a change in conductivity as
the reaction proceeds.
a. HCl(aq) + NaOH(aq) → NaCl(aq) + H O(l)

2
b. AgNO (aq) + NaBr(aq) → AgBr(s) + NaNO (aq)

3 3
20. In this section you have considered how to measure key types of variables:
mass, volume, time, temperature, pH, current and potential dierence.
For each variable, think of an experiment you have done in the past which
involved measuring that variable, and state the instrument used.
320
Applying experimental techniques
In this section, we will discuss experimental techniques for preparing, isolating
and analysing chemic al species and phenomena.
Preparation
Preparation of a standard solution
Preparation and dilution of standard solutions requires measuring masses and
volumes with high precision. This is achieved by using an analytic al balance
and volumetric glassware, such as burettes, pipettes and volumetric asks
(gure23).
A standard solution is usually prepared as follows:
1. The solid (or sometimes liquid) solute is weighed in a clean and dry beaker
using an analytic al balance.
2. A small volume of deionized water is added to the beaker, and the mixture is
stirred with a glass rod until the solid dissolves completely.

 Figure23 Volumetric ask and pipette
3. The solution is transferred to a volumetric ask using a glass funnel.
4. The beaker, glass rod and funnel are rinsed three times with deionized water,
each time adding this water into the volumetric ask to ensure that the solute
is transferred completely.
5. Deionized water is added to the volumetric ask until its level reaches the
graduation mark on the ask.
6. The ask is stoppered and turned over at least ten times to ensure that the
solution is mixed thoroughly.
7. The solution is transferred to a reagent bottle with a label showing the
formula or name of the substance, its concentration, the date and initials
of the person who prepared the solution, as well as any hazard labels, if
relevant.
stirring
rod
paper
wedge
wash
stirring rod bottle
18/08/2023,
P.M.D., 1.51
–3
mol dm
1 2 3 4 5  
 Figure 24 Preparation of a standard solution
Measuring cylinders and beakers with graduation marks should never be used
for preparing or diluting standard solutions, as they do not allow measurement of
volumes with sucient precision. Similarly, the balance must show the mass of a
sample with at least four signic ant gures.
321
Tools for Chemistry
Practice questions
3 3
22. A student prepares 100 cm of a 0.50 mol dm

21. These steps outline how to prepare a standard
solution of copper(II) sulfate by c arrying out the

solution. List them in the correct order.
following steps. Identify the mistakes.
A. Add deionized water up to the mark on the
A. A sample of 7.98 g of hydrated copper(II) sulfate

volumetric ask.
was weighed and transferred into a volumetric
B. Dissolve the solute in a small amount of deionized
ask using a funnel.
water in a beaker.
B. Tap water was added to the volumetric ask until
C. Transfer the solution to a labelled reagent bottle
it was close to the mark on the neck of the ask. At
for storage.
this point water was added dropwise. Too much
water was accidentally added, so the meniscus

D. Pour the solution into a volumetric ask.
went above the mark. Excess water was c arefully
E. Weigh the desired mass of the solute.
removed until the meniscus was back at the mark.
F. Rinse the beaker, funnel and stirring rod with
C. The ask was stoppered and inverted twice.
deionized water over the volumetric ask.
D. A label was placed on the volumetric ask
G. Stopper and invert the ask several times.
for storage.
23. Sodium hydroxide is hygroscopic, meaning that it
absorbs air moisture. Suggest the implic ations of this
property for the preparation of standard solutions of
sodium hydroxide.
Preparation of solutions by dilution
To dilute a standard solution, a certain volume of the solution is measured using
a burette or volumetric pipette and transferred to a volumetric ask. Deionized
water is added to the graduation mark, and the stoppered ask is turned over
several times to achieve a uniform composition of the nal solution.
bottle A bottle B
 Figure 25 The solution in bottle B c an be prepared by performing a simple dilution of the
stock solution in bottle A
322
Worked example 1
3 3
A teacher wishes to prepare 0.500 dm of 0.400 mol dm HCl for a class
practic al. A 11.0 mol dm HCl stock solution is available. Determine the
volume of stock solution required to prepare the desired solution.
Solution
We know that:
c × V = c × V
1 1 2 2
where 1 indic ates the stock solution and 2 indic ates the desired solution.
Substituting the known values gives:
3 3 3
(11.0 mol dm ) × V = (0.400 mol dm ) × (0.500 dm )

1
Solving for V gives:

1
3 3
0.400 mol dm × 0.500 dm
V =
1 3
11.0 mol dm
V = 0.01818182… dm
1
Convert to cm , which are more easily measured in a lab, and round to three
signic ant gures:
3 3
V = 18.1818182… cm ≈ 18.2 cm (3 sf )
1
Serial dilutions are used to accurately prepare a series of solutions of increasingly
C alibration curves are introduced
lower concentration. Solutions for c alibration curves are often prepared using this
in Structure 1.4
method, as extremely low concentrations are often required. Figure 26 shows
how to c arry out a serial dilution where the solution in each successive tube is
ten times more dilute than that in the previous one. The solution in each test tube
3 3
Practice questions
is prepared by transferring 1 cm of the preceding solution and adding 9 cm of
deionized water. This procedure is repeated until the desired final concentration
24. A technician wishes to prepare
is obtained.
the following solutions by
diluting a 5.00 mol dm stock
HCl solution. What volume of

3 3 3 3
1 cm 1 cm 1 cm 1 cm
the stock solution is needed in
each c ase?
3 3
3 3 3 3
+9 cm +9 cm +9 cm +9 cm a. 750 cm of 1.00 mol dm
HCl (aq)
b. 3.00 dm of
0.150 mol dm HCl (aq)
25. Suppose that the concentration
of the stock solution in gure
26 is 0.50 mol dm . Determine
stock 1 0.1 0.01 0.001

3
the concentration, in mol dm ,
solution 10 10 10 10
of each of the diluted solutions.
1 1 1
( 100 ( ( 1000 ( ( 10000 (
 Figure 26 A serial dilution
323
Tools for Chemistry
Reux and distillation
Reux and distillation are easily confused bec ause they involve similar equipment
(gure 27). However, these methods are used for very dierent purposes. Reux
is a method used to heat reaction mixtures, whereas distillation is a separation
method. A piece of equipment known as a condenser is used in both c ases.
The condenser is essentially a tube within another tube. The outer tube is cooled
by a continuous ow of cold water. As a result, the temperature of the gaseous
substances in the inner tube decreases, c ausing them to condense. You will also
notice that both techniques use anti-bumping granules to ensure smooth boiling.
Next, we will discuss the dierences between reux and distillation.
(a) (b)
thermometer
water
out
condenser
water out
condenser
water in
water in
impure product
anti-bumping granules
heat
reaction mixture
anti-bumping
granules purified product
heat
 Figure 27 (a) Reux apparatus (b) simple distillation apparatus
Reflux is used to minimize the loss of volatile substances during continuous
heating of a reaction mixture. A condenser is placed above the reaction ask, so
that any vapours rising from the reaction mixture condense and drip back down
into the ask instead of esc aping.
Distillation is used to separate the components of a mixture according to their
boiling points. The mixture is heated until the boiling point of the more volatile
component is reached. The substance with the lower boiling point rises into
the still head, condenses in the condenser, and is collected at the bottom of the
condenser. Remember that temperature stays constant during state changes, so
the temperature shown on the thermometer will remain constant at the boiling
point of whichever substance is being distilled o.
Figure 27(b) above depicts simple distillation, which separates a volatile
liquid from a non-volatile solid (or two liquids with very dierent boiling points).
For example, an aqueous solution of copper(II) sulfate c an be separated into
copper(II) sulfate and water using this method.
324
Fractional distillation is a related technique, used to separate mixtures of two
Practice questions
or more miscible and volatile liquids with similar boiling points (gure 28), such
as an ethanol–water mixture. A fractionating column is tted to the ask. As the

26. Compare and contrast reux
mixture is heated, the substances in the mixture continually vaporize, rise into the
and simple distillation.
column, condense on the glass beads and drip back down into the distillation
27. Compare and contrast simple
ask. The cycle repeats many times. The vapours contain a greater proportion
and fractional distillation.
of the lower-boiling-point component, which eventually reaches the top of the
column and enters the condenser. The receiving ask is sometimes placed in an 28. Primary alcohols such
ice-water bath, particularly if the distillate is volatile. A fresh receiver is used to as ethanol are oxidized
collect each distillate. by acidied potassium
dichromate, rst to aldehydes.
Eventually, and if there is
enough oxidizing agent, the
thermometer
aldehydes are further oxidized
to c arboxylic acids. Identify
and outline which technique,
distillation or reux, you would
fractionating water out
use if you were looking to

column with a
condenser
obtain (a) an aldehyde and
large surface area
(b) a c arboxylic acid.
cold
water in
distillation flask
receiver
anti-bumping
granules
heat
 Figure 28 Fractional distillation apparatus
Industrial-sc ale fractional distillation is used to separate mixtures such as crude oil
(gure 29) and liquid air.
t Figure 29 An industrial fractional
distillation facility, used to separate the
components of crude oil
325
Tools for Chemistry
Isolation
Drying to a constant mass
When a solid is obtained in the lab, it may contain trace amounts of water, even if it
looks dry. Solid samples are oen dried to a constant mass to ensure that they do
not contain any water (or other volatile impurities). Drying to a constant mass involves:
1. heating the sample
2. allowing it to cool for a few minutes
3. weighing it
4. repeating the process until two consecutive equal masses are obtained.
A suitable heating method should be chosen to ensure that the desired solid
does not decompose. Common heating equipment includes Bunsen burners,
hotplates and drying ovens.
Practice question
29. You c an determine the water of hydration of a hydrated salt, such as
magnesium sulfate, by heating the salt to remove the water and measuring
the mass before and aer heating:
heat
MgSO •xH O(s) xH O(g) + MgSO (s)

4 2 2 4
Explain why, when determining the water of hydration of magnesium
sulfate, the magnesium sulfate should be heated to a constant mass.
Separation of mixtures
The method used to separate a mixture depends on the properties of the mixture
components. For example, if one of the components is magnetic, it can be removed
using a magnet. Mixtures of solids and liquids can be separated using ltration,
crystallization or simple distillation. Mixtures of liquids can be separated with
fractional distillation or using a piece of equipment known as a separating funnel.
Filtration separates particles according to their sizes by passing them through a
medium, such as lter paper, which contains tiny holes or pores. Filtration is oen
used to separate insoluble solids from liquids. Liquid or aqueous particles are
usually much smaller than solid particles, so they easily pass through the holes in
the lter paper. The solid le behind in the lter paper is known as the residue
and the liquid that passes through is the filtrate.
In gravity filtration (gure 30), as its name suggests, the ltrate passes through
the paper due to gravity.

 Figure 30 Gravity ltration
326
This process c an be very slow, so it is sped up by fluting the lter paper. Fluting
involves folding the lter paper into an accordion shape (gure 31) before placing
it inside the funnel.
fold to crease the fold to crease the this is the open filter
quarter sections eighth sections “accordion” shape cone
 Figure 31 Figure showing the steps for making a uted cone from circular lter paper
Vacuum filtration is quicker than gravity ltration, and it is oen used when the
residue is the desired component of the mixture. The mixture is loaded onto a
sheet of moist lter paper laid at on the perforated plate inside a Buchner funnel.
Suction from a vacuum pump draws the liquid through the lter paper and into
filter paper
a receiving ask underneath (gure 32). C are must be taken not to overll the
funnel to prevent the solid from slipping under the lter paper. The residue is Buchner
funnel
usually rinsed three or four times with the solvent to remove soluble impurities.
A solid can be crystallized out of a solution by removing the solvent. Most of
the solvent is evaporated o by heating it over boiling water until the solution
vacuum pump
conical
becomes saturated. The solution c an be checked for saturation by spotting a
flask
drop of it onto a cold tile and watching for the formation of crystals as it cools. The
bulk of the remaining solution is le to cool slowly to allow crystals to form. Finally,
any remaining solvent is removed from the crystals by ltration (if necessary), and
the crystals are allowed to dry to a constant mass on a watchglass.  Figure 32 Vacuum ltration apparatus
copper(II) sulfate
solution
evaporating
basin
boiling
water
solution from
evaporating basin
Bunsen
burner
cold tile leave for a few
days to crystallize
 Figure 33 Crystallization apparatus
327
Tools for Chemistry
A solvent c an also be removed from a solute through simple distillation, or rotary
evaporation, which is a type of distillation performed at low pressures to reduce
the solvent’s boiling point.
Practice questions
30. Figure 34 shows the preparation and isolation of salt crystals from the reaction between an acid and an insoluble
base. Copper(II) sulfate crystals c an be made this way, from the reaction between sulfuric acid and copper(II) oxide.
salt unreacted
solution base
warmed
mixture of
base
filter
excess base
crystals
funnel
and acid
start to
form
filter to remove
evaporate the filtrate until

heat
unreacted base
crystals start to form
leave to
salt
cool
crystals
dry crystals to
constant mass
filter the cooled
mixture
 Figure 34 Summary of the preparation and isolation of an inorganic salt by reacting an insoluble base with an acid
a. Identify what is removed in the rst ltration step.
b. Sometimes solvents are evaporated by heating the evaporating dish
directly as shown. Discuss the advantages and disadvantages of doing
so, compared with heating the evaporating dish over a hot water bath as
discussed earlier in the chapter (gure 33).
c. Suggest why the solution is not evaporated to dryness.
328
Miscible liquids c an be separated by fractional distillation. Two immiscible
liquids (such as oil and water) c an be separated by placing them in a separating
funnel (gure 35). Aer ensuring that the stopcock is closed, the mixture is
oil
liquid
poured into the funnel. Soon aer, the liquids form two distinct layers. The
interface
water oil
denser, lower layer is then drained into an underlying beaker by opening the
stopcock, slowing down as the interface between the two layers approaches the
narrower neck at the bottom end of the funnel.
Separating funnels are also used to selectively extract solutes from one solvent
into another.
Recrystallization
Recrystallization is a puric ation process based on selective solubility that c an be
used to isolate a desired solid from a mixture of solids. Recrystallization is oen
used to purify organic synthesis products. This isolation technique requires a
water runs out
solvent that selectively dissolves dierent components of the mixture depending
of funnel
on the temperature.
 Figure 35 Separating an oil–water
The mixture of solids typic ally contains three types of components, each with
mixture with a separating funnel
dierent solubilities in the identied solvent:
• impurities that are insoluble in the solvent at all temperatures
Miscibility of liquids, molecular
• impurities that are soluble in the solvent at all temperatures polarity and intermolecular forces
are all discussed in Structure 2.2.
• the desired solid that we wish to isolate, which must be soluble in the solvent
when hot, but insoluble when cold.
The recrystallization process is detailed in gure 36.
insoluble impurities pure crystals

impure
solid
solvent
filter vacuum
hot cold pump
water
heat pure crystals forming
 Figure 36 Recrystallization process
1. First, the impure solid is dissolved in hot solvent. This c auses the desired
solid to dissolve, along with any soluble impurities.
2. Any insoluble impurities are removed by hot ltration.
3. The ltrate is allowed to cool slowly. Crystals of the desired solid form while
the soluble impurities remain in solution.
4. Cold vacuum ltration follows, removing the soluble impurities and isolating
the crystals which are then dried.
In a more complex form of recrystallization, two solvents are used. The process
starts o as usual, but aer the hot ltration step, a second solvent is added that
dissolves the remaining impurities but not the desired solid. This c auses the
desired solid to precipitate out.
329
Tools for Chemistry
Analysis
Practice questions
Melting point determination
31. What method would you
use to separate the following The purity of a solid c an be assessed by measuring its melting point. Organic
mixtures? solids frequently melt at low to moderate temperatures. A small sample of the
solid is placed in a c apillary tube. The sample is heated, observed closely, noting
a. a suspension containing
down the temperature(s) at which it starts and nishes melting. Pure substances
solid barium sulfate and an
have sharp melting points that agree with published values. If impurities are
aqueous sodium chloride
present, the melting point is usually lowered and the solid melts over a range of
solution
temperatures.
b. an ethanol–water mixture
Figure 37 shows how a Thiele tube c an be used in a melting point determination.
c. a sodium chloride solution
The c apillary tube containing the sample is attached to a thermometer and
lowered into an oil bath. The oil bath is then heated, slowing down the heating
d. a mixture of water and
rate as the expected melting point is approached. Two temperatures are

cyclohexane
recorded: rst, when the tiny yet visible droplets appear, and second, when the
e. aspirin, from a mixture
entire sample has just melted.
of soluble and insoluble
impurities
thermometer
opening to allow air in
and out of the apparatus
capillary tube
rubber band
oil or water bath
substance being tested
heat
 Figure 37 Melting point determination
with a Thiele tube
Electronic melting point apparatus may contain a built-in magnifying glass that
facilitates observation of the sample.
Data-based question
The following melting point data were collected aer performing certain organic syntheses. O utline what c an be
concluded about the purity of the products.
Experimental melting point of Theoretic al melting point of
Experiment
product / °C ± 1 °C product / °C
Synthesis of aspirin 122–129 136
Synthesis of methyl 3-nitrobenzoate 76–77 78
330
Chromatography
Chromatography is a collective term for a group of methods in which a mixture is
analysed by the separation of its components according to their relative anities
to the mobile and stationary phases. The two types of chromatography you
are likely to encounter as a DP chemistry student are paper chromatography
(gure38) and thin-layer chromatography (TLC) (gure 39).
solvent front
beaker
with lid
B B
C
chromatographic
L
paper 0
(stationary phase) L
B
A A
L
C
start line L
sample A
A B
start line
solvent
(mobile phase)
 Figure 38 The set-up for paper chromatography, and the resulting chromatogram
thin layer of atmosphere within
adsorbent the tank is saturated
coating – SiO with solvent vapour

2
solvent
front
components
separate out
on plate
plate
solvent
(plastic or metal)
1 2 3
TLC plate is prepared A small amount of the The end of the TLC
with a thin layer of sample in solution is plate is immersed in
adsorbent coating spotted onto the plate a pool of solvent
 Figure 39 Thin-layer chromatography (TLC)
In gure 38, the lengths marked L , L , L and L indic ate the distances travelled
A B C 0
by components A, B, C and the solvent, respectively. These lengths c an be used
to c alculate R values.
F
The c alculation of R values was discussed in Structure 2.2. Review the content of
F
Structure 2.2 and answer the practice questions on the next page.
331
Tools for Chemistry
Practice questions
32. Figure 40 shows a chromatography experiment involving leaf pigments.
a. O utline why a lid has been placed on the container.
b. Explain which component in the mixture has the greatest anity for the solvent.
33. A student investigating the components of a black food colouring sets up a
chromatography experiment as shownbelow:
beaker with lid
chromatography
paper
solvent
start line
A B C D E F
drawn in ink
black food
 Figure 40 Paper
colouring
chromatogram of leaf pigments
Describe and explain two errors in the set-up shown.
34. Complex mixtures c an be separated using a technique known as
two-dimensional chromatography. The chromatogram is run in one
solvent, rotated 90°, and run again in a second solvent (gure 41).
= origin
Leu
Leu
Glu
Glu
Asp
Asp
run the chromatogram in turn the paper 90° run the chromatogram
solvent 1 in solvent 2
(butanol / ethanoic acid / (phenol / water then add
water miture locating agent
 Figure 41 Two-dimensional chromatography of an amino acid mixture
Study gure 41 and answer the questions below:
a. State which amino acid has the greatest anity for solvent 1.
b. Amino acids all contain amino (–NH ) and c arboxyl (–COOH) groups, which are polar and form hydrogen
2
bonds. Between these two functional groups is a c arbon atom, to which a substituent known as an R group is
attached. The identity of the R group is dierent for dierent amino acids. The structures of aspartic acid (Asp),
glutamic acid (Glu) and leucine (Leu) are shown below. With reference to their structural features, suggest why
these amino acids have dierent anities for the two solvent systems.
H COOH H COOH H COOH

2 2 2
CH COOH CH CH COOH CH CH(CH )

2 2 2 2 3 2
aspartic acid, Asp glutamic acid, Glu leucine, Leu
332
Practice questions
35. Remember that the R value is c alculated as follows:

F
distance travelled by the spot
R =
F
B
Refer to the chromatogram below and:
a. c alculate the R value of the top spot. Assume that length A = 3.95 cm and B = 5.02 cm.
F
b. estimate the R value of the middle and bottom black spots.

F
Calorimetry
We c an measure the amount of heat released (or absorbed) during a
thermometer
chemic al reaction using a technique known as c alorimetry, which is
discussed in Reactivity 1.1. The basic principle of c alorimetry is that the
lid (with hole)
reaction’s enthalpy change (which we c annot measure directly) c auses
a measurable change in the temperature of a known mass of water. It is
assumed that no energy is lost to the surroundings, although in practice
heat loss is a large source of error in c alorimetry experiments. Heat loss

insulated
c an be minimized by insulation.
container
Figure 42 illustrates a c alorimetry experiment involving the reaction
magnesium
between magnesium and dilute hydrochloric acid. Note that it is
powder
dilute
c arried out in an insulated container, such as a polystyrene cup, to
hydrochloric
minimize heat loss to the surroundings.
acid
 Figure 42 C alorimetry of the
reaction between magnesium and dilute
Practice questions
hydrochloric acid
Review Reactivity 1.1 and answer these questions.
36. The experimental set-up in gure 42 is used to determine the enthalpy of
the reaction between magnesium and dilute hydrochloric acid.
a. Identify two measures shown in the diagram that will lower the heat
lost to the surroundings during the reaction.
b. Suggest a modic ation that would further minimize heat loss.
37. A c alorimetry experiment is performed in an insulated container using
5.0 g of zinc and excess hydrochloric acid to determine the enthalpy
of reaction. The temperature rise was 11.0 °C and the mass of the acid
solution was 200 g.
a. Write a balanced equation for this reaction, including state symbols.
b. State and explain whether the reaction is exothermic or endothermic.
c. C alculate the amount of heat released, in kJ.
d. Determine the enthalpy change for this reaction, in kJ mol
e. Identify two assumptions made in the c alculation above.
333
Tools for Chemistry
Enthalpies of combustion c an be determined using the apparatus shown in
gure43. A measured mass of the fuel is combusted in a spirit burner below
a copper c alorimeter containing a known mass of water. In this c ase, the
thermometer
c alorimeter is made of a thermally conductive material to facilitate the energy
calorimeter
transfer from the combustion reaction to the water. Heat from the combustion
reaction is also transferred to the c alorimeter, and this should be considered
clamp water
when processing the results. Heat is also transferred to the surrounding air, but
this is dicult to quantify and should therefore be minimized.
spirit burner
wick
fuel
Data-based question
 Figure 43 Determining the combustion
enthalpy of a fuel
A student c arried out the experiment shown in gure 43 to determine
the enthalpy of combustion of butan-1-ol, C H OH. The following results

4 9
wereobtained:
Practice question
M ass of copper c alorimeter / g ± 0.01 g 24.03
38. A student performed the
experiment shown in gure 43. M ass of copper c alorimeter and water / g ± 0.01 g 99.92
They took the following steps:
Temperature of water before combustion / °C ± 0.1 °C 21.7
• poured 20 cm of water
M ass of butan-1-ol spirit burner before combustion / 75.47
into the c alorimeter

g ± 0.01 g
• weighed and lit the spirit

Temperature of water aer combustion / °C ± 0.1 °C 60.1
burner without the c ap
M ass of butan-1-ol spirit burner aer combustion / g ± 0.01 g 74.38
• measured the temperature
of the water for one minute
Use these data to c alculate the experimental enthalpy of combustion. Note
–1 1
• extinguished the spirit that the specic heat c apacity of water is 4.18 kJ kg K and the specic heat
–1 1
burner, keeping the c ap o c apacity of copper is 0.385 kJ kg K
• replenished the water in
the c alorimeter
Titration
• weighed the spirit burner
The unknown concentration of a substance in solution c an be determined by
a second time to nd the
reacting it with a standard solution of known concentration and volume in a
mass of fuel consumed.
titration (gure 44).
Suggest two practic al measures
use a beaker and funnel
that would improve the

to fill burette
reliability of the experiment.
leave air gap
when filling
the burette reading is
taken from the bottom
of the meniscus
use left
swirl the flask

hand to
with right hand while

control the
the drops are being added

flow rate
 Figure 44 Titration apparatus. Note: le-handed chemists usually swirl the ask with their
le hand and control the ow rate with their right
334
The equivalence point, the point at which the reagents are present in
stoichiometric amounts, must be easily identiable, and this is oen achieved
by observing a colour change. In acid–base titrations, and many redox titrations,
an indic ator is added to the reaction mixture. This indic ator changes colour
at or near the equivalence point. Some redox titrations are said to be self-
indic ating bec ause the change in oxidation state of at least one of the reagents is
accompanied by a colour change.
Normally the burette holds the standard solution, and the ask below contains
the solution of unknown concentration (or analyte). The titration is performed
asfollows:
• Rinse the burette: A small amount of standard solution is added to the
burette, which is then tilted and rotated to ensure that its entire inner surface
comes into contact with the solution. The solution is then drained from the
burette through the tap and the process is repeated twice more.
• Fill the burette: With a funnel, the burette is lled with standard solution to
the zero mark or just below. The funnel is removed, bubbles are removed
from the tip by draining some of the titrant, and the burette volume is noted
 Figure 45 A student performing a
by taking a reading at the bottom of the meniscus.

redox titration. The solution in the burette
is potassium permanganate, KMnO , which

4
• Rinse the volumetric pipette: The volumetric pipette is rinsed with a small
is dark purple and obscures the meniscus.
amount of analyte three times.
In this c ase the top of the meniscus should
be read
• Prepare the conic al flask: Using the volumetric pipette, a known volume of
analyte is transferred into a clean conic al ask. A few drops of indic ator are
added, and the ask is placed under the burette. You may choose to place it
on a white paper or tile to be able to better distinguish the colour change.
• Rough titration: The standard solution is quickly delivered from the burette
into the conic al ask, which is continuously swirled, until the end point is
reached (when the indic ator changes colour). The purpose of this step is to
give you a rough idea of how much standard solution is required to reach
the end point. The nal burette volume is noted, and the burette is relled if
necessary. The contents of the conic al ask are disc arded in a suitable waste
container. The ask is rinsed with distilled water and it is placed back below
the burette. The results will not be aected if it is slightly wet, as long as it
is clean.
• Accurate titrations: The titration is repeated. This time, the standard solution
is added swily, with swirling, and the addition is slowed down within a few
cm of the end point. Dropwise addition of the standard solution as the end
point is approached will allow an exact (to the nearest drop) volume of titrant
to be established. The volume of titrant is recorded, and the accurate titration
is repeated until at least two concordant results are obtained (typic ally within
0.1 cm of each other).
335
Tools for Chemistry
Titrations do not always need indic ators. The end point c an be determined from
changes in certain properties of the solution, such as electric al conductivity or
temperature, which c an be measured over the course of the titration. These
titrations are known as conductometric and thermometric titrations, respectively.
Practice questions
39. a. Explain why the burette and pipette need to be rinsed with the
solutions of reagents, instead of purewater.
b. Explain why a rough titration is needed.
c. Explain why it does not matter if the conic al ask holding the analyte
is wet.
d. Identify at least three mistakes to avoid when performing a titration.
e. A group of students know that the concentration of a hydrochloric
acid in their lab is approximately 0.2 mol dm . They nd the exact
concentration of HCl(aq) by titrating it against a solution of sodium
c arbonate, Na CO (aq). Sodium c arbonate is a primary standard:

2 3
it is a stable solid that is available in a high-purity form and does not
absorb water or c arbon dioxide from the atmosphere.
i. Write a balanced equation for the reaction between hydrochloric
acid and sodium c arbonate.
ii. The students found that 0.300 g of sodium c arbonate was
neutralized exactly by 23.83 cm of the hydrochloric acid
solution. Determine the concentration, in mol dm , of HCl(aq) in
the solution from the students’ results.
Construction of electrochemical cells
In DP chemistry you need to know how to construct two types of electrochemic al
cells: electrolytic and voltaic. They both involve electrodes, electrolytes, and a
complete circuit, allowing electrons to be gained by chemic al species at one
electrode (reduction) and lost at the other (oxidation).
Electrolytic cells convert electric al energy into chemic al energy (Reactivity3.2).
Electrolysis is a non-spontaneous process and therefore it requires a continuous
energy input, usually in the form of a cell or battery pack. The electrodes
are usually made of an inert material, such as graphite or platinum. Some
applic ations, such as electroplating, involve active electrodes. These are
electrodes that are themselves oxidized or reduced, rather than simply acting as
a site for oxidation or reduction to occur.
336
The silver anode in gure 46 is an example of an active electrode.
+
Ag→ Ag + e
silver
nickel spoon
anode +
Ag + e → Ag to be plated
(cathode)
silver nitrate solution
 Figure 46 An electrolytic cell used to electroplate an object placed at the c athode
Electrode placement depends on the nature of the products released at the
electrodes. Gaseous products can be collected in inverted tubes. Figure47
showsa Hofmann voltameter, in which slightly acidied water is being
electrolysed, producing hydrogen gas and oxygen gas. The electrodes are located
at the bottom of the tube to allow the gas bubbles to rise for collection at the top.
oxygen
hydrogen
platinum
foils
anode (+) cathode ( )
 Figure 47 A Hofmann voltameter is used for electrolysing water. C an you explain the
relative volumes of the gases collected at the top of the tubes? How could the identity of the
gases be conrmed? Note that the power supply has been omitted from the diagram
If electrolysis leads to the formation of a solid product, it will usually plate the
electrode and therefore be readily observable. The quantic ation of solids
produced in electrolysis requires measuring the dierence in mass of the
electrode, as well as collecting any solid particles or akes that might fall to the
bottom of the electrolytic cell.
Quantitative electrolytic investigations require c areful control of many variables,
including electrode surface area, temperature, time and potential dierence
applied. The electrodes should be thoroughly cleaned and dried before the
experiment.
337
Tools for Chemistry
In voltaic cells, chemic al energy is spontaneously converted into electric al
energy. When two half-cells are connected in a circuit, a potential dierence
arises, c ausing current to ow as oxidation occurs in one half-cell, and reduction
Electrolytic and voltaic cells are
occurs in the other (see Reactivity 3.2). The potential dierence c an be measured
discussed in Reactivity 3.2.
by connecting a high-resistance voltmeter to the electrodes (gure 48).
e e
V
+
+
NO Na
3
Zn anode
Cu cathode
NO NO
3 3
+
2
Zn NO
3
+
2
NO Cu
3
+ +
2 2
Zn(s) → Zn (aq) + 2e Cu (aq) + 2e → Cu(s)
movement of cations
movement of anions
 Figure 48 A voltaic cell. Electrons ow in the external circuit from anode to c athode. In
the salt bridge, c ations and anions ow towards the c athode and anode, respectively
A salt bridge connects the two half-cells to complete the circuit and prevent
the build-up of charge. It is a source of mobile inert ions. A salt bridge c an be
constructed by lling a U-tube with agar mixed with an inert electrolyte (e.g.
potassium chloride or sodium sulfate) and plugging it at either end with cotton
wool. A simpler alternative is using a strip of lter paper soaked in a saturated
solution of the inert electrolyte and dipping its ends in the two half-cells
(gure49).
 Figure 49 The zinc and copper half-cells in this voltaic cell are connected
by a paper salt bridge
Electrode identity, electrolyte concentration and temperature are among the
factors aecting cell potentials. Other factors include electrode surface area,
placement and how long the cell has been running (bec ause this aects the
electrolyte concentrations). As with electrolytic cells, the electrodes should be
 Figure 50 A voltaic pile powering an
thoroughly cleaned and dried before connecting them in the circuit.
LED. It is a series of alternating copper coins,
paper soaked in vinegar and zinc washers,
similar to the rst battery constructed by

Practice question
Alessandro Volta in the 18th century
40. Compare and contrast electrolytic and voltaic cells.
338
Colorimetry and spectrophotometry
Spectrophotometry is an analytic al technique that is based on a sample’s
interaction with light of a certain wavelength. Spectrophotometry uses a range
of UV, visible or IR radiation. Colorimetry is a similar technique that is limited to
wavelengths of visible light.
In both spectrophotometry and colorimetry, light is passed through the sample,
then detected (gure 51). The incident and transmitted intensities of light are
compared to determine the absorbance. The relationship between absorbance
and concentration is quantiable, and it is oen presented in the form of a
calibration curve. The calibration curve can be used to determine the concentration
of a solution by measuring its absorbance of light of a particular wavelength.
wavelength
280 nm
absorbance
0.347
cuvette detector digital
with and output

light monochromator
sample amplifier device

source
 Figure 51 A single-beam UV-vis spectrophotometer
M athematic ally, the absorbance (A) is c alculated from light intensity as follows:
I
0
A = log
( I )
t
where I is the intensity of the incident light and I is the intensity of the
0 t
transmitted light.
Absorbance is also proportional to the concentration of the solute (c):
A = εcl
where l is the cuvette (sample container) length, in cm, and

2.0
ε is a constant (known as the molar extinction coecient)
that depends on the solvent nature and the temperature
of the solution. If the same cuvette and experimental

ecnabrosba
conditions are used, the product of ε and l also becomes a
absorbance of
constant. Therefore, the concentration c an be determined
unknown sample
by comparing an absorbance measurement to a c alibration 1.0
curve of absorbance vs concentration (gure 52). Note that
this relationship becomes non-linear at high concentrations,
so solutions with low concentrations should be used for

concentration of
precise measurements.
unknown sample
0 10 20 30 40 50
3
concentration/µg cm
 Figure 52 Use of a c alibration curve to determine the
concentration of an unknown sample
339
Tools for Chemistry
While spectrophotometers oen measure absorbance over a range of
wavelengths, a simple colorimeter c an only determine the sample’s absorbance
at a specic wavelength of visible light. The colorimeter ’s wavelength setting
should correspond to a wavelength that is strongly absorbed by the sample. The
light absorbed by a coloured solution is complementary to the colour observed.
Complementary colours are placed opposite each other in the colour wheel
(gure 53). For example, a blue solution absorbs orange light corresponding to
wavelengths between 585 and 647 nm. A colorimetry experiment involving this
substance should therefore use a wavelength that falls within this range.
647 nm 585 nm
orange
red yellow
700 nm
575 nm
400 nm
green
violet
blue
424 nm
491 nm
 Figure 53 The colour wheel
Data-based question
Practice questions
The absorbance of a protein solution of unknown concentration was found to
be 0.285. Using the c alibration curve below, determine the concentration of
41. A student constructed a
the protein in this solution.
c alibration curve by recording
the absorbance at 490 nm of
solutions containing varying
0.40
2+
concentrations of [FeSCN] .
a. Suggest the colour of the
2+
[FeSCN] solution.
0.30
ecnabrosba
b. The c alibration curve gave
a linear relationship with
the following equation:
0.20
A = 14 000 × c
where A is absorbance
at 490 nm and c is
0.10
the concentration of
2+ 3
[FeSCN] , in mol dm .
Determine the
0.00
concentration of a sample
0.00 0.10 0.20 0.30 0.40 0.50
2+
of [FeSCN] (aq) with an

3
protein concentration / mmol dm
absorbance of 0.225.
340
Molecular models
Certain features of molecules, such as molecular geometry, are not apparent
from Lewis or structural formulas. Models help us visualize the three-dimensional
structure of a molecule. In addition, models c an be rotated (manually or digitally)
to observe dierent structural features and molecular geometry, as well as
allowing us to predict how molecules might interact with one another.
Models c an be built from molecular model kits or constructed using digital
modelling soware. While model kits are usually ball-and-stick models, digital
models c an be toggled between this and other types of visualizations, including
space-lling models (oen based on van der Waals radii) and molecular
electrostatic potential (MEP) surfaces. Digital models c an easily be saved as les
for future reference or communic ation.
 Figure 54 A molecular model of ice
H
O
O
O
H
O O
H
O
O
H
O
O O
H H
structural formula ball-and-stick model
space-filling model MEP surface
 Figure 55 Various representations of sucrose
Practice questions
42. Discuss the advantages and disadvantages of digital molecular models
compared to physic al models in the following scenarios:
a. school science labs
b. scientic research.
The construction of digital models of very large molecules, such as proteins
and other biomolecules, has revolutionized modern drug development.
The interactions between potential drug c andidate molecules and their
biologic al targets are now explored using soware. This process is known as
computer-aided drug design. If a promising group of molecules is identied
computationally (in silico), they c an then be synthesized and investigated
in a laboratory (in vitro). Drug development is extremely resource-intensive;  Figure 56 Molecular model of the
technology and computing power c an help to streamline the process by quickly protein rhodopsin, which is involved in
vision
screening vast numbers of dierent molecules and targets.
341
Tool 2: Technology
Sensors
Sensors are digital devices that c an be used to measure physic al properties
and transmit the results electronic ally. Common sensors in school chemistry
labs include temperature probes, pH probes, light sensors and conductivity
probes. Digital sensors and other devices, such as colorimeters, are
convenientbec ausethey:
• provide a practic al and easy way to measure certain properties that would
otherwise require bulky equipment or time-consuming analyses (for example,
light sensors or dissolved oxygen sensors)
• oen produce more precise results than the alternative equipment or
traditional laboratory techniques (for example, pH sensors as compared to
acid–base indic ators)
• c an be connected to data loggers that collect and save large amounts of data
at regular intervals.
However, sensors oen require c alibration before use. If you are going to use
one, nd out how to c alibrate it by checking the manual rst. Colorimeters and
pH probes are examples of digital devices that require frequent c alibration.
Smartphones also contain sensors, and along with certain apps they c an make
useful measurements in a chemistry lab. US chemists Thomas Kuntzleman and
 Figure 57 The view through the

Erik Jacobson devised a way to create a simple yet eective colorimeter using
smartphone RGB analyser on a blank

a c ardboard cuvette-holding chamber, a smartphone red green blue (RGB)
cuvette (top) and a 0.50 mol dm copper(II)
app and coloured construction paper that was published in the Journal of
sulfate solution (bottom). The phone
Chemic al Educ ation. In the c ase of a blue copper(II) sulfate solution, where the
applic ation records the average R, G, and
complementary colour red is absorbed, the incident and transmitted R (red)
B values of the pixels within the circle.
values were used as I and I , respectively, to c alculate absorbance (gure 57).

0 t
Given the R values for the blank (190) and
the analysed solution (53), an absorbance
Bec ause phones are items that people frequently touch and c arry outside
of 0.554 was obtained for the copper(II)
the laboratory, c are must be taken to keep them well away from hazards.
sulfate sample
A3D-printed cuvette holder could be designed for sturdier support of the
analysed sample.
Activity
1. M ake a list of the sensors available in your school.
2. If available, download an RGB app onto a smartphone or tablet.
Investigate how the following aect the RGB values registered by the
app. Remember to get approval from your teacher before trying any of
these out.
a. Colour of a solution (you could experiment with distilled water and
dierent food colouring dyes, for example).
b. Concentration of a coloured solution of your choice.
c. Colour of the background placed behind the sample.
d. Path length (i.e. the length of sample the light travels through before
reaching the detector).
342
Tool 2: Technology
t Figure 58 Modern-day scientists
researching a frozen lake in Antarctic a.
What might they be investigating? Find
out about some of the current chemistry
research being done in the Antarctic
Spreadsheets
Spreadsheets are powerful data manipulation and analysis tools that you c an
use for entering and processing large amounts of data. Operators, formulas
and functions tell the soware to perform certain operations. Even with a small
selection of simple operators, spreadsheets will help you to process experimental
data quickly and eciently.
Figure 59 shows two screenshots of an Excel spreadsheet. The values in the last
two columns shown in the rst screenshot have been c alculated automatic ally
using the formulas shown in the same columns of the second screenshot.
Note that each formula in Excel begins with an equal sign (=) followed by cell
references (e.g. E7) and operators, such as multiplic ation (*) and division (/).
Brackets are used to change the order of operations. Note that all processed
values should be strictly numeric al bec ause most operators in Excel do not
recognize numbers that are entered into the same cell as letters.
(a)
A B C D E F G
Primary Mass of Change in Change in spirit Molar mass of Amount of Enthalpy change
1 alcohol water / g temperature / K burner mass / g alcohol / g mol-1 alcohol / mol / kJ mol-1
2 methanol 78.8 38.1 1.2 32.04 0.039325843 319. 11302
3 ethanol 80 38.8 1.22 4.07 0.02481441 489.9552052
4 butan-1-ol 79.9 38.4 1.09 74. 1 2 0.014705882 872.0937984
5 pentan-1-ol 80.3 41 1.12 88. 1 5 0.01270515 1083.12848
(b)
A B C D E F G
Primary Mass of Change in Change in spirit Molar mass of Amount of Enthalpy change
1 alcohol water / g temperature / K burner mass / g alcohol / g mol-1 alcohol / mol / kJ mol-1
methanol 78.8 38.1 1.2 32.04 =D2  E2 =–(B2 4.18C2 )  (1000F2)

2
ethanol 80 38.8 1.22 4.07 =D3 E3 =–(B34.18C3 )  (1000F3)

3
4 butan-1-ol 79.9 38.4 1.09 74. 1 2 =D4 E4 =–(B44.18C4 )  (1000F4)
5 pentan-1-ol 80.3 41 1.12 88. 1 5 =D5 E5 =–(B54.18C5 )  (1000F5)
 Figure 59 An Excel spreadsheet used to c alculate the enthalpy of combustion of primary alcohols from experimental data. The values
and formulas are shown in the upper and lower images, respectively
343
Tools for Chemistry
While symbols such as * and / and ^ are used in spreadsheets (and some
c alculators), you must not use this notation outside the spreadsheet, for example,
when explaining your c alculations as part of a lab report. Common spreadsheet
operators and functions are summarized in table 1.
Operator or function Action Example
+ addition =A5+B5
Finds the sum of values in cells A5 and B5.
− subtraction =A5−B5
Subtracts the value in cell B5 from that in A5.
* multiplic ation =A5*B5
Finds the product of values in cells A5 and B5
/ division =A5/B5
Divides the value in cell A5 by that in B5.
^ power =A5^2
Finds the square of the value in cell A5.
=EXP() exponent =EXP(A5)
R aises e (base of natural logarithm, 2.718282…) to the power of the
value in cell A5. This function is inverse of =LN()
=AVERAGE() mean (average) =AVERAGE(A5:A8)
Finds the mean (average) of the values in cells A5 to A8.
=MAX() maximum =MAX(A5:A8)
Finds the maximum value in cells A5 to A8.
=MIN() minimum =MIN(A5:A8)
Finds the minimum value in cells A5 to A8.
=SUM() sum =SUM(A5:A8)
Adds together the values in cells A5 to A8.
=LOG() logarithm (base 10) =LOG(A5)
Computes the log (base 10) of the value in cell A5.
=LN() natural logarithm =LN(A5)
Computes the natural log (base e) of the value in cell A5. This function
is inverse of =EXP().
 Table 1 Common spreadsheet functions
More advanced spreadsheet functions that you might want to explore next could
involve sorting data, conditional formatting, inserting scroll bars, vertic al lookup,
recording macros, etc.
You c an easily plot various types of graphs in spreadsheets. Remember to include
all the features of good-quality graphs (see the Graphing section in Tool 3 for
details).
Most spreadsheets and graphing soware packages c an be used to plot a simple
sc atter plot, line of best t and error bars. Depending on what program you use,
some functionality may be limited, particularly when trying to plot dierent error
bars on each point, drawing curves of best t, or omitting certain points from the
line of best t. In such c ases, you might be able to nd a workaround, or print the
graph and draw these on by hand.
344
Tool 2: Technology
Practice questions
43. State the formulas you would enter into a spreadsheet to c alculate the
following:
0.400
a.
5 × 4.18
b. The mean of 42, 32, 45, 46 and 48.
c. −log(0.0034)
12.5
d. 10
e. the range of the values in cells A5 to A8.
44. Describe the operation performed by each of the following spreadsheet
formulas:
a. =MAX(C6:C10)
b. =SUM(D5,E7,G3)
c. =−(A3*B3*4.18)/(C4/46.07).
45. An investigation into the eect of an impurity on the freezing point of water
gave the following results.
±
Freezing point / °C 0.5 °C
M ass of impurity / g ± 1 g
1 2 3 Mean
0 0.8 0.7 0.7
10 −1.6 −1.7 −1.4
15 −1.0 −1.2 −1.1
30 −3.2 −3.1 −3.3
45 −5.3 −5.5 −5.3
a. Enter these values into a spreadsheet and c alculate the mean
freezing points.
b. Use the spreadsheet to plot a graph of these results.
D atabases
D atabases are digital repositories of large amounts of information, all organized
to facilitate retrieval and continuous updates. In chemistry you might use
databases to gather information on:
• Elements and their properties (e.g. WebElements, created by M ark Winter at
the University of Sheeld, UK)
• Physic al properties (e.g. Chemspider, created by the Royal Society of
Chemistry, UK)
• Energetics data (e.g. NIST Chemistry WebBook, edited by Linstrom and
M allard at the National Institute of Standards and Technology, USA)
• Spectral data (e.g. SDBSWeb, created by the National Institute of Advanced
Industrial Science and Technology, Japan)
• Molecular geometry data (e.g. CoolMolecules, created by Hanson et al. at
St. Olaf College and Washington State University, USA).
345
Tools for Chemistry
You may use databases to look up two or three entries at a time, but sometimes
you will conduct more complex database investigations involving large amounts
of data. These tips will help you when extracting data from databases as part of
extended investigations:
• Spend some time exploring the database to get a sense of the types of data
that are available.
• M ake a note of the search terms and search parameters you c an use.
• Organize the data you collect into a spreadsheet as you go along.
• M any databases cite the original information source, so you should note this
as well as the reference to the database itself.
Choose one of the databases mentioned in this section. Spend 15 minutes
looking around the database. Come up with three independent and three
dependent variables that you could explore with data extracted from the
database.
Share your ideas with your class. Tell them:
• which database you looked at and what types of information it contains
• what you found easy and dicult when using the database
• your list of three independent and three dependent variables.
Listen to your peers’ database ideas and identify one that you would like to
look at further.
Activity
1. Using a database of your choice, investigate the melting points of:
• group 1 elements
• group 17 elements
• period 3 elements.
Explain any trends you observe. Refer to your knowledge of bonding and
physic al properties (Structure 2).
2. Explore the electric al conductivity of the elements in a periodic table
group or period of your choice by identifying and extracting data from a
database of your choice.
(Note: you might only nd resistivity values. A material’s resistance to
electric al ow is its resistivity. The relationship between resistivity and
electric al conductivity is electric al conductivity = ).
resistivity
346
Tool 2: Technology
Modelling
You have already come across models in your study of chemistry, for instance the
ideal gas model, or atomic models. Scatter graphs help us model the relationship
between two variables. As described in the NOS section of the subject guide,
“models are simplications of complex systems”. With the aid of technology,
scientists can model the structure and reactivity of intricate chemical phenomena.
The best way to develop a model is to start with a simple relationship or concept
and build up from there. Here we will look at two examples of modelling tasks that
are facilitated by technology: spreadsheet modelling and molecular mechanics.
Spreadsheet modelling
Spreadsheets c an be set up to transform input variables into output variables in
the context of a given system, such as equilibria. You c an explore the eect of
external disturbances on equilibrium concentrations, for example. US chemist
Charles M arzzacco proposed an introductory spreadsheet model of a simple
coin-ipping equilibrium:
k
f
heads (H) ⇌ tails (T)
k
r
The input parameters are the initial concentrations of H and T, and the forward and
reverse rate constants, k and k . These parameters then determine the H and T
f r
concentrations over time, from which a concentration vs time graph is generated.
We can now explore the eects of changing the initial concentrations and the rate
constants on the equilibrium concentrations and the equilibrium constant, K
The resulting spreadsheet values and formulas are shown in gure 60. Here we
have added scrollbars to the spreadsheet proposed by M arzzacco, as well as
a c alculation of the equilibrium constant, K, from the forward and reverse rate
k
f
constants k and k , where K =

f r
k
r
A B C D E F G H I J K
[H] an [T]  time for a coinfliin eqilirim tem
2 time / [H] [T]
0.25
3 0 =B4 =B
3
[H] =C5/100
4 = 3+1 =J3B10J3+B13K3 =K3B13K3+B10J3
m
5 23
= 4+1 =J4B10J4+B13K4 =K4B13K4+B10J4
0.2
6
= 5+1 =J5B10J5+B13K5 =K5B13K5+B10J5
lom / noitartnecnoC
=C8/100
7 [T]
= +1 =JB10J+B13K =KB13K+B10J
8 0 0.15
= +1 =JB10J+B13K =KB13K+B10J
9
= 8+1 =J8B10J8+B13K8 =K8B13K8+B10J8
10 k =C11/1000
= +1 =JB10J+B13K =KB13K+B10J
0.1
11 145 = 10+1 =J10B10J10+B13K10 =K10B13K10+B10J10
12
= 11+1 =J11B10J11+B13K11 =K11B13K11+B10J11
13 k =C14/1000 0.05 = 12+1 =J12B10J12+B13K12 =K12B13K12+B10J12
14 220 = 13+1 =J13B10J13+B13K13 =K13B13K13+B10J13
15 = 14+1 =J14B10J14+B13K14 =K14B13K14+B10J14
16 = 15+1 =J15B10J15+B13K15 =K15B13K15+B10J15
0 5 10 15 20 25 30 35 40
Outputs
17 = 1+1 =J1B10J1+B13K1 =K1B13K1+B10J1
Time / 
18 = 1+1 =J1B10J1+B13K1 =K1B13K1+B10J1
19 [H]eq =J31 =J18B10J18+B13K18

= 18+1 =K18B13K18+B10J18
20 = 1+1 =J1B10J1+B13K1 =K1B13K1+B10J1
21 [T]eq =K31 = 20+1 =J20B10J20+B13K20 =K20B13K20+B10J20
= 21+1 =J21B10J21+B13K21
22 =K21B13K21+B10J21
=B10/B13 = 22+1
23
Keq =J22B10J22+B13K22 =K22B13K22+B10J22
= 23+1
24 =J23B10J23+B13K23 =K23B13K23+B10J23
25 = 24+1 =J24B10J24+B13K24 =K24B13K24+B10J24
26 = 25+1 =J25B10J25+B13K25 =K25B13K25+B10J25
27 = 2+1 =K2B13K2+B10J2
=J2B10J2+B13K2
28 = 2+1 =K2B13K2+B10J2
=J2B10J2+B13K2
29 = 28+1
=J28B10J28+B13K28 =K28B13K28+B10J28
30 = 2+1 =J2B10J2+B13K2 =K2B13K2+B10J2
31 = 30+1 =J30B10J30+B13K30 =K30B13K30+B10J30
 Figure 60 Spreadsheet model of a simple equilibrium system. Source of data: C. M arzzacco, J. Chem. Ed. , 1993, 70(12), p.993
347
Tools for Chemistry
Activity
Replic ate the spreadsheet in gure 60. (If you are not able to include scroll
bars, leave them out and simply change the input parameters manually.)
a. Adjust the input parameters and explore the eect of changing the
following parameters on the equilibrium:
i. initial concentrations
LHA
ii. rate constants.
Remember to check what happens when you input both
intermediate values and the extremes (very low and very high values).
b. Explore the eect of a sudden addition of H to the equilibrium
mixture at 15 seconds by manually entering a number into cell J18
that is larger than the number currently in that cell.
c. Suggest how you could explore the eect of removing H or T.
d. Determine some of the limitations of this model.
e. Extend the spreadsheet to investigate:
i. an equilibrium system composed of three species, for example,
A + B ⇌ C
ii. two equilibria related by a common species, for example,
A ⇌ B ⇌ C.
Molecular mechanics
The development of molecular modelling has profoundly impacted our
understanding of chemistry by greatly extending the scope of what chemists
c an “see” and study. Here we will introduce molecular mechanics, which is a

Molecule R–O–R′ bond
eld of molecular modelling that treats atoms as balls joined by springs, in line
angle
with classic al mechanics. A more complex area of molecular modelling, which
water 104.0°
is beyond the scope of the DP chemistry course, involves the use of quantum
methanol 107.1°
mechanic al principles to study the distribution of electron density in reacting
species.
methoxymethane 111.5°
 Table 2 Bond angles in molecular

Figure 61 shows molecular models of water, methanol and methoxymethane,
models of water, methanol and

which c an be analysed to explore the eect of substituents bonded to the
methoxymethane (R and R’ represent either

oxygen on the R–O–R′ bond angle. The bond angle data derived from each
H or CH substituents)
3
model are shown in table 2.
*1
*1
*1
*3
*2
*2
*3
*3
*2
 Figure 61 Molecular models of water, methanol and methoxymethane
348
Tool 2: Technology
Activity
a. Outline the eect of replacing the H atoms with methyl groups on the
bond angle.
b. Using a molecular editor of your choice, replic ate the molecules shown
in gure 61.
i. Compare the bond angle values in your models with those given in
table 2.
ii. Suggest possible extensions to this activity.
Figure 62 shows a model of two water molecules approaching one another.
For each distance, the potential energy between the two water molecules was
c alculated. This is summarized in table 3.
*1
*1
*1
*1
*2
*2
*2
*2
 Figure 62 A molecular model of two

1
Distance between molecules / Å Potential energy / kJ mol
water molecules at distances of 15.5, 11.2,
15.5 −0.15
5.07 and 1.78 Å apart. In the last c ase, the
molecules are close enough for a hydrogen

11.2 −0.45
bond to form
5.07 −3.88
1.78 −27.66
 Table 3 Distances between two water molecules and the corresponding potential
energy values
To begin with, the hydrogen atom in one molecule is loc ated 15.5 Å (or
10 TOK
15.5 × 10 m) from the oxygen atom in the other molecule, and the potential
energy between the two molecules is –0.15 kJ mol . As the molecules approach
We observe the natural world
each other, the distance and energy both decrease until a hydrogen bond is
through our senses. Molecular
formed. The model predicts that the hydrogen bond will have a length of 1.78 Å
10 1
modelling allows us to observe
(or 1.78 × 10 m) and an energy of –27.7 kJ mol . The validity of the model c an
interactions at a molecular
be veried by comparing these predicted values with experimental data.
sc ale, which are invisible to the
naked eye. To what extent have
Activity
advancements in technology
extended our senses?
a. Build a model of the water molecule using a molecular editor of your
choice, such as Avogadro.
b. Explore the tools and visualizations available in that editor.
c. Add a second water molecule.
d. Using the molecular editor, c alculate the energy of the interaction
between the two water molecules.
e. Find out what happens when you add more water molecules and run an
energy optimization.
f. Build a dierent molecule and explore its interactions with other
molecules.
349
Tool 3: M athematics
The purpose of this section is to help you ensure, understand and evaluate
the reliability of your quantitative measurements and analyses as well as good
communic ation. M athematic al skills, units, signic ant gures, uncertainties and
graphs are relevant to nearly every topic in DP chemistry. If you take advantage of
every opportunity to reinforce these concepts, they will become habitual.
Units
According to the International Bureau of Weights and Measures (Bureau
International des Poids et Mesures, BIPM), SI units should be used, and these
conventions followed:
• A space between a numeric al value and its unit.
• Decimal markers should be preceded by a number, even if this number is zero.
• Dierent units should be separated by a space.
Practice questions
46. Which of the following are 48. Identify and correct the mistake in each of the
SI units? following:
• metre, m a. time for reaction to happen = 16 sec
• c alorie, c al b. temperature = 304 °K
• ounce, oz c. enthalpy of reaction = −77.5 kJmol
• foot,  d. mass = 0.33g
• cubic centimetre, cm e. melting point = 277 °F
• degree F ahrenheit, °F f. density = 0.78 g / dm
• millimetre of mercury, mmHg g. volume = 500 cc
• pasc al, Pa h. amount = .5 mol
• kelvin, K i. amount = 3.0 g
• metre per second, m/s j. R = 8.31 J/(Kmol)
47. What is the SI unit for each of the following quantities?
a. time
b. energy
c. volume
d. amount of substance
e. pressure
350
Uncertainties
Measurements (and the values derived from them) are always inexact.
Repeating a measurement under the same conditions and with the same
instrument produces randomly varying values. F actors inuencing this random
variation, known as random error, include instrument imprecision, uctuations
during readings and human reaction time. R andom error is described by the
uncertainty. Measurements should therefore be recorded along with their
associated uncertainty and unit. For example, the temperature is given as 36.6 °C
± 0.1 °C or (36.6 ± 0.1) °C in gure 63. This tells us that the measured value is
somewhere in the range of 36.5 °C to 36.7 °C.
 Figure 63 The temperature shown here is 36.6 °C ± 0.1 °C or (36.6 ± 0.1) °C
Instruments with greater precision give rise to measurements that have lower
uncertainties. For instance, while the uncertainty of a measuring cylinder may
3 3
be around ± 0.5 cm , the uncertainty of a burette is typic ally ± 0.05 cm . The
measurements obtained using the burette are therefore more precise.
Measured values should be recorded with the correct level of precision and the
uncertainty must be stated. The determination of the uncertainty of a particular
measurement usually involves one of the following:
• estimating the uncertainty based on the display or sc ale on the instrument
you are using
• uncertainty stated by the manufacturer of the measuring instrument
• estimating the range over which a value uctuates.
Estimating the uncertainty of an instrument
The way to estimate an instrument’s uncertainty depends on whether it is digital
or analogue (has a sc ale).
The uncertainty of a digital instrument is its least count, that is, the lowest value
above zero that the instrument c an register. This is usually the reading of “1” in
the lowest decimal place on the display. Consider the mass shown in gure 64.
 Figure 64 The uncertainty of the

The least count is 0.1 g, so the uncertainty is ± 0.1 g and the mass of the powder is
measurement is ± 0.1 g
recorded as 0.7 g ± 0.1 g.
351
Tools for Chemistry
Analogue instruments have sc ales marked on them. The uncertainty is estimated
as half the smallest sc ale division. The thermometer in gure 65 has sc ale
divisions at every 1 °C. The uncertainty is half the smallest sc ale division, ± 0.5 °C.
Therefore, the temperature should be recorded as 37.0 °C ± 0.5 °C. Remember
that the last digit in the temperature value is estimated. In this c ase, it is zero,
which means that the reading is on level with the 37 °C tick mark on the sc ale.
Practice questions
49. State the uncertainty of the measuring cylinder shown below. The sc ale
has tick marks at every 1 cm
 Figure 65 The temperature is
37.0 °C ± 0.5 °C
50. State the measurement, including units and uncertainties, shown in the
three images below.
3
2
4
1
5
0
80 °C 90 °C
Uncertainty given by the manufacturer
 Figure 66 The uncertainty of this
burette is stated in the label: ± 0.05 ml

Sometimes the uncertainty is stated on a label somewhere on the instrument
(or ± 0.05 cm ) (gure 66).
352
Values that uctuate
Sometimes the measured value uctuates over time, for instance in the c ase of
certain conductivity probe displays. In these c ases, you c an try to estimate the
uncertainty based on the variation in values you observe.
For example, the rate of reaction between marble chips (c alcium c arbonate,
C aCO ) and hydrochloric acid c an be explored by measuring the rate of c arbon

3
dioxide gas production using the apparatus in gure 67. However, determining
the volume of gas at specic points of time is dicult bec ause the bubbles
interfere with the meniscus. In this c ase the measurement uncertainty is greater
than half the smallest sc ale division on the measuring cylinder. To better estimate
the volume measurements and their associated uncertainties, you could try
slowing down the reaction. Alternatively, you could make a video recording
during the reaction and subsequently pause it at dierent points to examine the
sc ale. Another option is to use a gas syringe instead of the measuring cylinder.
gas collecting in
measuring cylinder
hydrochloric acid
water
and marble chips
look down at cross
 Figure 67 In this set-up for measuring the rate of a from above
gas-producing reaction, the bubbles interfere with the
volume measurements and increase the uncertainty
clear
solution
Further sources of uncertainty
Some sources of uncertainty c an be dicult to quantify. Examples
include human reaction time or change in the appearance of the
cloudy
reaction mixture. These should be noted by the experimenter.
solution
For example, the reaction between sodium thiosulfate and
hydrochloric acid produces a precipitate, making the reaction cross
mixture progressively opaque. The kinetics of this reaction c an be

white paper
studied by measuring how long it takes for a picture placed below
the mixture to be obscured by the precipitate (gure 68).
The stopwatch reading is 42 seconds, and the uncertainty of the
cross invisible
instrument is ± 1 s (the least count). However, the actual uncertainty
of the time measurement is probably much higher, as it must

 Figure 68 Studying the kinetics of the reaction between
include the human reaction time and the uncertainty associated

hydrochloric acid and sodium thiosulfate involves measuring
with the experimenter ’s perception of the moment when the the time taken for the reaction mixture to obscure a cross on a
cross becomes no longer visible. piece of paper under the ask
353
Tools for Chemistry
In the c ase of the reaction between sodium thiosulfate and hydrochloric acid
TOK
(gure 68), the random error c an be estimated by repeating measurements and
determining the range over which they vary. Suppose that the measurement
M athematic al techniques
is repeated ve times under the same conditions and the following data are
help scientists communic ate

obtained for the time taken for the cross to become invisible:
measurements and their
uncertainties, make predictions, 42 s 39 s 43 s 44 s 45 s
process and analyse data from
The mean time is 42.6 s ≈ 43 s. The uncertainty of a set of replic ate values c an be
experiments. What is the role of
estimated in two ways: one based on the range of readings, and the other on the
mathematics in the production
mean value.
of scientic knowledge? How
does this compare to the role

1. Estimating the uncertainty by halving the range of readings
of mathematics in other areas of
We c an estimate the uncertainty by halving the range of the readings. Here, the
knowledge?
range is 45 s − 39 s = 6 s. Half the range is = 3 s. Therefore, the time for the
cross to become invisible is 43 s ± 3 s.
2. Estimating the uncertainty by finding the furthest reading from the
meanvalue
The values range from 39 s to 45 s. The mean value is 2 s away from the top of the
range (45 s − 43 s = 2 s) and 4 s away from the bottom of the range (43 s − 39 s
= 4 s). The larger of the two is used as an estimate of the uncertainty. Therefore,
the mean time taken for the cross to be obscured under these conditions c an be
recorded as 43 s ± 4 s.
Data-based question
A student measured the volume of hydrogen produced in the reaction
between magnesium and dilute sulfuric acid aer 2 minutes, producing the
following results.
Volume of H (g) produced aer 2 minutes

2
3 3
/ cm ± 0.5 cm
47.7 43.5 44.0
a. C alculate the mean volume.
b. Estimate the uncertainty by halving the range of readings.
c. Estimate the uncertainty by nding the furthest reading from the
meanvalue.
d. Which uncertainty value would you report with the data? Why?
354
Measurement
Measurements are limited in precision and accuracy. Some values in
science are exact and have no uncertainty, for instance, the seven dening
constants in the SI system. These constants are shown below:
Dening constant Symbol Numeric al value Unit
hyperne transition Δv 9 192 631 770 Hz

Cs
frequency of C s–133
speed of light in vacuum c 299 792 458 m s
34
Planck constant h 6.626 × 10 J s
19
elementary charge e 1.602 176 634 × 10 C
23 1
Boltzmann constant k 1.380 649 × 10 J K
23 1
Avogadro constant N 6.022 140 76 × 10 mol

A
luminous ec acy K 683 lm W

cd
 Table 4 The seven dening constants of the SI
As we have seen, there are several ways of determining measurement
uncertainties. While the equipment uncertainty (least count or half the smallest
sc ale division) is a common way to do this, you might need to account for
additional uncertainties. Eective communic ation of data collected during
experiments includes noting how you estimated the uncertainty of the dierent
data you measured. (Was it the least count? Was it given by the manufacturer?
Did you estimate it based on uctuations in the values?) Doing so will help you
(and your reader) understand the impact of measurement uncertainty on your
conclusions.
Expressing uncertainties
Uncertainties c an be expressed in dierent formats: absolute, relative or
percentage. To illustrate this, consider the following volume measurement:
3 3 3
15.0 cm ± 0.2 cm . Let the measured value be x, in this c ase 15.0 cm , and the
associated uncertainty, u(x), which is ± 0.2 cm
• Absolute uncertainty: The uncertainty associated with a given value. It has
the same units as the value it is associated with. In the example above,
± 0.2 cm is the absolute uncertainty.
• Percentage uncertainty: The absolute uncertainty expressed as a
percentage of the value it is associated with.
absolute uncertainty of x
percentage uncertainty = × 100%
u(x)
= × 100%
Using the example above:
0.2 cm
percentage uncertainty = × 100%

3
15.0 cm
= 1.3% (2 sf )
355
Tools for Chemistry
• Relative (or fractional) uncertainty: The ratio comparing the magnitude of
the absolute uncertainty to the magnitude of the associated value:
absolute uncertainty of x
relative uncertainty =
u(x)
Using the example above:
0.2 cm
relative uncertainty =
3
15.0 cm
= 0.013 (2 sf )
Note that the relative uncertainty is the percentage uncertainty expressed as a
decimal fraction.
Uncertainties are oen stated to one signic ant gure. Sometimes two signic ant
gures are acceptable, particularly if the uncertainty is very small. Either
convention is acceptable, as long as you use it consistently.
Uncertainty is an estimate of precision, so the precision of a measured value
must correspond to that of its uncertainty. In other words, the value itself should
have the same number of decimal places as the uncertainty associated with it.
For example, a mass given as 10.3 g ± 0.01 g is inconsistent in terms of precision
bec ause the uncertainty suggests that the balance gives readings to 2 decimal
places, but the mass is given only to 1 decimal place. Perhaps the uncertainty
was incorrectly written down and it is in fact ± 0.1 g, giving a correct mass
10.3 g ± 0.1 g. Alternatively, the experimenter might have failed to write down a
trailing zero aer the 3 (which should not be omitted bec ause it is signic ant), so
the correct mass is 10.30 g ± 0.01 g.
Activity
Copy and complete the table:
Measured Absolute Percentage Relative
value uncertainty uncertainty uncertainty
3 3
19.96 cm ± 0.04 cm
1.08 V ± 2%
78.5 °C ± 0.01
Decimal places and signic ant gures
Any measurement involves uncertainty, so the result of the measurement always
has a limited number of signific ant figures (sf ). The length of a small object
measured with a ruler typic ally has no more than three sf as shown in gure69.
0 1 2 3 4 5
 Figure 69 Measurement uncertainty when using a ruler
356
In gure 69, the measured length is 3.67 cm. The rst two gures, 3 and 6, are
certain, as the length is greater than 3.6 but less than 3.7 cm. The last gure, 7, is
uncertain, as the actual length could be 3.66 or 3.68 cm. There is absolutely no
way of getting the fourth gure using this ruler, as we are not even sure about the
third gure.
As measurements are never exact, neither are the results of the c alculations
involving these measurements. There are two rules of thumb, which depend on
the type of c alculation being c arried out:
1. Adding and subtracting measured values: the answer should be recorded to
the least number of decimal places present in the values used.
2. Multiplying and dividing measured values: the answer should be recorded to
the least number of signic ant gures present in the values used.
Worked example 2
At the beginning of a titration, the initial burette reading was 1.03 cm . At
the end point, the nal burette reading was 24.13 cm . C alculate the volume
of the titrant used.
Solution
Volume used = nal volume − initial volume
3 3
= 24.13 cm − 1.03 cm
= 23.10 cm (2 dp)
Both values used have two decimal places. They are subtracted and therefore
the answer should also be stated to two decimal places.
Worked example 3
C alculate the amount of magnesium oxide, MgO, in mol, in a 0.500 g
sample of pure magnesium oxide.
Solution
Molar mass of MgO = M(MgO) = 24.31 + 16.00 = 40.31 g mol
n =
0.500 g
n(MgO) =
−1
40.31 g mol
= 0.012404… mol ≈ 0.0124 mol (3 sf )
This operation involves a multiplic ation, so the answer should be rounded
to the least number of signic ant gures in the values used. The answer is
therefore rounded to three signic ant gures.
M any c alculations require several steps. Rounding too early could lead to
incorrect answers due to rounding errors. Round the nal answer to the
required number of decimal places or signic ant gures, but not the answers to
intermediate steps. Always c arry two or three extra signic ant gures through
intermediate c alculations.
357
Tools for Chemistry
Propagating uncertainties
Processed data are obtained by manipulating raw measurements and therefore
also have uncertainties associated with them. The overall uncertainty of a
c alculated result c an be estimated by propagating the uncertainty introduced
by each of the measurements. The way this is done depends on the type of
c alculation done with the raw data and it c an be c ategorized into three types:
1. Addition and subtraction
2. Multiplic ation and division
3. Exponents (AHL only)
At this level, you will rarely need to consider the uncertainty of values or constants
that are not given to you with an uncertainty. Examples include the speed of
light, molar mass values and specic heat c apacities. For most purposes you c an
assume that values such as these are exact and have no associated uncertainty.
In this section, we will discuss only simplied methods of uncertainty propagation
that c an be used in typic al laboratory experiments with a small number of
variables. More advanced statistic al methods of uncertainty propagation will not
be assessed in this course.
In a c alculation involving addition or subtraction, we propagate uncertainties
by adding the absolute uncertainties of the values that are being added or
subtracted.
Worked example 4
The mass of an ethanol spirit burner is measured before and aer
combustion giving 70.971 g and 70.350 g, respectively. The uncertainty for
both mass values is ±0.001 g. C alculate the mass of ethanol combusted and
the associated uncertainty.
Solution
First, c alculate the change in mass:
mass of ethanol combusted = initial mass – nal mass
m = 70.971 g – 70.350 g
m = 0.621 g
Then propagate the uncertainties. You are subtracting the mass values, so you
must add the absolute uncertainties:
u(m) = ± 0.001 g + (± 0.001 g)
u(m) = ± 0.002 g
Finally, write the overall result:
m = 0.621 g ± 0.002 g
358
Worked example 5
3 3
A student uses a volumetric pipette to transfer 25.00 cm ± 0.05 cm of dilute acid into a conic al ask and then adds a
3 3
further 10.0 cm ± 0.5 cm of the acid solution using a measuring cylinder. C alculate the total volume of acid added to
the ask, along with its associated uncertainty.
Solution
First, c alculate the total volume added: You are adding the volume values and therefore to
propagate the uncertainties you must add the absolute
total volume of acid = rst volume + second volume
uncertainties:
3 3
V = 25.00 cm + 10.0 cm 3 3
u(V) = ± 0.05 cm + (± 0.5 cm )
V = 35.0 cm (1 dp) 3
= ± 0.55 cm
Note that the result is rounded to one decimal place 3
≈ ± 0.6 cm (1 sf )
to be consistent with the second volume, which has
the least number of decimal places in the raw data. This gives the overall result:
3 3
V = 35.0 cm ± 0.6 cm
The large uncertainty of the measuring cylinder largely
eclipses the high precision of the volumetric pipette.
Propagating uncertainties in c alculations involving multiplic ation or division
requires you to add the percentage uncertainties of the values that are being
multiplied or divided. Since percentage uncertainties are just the relative
uncertainty in decimal form, you c an also think of this as adding the relative
uncertainties and expressing them as percentages at the end of the c alculation.
Worked example 6
A sucrose solution is prepared by dissolving 10.35 g ± 0.02 g of solid sucrose in water to produce
3 3 –3
100.00 cm ± 0.10 cm of solution. C alculate the concentration of sucrose, in g dm , and the associated uncertainty.
Solution
First c alculate the mass concentration of sucrose: This gives the overall result:
m
–3
c = c = 103.5 g dm ± 0.3%
10.35 g This percentage uncertainty c an be converted to an
=
3 3
100.00 × 10 dm
absolute uncertainty:
= 103.5 g dm 0.3
–3
u(c) = × 103.5 g dm
100
Note that the result is given to four signic ant gures,

–3
= 0.3105 g dm
as this is the least number of signic ant gures in the
rawdata. –3
≈ 0.3 g dm (1 sf )
The c alculation involves a division, therefore to propagate

–3 –3
c = 103.5 g dm ± 0.3 g dm
the uncertainties you must compute the percentage
uncertainties and then add them together:
± 0.02 g ± 0.10 cm
u(c) =
( +
3 ) × 100%
10.35 g 100.00 cm
= ± 0.29324…% ≈ ± 0.3% (1 sf )
359
Tools for Chemistry
Worked example 7
The temperature of a 50.00 g ± 0.01 g sample of water is 23.0 °C ± 0.1 °C. The sample is then heated with an ethanol
spirit burner until it reaches 33.0 °C ± 0.1 °C.
C alculate the heat absorbed by the water, in J, and its associated uncertainty. The specic heat c apacity of water is
–1 –1
4.18 J g K
Solution
First, nd the temperature dierence, ∆T, and use this to determine the heat absorbed, Q:
∆T = T – T
nal initial
= 33.0 °C – 23.0 °C
= 10.0 °C
= 10.0 K
Q = mc∆T
–1 –1
= 50.00 g × 4.18 J g K × 10.0 K
= 2090 J (3 sf )
Note that the result is rounded to three signic ant gures to be consistent with the least number of signic ant gures in
the values used in the c alculation.
The rst c alculation involves a subtraction, so to propagate the uncertainties in temperature you add them together:
u(T) = ± 0.1 °C + (± 0.1 °C)
= ± 0.2 °C
= ± 0.2 K
Then, in Q = mc∆T, we are multiplying values and therefore we must add the percentage uncertainties:
± 0.01 g ± 0.2 K
u(Q) =
( +
) × 100%
50.00 g 10.0 K
= ± 2.02%
≈ ± 2% (1 sf )
Note the specic heat c apacity value is assumed to be exact (bec ause it was not measured in this experiment) and hence
is assumed to have no uncertainty. The overall result is as follows:
Q = 2090 J ± 2%
This percentage uncertainty c an be converted to an absolute uncertainty:
u(Q) = × 2090 J
100
= 42.8 J
≈ 40 J (1 sf )
Q = 2090 J ± 40 J
360
LHA
Propagating uncertainties in c alculations involving exponents requires
percentage uncertainties. The percentage uncertainty of the raw data is
multiplied by the value of the exponent. For instance, if the raw data is cubed
(raised to the third power), then propagating its uncertainty involves multiplying
the percentage uncertainty by three.
Worked example 8
The rate equation for the decomposition of hydrogen iodide is found to be:
rate = k[HI]
where k is the rate constant and [HI] is the concentration of hydrogen
iodide. C alculate the rate of the decomposition of hydrogen iodide when
–3 –3
[HI] = 0.60 mol dm ± 0.03 mol dm . The value of k at this temperature is
3 –1 –1
1.58 dm mol s
Solution
rate = k[HI]
3 –1 –1 –3 2
= (1.58 dm mol s ) × (0.60 mol dm )
–3 –1
= 0.5688 mol dm s
–3 –1
≈ 0.57 mol dm s (2 sf )
The result is rounded to two signic ant gures to be consistent with the least
number of signic ant gures in the values used.
The c alculation involves an exponent therefore we must rst compute the
percentage uncertainty:
±0.03 mol dm
u([HI]) = × 100%
3
0.60 mol dm
= ± 5%
Then, multiply it by the value of the exponent, which is 2 in this c ase:
u(rate) = ± 5% × 2 = ±10%
This gives the overall result:
–3 –1
rate = 0.57 mol dm s ± 10%
What is good mathematic al
We c an also express this as an absolute uncertainty:

communic ation? Why is it
10 important? Why are you

–3 –1
u(rate) = × 0.57 mol dm s
100 encouraged to show your working
–3 –1
out for all your c alculations?
= 0.057 mol dm s
–3 –1
≈ 0.06 mol dm s (1 sf )
–3 –1 –3 –1
rate = 0.57 mol dm s ± 0.06 mol dm s
You will notice that propagation increases the overall uncertainty. As raw data are
processed, the range of values they c an cover becomes greater.
361
Tools for Chemistry
Uncertainties and means
Trials are oen repeated to check for repeatability and minimize random error.
Uncertainties do not need to be propagated when c alculating the mean of a set
of values.
For example, consider the following set of results from a titration:
Titration trial
Rough 1 2 3
Initial burette 0.00 0.00 11.00 0.10
reading / cm ±
0.03 cm
Final burette 11.25 11.00 21.95 11.05
reading / cm
± 0.03 cm
Titrant 11.25 11.00 10.95 10.95
volume / cm
± 0.06 cm
Subtracting the nal volume from the initial volume gives the titrant volume,
hence the volume uncertainty is 2 × ± 0.03 = ± 0.06 cm .
The mean of the titrations, omitting the rough trial, is as follows:
3 3 3
11.00 cm + 10.95 cm + 10.95 cm
mean volume =
= 10.966... cm
3 3
≈ 10.97 cm ± 0.06 cm
The answer is rounded to two decimal places bec ause the measured values are
all given to two decimal places. Note that the uncertainty of the mean volume is
the same as the uncertainty of each of the three trials.
Data-based question
A student performed an experiment to nd the density of butan-1-ol. The
results are given below.
Volume of butan-1-ol / M ass of measuring M ass of butan-1-ol and
3 3
cm ± 0.5 cm cylinder / measuring cylinder /
g ± 0.01 g g ± 0.01 g
8.1 42.82 49.38
a. Determine the mass of the butan-1-ol sample.
b. C alculate the density of the butan-1-ol sample.
c. C alculate the uncertainty of the density. Express your answer as (i) an
absolute uncertainty and (ii) a relative uncertainty.
362
Graphs and tables
Graphs show how changes in an independent variable aect a dependent
variable. Graphic al techniques c an be used to examine the nature of the
relationship between the variables and to predict unknown quantities.
Sketching graphs
Sketched graphs have labelled but unsc aled axes, and they are used to show
qualitative trends, such as variables that are proportional or inversely proportional
to each other. Examples of sketched graphs are shown in gure 70.
(a) (b)
3
2 mol dm acid (highest concentration)
decudorp
V
2
3
OC fo
1 mol dm acid
,emulov
emulov
3
0.5 mol dm acid
(lowest concentration)
time
temperature, T (K)
(c) (d)
i
n
c
taht selucelom fo
r
e
i
E
g
aP/P
aP/P
t
,ygrene
p
e
r
,erusserp
,erusserp
a
t
u
r
e
evah
rebmun
energy, E
3
3
volume, V/dm 1/V / dm
 Figure 70 Examples of sketched graphs: (a) curves showing the eect of concentration on the rate of the reaction between an acid and a
metal c arbonate (b) graph showing that gas volume is directly proportional to temperature (c) two graphs showing that pressure is inversely
proportional to volume (d) M axwell–Boltzmann distributions of molecular energies for a xed mass of gas at three dierent temperatures
Activity
Sketch graphs to show:
a. concentration of reactants and products over time in an equilibrium
system
b. the melting point of the elements across period 3
c. how pH changes when a strong acid is added to a strong base.
363
Tools for Chemistry
D ata, particularly quantitative data, c an be organized into tables and then
processed into charts. There are dierent types of charts, including graphs.
Tables
Quantitative data c an be presented as a table. It is customary to include the
following features in data tables:
• Descriptive title to aid communic ation. If more than one table is being
presented, each should be numbered as well.
• Independent variable in the leftmost column , listed in order of increasing
value.
• Dependent variable(s) in the columns to the right of the independent
variable. List the results from repeating trials next to each other, and the
mean in the rightmost column.
• Descriptive column headings.
• Units and uncertainties in column headings.
• Consistent precision in each column.
• Clear identific ation of values of importance (for example, concordant
values in a titration, or anomalous results).
descriptive colun
eadings ic include

clear table title
units and uncertainties
Table 1. Boilling points of aqueous solutions containing different asses of NaCl.
M ass of NaCl Boilling point of solution
dissolved / °C ± 0.1°C
/ g ± 0.01 g
Trial 1 Trial  Trial  Mean
0.00 97.0 96.9 97.2 97.0
1.00 98.5 97.4 98.0 98.0
2.00 98.8 105.2* 99.7 99.3
3.00 99.9 100.0 100.2 100.0
4.00 101.6 100.5 101.8 101.3
independent
consistent decial
tis value is an anoal
variable in te
places for values
leost colun
obtained using te
anoalies identified
sae equipent
if applic able
 Figure 71 Common features of a data table
364
Control variables should be recorded but they are not usually included in
tables bec ause they should not change throughout the experiment. Tables c an
sometimes include a space for qualitative data, where applic able. Otherwise,
qualitative data c an be included directly above or below the table.
Sometimes you will need to think of a way to eectively record additional
information in your table (such as variables that need to be monitored or citations
for data that you have found in databases). You c an nd examples of how to do
this in scientic journal articles.
Activity
A student did an experiment looking at how the potential dierence of a
voltaic cell changes with dierent combinations of half-cells and wrote down
the following data during the practic al. Organize the data into a suitable
table.
zinc – copper: 0.80 V, 0.78 V, 0.74 V
copper – silver: 0.50 V, 0.53 V, 0.51 V
zinc – silver: 1.30 V, 1.25 V, 1.27 V
magnesium – copper: 2.05 V, 2.00 V, 1.34 V
magnesium – zinc: 1.54 V, 1.43 V, 1.23 V
Charts and graphs
Charts and graphs represent all the data simultaneously, allowing us to explore
trends and patterns in the data. There are dierent types of charts and graphs,
each used to present information in a way that aids interpretation. Examples
include:
• Pie charts allow us to compare parts of a whole, usually expressed as
percentages.
• Bar charts are used to group data into distinct c ategories known as
c ategoric al variables, such as type of intermolecular forces, or identity of a
substituent atom.
• Histograms involve grouping data according to a range in the value of the
quantitative variable such as length (e.g. 0–1 cm, 1–2 cm, 2–3 cm).
• Line graphs also show quantitative data, but they contain points joined by
straight lines. Line graphs are particularly useful for continuous data, which
means that they c an be organized along a numbered line and have any value
within a continuous range.
• Sc atter graphs represent the relationship between two variables. The
data points are plotted and then a line or curve of best t (also known as
a trendline) is added to show the relationship between the two variables.
Unlike line graphs, the points on sc atter graphs are not necessarily joined up
bec ause what matters is the overall relationship they show.
365
Tools for Chemistry
(1) (2)
carbon dioxide
argon
40
and methane
)%(
(1%)
(trace)
ecnadnuba
30
20
oxygen
21%
10
nitrogen 0
3.9 4.0–7.9 8.0–11.9 12.0–15.9 16.0 to

78%
and 19.9
under
size of microplastic (mm)
(3) (4)
temperature variation CO concentration

2 0.6
380 4
annual mean
vmpp
2
0.4 5-year mean
340
300
C°
2
/
0.2
4
2
260
OC
220 0
8
180 10
0
000 004
000 053
000 003
000 052
000 002
000 051
000 001
000 05
0.2
0.4
years before present 1880 1900 1920 1940 1960 1980 2000
ppmv = parts per million by volume
(5)
7000
mpp ni noitartnecnoc
6000
edixoid
5000
nobrac
4000
3000
0 100 200 300 400 500 600
time in seconds
 Figure 72 Dierent types of charts and graphs. (1) Pie chart showing the present composition of the Earth’s atmosphere (2) Histogram
showing the distribution in the size of microplastics in a sample (3) Line graph showing global temperature variation and atmospheric CO
2
concentration obtained through isotopic analysis of ice cores (4) Line graph showing global mean temperatures in recent years (5) Sc atter
graph showing the linear increase of c arbon dioxide concentration over time.
Note that the line of best t does not go through all the points bec ause it represents the overall relationship between the two variables
366
Plotting graphs
All graphs, regardless of whether they are drawn by hand or plotted using
technology should have the following elements:
• Descriptive title to aid communic ation. If more than one graph is being
presented, each should be numbered as well.
• Independent variable on the x-axis, dependent variable on the y-axis
• Axis sc ales that cover a suitable range and contain equally spaced marks
• Axis labels, including units and uncertainties
• Accurately plotted points.
D ata sometimes contains outliers, which are points that do not t the trend of
the line or curve. Sometimes scientists use advanced statistic al tests to determine
outliers. At this level, you c an identify outliers by eye. It is important to consider,
when discussing your results, possible underlying c auses of an outlier.
Logarithmic sc ales c an be used when plotting data that cover a very large range.
Doing so compacts the information in the graph and allows us to easily identify
signic ant changes in the data (gure 73).
18 000 000
16 000 000
airetcab fo noitalupop
14 000 000
12 000 000
10 000 000
8000 000
6000 000
4000 000
2000 000
2 4 6 8 10 12 14 16 18 20 22 24
time / h
1000 000 000
100 000 000

airetcab fo noitalupop
10 000 000
1000 000
100 000
10000
1000
100
10
2 4 6 8 10 12 14 16 18 20 22 24
time / h
 Figure 73 The sc ales on both axes on the rst graph are linear. Plotting the same data with a
logarithmic sc ale on the y-axis in second graph gives a straight line, conrming that the trend in the
data is exponential
367
Tools for Chemistry
1. Identify the outlier in the graph below:
120
100
)Cº (
80
erutarepmet
60
40
20
0 1 2 3 4 5 6 7
time (minutes)
LHA
2. The graph below shows the logarithm of the successive ionization energies for potassium.
Explain why a logarithmic sc ale on the y-axis is useful in this c ase.
2 electrons
very close
to nucleus,
n = 1 shell
ygrene noitazinoi
8 electrons close to
nucleus, n = 2 shell
01
gol
8 electrons far
from nucleus, n = 3 shell
1 electron very far from
2 nucleus, n = 4 shell
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
number of the ionization
368
Error bars
Error bars (also known as uncertainty bars) are graphic al representations of
uncertainties, eectively showing that a data point represents a range of values.
Vertic al error bars show the uncertainty of the y-axis variable, whereas horizontal
error bars show the uncertainty of the x-axis variable.
3.0
1
s
m /d e ep s
2.0
1.0
t Figure 74 Error bars show the uncertainty
0
of a point on a graph. The x and y values
0 0.1 0.2 0.3 0.4

for this point are, time = 0.2 s ± 0.05 s, and
time/s −1 −1
speed = 1.4 m s ± 0.2 m s
Graph-plotting soware oen has an option to include error bars when the absolute
or percentage uncertainty is specied. However, if there is a dierent uncertainty
associated with each point, the soware might not accommodate this. In this case
you can either draw the error bars for each point by hand or have the program draw
error bars corresponding to the largest uncertainty in the data set (and add a note to
this eect). You should determine which option is best in the context of your analysis.
Lines or curves of best t
A line or curve of best fit represents the general trend in a graph and can be used
for further analysis of the relationship between the variables. The line or curve of
best t does not have to pass through every single point, but it must have roughly
the same number of points on either side of it. If there are any obvious outliers
amongst your data, you might need to ignore them when drawing the line or
curve of best t. This does not mean, however, that they should be excluded from
the analysis. It is good practice to circle and label outliers on graphs, as well as
discussing their possible sources and signicance in the analysis.

elbairav tnedneped
line of
best fit
t Figure 75 A generalized graph showing
a line of best t
independent variable
369
Tools for Chemistry
emyzne fo etar
noitca er
yticolev
(a) time (b) temperature
 Figure 76 Depending on the nature of the data, curves of best t c an be simple (a) or complex (b)
Technology c an be useful when drawing lines and curves of best t, but you must
consider whether computer-generated lines or curves of best t make sense in
the context of the data. For example, soware may skew the line due to an outlier,
or it may show a straight line where a curve would be more suitable. Lines and
curves of best t do not always have to pass through the origin.
If points on a graph have error bars, then the curve or line of best t should pass
through as many of the error bars as possible. If the error bars of a point are
outside the line of best t, it may indic ate that the point is an outlier, or possibly
that the uncertainty is greater than expected.
A reaction rate investigation produced the following data:
Concentration of reactant A R ate of reaction
3 –3 1
/ mol dm ± 0.0002 / mol dm s ± 5%
0.0010 0.015
0.0020 0.031
0.0030 0.027
0.0040 0.065
0.0050 0.089
a. Plot a graph of the results.
b. Draw error bars on your graph.
c. Draw a line of best t.
d. Identify the outlier and suggest what might have c aused it.
370
Interpretation of features of graphs
The relationship between variables c an be further analysed by interpreting the
features of a graph: correlation, form, gradient, intercept, maxima and minima,
and area. The main thing to remember is that the features of a graph c an oen
represent an aspect of the idea being studied. We will also discuss the use of a
coecient of determination (R ), interpolation and extrapolation.
The rst thing to consider when interpreting a graph is the correlation it shows
(if any). If the dependent (y) variable increases when the independent variable
(x) increases, then the variables are positively correlated. A negative correlation
describes a relationship where an increase of the independent variable c auses
the dependent variable to decrease. If the points are randomly sc attered in the
graph, the correlation is weak or absent (gure 77).

Y
Y
elbairav
elbairav
elbairav
variable X variable X variable X
Positive correlation. Negative correlation. No correlation.
When X increases, When X increases,
Y also increases Y decreases.
 Figure 77 Sketched graphs showing positive, negative and absent correlation
The relationships shown in graphs c an be linear or non-linear. A linear relationship
corresponds to a straight line in the graph that is described by the equation
y = mx + c, where m is the gradient (slope) of the line and c is the y-intercept.
Direct proportionality is a special type of linear relationship, in which the two
variables are in a constant ratio. When one variable increases, the other increases
by the same rate. For example, the volume of a gas is directly proportional to
its temperature, provided that the temperature is in kelvin (gure78). If two
variables are directly proportional, the straight-line graph must go through
theorigin.
pressure of gas pressure of gas
0
temperature (K)
300 200 100 0 +100 +200
temperature (°C)
 Figure 78 Pressure and temperature of an ideal gas are linearly related, but the relationship is only directly
proportional when the temperature is in kelvin
371
Tools for Chemistry
Variables are inversely proportional when one increases and the other decreases
by the same rate. Unlike direct proportionality, graphs showing inverse
proportionality are not linear. Plotting one of the variables in its reciproc al form,
however, gives a straight-line graph. The relationship between pressure and
volume of an ideal gas is a good example of inverse proportionality (gure 79).
aP/p
aP/p
,erusserp
,erusserp
3 3
volume, V/ dm 1 /V/ dm
 Figure 79 Pressure and volume of an ideal gas are inversely proportional to each other:
plotting p vs gives a straight-line graph
Non-linear is a term that includes all relationships that are not straight lines.
Sometimes, non-linear relationships c an be described by functions, such as
exponential, logarithmic and quadratic functions.
1.000
(a) (b)
)retaw g 001
70
3
0.800
60
md
50
lom / ])g(O
0.600
rep g( ytilibulos
40
0.400
30
2
20
N[
0.200
10
0.000 0
0 50 100 150 200 250 0 10 20 30 40 50 60 70 80 90 100
time / s temperature (°C)
(c) 14
12
10
Hp
0 5 10 15 20 25 30 35 40 45 50
3
volume of 0.1 mol dm
3
acid added / cm
 Figure 80 Graphs showing non-linear relationships: (a) the decomposition of nitrous oxide,
(b) a solubility curve and (c) a pH curve for the addition of a strong acid to a strong base
372
Gradient (or slope)
The gradient (or slope) of a line is a measure of its steepness, but it also has a
physic al meaning: it is the rate of change of one variable with respect to the other
variable. To nd the gradient of a line, you need to choose two points on that line,
ideally well separated from each other. Gradients c an be positive or negative,
depending on whether the graph shows a positive or a negative correlation,
respectively.
Δy y − y
2 1
m = =
Δx x − x
2 1
For example, a graph of mass of a substance (along the y-axis, in g) vs its volume
(along the x-axis, in cm ) gives a straight line. The gradient of the line has units
g cm , which gives us the density of that substance.
The uncertainty for the gradient c an be determined by drawing the steepest
and most gradual lines of best t possible within the constraints of the error bars,
giving values for maximum and minimum gradients. Half the dierence between
these two lines c an be used to estimate the uncertainty of the gradient.
steepest gradient
a
ytitnauq
most gradual
gradient
quantity b
 Figure 81 M aximum and minimum gradients on a graph c an
be determined from the most and least steep lines of best t
Straight-line graphs have constant gradients while curves have changing
gradients. For instance, data for product volume vs time will produce a curve,
bec ause the rate decreases during the reaction (gure 82).
no further
reaction
reaction is slower
where gradient is
volume
less steep
of gas
reaction is faster where
gradient is steeper
time
 Figure 82 The rate decreases over the course of a
reaction, so the gradient decreases over time
373
Tools for Chemistry
We can determine the gradient at a specic point on the curve by drawing a
tangent line and working out its gradient. In gure 82, two tangent lines are
shown in green. The one at t = 0 is clearly steeper because the rate is higher at
that point in time. Figure 83 shows how to calculate the gradient of a tangent line.
3
md
lom/ ]X[ ,X
reaction rate at
time t
= gradient of graph at time t
Δ[X]
= at time t
Δt
fo noitartnecnoc
= gradient of tangent AB
AC
3 1
= mol dm s
BC
B C
 Figure 83 The rate of reaction at time
t c an be determined by c alculating the
gradient of the tangent line at that point

time / s
Intercepts
The intercepts are the points where the line or curve crosses the axes.
Intercepts c an be found by extending the line until it meets the axis (this is c alled
TOK
extrapolation). You c an also use the equation of the line in the form y = mx + c
International variations exist in the (or y = mx + b) where c (or b) represents the y-intercept.
equation for a straight-line graph.
As with gradient, the signic ance of the intercepts depends on the context of
It is oen given as y = mx + c or
the data being plotted. In some c ases, you would expect the y-intercept to be
y = mx + b, where m is the gradient
0, for instance when plotting the concentration of a product vs time as a part
and c or b is the y-intercept. To
of a kinetics investigation. In other c ases, the intercept c an be used to derive a
what extent do shared codes and
numeric al quantity (gure 84).
symbols help or hinder the pursuit
of knowledge on a global level?
ln A
E
a
m =
R
knl
0
1
1
 Figure 84 The y-intercept of a graph showing lnk vs is lnA,
T
T
where A is the Arrhenius factor
374
Similar to gradient, the uncertainty of the y-intercept c an be determined by
drawing the most and least steep lines of best t possible within the constraints of
the error bars. This gives maximum and minimum values for the y-intercept, from
which you c an nd the uncertainty (gure 85).
a
ytitnauq
maximum value
of intercept
best value
minimum value
for intercept
of intercept
quantity b
 Figure 85 M aximum and minimum values for the y-intercept c an be
determined from the most and least steep lines of best t
M axima, minima and areas on graphs
Further interpretation of graphs may involve inspecting maximum values,
minimum values or the area under a curve. The signic ance of each of these
depends on the variables being represented in the graph.
The absorbance spectrum of a solution of an unknown substance (gure 86)
shows a maximum at around 520 nm, which corresponds to the green region
of the visible spectrum. The colour of the unknown solution must be red, as it is
complementary to green.
ecnabrosba
400 500 600 700
wavelength / nm
 Figure 86 The maximum absorbance shown in this graph helps us to
determine the colour of the solution
The changes in the concentrations of ozone, O , and chlorine monoxide radic als,
3
ClO•, 18 km high in the atmosphere across dierent latitudes are shown in
gure87. The minimum in ozone concentration occurs at the same point as a
maximum in ClO• concentration, suggesting an association between low ozone
levels and high ClO• levels.
375
Tools for Chemistry
0.8
3.0
bpp / n oitartnecnoc OIC

3
mpp / n oitartnecnoc
0.6
2.0
0.4
3
1.0
O
0.2
CIO
0.0 0.0
62 64 66 68 70 72
latitude (°S)
 Figure 87 The minimum ozone, O , concentration corresponds to a maximum chlorine

3
monoxide radic al, ClO•, concentration
The area under a curve (or the area under a graph) is the area enclosed by the
curve and x-axis. It represents an accumulation of the y-axis variable over the
course of a certain x-axis variable change.
The area under the curve is useful in M axwell–Boltzmann distributions, where it
represents the number of particles in the sample. Figure 88 shows the M axwell–
Boltzmann distributions for the same species at two dierent temperatures.

ygrene citenik htiw selcitrap fo
T
1
T
2
E
a
noitcarf
kinetic energy
 Figure 88 The area under the curve in a M axwell-Boltzmann distribution represents the
number of particles, which c an be used to compare the proportion of particles that have
sucient energy to react at two temperatures T (red) and T (green), where T > T
1 2 2 1
The particles that have sucient energy to react are represented by the shaded
regions. Their kinetic energy is equal to or greater than the activation energy,
E . At the higher temperature, T , the shaded area is larger (red + green) and
a 2
therefore the number of particles with sucient energy to react is higher than at
T , at which the shaded area is smaller (red only).

1
376
1. Students investigating the eect of temperature on air volume plotted the following graph of their results:
140
120
)
3
100
mm(
ria fo emulov
80
60
40
20
0 5 10 15 20 25 30 35 40
temperature (°C)
a. State whether the correlation between volume and temperature is positive or negative.
b. Does the graph show direct proportionality? Why or why not?
c. Determine the gradient of the line of best t. State your answer to two signic ant gures and include the units.
d. Describe briey the physic al signic ance of the gradient.
2. The following data were recorded using six standard solutions in order to determine the concentration of a sample
of aqueous copper(II) sulfate using a technique c alled atomic emission spectroscopy.
Concentration, c / mol dm Absorbance, A
0.1002 0.130
0.2008 0.270
0.2819 0.380
0.4000 0.540
0.5082 0.685
0.6000 0.810
Unknown 0.460
a. Plot a suitable graph of these results and include a line of best t.
b. Determine the concentration, in mol dm , of copper(II) sulfate.
c. Deduce the equation of the line of best t, stating the gradient and y-intercept both to two signic ant gures.
d. Discuss whether this graph shows a direct proportionality between absorbance and concentration.
377
Tools for Chemistry
3. The graph (right) shows the volume of
50
hydrogen gas collected over time for two
experiments. A tangent line has been
drawn at 25 seconds for experiment 1.

45
3
15 cm
a. C alculate the instantaneous rate of
experiment 2
40
reaction for experiment 1 at t = 25 s.
(high temperature)
b. Describe and explain whether the
3
mc / n e g o r d y h
35
instantaneous rate of reaction for
25 s
experiment 2 at t = 25 s is greater or
30
less than that of experiment 1.
c. Describe and explain whether the experiment 1
25
overall rate of reaction in experiment (low temperature)
fo
em u l ov
2 is greater or less than that in
20
experiment 1.
15
10
5 10 15 20 25 30 35
time / s
4. The graph shows how the concentration of
dinitrogen pentoxide, N O , changes over

2 5
time. A tangent has been drawn at t = 0.
4 time concentration of
–3
a. C alculate the initial rate of reaction. /s N O / mol dm
2 5
Give your answer to two signic ant

3–
–8
0 3.40 × 10
md lom
gures and state the units. –8

10 2.60 × 10
3 –8
20 1.95 × 10
b. C alculate the average rate of reaction
–8
30 1.50 × 10
8–
in the rst 30 seconds.
–8
01
40 1.15 × 10
c. Explain why your answers to (a) and (b)

× / ]) g(
above are dierent. 2

5
O
Tangent
2
N[
at t = 0
0 10 20 30 40
time/s
378
Coecient of determination, R
We have se en that all me asurements, and data derive d from them, have an
associate d uncertainty. As a result of this, the data points in a graph are not
likely to fall dire ctly on the line of best t, but rather be sc attere d on either
side of it. One of the tools we c an use to assess the pre dictive power of
the relationship betwe en the v ariables in a graph is R , the coefficient of
determination .
In DP chemistry, you will use technology to nd R values, and you will be
expected to interpret them. However, you will not be required to c alculate R
yourself. The value of R lies between 0 and 1. The closer it is to 1, the more
closely the data points match the line of best t (gure 89) and the more
successful the model is at predicting the changes in the y-axis variable. R is only
suitable for linear models.
2 2
R = 1.000 R = 0.989
0.7
0.7
g / l o n a ht e
g / l o n a ht e
0.6
0.6
0.5
0.5
0.4
0.4
fo
0.3
0.3
fo
s s am
s s am
0.2
0.2
0.1
0.1
0
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
3 3
volume of ethanol / cm volume of ethanol / cm
2 2
R = 0.862 R = 0.250
0.7
0.7
g / l o n a ht e
g / l o n a ht e
0.6
0.6
0.5
0.5
0.4
0.4
0.3
fo
fo
0.3
s s am
s s am
0.2
0.2
0.1
0.1
0
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
3 3
volume of ethanol / cm volume of ethanol / cm
 Figure 89 The R value is 1 when the points are all on the line of best t (graph 1). The
points in graphs 2 to 4 become increasingly more spread out, c ausing the R to decrease
379
Tools for Chemistry
Interpolation and extrapolation
Lines and curves of best t c an be interpolated or extrapolated. Interpolation
involves predicting values within the range of the experimental data, whereas
extrapolation involves predicting values outside the range of these data
(gure90).
range of
interpolation
extrapolation
extrapolation
y intercept
x
x intercept
 Figure 90 Interpolation and extrapolation using a straight line
Consider the absorbance versus concentration graph shown in gure 91.
The points on the line were obtained by measuring the absorbance of six
solutions of known concentration.
plot of A versus c
0.9
(x , y )
2 2
0.8
0.7
0.6
0.5
0.4
0.3
0.2
(x , y )
1 1
0.1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
3
c/mol dm
 Figure 91 Interpolation involves nding values within the range of the experimental data
380
The absorbance of a sample of unknown concentration is found to be 0.460.
Its concentration c an then be found by interpolation, as shown, giving
0.34 mol dm . If known, the equation of the line could also be used to nd the
concentration, by entering 0.460 in for y and solving for x
In a c alorimetry experiment, the temperature of the reaction mixture containing
copper(II) sulfate solution and zinc metal is monitored over time and the results
are plotted on a graph (gure 92). The maximum temperature value is needed
to c alculate ∆T and subsequently the amount of heat, Q (and later, the enthalpy
change, ∆H). The highest temperature measured during the experiment is
lowered due to heat loss to the surroundings.
Extrapolating the cooling curve (the part of the graph that shows a decreasing
temperature over time) backwards to the time at which the zinc was added to the
copper(II) sulfate solution, allows us to predict a corrected value of T . Doing so

max
assumes a constant rate of heat loss during the reaction.
Extrapolation always involves the assumption that the relationship between
variables stays the same beyond the range of data. In practice, this is not always
the c ase. For example, the relationship between absorbance and concentration
in gure 91 is linear, but the linearity is lost at higher concentrations.
compensating for heat lost
T = initial temperature of
0
reactants
T = highest temperature
1
actually reached
T = temperature that would have

2
T
been reached if there were no
2
T
1
erutarepmet
ΔT
extrapolation at same
rate of cooling
ΔT for reaction = T T
2 0
T
0
reactants mixed
time
 Figure 92 Extrapolation of temperature data during a zinc metal and copper(II)
sulfate reaction to determine a corrected value of T , the maximum temperature

2
381
Tools for Chemistry
1. A student performed a c alorimetry experiment to determine the enthalpy change for the reaction between zinc
metal and copper(II) sulfate. A graph of the student’s results is shown below.
68
66
62
60
58
56
54
52
C
50
º
48
/ e r ut a r e pm e t
46
ΔT = 64.0 19.5
44
º
= 44.5 C
42
40
38
36
34
32
30
28
26
24
22
20
18
0 1 2 3 4 5 6 7 8
time / min
a. State the minimum temperature measured.
b. State, giving a reason, whether the reaction is exothermic or endothermic.
c. Explain why the student extrapolated the rate of cooling back to t = 2.5 min.
d. Outline what other information you would need to c alculate the heat, Q, and enthalpy change, ∆H, for this
reaction.
2. A student collected temperature data every minute while titrating

Volume of N aOH Temperature / °C
3
3
hydrochloric acid, HCl(aq), with 0.600 mol dm sodium hydroxide,
(aq) / cm
NaOH(aq). D ata for the volume of sodium hydroxide added and
0.00 22.4
temperature are shown in the table on the right.
5.00 23.1
a. Plot a graph of these data.
10.00 23.9
b. Find the maximum temperature by extrapolation of the heating

15.00 24.6
and cooling curves.
20.00 25.4
c. The volume of hydrochloric acid was 25.00 cm . Determine the

25.00 25.6
concentration of the acid.
30.00 25.5
d. C alculate the enthalpy change of neutralization, ∆H , for this

35.00 25.4
reaction, in kJ mol
40.00 25.3
45.00 25.2
50.00 25.1
382
Sources of experimental error
Experimental errors result from the fact that measurements are never exact: they
always have uncertainties associated with them. Experimental errors c an be
systematic or random.
The word “error ” in everyday language c an mean “mistake”. In science, “error ”
has a very dierent meaning. One of the features of a thorough scientic research
is the consideration of sources of experimental errors, their impact on the
outcome of an investigation, and possible ways to minimize them.
R andom and systematic error
R andom errors arise due to natural variations in measured values, leading to
measurements that are equally likely to be too high as too low. R andom errors
c an be minimized, but not eliminated, by repeating measurements. L arge
random errors reduce precision bec ause the values are spread over a greater
range. The uncertainty provides an estimate of random error.
Sources of random errors include readings that uctuate
over time, uncertainty associated with reading a sc ale,
and random variations in the measurements made with a
particular instrument. meniscus
Systematic errors aect results in the same direction
correct reading of volume

(either making the results too high or too low). For
at bottom of meniscus
example, consistently taking a burette reading from
above the meniscus will result in readings that are too
high (gure 93).
Systematic errors reduce accuracy and c an be
minimized, but not eliminated, by making changes to the
experimental methodology. If a particular systematic error
c an be quantied, the values c an then be corrected for it.
 Figure 93 Examples of systematic error
Sources of systematic errors include a misc alibrated temperature probe,

when taking burette readings
presence of background radiation, leaks in gas collection apparatus, and heat
loss to the surroundings during c alorimetry experiments.
Errors and processed results
Estimates of random errors, obtained by uncertainty propagation, are useful in
the analysis of errors in experimental results. Comparisons between percentage
uncertainties, and, where available, theoretic al values and percentage errors c an
give a basis for evaluating the precision and accuracy of a processed result.
Percentage error (not to be confused with percentage uncertainty) is a way of
quantifying how far an experimental value is from the theoretic al value:
experimental value − theoretic al value
Percentage error = × 100%
theoretic al value
Note that the theoretic al value is sometimes c alled the accepted value or
literature value.
383
Tools for Chemistry
For example, the theoretic al value for the activation energy of a reaction is
reported in the literature as 65 kJ mol ± 1%. Students A and B determine this
activation energy experimentally and obtain the data shown in table 5. Student A
nds the activation energy to be 60 kJ mol ± 10%. The ± 10% part is an estimate
of the random error, indic ating that the result is in the range of 54–66 kJ mol .
We c an see that the theoretic al value lies within the range of the experimental
value, suggesting that the two are aligned. However, the high percentage
uncertainty (10%) indic ates low precision, particularly when compared to that of
the theoretic al value (1%).
Experimental E Uncertainty Absolute R ange Percentage

a
1 1
value / kJ mol / % uncertainty / kJ mol error / %
/ ± kJ mol
student A 60 10 6 54–66 7.7
student B 50 4 2 48–52 23
 Table 5 Student results for the experimentally determined activation energy of a reaction
Now consider the result obtained by student B for the same reaction:
50 kJ mol ± 4%. The random error is smaller than that obtained by student A,
indic ating greater precision (though still not as precise as the theoretic al value).
The result is in the range of 48–52 kJ mol . This time, the theoretic al value does
not lie in this range, therefore the result is inaccurate. In addition, since the
uncertainty is 4% and the percentage error is 23%, only up to 4% of the 23%
error c an be attributed to random errors. This suggests that systematic errors
contributed signic antly to the dierence between student B’s result and the
theoretic al value.
Practice questions
51. Classify each of the following errors as systematic or random:
a. heat loss to the surroundings in an investigation involving c alorimetry
b. use of a misc alibrated colorimeter to determine the absorbance of
asample
c. taking a burette reading by positioning the viewer slightly below the
meniscus rather than positioning the eyes on a level with themeniscus
d. use of a pH probe that reports values to the nearest whole number.
52. A student c alculated the enthalpy change for the combustion of butan-1-
1 1
ol and obtained −1 430 kJ mol . The theoretic al value is −2 676 kJ mol .
C alculate the percentage error in the student’s result.
53. Two students investigated the enthalpy of neutralization of a strong acid
with a strong base. Their results were:
1 1
student C: −35 kJ mol ± 4 kJ mol
1 1
student D: −50 kJ mol ± 10 kJ mol
The theoretic al value for the enthalpy of neutralization is −57 kJ mol .
a. C alculate the percentage errors of the students’ results.
b. Comment on the relative impact of random errors on each of
theresults.
384
Errors and graphs
A ytitnauq
Graphs c an also provide information regarding systematic and random
error (gure 94). R andom errors c ause data points to deviate from the
line of best t. Systematic errors c ause all the data to shi in the same perfect results
random error
direction (either up or down). On graphs, this means that the points
systematic error
are systematic ally loc ated higher (or lower) than expected. This is
especially noticeable in the y-intercept: a y-intercept that is not where

quantity B
you would expect it to be suggests the presence of a systematic error.
 Figure 94 The presence of systematic and
random errors c an be inferred from graphic al data
Practice questions
54. The combustion of primary alcohols methanol to 55. A student investigated the eect of concentration of
octan-1-ol was determined experimentally (table 6). sodium hydrogencarbonate on the rate of its reaction
with citric acid. The reaction produces carbon dioxide,
3
Number of c arbon Experimental enthalpy
so the student timed how long it took to collect 25 cm of
atoms in primary of combustion

this gas. The student’s data collected is shown in table 7.
- -
alcohol / kJ mol ¹ ± 40 kJ mol ¹
Time taken to produce
1 –230
Concentration of sodium
25 cm³ of carbon
2 –400 hydrogenc arbonate /
dioxide / s ± 1 s
-
mol dm ³ ± 5 %
3 –680
1 2 3
4 –814
0.25 210 277 166
5 –990
0.50 195 135 118
6 –1300
1.00 66 93 53
7 –1440
1.50 21 27 35
8 –1700
2.00 15 25 15
 Table 6 Experimental enthalpy of combustion of the
 Table 7 Time taken to produce 25 cm of c arbon dioxide
primary alcohols
in the reaction of sodium hydrogenc arbonate and citric acid at
dierent concentrations of sodium hydrogenc arbonate
a. Plot a graph of the data in table 6, including error
bars and a line or curve of best t.
a. C alculate the mean time for each of the sodium
b. Using your graph, and published enthalpy of hydrogenc arbonate concentrations.
combustion data, comment on the impact of
b. Determine an estimate of the time uncertainty by
systematic error on the results.
halving the range of each set of three trials.
c. Using your graph, comment on the impact of
c. Plot a graph to show the relationship between
random error on the results.
concentration of sodium hydrogenc arbonate and
time, including error bars and a line or curve of
best t.
d. Using your graph, comment on the impact of
random error on the analysis.
e. C alculate the rate by nding for each
concentration.
f. Plot a graph to show the relationship between
concentration of sodium hydrogenc arbonate
and rate.
g. Using your graph, comment on the impact of
systematic and random error on the analysis.
385
Re a c t i v i t y 1
What drives chemic al
r e a c t i o n s?
Reactivity 1.1 Measuring enthalpy
changes
What can be deduced from the temperature change that accompanies chemical or
physic alchange?
Chemistry involves the study of chemic al reactions and An understanding of the relationships that exist between
physic al changes of state of the elements and their chemistry and energy involves understanding how
compounds. Conservation of energy is a fundamental energy is transferred between a chemic al system and
principle of science, which is examined through the surroundings. This information c an in turn be used
observation and experimentation. The use of models, to develop an understanding of the relative stability of
empiric al or experimental data, the language of reactants and products, leading to better control over the
mathematics and scientic terminology, all contribute to progress of the reaction being studied.
our understanding of energy changes associated with
chemic al reactions.
Understandings
Reactivity 1.1.1 — Chemic al reactions involve a transfer of Reactivity 1.1.4 — The standard enthalpy change for a
energy between the system and the surroundings, while chemic al reaction, ΔH , refers to the heat transferred at
total energy is conserved. constant pressure under standard conditions and states.
It c an be determined from the change in temperature of a

Reactivity 1.1.2 — Reactions are described as endothermic
pure substance.
or exothermic, depending on the direction of energy
transfer between the system and the surroundings.
Reactivity 1.1.3 — The relative stability of reactants and
products determines whether reactions are endothermic
or exothermic.
Energy transfer in chemic al reactions
(Reactivity 1.1.1)
In a chemic al reaction, total energy is conserved. Chemic al potential energy is
universe = system + surroundings stored in the chemic al bonds of reactants and products, while the temperature
of the reaction mixture is a function of the kinetic energy of the atoms, ions and
molecules present.
All chemic al reactions involve energy changes. Energy may be released into the
surroundings from the reaction system or it may be absorbed by the reaction

surroundings
system from the surroundings. Most commonly, the energy is transferred in the
system form of heat, but it may also be in the form of electricity, sound or light.
(contents
In an open system, the transfer of matter and energy is possible across its
of flask)
boundary (for example, matter c an be added to a beaker, and energy c an be
transferred through its sides). A closed system allows no transfer of matter,

Figure 1 The universe is the
combination of the system and its

though energy may be transferred across the boundary. In an isolated system,
surroundings matter and energy c an neither enter nor exit the system.
387
Reactivity 1 What drives chemic al reactions?
Figure 2 In each of the above scenarios, energy is transferred. In hot springs, energy is transferred as heat, and in reworks, as heat,
sound and light. Both scenarios are opensystems
Models
Most industrial processes take place in open or closed systems. The loss of
heat during an industrial process not only aects the eciency of the chemic al
reaction, but also contributes to a loss of useful energy, an increase in thermal
pollution. Thermography c an be used to model heat ow and loss from
structures in chemic al industries as a heat map, where red is hot and purple
iscold.
Figure 3 Thermograph of industrial engineering system
What are the advantages of modelling heat distribution and transfer? How
c an chemic al engineers use the data collected to improve the eciency of
industrial processes? How does this help our environment?
388
Reactivity 1.1 Measuring enthalpy changes
What is the dierence between heat and temperature?
Temperature, T, is an example of a state function. For a state function, any
change in value is independent of the pathway between the initial and nal
measurements.
For example, if you take the temperature of the water in a swimming pool early
in the morning (the initial value) and then again in the aernoon (nal value),
it will not tell you the complete story of any temperature uctuations that may
have occurred throughout the day. The c alculation of the temperature change
issimple:
ΔT = T − T
nal initial
Figure 4 If you record the temperature of a pool at the beginning and the end of a day,
it will not give you an indic ation of the heating and cooling that has occurred throughout the
day, only the overall temperature change
Other examples of state functions include volume, enthalpy and pressure.
Heat, q, is a form of energy that is transferred from a warmer body to a cooler
body, as a result of the temperature gradient. Heat is sometimes referred
to as thermal energy. It c an be transferred by the processes of conduction,
convection and radiation.
Heat has the ability to do work. When heat is transferred to an object, the result is
an increase in the average kinetic energy of its particles. This c auses an increase
in temperature and potentially a phase change, for example, a change of state
from liquid to gas.
At absolute zero, 0 K (−273.15 °C), all motion of the particles theoretic ally
stops and the entropy, S, of a system reaches its minimum possible value. The
absolute temperature (in kelvin) is proportional to the average kinetic energy of
Entropy is dened and explored in
the particles of matter. As the temperature increases, the kinetic energy of the
Reactivity 1.4
particles also increases.
389
Your communic ation skills will develop incrementally
throughout the entire chemistry programme.
Communic ation skills include consistent and accurate
applic ation of scientic terminology. Your use of the
terms “heat” and “temperature” in explanations will
demonstrate your understanding of theseconcepts.
For example, consider the simple reaction between
magnesium metal and hydrochloric acid.
Mg(s) + 2HCl(aq) → MgCl (aq) + H (g)

2 2
In this reaction, heat is released from the reaction
system into the surroundings, and the temperature of
the aqueous solution rises. When you think about heat,
you are considering the transfer of thermal energy in the
system. When you refer to the temperature of a system,
you are describing the average kinetic energy of the
particles within that system.
Figure 5 M agnesium ribbon reacting with hydrochloric acid
Thermochemistry is the study of heat changes that occur during chemical
reactions. Heat changes are oen described in terms of enthalpy. At constant
pressure, the enthalpy change, ∆H, is dened as the heat transferred from
a closed system to the surroundings during a chemical reaction. The terms
“enthalpy change” and “heat of reaction” are commonly used when describing
the thermodynamics of a reaction. The most common unit of enthalpy change is kJ.
Activity
Imagine a glass of water containing ice cubes sitting in the summer sun. It will
undergo a change in enthalpy.
• Is the glass of water an open, closed or isolated system?
• Identify the system and the surroundings.
• Explain the movement of energy in the form of heat, between the system
and the surroundings.
• What would you observe on the outside of the glass? Explain this
observation in terms of a change of state and transfer of energy.
390
Exothermic and endothermic reactions
(Reactivity 1.1.2)
A chemic al reaction in which heat is transferred from the system to the
surroundings is dened as an exothermic reaction. In contrast, chemic al
reactions in which heat is absorbed into the system from the surroundings are
dened as endothermic reactions.
When a chemic al reaction takes place, the atoms of the reactants are rearranged
to create new products. Chemic al bonds in the reactants are broken, and
new chemic al bonds are made to form products. Energy is absorbed by the
reaction system to break the chemic al bonds, and therefore bond breaking is
an endothermic process. This energy is termed the bond dissociation energy
and it c an be quantied for each type of bond. Energy is released into the
surroundings when new chemic al bonds are made, and therefore bond making
is an exothermic process. The transfer of energy between the surroundings and
the system is an important part of your understanding of the energy changes in
areaction.
Exothermic reactions have a negative enthalpy change, and endothermic
reactions have a positive enthalpy change. The sign of the enthalpy change
is dened from the perspective of the system and not the surroundings. For
example, in an exothermic reaction, heat is being lost by the system and so the
enthalpy change is negative. For an endothermic reaction, heat is absorbed by
the system, so the enthalpy change is positive.
To determine whether a reaction is endothermic or exothermic, we c an use a
c alorimeter. A c alorimeter is any apparatus used to measure the amount of heat
being exchanged between the system and the surroundings. In the school
laboratory, experiments focus on the change in temperature, ΔT, of the reaction
solvent, which in most c ases is water.
Observations
In the laboratory, observations c an be made using human senses, or with
the aid of instruments such as data-logging equipment. The applic ation of
digital technology to collect data is one of the essential skills in the study
ofchemistry.
Energy proles (Reactivity 1.1.3)
Energy proles are a visual representation of the enthalpy change during a reaction.
Activation energy, E , is the

a
From an energy prole, you can determine the enthalpy of the reactants and the
minimum energy required for the
products, the activation energy (E ), and the enthalpy change for the reaction.
a
reaction to take place. You will study
activation energy in Reactivity 2.2.

M any chemic al reactions are exothermic. In these reactions, energy is released
from the system to the surroundings. The reactants of this reaction are at a higher
energy level and considered to be lower in stability. Products for exothermic
reactions are at a lower energy level and considered to be more energetic ally
favourable.
391
Consider the reaction between zinc and copper(II) sulfate solution. It is a single
displacement reaction involving the displacement of the copper(II) ion by zinc:
Zn(s) + CuSO (aq) → Cu(s) + ZnSO (aq)

4 4
Measured quantities of copper(II) sulfate solution and zinc are mixed in a
c alorimeter. The mixture is stirred, and the change in temperature of the solution
is measured using a thermometer or data-logging equipment. In this reaction,
heat is generated by the reaction system. As a result, the temperature of the
solution increases, and the heat is transferred to the surroundings. The reaction is
therefore exothermic.
exothermic reaction
ygrene
E
a
reactants
laitnetop
ΔH
products
reaction coordinate
Figure 6 Using a thermometer or a temperature probe, you would observe an increase
in the temperature of the reaction mixture in an exothermic reaction. The enthalpy of the
products is lower than that of the reactants. You would describe the products as being
energetic ally more stable than the reactants
The graph in gure 6 is an example of an energy prole
If you consider an endothermic reaction, the products of the reaction are at a
higher energy level and therefore are less stable than the reactants.
Ammonium nitrate, NH NO , is an important component of fertilizers. When

4 3
the solid dissolves in water to form aqueous ammonium and nitrate ions, the
temperature of the solution decreases.
NH NO (s) → NH (aq) + NO (aq)

4 3 4 3
This heat is absorbed by the reaction system from the surroundings. The
apparatus containing the reaction mixture will feel cold to touch. This is an
example of an endothermic reaction (gure 7).
endothermic reaction
ygrene
products
E
a
l a i t n e t op
ΔH
reactants
reaction coordinate
Figure 7 Using a thermometer or a temperature probe, you would observe a decrease
in the temperature of the reaction mixture in an endothermic reaction. The enthalpy of
the products is greater than that of the reactants. The products are described as being
energetic ally less stable than the reactants
392
Developments in science may have ethical, environmental, political, social,
cultural and economic consequences, which must be considered during
decision making. The pursuit of science may have unintended consequences.
German chemist Fritz Haber was awarded the Nobel Prize in Chemistry in
1918 for developing a method to chemically extract nitrogen from the air
by reacting it with hydrogen. Haber ’s discovery allowed for the large-sc ale
production of fertilizers that began during the green revolution and continues
today. However, his process also provided Germany with a source of
ammonia that was used for the production of explosives during the First World
War. The global impact of science is evident in Haber ’s research.
Communic ation skills cover a wide range of skills and forms of
communic ation. Your ability to eectively communic ate verbally and in written
form most oen comes to mind when you are thinking about improving
communic ation skills. However, communic ation also involves your ability to
read and write dierent forms of texts intended for dierent audiences. In
science, you need to be able to write formal laboratory reports using specic
terminology and accepted writing styles. Another form of communic ation
you would utilize in writing reports and answering examination questions,
is your ability to sketch graphs and extract data and meaningful information
from graphs. C an you read and analyse the energy proles that represent
exothermic and endothermic reactions? Try to accurately sketch these
diagrams, including all of the components.
Practice question
1. Barium hydroxide, Ba(OH) , reacts with ammonium chloride, NH Cl:

2 4
Ba(OH) (s) + 2NH Cl(s) → BaCl (aq) + 2NH (g) + 2H O(l) ΔH = +164 kJ mol
2 4 2 3 2
Which of the following is correct for this reaction?
Temperature Enthalpy Stability
products have lower products are less stable
A increases
enthalpy than the reactants than the reactants
products have lower products are more
B decreases
enthalpy than the reactants stable than the reactants
products have higher products are less stable
C decreases
enthalpy than the reactants than the reactants
products have higher products are more
D increases
enthalpy than the reactants stable than the reactants
393
Standard temperature and pressure Standard enthalpy change, ΔH
(STP) conditions are denoted by the

(Reactivity1.1.4)
symbol ⦵. STP is a temperature of
The standard enthalpy change for a reaction, ΔH , refers to the heat
273.15 K and a pressure of 100kPa.
transferred at constant pressure under standard conditions and states. It c an be
Standard ambient temperature
determined from the change in temperature of a pure substance. The units of
and pressure (SATP) refer to more
⦵
1
ΔH are kJ mol
practic al reaction conditions of
298.15 K and 100 kPa. STP and ⦵
To calculate ∆H for a reaction, you therefore need to determine the amount of heat
SATP conditions are given in the
released or absorbed in the course of that reaction. This can be done by measuring
section 2 of the data booklet.
the change in temperature of a pure substance to or from which this heat is
transferred. When calculating the amount of heat lost or gained by a pure substance
such as water, you need to know the specic heat capacity, c, of thatsubstance.
Specic heat
Substance
1 1 The specic heat c apacity of a pure substance is dened as the amount of heat
c apacity / kJ kg K
needed to raise the temperature of 1 kg of that substance by 1 °C or 1 K. For
1 1
water 4.18
example, the specic heat c apacity of ethanol is 2.44 kJ kg K , so it takes
2.44 kJ to raise the temperature of 1 kg of ethanol by 1 K. The lower the specic
ethanol 2.44
heat c apacity of a given substance, the higher the rise in temperature when the
copper 0.385 same amount of heat is transferred to the sample.
Table 1 The specic heat c apacities of Specic heat c apacity is an intensive property that does not vary in magnitude
water, ethanol and copper with the size of the system being described. For example, a 10 cm sample of
copper has the same specic heat c apacity as a 1 ton block of copper. When you
heat up a pure substance, the rise in temperature depends on:
• the identity of that substance
• the mass of that substance
• the amount of heat supplied.
Practice questions
2. Using table 1, c alculate how much energy is required to raise the
temperature of the following by 1 K.
a. 1 kg of water
b. 1000 kg of copper
3. When equal masses of two dierent substances, X and Y, absorb the same
amount of energy, their temperatures rise by 5 °C and 10 °C, respectively.
Which of the following is correct?
a. The specic heat c apacity of X is twice that of Y.
b. The specic heat c apacity of X is half that of Y.
c. The specic heat c apacity of X is one h that of Y.
d. The specic heat c apacity of X is the same as that of Y.
4. Using table 1, state which of the following statements is correct.
a. More heat is needed to increase the temperature of 50 g of water by
50 °C than 50 g of ethanol by 50 °C.
b. If the same heat is supplied to equal masses of ethanol and water, the
temperature of the water will increase more.
c. If equal masses of water at 20 °C and ethanol at 50 °C are mixed
together, the nal temperature will be 35 °C.
d. If equal masses of water and ethanol at 50 °C cool down to room
temperature, ethanol gives out more heat.
394
Specic heat c apacity, c, is used to c alculate the amount of heat, Q, absorbed by
a pure substance using the relationship:
Q = mcΔT
where m is mass of the pure substance in kg and ∆T is the change in temperature
of that substance in K.
Heat, Q, is related to enthalpy change, ∆H, by the following equation:
ΔH = −
where n is the number of moles of the limiting reactant. In a reaction, the limiting
reactant is the reacting substance with the least stoichiometric amount present,
which therefore limits how much product c an be formed. In contrast, the other
reacting substances are said to be in excess
Measurement
Performing reactions in a polystyrene coee cup thermometer
to measure the enthalpy change is a convenient
experimental procedure. This method introduces
glass stirrer
systematic errors that c an be analysed and the eect of
cork stopper
their directionality assessed.
Systematic errors are a consequence of the experimental
two polystyrene cups
procedure. Their eect on empiric al data is constant
nested together
and always in the same direction. With the coee-cup
containing reactants
c alorimeter, the measured change in enthalpy for a
in solution
reaction will always be lower in magnitude than the actual
value, as some heat will be transferred between the

Figure 8 A coee-cup c alorimeter
contents and the surroundings in every experiment.
Worked example 1
1. When a 1.15 g sample of anhydrous lithium 2. 180.0 J of heat is transferred to a 100.0 g sample
chloride, LiCl, was added to 25.0 g of water in a ofiron, resulting in a temperature rise from 22.0°C
coee-cup c alorimeter, a temperature rise of 3.80K to 26.0 °C. C alculate the specic heat c apacity
was recorded. C alculate the enthalpy change of ofiron.
dissolution for 1 mol of lithium chloride. Assume that
the heat capacity of lithium chloride itself is negligible.
Solution
1. Q = mcΔT 2. First, determine the change in temperature, ∆T:
1 1
= 0.025 kg × 4.18 kJ kg K × 3.80 K ∆T = (299 − 295) K = 4 K.
= 0.397 kJ Substitute the values into Q = mcΔT:
Now you need to determine the energy gained for 0.180 kJ = 0.100 kg × c × 4 K
1 mol ofLiCl.
M ake c the subject of the equation and solve:
1.15 g
n(LiCl) = = 0.0271 mol 0.180kJ

− −
1 1
1
c = = 0.450 kJ kg K
42.39gmol
0.100kg×4K
Q −0.397kJ
1
ΔH = − = = −14.6 kJ mol
n 0.0271mol
395
Practice questions
5. C alculate the energy absorbed by water when the temperature of 30 g of
1 1
water is raised by 30 °C. The specic heat c apacity of water is 4.18 J g K
6. 0.675 kJ of heat is transferred to 125 g of copper metal. Copper metal has a
1 1
specic heat c apacity of 385 J kg K . C alculate the change in temperature
of the copper metal.
Investigation to nd the enthalpy change for a reaction
In this skills task, we will look at the method used to 3. At three minutes, introduce between 1.3 g and 1.4g
c alculate the enthalpy change for the exothermic metal of zinc powder, record the exact mass of zinc and
displacement reaction between zinc and copper(II) commence stirring.
sulfate:
4. Continue to take temperature readings for up to five
Zn(s) + CuSO (aq) → Cu(s) + ZnSO (aq) minutes after the maximum temperature has been
4 4
reached.
Relevant skills
5. Produce a temperature versus time graph to
• Tool 1: Measuring variables

determine the change in temperature.
• Tool 1: Applying techniques

6. Use your value of ∆T to c alculate the heat released,
Q, and the enthalpy change for the reaction, ∆H

• Tool 2: Applying technology to process data
• Tool 3: Processing uncertainties

Assumptions and errors
• Tool 3: Graphing A number of assumptions are made when using this
method:
• Inquiry 1: Controlling variables
• The heat released from the reaction is completely
• Inquiry 2: Processing data
transferred to the water.
• Inquiry 3: Evaluating
• The coffee cup acts as an insulator against heat loss to
the surroundings. However, the coffee cup also has
Materials
a heat c apacity and heat is transferred to it from the
• electronic balance
water, but it is much smaller than that of water.
• coffee-cup c alorimeter
• The maximum temperature reached is an accurate
• measuring cylinder representation of the heat evolved during the
reaction.
• thermometer or temperature probe
• The specific heat c apacity of an aqueous solution is

3
• 1.0 mol dm copper(II) sulfate solution
the same as that of water.
• zinc powder
Loss of heat from the system to the surroundings is the
main source of error in this experiment and one that is

Method
difficult to quantify. The change in temperature, ∆T,
1. Using an electronic balance, accurately measure

c alculated from a graph will include a systematic error.
3 3
the mass of 25 cm of 1.0 mol dm CuSO solution.

4 This loss of heat means that the maximum temperature
Transfer the solution to the coffee-cup c alorimeter.

recorded will be lower than the theoretic al value, making
the c alculated value of Q lower than the actual value. The

2. Using a thermometer or a temperature probe, record
effect of errors on the result of subsequent c alculations is

the temperature of the solution every 30 seconds for
important in considering improvements in experimental

up to threeminutes, or until a constant temperature is
procedures.
achieved.
396
An accepted method of c alculating the maximum
temperature to compensate for systematic errors in data
is to look at the cooling section of the curve after the
C° / erutarepmet
reaction is complete, and extrapolate this back to the
moment when zinc is introduced at 3 minutes, as shown
ΔT
in figure 9. Amore accurate value for ΔT c an then be
determined.
0 2 4 6 8 10
time / min
Figure 9 Example of a temperature vs time graph for a
c alorimetry experiment
Worked example 2
A coee-cup c alorimeter was used to measure the temperature change for the
reaction between zinc powder and a 1.0 mol dm solution of copper(II) sulfate.
The following results were recorded:
28.8
M ass of copper(II) sulfate solution / g
1.37
M ass of zinc / g
39.0
∆T / °C
Determine the amount of heat released and the enthalpy change for this
reaction.
TOK
Solution
First, use Q = mcΔT to determine the amount of heat released: In theory of knowledge, there
are 12 concepts in focus.
1 1
Q = 0.0288 kg × 4.18 kJ kg K × 39.0 K
These are: evidence, certainty,
truth, interpretation, power,

= 4.69 kJ
justic ation, explanation,
Then, determine the limiting reactant for the reaction. objectivity, perspective, culture,
values and responsibility.

m
Number of moles of zinc, n(Zn) =
Scientists perform experiments

M
r
and process the raw data to
1.37g
=
enable us to draw conclusions.
65.38gmol
We compare experimental
= 0.0210 mol
and theoretic al values. What
concepts do we utilize when
Number of moles of copper(II) sulfate, n(CuSO ) = c × v

4
justifying our conclusions?
3 3
= 1.00 mol dm × 0.0288 dm How do we use evidence?
Are our judgments subjective
= 0.0288 mol
or objective? When analysing
and appraising experimental
Zinc is present in a smaller amount, so it is the limiting reactant. You c an c alculate
limitations, how do
Q
the enthalpy change of reaction from ΔH = − :

assumptions have an impact on
4.69kJ our perceptions?

1
∆H = – = −223 kJ mol
0.0210mol
397
Combustion of primary alcohols
You c an determine the enthalpy change of combustion of 2. Determine the initial mass of the spirit burners using
common alcohols in a school laboratory. After repeating an electronic balance.
the experiment several times with a homologous series

3
3. Accurately determine the mass of 30 cm of water
of alcohols, you c an subsequently analyse this data and

3
contained in a 250 cm beaker or metal c alorimeter.
identify patterns.
4. Using either a temperature probe or a thermometer,
determine and record the initial temperature of

Relevant skills
thewater.
• Tool 1: Recognise and address the relevant safety,
ethic al or environmental issues in an investigation 5. Ignite a spirit burner under the beaker or c alorimeter
and allow the alcohol to burn to heat the water. The
• Tool 1: Measuring temperature and mass
period over which it burns c an be set in one of two
• Tool 1: C alorimetry
different ways:
• Inquiry 1: Appreciate when and how to insulate

a. allow each alcohol to burn until a temperature
against heat loss or gain

change of 30°C is reached

b. allow each alcohol to burn for a period of two
observations and sufficient relevant quantitative data

minutes.
6. Determine the final mass of each spirit burner
Materials
immediately after the flame is extinguished. Take extra
• five spirit burners, each containing one of the
c are bec ause the burner will be hot.
following alcohols: methanol, ethanol, propan-1-ol,
7. Use your values of ∆T of the water and ∆m of the

butan-1-ol and pentan-1-ol
burner to calculate the amount of heat released, Q,
• electronic balance
and the enthalpy change of combustion, ∆H, for
eachalcohol.
• beaker or metal c alorimeter
• tripod
• temperature probe or thermometer
thermometer
S afety
Alcohols should be handled and disposed of with c are
beaker
bec ause they are generally flammable, hazardous and
volatile.
clamp water
Instructions
spirit burner
1. Using suitable sources, identify the hazards and
wick
complete a risk assessment for this experiment. In
methanol
your risk assessment, you should:
Figure 10 A typic al arrangement of experimental

• identify the hazards
apparatus for an enthalpy of combustion determination
• assess the level of risk
• determine relevant control measures
• identify suitable disposal methods aligned with
your school’s health and safety policies.
398
ATL Research skills
Cite your sources fully, according to your school’s citing and referencing
system.
Worked example 3
A metal c alorimeter was used to measure the amount of heat released by
the combustion of methanol. The following results were recorded:
31.2
Mass of water / g
0.348
Change in mass of methanol / g
30.0
∆T / °C
Determine the amount of heat released and the enthalpy change of
combustion for methanol.
Solution
First, use Q = mcΔT to determine the amount of heat released:
1 1
Q = 0.0312 kg × 4.18 kJ kg K × 30.0 K
= 3.91 kJ
Methanol reacts with oxygen in a combustion reaction. Methanol is the
limiting reactant for this reaction bec ause oxygen is present in excess in the air.
Number of moles of methanol, n(CH OH) =

3
Mr
0.348g
32.05gmol
= 0.0109 mol
You c an c alculate the enthalpy change of reaction from ΔH = − :
3.91kJ
1
ΔH = − = −359 kJ mol
0.0109mol
Thermochemistry experiments provide a useful set of raw data, and involve
experimental procedures that c an be evaluated for random and systematic errors.
The identic ation of the systematic errors and examination of their directionality
are essential aspects of the analysis of experimental results. C alorimetry
experiments typic ally give a smaller change in temperature than is predicted
from theoretic al values. This is the result of heat loss from the system, which is
dicult to measure. Scientists usually make the assumption that the heat lost
to the environment is negligible. TOK helps us to understand our judgments of
discrepancies between experimental and theoretic al values.
399
Thermometric titration
The neutralization reaction between an acid and a 2. Review the titration, percentage error and
base is exothermic. In this skills task, you will determine uncertainties sections in the Skills chapter.
the unknown concentration of hydrochloric acid by
3. Rinse and fill the burette with sodium hydroxide
measuring the change in temperature while sodium
solution. Record its concentration.
hydroxide is added to the acid. The temperature will
4. Add 25 cm of acid solution to the cup and place it

reach a maximum when the acid and base are mixed
under the burette. Nest it inside a second cup, for

together in stoichiometric amounts.
additional thermal insulation. For safety,these cups
should be placed inside a beaker to avoid tipping over.

Relevant skills
• Tool 1: C alorimetry and acid–base titration 5. Position the temperature probe in the acid and record
the initial temperature of the acid in the cup.
• Tool 2: Use sensors
6. Add a small volume (~5 cm ) of sodium hydroxide
solution to the acid, stirring gently. Record the highest
• Tool 3: Understand the signific ance of uncertainties in

temperature reached with this addition.
raw and processed data
7. Continue adding small volumes of sodium hydroxide
• Tool 3: Propagate uncertainties and state them to an

solution and recording the temperature until the
appropriate level of precision

temperature decreases over several consecutive
readings.
8. Clear up as instructed by your teacher.
• Inquiry 1: Appreciate when and how to insulate
against heat loss or gain Questions
• Inquiry 3: Identify and discuss sources of systematic

1. Plot a graph showing temperature vs volume of
and random error

sodium hydroxide solution added.
2. Extrapolate the two sections of the graph to find the

S afety
maximum temperature reached during the titration.
3. Determine the concentration of the acid, along
• Sodium hydroxide solution is corrosive.
with absolute and percentage uncertainties. M ake
• Hydrochloric acid is corrosive. sure you state all values to an appropriate level of
precision.
Materials
4. C alculate the percentage error of your experimental
• two 250 cm polystyrene cups

acid concentration.
• thermometer or temperature probe

5. Determine the enthalpy of neutralization, along with
absolute and percentage uncertainties. State all

• graduated pipette and filler
values to an appropriate level of precision.
• burette
6. C alculate the percentage error of your experimental
• ~50.0 cm sodium hydroxide solution of known
enthalpy of neutralization.
concentration
7. Comment on the relative impacts of systematic and
• 30.0 cm hydrochloric acid of unknown concentration

random error on the values obtained for the acid
concentration and enthalpy of neutralization.
Method
8. Suggest and explain two improvements that could be
1. Read through the safety, materials and method. Use

made to this method.
this information, and relevant safety data, to complete
a risk assessment for this practic al work and show it to
your teacher.
400
Measurement
Experimental enthalpy values c an be assessed in terms of their accuracy and
precision. R andom errors in measurement lead to imprecision, whereas
systematic errors c ause inaccuracy. What are some of the sources of random
and systematic errors in an enthalpy of neutralization experiment? To what
extent are these errors quantiable?
ATL Thinking skills
C alorimetry experiments conducted in research laboratories utilize the same
principles as the c alorimetry experiments described in this chapter. The
instrument used is c alled a bomb c alorimeter (gure 11). A sample is burned
inside a chamber (c alled a “bomb”), and the resulting temperature change of
the surrounding water is measured.
ignition
device
oxygen
jacket
supply
temperature
stirrer
probe
calorimeter
water bath
bomb
Figure 11 Diagram of a bomb c alorimeter used in research laboratories
1. Study the diagram c arefully and list all the features that are labelled.
2. Deduce the purpose of each feature.
3. Consider why the measurements obtained with a bomb c alorimeter are
highly accurate and precise.
4. What properties of water make it suitable for c alorimetry experiments?
401
Topic review
1. Using your knowledge from the Reactivity 1.1 topic, answer the guiding question as fully as possible:
What can be deduced from the temperature change that accompanies chemical or physical change?
2. Which is correct for the following reaction?
2Al(s) + 6HCl(aq) → 2AlCl (aq) + 3H (g)

3 2
ΔH = −1049 kJ mol
A Reactants are less stable than products and the reaction is endothermic.
B Reactants are more stable than products and the reaction is endothermic.
C Reactants are more stable than products and the reaction is exothermic.
D Reactants are less stable than products and the reaction is exothermic.
A In an exothermic reaction, the products have more energy than the reactants.
B In an exothermic reversible reaction, the activation energy of the forward reaction is greater than that of the
reverse reaction.
C In an endothermic reaction, the products are more stable than the reactants.
D In an endothermic reversible reaction, the activation energy of the forward reaction is greater than that of the
reverse reaction.
4. Which statement is correct for this reaction?
Fe O (s) + 3CO(g) → 2Fe(s) + 3CO (g)

2 3 2
ΔH = −26.6 kJ mol
A 13.3 kJ are released for every mole of Fe produced.
B 26.6 kJ are absorbed for every mole of Fe produced.
C 53.2 kJ are released for every mole of Fe produced.
D 26.6 kJ are released for every mole of Fe produced.
5. In which reaction do the reactants have a lower energy than the products?
A CH (g) + 2O (g) → CO (g) + 2H O(g)

4 2 2 2
B HBr(g) → H(g) + Br(g)
C Na (g) + Cl (g) → NaCl(s)
D NaOH(aq) + HCl(aq) → NaCl(aq) + H O(l)

2
402
6. Nitrogen dioxide and c arbon monoxide react according to the following equation:
NO (g) + CO(g) → NO(g) + CO (g)

2 2
ΔH = −226 kJ mol
a. C alculate the enthalpy change for the reverse reaction. [1]
b. State the equation for the reaction of NO in the atmosphere to

2
produce acid deposition. [1]
3 3
7. Powdered zinc was reacted with 25.00 cm of 1.000 mol dm copper(II) sulfate solution in
an insulated beaker. Temperature was plotted against time.
55
50
45
C° / erutarepmet
40
ΔT
35
Y
30
25
20
0 2 4 6 8 10
time / min
a. Estimate the time at which the powdered zinc was placed in the beaker. [1]
b. State what point Y on the graph represents. [1]
The maximum temperature used to c alculate the enthalpy change of reaction was chosen
at a point on the extrapolated (red) line.
c. State the maximum temperature that should be used, and outline one assumption
made in choosing this temperature on the extrapolated line. [1]
d. To determine the enthalpy of reaction, the experiment was c arried out ve times.
The same volume and concentration of copper(II) sulfate was used but the mass of
zinc was dierent each time. Suggest, with a reason, if zinc or copper(II) sulfate
should be in excess for each trial. [1]
The formula q = mcΔT was used to c alculate the amount of energy released.
1 1
The values used in the c alculation were m = 25.00 g and c = 4.18 J g K .
e. State an assumption made when using these values for m and c. [1]
f. Predict, giving a reason, how the nal enthalpy of reaction c alculated from
this experiment would compare with the theoretic al value. [1]
8. A potato chip (crisp) was ignited, and the ame was used to heat a test
tube containing water.
M ass of water / g 7.8
M ass of chip / g 1.2
Initial temperature / °C 21.3
Final temperature / °C 22.6
a. C alculate the heat required, in kJ, to raise the temperature of the water, using
data in the table above and from section 2 of the data booklet. [1]
b. Determine the enthalpy of combustion of the potato chip, in kJ g . [1]
403
Reactivity 1.2 Energy cycles
in reactions
How does application of the law of conservation of energy help us to predict energy changes
during reactions?
The utilization of energy is central to our lives. Agricultural, This law is oen c alled the law of conservation of energy.
industrial, and domestic activities all consume vast According to this law, energy c an be neither created
amounts of energy daily. Thermodynamics is the nor destroyed; it c an only be converted from one form
study of energy and its interconversions. The rst law of to another. This means that for a given reaction we c an
thermodynamics states that energy c an be converted from account for and quantify all the energy changes. This is one
one form to another and that the total amount of energy for of the most fundamental principles of science.
a given system remains constant.
Understandings
Reactivity 1.2.1 — Bond-breaking absorbs and bond-
LHA
Reactivity 1.2.3 — Standard enthalpy changes of
forming releases energy.

⦵ ⦵
combustion, ΔH , and formation, ΔH , data are

c f
Reactivity 1.2.2 — Hess’s law states that the enthalpy

used in thermodynamic c alculations.
change for a reaction is independent of the pathway
Reactivity 1.2.4 — An applic ation of Hess’s law
between the initial and nal states.
uses enthalpy of formation data or enthalpy of
combustion data to c alculate the enthalpy change
of a reaction
Reactivity 1.2.5 — A Born–Haber cycle is an
applic ation of Hess’s law, used to show energy
changes in the formation of an ionic compound.
Bond-breaking and bond-forming
(Reactivity 1.2.1)
When a chemic al reaction takes place, the atoms of the reactants are rearranged
to create products. Chemic al bonds in the reactants are broken and new
chemic al bonds are made to form the products. Energy is required to break the
chemic al bonds: bond-breaking is an endothermic process. Energy is released
when new chemic al bonds form: bond-making is an exothermic process. This
transfer of energy between the system and the surroundings is an essential part of
understanding the energy changes involved in a chemic al reaction (Reactivity 1.1).
Laws and theories
The law of conservation of energy states that energy c an be neither created
nor destroyed; it c an only be converted between dierent forms. Laws allow
predictions to be made but, unlike theories, laws do not have explanatory
power. What other laws have you come across in your study of chemistry?
404
Reactivity 1.2 Energy cycles in reactions
Bond enthalpy
Imagine a simple hydrogen molecule, H . The breaking of the hydrogen

2
molecule into individual hydrogen atoms requires energy. The bond enthalpy
(BE) is dened as the energy required to break one mole of bonds by homolytic
ssion in one mole of gaseous covalent molecules under standard conditions.
The process of homolytic ssion distributes the electrons from the bond equally
between the two new species. This results in the formation of radic als, indic ated
by the • symbol.
For example, the bond enthalpy of the H–H bond is equal to the enthalpy change
of the following reaction:
H (g) → 2H•(g) ∆H = +436 kJ mol

2
Bond-breaking is an endothermic process, and therefore it has a positive
enthalpyvalue.
Selected BE values are provided in table 1 (on the next page) and section 12 of
the data booklet. Bond enthalpy values are derived from experimental data on
the breaking of the same bond in a wide variety of compounds. For example,
the C–H bond enthalpy will vary through the alkane series bec ause the chemic al
environment of the individual bonds changes.
If a molecule of methane underwent a series of steps in which one hydrogen
atom was removed at a time, the bond enthalpy for each removal would be
dierent. This is bec ause the chemic al environment changes upon the removal of
successive hydrogen atoms.
CH (g) → •CH (g) + •H(g) BE (C‒H) = +439 kJ mol

4 3 1
•CH (g) → •CH (g) + •H(g) BE (C H) = +462 kJ mol

3 2 2
•CH (g) → •CH(g) + •H(g) BE (C H) = +424 kJ mol

2 3
•CH(g) → •C(g) + •H(g) BE (C H) = +338 kJ mol

4
C an you recognize the dierences in the products of each equation and explain
how the chemic al environment changes for each successivestep?
Bond enthalpies are average values and are therefore only an approximation. The
average bond enthalpy value of the C H bond is +414 kJ mol
H
H
C
H
H
C
C
C
H
H
H
H
H
Figure 1 When you examine the structure of this hexane molecule, c an you see how the
chemic al environment of the C–H bonds diers throughout the molecule?
405
Average bond Average bond
Bond Bond
1 1
enthalpy / kJ mol enthalpy / kJ mol
H−H 436 C =O 804
O−O 144 C =N 615
O=O 498 C ≡N 890
O−H 463 N N 158
C−H 414 N =N 470
C C 346 N ≡N 945
C=C 614 Cl Cl 242
C≡C 839 Br Br 193
C−O 358 I I 151
Table 1 Average bond enthalpies at 298 K
TOK
Measured energy changes in chemic al reactions c an be explained by the
model of bonds broken and bonds formed. These explanations are based
on empiric al data and further data c an be obtained to modify and rene the
model. What role do models play in the acquisition of knowledge in the
natural sciences? How do we determine whether a model is useful? How are
models used in other areas of knowledge?
You can use bond enthalpy data to calculate the enthalpy change of reaction, ΔH:
H C
ΔH = Σ(BE of bonds broken) – Σ(BE of bonds formed)
The enthalpy change of a reaction c alculated from bond enthalpies will dier
Br from its actual value, as bond enthalpies are average values. Additionally, bond
enthalpy data do not take intermolecular forces into account, which is particularly
important when substances in a reaction are solid or liquid.

H
When performing bond enthalpy c alculations, it is useful to draw out the full
 Figure 2 A molecule of bromoethane,
C H Br, has one C C bond, one C Br bond

structural formulas of the reactants and products involved in the reaction. From
2 5
and ve C H bonds this, you c an determine the type and number of each chemic al bond present.
Models
The model of bond breaking and formation is used to represent the energy
changes taking place within a reaction system. We c an assess the extent
to which this model is in agreement with empiric al data, by comparing the
theoretic al values generated from bond energy data with experimental
evidence. Using empiric al data to replace or modify proposed models is a
central methodology in science.
406
Worked example 1
Using bond enthalpy data, determine the enthalpy change of reaction for the following process:
C H (g) + HBr(g) → C H Br(g)

2 4 2 5
Solution
Start by drawing the full structural formulas of all of the reactants and products:
H H H H
C C + H Br H C C Br
H H
H H
In the reactants, there are four C H bonds, one C=C bond and one H Br bond. In the product, there are ve C H
bonds, one C C bond, and one C Br bond. Therefore, the enthalpy change for the reaction is as follows:
ΔH = Σ(BE of bonds broken) − Σ(BE of bonds formed)
= [4BE(C H) + BE(C=C) + BE(H Br)] − [5BE(C H) + BE(C C) + BE(C Br)]
Then, substitute in the BE values from the data booklet:
= [(4 × 414) + 614 + 366] − [(5 × 414) + 346 + 285]
= 2636 − 2701
= −65 kJ mol
Practice questions
1. The chloralkali process is an industrial process used to make chlorine
gas and sodium hydroxide. Much of the chlorine gas is combined with
hydrogen gas to produce hydrogen chloride:
Cl (g) + H (g) → 2HCl(g)

2 2
The enthalpy change for this reaction is −185 kJ mol . Using section
1
Linking question
12 of the data booklet, c alculate the bond enthalpy, in kJ mol , for the
H–Clbond.
How would you expect bond
2. Enthalpy changes depend on the number and type of bonds broken and
enthalpy data to relate to bond
formed. Hydrogen gas c an be formed industrially by the reaction of natural
length and polarity? (Structure 2.2)
gas with steam:
CH (g) + H O(g) → 3H (g) + CO(g) How does the strength of a

4 2 2
1 c arbon–halogen bond aect the

Determine the enthalpy change, ΔH, for this reaction, in kJ mol , using
rate of a nucleophilic substitution

section 12 of the data booklet.
3. Methane and chlorine react to produce chloromethane and hydrogen
chloride.
a. Write the balanced chemic al equation for this reaction.
b. Using bond enthalpy values from the data booklet, determine the
enthalpy change for this reaction.
c. Deduce and explain whether this reaction is exothermic or
endothermic.
d. State which are more energetic ally stable, the reactants or
theproducts.
407
Hess’s law (Reactivity 1.2.2)
If you have travelled to New York City, Shanghai, Paris, Seoul, London, M adrid or
Delhi, you have experienced the subways that criss-cross these enormous cities
and transport millions of people every day. In any transport network there is more
than one way to travel between point A and B. If you are an adventurous traveller,
half the fun is oen working out the fastest route.
 Figure 3 The extensive metro system in Seoul provides many alternative
pathways for navigating the urban sprawl
The same idea c an be true for chemistry. A chemic al equation usually shows
the net reaction – it c an be a summary of a number of dierent reactions, which,
when added together, result in an overall reaction.
For example, the overall reaction for the oxidation of elemental sulfur, S(s), to
sulfur trioxide, SO (l), is as follows:

3
S(s) + O (g) → SO (l)

2 3
However, this process is dicult to c arry out in one step. Typic ally, sulfur is
oxidized rst to sulfur dioxide, SO (g), and then sulfur dioxide is oxidized further
2
to sulfur trioxide:
Step 1: S(s) + O (g) → SO (g)

2 2
Step 2: SO (g) + O (g) → SO (l)

2 2 3
If you add up the enthalpy changes that occur in each of these individual steps,
the total would be the same as the enthalpy change of the overall reaction. This is
the basis of Hess’s law:
∆H
y
Regardless of the route by which a chemic al reaction proceeds, the
∆H
x
enthalpychange will always be the same, as long as the initial and nal
statesof the system are the same.
∆H
z
Hess’s law is an applic ation of the conservation of energy law. Figure 4 illustrates
B
Hess’s law: the enthalpy change for reaction A → B (ΔH ) is equal to the sum of
x
 Figure 4 Hess’s law
the enthalpy changes for the reactions A → C and C → B (ΔH + ΔH ).

y z
Hess’s law c an be applied to nd the unknown enthalpy change for a given
reaction by combining other reactions with known enthalpy changes.
408
Worked example 2
The reaction for the formation of methanol is shown below:
C(s) + 2H (g) + O (g) → CH OH(l)

2 2 3
Use Hess’s law and equations 1–3 to c alculate the enthalpy change for the reaction above.
3
1 1
CH OH(l) + O (g) → CO (g) + 2H O(l)
3 2 2 2 ∆H = −726 kJ mol
2 C(s) + O (g) → CO (g) ∆H = −394 kJ mol

2 2
1
3 1
H (g) + O (g) → H O(l) ∆H = −286 kJ mol

2 2 2
Solution
There are two methods for using Hess’s law for a question like this: the summation of equations method, and the
enthalpy cycle diagram method
Summation of equations method
First, inspect the formation of methanol reaction scheme. In your c alculation, you need to use enthalpy values
corresponding to reactions that involve c arbon, hydrogen and oxygen as reactants, and methanol as a product.
Start with the reactants. C arbon is a reactant in equation2, so this equation c an be used as written:
C(s) + O (g) → CO (g) ΔH = −394 kJ mol

2 2
You require two moles of hydrogen as a reactant. Therefore, equation 3 c an be used in the direction as written, but with
doubled stoichiometric coecients. This means that the enthalpy value must also be doubled:
2H (g) + O (g) → 2H O(l) ΔH = −572 kJ mol

2 2 2
We also need half a mole of oxygen. Oxygen is present asa reactant in two of the above equations, so ignore this for now.
For the product methanol, you need to use equation1. However, the equation must be reversed to make methanol a
product, not a reactant. When reversing the chemic al equation, the sign of the enthalpy change must also be changed:
3
1
CO (g) + 2H O(l) → CH OH(l) + O (g) ΔH = +726 kJ mol

2 2 3 2
Now add the three equations together, c ancelling the species common to both sides of the reaction, and add the
enthalpy values:
C(s) + O (g) → CO (g) ΔH = −394 kJ mol

2 2
2H (g) + O (g) → 2H O(l) ΔH = −572 kJ mol

2 2 2
3
1
CO (g) + 2H O(l) → CH OH(l) + O (g) ΔH = +726 kJ mol

2 2 3 2
1 3
1
Total C + O + 2H + + O → + O + CH OH + ΔH = −240 kJ mol

2 2 2 2 2 2 2 3 2
2 2
C ancelling the common species gives the overall equation C + 2H + O → CH OH, which is identic al to the reaction
2 2 3
–1
in the question. Therefore, the total enthalpy change for the reaction is equal to –240 kJ mol . Note that here and below
the states are omitted to save space.
409
Enthalpy cycle diagram method
You c an represent the c alculations needed to determine the enthalpy change of reaction in the form of an enthalpy
cycle diagram.
First, write the equation you are trying to nd the enthalpy change for: C + 2H + O → CH OH. Below this, write the
2 2 3
other species from equations 1, 2 and 3 not included in the original reaction: CO + 2H O. Oxygen, O , is usually not
2 2 2
included in enthalpy cycle diagrams.
Then, draw two arrows from the reactants to the species at the bottom to represent
equations 2 and 3. Draw an arrow from the products to the species at the bottom to C + 2H + O CH OH
2 2 3
represent equation 1.
Finally, label the arrows with the enthalpy change values. As with the summation of
equations method, the enthalpy change for equation 3 needs to be doubled to give
394 286 726
the value for two moles of hydrogen. The resulting enthalpy cycle diagram is shown in
× 2
gure 5.
Then, calculate the sum of the enthalpy change values, following the alternative
pathway from the reactants to the products, via the CO and 2H O intermediates. If the
2 2
CO + 2H O
2 2
pathway you are following is in the opposite direction of an arrow (in this case, the last
arrow), reverse the sign of the enthalpy change. This calculation is summarized below:  Figure 5 Enthalpy cycle diagram
1 for the formation of methanol

(−394) + (−286 × 2) + (+726) = −240 kJ mol
In the previous worked example, you have seen two Whichever method you prefer, make sure you show
methods for representing and solving Hess’s law your reasoning clearly in assessments. Oen c andidates
calculations: the summation of equations method and the make arithmetic al errors when c alculating the enthalpy of
enthalpy cycle diagram method. In what situations would reaction. It is advisable to clearly show your full working
you use an enthalpy cycle? In what situations would you rather than simply recording the nal answer. This gives
use the summation of equations method? What are the the examiner the opportunity to assign partial marks
strengths and limitations of each method? To what extent are where applic able.
the methods dierent if they represent the same concept?
Practice questions
4. C alculate the enthalpy change for the following reaction, using the
summation of equations method, and equations 1–3 below:
3H (g) + 2C(s) + O (g) → C H OH(l)

2 2 2 5
1 C H OH(l) + 3O (g) → 2CO (g) + 3H O(l) ΔH = −1367 kJ mol

2 5 2 2 2
2 C(s) + O (g) → CO (g) ΔH = −394 kJ mol

2 2
1
1
3 H (g) + O (g) → H O(l) ΔH = −286 kJ mol

2 2 2
5. Determine the enthalpy change for the following reaction, using the
enthalpy cycle diagram method and equations 1–3 below:
4NH (g) + 5O (g) → 4NO(g) + 6H O(l)

3 2 2
1 N (g) + O (g) → 2NO(g) ΔH = +66 kJ mol

2 2
2 N (g) + 3H (g) → 2NH (g) ΔH = −92 kJ mol

2 2 3
3 2H (g) + O (g) → 2H O(l) ΔH = −572 kJ mol

2 2 2
410
Using Hess’s law to nd enthalpy change
When heated, potassium hydrogenc arbonate 6. Repeat the procedure, using potassium
decomposes to produce potassium c arbonate, c arbon hydrogenc arbonate instead of potassium c arbonate.
dioxide and water. The enthalpy change for this (Note that this time, record the lowest temperature
decomposition is dicult to determine directly. You will reached bec ause the reaction is endothermic.)
determine the enthalpy change for two other reactions,
Analysis
and then apply Hess’s law to nd the enthalpy change for
Part 1: Known enthalpy changes of reaction

the decomposition of potassium hydrogenc arbonate.
1. Write a balanced equation, including state symbols,
Relevant skills
for the reaction between:
• Tool 1: C alorimetry
a. potassium c arbonate and hydrochloric acid
• Tool 3: Record, propagate and express uncertainties

b. potassium hydrogenc arbonate and hydrochloric
acid
• Inquiry 2: C arry out relevant and accurate data
processing 2. Show that the acid is in excess in both c ases.
• Inquiry 3: Evaluate the implic ations of methodologic al 3. Process your experimental data to determine the
weaknesses, limitations and assumptions on the enthalpy change for the reaction between:
conclusions
a. potassium c arbonate and hydrochloric acid
b. potassium hydrogenc arbonate and hydrochloric
S afety
acid
Part 2: Applying Hess’s law

• Hydrochloric acid is an irritant.
4. Write a balanced equation, including state symbols, for
• Anhydrous potassium c arbonate is an irritant.
the decomposition of potassium hydrogencarbonate
• The reaction between c arbonates and acids

to produce potassium carbonate and other products.
effervesces. Cover the reaction vessel with a lid to
5. Draw an enthalpy cycle connecting the three reactions:
prevent loss of reagents and spillage.
• potassium c arbonate and hydrochloric acid
Materials
• potassium hydrogenc arbonate and hydrochloric
• 2 mol dm hydrochloric acid

acid
• anhydrous potassium c arbonate (solid) • thermal decomposition of potassium
hydrogencarbonate
• potassium hydrogenc arbonate (solid)
6. Apply Hess’s law, and your processed data from part1,
Method to determine the enthalpy change for the thermal
decomposition of potassium hydrogencarbonate.

1. Read through the method and write a list of
equipment required for the practic al. Show it to your

7. Propagate uncertainties to determine the absolute
teacher for approval before starting.

uncertainty of the enthalpy values you have obtained.
2. Place approximately 3 g of potassium c arbonate into a

8. Look up the theoretic al value for the enthalpy
weighing boat. Record the exact mass.

change for the decomposition of potassium
3
hydrogenc arbonate online. Use this value to
3. Use a measuring cylinder to collect 30 cm of
determine the percentage error of your result.

hydrochloric acid and transfer it into a coffee-cup
c alorimeter. Record the temperature of the acid.

9. Identify two assumptions made throughout this
investigation and discuss their validity.

4. Add the potassium c arbonate to the acid solution and
stir the mixture, monitoring the temperature. Record

10. Identify and explain two major sources of systematic
the maximum temperature reached.

error in this investigation.
5. Dispose of the reaction mixture appropriately.
411
LHA
Standard enthalpy changes of combustion,
⦵ ⦵
ΔHc , and formation, ΔHf (Reactivity 1.2.3
and Reactivity 1.2.4)
When describing a standard enthalpy change, there are a number of steps that
must be completed.
1. Determine the type of reaction.
2. Write an equation to describe the reaction.
3. Include state symbols in the equation.
The standard enthalpy change of combustion , ΔHc , is the enthalpy change
that occurs when one mole of a substance in its standard state is burned
completely in oxygen. The standard state of a pure substance is the form that it
takes under standard conditions: 25.00 °C (298.15 K), which is taken as being
room temperature, and a pressure of 1.00 × 10 Pa.
When a hydroc arbon undergoes combustion, it reacts with oxygen to produce
c arbon dioxide, CO , and water, H O. Butane, C H , is a highly ammable

2 2 4 10
gas and a component of liqueed petroleum gas (LPG). The equation for its
combustion is as follows:
13
C H (g) + O (g) → 4CO (g) + 5H O(l)

4 10 2 2 2
⦵
1
The standard enthalpy of combustion for butane, ΔHc , is −2878 kJ mol . This
value, and the standard enthalpies of combustion for other substances, are given
in section 14 of the data booklet, along with their standard states.
The chemic al equation for the combustion of butane c an also be written with
the enthalpy of combustion value included in the equation. The negative
enthalpy change indic ates an exothermic reaction, so energy is released into the
Exothermic and endothermic
surroundings. Therefore, the value is included on the product side:

reactions are introduced in
Reactivity 1.1. 13
1
C H (g) + O (g) → 4CO (g) + 5H O(l) + 2878 kJ mol

4 10 2 2 2
Activity
Write equations to describe the standard enthalpy change of combustion for
the following compounds, and state the enthalpy change values by referring
to section 14 of the data booklet. Ensure that you include state symbols and
that the equations are balanced:
a. octane, C H
8 18
b. cyclohexanol, C H O
6 12
c. methanoic acid, CH O
2 2
d. glucose, C H O
6 12 6
e. chloroethane, C H Cl (hint: a strong, corrosive acid is one of the products)

2 5
412
LHA
Much of the world’s energy supply is produced by the combustion of
hydroc arbons. Increasingly, the scientic community is researching alternative
energy sources to reduce harmful emissions of greenhouse gases. This
will enable governments to reach emission targets set by international
agreements, such as COP21 in Paris and COP26 in Glasgow.
The combustion of ammonia is being investigated as a possible c arbon-
neutral fuel source. However, one problem with this new technology
is the high level of NO emissions. Industrial processes are rarely totally

x
“green”: there are environmental costs associated with every method of
energy production. How do we measure the environmental impact of
dierent fuel sources, and which factors are most important for a fuel to be
sustainable? Who should make decisions about what fuel sources are used to
produceenergy?
The standard enthalpy change of formation, ΔHf , of a substance is the energy
change that occurs when one mole of a substance is formed from its constituent
elements in their standard states. Most elements are solids in their standard state,
but there are 11 elements that are gases under standard conditions, for example
argon, Ar, and uorine, F . Two elements are liquid under standard conditions:
2
mercury, Hg, and bromine, Br

2
The constituent elements of butane are c arbon, C, and hydrogen, H . Therefore,

2
the formation of butane is described by the following equation:
4C(s) + 5H (g) → C H (g)

2 4 10
⦵
1
The enthalpy change of formation of butane, ΔHf , is −126 kJ mol . This value,
and other values for the standard enthalpy change of formation for many common
compounds, c an be found in section 13 of the data booklet. The standard states
of these compounds are given in the same section.
Activity
Write equations to describe the standard enthalpy change of formation for
the following compounds, and state the enthalpy change values by referring
to section 13 of the data booklet:
a. propane, C H d. benzoic acid, C H COOH

3 8 6 5
b. chloromethane, CH Cl e. c arbon monoxide, CO

3
c. ethanol, C H O f. methylamine, CH NH
2 6 3 2
You will notice that when writing chemic al equations for standard enthalpy
changes of combustion and formation, fractional stoichiometric coecients may
be necessary to balance the equation. This is one of the few c ases when it is
correct to use fractions to balance the nal chemic al equation.
413
Under standard conditions, the element c arbon exists as several allotropes, for
LHA
example, diamond, graphite and buckminsterfullerene. Allotropes of c arbon
have dierent ΔHf values. If an element has several allotropes, the normal
convention is that the most stable allotrope is the standard state. The enthalpy
The allotropes of c arbon and

1
of formation is 0 kJ mol for all elemental substances in their standard states.
their structures are discussed in
Graphite is taken as the standard for the c arbon allotropes, and so it has a
Structure2.2
1
standard enthalpy of formation of 0 kJ mol .
Linking question
ATL Thinking skills
Would you expect allotropes of an element, such as diamond and graphite,

Reect on the rationale for
to have dierent ∆H values? (Structure 2.2)

averaging bond enthalpy values. f
Evaluate the strengths and
limitations of this approach.
Applying Hess’s law to enthalpy changes of combustion
As discussed earlier in this topic, enthalpy is a state function, so the enthalpy
change of a reaction is the dierence between the initial and nal values of
the enthalpy of the system. The pathway between this initial and nal state of a
chemic al reaction does not aect the overall enthalpy change.
The overall standard enthalpy change for a reaction, ΔHr , c an be c alculated
using enthalpy of combustion data. The dierence between the sum of the
enthalpy changes of combustion of the reactants and the sum of the enthalpy
changes of combustion of the products is equal to the overall enthalpy change
ofthe reaction:
⦵ ⦵ ⦵
ΔHr = Σ(ΔHc reactants) − Σ(ΔHc products)
This is a direct applic ation of Hess’s law.
Practice question
6. Using Hess’s law and enthalpy of combustion data, the enthalpy change of
−1
formation of pentane is determined to be −177 kJ mol , but the value given
in the data booklet is −173 kJ mol . Suggest why the values aredierent.
Applying Hess’s law to enthalpy changes of formation
The standard enthalpy change for a reaction c an also be c alculated using
enthalpy of formation data. The dierence between the sum of the enthalpy
changes of formation of the products and the sum of the enthalpy changes of
formation of the reactants is equal to the overall enthalpy change of the reaction:
⦵ ⦵ ⦵
ΔH = ∑(ΔH products) − ∑(ΔH reactants)

r f f
414
LHA
Worked example 3
C alculate the standard enthalpy change of formation of pentane, C H , using the enthalpy of combustion data from
5 12
section 14of the data booklet.
Solution
Step 1: Write a balanced chemic al equation for the formation of 1 mol of pentane: 5C(s) + 6H (g) → C H (l)
2 5 12
Step 2: Write equations for the combustion of c arbon, hydrogen and pentane and nd their standard enthalpy change
values from section 14 of the data booklet.
⦵
1
1 C(s) + O (g) → CO (g) ∆H = −394 kJ mol

2 2
⦵
1 1
2 ∆H = −286 kJ mol
H (g) + O (g) → H O(l)
2 2 2
⦵
1
3 C H (l) + 8O (g) → 5CO (g) + 6H O(l) ∆H = −3509 kJ mol

5 12 2 2 2
Step 3: Use these equations with either the summation of equations method or enthalpy cycle diagram method to
determine the enthalpy change for the reaction. These methods were introduced earlier in this topic.
Inspect the formation of pentane reaction scheme. In your c alculation, you need to use enthalpy values corresponding to
the combustion reactions that involve c arbon, hydrogen and pentane. C arbon is a reactant in equation 1, but ve moles
are required for the overall equation. Therefore you should multiply the enthalpy of combustion of c arbon by ve:
5C(s) + 5O (g) → 5CO (g) ΔH = −1970 kJ mol

2 2
You also require six moles of hydrogen as a reactant. Equation 2 should be used, with the enthalpy change multiplied by six:
⦵
1
6H (g) + 3O (g) → 6H O(l) ΔH = −1716 kJ mol

2 2 2 c
For the product pentane, you should use equation 1, but the equation must be reversed to make pentane a product, not
a reactant. As a result, the enthalpy change sign changes from negative to positive:
⦵
1
5CO (g) + 6H O(l) → C H (l) + 8O (g) ΔH = +3509 kJ mol

2 2 5 12 2
enthalpy values:
⦵
1
5C(s) + 5O (g) → 5CO (g) ΔH = −1970 kJ mol

2 2 c
⦵
1
6H (g) + 3O (g) → 6H O(l) ΔH = −1716 kJ mol

2 2 2 c
⦵
1
5CO (g) + 6H O(l) → C H (l) + 8O (g) ΔH = +3509 kJ mol

2 2 5 12 2
⦵
1
Total 5C + + 6H + + + → + + C H + ΔH = −177 kJ mol

2 2 2 2 2 2 2 5 12 2
C ancelling the common species gives the overall equation 5C(s) + 6H (g) → C H (l). Therefore, the total enthalpy
2 5 12
change for the reaction is −177 kJ mol
Enthalpy cycle diagram method ΔH
5C(s) + 6H (g) C H (I)

2 5 12
The enthalpy cycle diagram is on the right. Oxygen, O (g), is not included in enthalpy
2
cycle diagrams.
C alculate the sum of the enthalpy change values, following the arrows from the
6 ×
3509
reactants to the products, via the CO (g) and H O(l) intermediates. If you are going
2 2
5 × ( 286)
against the direction of an arrow, reverse the sign of the enthalpy change.
( 394)
This c alculation is summarized below:
⦵
1
ΔH = 5 × (−394) + 6 × (−286) + 3509 = −177 kJ mol

5CO (g) + 6H O(I)
2 2
415
LHA
Worked example 4
C alculate the enthalpy of combustion of pentane, C H (l), using the enthalpy of formation data from section 13 of the
5 12
data booklet.
Solution
Step 1: Write a balanced chemic al equation for the combustion of 1 mol of pentane:
C H (l) + 8O (g) → 5CO (g) + 6H O(l)

5 12 2 2 2
Step 2: Write equations for the formation of pentane, c arbon dioxide, and water from their elements and nd their
standard enthalpy change values from section 12 of the data booklet.
⦵
1
1 5C(s) + 6H (g) → C H (l) ∆H = −173 kJ mol

2 5 12 f
⦵
1
2 C(s) + O (g) → CO (g) ∆H = −394 kJ mol

2 2 f
1
⦵
1
3 H (g) + O (g) → H O(l) ∆H = −286 kJ mol

2 2 2
f
Step 3: Use these equations with either the summation of equations method or enthalpy cycle diagram method to
determine the enthalpy change for the reaction.
In your c alculation, you need to use enthalpy values corresponding to the formation reactions that involve pentane,
c arbon dioxide and water. Pentane is a reactant in the overall equation, but a product in equation 1. Therefore, equation
1 must be reversed. As a result, the enthalpy change sign changes from negative to positive:
⦵
1
C H (l) → 5C(s) + 6H (g) ∆H = +173 kJ mol

5 12 2
C arbon dioxide is a product in an equation 2, but ve moles are required for the overall equation. Therefore, you should
multiply the enthalpy of formation of c arbon dioxide by ve:
⦵
1
5C(s) + 5O (g) → 5CO (g) ∆H = −1970 kJ mol

2 2 f
You require six moles of water as a product. Equation 3 should be used, with the enthalpy change multiplied by six:
⦵
1
6H (g) + 3O (g) → 6H O(l) ∆H = −1716 kJ mol

2 2 2 f
enthalpy values:
⦵
1
C H (l) → 5C(s) + 6H (g) ∆H = +173 kJ mol

5 12 2
⦵
1
5C(s) + 5O (g) → 5CO (g) ∆H = −1970 kJ mol

2 2 f
⦵
1
6H (g) + 3O (g) → 6H O(l) ∆H = −1716 kJ mol

2 2 2 f
⦵
1
Total C H + 5C + 5O + 6H + 3O → 5C + 6H + 5CO + 6H O ∆H = −3513 kJ mol

5 12 2 2 2 2 2 2
(l) + 8O (g) → 5CO (g) + 6H O(l). Therefore, the total

5 12 2 2 2
enthalpy change for the reaction is−3513 kJ mol
ΔH
Enthalpy cycle diagram method C H (I) + O (g) 5CO (g) + 6H O(I)

5 12 2 2 2
The enthalpy cycle diagram is on the right.
C alculate the sum of the enthalpy change values, following the arrows
5 × 6 ×
from the reactants to the products, via the C(s) and H (g) intermediates.
2
173
( 394) ( 286)
If you are going against the direction of an arrow, reverse the sign of the
enthalpy change. This c alculation is summarized below:
⦵
1
ΔH = (+173) + 5 × (−394) + 6 × (−286) = −3513 kJ mol
5C(s) + 6H (g)
2
416
LHA
Practice questions
7. Calculate the enthalpy change of formation of propanone, 9. Consider the following enthalpy cycle diagram:
CH COCH (l), using enthalpy change of combustion data

3 3
Step 1
from section 14 of the data booklet. CH CH (g) + H CH (g)

2 2 3 3
Use the summation of equations method and the
enthalpy cycle diagram method to support your
7
answer. 7 + O (g)
2
+ O (g)
2 2
2
8. Hydrogen gas c an be made using the following
Step 3
reaction: Step 2
CH (g) + H O(g) → 3H (g) + CO(g)

4 2 2
Section 13 of the data booklet lists the standard
2CO (g) + 3H O(I)

⦵ 2 2
enthalpies of formation, ΔH , for some of the species

f
in the reaction above.

a. C alculate the standard enthalpy change, ΔH , of
a. O utline why no value is listed for H (g). step 2 using section 14 of the data booklet.
2
⦵ ⦵
1
b. Determine the value of ΔH , in kJ mol , for the b. Determine the standard enthalpy change, ΔH ,
reaction using the standard enthalpy change of of step 1.
formation values.
c. Suggest one reason why the c alculated value of
c. O utline why the value of enthalpy change of ΔH using Hess’s law in part b c an be considered
this reaction c alculated from bond enthalpies is accurate and one reason why it c an be considered
lessaccurate. approximate.
Comparing ∆H values
The standard enthalpy of combustion of propan-1-ol is Method
−2021 kJ mol . In this task, you will compare this value to

1. Determine the enthalpy of combustion of propan-1-ol
those obtained with some of the methods described in

by each of the following methods:
this topic.
a. Refer to average bond enthalpy values.
Relevant skills
b. Conduct a c alorimetry experiment. This could be
• Tool 3: Use arithmetic and algebraic c alculations to

real (as described in Reactivity 1.1), or simulated, if
solve problems
you have access to a suitable simulation software.
Record the relevant measurement uncertainties

and propagate them.
• Inquiry 3: Compare the outcomes of an investigation
c. Refer to standard enthalpies of formation.
to the accepted scientific context
2. Determine the percentage error of each of the values
• Inquiry 3: Identify and discuss sources and impacts of
obtained in methods a, b and c
systematic and random errors
3. Discuss and explain the differences between the
standard enthalpy of combustion of propan-1-ol and
each of your c alculated values obtained by methods
a, b and c
417
LHA
Born–Haber cycles (Reactivity 1.2.5)
Born–Haber cycles are another applic ation of Hess’s law. These cycles combine
the enthalpy changes associated with several steps involved in the formation of
an ionic compound. The steps in the cycle include ionization energy, enthalpy of
atomization, electron anity, lattice enthalpy, and enthalpy of formation.
Ionization energy, IE, is the standard enthalpy change that occurs on the
removal of one mole of electrons from one mole of atoms or positively charged
ions in the gaseous state. For metal ions with multiple valence electrons, the rst,
second, and sometimes further ionization energies are dened:
IE : M(g) → M (g) + e IE > 0

1
+ +
2
IE : M (g) → M (g) + e IE > 0

2
The process of ionization is endothermic. The values of rst ionization energy c an
be found in section 9 of the data booklet.
The enthalpy of atomization, ΔH , is the standard enthalpy change that occurs

at
when one mole of gaseous atoms of an element is formed. This process is
endothermic. For a solid monatomic species, the value of ΔH is equal to the

at
enthalpy of sublimation:
M(s) → M(g) ΔH > 0

at
For a gaseous diatomic species, ΔH is equal to half of the bond enthalpy

at
(section 12 of the data booklet):
1
⦵
X (g) → X(g) ΔH > 0

2 at
The electron anity, EA, is the standard enthalpy change on the addition of one
mole of electrons to one mole of atoms in the gaseous state:
– –
X(g) + e → X (g) EA < 0
Electron anity of non-metals is typic ally negative, but there are exceptions, such
as the electron anity of helium or nitrogen. Values of rst and second electron
anity c an be found in section 9 of the data booklet.
The lattice enthalpy, ∆H , is dened as the standard enthalpy change that

lattice
occurs when gaseous ions are formed from one mole of structural units of a solid
ionic lattice:
+ – ⦵
MX(s) → M (g) + X (g) ∆H > 0

lattice
The process is endothermic. Experimental values of lattice enthalpy at 298.15 K
c an be found in section 16 of the data booklet.
L attice enthalpies are oen quoted as negative values that represent the
exothermic formation of the solid lattice from gaseous ions. However, in DP
chemistry, the lattice enthalpy always refers to the endothermic formation of
gaseous ions from the solid lattice.
418
LHA
We have already dened the standard enthalpy of formation, ∆H , of a
f
substance as the enthalpy change that occurs when one mole of a substance is
formed under standard conditions from its constituent elements in their standard
states. Standard enthalpy of formation of an ionic substance, such as NaCl(s), c an
be represented by a single equation:
1
⦵ −
1
Na(s) + Cl (g) → NaCl(s) ∆H = −411 kJ mol

2 f
The correct use of subject-specic terminology is essential to your ability
to demonstrate your knowledge and understanding of new concepts in
chemistry.
You will encounter several key terms in this section: lattice enthalpy, standard
enthalpy of formation, standard state, enthalpy of atomization, ionization
energy and electron anity. M ake a glossary that has an entry for each term,
detailing the following:
Term Symbol Denition Equation
⦵ +
lattice ∆H Standard enthalpy change MX(s) → M (g) + X (g)

lattice
enthalpy that occurs on the formation
of gaseous ions from one
mole of a solid lattice
You c an continue to add terms to your chemistry glossary over time.
Using the Born–Haber cycle
The lattice enthalpy, enthalpy of atomization, ionization energy, electron anity
and enthalpy of formation c an be combined to construct a Born–Haber cycle. A
generalized Born–Haber cycle is shown in gure 6.
+
M (g) + X(g) + e
ΔH (X)
at
EA(X)
1
+
M (g) X (g) e
2
2
+
IE(M) M (g) + X (g)
M(g) + X (g)
2
2
ΔH
ΔH (M)
at
ΔH
f
1
+ X (g)
2
2
 Figure 6 A generalized Born–Haber cycle
419
The unknown value of enthalpy change for any step in a Born–Haber cycle c an
LHA
be determined by following the opposite pathway in the cycle. For example, if
you know the values of enthalpy of atomization, ionization energies, electron
anities and lattice enthalpy, you c an nd the standard enthalpy of formation of
an ionic compound. The enthalpy of formation is equal to the sum of the enthalpy
changes for each of the other steps. Much like with the enthalpy cycle diagrams
you constructed before, you should reverse the sign of any enthalpy changes
where the pathway goes against the direction of the arrow in the cycle.
Worked example 5
Determine the lattice enthalpy of potassium bromide using the Born–Haber
cycle in gure 7.
K (g) + Br(g) + e
ΔH (Br) +112 kJ mol

at
EA (Br) 325 kJ mol
1
+
K (g) Br (l) e
2
2
+
1
K (g) + Br (g)
IE (K) +419 kJ mol
K(g) + Br (l)
2
2
ΔH x kJ mol
lattice
ΔH (K) +89 kJ mol

at
ΔH
f
1
+ Br (l)
2
2
392 kJ mol
 Figure 7 Born–Haber cycle to c alculate the lattice enthalpy of potassium bromide
Solution
The lattice enthalpy is the enthalpy change for the reaction KBr(s) → K (g) +
Br (g). In gure 7, this step is shown from the bottom right of the cycle, to
the middle right, labelled ∆H . To nd the lattice enthalpy, follow the
lattice
+ −
alternative pathway, going from KBr(s) clockwise around to K (g) + Br (g).
Add the values of the enthalpy change for each step:
⦵ ⦵ ⦵ ⦵
∆H (KBr) = −∆H + ΔH (K) + IE(K) + ΔH (Br) + EA(Br)

lattice f at at
= −(−392) + (+89) + (+419) + (+112) + (−325)
–
1
= +687 kJ mol
Note that you followed the reverse of the enthalpy of formation reaction
arrow, so the sign was reversed: +392 instead of −392. Remember to express
your answer for the lattice enthalpy of an ionic compound as a positive value,
bec ause it is an endothermic process.
420
LHA
Practice question F actors aecting the value of
lattice enthalpy are detailed in
10. Interpret and utilize the values from the Born–Haber cycle in gure 8 to
Structure2.1.
c alculate the enthalpy of formation for the ionic compound magnesium
oxide, MgO. MgO has doubly charged ions.
2+
Mg (g) + O(g) + 2e
ΔH (O) +249 kJ mol

at 1
EA (O)
141 kJ mol
(1)
1
2+
Mg (g) + O (g) + 2e
2
2
2+
Mg (g) + O (g) + e
IE (Mg) +1451 kJ mol

(2)
1
EA (O)
+753 kJ mol
(2)
1
+
Mg (g) + O (g) + e
2
2
2+ 2
1
Mg (g) + O (g)
IE (Mg) +738 kJ mol
(1)
Mg(g) + O (g)
2
2
1
ΔH (MgO) +3791 kJ mol
lattice
ΔH (Mg) +148 kJ mol

at
ΔH (MgO)
f
1
+ O (g)
2
2
1
x kJ mol
Figure 8 Born–Haber cycle to c alculate the enthalpy of formation
for magnesium oxide
+
2 2–
Figure 9 The lattice structure of crystalline magnesium oxide: grey = Mg , red = O
Linking question
What are the factors that inuence the strength of lattice enthalpy in an ionic
compound? (Structure 2.1)
421
LHA
5. Using the Born–Haber cycle below, determine which
Topic review
c alculation represents the lattice enthalpy of strontium
1
1. Using your knowledge from the Reactivity 1.2 topic,
chloride, SrCl , in kJ mol
2
2+
Sr (g) + 2Cl(g)
How does application of the law of conservation
698
of energy help us to predict energy changes during
+1064
reactions?
2+
Sr (g) + 2Cl (g)
+
Sr (g) + 2Cl(g)
2. Which equation represents the N–H bond enthalpy
yplahtne
inNH ?
3
+549
A NH (g) → N(g) + 3H(g)

3
1 1
Sr(g) + 2Cl(g)
B NH (g) → N(g) + H(g)
3
3 3
lattice enthalpy
1 3 +242
Sr(g) + Cl (g)
C NH (g) → N (g) + H (g) 2
3 2 2
2 2
Sr(s) + Cl (g) +164

2
D NH (g) → •NH (g) + •H(g)

3 2
3. Bond enthalpies c an be used to c alculate the enthalpy
change of the following reaction, in kJ mol

829
SrCl (s)
2
N (g) + 3H (g) ⇌ 2NH (g)

2 2 3
A −(−829) + 164 + 242 + 549 + 1064 − (−698)

Referring to section 12 of the data booklet, deduce
which of the following represents the c alculation of the B −829 + 164 + 242 + 549 + 1064 − 698
enthalpy change of reaction from bond enthalpies.

C −(−829) + 164 + 242 + 549 + 1064 − 698
A (6 × 391) − [(3 × 436) + 945] D −829 + 164 + 242 + 549 + 1064 − (−698)
B (3 × 391) − (436 + 945)
C −[(3 × 436) + 945] + (3 × 391)
D −(6 × 391) + [(3 × 436) + 945]

LHA
4. Which equation represents lattice enthalpy?
A NaCl(g) → Na (g) + Cl (g)
B NaCl(s) → Na (g) + Cl (g)
C NaCl(s) → Na (aq) + Cl (aq)
D NaCl(s) → Na (s) + Cl (s)
422
LHA
6. The Born–Haber cycle for potassium oxide, K O, is

2
shown below:
7. The following equation describes the industrial
+ 2 production of ammonia using the Haber process.

2K (g) + O (g)
N (g) + 3H (g) ⇌ 2NH (g)

2 2 3
1
+612 kJ mol a. C alculate the enthalpy change of reaction for
this process using bond enthalpy data. [3]
+ –
2K (g) + 2e + O(g)
b. State and explain whether the reaction is
exothermic or endothermic. [2]
1
+838 kJ mol
8. Ammonia reacts with oxygen to form nitrogen and
2K (g) + O(g) lattice

steam.
enthalpy
a. Write a balanced chemic al equation for this

1
+428 kJ mol
reaction, showing the states of all species. [1]
1
b. Draw full structural formulas for all reactants and
2K(s) + O (g)
2 2
products to determine the nature of the covalent
bonds present. [4]
1
+361 kJ mol
c. Using bond enthalpy values from section 12 of the
data booklet, determine the enthalpy change for
K O(s)
2 this reaction. [3]
9. Octane, C H , is a component of liquid gasoline. When

8 18
Which c alculation represents the lattice enthalpy
gasoline is burned as fuel, octane is combusted in

1
inkJ mol ?
oxygen via the following reaction:
A −361 + 428 + 838 + 612
25
C H (l) + O (g) → 8CO (g) + 9H O(g)

8 18 2 2 2
B −(−361) + 428 + 838 + 612
C −361 + 428 + 838 − 612 a. Using bond enthalpy data, c alculate the enthalpy
change for this reaction. [3]

D −(−361) + 428 + 838 − 612
b. The enthalpy change for this reaction was
determined experimentally to be −5470 kJ mol .
Give two reasons why the enthalpy change value
you obtained from bond enthalpy data diers from
the experimental value. [2]
423
Reactivity 1.3 Energy from fuels
What are the challenges of using chemic al energy to address our energy needs?
When we burn fossil fuels, chemical energy is converted The challenges of using chemic al energy from non-
into thermal energy. Thermal energy can be used to renewable, c arbon-based fuels, such as crude oil, natural
generate electrical energy to power devices in our homes gas and coal, which provide 80% of our energy, are
and in industry. The use of fossil fuels is being increasingly clearly understood by the scientic community. M any
questioned as advances in science and technology reveal industrialized nations depend on the use of fossil fuels to
the damage that their use is having on our planet. In recent sustain their fast-developing economies. This is a major
years, the cost of alternative renewable energy sources has problem that has to be overcome if the use of renewable,
decreased and renewable energy technology has advanced. clean sources to meet our global energy needs is to
exceed the use of fossil fuels.
This, coupled with scientic evidence of the rate of change in
global warming, has increased the urgency for governments
to commit to net-zero carbon emissions by 2050.
Understandings
Reactivity 1.3.1 — Reactive metals, non-metals and organic Reactivity 1.3.4 — Biofuels are produced from the
compounds undergo combustion reactions when heated biologic al xation of c arbon over a short period of time
in oxygen. through photosynthesis.
Reactivity 1.3.2 — Incomplete combustion of organic Reactivity 1.3.5 — A fuel cell c an be used to convert
compounds, especially hydroc arbons, leads to the chemic al energy from a fuel directly to electric al energy.
production of c arbon monoxide and c arbon.
Reactivity 1.3.3 — Fossil fuels include coal, crude oil
and natural gas, which have dierent advantages and
disadvantages.
Combustion (Reactivity 1.3.1 and
Reactivity1.3.2)
In combustion reactions, substances are burned in oxygen. Metals, non-metals
and hydroc arbons all react with oxygen when combusted, producing dierent
products.
Combustion of metals
The combustion of reactive metals in the presence of oxygen results in the
Oxidation and reduction are
oxidation of the metal, the reduction of oxygen, and the formation of an
dened in terms of electron transfer
ionic compound. This type of reaction is therefore known as a redox reaction.
in Reactivity 3.2.
Oxidation c an be dened as a gain of oxygen or a loss of electrons. Reduction is
dened as a loss of oxygen or a gain of electrons.
The general equation for the reaction of a metal with oxygen is as follows:
metal + oxygen → metal oxide
424
Lithium burns in oxygen to release heat and produce lithium oxide:
4Li(s) + O (g) → 2Li O(s)

2 2
M agnesium readily reacts with oxygen, producing a brilliant white light and
magnesium oxide:
2Mg(s) + O (g) → 2MgO(s)

2
In both of these reactions, the reactive metals are being oxidized to form metal
ions. The half-equations for each of these metals reveal the loss of electrons:
Li → Li + e
2+
Most metal oxides are ionic
Mg → Mg + 2e
compounds. Rules for naming
The oxygen atoms are reduced to form O ions in each reaction: ionic compounds are outlined in
Structure 2.1
O + 4e → 2O
2
Combustion of non-metals
Non-metals are also oxidized when combusted in oxygen, forming non-metal
oxides:
non-metal + oxygen → non-metal oxide
Sulfur, a non-metal, c an be found as impurities in fossil fuels, such as coal
and crude oil. Coal may contain up to 3% of sulfur. The combustion of sulfur-
containing compounds in oxygen predominantly produces sulfur dioxide, SO :

2
S(s) + O (g) → SO (g)

2 2
Sulfur dioxide c an then further react with oxygen in the atmosphere to produce
sulfur trioxide:
Activity
2SO (g) + O (g) ⇌ 2SO (g)

2 2 3
Research the applic ations of
sulfur dioxide, and evaluate

Sulfur trioxide reacts with water in the atmosphere, to form sulfuric acid:
the environmental impact
SO (g) + H O(l) → H SO (aq)

3 2 2 4 of its industrial production.
Research other non-metal oxides
In industry, sulfur dioxide is produced in vast quantities as feedstock for the
and their applic ations and
synthesis of sulfuric acid. The majority of the sulfuric acid is then used in the
environmentalimpacts.
production of fertilizers, along with paper, paints, textiles and a wide variety of
other products.
Complete combustion of organic compounds
Hydroc arbons are organic compounds composed only of c arbon and
hydrogen atoms. Alkanes are the simplest hydroc arbons, which are present
in fossil fuels, such as crude oil and natural gas. They are relatively inert. This is
bec ause they have a low bond polarity, strong covalent c arbon–c arbon bonds
(bond enthalpy = 346 kJ mol ) and strong c arbon–hydrogen bonds (bond
enthalpy = 414 kJ mol ). However, alkanes do participate in some reactions,
includingcombustion.
425
Alkanes are commonly used as fuels, releasing large amounts of energy in
combustion reactions. For combustion to occur, a fuel must be volatile. Volatility
is the tendency of a substance to change state from liquid to gas. As the length of
the c arbon chain increases in the alkane series, the boiling point also increases,
and therefore volatility decreases. As a result, short-chain alkanes tend to be used
as fuels. Liqueed petroleum gas (LPG) consists predominantly of compressed
propane, C H , while petrol (gasoline) is a mixture of hydroc arbons from butane,

3 8
C H , to dodec ane, C H
4 10 12 26
Alkanes undergo complete combustion in the presence of excess oxygen. This
reaction is exothermic, and it produces c arbon dioxide and water. The general
equation for the complete combustion of alkanes is shown below:
alkane + oxygen → c arbon dioxide + water
 Figure 1 Liqueed petroleum gas
3n + 1
C H + O → nCO + (n + 1)H O
contains liquid propane, and is used as a n 2n+2 2 2 2
fuel for gas barbecues
In this, and following combustion reactions, the states of all species depend
on the reaction conditions. For example, at high temperatures, water c an be
The chemic al equation for the

produced as steam, H O(g), while at lower temperatures it will condense into
2
combustion of alkanes shows the

liquid, H O(l).
2
general formula of the homologous
Petrol, also known as gasoline, is a mixture of hydroc arbons obtained from oil,
series of alkanes: C H .
n 2n+2
with octane present in the highest proportion. The reaction for the combustion of
Homologous series of organic
octane is shown below:

compounds were introduced in
Structure 3.2 25 ⦵
1
C H (l) + O (g) → 8CO (g) + 9H O(l) ∆H = −5470 kJ mol

8 18 2 2 2 c
F alsication
Up until the late 18th century, combustion was explained in terms of the
phlogiston theory. A substance known as “phlogiston” was thought to
be present in all combustible materials. Burning was believed to release
phlogiston into the air. The combustion of c arbon would lead to a mass
loss, which was interpreted as the loss of phlogiston. The fact that some
substances, such as metals, gain mass when combusted was a puzzling
observation — further hypotheses were developed to justify it. Examination
of the mass losses and gains when dierent elements burnt in air, along with
the discovery of oxygen, led to the falsic ation of the phlogiston theory. It was
superseded by the theory of combustion that you have learnt about and that
explains combustion in terms of oxidation.
The phlogiston theory may seem unreasonable or even peculiar to someone
who knows what we know now. If we consider the knowledge base at the
time, however, phlogiston was not an implausible concept. Scientic claims,
hypotheses or theories c an be falsied. This c an lead to the development of
new theories, which must then be corroborated by experimental evidence
in order to eventually become accepted (although theories c an never be
proven with certainty). Scientists must remain open-minded with respect to
newevidence.
Think of a claim, hypothesis or theory you have encountered in your study
of science. What type of evidence could challenge it? How much evidence
would be needed to falsify it?
426
Alcohols are another class of organic compounds. They have a wide range
of applic ations, such as fuels, solvents and antiseptics. Like alkanes, alcohols
undergo complete combustion reactions releasing c arbon dioxide and water.
The general equation for the complete combustion of alcohols is shown below:
alcohol + oxygen → c arbon dioxide + water
3n
C H OH + O → nCO + (n + 1)H O
n 2n+1 2 2 2
Ethanol is used in medicine for its antiseptic properties. It is also used as a fuel for
vehicle engines. It is known as a biofuel bec ause it c an be produced by plants, a
renewable resource, as opposed to fossil fuels, the supply of which is nite. The
reaction for the complete combustion of ethanol is shown below:
⦵
1
C H OH(l) + 3O (g) → 2CO (g) + 3H O(l) ∆H = −1367 kJ mol

2 5 2 2 2 c
This reaction is strongly exothermic. The use of ethanol as a renewable biofuel
is increasing. The scientic community is working to resolve the problems
associated with the production of biofuels, such as the high cost of production,
the impact of using farmland on food supply, and the lower amount of energy
produced per unit mass or volume of the fuel.
C arbon dioxide has a signic ant environmental impact, as it contributes to
global warming. This is the major reason why governments around the world
promote clean energy, and legislate for limiting the production of new c ars
that use fossil fuels. Ethanol is seen as a more environmentally friendly fuel, as
it comes from a renewable source.
How c an the scientic community, industry and governments work together
to reduce the use of fossil fuels? Who has the greatest responsibility to reduce
our fossil fuel use?
Practice questions
1. Deduce balanced equations for the complete combustion of:
 Figure 2 Ethanol-fuelled public
a. methane
transport is becoming more common
b. propane
as governments look for ways to reduce
c. pentane reliance on fossilfuels
d. hexane
2. Deduce balanced equations for the complete combustion of:
a. propanol
b. pentanol
c. heptanol
427
Incomplete combustion of organic compounds
If there is a limited supply of a species participating in a chemic al reaction, this
species is known as the limiting reactant. Combustion reactions usually occur
in a system where atmospheric air and oxygen are in excess, so the limiting
reactant is the organic compound (fuel). However, when this is not the c ase,
such as in a c ar engine, oxygen becomes the limiting reactant, which c auses
incomplete combustion of the fuel.
In the incomplete combustion of hydroc arbons, c arbon monoxide, CO(g),
and/or elemental c arbon, C(s), c an be produced. C arbon monoxide is a
poisonous gas that irreversibly binds to hemoglobin in the red blood cells,
reducing the oxygen-c arrying c apacity of the blood (gure 3). Elemental c arbon
produced in incomplete combustion reactions is oen referred to as soot.
 Figure 3 The c arbon monoxide

carbon monoxide O
molecule irreversibly binds to the large
hemoglobin molecule
C
N
N
2+
Fe
N N
HN
The general equation for the incomplete combustion of an alkane to form c arbon
monoxide is as follows:
alkane + oxygen → c arbon monoxide + water
2n + 1
C H + O → nCO + (n + 1)H O
n 2n+2 2 2
The general equation for the incomplete combustion of an alkane to form c arbon
(soot) is as follows:
alkane + oxygen → c arbon + water
Practice questions
n + 1
C H + O → nC + (n + 1)H O
n 2n+2 2 2
3. Deduce balanced equations for
The incomplete combustion reactions of methane are shown below:

the incomplete combustion of
3
the following alcohols, where
CH (g) + O (g) → CO(g) + 2H O(l)

4 2 2
c arbon monoxide is one of the 2
products: CH (g) + O (g) → C(s) + 2H O(l)

4 2 2
a. propanol
These incomplete combustion reactions c an occur simultaneously with complete
b. pentanol
combustion reactions in dierent ratios. Incomplete combustion reactions are
c. heptanol
less exothermic than the corresponding complete combustion reactions.
Incomplete combustion c an be observed in the laboratory, with the appearance
of black soot on the bottom of glassware that has been heated over a Bunsen or
spirit burner ame.
428
Fossil fuels (Reactivity 1.3.3)

Linking questions
Fossil fuels include crude oil, coal and natural gas. Crude oil, or petroleum,
Why is high activation energy oen

is a non-renewable resource, and its use as a fuel is deeply embedde d in
considered to be a useful property

the global society. Crude oil is a natural mixture of hydroc arbons, organic
of a fuel? (Reactivity 2.2)

compounds containing nitrogen, sulfur and oxygen, and a wide v ariety of
Which species are the

other elements.
oxidizing and reducing agents
Coal, petroleum and natural gas are the main fuels used to generate electricity
in a combustion reaction?
in power stations and the internal combustion engines of c ars. As the global
(Reactivity3.2)
demand for energy increases, so does the consumption of fossil fuels. Globally,
What might be observed when
governments are making plans and legislating to limit the consumption of fossil
a fuel such as methane is burned
fuels and promote the use of renewable energy. However, the transition to clean
in a limited supply of oxygen?
energy will take many dec ades.

(Inquiry2)
How does limiting the supply of
One consequence of the use of fossil fuels is the release of large quantities of
oxygen in combustion aect the
c arbon dioxide, a product of the combustion reaction, into the atmosphere.
products and increase health risks?
C arbon dioxide is a greenhouse gas, which means that it traps heat energy
(Reactivity 2.1)
inside the E arth’s atmosphere. This is known as the greenhouse eect (gure 4).
e
n
e
r
g
y
f
r
o
m
t
h
e
S
u
n
s
e
e
s
r
a
e
g
h
p
e
s
s
o
u
m
o
h
ta
ne
eh
erg
t ni
 Figure 4 Greenhouse gases reduce the amount of heat radiated into space
Nitrogen, N , and oxygen, O , make up over 99% of atmospheric air. Neither

2 2
nitrogen or oxygen have the ability to absorb infrared radiation that enters
the E arth’s atmosphere from the Sun. By comparison, c arbon dioxide,
CO , constitutes approximately 0.04% of the atmosphere. Despite the

2
small proportion of c arbon dioxide, the increase in the concentration of this
greenhouse gas is c ausing signic ant damage to our environment. A c arbon
dioxide molecule c an absorb infrared radiation resulting in the vibration of bonds
within the molecule. Aer absorbing the infrared radiation and undergoing
vibration, the molecule will emit infrared radiation back into the atmosphere.
The IR activity of c arbon dioxide is
Some of this radiation will be directed towards the E arth’s surface, which will
increase the global temperature.
429
Other greenhouse gases include methane, nitrous oxide, water vapour and
uorinated substances such as hydrouoroc arbons.
As a result of the greenhouse eect, average temperatures around the world are
increasing, which is known as global warming. There is widespread agreement
in the scientic community that the main c ause of global warming is the increase
in the levels of greenhouse gases: in particular, c arbon dioxide (gure 5), and to a
lesser extent, methane.
 Figure 5 Annual mean atmospheric CO

2
420
levels recorded at M auna Loa Observatory
415
410
mpp /
405
400
2
OC
395
390
385
380
375
2004 2006 2008 2010 2012 2014 2016 2018 2020

2022
year
The combustion of dierent fuels releases dierent quantities of greenhouse
gases (gure 6).

hWG rep
1600
average emissions
intensity
1400
2
range between
OC sennot/snoissime sag esuohneerg
studies
1200
1000
800
600
400
200
lignite coal oil natural solar PV biomass nuclear hydro- wind
gas electric
 Figure 6 Greenhouse gas emissions by energy source
Figure 7 shows the historic patterns of atmospheric c arbon dioxide concentration
during the last three glacial cycles, constructed by the analysis of ice-core
samples. The current CO levels are much higher than historic al peaks,
2
suggesting that human-made emissions are largely responsible for the additional
quantities of c arbon dioxide in the atmosphere.
430
420
current
380
340
mpp /
highest historic CO level

2
300
2
OC
1950
260
220
180
400 350 300 250 200 150 100 50 0
thousands of years before today (0 = 1950)
 Figure 7 Historic CO levels during the last three glacial cycles, as reconstructed from ice cores
2
TOK
One of the optional themes in TOK is knowledge
and indigenous societies. The global population
of indigenous people is estimated to be over
450 million, living all over the world. Indigenous
communities have a long-standing relationship
with, and a highly developed understanding
of, the natural environment and biodiversity.
M any are particularly vulnerable to the adverse
eects of climate change, despite the fact that
their contribution to greenhouse gas emissions
is exceptionally low. International organizations
such as the United Nations (UN) have not only
c alled for awareness and action to protect
indigenous peoples, but also recognized that
their participation in decision-making processes is
of value to all: “indigenous peoples’ knowledge
should be considered an important element within

 Figure 8 Participants at the United Nations Permanent Forum for
the international debate regarding adaptation to

Indigenous Issues
climate change”.
What values and assumptions underpin the use of the term “indigenous” knowledge?
431
M any dierent sources of fuels are used in everyday life. The choice of fuels
depends on the economic development of nations and the natural resources
available. E ach fuel has a dierent specic energy: the amount of heat energy
released per mass of the fuel. Wood, a traditional means of generating energy for
cooking and heating, has the lowest specic energy of all commonfuels.
60
1
45
gk J M / y g r e n e c i f i c e p s
30
15
wood coal ethanol biodiesel crude oil diesel gasoline natural
gas
Practice questions  Figure 9 The specic energy of dierent fuels
4. Propane gas C H is a
3 8
hydroc arbon that is classied as

Common fuels vary in composition. The chain length of hydroc arbons present in
a fossil fuel.
these fuels also varies. In general, the longer the hydroc arbon chain, the greater
a. Write the balanced chemic al the tendency of the fuel to undergo incomplete combustion. As discussed,
equation for the complete incomplete combustion results in the release of poisonous c arbon monoxide
combustion of propane and and/or elemental c arbon (soot). But it also produces a smaller amount of heat
identify the greenhouse gas energy per unit mass of the fuel when compared to the complete combustion
that is produced. of the same hydroc arbon. L arger hydroc arbons have a reduced volatility
due to stronger London (dispersion) forces (LDFs). This aects the way the
b. Enthalpy of combustion of
–1
hydroc arbon molecules interact with the oxygen molecules and the type of
propane is –2219 kJ mol .
combustion that occurs.

Calculate the energy released
in burning 1 gram (the
specic energy) of propane.
c. C alculate the mass of c arbon
Linking questions
dioxide produced per gram
of propane burned.
Why do larger hydroc arbons have a greater tendency to undergo incomplete
d. C alculate the c arbon

combustion? (Structure3.2)
footprint, in tonnes of
LHA
c arbon dioxide, from Why is c arbon dioxide described as a greenhouse gas?
burning 1000 kg (1 tonne) of (Structure 3.2)
propane gas. Identify some
What are some of the environmental, economic, ethic al and

of the environmental issues
social implic ations of burning fossil fuels? (Reactivity 3.2)

c aused by the release of this
greenhouse gas that was
previously locked within
theE arth.
432
Air pollution database task
The concepts in this topic are directly and indirectly 2. Browse the database, carry out some background
related to air pollution, including c arbon monoxide research, and select one or two pollutants to focus on.
(released during the incomplete combustion of
3. Decide how much data to collect and the range of
hydroc arbons), NO and SO (released in the combustion

x x
data required to address your aim.
of substances containing nitrogen and sulfur, which is
4. Formulate a focused research question that includes

also discussed in Structure 3.1) and greenhouse gases
the variables, methodology and range of data.

(methane, c arbon dioxide and CFC s). In this task you will
explore a factor affecting the environmental impact of an

5. Collect data in a well-organized table, including the
atmospheric pollutant of your choice.

data sources.
Relevant skills
6. Estimate the uncertainty of the data, stating clearly

how you have done so and any assumptions you have
• Inquiry 1: Develop investigations that involve

made.
databases
7. Transform your data by processing and graphing.
• Inquiry 1: Justify the range and quantity of
Include an explanation of how you have processed
measurements
the data.
• Inquiry 2: C arry out relevant and accurate data
processing 8. Discuss and interpret the processed data and their
• Inquiry 2: Assess reliability and validity uncertainties.
• Inquiry 3: Relate the outcomes of an investigation to
9. Assess the validity and reliability of the outcome of
the stated research question
your investigation.
10. Evaluate the outcome of your investigation: how

conclusions
condent are you in your conclusion?

• Inquiry 3: Evaluate the implic ations of methodologic al
weaknesses, limitations and assumptions on

11. Evaluate the methodology: discuss the strengths and
conclusions
limitations of the data, assumptions and analysis.
Method
12. O utline possible extensions to your investigation. Try
1. Access an air quality database online. Possible to relate one of these proposed extensions to another
sources include: diploma subject, or TOK.
• World Health Organization’s air pollution data
portal
• World Air Q uality Index project
• Air pollution data shared by the European
Environment Agency
• Your loc al ministry of the environment
Biofuels (Reactivity 1.3.4)
With the global population continuing to increase at approximately 1% per
year, our understanding of how to eciently use our nite resources is of vital
importance. Alternatively, renewable energy resources c an be used instead
of fossil fuels. Sustainable energy is a UN initiative, with the goal of doubling
the share of renewable energy contributed to global energy production by
2030. The cost of renewable energy has decreased over the dec ades, and now
represents a viable option for governments, businesses and individuals.
Renewable energy resources include those that depend on the heat or motion of
the E arth (geothermal, wind, and tidal power) or the Sun’s radiation (solar power
and biomass). Non-renewable energy technology generally uses fossil fuels, such
as coal and natural gas, which are nite in their supply.
433
Biofuels are renewable resources, produced from organic compounds, which
in turn are generated from c arbon dioxide during biologic al processes. The
production of organic compounds from c arbon dioxide is known as biologic al
c arbon xation. For example, green plants use photosynthesis to absorb
c arbon dioxide from the atmosphere and transform it into glucose, which c an be
converted into ethanol, a biofuel, by fermentation.
In the process of photosynthesis, radiant energy in the form of sunlight is
converted by plants into chemic al energy. Plants contain chlorophyll molecules,
which are c apable of absorbing light energy. This light energy is used for
photosynthesis, a complex series of reactions that results in the conversion of
c arbon dioxide and water into glucose, C H O , and oxygen:

6 12 6
6CO (g) + 6H O(l) → C H O (aq) + 6O (g)

2 2 6 12 6 2
Glucose stores chemic al energy in its bonds. Photosynthesis is an example of
biologic al xation of c arbon.
Clean, renewable energy has become a global priority, as there is a growing
acceptance that the planet is undergoing rapid climate change leading
to global warming, more frequent extreme weather events, and oen
irreversible changes in habitats. The ability of scientists to eectively harness
energy and minimize the use of non-renewable energy sources in industry is of
paramount importancetoday.
Scientists are developing new types of c atalysts that absorb light energy and
transfer this energy to chemic al reactions.
 Figure 10 A light-powered catalyst at the M assachusetts Institute of Technology, USA
What would be the benets of utilizing light energy to promote chemic al
reactions, in the same way as plants using sunlight in the process of
photosynthesis?
434
The fermentation of glucose produces ethanol, C H OH, abiofuel:

2 5
C H O (aq) → 2C H OH(aq) + 2CO (g)

6 12 6 2 5 2
C arbon dioxide, a greenhouse gas, is also produced in the fermentation process.
However, this is oset by the absorption of a greater amount of c arbon dioxide in
the process of photosynthesis.
The industrial production of biofuels in many countries has economic and
environmental implic ations. Brazil has undertaken large-sc ale production of
ethanol from sugarc ane for dec ades. An increased demand for renewable
Practice questions
biofuels has both advantages and disadvantages (table 1).
5. a. Write the balanced
chemic al equation for the
Advantages Disadvantages
fermentation of glucose.
b. Explain why ethanol-based

Renewable resource Use of agricultural land, water
fuels are said to have a

resources, fertilizers and pesticides for
lower c arbon footprint than

growing crops
petroleum-based fuels, even
Reduced greenhouse emissions Diversion of food production to the
though they both release
production of biofuels
similar amounts of c arbon
dioxide upon combustion.

Sustainable resource Monocultures c an result in a reduction
of biodiversity c. Present the arguments
for both the advantages
Wide range of plant materials and waste Possible deforestation as the demand
and disadvantages of
can be used for biofuel production for biofuels increases
the production and use
of biofuels, if you were

Economic security with a reduced High cost of production
asked to address a United

dependence on imported oil supplies
Nations Climate Change
 Table 1 Advantages and disadvantages of the use of biofuels conference.
Source analysis
In this task, you will research information about biofuel from a variety of sources,
and evaluate the quality of the information.
Relevant skills
• Inquiry 1: Consult a variety of sources
Method
1. Consult a variety of sources related to biofuels. Try 2. E ach of your sources will provide information about
to cover at least three dierent types of sources, for biofuels. Summarize this information.
example:
3. Construct a table assessing the following aspects of
• Government or international organization website
each source you have chosen: citation, source type,
• Ac ademic journal article
accuracy, bias, credibility, relevance, advantages, and
• Secondary data from a database or publicly
disadvantages.
available data set
• Newspaper or newspaper article
• Textbook
• Video
• Online image search
435
D ata summarizing the global biofuel production are given in gure 11.
(a)
1,000 TWh
Aia acific
800 TWh
hWT / noitcudorp
urope
600 TWh
outh  entral
Aerica
400 TWh
l e u f o ib
200 TWh
North Aerica
0 TWh
1990 1995 2000 2005 2010 2015 2020
year
(b) 100%
noitcudorp latot % / noitcudorp leufoib
Aia acific
80%
urope
60%
South  entral
America
40%
20%
North America
0%
1990 1995 2000 2005 2010 2015 2020
year
 Figure 11 Biofuel production by world region (a) in terawatt-hours (b) as a percentage of total production.
(Source of data: Statistic al Review of World Energy, BP, 2021)
1. Describe three conclusions that c an be drawn from the graphs in gure 11.
2. Formulate two questions, stemming from the information in the graphs in gure 11.
3. The two graphs were produced from the same data, but they represent these data in slightly dierent ways.
Compare and contrast the purpose of the two graphs.
436
Fuel cells (Reactivity 1.3.5)
In Reactivity 3.2, you will learn that a primary (voltaic) cell is an electrochemical
cell that converts chemical energy from spontaneous redox reactions into electrical
energy. These reactions are mostly irreversible, and the cells of this type are mainly
used for low-current applications, such as hand torches, long-life re alarms,
calculators and wall clocks. However, primary cells oen contain materials that are
toxic to humans and the environment if they are not disposed of properly. Primary
cells typically contain zinc metal, manganese dioxide and potassium hydroxide.
In a secondary cell, the chemic al reactions are reversible, so the battery c an be
recharged. Therefore, secondary cells are more environmentally friendly than
primary cells. The lead–acid battery is a type of rechargeable battery, found in the
majority of gasoline-powered vehicles. Electric vehicles are powered by lithium-
ion batteries, another type of secondary cell.
While secondary cells have advantages over traditional primary cells, there are
still problems associated with these types of batteries, such as overheating,
limited lifespan and environmental concerns in terms of theirdisposal.
A fuel cell is used to convert chemic al energy of a fuel directly into electric al
energy. The rst fuel cell was invented in 1838 by Welsh scientist, William
Groves. The dierence between a fuel cell and a voltaic cell is that in a fuel cell,
the fuel is continuously supplied from an external source, whereas a voltaic cell
contains nite amounts of reactants locked within the cell. Therefore, a fuel cell
c an produce electricity indenitely, while a voltaic cell stops working when all
reactants within the cell are consumed.
Hydrogen fuel cell
electric current
The hydrogen fuel cell is an electrochemic al cell that uses hydrogen
and oxygen gases as fuel. The redox reaction between hydrogen and
oxygen produces water, electricity and heat.
fuel in air in
The following steps occur in a hydrogen fuel cell:
1. The proton exchange membrane (PEM) selectively allows
hydrogen ions to diuse between the c athode and anode but
prevents the passage of other ions, molecules and electrons

e
+
between these electrodes. H
H
2
2. Hydrogen gas is oxidized at the anode on the surface of a
platinum-based c atalyst. The half-equation for the reaction at the O

2
+
H
anode is as follows: unused
air, water,
+
excess
H (g) → 2H (aq) + 2e
2
and heat
fuel out H O
2
3. The electrons c annot move through the PEM, and therefore
have to leave the cell through an external circuit, producing the
electric al output of the cell.
anode cathode
4. The protons formed at the anode move across the PEM to the
PEM and electrolyte
c athode, where they combine with the oxygen gas and electrons.
 Figure 12 The main components of a

Oxygen gas is reduced to form water as a waste product. The
commercial hydrogen cell include an

half-equation for the reaction at the c athode is as follows:
electrolyte, a proton exchange membrane
O (g) + 4e + 4H (aq) → 2H O(l) (PEM) and the electrodes

2 2
437
The overall redox reaction is:
2H (g) + O (g) → 2H O(l)

2 2 2
Hydrogen fuel cells are considered to be a clean energy source bec ause their
only product is water. However, hydrogen gas, H (g), is not abundant on

2
E arth and needs to be produced by the following methods, one of which has
environmental implic ations.
1. Electrolysis of water
The electrolysis of water is the process of using electricity to split water into
oxygen and hydrogen gas. This is the reverse process of the reaction that occurs
in a hydrogen fuel cell.
2H O(l) → 2H (g) + O (g)

2 2 2
The electrolysis of water c an be powered by renewable energy sources, such as
solar energy. This environmentally friendly source of hydrogen gas only makes up
a small proportion of the global supply.
2. Steam reforming of hydroc arbons
Hydroc arbons, such as natural gas, gasied coal and biomass, diesel and other
liquid fuels, undergo steam reforming resulting in the production of toxic c arbon
monoxide gas and hydrogen gas. The general equation for the steam reforming
of alkanes is as follows:
C H (g) + nH O(g) ⇌ nCO(g) + (2n + 1)H (g)

n 2n+2 2 2
C arbon monoxide then reacts with steam to form the greenhouse gas c arbon
dioxide:
CO(g) + H O(g) ⇌ CO (g) + H (g)

2 2 2
The annual production of hydrogen from the various sources is responsible for
c arbon dioxide emissions greater than the total annual c arbon dioxide emissions
of the United Kingdom. The scientic community continues to search for new
green sources of hydrogen gas.
Experiments
Alternatives to fossil fuels, ranging from hydrogen fuel cells to biofuels, have
arisen from extensive experimentation by numerous scientists over time.
Creativity and imagination play a role in experimental design, interpretation
and conclusions. Once considered an electrochemic al curiosity, fuel cells are
now seen as a promising source of renewable energy.
Direct-methanol fuel cell
In a direct-methanol fuel cell (DMFC), the source of the hydrogen ions, H ,
is methanol rather than hydrogen gas. Methanol is a liquid fuel that c an be
produced from renewable resources through fermentation. Methanol is cleaner
than hydrogen bec ause the method of its production has less impact on the
environment in terms of formation of greenhouse gases. Methanol also has a far
greater energy density (energy per unit volume) than hydrogen gas.
438
DMFC s use the electrochemic al reactions below:
anode half-equation: CH OH(aq) + H O(l) → CO (g) + 6H (aq) + 6e

3 2 2
3
+
c athode half-equation: O (g) + 6H (aq) + 6e → 3H O(l)

2 2
overall reaction: CH OH(aq) + O (g) → CO (g) + 2H O(l)

3 2 2 2
The electrochemic al reaction produces c arbon dioxide, a greenhouse gas.
The reaction at the anode requires a c atalyst that contains expensive precious
metals, usually ruthenium and palladium. Another disadvantage is the toxicity of
 Figure 13 A portable direct-methanol
methanol.
fuel cell (DMFC), which c an be used to
power laptops and video c ameras
Methanol c an also be used to supply hydrogen gas for hydrogen fuel cells.
Steam reforming of methanol at 250 °C produces CO (g) and H (g), along with a
2 2
small amount of CO(g).
A distinct advantage of DMFC s is their high energy density (gure 14). The slope
of the graph gives the energy per unit volume, showing that the methanol fuel
cell has a much higher energy density than the lithium-ionbattery.
35
30
1
h
W / t n et n o c
25
20
15
yg r e n e
10 lithium-ion battery
direct methanol
fuel cell
0 50 100 150 200
3
volume /cm
 Figure 14 Comparison of the energy density for the lithium-ion battery and the
direct-methanol fuel cell
Practice questions
6. a. O utline the dierences between a primary and secondary cell.
b. What are the advantages a hydrogen fuel cell has over the traditional
lead-acid battery.
c. Identify and explain the function of the feature of a hydrogen fuel cell
that involves the passage of ions.
d. A direct methanol fuel cell (DMFC) converts chemic al energy to
electric al energy.
i. Deduce the anode and c athode half equations and the overall
chemic al equation for this electrochemic al cell.
ii. O utline one advantage and one disadvantage of the methanol cell
(DMFC) compared to a hydrogen fuel cell.
439
When comparing fuels, the energy density (energy released per unit volume)
andspecic energy (energy released per unit mass) c an give quite dierent
pictures (table 2).
Fuel source Energy density Specic energy
−3 −1
/ MJ dm / MJ kg
compressed hydrogen 1.9 120
methanol 16 20
liqueed natural gas 21 50
liquid propane 27 46
gasoline 32 46
 Table 2 Comparing fuels in terms of energy density and specic energy
The specic energy of hydrogen is more than double that of any otherfuel in
table 2. In hydrogen, H , 2.02 g contains 1 mol of fuel, compared with 32.05 g

2
for1 mol of methanol, CH OH, or approximately 110 g for 1mol of gasoline.

3
Therefore, it could be easy to believe thathydrogen is the best fuel choice.
However, fuels need to be stored and transported. The molar volume of a gas
at room temperature and 1 atm pressure is approximately 24 dm . One mole
of gaseous hydrogen under these conditions would require a 24 dm storage
tank, which adds to the weight if the device is to be portable, such as in a c ar.
3 3
One mole of methanol would occupy 40.4 cm , and the same 24 dm storage
tank could hold over 545 mol of methanol fuel. Even when compressed, the
hydrogen gas occupies a much larger volume, and regulators and compressors
further increase the weight of the storage system. Gasoline oers the highest
energy density but has associated environmental problems.
The general public needs to have a good understanding of certain scientic
issues in order to make informed choices. This presents scientists with
the challenge of accurately conveying complex information and specic
terminology in a succinct and accessible way. For example, this chapter
contains information about fuels that is communic ated in dierent types
of tables, diagrams, charts and graphs. What are the advantages and
disadvantages of dierent data communic ation methods?
Design an infographic to communic ate the science behind an issue of your
choice to a particular audience (also of your choice). Possible issues related
Linking question to this chapter include renewable energy, biofuels, fuel cells and incomplete
combustion. Possible audiences include younger pupils at your school, your
What are the main dierences family or your loc al community. You may even wish to discuss this with your
between a fuel cell and a primary creativity, activity, service (CAS) coordinator. Depending on the nature of the
(voltaic) cell? (Reactivity 3.2) issue and the audience, this task could be connected to a CAS experience.
440
5. Ethanol is a biofuel that c an be mixed with gasoline.
Topic review
a. Write the equation for the complete combustion

ofethanol. [1]
b. Outline the evidence that relates global warming to
What are the challenges of using chemical energy to

increasing concentrations of greenhouse gases in
address our energy needs?

the atmosphere. [3]
c. Explain, including a suitable equation, why biofuels
are considered to be c arbon neutral. [2]
Multiple-choice questions 6. A hydrogen fuel cell uses pure hydrogen gas as the fuel
and a proton exchange membrane as the electrolyte. A
2. Which of the following statements is false?
diagram of the hydrogen fuel cell is shown below.
A. The complete combustion of a hydroc arbon forms

electric current
c arbon dioxide and water.
B. All combustion reactions are endothermic reactions.
fuel in air in
C. The incomplete combustion of hydroc arbons and
e
alcohols form the same products.
D. Complete combustion reactions require an excess e
of oxygen gas as a reactant.
+
3. Which equation(s) represent the incomplete H
combustion of methane?
H
2
I. CH (g) + 2O (g) → CO (g) + 2H O(g)

4 2 2 2
O
2
+
H
unused
II. CH (g) + 1½O (g) → CO(g) + 2H O(g)
4 2 2
air, water,
excess
III. CH (g) + O (g) → C(s) + 2H O(g)
4 2 2
and heat
fuel out H O
2
A. I, II and III C. III only
B. II and III only D. II only
anode cathode
4. a. Write the chemic al equation for the incomplete

PEM and electrolyte
combustion of methane. [1]
a. Suggest an advantage of the hydrogen fuel cell
b. Explain how one of the products of incomplete

over the lead–acid battery for use in c ars. [1]
combustion c an lead to increased health risks. [2]
b. Outline one advantage and one disadvantage
c. C alculate the enthalpy change for the incomplete of the methanol cell (DMFC) compared with a
–1
combustion of methane, in kJ mol , using the bond hydrogen fuel cell. [2]
enthalpy data given below. [2]
7. Even though fuel cells, primary cells and rechargeable
cells have similar fundamental characteristics, there are
Average bond enthalpy /

important dierences between them.
Bond
–1
kJ mol
a. Suggest one common feature that fuel cells,
primary cells and rechargeable cells share. [1]

C H 414
b. Outline the dierence between primary and
O H 463
rechargeable cells. [1]
O O 498
c. Identify one factor that aects the voltage of a cell
C O 1077 and a dierent factor that aects the current it
c andeliver. [2]
441
Reactivity 1.4 Entropy and spontaneity
(AHL)
LHA
What determines the direction of chemic al change?
Systems that are approaching equilibrium, or that are 1. Theenthalpy change (whether the reaction is
in equilibrium, are common. Understanding the nature exothermic or endothermic)
of chemic al equilibrium enables chemists to control the 2. The entropy change (whether the reaction increases or
direction and rate of chemic al change, maximizing the decreases the disorder of the system).
yield of chemic al reactions and minimizing the formation Understanding these features allows chemists to predict
of waste and by-products. There are two key features how temperature and other factors, such as the states of
of a chemic al reaction that determine the direction of reactants and products, aect the direction of a particular
chemic al change for a given set of conditions: chemic al change.
Understandings
LHA
Reactivity 1.4.1 — Entropy, S, is a measure of the dispersal or distribution of matter and/or energy in a system.
Themore ways the energy c an be distributed, the higher the entropy. Under the same conditions, the entropy of
a gas is greater than that of a liquid, which in turn is greater than that of a solid.
Reactivity 1.4.2 — Change in Gibbs energy, ΔG, relates the energy that c an be obtained from a chemic al
reaction to the change in enthalpy, ΔH, change in entropy, ΔS, and absolute temperature, T
Reactivity 1.4.3 — At constant pressure, a change is spontaneous if the change in Gibbs energy, ΔG, is negative.
Reactivity 1.4.4 — As a reaction approaches equilibrium, ΔG becomes less negative and nally reaches zero.
Entropy, S (Reactivity 1.4.1)
Chemists need to understand the conditions under which chemic al reactions
will proceed, so that they c an modify and control chemic al systems to achieve
desired outcomes. A reaction is said to be spontaneous when it moves
towards either completion or equilibrium under a given set of conditions,

Chemic al equilibrium is achieved
without external intervention. This intervention may be in the form of a change

when the forward and backward
in temperature, pressure or concentration of a reactant. Reactions that are

reactions in a reversible process
spontaneous c an occur at dierent rates and may be either endothermic or

occur at the same rate. This is
exothermic. Reactions that do not take place under a given set of conditions are
detailed in Reactivity 2.3.
said to be non-spontaneous.
Exothermic reactions are usually spontaneous, but there are many exceptions to
this rule. To better understand the spontaneity of chemic al changes, we need to
examine a number of dierent aspects of a chemic al reaction.
Entropy, S, is a measure of the dispersal or distribution of the total available
energy or matter in a system. If energy and matter are loc alized in one place
within a chemic al system, the entropy of the system is low. Conversely, if energy
and matter are randomly distributed throughout a system, the entropy of the
system is high. Entropy is oen said to be a measure of the disorder of a system.
442
Reactivity 1.4 Entropy and spontaneity (AHL)
LHA
TOK
Entropy is dicult to conceptualize, so it is popularly dened in terms
of disorder or randomness. However, this is generally considered an
oversimplic ation that could lead to misconceptions. Have you come across
the notion of entropy-as-disorder? Have you found it useful? To what extent
do the benets of an explanation that is not entirely correct outweigh its
shortcomings?
Entropy c an be dened thermodynamic ally in terms of dispersal of matter
and energy (as it is done in DP chemistry). An alternative statistic al denition
of entropy looks at the number of possible ways, known as microstates, in
which molecular energy c an be distributed. The relationship between entropy
and the number of microstates was proposed by Austrian physicist Ludwig
Boltzmann, and the formula describing this relationship is written on his
tombstone in Vienna, Austria (gure 1).
The two perspectives of entropy, thermodynamic and statistic al, are
complementary.
 Figure 1 Ludwig Boltzmann's
Spontaneous reactions lead to an increase in the total entropy of the system and
tombstone, with the equation
its surroundings. If you understand the freedom of movement of particles in a

S = k log W. S is entropy, and W
system, you c an quantify the total entropy change during a reaction. This allows
is the number of microstates.
you to predict the direction of that reaction. Do you know what k is?
Entropy and physic al changes
Imagine the condensation that appears on the outside of a glass containing iced
water on a hot day (gure 2). There is a temperature dierence between the
system (iced water and the glass) and the surroundings (everything outside the
system). This temperature dierence results in thermal energy being transferred
from the surrounding atmosphere to the glass and its contents, until an
equilibrium is reached. With this thermal energy transfer, the entropy of the water/
ice mixture will increase, while the entropy of the surroundings will decrease.
When a substance changes state from solid to liquid, or from liquid to gas,
energy is absorbed by the particles of that substance. Therefore, the kinetic
energy of the particles increases. This increased kinetic energy gives the particles
more freedom of movement and more ways of distributing the energy. Therefore,
the entropy of a gas is greater than that of a liquid, which in turn is greater than
that of a solid, under the same conditions (gure 3). For example, in gure 2, the
condensed water (liquid state) on the surface of the glass is lower in entropy than
the water vapour (gaseous state) in the atmosphere.
 Figure 2 Changes in entropy are
increase in entropy (S)

associated with every chemic al and
physic al process
solid liquid gas
 Figure 3 Entropy increases from the solid phase to the liquid phase, and from the liquid
phase to the gaseous phase
443
LHA
The total entropy change that occurs during a reaction is the sum of the entropy
changes of the reaction system and the surroundings:
ΔS = ΔS + ΔS
total system sur roundings
The second law of thermodynamics says that chemic al reactions are
spontaneous if they result in an overall increase in the total entropy value.
When the total entropy remains constant, the system is at equilibrium. If the
total entropy change is found to be negative, we say that the reaction is non-
spontaneous. In this c ase, the spontaneous reaction would proceed in the
opposite direction to the way in which it was written. For a reversible reaction, if
the forward reaction has a negative entropy change, the reverse reaction has a
positive entropy change.
Entropy change Spontaneity of reaction
spontaneous (forward reaction is
ΔS > 0
total
spontaneous)
equilibrium (neither forward nor
ΔS = 0
total
backward reaction is favoured)
non-spontaneous (reverse reaction is
ΔS < 0
total
spontaneous)
 Table 1 The second law of thermodynamics allows us to predict the direction of a
spontaneous reaction
Theories vs laws
Scientic laws, like theories, c an be used to make predictions, but, unlike
theories, laws do not have explanatory power. In this chapter, you are learning
about the second law of thermodynamics. Think of another law that you have
come across in chemistry. What predictions c an you make from it?
You c an make predictions about whether you expect a chemic al reaction to
have a positive or negative entropy change based on the degree of disorder in
the products and the reactants. Begin by examining the states of matter of all
reactants and products — remember that entropy increases from a solid to a liquid
to a gas. The coecients used to balance the equation must also be considered
when predicting changes in entropy.
444
LHA
Worked example 1
Predict whether the following reactions will have a positive or negative
entropy change, ΔS.
a. NH Cl(s) → NH (g) + HCl(g)

4 3
b. 2C H (g) + 7O (g) → 4CO (g) + 6H O(l)

2 6 2 2 2
Solution
a. In this decomposition reaction, 1 mol of solid ammonium chloride
changes into 1 mol of ammonia gas and 1 mol of hydrogen chloride gas.
• A change in state from a solid to a gas indic ates an increase in the
entropy of the system.
• The coecients balancing the equation indic ate an increase in
disorder, with 1 mol of solid changing into 2 mol of gases.
This reaction will therefore have a positive entropy change, as there is an
increase in the disorder of the system.
b. In this combustion reaction, 2 mol of ethane and 7 mol of oxygen are
converted into 4 mol of c arbon dioxide and 6 mol of water.
• A change in state from gas to liquid indic ates a decrease in the
Practice questions
entropy of the system.
• The total number of moles of products (10) is greater than that of the
1. Predict and explain whether the
reactants (9). However, the number of moles of gaseous products

following reactions will have
(4) is lower than that of the gaseous reactants (9). Since gases have
a positive or negative entropy
much higher entropy values than liquids or solids, we c an ignore

change, ΔS.
condensed phases and pay attention only to gases. The decrease in

a. NH NO (s) → N O(g) +
4 3 2
the number of moles of gases, from 10 to 4, means that the overall

2H O(l)
2
order of the system increases.
b. N (g) + 3H (g) → 2NH (g)

2 2 3
This reaction will therefore have a negative entropy change, as there is a
c. N O (g) → 2NO (g)

2 4 2
decrease in the disorder of the system.
d. C aCO (s) → C aO(s) + CO (g)

3 2
C alculating entropy changes
Entropy is a state function, so a change in entropy across a reaction c an be
determined by the dierence between the nal entropy and the initial entropy
ofthe reacting species. Therefore, the standard entropy change, ΔS , of a
system c an be c alculated from standard entropy values, S , of the reactants and
the products.
⦵ ⦵ ⦵
ΔS = ∑S (products) − ∑S (reactants)
The ⦵ symbol indic ates standard conditions. Standard entropy values of some
substances are given in section 13 of the data booklet. The units for standard
1 1
entropy values are J K mol
445
LHA
When performing entropy change c alculations, the following points need to be
considered:
• Remember that values for entropy are specic for dierent states of matter, for
⦵ 1 1 ⦵ 1 1
example, S (H O(g)) = 189 J K mol while S (H O(l)) = 70 J K mol

2 2
• The coecients used to balance the equation must be applied to standard
entropy values when c alculating the entropy change for a reaction.
• Examine the chemic al reaction and predict whether you expect the reaction
to have a positive or negative entropy change, based on the degree of
disorder in the products and reactants. This prediction c an be used to check
your nal c alculation.
Worked example 2
C alculate the standard entropy change for the following reactions

⦵ −1 −1
Substance S / J K mol
using the standard entropy values given in thetable.
H (g) 131
2
a. H (g) + Cl (g) → 2HCl(g)

2 2
Cl (g) 223
1 2
b. H (g) + O (g) → H O(l)

2 2 2
2 O (g) 205
2
c. N O (g) → 2NO (g)

2 4 2
N O (g) 304
2 4
d. NH Cl(s) → NH (g) + HCl(g)

4 3
NO (g) 240
2
Solution NH Cl(s) 95
4
⦵ ⦵ ⦵
NH (g) 193
a. ΔS = ∑S (products) − ∑S (reactants) 3
⦵ ⦵ ⦵
HCl(g) 187
= [2S (HCl(g))] − [S (H (g)) + S (Cl (g))]
2 2
H O(l) 70
= (2 × 187) − (131 + 223) 2
1 1
= +20 J K mol
The entropy change is small and positive, indic ating a small increase in disorder.
The value is small bec ause there is no change in the number of moles of gas from
reactants to products.
1
⦵ ⦵ ⦵ ⦵
b. ΔS = [S (H O(l))] − [S (H (g)) + S (O (g))]

2 2 2
205
= (70) − (131 + )
1 1
= −164 J K mol
The large negative entropy change associated with this reaction indic ates a large
decrease in disorder (greater order), with 1.5 mol of gases changing into1 mol of
a liquid.
⦵ ⦵ ⦵
c. ΔS = [2S (NO (g))] − [S (N O (g))]

2 2 4
= (2 × 240) − (304)
1 1
= +176 J K mol
This reaction has a large positive entropy change that reects an increase in disorder,
from 1 mol of gas on the reactant side to 2 mol of gases on the productside.
⦵ ⦵ ⦵ ⦵
d. ΔS = [S (NH (g)) + S (HCl(g))] − [S (NH Cl(s))]

3 4
= (193 + 187) − (95)
1 1
= +285 J K mol
Transforming 1 mol of a solid into 2 mol of gases results in a large increase in disorder,
hence the large positive entropy change.
446
LHA
Practice questions
2. Which reaction c auses the greatest increase in entropy of the system?
A. HCl(g) + NH (g) → NH Cl(s)

3 4
B. (NH ) Cr O (s) → Cr O (s) + N (g) + 4H O(g)

4 2 2 7 2 3 2 2
C. C aCO (s) → C aO(s) + CO (g)

3 2
D. I (g) → I (s)
2 2
3. Which is correct for the reaction H O(g) → H O(l) ?

2 2
A. Enthalpy increases and entropy increases.
B. Enthalpy decreases and entropy increases.
C. Enthalpy increases and entropy decreases.
D. Enthalpy decreases and entropy decreases.
1 1
4. Determine the standard entropy change, in J K mol , for the
decomposition of dinitrogen monoxide:
N O(g) → N (g) + O (g)

2 2 2
Linking question
⦵ 1 1
N O(g) 220
2
Why is the entropy of a perfect
N (g) 192 crystal at 0 K predicted to be zero?

2
(Structure 1.1)
O (g) 205
2
Gibbs energy (Reactivity 1.4.2 and
Reactivity1.4.3)
An increase in heat energy (enthalpy) within a reaction system will result in
increased movement of particles, leading to greater disorder and an increase in
the entropy of the system. Therefore, you need to consider the eects that both
changes in enthalpy and entropy have on the spontaneity of a chemic al reaction:
• Exothermic reactions are more likely to be spontaneous, as this leads to a
decrease in enthalpy, and therefore greater stability of the reaction products.
• An increase in entropy makes reactions more likely to be spontaneous, as
greater disorder leads to a more random distribution of energy within the
system.
However, reactions that are spontaneous, and therefore thermodynamic ally
favourable, c an sometimes be kinetic ally unfavourable due to their high
activation energies.
The impact that the enthalpy change of a reaction has on the entropy of the
surroundings depends on the conditions existing in the system. Imagine if heat
energy is transferred into two separate systems, one at low temperature and one
at high temperature, such as a block of ice at 0 °C and a bowl of water at 60 °C.
Will the transfer of the same amount of energy into each system have the same
eect? The ice will begin to melt as the kinetic energy of the water molecules
increases, resulting in a signic ant change in entropy. However, the hot water
already has signic ant disorder compared to the ice, so the additional energy will
have a much less marked eect on the system entropy.
447
LHA
The combination of enthalpy, entropy and temperature of the system c an be used
to dene a new state function c alled Gibbs energy, G. The change in Gibbs
energy, ΔG, is the maximum amount of energy that c an be obtained from a
system. The change in Gibbs energy, ∆G, is related to the change in enthalpy,
ΔH, the change in entropy, ΔS, and the absolute temperature of the system, T,
according to the following equation:
⦵ ⦵ ⦵
∆G = ∆H − T∆S
The units of change in Gibbs energy are kJ mol . ΔG takes into account the direct
entropy change of the system resulting from the transformation of the chemic als
and theindirect entropy change of the surroundings resulting from the transfer of
heatenergy.
At constant pressure, a reaction is spontaneous if the change in Gibbs energy has
a negative value (∆G < 0). Therefore, if we know the enthalpy change, entropy
change and temperature, we c an determine whether a reaction is spontaneous
under standard conditions. This is summarized in table 2.
⦵ ⦵ ⦵
∆H ∆S ∆G Spontaneity
negative (< 0) at high T spontaneous only at high
positive (> 0): endothermic positive (> 0): more disorder

⦵ ⦵
positive (> 0) at low T temperatures when T∆S > ∆H
non-spontaneous at any
positive (> 0): endothermic negative (< 0): more order always positive (> 0)
temperature
negative (< 0): exothermic positive (> 0): more disorder always negative (< 0) spontaneous at any temperature
negative (< 0) at low T spontaneous only at low
negative (< 0): exothermic negative (< 0): more order

⦵ ⦵
positive (> 0) at high T temperatures when T∆S > ∆H
 Table 2 Factors aecting ΔG and the spontaneity of a reaction
It is not possible to predict whether every chemic al reaction is spontaneous.
Exothermic reactions with an increase in disorder will always be spontaneous,
with ∆G < 0. Similarly, endothermic reactions with a decrease in disorder will
always be non-spontaneous, with ∆G > 0. The spontaneity of other reactions
⦵ ⦵ ⦵
depends on the temperature of the system: if T∆S > ∆H , the value of ∆G will
⦵ ⦵ ⦵
be negative, while at T∆S < ∆H the value of ∆G will be positive.
C alculating the change in Gibbs energy for a reaction
To determine the spontaneity of a reaction under standard conditions, we need to
calculate the change in Gibbs energy for the reaction under the same conditions
⦵ ⦵ ⦵ ⦵ ⦵
using ∆G = ∆H − T∆S . We c an c alculate ∆H and ∆S for the reaction using
the thermodynamic data given in the data booklet.
448
LHA
Worked example 3
An equation for the combustion of propane is given c. Predict, giving a reason, whether the entropy
below. change, ∆S , for this reaction is negative or positive.
⦵ 1 1
d. C alculate ∆S for the reaction in J K mol , using
C H (g) + 5O (g) → 3CO (g) + 4H O(g)

3 8 2 2 2
the standard entropy values in section 12 of the data
a. Determine the standard enthalpy change, ∆H , in
booklet. The standard entropy for oxygen gas is
kJ mol , for this reaction, using the bond enthalpy 1 1
205 J K mol
data in section 11 of the data booklet.
e. C alculate the standard Gibbs energy change,
b C alculate the standard enthalpy change, ∆H , ⦵ 1
∆G , in kJ mol , for the reaction at 5 °C, using your
in kJ mol , for this reaction using the enthalpy of
answers to (b) and (d).
formation data in section 12 of the data booklet.
Solution
⦵ ⦵ ⦵
a. In the reactants, there are eight C–H bonds, two C C d. ΔS = ∑S (products) − ∑S (reactants)
bonds and ve O=O bonds. In the products, there
⦵ ⦵
= [3S (CO (g)) + 4S (H O(g))]

2 2
are six C=O bonds and eight O–H bonds. Therefore,
⦵ ⦵
− [S (C H (g)) + 5S (O (g))]
3 8 2
the enthalpy change for the reaction is as follows:
⦵
= [(3 × 214) + (4 × 189)]
ΔH = ∑(BE of bonds broken) − ∑(BE of bonds
− [(270) + (5 × 205)]
formed)
= 1398 − 1295
= [8BE(C–H) + 2BE(C–C) + 5BE(O=O)]
− [6BE(C=O) + 8BE(O H)] 1 1
= +103 J K mol
e. First, convert temperature from °C into K:

= [(8 × 414) + (2 × 346) + (5 × 498)]
− [(6 × 804) + (8 × 463)]
T = 5 + 273.15 = 278.15 K
1 1
= 6494 − 8528
Then, convert the entropy value into kJ K mol from
1 1
J K mol by dividing by 1000:

1
= −2034 kJ mol
–1 –1
+103 J K mol
⦵ −1 −1
∆S = = +0.103 kJ K mol
This reaction is exothermic.
1000
b. Use the equation:

Finally, substitute the values obtained into the
⦵ ⦵ ⦵
equation for change in Gibbsenergy:
ΔH = ∑(∆H products) − ∑(∆H reactants)

f f
⦵ ⦵ ⦵
⦵ ⦵
∆G = ∆H − T∆S
= [3∆H (CO ) + 4∆H (H O(g))]

f 2 f 2
− [∆H (C H )] −1
f 3 8
= −2045 kJ mol − (278.15 K ×
−1 −1
0.103 kJ K mol )
= [(3 × (−394)) + (4 × (−242))] − [−105]
−1
= −2074 kJ mol
= −2150 + 105
1
The negative value for the Gibbs energy change
= −2045 kJ mol
indic ates that the reaction is spontaneous. You c an
Alternatively, use the summation of equations method
predict this by looking at table 2 earlier in the topic:
or the enthalpy cycle diagrams method.
the negative value for enthalpy change and the
c. The change in entropy value for this reaction should

positive value for entropy change suggest that the
be positive (ΔS > 0) bec ause there is an increase in

reaction will be spontaneous at any temperature.
the number of moles of gaseous species from 6 mol
to 7 mol.
449
LHA
You c an practise c alculating ∆H Practice questions
from bond enthalpy data and
5. Ethane-1,2-diol, HOCH CH OH, reacts with thionyl chloride, SOCl ,

2 2 2
enthalpy of formation data using
according to the equation below.
the material in Reactivity 1.2.
HOCH CH OH(l) + 2SOCl (l) → ClCH CH Cl(l) + 2SO (g) + 2HCl(g)

2 2 2 2 2 2
a. C alculate the standard enthalpy change for this reaction using the
following enthalpy of formation data.
Substance HOCH CH OH(l) SOCl (l) ClCH CH Cl(l) SO (g) HCl(g)

2 2 2 2 2 2
ΔH /
f
−453 −246 −165 −297 −92

1
kJ mol
b. C alculate the standard entropy change for this reaction using the
following data.
Substance HOCH CH OH(l) SOCl (l) ClCH CH Cl(l) SO (g) HCl(g)

2 2 2 2 2 2
S /
167 279 209 248 187

1 1
J K mol
c. The standard Gibbs energy change, ΔG , for the above reaction is
−103 kJ mol at 298 K.
Suggest why ΔG has a large negative value considering the sign of
ΔH in part (a).
In a reaction where the change in enthalpy ΔH is positive (endothermic) and the
change in entropy ΔS is also positive (more disorder), the value of Gibbs energy
change c an be either positive or negative. The spontaneity of this type of reaction
is therefore dependent on the temperature of the system:
⦵ ⦵ ⦵
• At high temperature, TΔS > ΔH and ΔG is negative (spontaneous reaction)
⦵ ⦵ ⦵
• At low temperature, TΔS < ΔH and ΔG is positive (non-spontaneous
reaction)
This means that the temperature at which ∆G = 0 is the temperature above
which the reaction becomes spontaneous.
⦵ ⦵
0 = ∆H − T∆S
Rearranging the equation in terms of T gives:
∆H
T =
⦵
∆S
This expression c an be used to determine the temperature above which an
endothermic reaction with positive entropy change becomes spontaneous.
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LHA
Worked example 4
Hydrogen gas c an be produced industrially by the reaction of natural gas
with steam. The standard enthalpy change and entropy change of the
reaction are given.
⦵ 1
CH (g) + H O(g) → 3H (g) + CO(g) ∆H = 205 kJ mol

4 2 2
⦵ 1 1
∆S = 216 J K mol
⦵ 1
a. C alculate the standard Gibbs energy change, ΔG , in kJ mol , for the
reaction at 298 K.
b. Determine the temperature, in K, above which the reaction becomes
spontaneous.
Solution
⦵ ⦵ ⦵
a. ∆G = ∆H − T∆S
1 1 1
= 205 kJ mol − (298 K × 0.216 kJ K mol )
= +141 kJ mol
The positive value for the change in Gibbs energy indicates that the
reaction is non-spontaneous at 298 K. This can be predicted given the
positive value of enthalpy change (endothermic) and the low temperature.
b. M ake the assumption that the value for Gibbs energy is 0, and solve for T
⦵ ⦵
0 = ΔH − TΔS
0 = 205 − (T × 0.216)
205
T =
0.216
= 949 K
The reaction becomes spontaneous at a temperature greater than 949 K.
Practice questions
6. An equation for the hydrogenation of ethene is given below.
C H (g) + H (g)→ C H (g)

2 4 2 2 6
⦵ 1
a. Determine the standard enthalpy change, ∆H , in kJ mol , for this
reaction, using section 12 of the data booklet.
⦵ 1
b. C alculate the standard enthalpy change, ∆H value, in kJ mol , for this
reaction using section 13 of the data booklet.
c. Predict, giving a reason, whether the standard entropy change, ∆S ,
for this reaction is negative or positive.
⦵ 1 1
d. C alculate the ∆S value, in J K mol , for the reaction, using
section 13 of the data booklet. The standard entropy for
1 1
hydrogen gas is 131 J K mol
⦵ 1
e. C alculate the standard Gibbs energy change, ΔG , in kJ mol , for the
reaction at 150 °C, using your answers to (b) and (d). Use section 1 of
the data booklet.
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LHA
ATL Thinking skills
The chemistry guide states: “ΔG takes into account the direct entropy change
resulting from the transformation of the chemic als and the indirect entropy
change of the surroundings resulting from the transfer of heat energy.”
Explain, as fully as you c an, how the reaction described below illustrates this
statement.
The reaction between solid ammonium chloride and hydrated barium
hydroxide is endothermic:
2NH Cl(s) + Ba(OH) •8H O(s) → 2NH (g) + BaCl (aq) + 10H O(l) ∆H > 0
4 2 2 3 2 2
When the two white solid reactants are mixed together, the mixture quickly
turns into a slush and becomes so cold that it c an easily freeze a few drops of
water placed between the reaction ask and the block of wood underneath
(gure 4).
 Figure 4 The reaction between barium hydroxide and ammonium chloride is
endothermic
Linking question
How c an electrochemic al data also be used to predict the spontaneity of a
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LHA
The eect of temperature on spontaneity
In this skills task, you will investigate the effect of temperature, T, at which it went cloudy. The results are
temperature on the spontaneity of a process where a shown in table3.
polymer dissolves in water.
Solution composition T / °C
Relevant skills
PNIPAM in 0.3 mol dm LiCl 29.5

• Inquiry 1: Formulate hypotheses
• Inquiry 2: Interpret qualitative and quantitative data PNIPAM in 0.5 mol dm LiCl 27.1
• Inquiry 3: Relate the outcomes of an investigation to 3
PNIPAM in 0.3 mol dm LiBr 31.5
the stated research question or hypothesis

3
PNIPAM in 0.5 mol dm LiBr 30.7
Poly(N-isopropylacrylamide) (PNIPAM) is a polymer that
PNIPAM in water 32.5
dissolves in water, producing a clear solution. On heating,
PNIPAM precipitates out, c ausing the solution to become

 Table 3 The eect of varying LiCl and LiBr concentration on
cloudy (figure 5).

the temperature at which dissolution becomes non-spontaneous
for PNIPAM solutions (Source of data: D. E. Bergbreiter, A. J.
Mijalis, and H. Fu, J. Chem. Educ., 89 (5), pp. 675–677, 2012)
Questions
1. State the signs of ∆H and ∆S for the dissolution of
PNIPAM.
2. Explain in your own words why the dissolution of
PNIPAM is spontaneous at low temperatures, but
non-spontaneous at high temperatures.
3. Identify some of the control variables needed for the
experiment used to gather the data in table 3.
 Figure 5 PNIPAM (represented by the black lines) forms
4. The results in table 3 can be used to derive conclusions

hydrogen bonds with water and dissolves. This is shown on
about how two dierent factors aect the temperature

the le. At a certain temperature, PNIPAM no longer forms
at which dissolution becomes non-spontaneous, T:

hydrogen bonds and makes an insoluble precipitate. This is
shown on the right • the presence or absence of an aqueous ionic
compound
The reason for this temperature-dependent change is
• the concentration of an aqueous ionic compound.
explained using ∆G = ∆H − T∆S. The polymer dissolves
Choose one of the two factors to focus on.

due to the formation of hydrogen bonds between
water and the amido groups loc ated along the polymer
a. Identify which of the results in table 3 allow you to
chain. This dissolution process is exothermic and it

explore this relationship.
has a negative entropy change bec ause of the regular
b. With reference to the results you have identied,
arrangement of water molecules it requires. The process is
describe how the factor you chose aects T
therefore favourable in terms of enthalpy and unfavourable
in terms of entropy. At high temperatures, the entropy c. Using your knowledge of ion–dipole interactions,
term, T∆S, exceeds the enthalpy term, ∆H, making ∆G entropy and Gibbs energy, construct a hypothesis
positive, so the dissolution becomes non-spontaneous. of the eect of your chosen factor on T
Bergbreiter, Mijalis and Fi (2012) explored the effect of d. Discuss the extent to which the data in table 3 is
varying concentrations of LiCl and LiBr on the temperature at sucient to construct your hypothesis.
which dissolution of PNIPAM becomes non-spontaneous.
e. Give examples of further experiments that could
They slowly heated a PNIPAM solution and monitored the
be c arried out to explore your hypothesis.
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LHA
ΔG and equilibrium (Reactivity 1.4.4)
The ratio of concentration of products to reactants is c alled the reaction
quotient, Q
concentration of products
Q =
concentration of reactants
Chemic al equilibrium is achieved when the forward and backward reactions in
a reversible reaction occur at the same rate. The equilibrium arrow, ⇌, is used
instead of the normal reaction arrow to show reversible reactions. The Haber
process used to make ammonia is an example of a reversible reaction.
The concentration of
products is greater than that

N (g) + 3H (g) ⇌ 2NH (g)
2 2 3
Q > K at equilibrium, so the reverse
reaction is favoured until the When a chemic al system has reached equilibrium, the ratio of concentrations of
equilibrium is reached. products to concentrations of reactants is c alled the equilibrium constant, K
The concentration of
You c an compare the reaction quotient, Q, to the equilibrium constant, K, to
reactants is greater than that

determine the progress of the reaction as it moves towards equilibrium and the
Q < K at equilibrium, so the forward

direction (either forward or backwards) of the reaction that is favoured to establish
reaction is favoured until the

equilibrium. This is described in table 4.
equilibrium is reached.
We have already established in this topic how the change in Gibbs energy, ΔG,
The system is at equilibrium,
c an describe the spontaneity and temperature dependence of a reaction. When
Q = K so the forward and reverse
ΔG < 0, reactions taking place at constant pressure are spontaneous. From
reactions occur at equal rates.
the time a reaction begins, the Gibbs energy changes as the ratio of reactants
to products changes. For reversible reactions, the minimum Gibbs energy is

 Table 4 The relationship between the
reaction quotient, Q, and the equilibrium

reached at the point of equilibrium. At this minimum, ΔG = 0. Aer this point, the
constant, K Gibbs energy increases (gure 6).
G(reactants)
ΔG
ygrene sbbiG
G(products)
equilibrium
1 mol reactant 0 mol reactant
0 mol product 1 mol product
 Figure 6 How the Gibbs energy changes as a reversible reaction proceeds
454
LHA
Examine the shape of the curve and the ratio of reactants to products as the Gibbs
energy changes. You will notice that in region A, the forward reaction is favoured,
as the amounts of reactants decrease and the amounts of products increase.
At the point of equilibrium (Q = K), the Gibbs energy reaches a minimum and
then increases again. From this point onwards, the forward reaction becomes
non-spontaneous (region B), as it is now associated with a positive Gibbs energy
change. The reverse reaction in region B is therefore spontaneous until the Gibbs
energy reaches a minimum in the same way as during the forward reaction.
Relationship between ΔG, Q, K and T
At any point during a reaction, the ratio of reactants to products is dierent. The
reaction quotient, Q, gives you a snapshot of the ratio of reactants to products
at a given point in the reaction pathway. If you know the standard Gibbs energy
change for a reaction, ΔG , and the temperature, T, you c an determine the
change in Gibbs energy for the position indic ated by the reaction quotient, Q,
using the following equation:
ΔG = ΔG + RT lnQ
1 1
where R, the gas constant = 8.31 J K mol .
In gure 6, you saw that in a reversible reaction at the point of equilibrium,
ΔG = 0. At the point of equilibrium, Q = K. We c an substitute this information
into the equation above to nd the relationship between the standard Gibbs
energy change, ΔG , temperature, T, and the equilibrium constant, K:
ΔG = −RT lnK
You will nd these expressions in section 1 of the data booklet.
If the equilibrium constant is the unknown value, you c an rearrange the last
expression in terms of K
ΔG
RT
K = e
When the equilibrium constant K is determined for a reversible reaction, its value
indic ates whether the products or reactants are favoured at equilibrium. The
Gibbs energy change for a given reaction is an indic ation of whether the forward
or reverse reaction is favoured. The relationship between the standard Gibbs
energy change, ΔG , and the equilibrium constant, K, is summarized in table 5.
Equilibrium constant Description Standard Gibbs
energy change
K = 1 neither reactants nor ΔG = 0
products favoured
K > 1 products favoured ΔG < 0
K < 1 reactants favoured ΔG > 0
 Table 5 The values of K and ΔG indic ate whether products or reactants are favoured
atequilibrium
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LHA
Worked example 5
The synthesis of ammonia is an important industrial b. Substitute the ΔG value from (a), and the values of R
process that provides feedstock for the production of and T, into ΔG = −RT lnK. Remember that the units
fertilizers, plastics, explosives and pharmaceutic als. of gas constant, R, include J, notkJ, so the ΔG value
must be converted from kJ to J.
⦵ 1
N (g) + 3H (g) ⇌ 2NH (g) ΔH = −92 kJ mol

2 2 3
⦵ 1 1 ⦵
ΔS = −202 J K mol ΔG = −RT lnK
T = 298 K 1 1 1
−31800 J mol = −(8.31 J K mol × 298 K) lnK
a. Find the standard Gibbs energy change, ΔG , for Rearrange in terms of K:
the forward reaction and determine whether the
–31800
reaction is spontaneous.
lnK =
–(8.31 × 298)
b. Determine the equilibrium constant, K, for the
–31800
reaction and state whether you expect the forward
[–(8.31 × 298) ]
K = e
reaction to be favourable.
= 3.77 × 10
c. At a given point during the reaction, the reaction
quotient, Q, was 1 × 10 . Determine the change This large positive value of K tells us that the formation
in Gibbs energy, ΔG, of the forward reaction at of ammonia at room temperature is very favourable.
this point, and comment on the spontaneity of the
c. ΔG = ΔG + RT lnQ
reaction.
1 1 1
= −31800 J mol + (8.31 J K mol ) × 298 K
Solution 6
× ln(1 × 10 )
⦵ ⦵ ⦵
a. ∆G = ∆H − T∆S 1 1
= 2410 J mol = 2.41 kJ mol
1 1 1
= −92 kJ mol − 298 K × (−0.202 kJ K mol )
ΔG is positive, so the reaction is not spontaneous at
= −31.8 kJ mol
this point in the reaction pathway.
Practice questions
7. Consider the reaction between nitrous oxide (N O) and oxygen in the

2
formation of nitrogen dioxide (NO ).

2
2N O(g) + 3O (g) → 4NO (g)

2 2 2
⦵ 1
a. Determine the value of ∆H , in kJ mol , for the reaction using the
values in the table.
Substance N O(g) NO (g)

2 2
⦵ 1
ΔH / kJ mol 82 33.2
f
⦵ 1 1
b. C alculate the standard entropy change, ΔS , in J K mol , for the
reaction.
Substance N O(g) NO (g) O (g)

2 2 2
⦵ 1 1
S / J K mol 220 240 205
⦵ 1
c. C alculate the standard Gibbs energy change, ΔG , in kJ mol , for the
reaction at 298 K using your answer to (a) and (b).
d. C alculate the equilibrium constant at 298 K for the reaction.
456
LHA
⦵
Graphing the relationship between ∆G and T
In this task, you will explore the relationship between Method
∆G and T for the following process:
Part 1: C alculation
H O(l) → H O(g) 1. Predict and explain, with reference to the equation

2 2
above, the sign of ∆S
Relevant skills
2. Predict the sign of ∆H . Explain your reasoning.

• Tool 3: Use basic arithmetic and algebraic c alculations 3. Deduce how the spontaneity of the reaction changes
to solve problems with temperature.
• Tool 3: Sketch graphs with labelled but unsc aled
4. With reference to section 13 in the data booklet,
axes, to qualitatively describe trends ⦵ ⦵ ⦵
c alculate ∆H , ∆S and ∆G for the reaction at
• Tool 3: Interpret features of graphs including gradient

298 K. Show yourworking.
and intercepts
5. Calculate the temperature at which the spontaneity of
• Inquiry 2: Interpret diagrams, graphs and charts
the reaction changes.
6. The temperature value you have just c alculated
corresponds to the boiling point of water. C alculate
the percentage error of your value.
Part 2: Graphing the relationship between ∆G and T
7. Using a spreadsheet, compute the value of ∆G at
dierent temperatures. A suggested layout and formulas
are shown in gure 7.
Values:
fx =$B$4 (D5*$B$5/1000)
5
 B  D 
1 Reaction: H ) -> H )

 
 Thermodynamic parameters: D ata or raphic a anaysis:
1
4 ΔH 44 T/  ΔG/  mo
5 119 98 858

ΔS
 8 0 44
ΔG
 100 1
8 00 0
9 00 8
10 400 
11 500 155
Formulas:
fx =$B$4 (D5*$B$5/1000)
5
 B  D 
1 Reaction: H ) -> H )

 
 Thermodynamic parameters: D ata or raphic a anaysis:
1
4 ΔH 44 T/  ΔG/  mo
5 119 98 =$B$4 D5*$B$5/1000)

ΔS
 8 0 =$B$4 D*$B$5/1000)
ΔG
 =D +100 =$B$4 D*$B$5/1000)
8 =D +100 =$B$4 D8*$B$5/1000)
9 =D8 +100 =$B$4 D9*$B$5/1000)
10 =D9 +100 =$B$4 D10*$B$5/1000)
11 =D10 +100 =$B$4 D11*$B$5/1000)
 Figure 7 A possible spreadsheet arrangement for this task. The values (top) were c alculated using the formulas shown at the bottom.
The sign $ in the formulas is an absolute cell reference. It tells the spreadsheet to retrieve the same value every time. Note that the input
parameters in the yellow boxes are where you would enter the reaction being studied and the values c alculated in step 4 above
457
LHA
8. Plot a graph of ∆G vs. T. Include a line or curve of best t, axis labels, units, minor gridlines and a title.
⦵ ⦵ ⦵
9. With reference to the equation ∆G = ∆H − T∆S , identify the signic ance of the:
• gradient
• y-intercept
• x-intercept
10. Use your graph to approximate the temperature at which the process becomes spontaneous. How does it compare
to the value you c alculated in step 5?
11. Explain why the graph:
• is linear
• shows a negative relationship (has a negative gradient).
Part 3: Further exploration
⦵ ⦵
12. Below are examples of reactions for each of the three other possible combinations of ∆H and ∆S :
⦵ ⦵
• positive ∆H and negative ∆S (for example, formation of ethene, C H (g), from graphite and diatomic hydrogen)
2 4
⦵ ⦵
• negative ∆H and positive ∆S (for example, transformation of diamond into graphite)
⦵ ⦵
• negative ∆H and negative ∆S (for example, formation of ammonia from diatomic nitrogen and diatomichydrogen).
Using these examples or dierent reactions of your choice, search online databases for thermodynamic data that will
⦵ ⦵
allow you further explore the relationship between ∆G and T for the three other possible combinations of ∆H and
∆S . You will need to repeat the steps in Parts 1 and 2 for each reaction.
13. Sketch the four graphs on one pair of axes.
14. Explain the dierences in gradient and y-intercept between the four graphs you sketched above.
This chapter contains concepts that involve dierent types of c alculations.
M ake a list of the common mistakes, such as forgetting to convert J into kJ, or
°Cinto K and not including negative signs. For each, consider:
• Why might someone make this mistake?
• How could they avoid it?
Write three multiple-choice questions that specic ally check for some of the
common mistakes you have identied. Then, share your questions with a
partner and quiz each other.
Linking question
What is the likely composition of an equilibrium mixture when ΔG is
positive? (Reactivity 2.3)
458
LHA
LHA
b. The standard enthalpy change, ΔH , for the
Topic review
1
hydrogenation of propene is −124.4kJ mol .

Predict the temperature above which the

hydrogenation reaction is non-spontaneous. [2]
What determines the direction of chemical change?

6. A molecule of citric acid, C H O , is shown.
6 8 7
OH
O
O O
2. Which system has the most negative entropy change,
HO OH
ΔS, for the forward reaction?

OH
A. N (g) + 3H (g) ⇌ 2NH (g)

2 2 3
The equation for the rst dissociation of citric acid in water is
B. C aCO (s) → C aO(s) + CO (g)

3 2
+
C H O (aq) + H O(l) ⇌ C H O (aq) + H O (aq)

6 8 7 2 6 7 7 3
2 2
C. 2S O (aq) + I (aq) → S O (aq) + 2I (aq)

2 3 2 4 6
The value of K for this reversible reaction at 298 K
D. H O(l) → H O(g)
2 2
4
is 5.01 × 10 .
3. Which combinations of values will result in a a. C alculate the standard Gibbs energy change,
⦵ 1
spontaneous reaction? ΔG , in kJ mol , for this reaction at 298 K,
usingsection 1 of the data booklet. [1]
⦵ 1 ⦵ 1 1
ΔH / kJ mol ΔS / J K mol T / K
b. Comment on the spontaneity of the reaction
at298 K. [1]
I −100 −100 300
II +100 −100 300 7. The reaction for the formation of liquid
tetrac arbonylnickel is shown below:
III +100 +100 1500
Ni(s) + 4CO(g) ⇌ Ni(CO) (l)

4
A. I and II only C. II and III only

⦵
a. C alculate the standard entropy change, ΔS ,
B. I and III only D. I, II and III 1 1
ofthe forward reaction, in J K mol , using the
values given. [2]
A. If ΔH < 0, the reaction is always spontaneous. ⦵ 1 1
B. If ΔH > 0, the reaction is never spontaneous.
Ni(s) 3
C. If ΔS < 0, the reaction c an be spontaneous if the
CO(g) 198
temperature is low enough.
Ni(CO) (l) 313

D. If ΔS < 0, the reaction c an be spontaneous if the 4
⦵
temperature is high enough.
b. C alculate the standard enthalpy change, ΔH ,
ofthe forward reaction in kJ mol . [1]
⦵ 1
Substance ΔH / k J mol
f
5. The hydrogenation of propene produces propane.
CO(g) −110.5
C H (g) + H (g) → C H (g)
3 6 2 3 8
a. C alculate the standard entropy change, ΔS , Ni(CO) (l) −633.0

4
for the hydrogenation of propene. [2]

c. Use your answers to (a) and (b) to
determinethe temperature, in °C, below

⦵ 1 1
Substance ΔS / J K mol
which the reaction becomes favourable. [3]
H (g) +131
2
d. At a given point in the forward reaction pathway, the
reaction quotient, Q, is equal to 0.5. Calculate the

C H (g) +267
3 6
Gibbs energy change, ΔG, at this point and determine
C H (g) +270
3 8
whether the reaction is spontaneous at this point. [2]
459
H ow much, h ow fast and
h ow far?
Reactivity 2.1 How much? The amount of
chemical change
How are chemical equations used to calculate reacting ratios?
Chemical equations contain essential information about the It is important to understand that a chemic al equation
nature of chemical changes, the participating species, the reects only the changes in amounts or volumes of
states of these species and the proportions in which they are reacting species, but not the initial or nal quantities of
consumed or produced. In chemical changes, atoms can be these species. In many c ases, one of the reactants may
combined or rearranged, but never created or destroyed. be present in excess, or the reaction may not come to
So, the total number of atoms of each type remains constant completion. Even in these c ases, the mole ratios c an be
when reactants are transformed into products. As a result, used to c alculate any unknown quantity (amount, volume,
all species participating in a chemical reaction are used up mass and so on) of a reactant or product from given
or formed in xed mole ratios, which are described by the quantities of other species participating in the reaction.
stoichiometric coecients before these species. For gases,
the volumes of reacting species are also proportional to
their stoichiometric coecients.
Understandings
Reactivity 2.1.1 — Chemic al equations show the ratio of Reactivity 2.1.3 — The limiting reactant determines the
reactants and products in a reaction. theoretic al yield.
Reactivity 2.1.2 — The mole ratio of an equation c an be Reactivity 2.1.4 — The percentage yield is c alculated from
used to determine: the ratio of experimental yield to theoretic al yield.
• the masses and/or volumes of reactants and products Reactivity 2.1.5 — The atom economy is a measure of
eciency in green chemistry.
• the concentrations of reactants and products for
reactions occurring in solution.
Stoichiometry and the mole ratio
(Reactivity 2.1.1)
Stoichiometry is the quantitative study of the reactants and products involved
in a chemic al reaction. If you know the reactants and products, you c an write
a balanced chemic al equation by adding stoichiometric coecients before
each species to ensure that the number of each type of atom in the reactants and
products is identic al.
TOK
On the internet, nd the Wikipedia article on Stoichiometry. Then, select a
language that you are not familiar with from the menu on the le of the page.
Even though you will not be able to read the text, you will probably recognize
many of the diagrams, chemic al equations and related mathematic al
c alculations.
Chemic al equations describe processes using a universal and internationally
adopted set of symbols. To what extent does the use of universal “languages”
help knowledge development?
461
Reactivity 2 How much, how fast and how far?
Worked example 1
Ethane gas, C H , is completely combusted in oxygen, O , to form c arbon dioxide, CO , and water, H O, under
2 6 2 2 2
standard conditions. Write a balanced equation for this reaction.
Solution
First, write the unbalanced equation for the reaction, with • There are two oxygen atoms in the reactants and now
the reactants on one side of the reaction arrow and the seven in the products. Write the coecient “3.5”
products on the other: before O to balance the oxygen atoms.

2
C H + 3.5O → 2CO + 3H O
C H + O → CO + H O 2 6 2 2 2
2 6 2 2 2
Then, count the number of atoms of each type on both

• To get a whole-number ratio, multiply each coecient
sides of the equation, adding stoichiometric coecients

by 2.
where required:
2C H + 7O → 4CO + 6H O
2 6 2 2 2
• There are two carbon atoms in the reactants, and one
• If you know the physic al states of the species involved
in the products. Write the coecient “2” before CO to

2
in the reaction, you should write the state symbols
balance the carbon atoms.
aer each species:
C H + O → 2CO + H O
2 6 2 2 2
2C H (g) + 7O (g) → 4CO (g) + 6H O(l)

2 6 2 2 2
• There are six hydrogen atoms in the reactants and two
in the products. Write the coecient “3” before H O

2
to balance the hydrogen atoms.
C H + O → 2CO + 3H O
2 6 2 2 2
Practice questions
1. The anaerobic fermentation of glucose, C H O , forms ethanol, C H OH,

6 12 6 2 5
and c arbon dioxide, CO . Write the balanced equation for this reaction.
2
The stoichiometric coecients in a balanced chemic al equation are proportional
State Symbol
to the amounts of reacting species. The ratio of the stoichiometric coecients is
solid s
c alled the mole ratio. Reactants will always react in relative amounts equal to the
liquid l
mole ratio of the reactants, to produce relative amounts of the products equal to
the mole ratio of the products.

gas g
aqueous solution aq
For example, the equation for the photosynthesis of glucose, C H O , is given
6 12 6
below:
pTable 1 State symbols commonly used
in chemic al equations
6CO (g) + 6H O(l) → C H O (aq) + 6O (g)

2 2 6 12 6 2
The mole ratio of the reactants is 1 : 1, and the mole ratio of the products is 1 : 6.
This means that equal amounts of c arbon dioxide and water will be consumed in
the reaction to produce six times less glucose than oxygen.
Linking question
When is it useful to use half-equations? (Reactivity 3.2)
462
Reactivity 2.1 How much? The amount of chemic al change
Limiting reactants (Reactivity 2.1.2 and
Reactivity 2.1.3)
The relative amounts of reactants in a reaction mixture might not be equal to the
mole ratio, so some reactants could be le over even if all other reactants are
consumed completely. The limiting reactant is the reactant used up completely,
while other reactants are present in excess. It controls the amount of product
The reaction yield will be discussed

formed in the reaction and therefore the theoretic al yield of the reaction. The
in Reactivity 2.1.4.
excess reactant is the reactant that is added to the reaction mixture in a greater
proportion than that required by the mole ratio. Some of the excess reactant will
be le over when the reaction reaches completion.
For example, imagine that 1.0 mol of hydrogen is mixed with 3.0 mol of oxygen
and the mixture is ignited. An explosion occurs, and hydrogen and oxygen react
in a 2 : 1 mole ratio, producing water:
2H (g) + O (g) → 2H O(l)

2 2 2
The reaction stops when all the hydrogen is consumed: 1.0 mol of hydrogen
will react with 0.5 mol of oxygen and 2.5 mol of oxygen remains unreacted.
Therefore, the nal mixture will contain 1.0 mol of water and 2.5 mol of oxygen.
It is helpful to record the amounts of all substances as follows:
2H (g) + O (g) → 2H O(l)

2 2 2
n / mol 1.0 3.0 0

initial
Δn / mol −1.0 −0.5 +1.0
n / mol 0 2.5 1.0

nal
• The rst row under the equation represents the initial mixture, in which the
substances can be present in any proportions. We can take any amounts of
reactants and mix them together, regardless of the stoichiometric coecients.
• The second row shows how the amount of each substance changes in
the course of the reaction. The sign before each amount shows whether it
decreases (for reactants) or increases (for products). These changes must be
proportional to the mole ratio shown by the stoichiometric coecients.
• The last row represents the nal mixture, where the amounts of all substances
are calculated as n = n + Δn. As with the initial mixture, the composition

nal initial
of the nal mixture is not related to the stoichiometric coecients.
In this example, the amount of the reaction product (water) is limited by the
amount of hydrogen, which is consumed completely in the reaction. Therefore,
hydrogen is the limiting reactant and oxygen is in excess.
Practice questions You c an nd the amount of a
substance, n, from its mass, m,
2. Household lighters oen contain pressurized butane, C H , which is

4 10
m
using n = , where M is the molar
combusted upon release: M
−1
mass in g mol . Molar mass c an
2C H (g) + 13O (g) → 8CO (g) + 10H O(l)

4 10 2 2 2
be c alculated using the A values

r
Determine the limiting reactant in the following mixtures: given in the data booklet. This was
covered in Structure 1.4
a. 20 molecules of C H and 100 molecules of O

4 10 2
b. 0.20 mol of C H and 2.6 mol of O

4 10 2
c. 8.72 g of C H and 28.8 g of O

4 10 2
463
The concept of the limiting reactant allows us to determine the extent of
reaction. Consider the mixture of 1.0 mol of hydrogen and 3.0 mol of oxygen
again. If we double the amount of hydrogen, the amount of oxygen that reacts
doubles, and the amount of water formed will also double:
2H (g) + O (g) → 2H O(l) amount of 2H (g) + O (g) → 2H O(l)

2 2 2 2 2 2
hydrogen
n / mol 1.0 3.0 0 n / mol 2.0 3.0 0

initial initial
doubled
Δn / mol −1.0 −0.5 +1.0 Δn / mol −2.0 −1.0 +2.0
n / mol 0 2.5 1.0 n / mol 0 2.0 2.0

nal nal
However, if we double the amount of oxygen (which was already in excess),
the amount of hydrogen that reacts and the amount of water produced in the
reaction will not change:
2H (g) + O (g) → 2H O(l) 2H (g) + O (g) → 2H O(l)

2 2 2 amount of 2 2 2
oxygen
n / mol 1.0 3.0 0 n / mol 1.0 6.0 0

initial initial
doubled
Δn / mol −1.0 −0.5 +1.0 Δn / mol −1.0 −0.5 +1.0
n / mol 0 2.5 1.0 n / mol 0 5.5 1.0

nal nal
Worked example 2
A 16.0 g sample of c alcium c arbide, C aC (s), was placed into a sealed vessel
2
containing 19.3 dm of oxygen. The vessel was heated at 1000 °C until all
c arbide was converted into c alcium oxide, C aO(s), and c arbon dioxide,
CO (g). When the vessel was cooled down, the oxides reacted with each
2
other to produce c alcium c arbonate, C aCO (s). C alculate the mass of

3
c alcium c arbonate and the volumes of individual gases in the remaining
mixture. Assume that all reactions have come to completion. All volumes are
measured at standard temperature and pressure (STP).
Solution
First, write the balanced equation of the combustion reaction:
C aC (s) + 2.5O (g) → C aO(s) + 2CO (g)

2 2 2
Then, nd the amounts of the reactants:

Avogadro’s law states that equal
volumes of all gases, at the same
m(C aC )
2
n(C aC ) =
2
temperature and pressure, have
M(C aC )
2
the same number of molecules

16.0 g
=
–1
(Structure 1.4). At standard
64.10 g mol
temperature and pressure
= 0.250 mol
(STP), the molar volume,
3 −1
V(O )
V = 22.7 dm mol . This c an be 2
m
n(O ) =
2
V
m
used to work out the amount of gas
19.3 dm
when its volume is known, using
=
3 –1
22.7 dm mol
V
n = (Structure 1.5).
V = 0.850 mol
m
464
According to the equation, calcium carbide and oxygen react in 1 : 2.5
mole ratio. In our case, the ratio of the reactants in the reaction mixture is
0.250 : 0.850 = 1 : 3.4. Therefore, oxygen is in excess, so c alcium carbide
is the limiting reactant. All calcium c arbide will be consumed, while some
oxygen will remain unreacted:
C aC (s) + 2.5O (g) → C aO(s) + 2CO (g)

2 2 2
n / mol 0.250 0.850 0 0

initial
Δn / mol −0.250 −0.625 +0.250 +0.500
n / mol 0 0.225 0.250 0.500

nal
Next, write the balanced equation for the second reaction, in which the
oxides react with each other:
Practice questions
C aO(s) + CO (g) → C aCO (s)

2 3
3. Hydrogen and chlorine react
Calcium oxide and carbon dioxide react in a 1 : 1 mole ratio. However, the
with each other to produce
ratio of C aO to CO in the reaction mixture is 0.250 : 0.500 = 1 : 2. Therefore,

2
hydrogen chloride, HCl(g).
carbon dioxide is in excess, so calcium oxide is the limiting reactant. All calcium
3
A mixture of 4.54 dm of
oxide will be consumed, while some carbon dioxide will remain unreacted:
3
hydrogen, H (g), and 2.27 dm

2
of chlorine, Cl (g), was

2
2 3
heated until the reaction was
n / mol 0.250 0.500 0

initial
complete. All volumes are
Δn / mol −0.250 −0.250 +0.250
measured at STP.
n / mol 0 0.250 0.250

nal
a. Deduce the balanced
equation for this reaction.

The nal mixture will contain 0.250 mol of C aCO (s), 0.250 mol of CO (g) and
3 2
0.225 mol of O (g). Therefore:

2
b. Determine the limiting
reactant.
−1
m(C aCO ) = 0.250 mol × 100.09 g mol ≈ 25.0 g

3
c. C alculate the volumes,
3 −1 3
3
V(CO ) = 0.250 mol × 22.7 dm mol ≈ 5.68 dm in dm at STP, of each

2
substance in the nal

3 −1 3
V(O ) = 0.225 mol × 22.7 dm mol ≈ 5.11 dm

2
mixture.
Chemic al reactions are oen c arried out in aqueous solutions, which are
solutions where water is the solvent. Aqueous solutions are easier to handle
and mix than solids and gases. When solving quantitative problems involving
concentrations and volumes of solutions, you should focus on the amounts, in
Denitions for solutions, solutes,
mol, of the reacting substances and their mole ratios in the balanced chemic al
solvents and concentration are
equation. Typic al problems involving reactions in aqueous solutions are
given in Structure 1.4.
discussed in the following worked examples.
465
Worked example 3
Hydrochloric acid is an aqueous solution of hydrogen chloride, HCl(aq). The
reaction of hydrochloric acid with a sodium hydroxide solution, NaOH(aq),
3 −3
produces sodium chloride, NaCl(aq). A 1.00 dm sample of 0.500 mol dm
−3
hydrochloric acid was mixed with an equal volume of a 0.200 mol dm
sodium hydroxide solution.
a. Formulate the equation for the reaction of hydrochloric acid with
sodium hydroxide.
−3
b. Determine the nal concentrations, in mol dm , of all solutes in the
solution once the reaction is complete. Assume that the volumes of
solutions are additive.
Solution
a. HCl(aq) + NaOH(aq) → NaCl(aq) + H O(l)

2
b. First, work out the amounts of each solute using n = V × c:
You c an nd the amount of a
substance in a solution, n, from the

n(HCl) = V(HCl) × c(HCl)
volume of the solution, V, using
3 −3
= 1.00 dm × 0.500 mol dm

n = V × c, where is c is the molar
concentration of that substance
= 0.500 mol
−3
in mol dm . This was covered in
Structure 1.4
n(NaOH) = V(NaOH) × c(NaOH)
3 −3
= 1.00 dm × 0.200 mol dm
= 0.200 mol
According to the equation, HCl and NaOH react in 1 : 1 ratio. In the
reaction mixture, the amount of HCl (0.500 mol) is greater than that of
NaOH (0.200 mol). Therefore, NaOH is the limiting reactant, so it will be
consumed completely while some HCl will be le over:
HCl(aq) + NaOH(aq) → NaCl(aq) + H O(l)

2
n / mol 0.500 0.200 0 excess

initial
Δn / mol −0.200 −0.200 +0.200 +0.200
n / mol 0.300 0 0.200 excess

nal
The nal solution contains 0.300 mol of unreacted HCl(aq) and 0.200 mol
of NaCl(aq). The amount of the solvent (water) is not relevant, as it is
present in large excess in both the initial and nal solutions.
Assuming that the volumes of solutions are additive, V = V(HCl)

nal
n
3 3 3
+ V(NaOH) = 1.00 dm + 1.00 dm = 2.00 dm . You c an use to
V
final
c alculate the nal concentrations:
0.300 mol
−3
c (HCl) = = 0.150 mol dm

nal
3
2.00 dm
0.200 mol
−3
c (NaCl) = = 0.100 mol dm

nal
3
2.00 dm
466
Worked example 4
Measurement
Sulfur dioxide, SO (g), is a toxic gas with a strong smell of burnt matches.
2
All measurements are, to an
When released into the atmosphere in large quantities, sulfur dioxide
extent, limited in precision and
contributes to acid rain by reacting with water vapour to produce unstable
accuracy. However, sometimes
sulfurous acid, H SO (aq).

2 3
these limitations are negligible.
For example, strictly speaking,

Sulfur dioxide c an be absorbed by alkaline solutions, such as a solution of
the volumes of solutions are not

sodium hydroxide, NaOH(aq), to produce salts of sulfurous acid, such as
additive. If we mix the solutions

Na SO (aq).
2 3
from worked example3, the
a. Formulate equations for the reaction of sulfur dioxide with water

volume of the nal solution will be
3
vapour and for the reaction of sulfur dioxide with excess aqueous
2.01 dm , or approximately 0.5%
3
sodium hydroxide.
greater than expected (2.00 dm ).
However, such dierences are

−3
b. Determine the concentrations, in mol dm , of all solutes in a solution
usually small and comparable with

3 3
produced when 2.84 dm of sulfur dioxide is absorbed by 2.00 dm of
the accuracy of standard volumetric

−3
a 0.400 mol dm solution of sodium hydroxide at STP. Assume that the
glassware (0.2–0.5%). Therefore,
absorption does not aect the volume of the solution.
in most practic al situations, we
c an assume that the volume of the
Solution
solution at the end of the reaction is
a. SO (g) + H O(g) → H SO (aq) approximately equal to the sum of

2 2 2 3
volumes of the initial solutions.
SO (g) + 2NaOH(aq) → Na SO (aq) + H O(l)

2 2 3 2
Have you come across other
V negligible limitations to accuracy or
b. Sulfur dioxide is a gas at STP, so use n = to determine the amount present:
V
m
precision in chemistry? When do
2.84 dm
such eects become signic ant?
n(SO ) = = 0.125 mol
2
3 1
22.7 dm mol
Work out the amount of the sodium hydroxide solute using n = V × c:
3 −3
n(NaOH) = 2.00 dm × 0.400 mol dm = 0.800 mol
According to the equation, SO and NaOH react in a 1 : 2 ratio. The

2
amount of NaOH required to absorb 0.125 mol of SO is therefore

2
0.250 mol. The actual amount of NaOH in the reaction mixture (0.800 mol)
is greater than 0.250 mol. Therefore, SO is the limiting reactant, so it will

2
Practice questions
be consumed completely, while some NaOH will be le over:
4. Equal volumes of
SO (g) + 2NaOH(aq) → Na SO (aq) + H O(l)

2 2 3 2 −3
0.100 mol dm solutions of
n / mol 0.125 0.800 0 excess

initial
potassium hydroxide, KOH(aq),
Δn / mol −0.125 −0.250 +0.125 +0.125 and sulfuric acid, H SO (aq),

2 4
were mixed to produce

n / mol 0 0.550 0.125 excess
nal
potassium sulfate, K SO (aq),

2 4
The nal solution contains 0.550 mol of unreacted NaOH(aq) and

and water.
0.125 mol of Na SO (aq). The volume of the solution at the end of the
2 3
a. Formulate the balanced
reaction will be approximately equal to the volume of the initial solution,
equation for the

3
2.00 dm . Therefore:
neutralization.
0.550 mol
−3
c (NaOH) = = 0.275 mol dm

nal b. Determine the
3
2.00 dm
concentrations, in
0.125 mol
−3
c (Na SO ) = = 0.0625 mol dm −3

nal 2 3
3 mol dm , of all solutes in
2.00 dm
the nal solution.
467
The volumes of solutions and gases must never be added together. The densities
of most gases are approximately 1,000 times lower than those of aqueous
solutions, so when a gas is absorbed by a solution, the increase in the solution
volume is negligible for most practic al purposes.
The mole ratio techniques discussed in this topic are commonly used in titration
c alculations. In an acid–base titration, an acid and a base react with each other
to form water and a salt. An acid–base indic ator is added to the reaction mixture
to monitor the reaction progress. The indic ator changes colour when the
neutralization is complete. The mole ratio is shown by the balanced equation for
The method for performing
this neutralization reaction. If the volumes of both acid and base solutions are
a titration is discussed in the
known, and the concentration of one of the reactants is also known, the unknown
Skills chapter.
concentration of the second reactant c an be determined.
Worked example 5
20.0 cm of sulfuric acid solution, H SO (aq), of unknown concentration was

2 4
−3
titrated with a 0.200 mol dm solution of sodium hydroxide, NaOH(aq), in
the presence of an acid–base indic ator. The colour change was observed
when 14.3 cm of the sodium hydroxide solution was added.
a. Formulate the balanced equation for the neutralization reaction.
−3
b. Determine the concentration, in mol dm , of sulfuric acid in the
analysed solution.
Solution
a. H SO (aq) + 2NaOH(aq) → Na SO (aq) + 2H O(l)

2 4 2 4 2
b. Start by converting the volume of sodium hydroxide solution to dm :
3 3
V(NaOH) = 14.3 cm = 0.0143 dm

pFigure 1 An acid–base t i t ra t i o n with a
coloure d indic ator
Then, nd the amount of sodium hydroxide solute using n = V × c:
3 −3
n(NaOH) = 0.0143 dm × 0.200 mol dm = 0.00286 mol
According to the equation, H SO and NaOH react in 1 : 2 ratio,

2 4
so n(H SO ) = 0.00143 mol

2 4
Convert the volume of sulfuric acid solution to dm :
3 3
V(H SO ) = 20.0cm = 0.0200 dm

2 4
Practice question
n
Then, c alculate the concentration of sulfuric acid using c = :
5. Complete neutralization
0.00143mol
−3
3
of 10.0cm of a sodium c(H SO ) = = 0.0715 mol dm

2 4
3
0.0200 dm
hydroxide solution required
c V c V
1 1 2 2
3 −3
You c an also use the formula = , where x and x are the
9.10cm of a 0.500moldm 1 2
x x
1 2
hydrochloric acid. Determine

stoichiometric coecients before the reactants in the balanced equation.
−3
the concentration, in mol dm ,
This way, you c an skip the step where you nd the amounts of the
of sodium hydroxide in the
reactants used in titration.
initial solution.
468
Back titration
When an analyte c annot be easily quantified with a • Phenolphthalein indic ator solution
titration, a back titration is employed. In a back titration,
• Burette
the substance being analysed is first neutralized by a
• Burette clamp and stand

reagent of known volume and concentration. The excess
of this reagent is then determined by titration.

• Conic al flasks
Eggshells contain c alcium c arbonate. C alcium c arbonate

• Drying oven
is insoluble in water, so its quantity c an be conveniently
• Pestle and mortar

determined using a back titration method. The eggshells
are first crushed and reacted with a known amount of

• Top-pan balance
hydrochloric acid taken in excess. The leftover acid is then
• Volumetric pipette and filler
titrated against a standard sodium hydroxide solution
to find out how much of the acid was consumed in the • Wash bottle containing distilled water
reaction with the eggshells. The amount of c alcium
• Waste container(s)
c arbonate in the eggshells c an then be found using
stoichiometric c alculations. • Standard lab safety equipment
Relevant skills
2. Conduct a risk assessment of your method and show
it to your teacher for approval.

• Tool 1: Applying techniques: titration
3. Collect sufficient relevant data, including qualitative

• Tool 3: Propagate uncertainties in processed data
observations. You will have to decide how much data
• Inquiry 2: Collect and record sufficient relevant data
will be sufficient.
• Inquiry 2: C arry out correct and accurate
4. Process the data to determine the mass percentage
data processing
of c alcium c arbonate in each of the eggshell
samples.
Instructions
5. Propagate measurement uncertainties to obtain the

1. Using the list of equipment shown below, design a
uncertainties of the c alculated mass percentages

method to analyse the mass percentage of c alcium
found above.
c arbonate in eggshells. The equipment list is not
definitive: you do not have to use all the items in the

6. Graph your data using an appropriate software,
list, and you c an add further items or substances if

including error bars.
you wish.
7. If possible, compare your data to literature values.
• C alcium c arbonate chips, C aCO (s)

3
Comment on the accuracy and precision of
your results.
• A variety of different types of eggshells
−3 8. Discuss at least two sources of error in your

• 1.00 mol dm hydrochloric acid, HCl(aq)
investigation and propose improvements that could
−3
• 1.00 mol dm sodium hydroxide, NaOH(aq)

minimize these errors.
Linking questions
How does the molar volume of a gas vary with changes in temperature and
pressure? (Structure 1.5)
In what ways does Avogadro’s law help us to describe, but not
explain, the behaviour of gases? (Structure 1.4)
469
The reaction yield (Reactivity 2.1.4)
In any chemic al reaction, the total mass of the reaction products is equal to
the total mass of the consumed reactants. This principle, known as the law
of conservation of mass, follows from atomic theory. Since atoms c annot be
created or destroyed, their total number and therefore mass c annot be aected
by chemic al changes.
“Nothing comes from nothing” was one of the basic principles in ancient
Greek philosophy. The rst recorded experimental evidence for the
conservation of mass was obtained in 1748 by the Russian scientist Mikhail
Lomonosov, who c arried out chemic al reactions in sealed vessels and found
that chemic al changes did not aect the total mass of the mixtures. However,
the works of Lomonosov were almost unknown in western European
countries, so it was over 25 years before the French chemist Antoine L avoisier
formulated this principle in 1774 and was commonly credited for its discovery.
pFigure 2 Left: Mikhail Lomonosov; right: Antoine L av o i s i e r
Activity
This example shows the importance of sharing knowledge and ideas: a
C alculate the masses, in g, of
valuable discovery that remains hidden from the global scientic community
the initial and nal mixtures from
may go unnoticed for some time and have little impact on the advancement
worked example2 and verify the
of science. What conditions facilitate an individual’s access to the international
validity of the law of conservation
scientic community? How c an the number of valuable contributions of
of mass.
scientists from around the world be maximized?
When chemic al reactions are c arried out experimentally, the amounts of the
reaction products are usually lower than the theoretic al amounts predicted
by the equation. This c an happen for many reasons, including incomplete
conversion of the reactants or simply bec ause some product was lost during its
isolation and puric ation. In such c ases, we c an c alculate the percentage yield,
which is the ratio of the experimental and theoretic al amounts of the product.
Since the amount of an individual substance is proportional to its mass (n = ),
the yield c an also be found as the ratio of the experimental and theoretic al
masses of the product:
n m
experimental experimental
percentage yield = × 100% = × 100%
n m
theoretical theoretical
470
The term “yield” can also refer to the amount or mass of the reaction product. In
this sense, the theoretical yield is the amount or mass of the product that could
be obtained from a particular reaction if the reaction went to completion and no
product was lost. In contrast, the experimental yield is the actual amount or mass
of the product isolated from a particular laboratory experiment. The experimental
yield can be lower than or equal to the theoretical yield, but it can never exceed it.
The percentage yield, and theoretic al and experimental yields of a reaction, are
related as follows:
experimental yield
percentage yield = × 100%
theoretic al yield
Worked example 6
A mixture of 10.0 g of c alcium metal and 9.62 g of elemental sulfur was heated for some time to
produce 17.0 g of c alcium sulde, C aS(s).
a. Calculate the theoretical yield, in g, of calcium sulde. b. Using your answer to part a, c alculate the
percentage yield of c alcium sulde.
Solution
a. First, write the balanced equation for the reaction: b. The reaction produced 0.236 mol of c alcium sulde,
while the theoretic al yield of this compound was
C a(s) + S(s) → C aS(s)
0.250 mol. Therefore:
Then c alculate the amounts of the reactants and

n
experimental

m
n
products using n = : theoretical
0.236 mol
10.0 g = × 100% = 94.4%
n(C a) = ≈ 0.250 mol 0.250mol

–1
40.08 g mol
The same result could be obtained through the
9.62 g
n(S) = ≈ 0.300 mol

experimental and theoretic al masses of c alcium
–1
32.07 g mol
sulde:
17.0 g
n(C aS) = ≈ 0.236 mol

–1
72.15 g mol m
experimental
m
theoretical
The limiting reactant is c alcium, as c alcium and sulfur
are consumed in a 1 : 1 ratio. The theoretic al amount 17.0 g
= × 100% = 94.4%
of c alcium sulde is 0.250 mol (the same as the initial 18.0 g
amount of the limiting reactant, c alcium). Therefore,
the theoretic al yield of c alcium sulde is:
–1
m (C aS) = 0.250 mol × 72.15 g mol ≈ 18.0 g

theoretical
Practice question
6. C alculate the theoretic al and percentage yields of the reaction between
9.443 g of aluminium and 7.945 dm (STP) of oxygen that produced
17.13 g of aluminium oxide, Al O (s).

2 3
471
Salicylic (2-hydroxybenzoic) acid was isolated from the bark E ach step of the procedure outlined c auses some loss of
of willow trees in the rst half of the 19th century and used the product and therefore reduces the yield of aspirin.
as a pharmaceutical drug for pain and fever relief. However, In particular, the reaction of salicylic acid with ethanoic
pure salicylic acid caused severe stomach irritation and anhydride is never 100% complete, some aspirin stays in
bleeding. These side eects could be signicantly reduced the solution, small crystals of aspirin c an be trapped in the
by the use of a chemically modied salicylic acid, which is paper lter, and so on. The results of three experiments
now known as acetylsalicylic acid or aspirin. performed by students are shown in table2.
O OH
Experimental Experiment Experiment Experiment
data 1 2 3
OH + H C O CH
3 3
mass of salicylic
2.06 2.57 2.35

C C
acid / g
mass of ethanoic
O O
2.49 2.85 3.11
anhydride / g
salicylic acid ethanoic
(2-hydroxybenzoic acid) anhydride
mass of aspirin / g 3.42 2.31 1.87
M 138.13 M 102.10
r r
recrystallization
none once twice
from ethanol
H PO
3 4
melting point of
122–128 133–135 135–136
product / °C
O OH
C pTable 2 Synthesis of aspirin data. The literature value for the
melting point of pure aspirin is 136 °C
O CH + CH COOH
3 3
Impurities usually lower the melting point and widen the
melting range of substances. The most common example
is sea water, which freezes between −2.5 and −1.8 °C
instead of at 0 °C like pure water.
asirin ethanoic
(acetylsalicylic acid) acid

Q uestions
M 180.1 M 0.0
r r
1. C alculate the amounts of the reactants for each
experiment and determine the limiting reactant in

The reaction of salicylic acid with ethanoic anhydride
each c ase.
c an be used in a school laboratory for the preparation
2. Determine the percentage yield of aspirin in

of aspirin. In a typic al experiment, salicylic acid is mixed
each experiment.
with excess ethanoic anhydride and several drops of the
c atalyst (concentrated phosphoric acid, H PO ). The

3 3. Identify which experiment produced an impossible
4
mixture is heated for a short time, then diluted with water

percentage yield of aspirin. Using the data in table 2,
and allowed to cool down slowly, producing crystals of

suggest a reason for this and provide supporting data
aspirin. The crystals are isolated by ltration and dried in

for your answer.
the open air.
4. Suggest which experiment produced the purest
sample of aspirin. Explain your answer.

The aspirin obtained in this way is usually impure, so it
needs to be recrystallized. To do so, impure aspirin is
The identity of aspirin c an be conrmed by
dissolved in hot ethanol, and the solution is allowed
IR spectroscopy, NMR spectroscopy, mass
to cool down. Pure aspirin precipitates while most of
spectrometry (Structure 3.2, AHL) or by determining
the impurities remain in the solution. The crystals of
its melting point (Structure 1.1) and comparing the
pure aspirin are ltered and dried until all the ethanol
result with the literature data.
evaporates.
472
Gravimetric analysis of a precipitation reaction
The reaction between c alcium chloride and sodium Instructions
c arbonate solutions produces a precipitate of c alcium
1. Write your initials on the lter paper in pencil and
c arbonate, which c an be removed by ltration:
pre-weigh it.
C aCl (aq) + Na CO (aq) → C aCO (s) + 2NaCl(aq)

2 2 3 3 3 3 −3
2. In a 100 cm beaker, add 25 cm of 0.50 mol dm
3 −3
c alcium chloride solution to 15 cm of 1.0 mol dm

In this practic al, you will c arry out this reaction, isolate the
sodium c arbonate solution.

resulting c alcium c arbonate and c alculate the yield.
3. Stir the reaction mixture. Remember to record
Relevant skills
relevant qualitative observations throughout.
• Tool 1: Measuring mass and volume

4. Filter the mixture (gure 3). Rinse the beaker and
stirring rod with distilled water to completely transfer

• Tool 1: Drying to a constant mass
all traces of the precipitate onto the lter paper.
• Tool 3: Applying general mathematics
5. Allow the lter paper to dry undisturbed, inside a
• Inquiry 2: Identify and record relevant
drying oven if possible. Once it looks dry, weigh it.
qualitative observations
Repeat until the mass remains constant.
• Inquiry 2: Collect and record sucient relevant
6. Clean up as instructed by your teacher.
quantitative data
filter paper
• Inquiry 2: C arry out relevant and accurate
data processing Buchner
funnel
S afety
• Wear eye protection
vacuum pump
conic al
• Sodium c arbonate solution is an irritant, wear gloves

flask
when handling it
M aterials
pFigure 3 Va c u u m f i l t ra t i o n
• two 25 cm graduated pipettes or burettes
Q uestions
• 100 cm beaker
1. Determine the limiting and excess reactants.
• stirring rod
2. C alculate the theoretic al yield of c alcium c arbonate.
• vacuum ltration apparatus
3. C alculate the experimental yield of c alcium c arbonate
• top-pan balance
and hence, the percentage yield.
• lter paper
4. Compare and contrast your results to your
• wash bottle containing distilled water

classmates’ results.
• drying oven (if available)

5. O utline two ways to improve the eciency of
–3
this synthesis.
• 0.50 mol dm c alcium chloride solution, C aCl (aq)
2
–3
• 1.0 mol dm sodium c arbonate solution, Na CO (aq)

2 3
473
The following steps show a general approach to solving problems involving
stoichiometric c alculations. To help you remember all the steps, describe
each step in three words, and then again in one word.
1. Formulate and balance the chemic al equation(s) for any chemic al changes
mentioned in the problem.
2. C alculate the amounts of as many substances as you c an using the
m V
formulas n = and n = . If you know a mass percentage, convert it rst
M V
m
to mass (if possible) and then to amount.
3. Write all known amounts of substances below their formulas in chemic al
equations. Any missing values may suggest the next step of the solution.
4. Determine the limiting reactant and use the mole ratio shown by
stoichiometric coecients in the balanced equation to c alculate the
changes in amount for all substances. Remember that the mole ratio does
not reect the initial or nal amounts of reactants and products.
5. Check the mass balance. The total mass of products must be equal to the
total mass of reactants. If it is not the c ase, revise your solution.
6. Check that the answer makes sense. All percentages should add up to
100%, and no individual percentage c an be greater than 100%. The yield
of the nal product must not exceed 100%. Finally, treat very low or very
high percentages with c aution.
In practice, chemists oen have to nd a balance between yield and purity. For
example, most medic al drugs must have a purity of 99% or even higher, as any
impurities could have unpredicted eects on the patient’s health. As a result, the
strict safety requirements reduce the yields and increase the prices of medic al-
grade products. At the same time, the acceptable purity for many industrial and
agricultural materials, such as detergents and fertilizers, could be well below
50%, as long as the impurities do not compromise the safety and intended use of
the product.
The yields of chemic al reactions are particularly important in the chemic al
industry, where the loss of even a small percentage of the nal product could
mean a signic ant drop in prot. Low reaction yields increase the amount of
waste, which needs to be disposed of safely or reused. The development of
highly ecient synthetic procedures with low environmental impact is reected
in the concept of green chemistry, which is now adopted by the majority of
commercial and research organizations around the world.
Linking question
What errors may c ause the experimental yield to be i) higher and ii) lower than
the theoretic al yield? (Tool 1, Inquiry 1, 2, 3)
474
Green chemistry and atom economy
(Reactivity 2.1.5)
In traditional chemistry, the eciency of a synthetic procedure is measured in
terms of the product yield and the cost of raw materials. M any other factors, such
as the toxicity of reagents and solvents, energy consumption and the amount
of waste produced are oen ignored. A completely dierent approach, known
as green chemistry, takes into account the environmental impact of the entire
technologic al process. Green chemistry encourages scientists to minimize the
use and generation of hazardous chemic als when designing reactions that are
used in industrial processes. Common practices of green chemistry include
aqueous or solvent-free reactions, renewable starting materials, mild reaction
conditions, ecient c atalysis and the utilization of any by-products formed during
the synthesis.
The term “green chemistry” was coined in 1991 by Americ an chemists
Paul Anastas and John Warner, who formulated 12 principles for their
approach to chemic al technology. These principles include the use of non-
hazardous chemic als and solvents, reduction of energy consumption and
waste production: “the best form of waste disposal is not to create it in the
rst place”. Other principles include the use of renewable materials and
prevention of accidents. The philosophy of green chemistry has passed into
national and international laws, which restrict the use of certain chemic al
substances and promote environmentally friendly technologies. To what
extent c an you incorporate the 12 green chemistry principles into your
practic al work in DP chemistry?
Another key concept of green chemistry is the atom economy, which is a
The equation for the c alculation
measure of the eciency of a reaction. The atom economy is the ratio of the
of atom economy is given in the
molar mass of the isolated target product to the combined molar masses of all
data booklet.
starting materials, c atalysts and solvents used in the reaction:
molar mass of desired product
atom economy = × 100%
total molar mass of reaction mixture
For example, the atom economy of a solvent-free reaction A + B → C is equal to the
experimental yield and can potentially reach almost 100%. However, in the reaction
A + B → C + D, where C is the target product, the atom economy will always be
signicantly lower than 100% because the unwanted by-product D is formed. The
use of solvents and catalysts will further reduce the atom economy because their
constituent atoms do not form the target product and must be disposed of or
recycled. Therefore, the atom economy is inversely proportional to the percentage
of waste generated in an industrial process or laboratory experiment.
475
Examples of atom-ecient Worked example 7
reactions are addition
Dimethyl c arbonate, (CH O) CO, is a non-toxic and highly ecient “green”

3 2
polymerization (Structure 2.4)
solvent. C alculate the percentage atom economy for the synthesis of
and the hydrogenation of alkenes
dimethyl c arbonate by the following reaction:
(Reactivity 3.2), which proceed
with high yields, require no

4CH OH(l) + 2CO(g) + O (g) → 2(CH O) CO(l) + 2H O(l)
3 2 3 2 2
solvents and form almost no
Assume that the percentage yield of the reaction is 100%.

by-products under appropriate
conditions. At the same time,
Solution
many traditional organic reactions,
such as the oxidation of alcohols
The total molar mass of the products is equal to the total molar mass of the
(Reactivity3.2) or electrophilic
reactants, so either can be used as the total molar mass of the reaction mixture.
substitution in aromatic
compounds (Reactivity3.4, AHL), Using the molar mass of reactants in the denominator:
are very inecient. This is because
2 × M((CH O) CO)
3 2
they oen require large volumes atom economy = × 100%
4 × M(CH OH) + 2 × M(CO) + M(O )

3 2
of solvents, have low yields and in
2 × 90.09
some cases produce mixtures of = × 100% = 83.33%
4 × 32.05 + 2 × 28.01 + 32.00
isomers (Structure 3.2) instead of
Using the molar mass of products in the denominator:

individual target products.
2 × M((CH O) CO)
3 2
atom economy = × 100%
2 × M(CH O) CO) + 2 × M(H O)

3 2 2
2 × 90.09
= × 100% = 83.33%
2 × 90.09 + 2 × 18.02
Practice questions
7. Dimethyl c arbonate c an be used to convert phenylamine, C H NH (l), into

6 5 2
N-methylphenylamine, C H NHCH (l). The by-products of this reaction are

6 5 3
methanol, CH OH(l), and c arbon dioxide, CO (g).

3 2
a. Formulate the balanced equation for this process and c alculate its atom
economy.
b. Suggest, by referring to the chemic al equation in worked example7,
how the atom economy of the synthesis of N-methylphenylamine c an
be improved.
The cost of green chemistry
Green technologies vary in eciency and in many c ases involve expensive
equipment, raw materials and recycling facilities. However, these initial
investments reduce the costs associated with environmental remediation, waste
management and energy consumption. Therefore, in the long term, green
chemistry is a commercially attractive and sustainable alternative to traditional
organic chemistry.
476
Inc re asing adoption of gre en industrial processes in develope d countries
has signic antly re duce d the emissions of many hazardous chemic als, such
as chlorinate d solvents or gre enhouse gases. At the s ame time, some non-
hazardous substances brande d as “gre en” or “environmentally f riendly”
still re quire toxic chemic als or large amounts of energy for their production.
The industrial use of natural products, such as plant oils and starch, takes
up agricultural resources, re duces biodiversity and inc re ases the cost of
food. This c an le ad to v arious e cologic al and social issues. Therefore, the
“gre enness” of a product must be assesse d using all dire ct and indire ct
environmental implic ations of its entire life cycle. This is one of the most
controversial problems in gre en chemistry.
pFigure 4 Left: superc ritic al c arbon d i ox i d e is widely used in food industry as a
n o n - t ox i c , gre en alternative to chlorinated solvents; right: a biofuel p ow e r plant
Create your own practice question involving mole ratios. Depending on
how condent you feel about this topic, you could develop a relatively
straightforward question based on reacting masses, or a more complex one
that brings in your knowledge of concentrations and/or gas volumes. Try to
address some of the common mistakes and misconceptions related to mole
ratios. Create a booklet or record a video showing the step-by-step solution
to the problem and share it with a partner. Give each other feedback in the
form of “two stars and a wish”: two things they have done well and one
constructive suggestion for improvement. Improve your work, then share it
with the rest of your class.
Linking question
The atom economy and the percentage yield both give important information
about the “eciency” of a chemic al process. What other factors should be
considered in this assessment? (Structure 2.4, Reactivity 2.2)
477
5. Which of the following expressions gives the atom
Topic review
economy of the synthesis of methanal, HCHO(g), from
methanol, CH OH(l), if the experimental yield is 100%?

3
How are chemical equations used to calculate CH OH(l) + 0.5O (g) → HCHO(g) + H O(l)
3 2 2
reacting ratios?
M(HCHO)
M(CH OH) + M(HCHO)

3
M(HCHO)
II
M(CH OH) + 0.5 × M(O )
3 2
2. Pyrite, FeS , reacts with oxygen according to the M(HCHO)

2
III
M(HCHO) + M(H O)
following equation: 2
A. I and II only
4FeS (s) + 11O (g) → 2Fe O (s) + 8SO (g)

2 2 2 3 2
B. I and III only
How many grams of SO (g) will be produced from

2
C. II and III only

0.25 mol of FeS ?
2
D. I, II and III
A. 16
B. 32
C. 64
6. Potassium superoxide, KO (s), is used to regenerate

D. 128 2
oxygen from the c arbon dioxide exhaled by the crew of
3. In which mixture is sulfuric acid the limiting reactant?

a submarine or spacecra.
A. 0.10 mol H SO + 0.20 mol KOH

2 4
a. Formulate the balanced equation for the reaction
B. 0.20 mol H SO + 0.10 mol KOH

2 4
between potassium superoxide and c arbon
C. 0.10 mol H SO + 0.20 mol C a(OH) dioxide that produces oxygen and potassium
2 4 2
c arbonate, K CO (s).
D. 0.20 mol H SO + 0.10 mol C a(OH) 2 3
2 4 2
b. Deduce the limiting reactant in the reaction of

3
4. What is the percentage yield when 18 dm of ethane,

3
28.44 g of potassium superoxide and 6.81 dm

3
C H (g), is produced from 20 dm of ethene, C H (g)?

2 6 2 4
(STP) of c arbon dioxide.
All volumes are measured at STP.
c. C alculate the mass, in g, of potassium c arbonate
C H (g) + H (g) → C H (g) and the volume, in dm at STP, of oxygen produced

2 4 2 2 6
in this reaction.
A. 10%
B. 20% 7. Chlorine gas is produced in the laboratory by
the reaction of hydrochloric acid, HCl(aq), with

C. 80%
manganese(IV) oxide, MnO (s):

2
D. 90%
MnO (s) + 4HCl(aq) → MnCl (aq) + Cl (g) + 2H O(l)

2 2 2 2
A 17.4 g sample of manganese(IV) oxide was added to
3 −3
0.100 dm of 10.0 mol dm hydrochloric acid, and the
mixture was heated until the reaction was complete.
a. Deduce the limiting reactant in this experiment.
b. C alculate the volume, in dm at STP, of chlorine
gas produced.
−3
c. C alculate the molar concentrations, in moldm ,
of all solutes in the nal solution. Assume that the
volume of the solution did not change during
the reaction.
478
8. A 10.0 cm sample of a solution with unknown 11. C alculate the atom economy for the following
concentration of barium hydroxide, Ba(OH) (aq), was reactions, assuming that the organic compound is the
2
−3
titrated with 0.100 mol dm hydrochloric acid, HCl(aq), target product in each c ase.
in the presence of an acid–base indic ator. The colour

a. CH CH OH(l) → H C=CH (g) + H O(l)
3 2 2 2 2
change was observed when 11.7 cm of the standard

b. 6CO (g) + 6H O(l) → C H O (aq) + 6O (g)
2 2 6 12 6 2
solution was added.
c. nH C=CH (g) → –CH (s)

2 2 2 2 n
a. Formulate the balanced equation for the
12. Nitrogen dioxide, NO (g), c an be synthesized from

neutralization if the reaction products are barium 2
nitrogen monoxide, NO(g), and oxygen.

chloride, BaCl (aq), and water.
2
−3
a. Formulate the balanced equation for this reaction.
b. Determine the concentration, in mol dm , of
barium hydroxide in the analysed solution. b. C alculate the theoretic al atom economy for the
equation from part a
9. The thermal decomposition of sodium
c. In a particular experiment, 1.00 dm of nitrogen
hydrogenc arbonate, NaHCO (s), produces sodium

3
monoxide was mixed with 1.00 dm of oxygen to
c arbonate, Na CO (s), c arbon dioxide and water.

2 3
produce 0.700 dm of nitrogen dioxide. C alculate
a. Formulate the balanced equation for this reaction.

3
the theoretic al yield, in dm , and the percentage
b. C alculate the theoretic al yield, in g, of c arbon

yield of nitrogen dioxide.
dioxide produced by the decomposition of 10.0 g
d. C alculate the actual atom economy for the
of sodium hydrogenc arbonate.
synthesis in part c
c. The decomposition of 10.0 g of sodium
hydrogenc arbonate produced 1.20 dm (STP) of
c arbon dioxide. C alculate the theoretic al yield, in
dm , of c arbon dioxide and its percentage yield in
this reaction.
d. C alculate the masses of solid substances in the nal
mixture obtained in part c
10. Copper(I) sulde, Cu S, is found in nature as the mineral

2
chalcocite, which is a major component of copper ores.
At high temperatures, chalcocite reacts with oxygen to
produce copper metal and sulfur dioxide, SO (g).

2
a. Formulate the balanced equation for the reaction
of copper(I) sulde with oxygen.
b. Determine the theoretic al yield, in kg, of copper
metal that could be obtained from 1.00 ton
(1000 kg) of an ore that contains 75.3% of
chalcocite. Assume that other components of the
ore are unreactive.
c. Using your answer to part b, determine the
percentage yield of copper metal if its practic al
yield is 506 kg.
479
Reactivity 2.2 How fast? The rate of
chemical change
How can the rate of a reaction be controlled?
One of the main considerations in designing a synthetic Chemic al kinetics is the branch of chemistry that studies
procedure is whether it c an be c arried out fast enough to the rates of chemic al reactions. Kinetics studies provide
be useful. There is no point in starting a reaction if it takes important information about reaction mechanisms and the
a hundred years before any product could be isolated! ways the reaction rates c an be controlled by altering the
Chemists oen have to nd a balance between the rate experimental conditions, such as pressure, temperature,
and yield of a reaction to make it feasible from both the concentration, surface area and the presence of c atalysts.
practic al and commercial points of view.
Understandings
LHA
Reactivity 2.2.1 — The rate of reaction is expressed as the Reactivity 2.2.9 — R ate equations depend on
change in concentration of a particular reactant/product the mechanism of the reaction and c an only be
per unit time. determined experimentally.
Reactivity 2.2.2 — Species react as a result of collisions of Reactivity 2.2.10 — The order of a reaction with
sucient energy and proper orientation. respect to a reactant is the exponent to which the
concentration of the reactant is raised in the rate

Reactivity 2.2.3 — F actors that inuence the rate of a
equation. The order with respect to a reactant c an

reaction include pressure, concentration, surface area,
describe the number of particles taking part in the

temperature and the presence of a c atalyst.
rate-determining step. The overall reaction order is
Reactivity 2.2.4 — Activation energy, E , is the minimum

a
the sum of the orders with respect to each reactant.
energy that colliding particles need for a successful
Reactivity 2.2.11 — The rate constant, k, is

collision leading to a reaction.
temperature dependent and its units are determined
Reactivity 2.2.5 — C atalysts increase the rate of reaction
from the overall order of the reaction.
by providing an alternative reaction pathway with lower E

a
Reactivity 2.2.12 — The Arrhenius equation uses the

LHA
Reactivity 2.2.6 — M any reactions occur in a series
temperature dependence of the rate constant to
of elementary steps. The slowest step determines
determine the activation energy.
the rate of the reaction.
Reactivity 2.2.13 — The Arrhenius factor, A, takes
Reactivity 2.2.7 — Energy proles c an be used to
into account the frequency of collisions with
show the activation energy and transition state of the
proper orientations.
rate-determining step in a multistep reaction.
Reactivity 2.2.8 — The molecularity of an elementary
step is the number of reacting particles taking part in
that step.
The rate of reaction (Reactivity 2.2.1)
Chemic al reactions proceed at dierent speeds. F ast reactions, such as
explosions, occur within milliseconds. Slow reactions, such as the formation
of fossil fuels, take millions of years. However, the terms “fast” and “slow” are
very vague, so chemists need to describe the speed of chemic al changes
moreprecisely.
480
Reactivity 2.2 How fast? The rate of chemic al change
Therefore, it is convenient to dene the rate of reaction, ν, as the change in
concentration, Δc, of a reactant or product per unit time, Δt:
|Δc |
ν =
Δt
This is the average rate of reaction, that is, the mean reaction rate over a period
of time, Δt, rather than the reaction rate at a given moment in time. Typic ally,
3 1
reaction rates are measured in mol dm s , although other units, such as
3 1 3 1
mmol dm min or mol m h , c an also be used.
A reaction rate cannot be negative, so it must be calculated using the absolute value
(modulus) of the concentration change. For example, if the concentration of species
X in a reaction mixture decreases from 0.50 to 0.20 mol dm over 25 seconds, the
rate of reaction with respect to that species is calculated as follows:
3 3
| 0.20 − 0.50 | mol dm 0.30 mol dm

3 1
ν (X) = = = 0.012 mol dm s
25 s 25 s
When the mole ratio of two or more species participating in a chemic al reaction
pFigure 1 F i r ew o r k s use fast chemic al
diers from 1 : 1, the reaction rates with respect to these species will also be
re actions, where as corrosion of metal
dierent. To avoid ambiguity, the rates for individual species c an be divided
constructions takes centuries
by their stoichiometric coecients. The resulting overall rate of reaction is
independent of the species used in c alculations.
Worked example 1
Consider the following reaction:
2N O(g) → 2N (g) + O (g)

2 2 2
Under certain conditions, the concentration of nitrogen(I) oxide in the
reaction mixture decreases by 0.20 mol dm over 10 seconds, producing
3 3
0.20 mol dm of nitrogen and 0.10 mol dm of oxygen over the same
period of time. C alculate:
3 1
a. the rate of reaction, in mol dm s , with respect to each of the three
species involved in the reaction
b. the overall rate of reaction, in the same units as above.
Solution
|Δc |
a. Use ν = to nd the rate of reaction for each species:
Δt
0.20 mol dm
3 1
ν (N O) = = 0.020 mol dm s
2
10 s
0.20 mol dm
3 1
ν (N ) = = 0.020 mol dm s
2
10 s
0.10 mol dm
3 1
ν (O ) = = 0.010 mol dm s
2
10 s
b. To nd the overall rate of reaction, you c an divide any of the rates for
individual species by their stoichiometric coecients:
ν (N O) ν (N ) ν (O )
2 2 2 3 1
ν = = = = 0.010 mol dm s
overall
2 2 1
481
Practice questions
1. Under certain conditions, ammonia c an be oxidized to nitrogen(II) oxide:
4NH (g) + 5O (g) → 4NO(g) + 6H O(g)

3 2 2
O ver a period of 5 s, the concentration of nitrogen(II) oxide in the reaction
3 3
mixture increased from 0 to 6.0 × 10 mol dm . C alculate:
3 1
a. the rate of reaction, in mol dm s , with respect to NO(g) and O (g)

2
b. the overall rate of reaction, in the same units as above.
In addition to mass and volume,

Direct measurement of concentrations c an be problematic, so the change in
the following quantitative

concentration is oen c alculated from other experimental data, such as changes
characteristics are oen used

in mass or volume of the reaction mixture or a particular substance.
to c alculate the concentration
changes: For instance, the reaction of magnesium metal with hydrochloric acid c an be
investigated by measuring the volume of hydrogen gas released from
• pressure (for reactions the solution:
involving gases, Structure 1.5)

2 2
• pH (for acid–base reactions,
In a typic al experiment, a c arefully measured volume of hydrochloric acid with
Reactivity 3.1)
known concentration is placed into a conic al ask, and a sample of magnesium
• electric al conductivity is added. The ask is immediately closed with a rubber bung and connected to
(for reactions involving a gas syringe (gure 2). The gas volume is recorded at regular time intervals until
electrolytes, Structure 2.1) the reaction is complete.
• colour (for reactions involving
gas
transition metals or other
syringe
coloured compounds, connector
Structure 3.1, AHL).
Any of these characteristics c an 0 2 4 6 8 10 12 14 16 18 cm

3
glass tube
be recorded automatic ally using
a data logger and then related to
bung
concentration using an appropriate
mathematic al expression or a
c alibration curve (Structure 1.4).
Alternatively, small samples of the
conical
reaction mixture could be taken at
flask
hydrochloric
certain time intervals and analysed
acid
by spectroscopic techniques
(Structure 3.2, AHL) or titration
(Reactivity 2.1).
magnesium
pFigure 2 Me asuring the re action ra t e using a gas sy r i n g e
The change in concentration of hydrochloric acid and the reaction rate c an be
c alculated using gas laws and reaction stoichiometry.
482
Worked example 2
The experiment shown in gure 2 was c arried out using a piece of magnesium ribbon and 0.100 dm
of 0.250 mol dm hydrochloric acid. The volume of gas released by the reaction was recorded every
10 seconds until a constant reading was obtained (table 1).
t / s 0 10 20 30 40 50 60 70 80 90 100
V(H ) / cm 0 111 164 192 210 223 234 241 246 248 248
2
pTable 1 Volume of hydrogen gas released by the reaction of hydrochloric acid with magnesium metal at SATP
3 1
a. C alculate the rate of reaction, in mol dm s , with b. C alculate the overall rate of reaction for the time
respect to H (g), for the following time intervals: interval in (a)(ii).

2
i. between 0 and 10 s Assume that the reaction was c arried out at SATP (25 °C
and 100 kPa), and the solution volume did not change
ii. between 0 s and the moment when the reaction
during the reaction.
was complete.
Solution
ΔV
released from a unit volume of the solution.
a. i. Use Δn = to calculate the change in the amount
V
m
An alternative approach could involve the
of hydrogen. Note that V depends on temperature.

m
concentration change of another species,
3 1
The value of 22.7 dm mol can be used only at

such as HCl(aq) or MgCl (aq), which remains
2
T = 0 °C (273.15 K) and p = 100 kPa (STP). The

in the aqueous solution. That approach will be
V at SATP or any other conditions can be calculated

m demonstrated in worked example 3.
using the ideal gas equation (Structure 1.5):
|Δc |
Finally, use ν = to c alculate the rate of

p V p V
1 1 2 2
Δt
=
reaction:
T T
1 2
3 1
3
100 kPa × 22.7 dm mol 100 kPa × V (SATP)
m 0.0448 mol dm
3 1
=
ν = = 0.00448 mol dm s
273.15 K 298.15 K
10 s
3 1
V (SATP) = 24.8 dm mol

m ii. According to table 1, the gas volume between 90
and 100 s remained constant, so the reaction was

3
O ver the rst 10 s of the reaction, 111 cm

3
complete at 90 s. O ver the same period, 248 cm

3
(0.111 dm ) of hydrogen was released at SATP, so

3
(0.248 dm ) of hydrogen was released, so:

3
0.111 dm
Δn(H ) = = 0.00448 mol.

2
3 1
3
24.8 dm mol
0.248 dm
Δn(H ) = = 0.0100 mol

2
3 1
To determine the change in concentration, 24.8 dm mol
Δn
0.0100 mol
use Δc = , where V is the volume of the 3
V Δc(H ) = = 0.100 mol dm

2
3
0.100 dm
reaction mixture:
−
3
0.100 mol dm
− −
3 1
ν(H ) = = 0.00111 mol dm s

0.00448 mol 2
3
90 s
Δc(H ) = = 0.0448 mol dm
2
3
0.100 dm
b. The stoichiometric coecient of H (g) is 1, so the

2
Note that molecular hydrogen is a gas while −

3
−
1
overall reaction rate is also 0.00111 mol dm s .
the reaction mixture is an aqueous solution.
Therefore, the value of Δc(H ) is not the actual

2
concentration of H (g) in the solution but only

2
the ratio that shows the amount of the product
483
3 1
Chalk (c alcium c arbonate) reacts with hydrochloric acid to C alculate the rate of reaction, in mol dm s , for the
release c arbon dioxide: following time intervals:
a. between 0 and 30 s
C aCO (s) + 2HCl(aq) → C aCl (aq) + CO (g) + H O(l)
3 2 2 2
b. between 0 s and the moment when the reaction

3
A conic al ask was charged with 50.0 cm of
was complete.
3
0.500 mol dm hydrochloric acid and powdered chalk,
plugged with cotton wool to prevent droplets of water Assume that the solution volume did not change during
from esc aping but let the gas through (gure 3), placed the reaction.
on a digital balance and tared. The balance readings were
recorded every 30 s using a data logger (table 2).
t / s Δm / g
0 0
30 −0.161
60 −0.262
90 −0.326
120 −0.368
150 −0.396
180 −0.415
210 −0.428
Table 2 Balance
240 −0.437
Figure 3 Monitoring
readings for the ask
270 −0.440
the loss of mass of the
with the reaction
300 −0.440
reaction mixture
mixture
Instantaneous reaction rate
TOK
If you examine table 1, you will notice that the rate of the reaction between
Instantaneous and initial magnesium metal and hydrochloric acid changes with time. Indeed, the volume
reaction rates are mathematic al of hydrogen released during the rst 10 s of the reaction (111 cm ) was more
abstractions, as they refer to than 50times greater than that produced during the last 10 s (2 cm ). Therefore,
changes in concentration over the average reaction rate gives us only a general idea of how fast (or slow) the
innitesimally small periods of reaction proceeds over a period of time but tells us nothing about the reaction
time. Nevertheless, these abstract rate at any given moment.
quantities are used by chemists
To obtain this information, we need to introduce the concept of instantaneous
for various practic al purposes,
reaction rate, ν , which is dened as the concentration change (dc) over an

inst
from optimizing reaction yields to
innitesimally small period of time ( dt):
deducing reaction mechanisms.
| dc |
C an you think of any other
ν =
inst
dt
examples of how abstract concepts
Like the average rate of reaction, instantaneous reaction rate cannot be negative,
are used in science to benet real
so it must be calculated using absolute values of concentration changes. If an

life applic ations?
instantaneous rate is measured with respect to a particular substance, it must
be divided by the stoichiometric coecient of that substance to give the overall
reaction rate. The initial reaction rate, ν , is the instantaneous rate measured
init
at t = 0. Both initial and instantaneous rates have the same units (typically
3 1
mol dm s ) as average reaction rate.
The instantaneous reaction rate, ν , at a given time, t, c an be determined by

inst
plotting the concentration of a reactant or product against time. If you draw a
tangent line to the curve at t, the gradient of the tangent line will be numeric ally
equal to ν at t. Similarly, the initial reaction rate, ν , c an be determined by

inst init
measuring the slope of the tangent line at t = 0 s.

484
Worked example 3
3 1
Determine the initial rate, in mol dm s , and the instantaneous rate, in the same units, at
t = 55 s for the reaction of hydrochloric acid with magnesium metal in worked example 2.
Solution
First, we need to nd concentrations of hydrochloric acid To determine the gradient, we can select any two points on
every 10 seconds: each tangent line and divide the dierence in their
y-coordinates (Δc) by the dierence in their x-coordinates (Δt).
• At t = 0 s, the initial concentration of the acid
(0.250 mol dm ) is given in the problem. y − y

2 1
gradient =
x − x
2 1
• At t = 10 s, Δn(H ) was c alculated to be 0.00448 mol

2
For the tangent at t = 0 s, the most obvious point is

in worked example 2. The mole ratio of H (g) to
2
(0, 0.250) while the second point could be, for example,
HCl(aq) is 1 : 2, so Δn(HCl) at t = 10 s is 0.00448 mol ×
(14, 0.100). In this c ase:

2 = 0.00896 mol. Therefore:
0.100 − 0.250
3 1
0.00896 mol gradient(0) = = −0.0107 mol dm s
Δc(HCl) =
14 − 0
3
0.100 dm
Since the stoichiometric coecient before HCl(aq) is 2, the

3
= 0.0896 mol dm
overall initial rate of the reaction will be half the absolute
To nd the concentration of HCl at t = 10 s, subtract

slope value:
the change in concentration of HCl from the initial

| gradient(0) | | −0.0107 |
3 1
ν = = = 0.0054 mol dm s
concentration: init
2 2
3
For the tangent at t = 55 s, two possible points are
c(HCl) = 0.250 0.0896 ≈ 0.160 mol dm
(32, 0.085) and (78, 0.045), so:
All other concentrations up to t = 90 s c an be c alculated in

0.045 − 0.085
4 3 1
gradient(55) = ≈ −8.7 × 10 mol dm s

the same way (table 3).
78 − 32
−4
| gradient(55) | | −8.7 × 10 |
Now we can plot these concentrations against time and draw
ν (55) = =
inst
tangent lines to the curve at t = 0 s and t = 55 s (gure 4). 2 2
4 3 1
≈ 4.4 × 10 mol dm s
t / s 0 10 20 30 40 50 60 70 80 90
c(HCl) 0.250 0.160 0.118 0.095 0.081 0.070 0.061 0.056 0.052 0.050
−3
/ mol dm
pTable 3 Concentration of hydrochloric acid in the reaction with magnesium metal
0.250
(x , y ) = (0, 0.250)
0 0
0.200
3
md
0.150
lom / )ICH(c
0.100
t = 55s
(x , y ) = (14, 0.100)
1 1
0.050
(x , y ) = (32, 0.085)
2 2
(x , y ) = (78, 0.045)
3 3
0.000
Figure 4 Determining initial and
0 10 20 30 40 50 60 70 80 90
instantaneous reaction rates from
t / s
concentration changes
485
Tips for plotting experimental data

Activity
as a graph, drawing tangent lines
and determining the gradient c an

For all the values of t listed in table 2, c alculate the concentrations of c alcium
be found in the Skills chapter.

chloride in the reaction mixture and plot these concentrations against time
on a graph paper. Using the tangent line method, determine the initial
3 1
reaction rate, in mol dm s , and the instantaneous reaction rate, in the
same units, at t = 150 s.
By denition, reaction rates should always be expressed through the changes in
concentration of reactants and/or products. However, reaction rates are oen
expressed through changes in volume, mass or other parameters that c an be
measured directly in the course of the experiment. In such c ases, the units of the
c alculated reaction rate are dened by the chosen parameter.
Worked example 4
3 1
a. Determine the initial rate, in cm s , for the reaction b. Use your answer to part a to c alculate the overall
3 1
of hydrochloric acid with magnesium metal in initial rate in mol dm s
worked example 2.
Solution
3 1
a. The units cm s suggest that the rate should be b. Initially, the volume of hydrogen gas released per
expressed through the volume of hydrogen gas from second from 0.100 dm of the reaction mixture was
3 3
table 1. The plot of V(H ) against time is shown in 13.3 cm , or 0.0133 dm . Therefore:
2
gure 5.
3
V(H ) 0.0133 dm
2
Δn(H ) = = ≈ 0.00054 mol

2
3 1
V 24.8 dm mol
To nd the instantaneous rate, we need to draw a m
tangent line to the curve at t = 0 s and select any two
Δn 0.00054 mol
3
points on that line, for example, (0, 0) and (12, 160). In Δc = = = 0.0054 mol dm
3
V(solution) 0.100 dm
this c ase:
0.0054 mol dm
|Δc |
3 1
160 − 0
ν = = = 0.0054 mol dm s
3 –1 init
gradient(0) = ≈ 13.3 cm s Δt 1 s
12 − 0
Note that the ν value for the overall reaction is the same
init
The stoichiometric coecient before H (g) is 1, so the

2
as that obtained in worked example 3.
initial reaction rate is numeric ally equal to the absolute
slope value:
3 1
v = |gradient(0)| = 13.3 cm s
init
250
200
(x , y ) = (12, 160)
1 1
3
mc / )
150
2
H(V
100
50
(x , y ) = (0, 0)
0 0
0 10 20 30 40 50 60 70 80 90
t / s
pFigure 5 Determining initial and instantaneous reaction rates from volume changes
486
Practice questions
Linking questions
2. a. Using the data from
Concentration changes in reactions are not usually measured directly. What
table2, plot on a graph
methods are used to provide data to determine the rate of reactions? (Tool 1,
paper the change in mass
3, Inquiry 2)
of the reaction mixture as a
What experiments measuring reaction rates might use time as i) a dependent

function of time.
variable ii) an independent variable? (Tool 1)
b. Using the tangent line
method, determine the
initial reaction rate in g s
c. Use your answer to part(b)
The collision theory (Reactivity 2.2.2)

to c alculate the overall
3 1
initial rate in mol dm s
The kinetic molecular theory (Structure 1.1) describes an ideal gas as a collection
of randomly moving particles that collide elastic ally. Elastic collisions do not aect
the total energy of gas particles, which means that an ideal gas is chemic ally inert
and therefore has a constant molecular composition.
The kinetic molecular theory also states that the average kinetic energy, E , of
k
gas particles is proportional to the absolute temperature of the gas. At absolute
zero (0 K), the movement of all particles slows down to a point at which they
c annot transfer energy to the surroundings and so they c annot get any colder.
When the temperature increases, the particles move faster and exchange energy
with one another through collisions. If we know the temperature of an ideal gas
in kelvin, we c an always c alculate the average kinetic energy of the gas particles.
However, such c alculations are not required in DP chemistry.
The collision theory expands the kinetic molecular theory by allowing the
particles to collide non-elastic ally and undergo chemic al changes. In contrast to
the kinetic molecular theory, this theory is not limited to gases and c an be applied
to reacting species in any state of matter.
According to the collision theory, the kinetic energy, E , of most particles is

k
insucient for breaking chemic al bonds. Such particles bounce o each other
like billiard balls and y in opposite directions. These are c alled unsuccessful
collisions, as they do not aect the chemic al nature of the colliding particles.
Collisions redistribute kinetic energy between particles unequally, so some
particles accelerate while others slow down. A collision between two fast-
moving particles might be violent enough to break or rearrange chemic al bonds
C
and transform the reactants into products. Such successful collisions lead to B B C
chemic al changes.
+
D
A A D
In addition to kinetic energy, the orientation of colliding particles is also
important. As an example, consider the following exchange reaction:
AB + CD → AD + BC
B D
For a collision to be successful, existing covalent bonds A–B and C–D must be
+ no reaction
broken, and new covalent bonds A–D and B–C must be formed. This is only
A C
possible if atom A comes into close proximity with atom D, and atom B comes
into close proximity with atom C (gure 6, top). Collisions in other orientations
pFigure 6 F av o u ra b l e ( t o p) and
will be unsuccessful, even if the kinetic energies of molecules AB and CD are u n f av o u ra b l e ( b o tt o m ) orientations of
high enough for the reaction to take place (gure 6, bottom). colliding molecules
487
Some reacting species, such as individual atoms and monatomic ions, are
Linking question
symmetric al, so the results of their collisions do not depend on orientation.
Chemic al reactions between these species tend to proceed faster than reactions
What is the relationship between

involving large and complex molecules, where the orientation of reactants is
the kinetic molecular theory and

particularly important.
collision theory? (Structure 1.1)
In summary, for a chemic al reaction to occur, the following conditions must
be satised:
1. Two (or more) particles must collide with each other.
2. The colliding particles must have the correct mutual orientation.
3. The sum of kinetic energies of the particles must be sucient to initiate
the reaction.
Factors aecting reaction rates
(Reactivity 2.2.3)
It follows from collision theory that the rate of a chemic al reaction is proportional
to the frequency of successful collisions in a given volume of the reaction mixture.
Any change in reaction conditions that aects the number of collisions per
second, or the average kinetic energy of colliding particles, will also aect the
reaction rate.
An increase in concentration of a reactant leads to more frequent collisions
between the particles of that reactant and other species, so the reaction rate
increases (gure 7). Conversely, a decrease in concentration of any reactant slows
down the reaction.
Figure 7 Effect of c o n c e n t ra t i o n on
the f re quency of collisions
low concentration high concentration
Pressure aects the rates of reactions with gaseous reactants in the same way
as concentration: an increase in pressure increases the reaction rate, while a
decrease in pressure has the opposite eect. Unlike gases, liquids and solids are
almost incompressible, so pressure has no eect on reactions that do not involve
gaseous reactants.
In heterogeneous mixtures, the collisions between reactant molecules are
possible only at the surface where the dierent phases meet. A phase is an
individual substance or mixture that has uniform chemical and physical properties.
Although the term “phase” is oen used as a synonym for “state of matter ”,
immiscible liquids can form two or more separate phases with dierent chemical
compositions.
488
Similarly, each solid substance in a heterogeneous mixture is a separate phase.
Therefore, the rates of heterogeneous reactions depend on the surface area of
reacting species. When a solid reactant is broken down into smaller pieces, its
surface area increases, and so does the reaction rate (gure 8).
Figure 8 Effect of surface are a on
the f re quency of collisions (left: one
large piece of a solid re actant, smaller
surface are a, l e ss f re quent collisions,
l ow e r re action ra t e ; right: s e v e ra l smaller
pieces of the solid re actant, larger
surface are a, more f re quent collisions,
higher re action ra t e)
Heterogeneous reactions oen proceed more slowly than homogeneous
reactions, in which the reaction mixture is a single phase. However, when the
surface area of reactants is extremely large, heterogeneous reactions can also be
very fast. Combustion of powdered substances, such as our or coal dust, can be
very violent, which in the past led to many major explosions in grain mills and coal
mines. Similarly, ne powders of active metals ignite spontaneously in air and react
explosively with water and acids. For example, the reaction between hydrochloric
acid and magnesium from worked example 2 would be complete within a few
seconds if the magnesium ribbon were replaced with magnesium powder. When
a reaction involves a liquid and a gas, the reaction rate increases when the gas is
bubbled through the liquid rather than passed over the liquid surface.
Concentration, pressure and surface area aect reaction rates by increasing or
decreasing the frequency of collisions between reacting species. However, none

ATL Thinking skills
of these factors aects the kinetic energy of colliding particles, so the proportion
Bacterial activity in food is

of successful collisions remains the same. This proportion depends on the
slowed down at low temperatures,

temperature of the reaction mixture.
so refrigerated food remains fresh
for much longer than that stored

When temperature increases, the average speed and kinetic energy of particles also
at room temperature. What other

increase. As particles move faster, they collide with one another more oen. At the
examples of chemic al activity

same time, a higher percentage of these collisions become successful, as a greater
decreasing at low temperatures

number of particles have sucient kinetic energy for the reaction to occur (gure 9).
c an you think of in the world

Therefore, the rate of almost any reaction increases with temperature. Conversely,
around you?
low temperature slows down almost all chemical and biochemical reactions.
Figure 9 Effect of t e m p e ra t u r e on
the f re quency of collisions (left: l ow
t e m p e ra t u r e ; right: high t e m p e ra t u r e)
489
Activity
Hydrogen peroxide in aqueous solutions decomposes as follows:
2H O (aq) → 2H O(l) + O (g)

2 2 2 2
The graph in gure 10 shows the volume of oxygen gas released in this
reaction as a function of time.
sag
fo
emulov
time
pFigure 10 Volume of oxygen gas released by decomposition of
aqueous hydrogen peroxide over time
Copy gure 10 and, on the same graph, sketch and label three curves for the
following changes in experimental conditions:
• increased initial concentration of hydrogen peroxide
• lowered temperature of the reaction mixture
• increased atmospheric pressure.
Eective note-taking is a valuable skill. If done well, c an were written. Eective note-taking is particularly important
help you follow and engage with a particular set of ideas, when learning concepts such as the ones covered in this
while also developing a useful set of notes to revise chapter, which contain a large amount of interlinked ideas
from. You may take notes during class discussion, while and key voc abulary.
reading a textbook, or doing research, for example. One
On the internet, search for a reliable explanation of
note-taking method, known as the Cornell method, is
Cornell note-taking, then try it out. You might want to
useful bec ause it reminds you to write in your own words,
compare how eective this method is for taking notes in
as well as prompting you to come up with “cues” that
class compared to note-taking while you read a certain
identify key ideas and the connections with other areas of
section in this book. L ater, reect on your experience and
the subject. Typic ally, the Cornell method also includes
adjust your note-taking strategies as needed.
summarizing the set of notes a short time aer the notes
490
Investigating the eect of concentration on rate of reaction
Dilute hydrochloric acid reacts with c alcium c arbonate to

Concentration of Time taken, t, to collect
produce c arbon dioxide, water and c alcium chloride: −3 3
HCl / mol dm 50 cm of CO / s
2
1 2 3
2HCl(aq) + C aCO (s) → CO (g) + H O(l) + C aCl (aq)
3 2 2 2
0.2 202 498 215
The rate of the reaction c an be monitored by measuring
0.4 118 104 98
the volume of gas produced over time.
0.6 62 58 65
Relevant skills
0.8 54 48 52
• Tool 3: C alculate mean 1.0 30 35 33
• Tool 3: Plot linear and non-linear graphs

pTable 4 The student’s results
• Tool 3: Draw lines or curves of best fit
Questions
• Inquiry 1: Identify independent, dependent and
1. Identify the independent and dependent variables in
control variables
the investigation.
• Inquiry 2: Identify and justify the removal or inclusion
2. Describe two control variables that were, or should
of outliers in data
have been, kept constant.
• Inquiry 2: Assess accuracy and precision

3. Identify the outlier.
1 1
• Inquiry 3: Evaluate the implications of methodological
4. The rate of reaction is proportional to . C alculate
t t
weaknesses, limitations and assumptions on conclusions.
for each of the acid concentrations.

5. Using graph-plotting soware, plot graphs to show:
to an investigation. 3
a. time taken, t, to collect 50 cm of CO vs

2
concentration of HCl
A student investigating the effect of the concentration of
1
acid on the rate of production of c arbon dioxide, c arried
b. vs concentration of HCl
out this reaction at five different concentrations of acid
6. Draw lines or curves of best t on your graphs.
using the apparatus shown below. The student recorded
7. Explore the eect of including and excluding the

3
the time taken to collect 50 cm of gas in the measuring
outlier on the results. Decide whether it should be
cylinder.
disc arded from the data set. Justify your choice.
gas collecting in
8. By referring to the graphs, comment on the relative
measuring cylinder
impact of systematic and random errors on the
outcome of the investigation.
9. Describe and explain three major sources of error in
this investigation.
10. Suggest changes to the methodology that would
help to eliminate or minimize the sources of error you
have identied.
11. Describe and explain one extension which would
build on the outcome of this investigation.
12. Outline how you could investigate the rate of the
following reactions:
hydrochloric acid
water
a. magnesium and hydrochloric acid,
and marble chips

2 2
b. hydrochloric acid and sodium thiosulfate,

pFigure 11 Apparatus for investigating the eect of
concentration on the rate of reaction

2HCl(aq) + Na S O (aq) → 2NaCl(aq) + H O(l) + SO (g) + S(s)
2 2 3 2 2
c. bromine and methanoic acid,

C alcium c arbonate in the form of marble chips was
− +
Br (aq) + HCOOH(aq) → 2Br (aq) + 2H (aq) + CO (g)

addedin large excess. The results are shown in table 4. 2 2
13. Formulate a research question that investigates an
aspect of the kinetics of a reaction of your choice.
Outline your plan, referring to the Inquiry 1 skills.
491
Linking questions
What variables must be controlled in studying the eect of a factor on the rate
of a reaction? (Tool 1)
How c an graphs provide evidence of systematic and random error?
(Tool 3, Inquiry 3)
Activation energy (Reactivity 2.2.4)
The minimum kinetic energy, E , of colliding particles required for the reaction to
k
occur is known as the activation energy, E

a
• When the sum of kinetic energies of colliding particles is less than the
activation energy (E < E ), the collision between these particles will always
k a
be unsuccessful, regardless of their mutual orientation.
• When E ≥ E , the collision c an be successful if the mutual orientation of the

k a
particles is correct.
E
a
The concept of activation energy c an be illustrated by a simple analogy. Imagine
a ball at the bottom of a hill (gure 12). On its own, the ball c annot reach the
lower ground at the opposite side of the hill. However, if we spend some
∆H
r
energy and push the ball over the top, it will roll down and eventually reach the
lowest point. In this analogy, the hill height represents the activation energy, E ,
a
pFigure 12 An analogy of activation

while the dierence in elevation between the initial and nal levels of the ball
energy, E , and the reaction enthalpy, ΔH

a r
represents the reaction enthalpy, ΔH
r
The progress of a chemic al reaction c an be represented by its energy prole
(gure 13). The reaction coordinate on the horizontal axis shows the general
direction of the chemic al change from reactants to products, while the vertic al
axis shows the energy at each stage of the reaction. For an exothermic process
(ΔH < 0), the reactants have a higher energy than the products (gure 13, le),
r
Enthalpy changes and thermal
so excess energy is released in the form of heat. In contrast, an endothermic
eects of chemic al reactions are
process (ΔH > 0) requires energy bec ause the energy of the products is higher
r
discussed in Reactivity 1.1
than that of the reactants (gure 13, right).

ygrene
ygrene
E
a
E
a
reactants
products
∆H < 0 ∆H > 0
r r
reactants
products
reaction coordinate reaction coordinate
pFigure 13 Energy proles for exothermic (le) and endothermic (right) reactions
492
The activation energy, E , is equal to the dierence in energy between the

a
The enthalpy changes associated
reactants and the transition state. The transition state is the least stable
with the breaking and formation
arrangement of atoms in the reacting species. In this state, some of the chemical
of chemic al bonds are discussed
bonds in the reactants are broken or weakened while the new bonds have not
in Reactivity 1.2. The structures
been fully formed. This situation is very unfavourable, as the energy used for bond
of transition states for certain
breaking is not compensated by the energy released by bond forming. Therefore,
reaction types will be discussed in
the transition state has the highest energy along the reaction coordinate.
Reactivity 3.4
Practice questions
3. Consider the following reaction that proceeds in a single step:
A + B → C + D ΔH = −10 kJ mol
r
The activation energy, E , for this reaction is 20 kJ mol

a
a. Sketch the energy prole for this reaction.
b. Deduce the activation energy, in kJ mol , for the reaction
C + D → A + B that has the same transition state as the forward reaction.
The eects of temperature on reaction rates c an be explained by analysing the
distribution of kinetic energies (E ) of reacting species. According to the kinetic

k
molecular theory, the average kinetic energy, E , of gas particles is proportional

k
to the absolute temperature of the gas. The particles move randomly and collide
with one another, so their kinetic energies change constantly. Although it is not
possible to predict the E value for each individual particle, we c an plot the
k
statistic al distributions of these energies at various temperatures (gure 14). These
plots, known as M axwell Boltzmann energy distribution curves, show the
probability of nding a particle with a certain kinetic energy against that energy.
The maximum of the curve shows the kinetic energy of the highest proportion of
particles, and the average kinetic energy of all the particles, E , is slightly to the
k
right of this maximum. The area under the curve represents the total number of
particles in the sample.
At moderate temperatures (T ), the majority of particles are unreactive, as

1
their kinetic energies are lower than the activation energy. As the temperature
increases to T , the M axwell Boltzmann curve attens and broadens, so its

2
maximum shis to the right. As a result, the proportion of reactive particles with
E > E increases, and so does the reaction rate.

k a
Activity
T
1
selcitrap
T
2
Copy the plot shown in gure14
and sketch a third M axwell

fo
Boltzmann curve at a temperature

noitroporp
T , where T < T . Outline the

3 3 1
reactive particles
main features of the new curve
(the position and height of
its maximum). Predict, with a
E E E reference to E and E , whether the

k1 k2 a k a
proportion of reactive particles at

kinetic energy
T will be lower, higher or the same

3
pFigure 14 M axwell Boltzmann energy distribution curves for gas
as that at T
1
particles at two temperatures, where T > T

2 1
493
Although the M axwell Boltzmann distribution of kinetic energies applies to
gaseous particles only, the general relationship between reaction rate and
temperature remains valid for substances in any state of matter. For most reactions
at moderate temperatures (0 100 °C), the rate increases two to four times when
the temperature rises by 10 °C.
C atalysts (Reactivity 2.2.5)
In addition to raising the temperature, the proportion of successful collisions in a
reaction mixture c an be increased using a c atalyst. A c atalyst is a substance that
increases the rate of a chemic al reaction but is not consumed in that reaction.
Typic ally, a c atalyst reacts with a reactant to form an unstable compound known
as an intermediate. An intermediate c an exist in a reaction mixture for a certain
period of time. In contrast, a transition state is a particular conguration of atoms
along the reaction pathway that c annot exist for any prolonged period of time.
A useful analogy of a reaction intermediate is a pencil standing upright on its at
end. Although its balance is prec arious, the pencil will not fall until someone taps
on the table or disturbs the air in the room. In contrast, a transition state is like a
pencil standing upright on its sharpened tip — the pencil will fall at once, even
without a disturbance.
The intermediate undergoes further chemic al changes and eventually forms the
reaction product, releasing the c atalyst in an unchanged form. Therefore, the
c atalyst itself is both a reactant and product of the same reaction.
By providing an alternative pathway for a reaction, a c atalyst reduces the
activation energy of that reaction (gure 15). A c atalysed reaction usually
proceeds in several steps and involves at least one intermediate and two or more
transition states. E ach step requires less energy than the unc atalysed reaction
(E ' < E ), so a greater proportion of collisions between reacting particles are

a a
successful.
The overall enthalpy change for the reaction, ∆H , is the same with and without
r
a c atalyst.
The eect of a c atalyst on the reaction rate c an also be explained using a
M axwell Boltzmann distribution curve (gure 16). A lower activation energy
means that more particles have enough energy to react with one another, so the
reaction rate increases.
transition state (unc atalysed)

selcitrap
transition states
(c atalysed)
reactive particles
ygrene
fo
E (c atalysed)
a
noitroporp
reactive particles
Eʹ
a
(unc atalysed)
reactants
intermediate
∆H
r
products
Eʹ (c atalysed) E (unc atalysed)

a a
reaction progress kinetic energy
pFigure 15 Energy proles for unc atalysed and c atalysed reactions pFigure 16 M axwell–Boltzmann energy distribution curves for
unc atalysed and c atalysed reactions
494
Both temperature and c atalysts aect reaction rates by altering the proportion of
particles with E > E . A rise in temperature does not aect E but increases the
k a a
average E . In contrast, a c atalyst does not aect the average E but reduces E .
k k a
In both c ases, the frequency of successful collisions increases, and so does the
reaction rate.
Practice questions
4. Sulfur(IV) oxide reacts with molecular oxygen as follows:
2SO (g) + O (g) → 2SO (g) ∆H < 0

2 2 3 r
In the presence of nitrogen(IV) oxide, the rate of this reaction increases up
to 10,000 times owing to the following two-step process:
SO (g) + NO (g) → SO (g) + NO(g)

2 2 3
NO(g) + 0.5O (g) → NO (g)

2 2
a. State the roles of the nitrogen oxides in this process and explain their
eects on the reaction rate.
b. Sketch an energy prole showing the unc atalysed and c atalysed
reactions, labelling the reactants, products and any intermediates.
Biochemic al reactions are c atalysed by proteins c alled enzymes. Without
enzyme c atalysis, many processes in living organisms would be impossible,
and life itself would not exist in its present form. The eciency of enzymes
greatly exceeds the c atalytic power of synthetic c atalysts. Some enzymes c an
16
accelerate reactions as much as 10 times, so chemic al transformations that
would normally take millions of years proceed within milliseconds. At the same
time, every enzyme is very specic and will usually c atalyse only one or very few
chemic alreactions.
ATL Research skills
Catalysis is one of the green chemistry principles, and a • zeolites in c atalytic cracking
focus of much chemical research. Catalysts can help to

• lactase in the digestion of lactose
lower the environmental impact of a process by reducing
• organoc atalysts, such as proline, in asymmetric
its energetic demands, and in some cases, decreasing the
aldol reactions.
amount of waste. For example, the now shorter and more
ecient synthesis of the anti-inammatory drug ibuprofen is

Prepare a ve-minute explanation for a non-scientist,
due to the use of catalysts. Several chemistry Nobel Prizes

outlining:
have been awarded for work relating to catalysis.
1. The specic problem or issue the c atalyst helps
to address.
Choose a c atalyst to research, for example:
2. How the c atalyst helps to address the problem.
• iron in the production of ammonia
3. Social, economic and/or environmental impacts
• transition elements in c atalytic converters

related to the use of the c atalyst.
495
Activity
State the eects of various factors on the reaction rate by copying and completing the table below. In each c ase, assume
that all other reaction conditions remain unchanged. Some cells are already lled as examples.
Factor Frequency of Average E Activation R ate of

k
collisions of reacting energy forward
species reaction
decrease in a reactant concentration
increase in pressure of a gaseous reactant increases
decrease in pressure of a gaseous product no change
increase in volume of a gaseous reaction mixture no change
decrease in temperature decreases
increase in surface area of a solid reactant
addition of a c atalyst
Linking questions
What is the relative eect of a c atalyst on the rate of the forward and
backward reactions? (Reactivity 2.3)

LHA
What are the features of transition elements that make them useful as
c atalysts? (Structure 3.1)

LHA
Multistep reactions (Reactivity 2.2.6, 2.2.7
and 2.2.8)
As mentioned earlier, an intermediate is an unstable compound or other
molecular species that c an exist in a reaction mixture for a certain period of
time. In contrast, a transition state is a particular conguration of atoms along the
reaction pathway that c annot exist for any prolonged period of time.
M any reactions involve a series of chemic al changes across multiple
intermediates and transition states. The sequence of these changes along the
reaction pathway is known as the reaction mechanism. A reaction mechanism
involves one or more elementary steps. A reaction mechanism with more than
one elementary step is c alled a multistep reaction.
In each elementary step, one, two or (very rarely) three molecular species
undergo a chemic al change through a single transition state and no
intermediates. The number of species (atoms, molecules or ions) involved in an
elementary step denes its molecularity: a unimolecular step involves a single
species, a bimolecular step involves two colliding species, and a termolecular
step involves three species colliding at the same time.
496
LHA
Termolecular reactions are very rare bec ause three particles are very unlikely to
collide with each other at exactly the same time and in the correct orientation.
This situation is similar to snooker (gure 17), in which two-ball collisions occur all
the time, while three-ball collisions are uncommon.
Each elementary step is characterized by its own activation energy, E . The slowest
a
step, known as the rate-determining step, limits the overall rate of reaction for any
given concentrations of the reactants. Typically, the rate-determining step has the
highest E among all other elementary steps of the reaction.

a
The concept of the rate-determining step can be illustrated by a simple analogy.

pFigure 17 Yo u c an think of balls on
Before leaving an international airport, passengers must go through passport a snooker table as a model of colliding
control and collect their luggage. A long queue at the passport control desks might particles in elementary re actions
hold the passengers at the airport for a long time, even if the luggage has already
been delivered. In contrast, if there is no queue at passport control but the luggage
has not arrived yet, the rate at which the passengers leave the airport will depend
on the rate at which the luggage will appear on the carousel. In the same way, the
rate of the slowest elementary step determines the rate of a chemical reaction.
Reaction mechanisms, including intermediates, transition states and activation
energy, c an be represented by energy proles. For a single-step reaction, the
energy prole includes a single transition state and no intermediates. A two-step
reaction typic ally involves one intermediate and two transition states. Use the
following rules when sketching an energy prole diagram for multistep reactions:
1. The less stable the species, the higher it appears in the prole.
2. Reactants are less stable than products if the reaction is exothermic (ΔH < 0)
r
and more stable than products if the reaction is endothermic (ΔH > 0).
r
3. An intermediate is less stable than both the reactants and products.
4. The rate-determining step usually has the highest E value.

a
5. The number of transition states is equal to the number of elementary steps.
6. The number of intermediates is equal to the number of elementary steps
minus one.
7. An annotated diagram must have the labels for reactants, products,
intermediate(s), transition states and activation energies.
8. The y-axis should be labelled “energy” and the x-axis should be labelled
“reaction coordinate” or “progress of reaction”.
TOK
The reaction mechanism is a hypothesis about the sequence of events
that transform the reactants into products. A correct hypothesis must not
contradict the experimental data. If two or more alternative mechanisms are
compatible with the data, further studies of the reaction kinetics are required.
Hypotheses are falsiable by any evidence that contradicts them. However,
no amount of evidence c an ever prove a hypothesis to be true with complete
certitude. To what extent are some things unknowable?
497
LHA
Worked example 5
Consider the following reaction:
NO (g) + CO(g) → NO(g) + CO (g)

2 2
At low temperatures, the reaction proceeds in two steps.
step 1 NO (g) + NO (g) → NO (g) + NO(g)

2 2 3
step 2 NO (g) + CO(g) → NO (g) + CO (g)

3 2 2
The concentration of CO(g) does not aect the rate of reaction.
a. Deduce the rate-determining step for this reaction at low temperatures.
b. Identify the reaction intermediate at low temperatures.
The overall reaction has a ΔH value of −126 kJ mol . At high temperatures, the reaction proceeds
r
in a single step.
c. Using the kinetics data, sketch the energy proles for this reaction at low and high temperatures.
Solution
a. C arbon monoxide, CO(g), participates only in the second step of the reaction. If this step were the
rate-determining step (RDS), any change in the concentration of CO(g) would aect the frequency
of successful collisions of the reactants and therefore the overall rate of reaction. However, the
experimental data show that the concentration of CO(g) has no eect on the reaction rate. Therefore,
the second step is fast while the rst step is slow (RDS).
b. The reaction intermediate is NO (g), which is formed on the rst step and consumed on the second
3
step. As any intermediate, it does not appear in the overall equation for the reaction.
c. At low temperatures, the reaction proceeds in two steps, so it has a single intermediate, NO (g),
3
and two transition states. The reaction is exothermic (ΔH < 0), so the products will appear lower in
r
the energy prole. The intermediate is likely to be less stable than both the reactants and products
(otherwise, the reaction would probably stop aer the rst step). Finally, the activation energy of the
rate-determining rst step is likely to be higher than that of the second (fast) step. This is summarized
in gure 18.
transition state 1
transition state 2
E
a2
0.5NO (g) + 0.5NO(g)

3
E
a1
+ CO(g)
ygrene
intermediate
NO (g) + CO(g)
2
reactants
∆H < 0
r
NO(g) + CO (g)
2
products
reaction progress
pFigure 18 Energy prole for the reaction at low temperatures
498
LHA
At high temperatures, the reaction has a single transition state and no intermediates.
The relative energies of the reactants and products remain unchanged (gure 19).
transition state
ygrene
E
a
NO (g) + CO(g)
2
reactants
∆H < 0
r
NO(g) + CO (g)
2
products
reaction progress
pFigure 19 Energy prole for the reaction at high temperatures
Evidence
Scientists make provisional explanations, known as hypotheses, using the patterns that emerge from their
observations. Results from further experimentation c an then refute or support these hypotheses.
Until recently, many reaction intermediates and all transition states were hypothetic al species that could not
observed directly. The development of femtosecond lasers (gure 20) allowed scientists to detect these species
and analyse their structures, eectively observing chemic al reactions at the timesc ales on which they occur.
15
pFigure 20 A femtosecond (1 fs = 10 s) laser is used for studying reaction intermediates and transition states
These studies were pioneered by the Egyptian chemist Ahmed Zewail, the “father of femtochemistry”. He was
awarded the 1999 Nobel Prize in Chemistry for his works in the eld of chemic al kinetics.
499
LHA
Linking question
Which mechanism in the hydrolysis of halogenoalkanes involves an
intermediate? (Reactivity 3.4)
R ate equations (Reactivity 2.2.9, 2.2.10
and 2.2.11)
You already know that reaction rates depend on the reactant concentrations.
Generally, an increase in concentration of a particular reactant by a certain
factor increases the reaction rate by a power of that factor. For most reactions,
this power has a small integer value ranging from 0 to 2. In other words, for the
reaction A + B → C, the rate ν depends on the concentrations of reactants A and
B as follows:
ν ∝ [A]
ν ∝ [B]
where n, m = 0, 1 or 2. Notice that the reaction rate does not depend on the
concentrations of products of that reaction.
The expressions describing the proportionality of the rate to the reactant
concentrations c an be combined into a single equation, known as the rate
equation:
n m
ν = k[A] [B]
where n, m = 0, 1 or 2 and k is the rate constant. The value of the rate constant
is specic for each reaction, and its units depend on the values of n and m. The
integer exponents n and m are known as the reaction orders with respect to the
individual reactants A and B. The sum of these exponents, n + m, is the overall
reaction order
Molar concentrations are oen denoted by square brackets around the substance
formulas or names. For example, the molar concentration of reactant A c an be
th
denoted as either c(A) or [A]. Similarly, a concentration raised to the n power c an
n n
be written as (c(A)) or [A] . The second expression takes less space, so it is used
more commonly.
In many c ases, the rate equation for a multistep reaction c an be determined
from the knowledge of the reaction mechanism and the rate-determining step.
Conversely, the reaction mechanism c an be evaluated using the experimentally
determined rate equation for that reaction.
500
LHA
Worked example 6
Consider the following reaction from worked example 5: a. Deduce the rate equation for this reaction at low
temperatures.
NO (g) + CO(g) → NO(g) + CO (g)

2 2
b. Determine the order of the reaction with respect
You saw that at high temperatures, the reaction proceeds to NO (g) and CO(g), and the overall order of the
2
in a single step, and at low temperatures, the reaction reaction, at low temperatures.
proceeds in two steps:
c. Deduce the rate equation for this reaction at high
temperatures.
step 1 NO (g) + NO (g) → NO (g) + NO(g)
2 2 3
d. Determine the order of the reaction with respect
step 2 NO (g) + CO(g) → NO (g) + CO (g)

3 2 2
to NO (g) and CO(g), and the overall order of the

2
reaction, at high temperatures.
Solution
a. In worked example 5, we determined that step 1 c. If the reaction proceeds in a single step, then the rate
was the rate-determining step at low temperatures. of this bimolecular reaction depends on the frequency
Therefore, the reaction rate depends on the frequency of collisions between NO (g) and CO(g) molecules,
2
of collisions between two NO (g) molecules, which is which is proportional to both [NO ] and [CO]:
2 2
proportional to the square of [NO ]:

2
ν = k[NO ][CO]
2
ν = k[NO ]
2
d. The reaction is rst order (n = 1) with respect to
b. The reaction is second order (n = 2) with respect to nitrogen dioxide, NO (g), and rst order (m = 1) with
2
nitrogen dioxide, NO (g), and zero order (m = 0) with respect to c arbon monoxide, CO(g). O verall, this is a
2
respect to c arbon monoxide, CO(g). Remember that second order reaction (n + m = 2).
any number raised to the zero power equals one, so
[CO] = 1, and therefore the concentration of c arbon
monoxide does not appear in the rate equation.
O verall, this is a second order reaction (n + m = 2).
It is important to understand that reaction orders depend on the mechanism of
the reaction and cannot be deduced from the mole ratio of the reactants. In the
n m
general c ase, the reaction aA + bB → cC + dD has the rate equation ν = [A] [B] ,
in which n and m might or might not be equal to a and b, respectively.
The orders of reactants, and therefore the exponents in the rate equation
c an be determined experimentally by measuring the eect that changing the
concentrations of the reactants will have on the initial rate of reaction.
For example, consider the hypothetic al reaction:
A + B + C → D
Imagine that data showed that doubling the concentration of A doubles the initial
rate of reaction. This means that the rate is proportional to the concentration of A,
or ν ∝ [A]. Therefore, the reaction is rst order with respect to A.
Doubling the concentration of B quadruples the initial rate. This means that the
rate is proportional to the square of the concentration of B, or ν ∝ [B] . Therefore,
the reaction is second order with respect to B.
501
LHA
Doubling the concentration of C has no eect on the initial rate, so the reaction is zero
order with respect to C. Therefore, the overall rate equation would be as follows:
ν = k[A][B]
The overall reaction order is the sum of the exponents, 1 + 2 = 3, so the reaction
is third order overall. Notice that the exponent of [A] is 1, so it is not shown in the
rate equation, but it contributes to the overall reaction order.
Once the exponents have been determined, the value of k c an be c alculated by
substituting known values of concentrations and initial rate into the rate equation.
The temperature in all experiments must be kept constant bec ause the rate
constant, k, is temperature-dependent.
Worked example 7
Iron(III) c ations are reduced by iodide anions as follows: d. Determine the initial reaction rate at 298 K and
+
3 2 3
[Fe ] = [I ] = 3.00 × 10 mol dm

+ +
3 2
2Fe (aq) + 2I (aq) → 2Fe (aq) + I (aq)

2
3+
Experiment [Fe ] [I ] ν
init
The experimental data obtained for this reaction at 298 K
3 3 3 1
/ mol dm / mol dm / mol dm s

are shown in table 5.
2 2 5
1 1.00 × 10 1.00 × 10 1.62 × 10
+
3
a. Deduce the reaction orders with respect to Fe (aq)

2 2 5
2 2.00 × 10 1.00 × 10 3.24 × 10
and I (aq).
2 2 4
3 2.00 × 10 2.00 × 10 1.30 × 10
b. State the rate equation and the overall reaction order.
pTable 5 Kinetics data for the reaction between iron(III) and
c. C alculate the value of the rate constant at 298 K and iodide ions at 298 K. Source of data: G. S. Laurence and K. J. Ellis,
state its units. J. Chem. Soc., Dalton Trans., 1972, pp. 2229–2233
Solution
a. The concentration of iodide ions in experiments 1 and c. The value of k does not depend on concentrations, so
2 3
2 is the same (1.00 × 10 mol dm ), so any change we c an use data from any row in table 5. The rst row
in the reaction rate is c aused by the change in the gives the following:
+
3
concentration of iron(III) ions. When [Fe ] doubles

ν
init
2 2 3
k =
(increases from 1.00 × 10 to 2.00 × 10 mol dm ), +
3 2
[Fe ][I ]
the rate also doubles (increases from 1.62 × 10 to −

5
−
3
−
1
1.62 × 10 mol dm s
5 3 1 =
− − − −
3.24 × 10 mol dm s ). Therefore, the reaction is 2 3 2 3 2
(1.00 × 10 mol dm ) × (1.00 × 10 mol dm )
+
3
rst order with respect to Fe (aq). − −

6 2 1
= 16.2 dm mol s
In experiments 2 and 3, the concentration of iron(III) is + −

3
d. Substitute the values of k, [Fe ], and [I ] into the rate

2 3
constant (2.00 × 10 mol dm ), so the rate is aected
equation:
by the concentration of iodide ions only. When [I ]
2 + −
3 2
doubles (increases from 1.00 × 10 to ν = k[Fe ][I ]

init
2 3
2.00 × 10 mol dm ), the rate increases four times (from
− − − −
6 2 1 2 3
5 4 3 1 = 16.2 dm mol s × 3.00 × 10 mol dm ×

3.24 × 10 to 1.30 × 10 mol dm s ). Therefore, the
− −
2 3 2
(3.00 × 10 mol dm )
reaction is second order with respect to I (aq).
− − −
4 3 1
+
3 2 = 4.37 × 10 mol dm s
b. R ate equation: ν = k[Fe ][I ]
O verall reaction order: 1 + 2 = 3
502
LHA
Practice questions
5. Consider the following reaction and experimental data from table 6:
A(g) + 2B(g) → C(g)
−3 −3 −3 −1
Experiment [A] / mol dm [B] / mol dm v / mol dm s

init
1 0.020 0.015 2.0 × 10
2 0.020 0.030 4.0 × 10
3 0.030 0.015 3.0 × 10
pTable 6 Kinetics data for the reaction between A(g) and B(g) at 298 K
a. Deduce the reaction orders with respect to A(g) and B(g).
b. State the rate equation and the overall reaction order.
c. C alculate the value of the rate constant at 298 K and state its units.
Graphic al representations of reaction order
Orders of chemic al reactions c an be deduced from their kinetic curves. One
type of kinetic curve, a rate concentration curve, represents the relationship
between rate and concentration in graphic al form (gure 21). E ach of these
curves c an be constructed from experimental data with ve or more data points.
second
first
)ν (
etar
noitca er
zero
reactant concentration
pFigure 21 The rate–concentration curves for zero, rst
and second order reactions
For a zero order reaction, the rate is independent of the reactant concentration, so
the rate concentration curve is a horizontal line that intersects the y-axis at ν = k.
For a rst order reaction, the rate is proportional to the reactant concentration, so
the curve is a straight line that begins at the origin and has a slope of k. For a second
order reaction, the rate is proportional to [A] , so the curve is parabolic, and the k
is numerically equal to the rate at [A] = 1 mol dm . Interpreting rate concentration
curves is summarized in table 7.
Reaction order R ate equation Curve k
0 ν = k horizontal line y-axis intercept
1 ν = k[A] sloped line slope
−
2 3
2 ν = k[A] parabola ν at [A] = 1 mol dm

init
pTable 7 Interpretation of rate–concentration curves for reactant A
503
LHA
The construction of rate–concentration curves is a time-consuming process, as
each curve requires a series of kinetic experiments using dierent concentrations
of the reactant(s). In contrast, a concentration–time curve c an be obtained
from a single experiment, in which the concentration of a particular reactant is
recorded at certain time intervals using a data logger (gure 22).
]A[
first
zero
second
time
pFigure 22 The concentration–time graph for zero, rst and second
order reactions
However, the interpretation of these curves is straightforward only in the c ase of
zero order reactions, where the concentration–time plot is a straight line. For a
zero order reaction, the y-axis intercept shows the initial concentration, [A] , and
0
the line slope gives −k. The concentration–time curves for the rst and second
order reactions look similar, so they c annot be distinguished from sketches.
These reactions c an instead be represented by linear plots (gure 23), which
allow you to determine the rate constant from the line slope.
Interpreting concentration–time curves is summarized in table 8.
second order
In[A] = kt + In[A] 1/[A] = kt + 1/[A]
0 0
intercept = In[A] intercept =1/[A]

0 0
slope = k slope = k
]A[/1
]A[nI
first order
0 0
time time
pFigure 23 Linear plots for rst order (le) and second order (right) reactions
Reaction Curve Linear function
order
Equation Slope y-axis intercept
0 negatively sloped line [A] = −kt + [A] −k [A]

0 0
1 exponential dec ay ln[A] = −kt + ln[A] −k ln[A]

0 0
2 hyperbolic dec ay 1 1 k 1
= kt +
(faster than exponential) [A] [A] [A]

0 0
pTable 8 Interpretation of concentration–time curves for reactant A
504
LHA
Worked example 8
Rec all the reaction of magnesium metal with hydrochloric acid:

2 2
In worked example 3, the following concentrations for HCl(aq) were determined (table 9).
Using the rst six data points, determine the order of this reaction with respect to hydrochloric acid.
t / s 0 10 20 30 40 50 60 70 80 90
c(HCl) /
0.250 0.160 0.118 0.095 0.081 0.070 0.061 0.056 0.052 0.050
−3
mol dm
pTable 9 Concentration of hydrochloric acid in the reaction with magnesium metal
Solution
The kinetic curve shown in gure 5 (worked example 4)

1.3
may represent either a rst or second order reaction.
Therefore, we need to process the experimental data and
plot the linear functions from table 8 for these two reaction
1.7
]A[nI
types. The function that produces a linear plot will give us
the reaction order.
2.1
The initial concentration of HCl(aq) is 0.250 mol dm ,
1
3 1
so ln[HCl] = −1.39 and = 4.00 dm mol . The

0
[HCl]
0
logarithms and reciproc al values for other data points c an 2.5
0 10 20 30 40
be c alculated in the same way (table 10).
time / s
t / s 0 10 20 30 40 50
13.0
[HCl]
0.250 0.160 0.118 0.095 0.081 0.070

1
−3
/ mol dm
lom
10.0
ln[HCl] −1.39 −1.83 −2.14 −2.35 −2.51 −2.66
3
md /
[HCl] 4.00 6.25 8.47 10.5 12.3 14.3

]A[/1
7.0
3 −1
/ dm mol
pTable 10 The rst six data points for the concentration of
hydrochloric acid in the reaction with magnesium metal

4.0
0 10 20 30 40
Now we c an use the data from table 10 to plot ln[HCl] and

time / s
against time (gure 24).

pFigure 24 Logarithmic (top) and reciproc al (bottom)
[HCl]
concentration–time curves for the reaction of magnesium
The second plot is linear, so the reaction is second order metal with hydrochloric acid
with respect to hydrochloric acid. Notice that the points in
this plot deviate slightly from the straight line bec ause of
random errors in the experimental data.
505
LHA
Practice questions
6. Consider the reaction of magnesium metal with hydrochloric acid, which
is discussed in worked examples 3 and 8.
a. Using the instantaneous reaction rates at t = 0 and 55 s from worked
example 3, determine the reaction order with respect to hydrochloric
acid. Round your answer to the nearest integer number.
b. Suggest one advantage and one disadvantage of this method
compared to the graphic al technique used in worked example 8.
Linking questions
What measurements are needed to deduce the order of reaction for a
specic reactant? (Tool 1, 3, Inquiry 2)
Why are reaction mechanisms only considered as “possible
mechanisms”?
What are the rate equations and units of k for the reactions of primary and
tertiary halogenoalkanes with aqueous alkali? (Reactivity 3.4)
The Arrhenius equation
(Reactivity 2.2.12 and 2.2.13)
You already know that the rate constants are temperature-dependent. This
dependence is quantitatively described by the Arrhenius equation, which was
rst derived by the Swedish scientist Svante Arrhenius:
Ea
RT
k = Ae
In this equation k is the rate constant, A is the Arrhenius factor, e is the base of
natural logarithms (2.718…), E is the activation energy of the reaction, R is the

a
ideal gas constant and T is the absolute temperature.
The value of the Arrhenius factor is specic to each reaction, as it takes into
account the frequency of collisions of the reacting particles with proper mutual
orientation. The units of A are identic al to those of the rate constant, k, so they
c an be derived from the rate equation.
For simple and highly symmetric al reactant particles, such as individual atoms or
diatomic molecules, A values are high, bec ause collisions c an lead to reaction
of the particles at any mutual orientation. In contrast, reactions between large
molecules occur only at specic orientations, so their A values are low.
For a rst order reaction, the units of both A and k are s , so the Arrhenius factor
is sometimes c alled the frequency factor (as frequency is oen expressed in the
same units, s ). Both A and E in the Arrhenius equation are almost independent
a
of temperature. In contrast, the value of k increases exponentially with temperature,
T
1/T
as k ∝ e = e .
506
LHA
The exact rate of this increase depends on the E value.
a
This means that by analysing the temperature dependence of the rate constant
for a particular reaction, you c an determine the activation energy. To do so, the
x
The Arrhenius equation in both its
Arrhenius equation c an be rearranged using the formula ln(e ) = x:
linear and logarithmic forms is given
E
a
ln k = − + ln A
in the data booklet.
RT
If you know two k values for the same reaction at dierent temperatures, or the
ratio of these two k values, you c an determine E without knowing the value of A.
a
To do this, the Arrhenius equations for k at T and k at T c an be subtracted

1 1 2 2
asfollows:
E E
a a
ln k − ln k = − + ln A − − + ln A
1 2
RT RT
1 2
By using the formula ln x − ln y = ln and c ancelling out the terms ln A and −ln A,
the equation c an be rearranged as follows:
k E 1 1
1 a
ln = −
k R T T
2 2 1
Now the activation energy of the reaction c an be found by substituting k , k , T

1 2 1
Practice question
and T with experimental data and solving the equation. If the concentrations
2
of all reactants are kept constant, the reaction rate shows the same temperature
7. The rate of a certain reaction at
v k
1 1
dependence as the rate constant: = . Therefore, the E value c an also be

a
constant concentrations of all
v k
2 2
reactants increases 8.2 times

determined from the reaction rates (instead of rate constants) at two dierent
when the temperature rises

temperatures.
from 25 to 45 °C. Determine
The logarithmic form of the Arrhenius equation is also useful for the analysis of
the activation energy, in
1 1
kJ mol , of that reaction.

reaction kinetics in graphic al form, as the plot of ln k against is a straight line.
T
E
a
The slope of this line gives − , and the intercept on the y-axis gives ln A
Worked example 9 6.0
The decomposition of nitrogen(V) oxide in the gas
phase is a rst order reaction:
7.0
2N O (g) → 2N O (g) + O (g)

2 5 2 4 2
The plot of ln k against for this reaction is shown

8.0
T
in gure 25.
k
nI
a. Determine the activation energy, E , in kJ mol ,

a
9.0
for this reaction.
b. Determine the Arrhenius factor, A, and state
its units.
10.0
11.0
0.0029 0.0030 0.0031 0.0032 0.0033 0.0034

1
Figure 25 Plot of ln k against for the
T 1
1/T / K
decomposition of N O (g)
2 5
507
LHA
Solution
a. To determine the activation energy, we need to b. First, choose any point on the line, for example, the
choose two points on the line as far apart as possible, point (0.00296, −6.02). This gives the following values:
for example, (0.00302, −6.8) and (0.00334, −10.8).
ln k = −6.02
For the linear form of the Arrhenius equation, the line
E
a 1
1
slope gives − , in K. Therefore:
= 0.00296 K
R
T
E − 6.8 − (−10.8)
a
− = From part a, we know that the gradient is as follows:
R 0.00302 − 0.00334
E
a
= −12 500 K
− = −12 500 K
You c an nd E by substituting the value of R into the

a Then, substitute these values into the logarithmic form of
E
expression for the slope: a
the Arrhenius equation (ln k = − + ln A) and solve for A:
RT
E
a
1
− = −12 500 K
−6.02 = −12 500 K × 0.00296 K + ln A
1 1
8.31 J K mol
1 1
E = −(−12 500 K × 8.31 J K mol )

a ln A = 30.98
= 104 000 J mol

30.98 13
A = e = 2.85 × 10
= 104 kJ mol
The Arrhenius factor, A, has the same units as the rate
The E values for many chemic al reactions fall into a

a
constant, k. Therefore, you should construct the rate
narrow range (50–100 kJ mol ), so the rates of dierent
equation and nd the units of k. The decomposition of
reactions show similar temperature dependence.
N O (g) is a rst order reaction, so it has the following

2 5
Remember that for most reactions at moderate
rate equation:
temperatures (0–100 °C), the rate increases two to four
times when the temperature rises by 10 °C. ν = k[N O ]

2 5
3 1
If the rate is measured in mol dm s and [N O ]

2 5
3 1
in mol dm , then the units for k are s ,
13 1
so A = 2.85 × 10 s
Determination of the activation energy of a reaction
In this practic al, you will determine the activation energy • Inquiry 1: Pilot methodologies
of a reaction of your choice.
• Inquiry 1: M aintain constant environmental conditions
Relevant skills of systems
• Tool 1: Addressing safety of self, others and • Inquiry 2: Assess validity and reliability
the environment
S afety
• Tool 2: Use technology to represent data in
graphic al form.
• Conduct a full risk assessment. Consider all the
• Tool 3: Interpret features of graphs including gradient
substances and methods used, as well as the
• Inquiry 1: Develop investigations that involve hands- behaviour of all substances when heated
on laboratory experiments
• Minimize the amounts of substances used
• Inquiry 1: Design and explain a valid methodology • Dispose of all substances appropriately
508
LHA
Choose one of the following experimental procedures to c arry out:
Reaction Method for monitoring rate
“Sulfur clock”: sodium thiosulfate and Due to the gradual formation of a sulfur precipitate, you c an measure the time
hydrochloric acid taken for the reaction mixture to obscure a mark below the ask.
Decomposition of hydrogen Due to the formation of oxygen gas, you c an measure the rate of oxygen
peroxide, c atalysed by c atalase, production with a gas syringe, or by collecting the gas over water, in an
copper(II) ions, or iodide ions inverted measuring cylinder.
“Iodine clock”: hydrogen peroxide The reaction involves multiple steps. In the last step, the reaction mixture
and iodide ions, in acid solution and undergoes a sudden change from colourless to blue-black when there is no
in the presence of thiosulfate ions more thiosulfate le to react with the free iodine produced in an earlier step.
andstarch You c an therefore measure the time taken for the colour change to occur.
Reduction of permanganate ions by The solution is decolorized as the purple manganate(VII) ions, MnO (aq), are
4
ethanedioate ions in acid solution consumed, so you can measure the time taken for this colour change to happen.
A chemiluminescent reaction, such as In the absence of other light sources, the light intensity of the reaction c an be
that in a light stick (gure 26) measured by a digital sensor (or suitable smartphone app).
Method
1. Conduct background research to determine a basic 8. Using appropriate soware, construct an Arrhenius
procedure that you will follow. Do not forget to cite plot of the data.
all sources appropriately.

9. Draw a line of best t and determine the gradient.
2. Have your risk assessment checked by your teacher,

10. C alculate the experimental value for the activation
and act on any feedback given.

energy of the reaction you chose.
3. Liaise with your teacher to obtain and prepare the

11. If possible, compare your experimental value to the
reagents required for your preliminary trials.

literature value by c alculating the percentage error.
4. Conduct the reaction at room temperature to get

12. Comment on the validity and reliability of the value
a sense of how to c arry it out. M ake note of any

you have obtained.
adjustments you need to make to the concentrations

13. Outline some of the possible sources of error.
of solutions, volumes, equipment sizes, etc.
5. Repeat the reaction, this time at a higher temperature
(for example, 50 °C, checking whether it is safe to
do so rst). You will need to devise a way to maintain
the reaction mixture at a constant temperature and
monitor the temperature to see if it varies during
thereaction.
6. Once you have made the necessary changes to your
materials and method, collect reaction rate data
for at least ve dierent temperatures. Repeat the
experiment three times at each temperature.
7. Process your data to compute the rate, or an
approximation of the rate of reaction. Depending on
your chosen reaction and method, this could involve:
pFigure 26 Chemiluminescent reactions produce light.
• Determining the initial rate of reaction by drawing
When the thin glass vial inside a light stick is snapped open, the
a tangent line at (0,0) on graphs of volume,
reactants are mixed, and a spontaneous reaction occurs. Some
concentration or absorbance against time

energy of this reaction is released in the form of visible light
or
• C alculating for each of the times measured.
509
Topic review
4. The questions below refer to the experiments

described in question 2.
a. Explain the shape of curve 1 from gure 27 in terms

How can the rate of a reaction be controlled?
of the collision theory.
b. Using the same graph, sketch the third curve that
would be produced if the original experiment were

run at a lower temperature.
2. Excess magnesium powder was added to a beaker
c. Using a dierent graph, sketch the concentration of
containing dilute hydrochloric acid. The mass of the

+
2
Mg (aq) ions against time for experiments 1 and 2.
beaker and its contents was recorded and plotted
5. C alcium oxide reacts with c arbon dioxide as follows:

against time (gure 27, curve 1).

2 3
Excess c alcium oxide was placed into a pressurized
vessel with a volume of 1.00 dm . The vessel was lled

ssam
with gaseous c arbon dioxide and sealed o. A constant
temperature of 25.0 °C was maintained during the
whole experiment. The plot of the pressure inside the

2
vessel against time is shown below.

Figure 27 M ass
of the beaker as a
300
time function of time
250
Which change could produce curve 2 in gure 27?

aPk / erusserp
A. Increasing the temperature 200
B. Using the same mass of Mg ribbon

150
C. Doubling the mass of powdered Mg
100
D. Using the same volume of concentrated HCl(aq)
50
LHA
3. Thiosulfate ions, S O (aq), are oxidized by hydrogen

2 3
peroxide, H O (aq), as follows: 0

2 2
+
2 2 0 5 10 15 20 25 30 35 40
H O (aq) + 2S O (aq) + 2H (aq) → S O (aq) + 2H O(l)
2 2 2 3 4 6 2
time / min
Which graph is consistent with the experimentally
determined rate equation, ν = k[H O ][S O ]?

2 2 2 3 a. Using the ideal gas law (Structure 1.5), c alculate the
concentrations of CO (g) in the vessel at t = 0, 5,

2
A.
B.
10, …, 40 min. Assume that the volume occupied

)ν (
)ν (
by solid substances is negligible.

etar
etar
− −
3 1
b. Calculate the average reaction rate, in mol dm min ,
for the period between 0 and 20 min.
0
0
2
2 c. Plot the concentration of c arbon dioxide against
[S O ]
3 [S O ]
2 3
2
time on graph paper.
C. D.
d. Using the tangent line method, determine the
)ν (
)ν (
initial reaction rate and the instantaneous reaction

etar
etar
rate at t = 10 min.
6. Consider the following process:
− + −
0 0
3I (aq) + H O (aq) + 2H (aq) → I (aq) + 2H O(l)
2 2 3 2
2 2
[S O ] [S O ]
3 3
2 2
O ver a period of 2.0 min, the concentration of
iodide ions in the solution decreased from 0.050 to
−
3
0.020 mol dm .
510
LHA
a. C alculate: b. State the rate equation and the overall reaction order.
3 1
i. average reaction rates, in mol dm s , with c. C alculate the value of the rate constant at 260 K.
respect to I (aq) and H O (aq)

2 2 The reaction proceeds in two steps:
ii. overall average reaction rate expressed in the

step 1 2NO(g) → N O (g)
2 2
same units.
step 2 N O (g) + Cl (g) → 2NOCl(g)
2 2 2
b. Sketch a graph to show the changes in

d. Using the rate equation deduced in part (b), identify
concentrations of I (aq), H O (aq) and I (aq)

2 2 3
the rate-determining step (RDS) in this reaction.
over time. Assume that the initial concentrations
9. Consider the following two-step reaction mechanism:
of I (aq) and H O (aq) were equal, and the initial

2 2
step 1 (slow) N O(g) → N (g) + O(g)

2 2
concentration of I (aq) was zero.

3
step 2 (fast) N O(g) + O(g) → N (g) + O (g)

2 2 2
c. Suggest how the change in concentration of
a. Formulate the equation for the overall reaction.

iodine, I (aq), could be monitored.
2
b. Identify the role (reactant, product or intermediate)

d. The experiment was repeated with the following
of each species involved in the reaction

changes:
mechanism.
i. the concentration of H O (aq) was doubled at

2 2
c. Identify the molecularity of the rate-determining step.

constant temperature
d. Deduce the rate equation of the overall reaction

ii. the reaction was c arried out in a pressurized
and state the overall reaction order.

vessel at 200 kPa instead of 100 kPa
e. The overall reaction has a ΔH value of −164.1 kJ mol .

r
iii. the temperature of the reaction mixture was
Sketch the energy prole for this reaction.

lowered by 5 °C
10. The rate constants of a certain reaction at 30 and 60 °C

iv. the solution of iodide ions, I (aq), was prepared
3 1 1
are 0.183 and 5.45 dm mol s , respectively.

from a ne powder of sodium iodide, NaI(s),
a. Identify the overall order of this reaction.

instead of large crystals of this compound.
b. Determine the activation energy, in kJ mol , of

For each of the changes, predict, stating a reason, its
the reaction.
eect on the rate of reaction.
3 1 1
c. C alculate the rate constant, in dm mol s , of this

7. Phosgene, COCl , is usually produced by the reaction
2
reaction at 45 °C.
between c arbon monoxide, CO, and chlorine, Cl ,
2
according to the equation: 11. Chlorine monoxide, ClO•, is an unstable radic al
1
that plays an important role in the process of ozone
CO(g) + Cl (g) → COCl (g) ΔH = −108 kJ mol
2 2 r
depletion. In the absence of ozone, chlorine monoxide

a. Sketch the potential energy prole for the synthesis
decomposes as follows:
of phosgene, indic ating both the enthalpy of
2ClO•(g) → Cl (g) + O (g)

reaction and the activation energy. 2 2
Kinetics studies show that this reaction has the second

b. This reaction is normally c arried out using a c atalyst.
order with respect to ClO•(g). The plot of ln k against

Sketch a second curve labelled “c atalysed” on the
1/T for this reaction is shown below.

diagram to indic ate the eect of the c atalyst.
c. Sketch a Maxwell–Boltzmann energy distribution

16.0
curve for gaseous reactants at a certain temperature.
d. Using your sketch from part c, explain the eect of
15.5
c atalyst on the reaction rate.

LHA
8. Nitrogen(II) oxide reacts with chlorine as follows:

k nI
15.0
2NO(g) + Cl (g) → 2NOCl(g)

2
The following experimental data were obtained for this
reaction at 260 K: 14.5
[NO] [Cl ] ν
2
init
−3 −3 −3 −1
/ mol dm / mol dm / mol dm min

14.0
0.0028 0.0030 0.0032 0.0034 0.0036 0.0038 0.0040

2 2 3
1.50 × 10 1.50 × 10 5.30 × 10
–1
1/T / K
2 2 2
1.50 × 10 3.00 × 10 1.06 × 10
a. Determine the activation energy, E , in kJ mol , for

a
2 2 2
3.00 × 10 3.00 × 10 4.24 × 10
this reaction.
a. Deduce the reaction orders with respect to Cl (g)

2
b. Determine the Arrhenius factor, A, for this
and NO(g).
511
reaction and state its units.
Reactivity 2.3 How far? The extent of
chemical change
How can the extent of a reversible reaction be inuenced?
Chemic al reactions are oen reversible, which means that pressure and concentrations of reacting species. The
they c an proceed both forwards and backwards at the optimum conditions for a chemic al process c an be
same time. In most practic al situations, chemists want to determined using Le Châtelier ’s principle, which enables
maximize the yield of the target product by facilitating the chemists to predict the eects of specic changes in these
forward reaction and suppressing the reverse reaction. conditions on the extent of a reversible reaction.
This goal c an be achieved by controlling the temperature,
Understandings
LHA
Reactivity 2.3.1 — A state of dynamic equilibrium is Reactivity 2.3.5 — The reaction quotient, Q, is
reached in a closed system when the rates of forward and c alculated using the equilibrium expression with
backward reactions are equal. non-equilibrium concentrations of reactants and
products.
Reactivity 2.3.2 — The equilibrium law describes how
the equilibrium constant, K, c an be determined from the Reactivity 2.3.6 — The equilibrium law is the basis
stoichiometry of a reaction. for quantifying the composition of an equilibrium
mixture.
Reactivity 2.3.3 — The magnitude of the equilibrium
constant indic ates the extent of a reaction at equilibrium Reactivity 2.3.7 — The equilibrium constant and
and is temperature dependent. Gibbs energy change, ΔG, c an both be used to
measure the position of an equilibrium reaction.

Reactivity 2.3.4 — Le Châtelier ’s principle enables
the prediction of the qualitative eects of changes in
concentration, temperature and pressure to a system
at equilibrium.
D ynamic equilibrium (Reactivity 2.3.1)
M any physic al and chemic al changes are reversible, so the interconversion
of reactants and products c an proceed simultaneously in both directions. In
equations that represent reversible changes, the reaction arrow (→) is replaced
with the equilibrium sign (⇌), which symbolizes the bidirectional nature of the
process. For example, the evaporation of liquid bromine, Br (l) → Br (g), and
2 2
the condensation of gaseous bromine, Br (g) → Br (l), c an be represented by a

2 2
single equation:
Br (l) ⇌ Br (g)
2 2
If a reversible change occurs in a closed system, it eventually reaches the state of
dynamic equilibrium, in which the rates of the forward and reverse processes are
equal. For example, if we place a small quantity of liquid bromine into a closed
ask, some of the bromine will evaporate (gure 1). The evaporation will increase
the concentration of Br (g) in the ask and the frequency of collisions between
2
gaseous molecules, some of which will lose energy and return to the condensed
phase, Br (l).
2
512
Reactivity 2.3 How far? The extent of chemic al change
pFigure 1 The colour of gaseous bromine in a closed ask rst darkens and then
remains unchanged when the state of dynamic equilibrium between Br (g) and Br (l)
2 2
is reached
At some point, the rate of evaporation will equal the rate of condensation, so
there will be no further changes in the amounts of Br (g) and Br (l) present in the
2 2
ask (gure 2). Both phases will remain in dynamic equilibrium indenitely unless
there is a change in external conditions, such as temperature or pressure.
liquid phase gaseous phase
pFigure 2 In a dynamic equilibrium, the forward and reverse reactions occur at equal rates
Equilibrium is a dynamic state, in which two or more ongoing processes perfectly
balance one another. This means that each participating species is consumed
and produced at the same rate. Although this might give the illusion that no
change is occurring during dynamic equilibrium, all components of the mixture
are constantly being transformed into one another. In other words, the changes
at equilibrium stop only at the macroscopic level but not at the microscopic level.
The dynamic nature of equilibrium c an be observed experimentally. Naturally
79 81
occurring bromine is a mixture of two stable isotopes, Br (51%) and Br (49%).
Imagine that we have allowed the system shown in gure 1 to reach equilibrium
and then replaced some of the liquid bromine with the same quantity of
80
radioactive bromine, Br (l). The concentrations of both liquid and gaseous

2
80
bromine will not change, but radioactive Br molecules will appear in the
2
gas phase almost immediately. This is only possible if the evaporation and
condensation of bromine continues even aer the dynamic equilibrium has
been established.
513
Figures 1 and 2 illustrate a heterogeneous equilibrium, in which the two
participating species, Br (l) and Br (g), are present in dierent phases. Another
2 2
type of heterogeneous equilibrium is established between a solid substance and
its solution if the solid substance is present in excess. If we mix excess sodium
chloride, NaCl(s), with water, the salt will begin to dissolve and form aqueous
ions, Na (aq) and Cl (aq). Some of these ions will recombine and precipitate out
of the solution as solid sodium chloride:
dissolution +
NaCl(s) Na (aq) + Cl (aq)
precipitation
Initially, the rate of dissolution greatly exceeds the rate of precipitation (gure3,
le). However, as the concentration of aqueous ions increases, the rate of
precipitation also increases and eventually becomes equal to the rate of
dissolution (gure 3, right). At this point, the solution becomes saturated, and
a dynamic equilibrium is established.
initial equilibrium
Evidence
Some salts are described as
insoluble in water. In practice,
minuscule amounts of these salts
c an still dissolve in water, so traces
of respective ions c an be detected
Cl (aq) +
Na (aq)
when analysing these salts in
+
+
Na (aq) Cl (aq)
Na (aq)
aqueous media. The resolution of Cl (aq)

Cl (aq)
+
Na (aq)
detection methods has increased
over time, allowing us to detect
ever-smaller trace amounts. Is the
pFigure 3 D ynamic equilibrium in a saturated solution of sodium chloride

term “insoluble” incorrect? What
type of evidence could c ause a
revision of scientic terminology?
A saturated solution has the highest possible concentration of the solute under
You might want to look up
given conditions. An unsaturated solution contains less solute than possible, so
denitions that have evolved over
it c an dissolve an additional quantity of that solute under given conditions. The
time such as transition element or
highest possible concentration of the solute in a solution under given conditions
hydrogen bond.
is known as the solubility of that solute.
Chemic al equilibrium
Reversible chemic al reactions c an proceed in both directions at the same time. A
typic al example of a reversible chemic al change is the reaction involving gaseous
nitrogen, hydrogen and ammonia:
N (g) + 3H (g) ⇌ 2NH (g)

2 2 3
In this reversible reaction, two processes take place: the synthesis of ammonia
from nitrogen and hydrogen (forward reaction) and the decomposition of
ammonia into nitrogen and hydrogen (backward reaction). The equilibrium sign
in this equation tells us that both processes take place simultaneously, so reactant
and product molecules are constantly interconverted.
514
The concept of reactants and products in a reversible process is somewhat
ambiguous, as the same substance c an be a reactant in the forward reaction but
a product in the reverse reaction. However, in DP chemistry, species on the le of
the equilibrium sign are referred to as reactants, and species on the right of the
equilibrium sign are referred to as products.
The main direction in which a reversible reaction will proceed depends on
the initial concentrations of all participating species. For example, if the initial
mixture contains only nitrogen and hydrogen, only the forward reaction takes
place: some molecules of nitrogen and hydrogen combine to form ammonia.
O ver time, the concentrations of nitrogen and hydrogen in the reaction mixture
decrease while the concentration of ammonia increases (gure 4a).
3.00 3.00
3
3
2.50 2.50
md
md
lom / noitartnecnoc
lom / noitartnecnoc
2.00 2.00
H (g) H (g)
2 2
1.50 1.50
NH (g) NH (g)
3 3
1.00 1.00
N (g) N (g)
2 2
0.50 0.50
0.00 0.00
0 20 40 60 80 100 0 20 40 60 80 100
time / s time / s
(a) (b)
pFigure 4 Concentrations of N (g), H (g) and NH (g) in reaction mixtures approaching

2 2 3
equilibrium at 475 K
Once the molecules of ammonia appear in the reaction mixture, the reverse
reaction becomes possible, so these ammonia molecules begin to decompose
into nitrogen and hydrogen. This process accelerates as the concentration of
ammonia increases. At the same time, the forward reaction slows down, as
the mixture contains fewer and fewer molecules of nitrogen and hydrogen.
Eventually, the rates of the forward and reverse reactions become equal, and the
concentrations of all three substances (nitrogen, hydrogen and ammonia) remain
constant even though the forward and reverse reactions continue. This state is
known as chemic al equilibrium.
Chemical equilibrium can be achieved from any initial state of the system. In
–3 –3
gure4a, the initial mixture contained 1.00 mol dm of nitrogen, 3.00 mol dm
of hydrogen and no ammonia, while the equilibrium concentrations of these
–3
species were 0.50, 1.50 and 1.00 mol dm , respectively. The same equilibrium
concentrations of all three species will be produced if we start the reaction with
–3
2.00 mol dm of ammonia only, with no nitrogen or hydrogen in the initial mixture
(gure4b). In this case, some ammonia will decompose into nitrogen and hydrogen:
2NH (g) ⇌ N (g) + 3H (g)

3 2 2
515
As the process continues, the concentration of ammonia will decrease, while the
concentrations of nitrogen and hydrogen will increase. Eventually, the rates of
forward and reverse reactions will become equal, and the state of equilibrium will
be established.
In summary, when a system is at equilibrium:
• chemic al and/or physic al changes continue at the microscopic level
• forward and reverse reactions proceed at equal rates
• concentrations of reactants and products remain constant
• macroscopic properties of the system, such as colour or density,
remain unchanged
• the same equilibrium state c an be achieved from either direction.
The equilibrium law (Reactivity 2.3.2 and
Reactivity 2.3.3)
When a chemic al system is at equilibrium, the ratio of the equilibrium
concentrations of reactants and products raised to the power of their
stoichiometric coecients is a constant, if the temperature is kept constant.
This observation is known as the equilibrium law, and the constant is c alled the
equilibrium constant, K.
Consider the general c ase of a chemic al equilibrium involving several species
with various stoichiometric coecients:
aA + bB + … ⇌ xX + yY + …
In the K expression, the products of the forward process (X, Y, …) appear in the
numerator while the reactants of the forward process (A, B, …) appear in the
denominator:
x y
…
[X] [Y]
K =
a b
…
[A] [B]
The use of square brackets and the omission of state symbols saves space and
focuses our attention on the most important information about the system at
equilibrium. For the same reason, K values are treated as unitless quantities,
although all equilibrium concentrations must still be expressed using appropriate
units (typic ally mol dm ).
For example, here is the K expression for the synthesis of ammonia from nitrogen
and hydrogen:
[NH ]
3
N (g) + 3H (g) ⇌ 2NH (g) K =

2 2 3 3
[N ][H ]
2 2
If a reaction takes place in a solution, the concentration of solvent does not
change signic antly during the reaction, so it is not included in the K expression.
For example, the K expression for the hydrolysis of an ester in an aqueous
solution does not include the concentration of water:
[HCOOH][CH OH]
3
HCOOCH (aq) + H O(l) ⇌ HCOOH(aq) + CH OH(aq) K =

3 2 3
[HCOOCH ]
3
516
However, if the same reaction takes place in a non-aqueous solution, water
is treated as any other reactant, so its concentration must be included in the
K expression.
Worked example 1
C alculate the K value for the synthesis of ammonia at 475 K, using the data
from gure 4.
Solution
First, write the K expression for the reaction:

Practice questions
[NH ]
3
K =
3 1 a. State the K expression for
[N ][H ]
2 2
the following equation:
Then input the values of concentration at equilibrium into the expression:
2NH (g) ⇌ N (g) + 3H (g)

3 2 2
1.00
=
3 b. Using the data from gure
0.50 × 1.50
4, c alculate the K value for
= 0.59
this process.
For any given process, the value of the equilibrium constant depends on
temperature, but not on other reaction conditions, such as pressure or
concentration. For example, if we increase the initial concentration of
–3
N (g) from 1.0 to 2.5 mol dm , the state of equilibrium in the reaction
2
N (g) + 3H (g) ⇌ 2NH (g) will be achieved at dierent concentrations of

2 2 3
nitrogen, hydrogen and ammonia (gure 5). However, these new concentrations
–3
(1.85, 1.13 and 1.25 mol dm , respectively) will still give the same value of K:
1.25
K = = 0.59
3
1.85 × 1.13
3.00
3
2.50
md
N (g)
lom / noitartnecnoc
2.00 2
1.50
NH (g)
3
1.00
H (g)
2
0.50
0.00
0 20 40 60 80 100
time / s
pFigure 5 Concentrations of N (g), H (g) and NH (g) in a reaction

2 2 3
mixture approaching equilibrium at 475 K
The value of K provides important information about the direction and extent of
the spontaneous process under standard conditions. If K > 1, the products are
favoured over the reactants, so the forward reaction will proceed spontaneously
until most reactants are converted into products.
517
Conversely, if K < 1, the reactants are favoured, so the reverse reaction will be
spontaneous, and the reaction mixture at equilibrium will consist predominantly
of reactants. Finally, if K =1, the equilibrium will be established at approximately
equal concentrations of reactants and products. However, the exact ratio
between these concentrations will depend on the stoichiometric coecients in
the equation.
Chemic al reactions with very large and very small K values are practic ally
The relationship between K and
irreversible. If K >> 1, the forward reaction is favoured so strongly that the extent
⦵
ΔG will be discussed in the AHL
of the reverse reaction becomes negligible. In other words, the reaction with
section of this topic.
K >> 1 will proceed from le to right until the reactants are used up completely.
In contrast, when K << 1, only the reverse reaction will be observed while the
forward reaction will not proceed to any noticeable extent.
The value of K for a given reaction depends on the stoichiometric ratio of
reactants and products. If all stoichiometric coecients are halved, the new K will
be the square root of the original constant (table 1). Conversely, if the coecients
are doubled, the K will be squared. Finally, if the equation is reversed, the new K
will be reciproc al to the original constant.
Change in the equation Eect on the K value
coecients halved K' = √K
coecients doubled K' = K
equation reversed K' =
two equations added together K' = K × K

1 2
p Table 1 The equilibrium constant and reaction stoichiometry
Worked example 2
At 475 K, the equilibrium constant K for the reaction
N (g) + 3H (g) ⇌ 2NH (g) has a value of 0.59.

2 2 3
Calculate the K′ values for the following reactions at the same temperature:
a. 2NH (g) ⇌ N (g) + 3H (g)

3 2 2
b. NH (g) ⇌ 0.5N (g) + 1.5H (g)

3 2 2
Solution
a. According to table 1, for a reversed reaction K′ = so:
K′ = ≈ 1.7
0.59
b. The stoichiometric coecients in reaction (b) are halved, as compared to
those in reaction (a). According to table 1, K′ = √1.7 ≈ 1.3.
Linking question
How does the value of K for the dissociation of an acid convey information
about its strength? (Reactivity 3.1)
518
Le Châtelier ’s principle (Reactivity 2.3.4)
Chemic al equilibrium is a dynamic process, so it c an be easily disturbed by
any change in the reaction conditions, such as temperature, pressure or the
concentrations of reacting species. The eects of such changes c an be predicted
by using Le Châtelier ’s principle, which was formulated at the end of the 19th
century by the French chemist Henry Le Châtelier:
If a dynamic equilibrium is disturbed by a change in the reaction conditions,
the balance between the forward and reverse processes will shi to
counteract the change and return the system to equilibrium.
In other words, a system at equilibrium will counteract any changes in
concentration, pressure or temperature by altering the rates and spontaneity of
the forward and backward reactions until a new equilibrium is established. If the
forward reaction becomes more favourable than the reverse reaction, we say that
the position of the equilibrium shis to the right. Conversely, if the backward
reaction becomes more favourable than the forward reaction, the equilibrium
position shis to the le. Shiing the equilibrium position to the right increases
the concentrations of products, and shiing the equilibrium to the le increases
the concentrations of reactants.
Eect of concentration on equilibrium
Imagine an equilibrium mixture of nitrogen, hydrogen and ammonia. The
temperature is 475 K and the concentrations are as follows: [N ] = 0.50 mol dm ,

2
3 3
[H ] = 1.50 mol dm , [NH ] = 1.00 mol dm

2 3
1.00
N (g) + 3H (g) ⇌ 2NH (g) K = = 0.59

2 2 3
3
0.50 × 1.50
The changes in concentrations of the reacting species over time are shown in
gure 6.
3.00
3
md
H (g)
2
2.50
lom / noitartnecnoc
2.00
NH (g)
3
1.50
1.00
0.50 N (g)
2
0.00
0 20 40 60 80 100 120 140 160
time / s
pFigure 6 The eect of a concentration change on the equilibrium position
Initially, the concentrations of all three gases remain constant, as the mixture
is already at equilibrium, and the rates of the forward and reverse reactions
are equal. At t = 40 s, we disturb the equilibrium by injecting more hydrogen
into the reaction mixture, so the concentration of H (g) increases from 1.5 to
2
−
3
3.0 mol dm .
519
This change in concentration leads to more frequent collisions between
hydrogen and nitrogen molecules and so increases the rate of the forward
reaction. As a result, the concentrations of hydrogen and nitrogen in the reaction
mixture decrease while the concentration of ammonia increases. In other words,
the system counteracts the presence of excess reactant (hydrogen) by converting
it into product (ammonia) and shiing the equilibrium position to the right.
Practice questions
2. O utline how the following The new equilibrium concentrations of nitrogen, hydrogen and ammonia (0.28,
changes will aect the 2.33 and 1.45 mol dm , respectively) still satisfy the K expression:
equilibrium position and the 2
1.45
K = = 0.59
3
K value of the reaction
0.28 × 2.33
N (g) + 3H (g) ⇌ 2NH (g):

2 2 3
The opposite eect would be observed if we increased the concentration
of ammonia instead of hydrogen. Since ammonia is the product, its higher

a. increase in concentration
concentration would accelerate the reverse reaction and shi the equilibrium
of nitrogen
position to the le. In this case, the system would counteract the presence of
b. decrease in concentration excess product (ammonia) by converting it into reactants (nitrogen and hydrogen).
of ammonia.
C ase study: the chromate–dichromate equilibrium
Le Châtelier ’s principle c an be studied in a school laboratory using the following
reversible reaction:
2 + 2
2CrO (aq) + 2H (aq) ⇌ Cr O (aq) + H O(l)

4 2 7 2
chromate dichromate
(yellow) (orange)
The colours of transition metal Both chromate and dichromate ions contain a transition metal, chromium(VI), so
ions are discussed in Structure3.1 they are brightly coloured (gure 7). Therefore, any change in the equilibrium
(AHL ). The concentrations of position c an be detected by observing the colour of the solution.
chromate and dichromate ions in
If we add a small amount of acid to a solution of CrO (aq), the concentration of

4
the solution c an be measured by
H (aq) ions in the solution increases. To counteract this change, some hydrogen
spectrophotometry (Structure 1.4).
ions will react with chromate ions to produce dichromate ions. The equilibrium
position will shi to the right, so the solution colour will change from yellow
to orange.
The opposite eect c an be achieved by the addition of an alkali. The alkali will
neutralize the acid, decreasing the concentration of H (aq) ions in the solution:
H (aq) + OH (aq) → H O(l)

2
This change will favour the reverse reaction that will increase the concentration of
H (aq) ions and therefore counteract the change: the position of equilibrium will
shi to the le. Therefore, dichromate ions will turn into chromate ions, and the
solution colour will change from orange to yellow.
The chromate–dichromate equilibrium involves water, which acts as both the
solvent and the product of the forward reaction. However, water is present in
the solution in large excess, so the addition or evaporation of water has very little
eect on the equilibrium position. If an orange solution of dichromate is diluted
with water, its colour will become paler, but it will still be orange, not yellow. For
this reason, the concentration of water is never included in the K expressions for
2
equilibria in aqueous solutions:
p
Figure 7 Aqueous chromate, CrO (aq),
4
is yellow, while aqueous dichromate, [Cr O ]

2 7
K =
+
2 2 2 2
Cr
2
O
7
(aq), is orange [CrO ] [H ]
4
520
Eect of pressure on equilibrium

The chemistry of acidic and alkaline
species is detailed in Reactivity 3.1

The eect of pressure on the equilibrium position depends on the stoichiometric
ratio of gaseous reactants and products. For example, the reaction
N (g) + 3H (g) ⇌ 2NH (g) involves four gaseous molecules (one N and three
2 2 3 2
H ) on the le-hand side of the equation but only two gaseous molecules of
2
NH on the right-hand side. If the pressure increases, the system will counteract
3
this change by converting the reactants into the products, as this will reduce
the number of gaseous molecules in the reaction mixture. Therefore, the
equilibrium position will shi to the right. Conversely, a decrease in pressure will
shi the equilibrium position to the le, towards the greater number of gaseous
molecules. In both c ases, the K value of the reaction will not change.
If an equation contains more gaseous molecules on the right-hand side than on
the le-hand side, an increase in pressure will shi the equilibrium position to the
le, while a decrease in pressure will shi the equilibrium position to the right.
If the numbers of gaseous molecules on each side of the equation are equal, a
change in pressure will have no eect on the equilibrium position. Once again,
the K value will remain unchanged in all c ases.
Changes in pressure have no eect on equilibria in condensed phases bec ause
solids and liquids are almost incompressible. However, heterogeneous equilibria
that involve gaseous species are aected by pressure changes in the same
way as homogeneous equilibria in the gas phase. For example, consider the
heterogeneous equilibrium between liquid and gaseous bromine that was
discussed at the beginning of this topic:
Br (l) ⇌ Br (g)
2 2
If the pressure increases, the concentration of Br (l) will remain unchanged

2
(bec ause liquids are incompressible) while the concentration of Br (g) will
2
increase. According to Le Châtelier ’s principle, the system will counteract this
change by increasing the rate of the reverse reaction (condensation of bromine),
so the equilibrium position will shi to the le. Conversely, a decrease in pressure
will shi the equilibrium position to the right, making the forward reaction
(evaporation of bromine) more favourable than the reverse reaction.
In the general c ase, when predicting the eects of pressure on heterogeneous
equilibria, you c an consider only gases and ignore solids, liquids and aqueous
species.
According to the ideal gas law (Structure 1.5), the pressure of a gas mixture is
inversely proportional to its volume. When the volume of a system decreases,
the pressure increases, and when the volume increases, the pressure decreases.
Therefore, the eects of a change in volume on the equilibrium position are
opposite to the eects of pressure. Like pressure, a change in the volume of
system has no eect on the value of K
Practice questions
3. State the eects of increasing pressure on the equilibrium positions and
K values for the following reactions:
a. N O (g) ⇌ 2NO (g)

2 4 2
b. SO (g) + NO (g) ⇌ SO (g) + NO(g)

2 2 3
c. 4HCl(g) + O (g) ⇌ 2H O(g) + 2Cl (g)

2 2 2
d. SO (g) + H O(l) ⇌ H SO (aq)

2 2 2 3
521
Eect of temperature on equilibrium
Temperature is the only factor that aects both the position of equilibrium and the
equilibrium constant. The synthesis of ammonia from nitrogen and hydrogen is
an exothermic process (ΔH < 0), so heat is released by the forward reaction and
r
consumed by the reverse reaction:
⦵
1
N (g) + 3H (g) ⇌ 2NH (g) ΔH = −91.8 kJ mol

2 2 3 r
At equilibrium, the forward and reverse reactions proceed at the same rates,
so the total amount of heat in the system remains constant. If we increase the
temperature, more heat will be introduced into the system. In accordance with
LeChâtelier ’s principle, the system will counteract this change by consuming
excess heat, so the reverse reaction will be favoured, and the equilibrium position
will shi to the le. As a result, the concentration of ammonia in the reaction
mixture will decrease while the concentrations of both nitrogen and hydrogen
will increase.
Now consider the K expression for this reaction:
[NH ]
3
K =
3
[N ] [H ]
2 2
The numerator contains [NH ], which decreases with temperature. The

3
denominator contains [N ] and [H ], both of which increase with temperature.

2 2
Therefore, an increase in temperature lowers the K value of this reaction. The
same result would be observed for any other exothermic process. Conversely, a
decrease in temperature shis the equilibrium position of an exothermic process
to the right and thus increases its K value.
For an endothermic process, the reverse is true: an increase in temperature will
shi the equilibrium position to the right and increase the K value. A decrease in
temperature will have opposite eects, shiing the equilibrium position to the le
and decreasing the K value.
Chemic al or physic al changes with ΔH = 0 are very rare but still possible. For
r
example, the isotopic exchange in a mixture of normal water (H O, hydrogen

2
oxide) and heavy water (D O, deuterium oxide) proceeds as follows:

2
H O(l) + D O(l) ⇌ 2DOH(l)

2 2
The chemic al properties of isotopes are nearly identic al (Structure 1.2), so the
ΔH value for this reaction is very close to zero. As a result, temperature has no
r
eect on the equilibrium position or the K value for this, or any other reaction
with ΔH = 0.
r
To predict the eect of a temperature change on the equilibrium position, it
is convenient to treat heat as an imaginary substance (Q) participating in the
reaction. For an exothermic process, this “substance” is a reaction product, and
for an endothermic process, it is a reactant:
reactants ⇌ products + Q ΔH < 0 (exothermic)

r
reactants + Q ⇌ products ΔH > 0 (endothermic)

r
522
An increase in temperature will increase the “concentration” of heat in the
system, so the equilibrium position of the exothermic reaction will shi to the le,
and the equilibrium position of the endothermic reaction will shi to the right.
Conversely, a decrease in temperature decreases the “concentration” of heat and
has the opposite eects on the above equilibria.
The eect of c atalysts on equilibrium
A c atalyst provides an alternative pathway for the reaction and therefore lower its
activation energy. This increases the rate of a chemic al reaction (Reactivity2.2).
In a reversible process, the forward and reverse reactions follow the same
pathway in opposite directions, so the rates of both reactions increase to the
same extent. Therefore, in the presence of a c atalyst, the equilibrium state of
the system is achieved faster, but the position of this equilibrium and the K value
remainunchanged.
The eect of a c atalyst on the equilibrium position c an be illustrated by a simple
analogy. Imagine two communic ating vessels that represent reactants and
products (gure 8). The levels of liquid in the vessels represent the relative rates
of the forward and reverse reactions.
reactants products reactants products
no c atalyst no c atalyst
reactants products reactants products
c atalyst c atalyst
pFigure 8 Communic ating vessels as a model of chemic al
equilibrium
The ow of liquid between the vessels is limited by the diameter of the
connecting tube. If we increase this diameter, the levels of liquid in the vessels
will become equal faster, but the nal state of the system will not be aected.
Similarly, a c atalyst allows a chemic al system to reach the state of equilibrium
faster but does not aect the position of that equilibrium.
The same analogy c an be used for illustrating Le Châtelier ’s principle with
respect to concentrations. If we add liquid to the le vessel (“increase a reactant
concentration”), some of the liquid will ow to the right vessel (“the forward
reaction will be favoured”) until the levels become equal again (“a new chemic al
equilibrium will be established”).
523
The eects of reaction conditions on the equilibrium position and K value are
summarized in table 2.
Change in condition Shi of equilibrium K
concentration of reactant to the right no change
increases (towards products)
concentration of product
decreases
concentration of reactant to the le
decreases (towards reactants)
concentration of product
increases
pressure increases to the side with a smaller
number of gas molecules

volume decreases
pressure decreases to the side with a greater
number of gas molecules

volume increases
⦵ ⦵
temperature increases ΔH < 0: to the le ΔH < 0: decreases

r r
⦵ ⦵
ΔH > 0: to the right ΔH > 0: increases

r r
⦵ ⦵
ΔH = 0: no change ΔH = 0: no change
r r
⦵ ⦵
temperature decreases ΔH < 0: to the right ΔH < 0: increases

r r
⦵ ⦵
ΔH > 0: to the le ΔH > 0: decreases

r r
⦵ ⦵
ΔH = 0: no change ΔH = 0: no change
r r
c atalyst is added no change no change
pTable 2 The eects of reaction conditions on the equilibrium position and K value
C ase study: the Haber process
Le Châtelier ’s principle allows chemists to maximize the yield of the desired
product by altering the reaction conditions. In particular, the synthesis of
ammonia on an industrial sc ale becomes protable only when a ne balance
between pressure, temperature and concentrations of reacting species is
achieved. This synthesis, developed in early 20th century by the German chemist
H (g)
2 2 Fritz Haber, utilizes the reaction that has already been discussed in this topic:
N (g) + 3H (g) ⇌ 2NH (g) + Q

2 2 3
Compressor Since the number of gas molecules in the forward reaction decreases from four
to two, the Haber process is carried out at high pressure (200 atm, or 20 MPa),
which pushes the equilibrium position to the right and at the same time increases
the reaction rate. Nitrogen and hydrogen are constantly injected into the reaction
Return Reaction
mixture while ammonia is condensed and removed aer each cycle of the process
pump chamber
(gure 9). These measures maximize the concentrations of reactants and minimize
the concentration of the product, shiing the equilibrium even further to the right.
Condenser ⦵
The forward reaction is exothermic (ΔH < 0), so it is favoured by a low

r
temperature. However, this reduces the kinetic energy and frequency of
collisions between reactant particles. Therefore, a lower temperature will
decrease the reaction rate. As a compromise, the reaction is c arried out at a

NH (l)
3
moderate temperature (400–450 °C) and in the presence of a c atalyst (iron
powder with various additives). While the c atalyst itself does not aect the
pFigure 9 Flow chart of the Haber process
equilibrium position, it greatly increases the reaction rate.
524
In modern industrial plants, the eciency of the Haber process is improved by
recycling unreacted gases and utilizing the heat released by the forward reaction.
Such improvements increase the overall reaction yield to 98%, while reducing
the cost and environmental impact of ammonia production.
TOK
The Haber process has had signic ant impacts – positive and negative –
on society. On the one hand, ammonia is widely used for making urea,
ammonium nitrate and other fertilizers. Without these, current farming
practices could not feed the growing world population. According to some
estimates, a half of the nitrogen in our bodies comes from the Haber process,
making it arguably the most important invention of the 20th century.
However, the Haber process was also vital to produce explosives and
ammunition in both world wars. Haber himself also worked on and promoted
the use of poison gases during the First World War, earning him the name
“the father of chemic al warfare”. His story illustrates how advances in scientic
knowledge c an benet society or be used for creating weapons of
mass destruction.
Is science, or should it be, value-free?
Linking question
Why do c atalysts have no eect on the value of K or on the equilibrium
composition? (Reactivity 2.2)
LHA
Reaction quotient (Reactivity 2.3.5)
If a system has not reached equilibrium, the ratio of actual concentrations
of products and reactants diers from the K value. This ratio is known as the
reaction quotient, Q. It c an be used for determining the direction of ongoing
chemic al changes within the system.
The reaction quotient, Q, is c alculated just like the K expression, but with
non-equilibrium concentrations of all reacting species. So, for the reaction
aA + bB + … ⇌ xX + yY + … not at equilibrium, the Q expression is as follows:
x y
…
[X] [Y]
Q =
a b
…
[A] [B]
You c an make the following conclusions from the relative values of Q and K:
• When Q < K, the reaction mixture contains more reactants and less products
than needed for equilibrium, so the forward reaction will be favoured.
• When Q > K, there are less reactants and more products than needed for
equilibrium, so the reverse reaction will be the dominant process.
• When Q = K, the system is already at equilibrium, so the forward and reverse
reactions will proceed at the same rate.
525
LHA
Worked example 3
Calculate the reaction quotient for a mixture of nitrogen, hydrogen and
Practice question ammonia at 475 K, where K = 0.59 and the concentration of each species is
0.50 mol dm . Predict the direction of the spontaneous reaction in this mixture.
4. Consider the following reaction
[NH ]
3
at 283 K:
N (g) + 3H (g) ⇌ 2NH (g) K = = 0.59
2 2 3 3
[N ][H ]
2 2
2NO (g) ⇌ N O (g) K = 11.5

2 2 4
Solution
The reaction mixture contains

To c alculate the reaction quotient, we need to use the K expression with the
0.025 mol dm of nitrogen

actual concentrations instead of the equilibrium concentrations:
dioxide and 0.10 mol dm

2
0.5
Q = = 4
of dinitrogen tetroxide. 3
0.5 × 0.5
Determine the direction of the
Since Q > K, the system contains too much ammonia and too little nitrogen
spontaneous reaction in this
and hydrogen, so the reverse reaction is favoured.
mixture at 283 K.
The oceans are an important store of c arbon dioxide in the c arbon cycle.
The determination of [CO ] in seawater is a complex process bec ause

2
c arbon dioxide participates in various equilibria. Japanese geochemist
K atsuko S aruhashi explored and modelled the relationship between the total
concentration of c arbonic acid, pH and temperature. Based on equilibrium
constants, she devised a methodology to determine the CO levels in

2
seawater. This information was compiled for easy access in what bec ame
known as “S aruhashi’s Table”. S aruhashi also investigated the eects of
nuclear testing on seawater, co-founded the Society of Japanese Women
Scientists in 1958 and established the annual S aruhashi Prize in 1981, awarded
to female scientists for their contributions to scientic research.
What makes an idea worthy of a scientic prize? What is the purpose of
scientic prizes? What is the role of scientic societies?
pFigure 10 Japanese geochemist K atsuko
S aruhashi
C alculations involving K (Reactivity 2.3.6)
The K value c an be used for determining the composition of a reaction mixture
at equilibrium if the initial or equilibrium concentrations of some participating
species are known. Alternatively, the initial concentrations c an be determined
from the K value and equilibrium concentrations.
In esterific ation re actions, a c a r b ox y l i c acid re acts with an alcohol to
form an e s t e r. The equilibrium constant, K, for esterific ation re actions
c an be determined by a n a l ys i s of the c o n c e n t ra t i o n s of the re acting
species at equilibrium. Va l u e s for K were determined in this w ay for the
esterific ation of s e v e ra l different alcohols and c a r b ox y l i c acids, s h ow n in
table 3.
526
LHA
2. Describe the trends, patterns and relationships you
ethanoic propanoic butanoic
observe in the data.
acid acid acid
3. Research ways to determine the equilibrium constant,
methanol 5.03 4.72 4.08
K, for an esteric ation reaction. Use this information
ethanol 4.86 2.13 2.28 and your answers to this task to brainstorm possible
investigations exploring a factor connected to
propan-1-ol 4.21 4.10 2.33
esteric ation.
butan-1-ol 2.85 1.10 1.34

4. Choose one of your ideas and plan an investigation.
Remember to:
2-methylpropan-1-ol 2.02 1.23 0.92
• outline the independent and dependent variables
–3
pTable 3 Equilibrium constants, in mol dm , for esteric ation
• state the major control variables
reactions at reux temperature (Source of data: E. S arlo, P.
• state the research question
Svoronos, and P. Kulas, J. Chem. Ed., 1990, 67 (9), 796)
• outline the context of the research question
1. Prepare a graph of the results.
• outline the methodology
Worked example 4
A mixture of sulfur(IV) oxide and oxygen was heated in and sulfur(VI) oxide in the nal mixture were 0.12 and
a sealed vessel at 1 000 K until the following equilibrium 0.18 mol dm , respectively.
was reached:
a. C alculate the concentration of oxygen at equilibrium.
2SO (g) + O (g) ⇌ 2SO (g) K = 3.0

2 2 3
b. Determine the initial concentrations of both
The equilibrium concentrations of sulfur(IV) oxide reactants.
Solution
0.18
a. First, we need to write the K expression: 3 3
0.18 mol dm of SO (g) and = 0.090 mol dm of

2
2
2
[SO ]
3
K = O (g) were consumed:

2
2
[O ][SO ]
2 2
2SO (g) + O (g) ⇌ 2SO (g)

2 2 3
Since we know three of the four values in this expression,
we can nd the equilibrium concentration of oxygen: c / mol dm x y 0

initial
2 3
0.18 Δc / mol dm −0.18 −0.09 +0.18
3.0 =
2
[O ] × 0.12 3
2
c / mol dm 0.12 0.75 0.18
eq
[O ] = 0.75 mol dm
2
Therefore:
2. To nd the initial concentrations of SO (g) and

2
x − 0.18 = 0.12, so x = 0.12 + 0.18 = 0.30
O (g), we need to look at their stoichiometric ratio.

2
y − 0.09 = 0.75, so y = 0.75 + 0.09 = 0.84

The formation of each mole of SO (g) requires the
3
same quantity of SO (g) and twice as little O (g). [SO ] = 0.30 mol dm
2 2 2 initial
3
3
[O ] = 0.84 mol dm
If 0.18 mol dm of SO (g) was produced, then 2 initial
3
Practice question
5. Nitrogen dioxide was cooled down to 283 K in C alculate the equilibrium and initial concentrations of
a sealed vessel until it reached equilibrium with NO (g) if the equilibrium concentration of N O (g) was
2 2 4
dinitrogen tetroxide: 0.041 mol dm
2NO (g) ⇌ N O (g) K = 11.5

2 2 4
527
LHA
Using a spreadsheet scrollbar to determine equilibrium concentrations
Equilibrium concentrations of reactants and products depend on factors such as the value of the equilibrium constant
and the concentrations of the other species. In this task, you will use a method developed by Andrés R aviolo and
published in the Journal of Chemical Education for analysing an equilibrium mixture by creating a spreadsheet model
containing a scrollbar (2012).
Relevant skills
• Tool 2: Generate data from models and simulations • Inquiry 3: Evaluate methodologic al limitations
Nitrogen and hydrogen react reversibly to form ammonia: N (g) + 3H (g) ⇌ 2NH (g)
2 2 3
[NH ]
3
The equilibrium constant expression for this equation is K =

3
[N ][H ]
2 2
Instructions
Part 1: Create the spreadsheet model
a. Nitrogen and hydrogen are placed in a 4.00 dm container and allowed to reach equilibrium. The initial amounts,
in mol, of nitrogen and hydrogen are 0.200 and 0.500, respectively. The equilibrium constant, K, at a certain
temperature is 269. Enter this information into a spreadsheet:
A B C D E F
3
1 V (dm ) K x Q
4 n(N ) n(H ) n(NH )

2 2 3
5 I (mol)
6 C (mol)
7 E (mol)
b. Next, enter the formulas needed to c alculate:
• reaction quotient, Q (cell E2), • parameter labelled x (cell D2) is related to the
concentration change and is computed based on a

• changes in concentration (cells D6, E6 and F6)
value in cell B10, which is currently empty.
• equilibrium concentrations (cells D7, E7 and F7).
A B C D E F
3
1 V (dm ) K x Q
2 =B10/100000 =F7^2/(D7*E7^3)*B2^2
4 n(N ) n(H ) n(NH )

2 2 3
5 0.2 0.5 0
I (mol)
6 C (mol) =–1*D2 =–3*D2 =2*D2
7 E (mol) =D5+D6 =E5+E6 =F5+F6
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LHA
3. Now insert a scroll bar into the space between cells B9 and F9. If you are using Excel, you will need to show the
“Developer tab”, and select “Scroll bar ” from the “Form control” section of this tab. In the scroll bar settings, set the
cell link to B10, the minimum value to 1 and maximum value to 10 000. For clarity, cells B10 to F10 have been merged
and centred in the image below:
A B C D E F
3
1 V (dm ) K x Q
4 n(N ) n(H ) n(NH )

2 2 3
5 0.200 0.500 0.000

I (mol)
6 C (mol) 0.085 0.254 0.169
7 E (mol) 0.115 0.246 0.169
10 8474
4. The scroll bar allows you to change the value of x, and the spreadsheet computes the corresponding value of
the reaction quotient, Q. Use the scroll bar to change x until Q = K, which indic ates that the reaction mixture
is at equilibrium.
Part 2: Use the spreadsheet model
5. Using your knowledge of equilibrium, predict what will happen to the equilibrium concentrations of N , H and NH
2 2 3
if there are changes to the following:
• volume of the container
• value of K
• initial amounts of reactants
6. Using your spreadsheet model, investigate your ideas above.
7. Explain the formula used to compute Q, in cell E2: “=F7^2/(D7*E7^3)*B2^2”.
Part 3: Evaluate the model
8. Identify and explain at least one advantage of this spreadsheet model.
9. Identify and explain at least two limitations of this spreadsheet model.
Part 4: Create a new model
Sulfur dioxide, SO (g), reacts with oxygen, O (g), to form sulfur trioxide, SO (g), according to the following reversible
2 2 3
reaction:
2SO (g) + O (g) ⇌ 2SO (g)

2 2 3
The value of K at a certain temperature is 7.5 × 10
10. Create a new spreadsheet model, like the one above, that c an be used to determine the equilibrium concentrations
of SO (g), O (g), and SO (g), when 1.0 mol of SO (g) and 1.4 mol of O (g) are placed in a 3.0 dm container and
2 2 3 2 2
allowed to reach equilibrium.
529
LHA
Weak acids and bases in aqueous solutions undergo reversible ionization,
producing H (aq) and OH (aq) ions, respectively. Here are the general equations
for these ionizations:
weak acid: HA(aq) ⇌ H (aq) + A (aq)
weak base: B(aq) + H O(l) ⇌ BH (aq) + OH (aq)

2
Acid–base equilibria will be The equilibrium constants for these processes are usually very low, so only a
discussed in greater detail in small proportion of the weak acid or base exists as ions, while most of these
Reactivity 3.1 species remain in molecular form. Therefore, we c an assume that the equilibrium
concentration of a weak acid or base is approximately equal to its initial
concentration:
[HA] ≈ [HA]
eq initial
[B] ≈ [B]
eq initial
These assumptions simplify the c alculations involving K of acid–base equilibria,
as shown in the worked example below.
Worked example 5
The weak ethanoic acid, CH COOH, dissociates in At 298 K, the K value for this process is 1.74 × 10
3
aqueous solutions as follows:
Determine the equilibrium concentrations, in mol dm ,
+
3
CH COOH(aq) ⇌ CH COO (aq) + H (aq) of all species in a 0.100 mol dm solution of ethanoic
3 3
acid at 298 K.
Solution
We c an assume that the initial concentration of ethanoic The concentrations of CH COO (aq) and H (aq) are
3
acid is equal to its equilibrium concentration, as the value approximately the same, so:
of K is very low:
2
[CH COO ]
5 3
1.74 × 10 ≈
0.100
[CH COOH] ≈ [CH COOH]
3 eq 3 initial
–6
[CH COO ] ≈ √1.74 × 10

3
= 0.100 mol dm
+ 3
[CH COO ] ≈ [H ] ≈ 0.00132 mol dm

3 eq eq
Write the expression for K:
Without assuming that [CH COOH] = [CH COOH] ,

3 eq 3 initial
+
[CH COO ][H ]

3
K = we would have to solve a quadratic equation, which is
[CH COOH]
3
not assessed in DP chemistry examination papers. The
Then substitute in the values for K and [CH COOH]

3 eq
exact solution of the quadratic equation would give
[CH COO ] ≈ 0.0131, which is very close to the result of

[CH COO ][H ] 3 eq
5 3
1.74 × 10 =
0.100 our approximate calculations.
Practice question
6. Phenylamine, C H NH , also known as aniline, is a weak base. In aqueous

6 5 2
solutions, it undergoes a reversible ionization:
C H NH (aq) + H O(l) ⇌ C H NH (aq) + OH (aq)

6 5 2 2 6 5 3
10
At 298 K, the K value for this process is 7.41 × 10
Determine the concentration of OH (aq) in a 0.100 mol dm aqueous
solution of phenylamine.
530
LHA
Linking question
How does the equilibrium law help us to determine the pH of a weak acid,
weak base or a buer solution? (Reactivity 3.1)
Gibbs energy and equilibrium (Reactivity 2.3.7)
In the SL section of this topic, we discussed the relationship between the K value
and spontaneity of a reaction under standard conditions. If K > 1, the forward
reaction proceeds spontaneously while a K < 1 favours the reverse reaction. If
K =1, neither reaction is favoured under standard conditions, as the equilibrium
is already established.
Another measure of the reaction spontaneity is its Gibbs energy change, ΔG
(Reactivity 1.3). For a reversible chemic al reaction, a negative ΔG value favours
the forward reaction, while a positive ΔG value favours the reverse reaction.
The standard Gibbs energy change for a reaction, ΔG , refers to the chemic al
change from reactants to products in their standard states (p = 100 kPa for gases
or c = 1 mol dm for aqueous species) at a given temperature. If the temperature
is not specied, it is assumed to be 298 K. If the spontaneity is determined under
standard conditions, the value of ΔG must be used instead of ΔG
⦵
Equilibrium Standard Gibbs Spontaneous process
The expression ΔG = −RT ln K
constant energy change under standard conditions

and the value of R are given in the
K > 1 ΔG < 0 forward reaction (products are favoured) data booklet.
K < 1 ΔG > 0 reverse reaction (reactants are favoured)
K = 1 ΔG = 0 neither forward nor reverse (equilibrium)
C alculations involving standard
⦵
Gibbs energy changes and
pTable 3 Equilibrium position and the values of K and ΔG
thermodynamic data for reactants
The relationship between K and ΔG is described by the following equation:

and products are discussed in
Reactivity 1.4. Thermodynamic data

⦵
ΔG = −RT ln K
for selected compounds are given
1 1
where R = 8.31 J K mol is the gas constant and T is the absolute temperature in
⦵
1
kelvin. Notice that ΔG is usually expressed in kJ mol , so it must be converted to
J mol to match the units of R
This equation is very useful bec ause standard Gibbs energies of formation,
ΔG , are known for many compounds. These data allow us to c alculate

f
rst the ΔG value and then the K value for almost any chemic al or physic al
change. Conversely, an unknown ΔG value for a particular compound c an be
determined from the K value of a reversible reaction involving this compound
and the thermodynamic data for other species participating in that reaction.
Activity
C alculate the equilibrium constant, K, for a reversible reaction with
⦵
1
ΔG = −3.9 kJ mol at 298 K.
531
LHA
Worked example 6
Dinitrogen dioxide, N O (g), is highly unstable, so its Gibbs energy

2 2
change of formation, ΔG , c annot be determined directly. However, the

f
equilibrium constant for the following process at 298 K c an be c alculated
from spectroscopic data:
2NO(g) ⇌ N O (g) K = 1.39 × 10

2 2
⦵
1
a. Determine ΔG , in kJ mol , for the forward reaction at 298 K.
⦵
1
b. Using your answer to part a, determine ΔG for N O (g), in kJ mol , at

f 2 2
⦵
1
298 K if ΔG for NO(g) at the same temperature is 87.6 kJ mol

f
Solution
a. ΔG = −RT ln K
–1 –1 5
= −8.31 J K mol × 298 K × ln(1.39 × 10 )
= 27 700 J mol
= 27.7 kJ mol
b. Using the enthalpy cycle diagram method from Reactivity 1.2:
⦵
∆G
2NO(g) N O (g)
2 2
2 ×
⦵ ⦵
∆G (NO(g)) ∆G (N O (g))
f f 2 2
N (g) + O (g)
2 2
⦵ ⦵ ⦵
ΔG = − [2 × ΔG (NO(g))] + ΔG (N O (g))
f f 2 2
⦵ ⦵
Substitute in the values of ΔG and ΔG (NO(g)):

f
⦵
1 1
27.7 kJ mol = − [2 × 87.6 kJ mol ] + ΔG (N O (g))

f 2 2
⦵
1
ΔG (NO(g)) = 202.9 kJ mol

f
Linking question
How c an Gibbs energy be used to explain which of the forward or backward
reaction is favoured before reaching equilibrium? (Reactivity 1.4)
532
LHA
Graphic-display c alculator (GDC) skills that you have learnt in maths, such as using numeric al solvers and nding the
intersection of two graphs, c an also be applied to chemistry.
Consider the following practice question: C alculate the equilibrium constant, K, for a reaction at 298 K. The value of
⦵
1
∆G for the reaction at this temperature is −0.82 kJ mol .
This c an be done by solving ∆G = −RT ln K for K, as shown in the text. Two further ways of c alculating K are possible,
using your GDC:
1. Numeric al solver
⦵
1 1
Enter the equation (remembering to express ∆G in J mol , not kJ mol ) into the numeric al solver (usually c alled nSolve,
Nsolve or solveN) and compute K:
*
Doc DEG
1.1
3
nSolve( 0.82• 10 = –8.31• 298• In(x),x)
1.39254
2. Graphing both sides of the equation and nding the intersection
Graph both sides of the equation as two separate functions. In the example above, the two functions are f (x) = −820
1
and f (x) = −8.31 × 298 × ln(x). Fit the graphs to the screen if necessary, then nd the intersection. The x-coordinate of
2
the intersection is the value you are looking for:
*
Doc DEG
1.1
y
10829.97
f 2(x)= –8.31• 298• In(x)
1000
–10 1 10
3
(1.39, –820)
f 1(x)= –0.82• 10
–7205.23
533
LHA
6. For a certain reversible reaction in a closed system,
Topic review
Q > K. Which changes will occur when the system will

be approaching equilibrium at constant temperature?

A Q will decrease
How can the extent of a reversible reaction

B K will increase
be inuenced?
C Concentrations of reactants will decrease
D Concentrations of products will increase

Multiple-choice questions 7. At 1 000 K, the forward reaction has a negative ΔG
value:
2. Which of the following statements is correct?
2NO (g) ⇌ 2NO(g) + O (g)

2 2
A The changes at equilibrium stop only at the
Which expression is correct for the equilibrium at this

microscopic level but not at the macroscopic level.
temperature?
B The changes at equilibrium stop at both the
2 2
A [NO ] > [NO] [O ]

2 2
macroscopic level and the microscopic level.
B [NO ] < [NO]

2
C The rates of both forward and reverse reactions at
equilibrium are equal to zero. C [NO] = 2[O ]

2
D The equilibrium constant expression c an be D K > 1
deduced from the reaction stoichiometry.
3. Which factors increase the rates of both forward and

8. Deduce the equilibrium constant expressions for the
reverse reactions in any system at equilibrium?

following reactions.
I. Increase in temperature
a. 3O (g) ⇌ 2O (g)
2 3
II. Increase in pressure

b. 2NO (g) ⇌ 2NO(g) + O (g)
2 2
III. Addition of a c atalyst

c. NO (g) ⇌ NO(g) + 0.5O (g)
2 2
A I and II only
d. CH COOH(aq) ⇌ CH COO (aq) + H (aq)
3 3
+
B I and III only
e. NH (aq) + H O(l) ⇌ NH (aq) + OH (aq)
3 2 4
C II and III only

f. C aCO (s) ⇌ C aO(s) + CO (g)
3 2
D I, II and III
9. At a certain temperature, the K value for reaction b from
4. What will happen in the following reaction mixture at the previous problem is 0.81. Deduce the K value for
equilibrium if the pressure decreases? reaction c from the same problem.
SO (g) + H O(l) ⇌ H (aq) + HSO (aq)

2 2 3
10. Consider the following reaction:
A The equilibrium position will shi to the le and
H (g) + I (g) ⇌ 2HI(g)

2 2
[H ] will increase
The equilibrium concentrations of hydrogen, iodine
B The equilibrium position will shi to the right and
and hydrogen iodide in the reaction mixture at 760 K
[H ] will increase
3
were found to be 0.012, 0.015 and 0.091 mol dm ,
C The equilibrium position will shi to the le and

respectively.
[H ] will decrease
a. Deduce the equilibrium constant expression and
D The equilibrium position will shi to the right and

determine the K value for this reaction at 760 K.
[H ] will decrease
b. The K value for the same reaction at 715 K is 48.0.

LHA
Deduce the sign of the standard enthalpy change

5. What is true for any system at equilibrium?
for the forward reaction.
A K = 1
B Q = 1
C Q = K
D ΔG = 0
534
LHA
11. Consider the following reaction: 14. Benzoic acid, C H COOH, dissociates in aqueous
6 5
solutions as follows:
⦵
1
2CO(g) + O (g) ⇌ 2CO (g) ΔH = −566 kJ mol

2 2
+
C H COOH(aq) ⇌ C H COO (aq) + H (aq)

6 5 6 5
O utline how the following changes will aect the

5
At 298 K, the K value for this equilibrium is 6.31 × 10
equilibrium position and the K value of this reaction:
a. Determine the equilibrium concentration, in
a. decrease in pressure
+
3 3
mol dm , of H (aq) ions in a 0.0200 mol dm
b. increase in temperature
solution of benzoic acid at 298 K.
c. increase in concentration of oxygen gas ⦵

1
b. C alculate the ∆G value, in kJ mol , for the forward
d. decrease in concentration of c arbon monoxide

reaction at 298 K.
e. addition of a c atalyst
15. Consider the equilibrium between two oxides of nitrogen:
⦵
12. At high temperature, ammonia decomposes into 1
N O (g) ⇌ 2NO (g) ΔH = +58 kJ mol

2 4 2
nitrogen and hydrogen:
The graph below shows the concentrations of both
2NH (g) ⇌ N (g) + 3H (g)

3 2 2
oxides at 320 K as a function of time.
The progress of this reaction under certain conditions
1.00
without a c atalyst is shown in the graph below.
NO (g)
2
3
0.80
md
H (g)
2
lom / noitartnecnoc
noitartnecnoc
0.60
NH (g)
3
N O (g)
2 4
0.40
N (g)
2
0.20
0.00
time
0 2 4 6 8 10
On a copy of the same graph, sketch the changes in

time / min
concentrations of NH (g), N (g) and H (g) over time

3 2 2
a. State the K expression for this equilibrium and
for the same reaction under the same conditions in the
determine the K value at 320 K.
presence of a catalyst.
⦵
1
b. C alculate the ∆G value, in kJ mol , for the forward

LHA
13. The esteric ation reaction between ethanoic acid and

reaction at 320 K.
ethanol proceeds as follows:

c. Determine the direction of the spontaneous reaction
3
CH COOH(org) + CH CH OH(org) ⇌
3 3 2
at 320 K in the mixture containing 0.50 mol dm of
3
CH COOCH CH (org) + H O(org)
3 2 3 2
N O (g) and 0.10 mol dm of NO (g).
2 4 2
A mixture of 1.00 mol of ethanoic acid and 2.00 mol
of ethanol was dissolved in an inert organic solvent
(designated as “org”) to produce 1.00 dm of the
solution and heated at 50 °C in the presence of an acid
c atalyst until equilibrium was reached. The equilibrium
mixture contained 1.40 mol of ethanol.
a. C alculate the K value for this equilibrium at 50 °C.
b. Determine the direction of the spontaneous
reaction at 50 °C in the mixture containing equal
concentrations of all four species participating in
this equilibrium.
535
What are the mechanisms
of chemic al c h a n g e?
Reactivity 3.1 Proton transfer reactions
What happens when protons are transferred?
Acids and bases have been known for thousands of years. In previous chapters, you learned that acids and bases
The term “acid” is derived from the L atin word acere, are two classes of chemic al compounds with opposing
which means “sour ” and refers to the characteristic taste properties. One of the most common reaction types,
of vinegar, lemon juice and other acidic solutions. Basic neutralization, usually involves an acid and a base as
substances, such as potash (potassium c arbonate) and reactants and a salt and water as products. At the same
lime water (a solution of c alcium hydroxide), were used by time, some salts and even water itself demonstrate acidic
ancient Egyptians for making soap and parchment. People or basic properties by reacting with bases or acids,
who worked with basic solutions noted their slippery, respectively. During acid–base reactions, protons are
soap-like feeling to the touch, bitter taste and ability to transferred from one chemic al species (acid) to another
react with acids. (base). In this chapter, we will discuss the nature of acids
and bases, proton transfer reactions and acid–base
equilibria in aqueous solutions.
Understandings
LHA
Reactivity 3.1.1 — A Brønsted–Lowry acid is a proton
Reactivity 3.1.11 — For a conjugate acid–base pair,
donor and a Brønsted–Lowry base is a proton acceptor.
the relationship K × K = K c an be derived from

a b w
the expressions for K and K

a b
Reactivity 3.1.2 — A pair of species diering by a single
proton is c alled a conjugate acid–base pair.

Reactivity 3.1.12 — The pH of a salt solution
depends on the relative strengths of the parent acid
Reactivity 3.1.3 — Some species c an act as both
and base.
Brønsted–Lowry acids and bases.
Reactivity 3.1.13 — pH curves of dierent
Reactivity 3.1.4 — The pH sc ale c an be used to describe

combinations of strong and weak monoprotic acids
+ + +
pH
the [H ] of a solution: pH = −log [H ]; [H ] = 10

10
and bases have characteristic shapes and features.
Reactivity 3.1.5 — The ion product constant of water, K , Reactivity 3.1.14 — Acid–base indic ators are weak
w
shows an inverse relationship between [H ] and [OH ]. acids, where the components of the conjugate
K = [H ][OH ] acid–base pair have dierent colours. The pH of the

w
end point of an indic ator, where it changes colour,
Reactivity 3.1.6 — Strong and weak acids and bases dier
approximately corresponds to its pK value.

a
in the extent of ionization.
Reactivity 3.1.15 — An appropriate indic ator for a
Reactivity 3.1.7 — Acids react with bases in neutralization

titration has an end point range that coincides with
reactions.
the pH at the equivalence point.
Reactivity 3.1.8 — pH curves for neutralization reactions Reactivity 3.1.16 — A buer solution is one that
involving strong acids and bases have characteristic resists change in pH on the addition of small
shapes and features. amounts of acid or alkali.

LHA
Reactivity 3.1.17 — The pH of a buer solution

Reactivity 3.1.9 — The pOH sc ale describes the
depends on the pK or pK of its acid or base, and

a b
[OH ] of a solution. pOH = −log [OH ];

10
pOH
the ratio of the concentration of acid or base to the
[OH ] = 10
concentration of the conjugate base or acid.
Reactivity 3.1.10 — The strengths of weak acids
and bases are described by their K , K , pK or pK

a b a b
values.
537
Reactivity 3 What are the mechanisms of chemic al change?
Theories of acids and bases (Reactivity 3.1.1)
The rst rational approach to acids and bases was proposed by the Irish scientist
Robert Boyle in the 17th century. According to Boyle, acids and bases c an be
dened as follows:
• acids taste sour, react with metals, turn litmus red and c an be neutralized
bybases
• bases feel slippery, turn litmus blue and c an be neutralized by acids.
In 1884, the Swedish scientist Svante Arrhenius dened acids and bases in terms
of the ions they produced in aqueous solutions:
• an Arrhenius acid is a substance that dissociates in water to form hydrogen
ions (H )
• an Arrhenius base is a substance that dissociates in water to form hydroxide
ions (OH ).
For example, hydrogen chloride is an acid, as it produces H ions when dissolved
in water:
HCl(aq) → H (aq) + Cl (aq)
Similarly, sodium hydroxide is a base, as it produces OH ions in aqueous
solutions:
NaOH(aq) → Na (aq) + OH (aq)
According to Arrhenius, neutralization is a combination reaction between H and
OH ions:
H (aq) + OH (aq) → H O(l)

2
The Arrhenius theory has limitations. First, all Arrhenius acids and bases must
be soluble in water, or they will not be able to produce any ions in aqueous
solutions. Second, some bases, such as ammonia, NH , contain no oxygen and

3
thus c annot produce hydroxide ions by dissociation. When dissolved in water,
ammonia does produce some OH ions by reacting reversibly with water:
NH (aq) + H O(l) ⇌ NH (aq) + OH (aq)

3 2 4
However, the source of hydroxide ions in this reaction is water, not ammonia
itself, so in the absence of water, no OH ions would be formed. Nevertheless,
gaseous ammonia behaves as a typic al base. For example, it readily reacts with
gaseous hydrogen chloride, producing a salt, ammonium chloride, in the form of
a white smoke (gure1). This is an example of a neutralization reaction.
NH (g) + HCl(g) → NH Cl(s)

3 4
To overcome the limitations of the Arrhenius approach, a new acid–base theory
was proposed in 1923 by two physic al chemists, Johannes Brønsted from

pFigure 1 Re a c t i o n of hy d r o g e n
chloride with ammonia. “A m m o n i u m Denmark and M artin Lowry from England. Working independently of each other,
hy d r ox i d e” is a common name for Brønsted and Lowry concluded that both acids and bases could be dened by
aqueous ammonia
their roles in the transfer of protons (H ):
538
• a Brønsted–Lowry acid is a proton donor: a species that c an lose an H ion
• a Brønsted–Lowry base is a proton acceptor: a species that c an gain an
H ion.
Consider the reaction of hydrogen chloride with gaseous ammonia:

3 4
Hydrogen chloride formally loses a proton and therefore acts as a Brønsted–
Lowry acid:
HCl(g) → H + Cl
In turn, ammonia accepts a proton and therefore acts as a Brønsted–Lowry base:
+ +
NH (g) + H → NH
3 4
The ammonium c ation and chloride anion form ammonium chloride:
NH + Cl → NH Cl(s)
4 4
+ +
If we add the last three equations together, the H , NH and Cl ions will c ancel
4
one another, and the resulting equation will represent the overall neutralization
reaction:

3 4
It is important to note that the Brønsted–Lowry approach to acids and bases
does not replace the Arrhenius theory but rather expands it by removing any
references to the solvent (water) and recognizing a wider range of species as
acids and bases. For example, any Arrhenius acid, such as HCl(aq), will be a
Brønsted–Lowry acid too, as it acts as a proton donor. At the same time, many
Arrhenius bases, such as sodium hydroxide (NaOH), are treated by the Brønsted–
Lowry theory as complexes of a base (OH ) with a metal c ation (Na ). Sodium
hydroxide c annot act as a proton acceptor without losing another ion (Na ),
while the hydroxide ion c an:
OH (aq) + H (aq) → H O(l)

2
Theories
Boyle’s denitions of acids and bases emphasize the most characteristic
properties of these compounds (reactivity towards metals and each other).
Boyle’s theory also suggested a simple experimental procedure (the colour
change of litmus, a natural acid–base indic ator) for distinguishing between
acidic and basic solutions. This approach is a good illustration of the scientic
method, which is based on systematic observations and experimental
evidence.
At the same time, Boyle was unable to explain why some compounds
behaved as acids and others as bases. In the 17th century, the chemic al
composition of most substances was still unknown, and even the existence
of chemic al elements was not universally accepted. As a result, Boyle’s
classic ation had no theoretic al background or predictive power, so it was not
a scientic theory but rather a set of empiric al rules.
How does the meaning of the word “theory” in science compare to its
meaning in other contexts?
539
Worked example 1
The equation for the neutralization of sulfuric acid, H SO (aq), with potassium hydroxide, KOH(aq), is shown below:
2 4
H SO (aq) + 2KOH(aq) → K SO (aq) + 2H O(l)

2 4 2 4 2
Deduce the Brønsted–Lowry acid and base in this reaction.
Solution
Sulfuric acid loses two protons and therefore acts as a The potassium c ation and sulfate anion form a salt,
Brønsted–Lowry acid: potassium sulfate:
+ −
2 + −
2
H SO (aq) → 2H (aq) + SO (aq) 2K (aq) + SO (aq) → K SO (aq)

2 4 4
4 2 4
In Brønsted–Lowry theory, potassium hydroxide is To double check that these assignments match the overall
considered a complex of a base (OH ) with a metal c ation equation, we c an add these four equations together. The
+
+ + − −
2
(K ). In aqueous solution, potassium hydroxide dissociates H (aq), K (aq), SO (aq) and OH (aq) ions will c ancel one
4
into potassium and hydroxide ions: another, giving the original neutralization equation:
+ −
KOH(aq) → K (aq) + OH (aq) H SO (aq) + 2KOH(aq) → K SO (aq) + 2H O(l)

2 4 2 4 2
The hydroxide ion accepts a proton and therefore acts as a
Brønsted–Lowry base:
− +
OH (aq) + H (aq) → H O(l)

2
According to the Brønsted–Lowry theory, the reaction of ammonia with water
Practice questions
is also a neutralization process. Water acts as an acid by losing a proton while
ammonia acts as a base by accepting a proton:

1. Deduce the molecular and
+
net ionic equations for the
H O(l) ⇌ H (aq) + OH (aq)
2
neutralization of
+ +
NH (aq) + H (aq) ⇌ NH (aq)

3 4
a. nitric acid with sodium
When these two equations are combined, the resulting equation represents the
hydroxide
ionization of ammonia in water:
b. hydrogen bromide with

barium hydroxide. 3 2 4
2. Deduce the equation for the
The reaction of ammonia with water is usually referred to as ionization rather than
reaction between hydrogen
dissociation. While these two terms are oen used interchangeably, there is a
chloride andwater.
subtle dierence between them. Dissociation means that a single molecule (or
other species) breaks into two or more species, while ionization refers to any
process that produces ions. Since the reaction of ammonia with water involves
more than one reactant, it should not be c alled dissociation.
Hydronium ion
Modern studies show that a free proton, H , c annot exist in aqueous solutions
bec ause it immediately reacts with water and produces a hydronium ion (also
known as hydroxonium), H O :
3
+
+ O O
H
H H H H
In the above scheme, the oxygen atom donates one of its lone electron pairs to the
empty orbital of the hydrogen cation. All three O–H bonds in the hydronium ion have
identical lengths, and the overall shape of the ion is a trigonal pyramid (Structure 2.2).
540
+ +
In this book, the H symbol will be used as a shorthand equivalent of H O .

3
However, you should always remember that all acid–base processes in aqueous
solutions involve hydronium ions rather than isolated protons.
Alkaline species
“Alkali” is a collective name for water-soluble bases, such as hydroxides of alkali
metals (group1 elements) and alkaline earth metals (group2 elements). The
broader term “base” includes all substances that demonstrate basic properties,
regardless of their strength and solubility in water. For example, sodium
hydroxide, NaOH, is both an alkali and a base while iron(II) oxide, FeO, is a base
but not an alkali.
Conjugate acid–base pairs (Reactivity 3.1.2)
Another consequence of the Brønsted–Lowry theory is that any Brønsted–Lowry
acid that loses a proton produces a Brønsted–Lowry base. In turn, any Brønsted–
Lowry base that gains a proton produces a Brønsted–Lowry acid. The acid–base
pairs in which the species dier by exactly one proton are c alled conjugate acid–
base pairs.
For example, hydrogen cyanide (HCN) acts as a Brønsted–Lowry acid by losing a
Practice questions
proton and producing a conjugate base, the cyanide anion (CN ):
3. Hydrogenc arbonate ions,

+
HCN(aq) ⇌ H (aq) + CN (aq)
HCO (aq), c an participate in

3
conjugate acid conjugate base

the following equilibria:
If we expand this equation to include a molecule of water, two dierent conjugate HCO (aq) + H O(l) ⇌
3 2
+
2
acid–base pairs will be formed: CO (aq) + H O (aq)

3 3
conjugate conjugate
HCO (aq) + H O(l) ⇌
3 2
base2 acid2
H CO (aq) + OH (aq)
2 3
+ −
HCN(aq) + H O(l) H O (aq) + CN (aq)

2 3
Identify two conjugate acid–
conjugate conjugate base pairs in each equation
acid1 base1 and state which species act
as Brønsted–Lowry acids and
In a conjugate acid–base pair, the acid and the base dier by exactly one proton
which as Brønsted–Lowry bases.
(the acid has one more proton than the base). For example, in the following
−
2
4. Deduce the formula of the
equation, sulfuric acid (H SO ) and the sulfate ion (SO ) do not form a conjugate
2 4 4
conjugate base of phosphoric

acid–base pair, as they dier by two protons instead of one:
acid, H PO
3 4
+ −
2
H SO (aq) → 2H (aq) + SO (aq)

2 4 4
5. Deduce the formula of the
However, if we formulate the equations for stepwise dissociation of sulfuric acid, conjugate acid of the ethanoate
each of these equations will contain a pair of conjugates: ion, CH COO

3
+ −
H SO (aq) → H (aq) + HSO (aq)

2 4 4
conjugate conjugate
acid base
− + −
2
HSO (aq) → H (aq) + SO (aq)

4 4
conjugate conjugate
acid base
Notice how the same species (HSO ) acts as a Brønsted–Lowry base in one
4
process and as a Brønsted–Lowry acid in another.
541
Amphiprotic and amphoteric species
(Reactivity 3.1.3)
An interesting consequence of the Brønsted–Lowry theory is that the same
species c an behave as both an acid and a base. For example, water c an lose
a proton and produce a hydroxide anion, or accept a proton and produce a
hydronium c ation:
H O(l) ⇌ H (aq) + OH (aq) (water acts as an acid)

2
+ +
H O(l) + H (aq) ⇌ H O (aq) (water acts as a base)

2 3
Moreover, one molecule of water can pass a proton to another molecule of water, in
which case the rst molecule will act as an acid and the second molecule as abase:
H O(l) + H O(l) ⇌ H O (aq) + OH (aq)

2 2 3
Water and other species that c an be both Brønsted–Lowry acids and Brønsted–
Lowry bases are oen c alled amphiprotic (as they c an accept or donate a
proton). A broader term, amphoteric, refers to species that c an react with both
acids and bases (and therefore have both acidic and basic properties).
Any amphiprotic species is amphoteric: if it c an donate a proton, it is an acid,
and if it c an accept a proton, it is a base. However, not all amphoteric species are
amphiprotic. For example, zinc oxide c an react with both acids and bases, so it is
amphoteric:
ZnO(s) + 2HCl(aq) → ZnCl (aq) + H O(l)

2 2
ZnO(s) + 2NaOH(aq) + H O(l) → Na [Zn(OH) ](aq)

2 2 4
At the same time, ZnO c annot donate a proton (as it has none), so it is not
amphiprotic.
2-Amino acids are amphiprotic organic compounds with the general formula
H N–CH(R)–COOH, where R is a hydroc arbon or other organic substituent. In

2
neutral aqueous solutions, 2-amino acids exist as zwitterions (from the German
zwitter, “hybrid”), which have both a positive and a negative charge within the
same species:
+ +
+ – H + – H
H N CH COOH H N CH COO H COO

3 3 2
+ +
+ H + H
R R R
c ation zwitterion anion
(acidic solution) (neutral solution) (basic solution)
In acidic solutions, zwitterions act as Brønsted–Lowry bases by accepting a
2-Amino acids are structural proton and producing c ations. In basic solutions, zwitterions act as Brønsted–
units of peptides, proteins and Lowry acids by losing a proton and producing anions.
other biologic ally important
macromolecules (Structure 2.4).
Activity
Another type of amphiprotic
organic species, anthocyanins, will +

2
Consider the following species: HF, F , NH , NH , H PO , H PO , HPO ,

3 4 3 4 2 4 4
be discussed later in this topic. +

3 2
PO , Al O , Zn . State, with a reason, which of these species c an act as

4 2 3
Brønsted–Lowry acids, Brønsted–Lowry bases, or both. Identify amphiprotic
and amphoteric species.
542
The pH sc ale (Reactivity 3.1.4)
+ +
The value of [H ] in an aqueous solution c an be very small, so [H ] is oen +
[H ] pH Example
represented by its negative decimal logarithm, known as the potential of
liquid drain
–14
hydrogen, pH: 1×10 14
cleaner
–13
pH = −log [H ]
1×10 13 bleach
–12
1×10 12 ammonia solution

pH is used to characterize the acidity or basicity of aqueous solutions over a
+
–11
broad range of H concentrations (table1). 1×10 11 mild detergent
–10
+ 1×10 10 toothpaste
Acidic solutions with high concentration of H ions have low pH, while
+ –9
1×10 9 baking soda

basic solutions with low [H ] have high pH. This follows from the denition
–8
pH = −log [H ]: the higher the value, the lower its negative logarithm. At
1×10 8 seawater
25°C (298 K), pure water and solutions with pH = 7 are c alled neutral, as they
–7
1×10 7 pure water

+
have equal concentrations of H and OH ions. The pH of an acidic solution is
–6
1×10 6 urine
less than 7, while the pH of a basic solution is greater than 7. These denitions
–5
are summarized in table 2. 1×10 5 black coee
–4
1×10 4 tomato juice
Solution pH [H ] and [OH ]

0.001 3 orange juice
acidic < 7 [H ] > [OH ]

0.01 2 vinegar
neutral 7 [H ] = [OH ]
0.1 1 gastric juice
basic > 7 [H ] < [OH ]

1 0 battery acid
pTable 2 Ac i d i c , n e u t ra l and basic aqueous solutions at 298 K
pTable 1 The pH sc ale
If you know the concentration of H (aq) in solution, you c an work out the pH. A
+
3 3
0.100 mol dm solution of hydrogen chloride contains 0.100 mol dm H (aq)

+
The formulas pH = −log[H ] and
ions. The pH value of this solution will be −log 0.100 = 1.00. As expected,
+
pH
[H ] = 10 are given in the data
1.00<7, so the solution is acidic.
booklet.
If the pH of a solution is known, the concentration of H ions in that solutions c an
+
pH
be c alculated using the formula [H ] = 10 . Hydrochloric acid with pH = 3 will
3 3
have a hydrogen chloride concentration of 10 = 0.001 mol dm
Practice questions
–3
6. C alculate the pH value for 0.0100 mol dm aqueous solution of
sulfuric acid.
7. C alculate the concentration of nitric acid in its aqueous solution with
pH = 4.2.
In a modern chemic al laboratory, the pH of a solution c an be measured with high
accuracy and precision by a digital pH meter (gure2). Alternatively, the pH c an
be estimated using universal indic ator, which gradually changes colour across
the whole pH range, as shown in table1.
pFigure 2 D igital pH meter
543
The pH sc ale
In this task, you will explore the logarithmic nature of the 3. Create another solution that is ten times more dilute
pH sc ale by performing serial dilutions and measuring the again and so on until you end up with five solutions,
pH of the resulting solutions. You will also consider the each with a concentration different from the next by a
advantages and disadvantages of measuring pH with a factor of 10.
probe compared to pH paper.
4. Repeat step 2 for sodium hydroxide.
Relevant skills
5. Arrange your five HCl(aq) solutions and five NaOH(aq)
solutions in a rack. Calculate the concentration of

• Tool 1: Measuring pH of a solution
hydrogen ions in each. Calculate the pH.
• Tool 1: C arrying out dilutions
6. Calibrate the pH probe by following the instructions in
the accompanying manual.
• Tool 2: Represent data in graphic al form

7. Using the pH probe, measure the pH of each solution.
• Tool 3: C alculations involving logarithmic functions

8. Measure the pH of each solution again, but this time
using pH paper.
• Inquiry 1: C alibrate measuring apparatus, including
sensors
Questions
S afety 1. Comment on the difference between the pH values
measured with the probe and those measured with

pH paper.
• Wear gloves when handling chemic als (hydrochloric
2. What are the advantages and disadvantages of pH

acid and sodium hydroxide at these concentrations
probes and pH paper?

are irritants)
3. Comment on any differences you observe between
• Dispose of all substances appropriately
your c alculated and measured pH values.
Materials
4. Which pH values have greater reliability: those you
• 1.0 mol dm hydrochloric acid, HCl(aq)

measured with a probe or the ones you obtained with
3 pH paper?
5. Table 3 shows the change in pH of a strong acid
• graduated pipettes
during the addition of a strong base. Enter the data
• distilled water
into a spreadsheet.
• test tubes and rack

6. Plot a graph showing the relationship between pH
and volume of NaOH(aq) added.

• pH probe, including c alibration solutions
7. Using the spreadsheet, convert the pH values into
• pH (universal indic ator) paper
concentrations of hydrogen ions.
Instructions
8. Plot a graph showing the relationship between
1. Review the section in the Tools for chemistry chapter

hydrogen ion concentration and volume of NaOH(aq)
that discusses serial dilutions.

added.
2. Prepare and label five consecutive solutions of HCl(aq),

9. Based on your graphs, discuss the advantages of
by performing serial dilutions. Start with 1.0 mol dm

using a logarithmic sc ale such as the pH sc ale for
HCl(aq), and carry out a ten-fold dilution, resulting in a

measuring acidity.
–3
0.10 mol dm solution.
Volume of NaOH(aq) 0 1.0 2.0 3.0 4.0 4.5 5.0 5.5 6.0 7.0 8.0
added / cm
pH 1.30 1.35 1.60 2.15 3.6 10.00 12.80 13.30 13.40 13.50 13.51
pTable 3 pH me asure d on the addition of a strong base to a strong acid
544
Ionic product of water (Reactivity 3.1.5)
Water dissociates into H and OH ions:

2
Like any other equilibrium, the dissociation of water c an be characterized by its
equilibrium constant, K:
[H ][OH ]
K =
[H O]
2
where [H ], [OH ] and [H O] are the equilibrium concentrations of participating

2
species. As the density of pure water at room temperature is approximately
3 3
1,000 g dm , the mass of each dm of water is about 1,000 g, and the amount of
water in 1 dm is:
m(H O) 1000 g
2
= = 55.5 mol
1
M(H O) 18.02 g mol

2
Nearly all water molecules exist in undissociated form. Therefore, in any dilute
solution, the equilibrium concentration of water will have approximately the same
value, 55.5 mol dm .
The equation for K c an be rearranged as follows:
K × [H O] = [H ][OH ]
2
Both factors on the le, K and [H O], are constants, so their product is also a
2
constant. This new constant, K = K × [H O], is c alled the ionic product of

w 2
water:
K = [H ][OH ]
w
14
At room temperature (25 °C, or 298 K), K = 1.00 × 10 .

w
The equation for K and its value at

w
14
298 K are given in the data booklet.
The value of K = 1.00 × 10 c an be used only for dilute aqueous solutions. In
w
a concentrated solution (for example, in battery acid containing 30% H SO by

2 4
mass), the concentration of water becomes signic antly less than 55.5 mol dm ,
which aects the value of K . In addition, the K value increases with

w w
temperature. In this book, we will assume that all solutions are dilute and have a
temperature of 25 °C (298 K), so the K value remains constant.

w
If we remove a proton from a water molecule, a hydroxide ion will be le, so the
amounts and concentrations of these ions in pure water will always be equal.
Therefore, [H ] = [OH ] and so each concentration c an be found as a square root
of K :
w
+
14 7 3
[H ] = [OH ] = √ 1.00 ×10 = 1.00×10 mol dm
This means that for each 55.5 mol of water, only 1.00 × 10 mol exists as ions.
In other words, only one in approximately 1,800,000,000 water molecules
dissociates into H (aq) and OH (aq) ions, while the rest of the molecules stay in
the form of H O(l) species. This is the reason why water is represented as H O(l)
2 2
molecules rather than H (aq) and OH (aq) ions in ionic equations.
545
Acids and bases c an aect the concentrations of H (aq) and OH (aq) ions in
aqueous solutions. For example, if we dissolve hydrogen chloride in water, more
H (aq) ions will be produced:
According to LeChâtelier ’s principle (Reactivity 2.3), the increased concentration
of H (aq) ions will shi the position of the following equilibrium to the le:
H O(aq) ⇌ H (aq) + OH (aq)

2
As a result, the concentration of OH (aq) ions will decrease. Therefore, in an
acidic solution, [H ] will always be greater than [OH ].
Worked example 2
C alculate the concentration of OH (aq) ions in a 0.100 mol dm solution of
hydrogen chloride at 25 °C.
Solution
+
3 3
A 0.100 mol dm HCl solution will contain 0.100 mol dm H (aq) ions:
c, mol dm 0.100 0.100 0.100
Since K = [H ][OH ], we can nd the concentration of OH (aq) ions as follows:

w
14
1.00 × 10 = 0.100 × [OH ]

Activity
14
1.00 × 10
[OH ] =
C alculate the concentrations
0.100
of H (aq) and OH (aq) ions in a 13 3
= 1.00 × 10 mol dm
0.0500 mol dm aqueous solution
+
13
of potassium hydroxide. As expected, 0.100>1.00 × 10 , so [H ] > [OH ].
An addition of a base will increase the concentration of OH (aq) ions in the
solution and decrease the concentration of H (aq) ions. Therefore, in a basic
+ −
solution, [H ] will be lower than [OH ].
Properties of acids and bases (Reactivity 3.1.6)
Properties of acids
All Brønsted–Lowry acids must contain at least one exchangeable (weakly
bound) hydrogen atom that c an detach from the rest of the acid molecule.
Exchangeable hydrogen atoms usually form bonds with highly electronegative
atoms, such as oxygen, halogens or sulfur. In almost all organic acids,
exchangeable hydrogen atoms are bonded to oxygen.
546
For example, hydrogen chloride, sulfuric acid and ethanoic (acetic) acid have the
following structural formulas:
H O O O
H Cl S H C C
H O O O H
The nomenclature, structure and
H
properties of organic acids are

hydrogen chloride sulfuric acid ethanoic acid
The exchangeable hydrogen atoms are shown in red. In aqueous solutions, these
+ +
hydrogen atoms dissociate and form H (aq) (or H O (aq)) c ations, while the
3
remaining part of the acid produces an anion, also known as the acid residue.
Here are three examples of acid dissociation:
+
2
H SO (aq) → 2H (aq) + SO (aq)

2 4 4
CH COOH(aq) ⇌ H (aq) + CH COO (aq)

3 3
Notice that ethanoic acid contains four hydrogen atoms, but only one of them
is exchangeable. To explain this, you need to consider the electronegativities of
hydrogen (χ =2.2), c arbon (χ =2.6) and oxygen (χ =3.4). Hydrogen and carbon
have similar electronegativities (Δχ = 2.6 − 2.2 = 0.4), so the C–H bond has low Electronegativity and bond polarity
polarity and does not break easily. In contrast, the dierence in electronegativity are discussed in Structure 2.2.
between hydrogen and oxygen is signicant (3.4 − 2.2 = 1.2), so the O–H The electronegativity values for
bond is highly polar. Since the bonding electron pair is shied towards the more all elements are given in the data
electronegative O atom, the less electronegative H atom develops a partial booklet.
positive charge. As a result, it dissociates readily to form an H (aq) ion.
In inorganic acids containing oxygen (oxoacids), all hydrogen atoms are usually
bonded to oxygen, and so are exchangeable.

Activity
H O Cl H O Cl O
Draw the structural formulas for
hypochlorous acid chlorous acid
the following oxoacids: chloric
(HClO ), perchloric (HClO ),

3 4
Depending on the number of exchangeable hydrogen atoms, acids are
c arbonic (H CO ) and phosphoric

2 3
classied as:
(H PO ).
3 4
• monoprotic (one exchangeable hydrogen atom), for example, HCl
• diprotic (two exchangeable hydrogen atoms), for example, H SO

2 4
• triprotic (three exchangeable hydrogen atoms), for example, H PO

3 4
In contrast to inorganic acids, organic acids oen contain both exchangeable
and nonexchangeable hydrogen atoms. For example, both methanoic and
ethanoic acids are monoprotic, even though their molecules contain two and
four hydrogen atoms, respectively.
547
The formulas and names of common acids and their anions are given in table4.
Along with the systematic names, many organic acids have trivial names, which
are shown in brackets.
Acid Anion
Formula Name Strength Formula Name
HF hydrogen uoride weak F uoride
HCl hydrogen chloride strong Cl chloride
HBr hydrogen bromide strong Br bromide
HI hydrogen iodide strong I iodide
−
2
H S hydrogen sulde weak S sulde

2
HCN hydrogen cyanide weak CN cyanide
HNO nitric strong NO nitrate

3 3
HNO nitrous weak NO nitrite

2 2
−
2
H SO sulfuric strong SO sulfate

2 4 4
−
2
H SO sulfurous weak SO sulte

2 3 3
−
3
H PO phosphoric weak PO phosphate

3 4 4
−
3
H PO phosphorous weak PO phosphite

3 3 3
HClO perchloric strong ClO perchlorate

4 4
HClO chloric strong ClO chlorate

3 3
HClO chlorous weak ClO chlorite

2 2
HClO hypochlorous weak ClO hypochlorite
2–
H CO c arbonic weak CO c arbonate

2 3 3
HCOOH methanoic (formic) weak HCOO methanoate (formate)
CH COOH ethanoic (acetic) weak CH COO ethanoate (acetate)

3 3
−
2
H C O ethanedioic (oxalic) weak C O ethanedioate (oxalate)

2 2 4 2 4
pTable 4 Common acids and their anions. E xc h a n g e a b l e protons are s h ow n in re d
Although the names hydrogen chloride and hydrochloric acid refer to the same
substance, HCl, they have slightly dierent meanings in chemistry. When we say,
“hydrogen chloride”, we mean an individual compound, HCl, which is a gas
under normal conditions, while “hydrochloric acid” is a solution of HCl in water.
Therefore, it is incorrect to say, “a solution of hydrochloric acid”, as “hydrochloric
acid” already refers to a solution.
Similar problems may arise when we talk about sulfuric acid, which is oen used as
an aqueous solution but can also exist in pure form (so-called “100% sulfuric acid”).
When this dierence is important, we should always say, “aqueous sulfuric acid” when
we refer to a solution, or “anhydrous sulfuric acid” when we refer to pure H SO .

2 4
An important characteristic of any acid is its strength. Strong acids, such as
hydrogen chloride, dissociate completely in aqueous solutions. If we dissolve
one mole of HCl in water, the resulting solution will contain one mole of hydrogen
cations and one mole of chloride anions but no HCl molecules. In other words,
the dissociation of HCl is irreversible, which is represented by the single arrow:
+ −
In addition to hydrogen chloride, six other strong acids are listed in table4. You
are advised to memorize their formulas and names.
548
Weak acids, such as ethanoic acid, dissociate only to a small extent when
dissolved in water. For example, table vinegar (an aqueous solution of ethanoic
acid) contains both CH COOH molecules and the products of their dissociation,
3
H (aq) and CH COO (aq) ions. The reversible nature of this process is
3
represented by the equilibrium sign:

3 3
Almost all organic and many inorganic acids are weak, so if an acid is not listed
Activity
in table4, it is safe to assume that it is weak. There are a few exceptions, but they
are not discussed in DP chemistry.
Formulate the equations for the
The strengths of acids and bases have no direct relationship to the concentrations dissociation of hydrogen bromide,
of their solutions, so the terms “strong” and “weak” should not be confused with hydrogen cyanide and methanoic
“concentrated” and “dilute” (table5). The colloquial phrases “strong solution” acid. Do not forget to use a single
and “weak solution” will not be accepted in the IB assessments. arrow for strong acids and an
equilibrium sign for weak acids.
Concentrated Dilute
3 3
Strong 10 mol dm HCl 0.1 mol dm HCl
3 3
Weak 10 mol dm CH COOH 0.1 mol dm CH COOH

3 3
pTable 5 Examples of solutions of acids with different strength and c o n c e n t ra t i o n
The strength of oxoacids generally increases with the oxidation state of the
Oxidation states of elements were

central atom. In turn, a higher oxidation state usually means that the acid
introduced in Structure 3.1

molecule contains more oxygen atoms. For example, the nitrogen atom in weak
nitrous acid, HNO , is bound to two oxygen atoms and has an oxidation state of
2
+3. An addition of another oxygen increases the oxidation state of nitrogen from
+3 to +5 and produces strong nitric acid, HNO . Similarly, strong sulfuric acid,
Activity
3
H SO , has a higher oxidation state of sulfur and more oxygen atoms than weak
2 4
Write down the formulas of

sulfurous acid, H SO
2 3
all oxoacids of chlorine and
Binary acids (acids that consist of only two elements) demonstrate clear periodic phosphorus from table 3. Deduce
trends: their strength increases along the period and down the group (gure3). the oxidation states of these
For example, in the third period, phosphine (PH ) does not show any acidic elements in each acid and outline
3
properties in aqueous solutions, hydrogen sulde (H S) is a weak acid, and how they aect the acid strength.
2
hydrogen chloride (HCl) is a strong acid. Similarly, down group17, hydrogen
uoride (HF) is a weak acid while the other three hydrogen halides (HCl, HBr and
HI) are strong acids.
groups
14 15 16 17
2 CH NH H O HF
4 3 2
sesaercni htgnerts
soirep
3 PH H S HCl
3 2
4 H Se HBr
2
5 HI
strength increases
pFigure3 Pe r i o d i c trends in the strength of binary acids
549
Diprotic or triprotic weak acids dissociate stepwise, for example:
H SO (aq) ⇌ H (aq) + HSO (aq)

2 3 3
+
2
HSO (aq) ⇌ H (aq) + SO (aq)

3 3
The second proton dissociates to a much smaller extent than the rst, so nearly
all H ions produced by a polyprotic acid are formed on its rst dissociation step.
Activity
The reason for that becomes clear if we consider the charges on the ions involved
Formulate the equations for

in the above equations. The rst step produces H (aq) and HSO (aq) ions. These
3
the stepwise dissociation of

ions exert electrostatic attraction on each other, so pulling them apart requires
phosphoric acid.
some energy. On the second step, the electrostatic attraction between H (aq)
2 2
and SO (aq) ions is much greater, as the anion SO (aq) is doubly charged. As
3 3
a result, the second step requires more energy, which makes this process less
likely to occur.
Properties of bases
Despite the dierence in chemic al properties, bases show many similarities to
acids in terms of their behaviour in aqueous solutions. Where an acid produces
an H (aq) ion, a base either produces an OH (aq) ion (Arrhenius base) or accepts
an H (aq) ion (Brønsted–Lowry base). However, the general principles behind
these processes remain the same and thus c an be explained by similar concepts
and equations.
Most inorganic bases are metal hydroxides, which contain a metal atom and
one or more OH groups. The nature of the chemic al bond between the metal
and the OH group depends on the metal electronegativity. Alkali metals (Li,
Na, K, Rb and C s) and most group2 metals (Mg, C a, Sr and Ba) have very low
electronegativities, so they form ionic hydroxides. Such hydroxides consist of a
+
n
metal c ation (M ) and one or more hydroxide anions (OH ).
All ionic hydroxides are strong bases. Except for Mg(OH) and C a(OH) , they are
2 2
readily soluble in water and fully dissociate into ions, for example:
NaOH(aq) → Na (aq) + OH (aq)
+
2
Ba(OH) (aq) → Ba (aq) + 2OH (aq)

2
C alcium hydroxide is only slightly soluble in water, and magnesium hydroxide
is almost insoluble. If an excess of such hydroxide is added to water, a
heterogeneous equilibrium between the solid base and aqueous ions is
established:
+
2
Mg(OH) (s) ⇌ Mg (aq) + 2OH (aq)

2
+
2
C a(OH) (s) ⇌ Ca (aq) + 2OH (aq)

2
These hydroxides are strong bases, so their solutions contain no undissociated
molecules of Mg(OH) or C a(OH) . The reversible nature of the above processes

2 2
is c aused by low solubility of these bases in water, not by their low strength.
550
Less active metals, such as beryllium, aluminium and all transition elements, form
covalent hydroxides, in which the metal atom and the oxygen of the OH group
are linked together by a polar covalent bond. For example, both Fe(OH) and
2
Fe(OH) are covalent hydroxides. Almost all covalent hydroxides are weak bases.
3
In addition, these hydroxides are virtually insoluble in water, so they only show
their basic nature in reactions with acids.
Ammonia (NH ) is one of the few inorganic bases that does not contain a metal.
3
As discussed earlier, aqueous ammonia acts as a weak Brønsted–Lowry base by
accepting a proton from an acid or water:
+ +
NH (aq) + H (aq) ⇌ NH (aq)

3 4

3 2 4
In chemic al equations, aqueous ammonia is oen represented as ammonium
hydroxide, NH OH(aq), which is unstable and exists only in solutions:

4
NH (aq) + H O(l) ⇌ NH OH(aq)

3 2 4
The organic derivatives of ammonia, amines (Structure 3.2), contain one, two or
three hydroc arbon substituents at the nitrogen atom:
H H CH CH
3 3
H N H H N CH H N CH H C N CH
3 3 3 3
ammonia methylamine dimethylamine trimethylamine
Instead of methyl groups (–CH ), amines may contain any other hydroc arbon
3
substituents, such as ethyl (–CH CH ), phenyl (–C H ) and so on. Acid–base

2 3 6 5
properties of amines are similar to those of ammonia, for example:
+ +
CH NH (aq) + H (aq) ⇌ CH NH (aq)

3 2 3 3
CH NH (aq) + H O(l) ⇌ CH NH (aq) + OH (aq)

3 2 2 3 3
Practice questions
8. Amines are organic derivatives of ammonia.
a. Formulate molecular and ionic equations for the reaction of
hydrochloric acid with the following amines:
i. dimethylamine
ii. trimethylamine.
b. Identify conjugate acid–base pairs in each ionic equation and state the
role (Brønsted–Lowry acid or Brønsted–Lowry base) of each species.
551
The anions of weak acids c an also act as Brønsted–Lowry bases. For example, the
ethanoate ion is produced by the dissociation of ethanoic acid:

3 3
If we reverse this equation, the basic nature of the ethanoate ion will become
obvious:
CH COO (aq) + H (aq) ⇌ CH COOH(aq)

3 3
The driving force of acid–base reactions is the formation of weak conjugates. For
example, ethanoic acid, CH COOH, is a weak acid. Therefore, the dissociation

3
of ethanoic acid is an unfavourable process, so only a small proportion of the acid
exists as ions while most CH COOH molecules remain undissociated. In contrast,

3
the reaction of a CH COO (aq) ion (base) with a proton produces CH COOH
3 3
(weak conjugate acid), so the equilibrium of this process is shied almost
completely to the right.
In aqueous solutions, ethanoate ions react with water, producing OH (aq) ions:
CH COO (aq) + H O(l) ⇌ CH COOH(aq) + OH (aq)

3 2 3
Practice questions
This reaction involves two conjugate acid–base pairs: CH COO (base)/
3
CH COOH (acid) and H O (acid)/OH (base). Water is a weaker acid than

3 2
9. Formulate the equations,
ethanoic acid, so the equilibrium of this reaction is shied to thele.

showing the states of all species,
in which the following ions act
Anions of polyprotic acids behave as polyprotic bases, for example:
as Brønsted–Lowry bases:
+
2
CO (aq) + H (aq) ⇌ HCO (aq)

3 3
a. cyanide ion, CN
3−
HCO (aq) + H (aq) ⇌ H CO (aq)
b. phosphate ion, PO 3 2 3
c. hydrogenphosphate ion, These processes are similar to the stepwise dissociation of weak polyprotic acids,
HPO except that all reactions are now reversed.

4
Patterns and trends
Chemists classify substances based on patterns they observe. Three main
acid–base classic ation systems have evolved over time: Arrhenius, Brønsted-
Lowry and Lewis. According to Arrhenius theory, acids release H ions
in aqueous solution, whereas bases release OH ions. Brønsted–Lowry
theory is based on the ability of species to donate or accept protons (H
ions). Both these theories are relevant in the study of acid–base systems in
aqueous media. Lewis theory (which you will learn about in Reactivity 3.4)
denes acids and bases in terms of their ability to accept or donate electron
pairs and is therefore independent of the solvent. These theories represent
related, but dierent, classic ation systems, each with its own advantages and
disadvantages. For instance, Lewis theory covers a broad range of reactions,
whereas Brønsted–Lowry theory underpins many of the pH c alculations and
equilibria you are familiar with.
What other classic ation systems have you encountered in chemistry? Why do
scientists oen classify their objects of study?
552
Reactions of acids and bases (Reactivity 3.1.7)
You have already seen how acids react with bases in neutralization reactions. In
addition to these reactions, most acids react with metals, metal oxides and salts
of weak acids, such as c arbonates and hydrogenc arbonates. The reactions of
acids with active metals produce salts and hydrogen gas (gure4), for example:

2 2
For strong acids, the actual reacting species are hydrogen ions, H (aq), which
c an be shown by ionic equations. In the total ionic equation, all ions present in
the solution are shown:
+ +
2
Mg(s) + 2H (aq) + 2Cl (aq) → Mg (aq) + 2Cl (aq) + H (g) total ionic equation
2
Ions that do not participate in the reaction are c alled spectator ions. The anions
of a strong acid are spectator ions, and hence the chloride anions c an be
pFigure4 Reaction of magnesium metal
c ancelled out to give the net ionic equation: with hydrochloric acid (le) and ethanoic
acid (right) of equal concentrations
+ +
2
Mg(s) + 2H (aq) → Mg (aq) + H (g) net ionic equation

2
In contrast, ionic equations involving weak acids must show the acids in the
molecular form, as they are less likely to dissociate:
Mg(s) + 2CH COOH(aq) → Mg(CH COO) (aq) + H (g) molecular equation

3 3 2 2
The term “active metals” refers
+
2 to elements above hydrogen in
Mg(s) + 2CH COOH(aq) → Mg (aq) + 2CH COO (aq) + H (g) ionic equation
3 3 2
the activity series, which is given
In the last example, there are no spectator ions, so the total and net ionic
in section 19 of the data booklet.
equations are identic al.

Copper, silver and other metals
aer hydrogen in the activity series
Strong and weak acids c an be distinguished by comparing the rates of their
do not react with most acids and
reactions with an active metal (gure4). However, such comparison will be valid
never produce hydrogen gas in
only if the concentrations of both acids are equal, as the reaction rate depends on
such reactions.
the reactant concentrations (Reactivity 2.2).
Reactions of acids with metal oxides produce salts and water. For example:
MgO(s) + 2HCl(aq) → MgCl (aq) + H O(l) molecular equation

2 2
+ +
2
MgO(s) + 2H (aq) + 2Cl (aq) → Mg (aq) + 2Cl (aq) + H O(l) total ionic equation
2
+ +
2
MgO(s) + 2H (aq) → Mg (aq) + H O(l) net ionic equation

2
The last equation shows that magnesium oxide accepts two H ions and thus acts
as a Brønsted–Lowry base. Therefore, reactions of acids with metal oxides c an be
classied as neutralization reactions.
Practice questions
10. Formulate the molecular and ionic equations for the reactions of
a. lithium metal with ethanoic acid
b. aluminium metal with dilute sulfuric acid.
11. Formulate the molecular and ionic equations for the reaction of
iron(III) oxide, Fe O (s), with:

2 3
a. hydrochloric acid
b. dilute sulfuric acid.
553
Metal carbonates also react with acids, producing unstable carbonic acid, H CO :
2 3
Na CO (aq) + 2HCl(aq) → 2NaCl(aq) + H CO (aq)

2 3 2 3
C arbonic acid quickly decomposes into water and c arbon dioxide, which
bubbles out of the solution (gure5):
H CO (aq) → CO (g) + H O(l)

2 3 2 2
These two reactions are oen combined together:
Na CO (aq) + 2HCl(aq) → 2NaCl(aq) + CO (g) + H O(l)

2 3 2 2
pFigure5 Reaction of baking soda with

Again, the net ionic equation reveals the nature of this process:
an acid
+ + +
2
2Na (aq) + CO (aq) + 2H (aq) + 2Cl (aq) → 2Na (aq) + 2Cl (aq) + CO (g) + H O(l) total ionic equation
3 2 2
+
2
CO (aq) + 2H (aq) → CO (g) + H O(l) net ionic equation

3 2 2
As in the previous example, the anion of weak c arbonic acid, CO , acts as a

3
Brønsted–Lowry base by accepting two protons before decomposing to c arbon
dioxide and water.
Metal hydrogenc arbonates, such as baking soda, NaHCO , react with acids in
3
the same way as c arbonates:
NaHCO (aq) + HCl(aq) → NaCl(aq) + CO (g) + H O(l) molecular equation

3 2 2
+ + +
Na (aq) + HCO (aq) + H (aq) + Cl (aq) → Na (aq) + Cl (aq) + CO (g) + H O(l) total ionic equation
3 2 2
HCO (aq) + H (aq) → CO (g) + H O(l) net ionic equation

3 2 2
In this c ase, the hydrogenc arbonate ion, HCO , acts as a Brønsted–Lowry base
3
by accepting a proton before decomposing to c arbon dioxide and water.
Acid deposition, a secondary pollutant, c an take many dierent forms
including rain, snow, fog and dry dust. The components of acid deposition
(the primary pollutants) may be generated in one country and, depending
on climate patterns, may be deposited in neighbouring countries or even
dierent continents. There are no boundaries for acid deposition. The eects
of acid rain may occur away from the actual source leading to widespread
deforestation and pollution of lakes and river systems. National and regional
Practice questions
environmental protection agencies throughout the world collaborate in an
eort to better understand and control acid deposition. The US Environmental

12. Formulate the molecular and
Protection Agency and the Acid Deposition Monitoring Network in E ast

ionic equations for the reaction
Asia (EANET) websites provide data that c an be used in the discussion of

of dilute sulfuric acid with
secondary pollutants and their politic al implic ations.
a. potassium
How c an our understanding of chemistry help to address environmental

hydrogenc arbonate
problems such as acid deposition?
b. c alcium c arbonate.
554
Antacids
Heartburn and other symptoms of indigestion are c aused by excess hydrochloric
acid in the stomach. These symptoms c an be alleviated by medicines known
as antacids (gure6). The active ingredients in antacids are weak bases, such
as metal oxides, hydroxides, c arbonates and hydrogenc arbonates. All these
compounds neutralize the excess acid.
Like any pharmaceutic al drugs, antacids have various side eects. In particular,
c arbon dioxide produced in the body from the reaction of stomach acid with
pFigure6 “Milk of magnesia”, a

c arbonates and hydrogenc arbonates c auses bloating and belching, while the
suspension of magnesium hy d r ox i d e in
intake of metal ions disturbs the balance of electrolytes in the body.
w a t e r, is a common antacid
TOK
Pharmaceutic al drugs (for example, antacids) are subject to rigorous eciency
tests prior to approval by the relevant health authorities. This process oen
includes placebo-controlled clinic al trials, where participants are placed into
two groups. Half of the study participants are given the drug and the other
half are administered an inactive placebo. Participants do not know which
group they are in and therefore do not know whether they have received the
active drug or the placebo. The results from the two groups are compared to
ascertain that any observed physiologic al reactions are due to the treatment.
If the drug works, it should have the desired therapeutic eect on the
participants who received the active drug, but not on the members of the
placebo group.
Sometimes, a therapeutic eect is observed in people who are given the
placebo. This is known as the placebo eect. Statistic al and methodologic al
approaches c an be used to assess and control the impact of the placebo
eect on the results.
How could a participant’s (or a doctor ’s) awareness of the existence and
administration of placebos aect the results of the trial? To what extent is bias
inevitable in the production of knowledge? The mechanism of the placebo
eect is not fully understood. Are some things unknowable?
When balancing acid–base equations, you should use the following steps:
1. Balance all nonmetals except hydrogen and oxygen.
2. Balance all metals. If you need to change any stoichiometric coecients
deduced earlier, return to step1.
3. Balance hydrogen. Again, if you need to change any coecients, return to
step1.
4. At this point, the equation should be balanced already. To verify it, count the
oxygen atoms in the reactants and products. If their numbers do not match,
return to step1.
In most c ases, this strategy produces a balanced equation with the fewest trials.
This strategy works well for acid–base reactions, in which none of the elements
change their oxidation state. It c an also be used for most reactions of acids with
metals.
555
Worked example 3
Deduce the balanced equation for the following chemic al H PO + C aCO → Ca (PO ) + CO + H O
3 4 3 3 4 2 2 2
reaction:
Solution
Besides H and O, the equation involves two nonmetals, 2H PO + 3C aCO → Ca (PO ) + 3CO + H O
3 4 3 3 4 2 2 2
P and C, which should be balanced rst. There are two P
Steps 1 and 2 are complete, so the next element is
atoms on the right but only one on the le, so we need to
hydrogen. There are six H atoms on the le but only two on
write “2” in front of H PO :

3 4
the right, so we need to write “3” before H O:

2
2H PO + C aCO → Ca (PO ) + CO + H O
3 4 3 3 4 2 2 2
2H PO + 3C aCO → Ca (PO ) + 3CO + 3H O

3 4 3 3 4 2 2 2
C arbon seems to be balanced already (one atom on each
Step3 is complete, so we need to check the last remaining
side), so we c an now look at metals. The only metal in the
element, oxygen. There are 2×4=8 O atoms in 2H PO

3 4
equation is Ca (one atom on the le, three atoms on the
and 3 × 3 = 9 O atoms in 3C aCO , so we have a total of

3
right), so we write “3” in front of C aCO :

3
8+9=17 O atoms on the le. On the right, there are
2H PO + 3C aCO → Ca (PO ) + CO + H O 4×2=8 O atoms in Ca (PO ) , 3×2=6 O atoms in 3CO

3 4 3 3 4 2 2 2 3 4 2 2
and 3 O atoms in 3H O, so the total number of O atoms

2
However, this changes the balance of c arbon (three atoms
on the right is also 8+6+3=17. Therefore, oxygen is
on the le, one on the right), so we need to write “3”
balanced and so is the equation.
beforeCO :
2
Identic ation of parent acids and bases

The balancing of redox equations
(those involving changes in the

S alts are oen produced by neutralization reactions. One way to identify the
oxidation state of participating

parent acid and base for a particular salt is to formally split the salt into c ation(s)
elements) will be discussed in

and anion(s). For example, sodium sulfate, Na SO , consists of two Na c ations
2 4
2
Reactivity 3.2.
and one SO anion:
4
+
2
Na SO → 2Na + SO
2 4 4
Now we c an add hydroxide ions to c ations and protons to anions according to
their charges:
Na + OH → NaOH
+
2
2H + SO → H SO
4 2 4
Therefore, the parent base and acid for Na SO are NaOH and H SO ,
2 4 2 4
respectively.
The same result could be obtained by analysing the systematic name of the salt.
The word “sodium” in “sodium sulfate” refers to sodium hydroxide, NaOH, while
the word “sulfate” refers to sulfuric acid, H SO (table4).

2 4
For ammonium salts, such as NH Cl (ammonium chloride), the parent base could
4
be either NH (ammonia) or NH OH (ammonium hydroxide). Both answers will

3 4
be accepted in IB assessments.
556
pH curves (Reactivity 3.1.8) Standard solution is a solution
with a known concentration of the
The unknown concentration of an acid or base in a solution c an be determined by
solute (Structure 1.4). Analyte is the
titration (Reactivity 2.1) using a standard solution of a base or acid, respectively.
analysed substance or the solution
The reaction progress c an be monitored using a digital pH meter (gure7) and
of this substance with unknown
a data logger, which automatic ally records the pH of the reaction mixture as the
concentration. Titrant is the
standard solution is added to the analysed solution.
reactant added to the analyte or a
The pH data collected during a titration experiment c an be plotted against the standard solution of that reactant
added volume of the standard solution, producing a pH curve (gures8 and 9). (Reactivity 2.1).
The overall shape of the pH curve depends on the strengths and concentrations
of the reactants and on the addition order.
When a strong acid, such as HCl, is titrated with a strong base, such as NaOH,
the curve intercepts the y-axis at a low pH value (gure8), as the analysed solution
is strongly acidic. Typical concentrations of acids and bases used in titration
experiments are from 0.01 to 1 mol dm , so the initial pH may vary from 2 to 0.
14
NaCl + NaOH
equivalence point
(NaCl only)
Hp
7 pH jump
intercept
(HCl only)
pFigure7 Ac i d – b a s e t i t ra t i o n with a
HCl + NaCl
pH meter
V(NaOH)
Activity
pFigure8 Ty p i c a l pH curve for the t i t ra t i o n of a strong acid (HCl) with a strong base
The pH curve shown in gure8
(N aOH)
represents the titration of
At the beginning of the titration, the pH of the mixture increases very slowly, 3
0.1 mol dm HCl(aq) with
as the solution still contains large excess of acid. For example, if the initial 3
0.1 mol dm NaOH(aq). Copy the
concentration of the acid were 0.1 mol dm and half of the acid were neutralized,
axes and curve from gure9 and
the pH of the mixture would increase from 1.0 to approximately 1.5.

sketch the second pH curve for the
titration of 0.01 mol dm HNO (aq)

3
As the acid concentration decreases, the pH curve becomes progressively

3
with 0.01 mol dm KOH(aq).
steeper. At the equivalence point, the pH raises sharply to 7.0, as the acid is
Explain whether the changes in the

neutralized completely, and the reaction mixture contains only NaCl(aq):
nature and concentrations of the
HCl(aq) + NaOH(aq) → NaCl(aq) + H O(l) reactants will aect the following

2
features of the curve:
The pH continues to rise sharply immediately aer the equivalence point, as an
• y-axis intercept
excess of NaOH(aq) makes the solution basic. When the excess of the titrant
• pH at equivalence
becomes very large, the curve attens out and gradually approaches the pH of
• pH at which the curve attens
the standard NaOH(aq) solution, typic ally between 12 and 14.
out.
To construct the complete pH curve, we need to continue the titration beyond
the equivalence by adding excess titrant. In contrast, a titration experiment with
an acid–base indic ator must be stopped at or near the equivalence point, when
the indic ator changes colour. In both c ases, the concentration of the analysed
acid or base is c alculated using the volume of the standard solution at the
equivalence point, as explained in Reactivity 2.1. The use of acid–base indic ators
in titrations is discussed in the AHL section of this topic.
557
When a strong base is titrated with a strong acid, the pH curve is inverted
The construction and interpretation
(gure9). Since the initial solution is basic, the curve intercepts the y-axis at a
of pH curves involving weak acids
high pH value and declines gradually as the titrant is added. The equivalence is
and bases will not be assessed
achieved at the same pH value (7.0), as the solution at that point contains only a
at SL. The shapes and features of
neutral salt (in our example, NaCl). At the end of the titration, the curve attens at
these curves are discussed in the
a low pH, as the solution contains excess strong acid.
AHL section of this topic.
14
NaOH + NaCl
intercept
(NaOH only)
Hp
7 pH drop
equivalence point
(NaCl only)
NaCl + HCl
V(HCl)
pFigure9 Ty p i c a l pH curve for the t i t ra t i o n of a strong base
(N aOH) with a strong acid (HCl)
The main features of pH curves for titration experiments involving strong acids
and bases are summarized in table6.
pH
Analyte Titrant
y-axis
equivalence attening out
intercept
strong acid strong base low 7.0 high
strong base strong acid high 7.0 low
pTable 6 S ummary of pH curves for t i t ra t i o n s i nv o l v i n g strong acids and bases
Conductometric acid–base titration
The progress of an acid–base reaction c an be monitored Relevant skills
by measuring the conductivity of the reaction mixture.

• Tool 1: Titration
This is possible bec ause the concentration of aqueous
ionic species changes during the reaction. For example,
• Tool 3: Sketch graphs with labelled but unsc aled axes

in the reaction between hydrochloric acid and sodium
hydroxide, the conductivity of the solution decreases

bec ause water is molecular, and all the other species
• Tool 3: Interpret features of graphs
present are fully dissociated into ions:
+ + +
S afety
H (aq) + Cl (aq) + Na (aq) + OH (aq) → Na (aq) +
Cl (aq) + H O(l) • Wear eye protection.

2
• Dilute hydrochloric acid and sodium hydroxide are
In this practic al, you will perform a conductometric
irritants.
titration. You will analyse and interpret the resulting data in
graphic al form. Then, you will consider how the strength • Dispose of all substances appropriately.
of the acid aects the shape of the titration curve.
558
Materials Questions
• 0.01 mol dm hydrochloric acid, HCl(aq) 1. Plot a graph showing conductivity vs. volume of
3
NaOH(aq) added.
• 250 cm beaker 2. Draw two lines of best fit (one for the points before the
equivalence point and another for the points after).

• burette, burette clamp and stand
Identify the equivalence point by extrapolating the
• magnetic stir bar and stir plate
two lines.
• conductivity probe
3. Compare and contrast this graph to your initial sketch.
Explain any differences between the two plots.

Instructions
1. You will titrate a known volume of 0.01 mol dm 4. Interpret and explain the shape of the graph, noting
HCl(aq) with 0.1 mol dm NaOH(aq) and measure and explaining the following:
how the volume of NaOH(aq) added affects the a. change in conductivity before the equivalence point
conductivity. With reference to the ionic equation b. conductivity at the equivalence point
above, explain why the conductivity should decrease c. change in conductivity after the equivalence point.
as the reaction approaches the equivalence point.
5. Interpret your graph to compare and explain the
+ +
2. Predict and explain the shape of the graph of conductivity of H (aq) ions and Na (aq) ions.
conductivity vs volume of NaOH(aq) added that you
6. The total volume of solution in the beaker was
expect to obtain.
kept roughly constant by ensuring that the sodium
3. Use the conductivity probe, and any other hydroxide concentration was ten times that of
necessary equipment, to prepare and measure the hydrochloric acid. Suggest why the volume in the
conductivityof: beaker should be kept constant in this practic al.
a. 0.1 mol dm HCl(aq)

3
A conductometric titration of 0.1 mol dm ethanoic acid,

3
b. 0.01 mol dm NaOH(aq)

3
CH COOH(aq), with 0.1 mol dm sodium hydroxide,

3
c. distilled water
3
NaOH(aq) added in 2.0 cm increments was c arried out.
4. Using the measurements you obtained in step 3, The data recorded are shown in gure 11.
make any necessary changes and refinements to the
graph you sketched in step 2.

)
1
5. Set up the equipment as shown in figure 10:

mc
4
Sm( / ytivitcudnoc
3
0.1 mol dm NaOH
2
500
μS cm
3
100 cm of
conductivity
0
3
probe 0.01 mol dm HCl
0 5 10 15 20 25 30 35
magnetic stir bar

3
volume of NaOH added / cm
p
 Figure 11 Conductivity against volume of sodium
 p
 Figure10 Experimental a p p a ra t u s for conductometric hy d r ox i d e for the t i t ra t i o n of 0.1 m o l d m CH CO O H ( a q )
3
acid–base t i t ra t i o n with 0.1 m o l d m N aOH(aq). Source of data: Smith, C.
K., Ed i o nw e, E. and Michel, B., J. Chem. Educ., 2 0 1 0, 87,
6. Record the initial conductivity. Add the NaOH(aq) in
11, 1217–1221
small (~1 cm ) increments. Record the exact volume
7. Compare and contrast the graph in figure 11 with

of NaOH(aq) added and the conductivity. Continue
the graph you obtained. Explain any differences you

adding NaOH(aq) well past the equivalence point,
observe.
so you c an later compare the conductivity changes
before and after the equivalence point.
559
LHA
The pOH sc ale (Reactivity 3.1.9)
The pOH sc ale allows us to represent the basicity of aqueous solutions over
a broad range of OH (aq) concentrations. The pOH sc ale is particularly useful
for solutions of Arrhenius bases, in which the concentration of hydroxide ions is
related to the solution pOH as follows:
pOH
pOH = −log[OH ] [OH ] = 10
Basic solutions with high concentrations of OH (aq) ions have low pOH values
The equations for the

while acidic solutions with low concentrations of OH (aq) ions have high pOH
interconversion of pH, pOH, [H ]

values.
and [OH ] are given in the data
booklet. The pOH sc ale is a logarithmic sc ale, like the pH sc ale. Working with logarithms
requires some practice but greatly simplies the c alculations. The expression
14 3
“pOH=14” is more compact than “[OH ]=1.00×10 mol dm ” and less
likely to c ause errors when written. Also, logarithms and p-numbers allow us to
use addition and subtraction instead of multiplic ation and division:
log(a × b) = log a + log b
log = log a − log b

( )
b
As a result, formulas with logarithms or p-numbers are easier to memorize and
use in c alculations (table7).
Without p-numbers With p-numbers
+
14
[H ][OH ] = 1.00 × 10 pH + pOH = 14
14
+ 1 × 10
pH = 14 − pOH
[H ] =
[OH ]
14
1 × 10
pOH = 14 − pH
[OH ] =
+
[H ]
pTable7 Useful expressions involving K , [H ], [OH ], pH and pOH

w
Worked example 4
C alculate the pOH values for the following solutions:
a. 0.025moldm KOH(aq)
b. 0.025moldm H SO (aq).
2 4
Solution
a. First, write the equation for the dissociation of potassium hydroxide:
KOH(aq) → K (aq) + OH (aq)
The concentration of KOH is equal to the concentration of hydroxide ions:
[OH ] = [KOH] = 0.025 mol dm
Then, use the expression pOH = −log[OH ] to determine pOH:
pOH = −log 0.025 = 1.60
560
LHA
b. Write the equation for the dissociation of sulfuric acid: Practice questions
+
2
H SO (aq) → 2H (aq) + SO (aq) 13. C alculate:

2 4 4
+
a. the pOH of a
When one mole of sulfuric acid dissociates, it produces two moles of H
3 3
+
5.0 × 10 mol dm
ions. Therefore, the concentration of H ions is double that of sulfuric
solution of Ba(OH) (aq)

2
acid:
b. the concentration of
+
3 3
[H ] = 2×[H SO ] = 2 × 0.025 mol dm = 0.050 mol dm

2 4
hydroxide ions in a solution
+
with pOH = 4.70.
You c an use the expression K = [H ][OH ] to determine [OH ]:
w
14
K 1.00 × 10
w 13 3
[OH ] = = = 2.00 × 10 mol dm

+
[H ] 0.050
Then, use the expression pOH = −log[OH ] to determine pOH:
13
pOH = −log(2.00 × 10 ) ≈ 12.70
The same answer could be obtained using the formula pH + pOH = 14:
pH = −log0.050 ≈ 1.30
pOH = 14 − 1.30 = 12.70
Weak acids and bases (Reactivity 3.1.10 and
Reactivity 3.1.11)
As with any other equilibria, the dissociation of a weak acid c an be characterized
by an equilibrium constant. This equilibrium constant is known as the acid
dissociation constant, K :
a
+ [H ][A ]
HA(aq) ⇌ H (aq) + A (aq) K =

a
[HA]
Bases c an be characterized by the base dissociation constant, K :

b
+ [BH ][OH ]
B(aq) + H O(l) ⇌ BH (aq) + OH (aq) K =

2 b
[B]
Notice that the concentration of the solvent (water) is not included in the
equilibrium constant expressions.
Stronger acids and bases dissociate to a greater extent and therefore have larger
dissociation constants. Therefore, K and K values c an be used to compare the

a b
relative strengths of dierent acids and bases.
Like [H ], [OH ] and K , the values of K and K are oen expressed as p-numbers
w a b
(their negative decimal logarithms):
Ka
p
pK = −log K K = 10
a a a
Kb
p
pK = −log K K = 10
b b b
In contrast to K and K , larger values of pK and pK correspond to weaker acids

a b a b
and bases, respectively (table8). For example, methanoic acid (pK =3.75) is
a
stronger than ethanoic acid (pK =4.76), while methylamine (pK =3.34) is a
a b
stronger base than ammonia (pK =4.75).

b
561
LHA
Acid K pK Base K pK
a a b b
4 4
sesaercni
HF 6.76 × 10 3.17 (CH ) NH 5.37 × 10 3.27
htgnerts
3 2
4 4
HCOOH 1.78 × 10 3.75 CH NH 4.57 × 10 3.34

3 2
5 5
CH COOH 1.74 × 10 4.76 NH 1.78 × 10 4.75

3 3
10 10
HCN 6.17 × 10 9.21 C H NH 7.41 × 10 9.13

6 5 2
pTable8 Dissociation constants of weak acids and bases at 298 K
The dissociation constants for weak acids and bases c an be determined
experimentally by measuring the pH of their standard solutions. Conversely, if
we know the dissociation constant for a weak acid or base and its concentration
in the solution, we c an c alculate the pH of that solution, as shown in the worked
examples below.
Worked example 5
A 0.0100 mol dm solution of propanoic acid, CH CH COOH(aq), has a pH of 3.44. Determine the pK of propanoic
3 2 a
acid.
Solution
First of all, we need to consider all acid–base equilibria in the solution:
+ [CH CH COO ] [H ]
3 2
CH CH COOH(aq) ⇌ CH CH COO (aq) + H (aq) K =

3 2 3 2 a
[CH CH COOH]
3 2
+ +
14
H O(l) ⇌ H (aq) + OH (aq) K = [H ][OH ] = 1.00 × 10

2 w
Although H (aq) ions are formed by the dissociation of both propanoic acid and water, typic al K values of organic acids
a
(table8) are much higher than K . Therefore, we c an assume that nearly all H (aq) ions in the solution are produced by
w
the acid. In such c ase, [CH CH COO ] ≈ [H ], which follows from the rst equilibrium.
3 2
+
3.44 4 3
[CH CH COO ] ≈ [H ] = 10 ≈ 3.63 × 10 moldm

3 2
Weak acids dissociate to a very small extent, so most of the propanoic acid in the solution exists as undissociated
molecules, CH CH COOH(aq). Therefore, we c an assume that the equilibrium concentration of CH CH COOH(aq) is

3 2 3 2
approximately the same as its initial concentration. In that c ase:
[CH CH COOH] ≈ 0.0100 mol dm

3 2
When performing equilibrium c alculations, always state any approximations you make and explain why these
approximations are valid. In many c ases, approximations greatly simplify the c alculations, which otherwise would involve
quadratic equations. The use of quadratic equations will not be required in examination papers, so any reasonable
approximations will be accepted.
Substitute the values into the expression for K :

a
− −
4 4
(3.63 × 10 )(3.63 × 10 ) −
5
K = ≈ 1.32 × 10
a
0.0100
Then use pK = −log K to determine pK :

a a a
−
5
pK = −log(1.32 × 10 ) ≈ 4.88.
a
The approximations made in this example could potentially reduce both the accuracy and precision of our c alculations.
However, the nal answer is very close to the actual pK value of propanoic acid (4.87), so all the approximations
a
arevalid.
562
LHA
Worked example 6
Using the pK value from the previous example, c alculate the pH of a 0.100 mol dm solution of propanoic acid.
a
Solution
+
5
We determined K to be 1.32 × 10 in the previous example. We c an assume that [CH CH COO ] ≈ [H ], so

a 3 2
+ +
2
[CH CH COO ][H ] ≈ [H ] , giving the following expression for K :

3 2 a
+
2
[H ]
K =
a
[CH CH COOH]
3 2
The concentration of propanoic acid is given in the question (0.100 mol dm ). Substitute the values of K and
a
[CH CH COOH] into the above expression to determine [H ]:

3 2
+
2
[H ]
5
1.32 × 10 =
0.100
+
2 6
[H ] = 1.32 × 10
+
6 3 3
[H ] = √ 1.32 ×10 ≈ 1.15 × 10 mol dm
Then use pH = −log [H ] to determine pH:
pH = −log(1.15 × 10 ) = 2.94.
Worked example 7
A 0.0100moldm solution of trimethylamine, (CH ) N(aq), has a pH of 10.90. Determine the pK of trimethylamine.
3 3 b
Solution
Similar to worked example5, we need to consider all acid–base equilibria in the solution:
[(CH ) NH ][OH ]
+ 3 3
(CH ) N(aq) + H O(l) ⇌ (CH ) NH (aq) + OH (aq) K =

3 3 2 3 3 b
[(CH ) N]
3 3
+ +
14
H O(l) ⇌ H (aq) + OH (aq) K = [H ][OH ] = 1.00 × 10

2 w
Amines are stronger bases than water, so we c an assume that all OH (aq) ions in the solution are formed by the ionization
+
3
of the amine. In such c ase, [(CH ) NH ] ≈ [OH ]. Since amines are weak bases, [(CH ) N] ≈ 0.0100 mol dm
3 3 3 3
pOH
Use pOH = 14 − pH to work out the value of pOH, and then use [OH ] = 10 to determine the concentration of
hydroxide ions:
pOH = 14 − pH = 14 − 10.90 = 3.10
3.10 4 3
[OH ] = 10 = 7.94 × 10 mol dm
Then substitute the values in the expression for K :

b
− −
4 4
(7.94 × 10 ) (7.94 × 10 ) −
5
K = ≈ 6.31 × 10
b
0.0100
−
5
pK = −log(6.31 × 10 ) ≈ 4.20
b
Our answer matches the actual pK of trimethylamine.

b
563
LHA
Worked example 8
Using the pK value from the previous example, c alculate the pH of a

b
0.100 mol dm solution of trimethylamine.
Solution
K was determined to be 6.31 × 10 in the previous example. We c an assume

b
+ +
2
that [(CH ) NH ] ≈ [OH ], so [(CH ) NH ][OH ] ≈ [OH ] , giving the following

3 3 3 3
expression for K :
b
[OH ]
K =
b
[(CH ) N]
3 3
Substitute the values into the K expression:

b
[OH ]
–5
6.31 × 10 =
0.100
2 6
[OH ] = 6.31 × 10
6 3 3
[OH ] = √ 6.31 ×10 ≈ 2.51 × 10 mol dm
Then determine the pOH, and nally the pH:
pOH = −log(2.51 × 10 ) ≈ 2.60
pH = 14 − 2.60 = 11.40
A conjugate acid–base pair c an be characterized by a single ionization constant,
Practice questions
as the pK of the acid and pK of the base are related to each other. For example,
a b
the acid–base equilibria involving the acid HA and its conjugate base A c an be
14. C alculate the pH values for the
represented as follows:
following solutions:
3 + [H ][A ]
a. 0.0200 mol dm
HA(aq) ⇌ H (aq) + A (aq) K =
a
[HA]
hydrogen cyanide,
[HA][OH ]
HCN(aq) A (aq) + H O(l) ⇌ HA(aq) + OH (aq) K =

2 b
[A ]
3 3
b. 5.00 × 10 mol dm
When these two equations are added together, HA(aq) and A (aq) c ancel out,
phenylamine,
giving the equation for the ionic product of water:
C H NH (aq).
6 5 2
+ +
H O(l) ⇌ H (aq) + OH (aq) K = [H ][OH ]

2 w
Refer to table 8.
According to table1 from Reactivity 2.3, when two chemic al equations are
added together, the equilibrium constant of the resulting equation is equal to
the product of the equilibrium constants of the individual equations. As a result,
K = K ×K and pK = pK + pK .
w a b w a b
At 298 K, pK =14, so:

w
pK = 14 − pK
a b
pK = 14 − pK
b a
Note that these equations are valid only for conjugate acid–base pairs, as the pK
a
and pK values of non-conjugated acids and bases are not related to one another
b
in any way.
The equation K = K × K c an be rearranged as follows:

w a b
K
w
K =
a
K
b
564
LHA
This equation shows the inverse relationship between the strengths of
Practice questions
conjugates: the stronger the acid, the weaker its conjugate base, and the
stronger the base, the weaker its conjugate acid.

15. The pK and pK expressions
a b
for the hydrogenc arbonate ion,
HCO (aq), are 10.32 and 7.64,

3
Acid–base equilibria in solutions of salts

respectively.
(Reactivity 3.1.12)
a. Formulate the equations
As you already know, any salt c an be considered as a product of a neutralization

that represent the
reaction between an acid and a base. The ions produced by the salt in an
acid–base equilibria
aqueous solution c an react with water and form conjugate acids and/or bases,
characterized by
therefore aecting the solution’s pH. The reactions between salts and water
K and K of the
a b
are c alled hydrolysis reactions. The direction and extent of hydrolysis reactions
hydrogenc arbonate ion.
depend on the strengths of the acid and base that form the salt. The four possible
b. C alculate the pK value for

a
combinations of parent acids and bases are strong acid–strong base, strong
c arbonic acid, H CO (aq),

2 3
acid–weak base, weak acid–strong base and weak acid–weak base.
and the pK value for the

b
c arbonate ion, CO (aq),

3
S alts of strong acids and strong bases

at 298 K.
Both the c ation and the anion in salts of this type have strong conjugates (base
and acid, respectively), so they do not undergo hydrolysis. For example, sodium
chloride dissociates in aqueous solutions as follows:
NaCl(aq) → Na (aq) + Cl (aq)
The hypothetic al reaction of Na (aq) with water would produce the strong base
NaOH(aq), which c annot exist in aqueous solutions in undissociated form:
Na (aq) + H O(l) no reaction

2
Similarly, the reaction of Cl (aq) with water would produce the strong acid
HCl(aq), which also does not exist in aqueous solutions in molecular form:
Cl (aq) + H O(l) no reaction

2
Therefore, neither ion is involved in acid–base equilibria.
The only equilibrium in solutions of salts formed by strong acids and strong bases
is the dissociation of water:
+ −

2
+ − + −
The H (aq) and OH (aq) ions are produced in equal amounts, so [H ] = [OH ],
and the solution remains neutral (pH=7). In other words, the presence of a salt
formed by a strong acid and a strong base has no eect on the solution’s pH.
S alts of strong acids and weak bases
In salts of this type, the hydrolysis involves c ations only, as the formation of weak
conjugates is a favourable process. For example, ammonium chloride in aqueous
solutions produces the following ions:
+ −
NH Cl(aq) → NH (aq) + Cl (aq)

4 4
The conjugate of the Cl (aq) ion is a strong acid, HCl(aq), so the chloride anion
does not undergo hydrolysis. In contrast, the conjugate of the NH (aq) ion is a
4
weak base, NH (aq), so the ammonium c ation itself behaves as a weak acid:
3
+ +
NH (aq) ⇌ NH (aq) + H (aq)

4 3
565
+
LHA
According to table8, pK (NH ) = 4.75, so pK (NH ) = 14 − 4.75 = 9.25.

b 3 a 4
Therefore, the acidity of NH (aq) is comparable to that of hydrogen cyanide,

4
HCN(aq), which is a very weak acid with a pK of 9.21.

a
The last equation c an be expanded to include a molecule of water and show the
true nature of the hydrolysis process:
+ +
NH (aq) + H O(l) ⇌ NH (aq) + H O (aq)

4 2 3 3
+ +
As mentioned earlier, the H symbol is used as a shorthand equivalent of H O ,

3
so the hydrolysis of the ammonium ion c an be represented by either of the
+ +
two equations. In IB assessments, the use of H or H O ions will be equally

3
accepted.
+ + +
The excess H (aq) or H O (aq) ions means that [H ] > [OH ], so the solution
3
becomes acidic (pH<7).
S alts of weak acids and strong bases
In salts of this type, the hydrolysis involves anions only. For example, sodium
ethanoate in aqueous solutions produces the following ions:
CH COONa(aq) → CH COO (aq) + Na (aq)

3 3
The conjugate of the CH COO (aq) ion is a weak acid, CH COOH(aq), which is
3 3
formed in the reversible reaction of the ethanoate ion with water:

3 2 3
This reaction produces excess OH (aq) ions, so [H ] < [OH ], and the solution
becomes basic (pH>7).
Anions of polyprotic weak acids accept a single proton to form their conjugates,
Practice question
for example:
2
16. Using table8, c alculate the pK
b
CO (aq) + H O(l) ⇌ HCO (aq) + OH (aq)
3 2 3
value for the ethanoate anion,
HCO (aq) + H O(l) ⇌ H CO (aq) + OH (aq)

CH COO (aq), and show 3 2 2 3
3
that this ion is a weak base.
Notice that each equation involves only one molecule of water and produces a
Compare the strength of this
single hydroxide anion.
base with other basic species
listed in table8.
S alts of weak acids and weak bases
In these salts, both the c ation and the anion undergo hydrolysis. For example,
ammonium ethanoate produces the following ions:
CH COONH (aq) → CH COO (aq) + NH (aq)

3 4 3 4
Both ions have weak conjugates, so they react reversibly with water:

3 2 3
+ +
NH (aq) + H O(l) ⇌ NH (aq) + H O (aq)

4 2 3 3
or
+ +
NH (aq) ⇌ NH (aq) + H (aq)

4 3
566
LHA
These reactions produce both H (aq) and OH (aq) ions, so the acidity (or
basicity) of the solution depends on the relative strengths of the parent acid and
base. If the conjugate acid for the salt anion is slightly stronger than the conjugate
base for the salt c ation, the solution will be slightly acidic (pH<7); otherwise, it
will be slightly basic (pH>7).
In the c ase of ammonium ethanoate, the pK of the parent acid (4.76) and the
a
pK of the parent base (4.75) are almost identic al, so the solution pH will be 7.0.
b
For many salts, the relative strengths of their parent acid and base are similar to
each other, so [H ] ≈ [OH ] and pH≈7.
ATL Thinking skills
Hydrolysis of salts: summary Certain chemistry topics, such as
acids and bases, involve several
The pH of a salt solution depends on the relative strengths of the parent acid and
dierent types of c alculations. This
base, as shown in table9.
task will help you to organize the
Ions
c alculations covered in this chapter,
Parent acid Parent base Hydrolysis Solution pH
produced
so you c an better understand how
they are interconnected. First,

strong strong none [H ] = [OH ] 7
+ make a list of the various types of
strong weak c ation only [H ] > [OH ] < 7
c alculations covered in this chapter.

+
weak strong anion only [H ] < [OH ] > 7
Two examples are shown below:
weak weak c ation and anion [H ] ≈ [OH ] ≈ 7

• Converting between
pH and [H ]:
pTable9 Hydrolysis of salts and solution pH
+ pH
[H ] = 10
This table c an be summarized by the following informal rules:
+
• “hydrolysis is for the weak”
pH [H ]
• “the stronger wins”.
+
pH = –log [H ]
10
These rules emphasize the fact that the pH of a salt solution depends on the
relative strengths of the parent acid and base: if the acid is stronger, the solution
• Converting between
will be acidic, and if the base is stronger, the solution will be basic.
K and [H ]:
a
+
[H ] =  K [HA]
a
Practice questions
17. Formulate the equations for acid–base equilibria in aqueous solutions of +

K
[H ]
a
the following salts:
a. potassium cyanide, KCN + 2

[H ]
K =
a
[HA]
b. potassium sulfate, K SO
2 4
As shown in the worked examples,

c. methylammonium methanoate, HCOONH CH
3 3
you will oen need to apply several
d. methylammonium bromide, CH NH Br.

3 3
dierent c alculations when solving
a single problem involving acids

For each solution, predict whether it will be neutral, acidic or basic.
and bases. Create a scheme
that shows and interconnects
pH curves of strong and weak acids and

all the c alculations you have
bases (Reactivity 3.1.13) listed. Refer to this scheme when
answering practice questions. You

The shape of the pH curve in an acid–base titration depends on the strengths
will eventually memorize these

of the acid and the base. There are four distinct shapes that correspond to the
quantitative relationships and no

following types of acid–base pair: strong acid–strong base, strong acid–weak
longer need this sc aold.

base, weak acid–strong base and weak acid–weak base.
567
LHA
pH curves involving strong acids and strong bases
The pH curves for titration experiments involving strong acids and bases are
shown in gures8 and 9 in the SL section of this topic. At typic al concentrations
of the analyte and titrant (approximately 0.1 mol dm each), these pH curves have
the following features:
• y-axis intercept at pH≈1 (when the analyte is an acid) or pH ≈13 (when the
analyte is a base)
• gradual rise or fall in pH at the beginning of the titration
• sharp rise or drop in pH near the equivalence point
• equivalence at pH=7 (no hydrolysis of the salt)
• attening out at the end of the titration to pH≈13 (when the titrant is a base)
or pH≈1 (when the titrant is an acid).
pH curves involving weak acids and strong bases
A typic al pH curve for the titration of a weak acid with a strong base is shown in
gure12. Although the overall shape of this curve is somewhat similar to that in
gure8, there are several important dierences:
• The curve intercepts the y-axis at a higher pH. This is bec ause the weak acid
dissociates only partially and therefore produces a lower concentration of
H (aq) ions.
• There is a buer region before the equivalence point. This is when the
Buer solutions will be discussed
solution contains both components of a weak conjugate acid–base pair.
later in this topic.
• The jump in pH near the equivalence point is smaller than that in gure8.
• The equivalence is achieved at a pHgreater than7, as the salt anion
undergoes hydrolysis and produces OH (aq) ions.
14
1
CH COONa + NaOH
3
equivalence point
1
(CH COONa only)

3
pH jump

Hp
buffer region
CH COOH + CH COONa
3 3
intercept
(CH COOH only)

3
  1 1 
3
V(NaOH), cm
pFigure12 pH curve for the titration of 0.1 mol dm CH COOH(aq) (weak acid) with
3
0.1 mol dm NaOH(aq) (strong base)
568
LHA
The nal part of the curve in gure12 is very similar to that in gure8, as in both
c ases the solution contains excess strong base, NaOH(aq). Therefore, both
curves atten out at pH≈13.
The stage of the titration at which exactly one-half of the acid has been
neutralized is known as the half-equivalence point. The pH at half-equivalence
is equal to the pK of the weak acid. In our example, the weak ethanoic acid
a
dissociates as follows:
CH COOH(aq) ⇌ CH COO (aq) + H (aq)

3 3
[CH COO ][H ]

3
K =
a
[CH COOH]
3
At half-equivalence, [CH COO ] = [CH COOH], so K = [H ] and pK = pH.

3 3 a a
Figure12 shows that the equivalence is achieved at V(NaOH) = 10 cm , so the
half-equivalence occurs at V(NaOH) = 5 cm . At this point, the solution pH is
approximately 4.8, which is very close to the pK of ethanoic acid (4.76, table8).
a
The pH curve for the titration of a strong base with a weak acid would be almost
a mirror image of gure12, except that the buer region would be much longer
and occur in the second half of the curve. Titrations of this type are uncommon, as
the use of a weak acid as a titrant has no practic al value.
pH curves involving strong acids and weak bases
A typic al pH curve for the titration of a weak base with a strong acid is shown
in gure13. The overall shape of this curve is similar to that in gure9, with the
following dierences:
• The curve intercepts the y-axis at a lower pH. This is bec ause the weak
basedissociates only partially and thus produces a lower concentration
ofOH (aq) ions.
• There is a buer region before the equivalence point.
• The drop in pH near the equivalence point is smaller than that in gure9.
• The equivalence is achieved at pH<7, as the salt c ation undergoes
hydrolysis and produces H (aq) ions.
4
intercept
(NH only)
3
2
NH + NH Cl
3 4
0

Hp
buffer region
pH drop
equivalence point
(NH Cl only)
4
NH Cl + HCl
4
Figure13 pH curve for the titration
0
−
3
of 0.1 mol dm NH (aq) (weak base)

3
0  0  20
−
3
with 0.1 mol dm HCl(aq) (strong acid)
3
V(HCl), cm
569
LHA
The nal part of the curve in gure13 is very similar to that in gure9, as in both
c ases the solution contains excess strong acid, HCl(aq). Therefore, both curves
atten out at pH≈1.
The half-equivalence point of this titration experiment c an be used to determine
the pK of the weak base. The acid–base equilibrium in the solution of ammonia
b
c an be represented as follows:

3 2 4
[NH ][OH ]
4
K =
b
[NH ]
3
At half-equivalence, [NH ] = [NH ], so K = [OH ] and pK = pOH.

4 3 b b
Figure13 shows that the half-equivalence is achieved at V(HCl) = 5 cm . At this
point, the solution pH is approximately 9.2, so pOH = 14 − 9.2 = 4.8. The last
value is very close to the pK of ammonia (4.75, table8).

b
The pH curve for the titration of a strong acid with a weak base would be almost
a mirror image of gure13, except that the buer region would be much longer
and occur in the second half of the curve. Like the titration of a strong base with a
weak acid, titrations of this type are uncommon.
pH curves involving weak acids and weak bases
A typic al pH curve for the titration of a weak acid with a weak base is shown in
gure14. This curve has the following features:
• y-axis intercept at pH≈3, as the weak acid dissociates only partially and
therefore produces a relatively low concentration of H (aq) ions
• a buer region before the equivalence point
• no sharp change in pH near the equivalence point
• the equivalence is achieved at pH≈7, as both the c ation and anion of the
salt undergo hydrolysis
• very gradual attening out above pH≈9 bec ause of the second buer
region aer the equivalence point.
14
NH + CH COONH
3 3 4
12
buffer region 2
1
intercept
(CH COOH only)

3

Hp
equivalence point
(CH COONH only)

3 4
buffer region 1
CH COOH + CH COONH
3 3 4
Figure14 pH curve for the titration of


−
3
0.1moldm CH COOH(aq) (weak acid)

3
  1 1 2
−
3
with 0.1moldm NH (aq) (weak base)

3
3
V(NH ), cm
3
570
LHA
The two buer regions of the pH curve in gure14 are formed by dierent
Activity
conjugates. Before the equivalence point, the weak acid and its anion form a buer.
Aer the equivalence point, the weak base and its cation form another buer.
• Sketch the pH curve for
3 3
The half-equivalence point is achieved at V(NH ) = 5 cm . At this point, the the titration of 0.1 mol dm
3
solution pH is equal to the pK of the weak ethanoic acid (4.76, table8). At NH (aq) with 0.1 mol dm
a 3
V(NH ) = 20 cm , the solution contains equal concentrations of NH (aq) and CH COOH(aq).

3 3 3
NH (aq), so pOH = pK (NH ) = 4.75 and pH = 14 – 4.75 = 9.25. • Identify and label the following
4 b 3
features of the curve:
The pH curve for the titration of a weak base with a weak acid would be almost a
intercept with the pH axis,
mirror image of gure14. Titrations involving both a weak acid and a weak base
equivalence point, buer
have little practic al value, as the equivalence point is dicult to determine.

regions and the points where
pH=pK (CH COOH) and

a 3
Acid–base indic ators (Reactivity 3.1.14) pOH=pK

b
(NH
3
).
Acid–base indic ators are weak acids or bases that dier in colour from their
conjugates. If the indic ator (HInd) is a weak acid, its dissociation scheme c an be
represented as follows:
HInd(aq) ⇌ H (aq) + Ind (aq)
conjugate conjugate
acid base
When the pH is much lower thanpK , the indic ator exists predominantly in its
a
The absorption spectra of chemic al

protonated form, HInd(aq). At pH>>pK , the indic ator loses a proton and
a
compounds are discussed in

forms the conjugate base Ind (aq). If HInd(aq) and Ind (aq) absorb visible light at
Structure 1.3
dierent wavelengths, their solutions have dierent colours (gure15).
For each indic ator, the colour change occurs within a certain pH range, typic ally
from pK −1 to pK +1, which is known as the transition range of the indic ator.
a a
However, some indic ators have slightly narrower or broader transition ranges
(table10).
Colour
pH transition
Indic ator pK
a
range
Acid Base
methyl orange 3.7 3.1–4.4 red yellow
bromothymol blue 7.0 6.0–7.6 yellow blue
phenolphthalein 9.6 8.3–10.0 colourless pink
pTable10 Common acid–base indic ators

pFigure15 Methyl orange indic ator is
red in acidic solutions and yellow in neutral
and alkaline solutions

The universal indic ator is a mixture of several acid–base indic ators with
overlapping transition ranges. As a result, the universal indic ator has no specic
transition range, and its colour changes gradually over the whole pH range from
0 to 14, as shown in table1.
The colours and transition ranges
Acid–base indic ators are oen used in titration experiments, as they allow
of common acid–base indic ators
chemists to monitor the reaction progress by observing the solution colour
are given in section 18 of the data
and stop the titration when the colour changes. This moment, known as the
booklet.
end point of the titration, depends on the pK of the indic ator. The pK of the
a a
indic ator approximately corresponds to the pH at the end point.
571
LHA
Identifying appropriate indic ators
(Reactivity 3.1.15)
A suitable indic ator for a titration should have a transition range that includes the
pH at the equivalence point in a pH curve. When a titration involves a strong acid
and a strong base, the equivalence is achieved at pH=7, so the best indic ator
for this type of titration is bromothymol blue, which changes colour within the pH
range 6.0–7.6 (table 10). However, all three common indic ators would produce
satisfactory results due to the large pH jump at the equivalence point in strong
acid–strong base titrations (gure 16).
14
phenolphthalein
Hp
7 bromothymol blue
methyl orange
V(NaOH)
pFigure16 Titration of a strong acid with a strong base using
various indic ators
The amount of indic ator added to the analysed solution c an aect the titration
result. E ach indic ator is a weak Brønsted–Lowry acid or base, so when the
indic ator changes colour, it reacts with the titrant. The more indic ator you add,
the greater systematic error you introduce. On the other hand, adding too little
indic ator to the solution makes it dicult to see the solution colour. Therefore,
you should always try to use just enough indic ator to make the colour change
clearly visible.
In titrations involving a weak acid and a strong base, the equivalence is achieved
at pH>7, so the best indic ator for this type of titration is phenolphthalein, which
also changes colour at pH>7 (gure17). Bromothymol blue could also be used.
Methyl orange c annot be used, as it would produce a very large systematic error.
14
phenolphthalein
Hp
7 bromothymol blue
methyl orange
V(NaOH)
pFigure17 Titration of a weak acid with a strong base using
various indic ators
572
LHA
In titrations involving a strong acid and a weak base, the equivalence is achieved
at pH<7, so the best indic ator for this type of titration is methyl orange with a
transition range closest to the equivalence point (gure18). Bromothymol blue
could also be used, whereas phenolphthalein is not suitable for this type of
titration.
14
phenolphthalein
Hp
7 bromothymol blue
methyl orange
V(HCl)
pFigure18 Titration of a weak base with a strong acid using
various indic ators
Section 18 of the data booklet lists many other acid–base indic ators, including
methyl red with the transition range 4.4–6.2. This range includes the equivalence
point (pH≈5.5), so methyl red is a better choice than methyl orange.
Worked example 9
An acid–base titration produces sodium methanoate, HCOONa, at the
equivalence point. Identify an appropriate indic ator for this titration.
Solution
Practice questions
First, you need to identify the parent acid and base for sodium methanoate.
18. Using table10, identify the
You c an do this by splitting the salt into the c ation and anion:
most suitable acid–base
+ indic ator for the titration of:
HCOONa → HCOO + Na
a. dimethylamine,
+
Then, you formally add OH to the c ation and H to the anion:
(CH ) NH(aq), with sulfuric

3 2
+
acid, H SO (aq)
2 4
Na + OH → NaOH
b. barium hydroxide,
+
HCOO + H → HCOOH
Ba(OH) (aq), with

2
hydrochloric acid, HCl(aq)

Therefore, the titration involves a strong base, NaOH, and a weak acid,
HCOOH, so the pH at the equivalence point will be greater than 7. The most
c. methanoic acid,
suitable indic ator for this type of titration is phenolphthalein (gure 18). You
HCOOH(aq), with sodium
c an also use any other indic ator with pK > 7, such as phenol red (see section
a
hydroxide, NaOH(aq).
18 of the data booklet).
19. Identify an appropriate
indic ator for an acid–base
Titrations involving a weak acid and a weak base c annot be performed using titration that produces
acid–base indic ators. In such titrations, the change in pH is very gradual during ammonium bromide,
the whole experiment (gure14), so the colour of the solution will also change NH Br(aq), at the equivalence
4
gradually, and the end point will be impossible to determine. The equivalence point. Refer to table10 and
point in titrations of this type c an only be determined using a pH meter. section 18 of the data booklet.
573
LHA
Buer solutions (Reactivity 3.1.16)
In many chemic al and biologic al experiments, it is important to maintain a
constant pH of the reaction mixture. This c an be achieved using buer solutions.
These solutions resist changes in pH when small amounts of acids or bases are
added to the solution.
E ach buer solution contains both components of a conjugate acid–base pair,
in which both the acid and the base are weak. When a strong acid is added to a
buer, it is neutralized by the weak base. Similarly, when a strong base is added,
it is neutralized by the weak acid. As a result, the solution pH remains almost
unchanged.
Acid–base buers are extremely ecient in maintaining their pH. For example, if
−
3 3 3
we add a single drop (about 0.05 cm ) of 0.1 mol dm HCl(aq) to 100 cm of pure
water, the pH of the resulting solution will drop by 2.7, from 7.0 to approximately
4.3. However, if we add the same quantity of HCl(aq) to 100 cm of a typic al
phosphate buer (pH≈7.0) used in biologic al experiments, the pH of the
solution will decrease by less than 0.001. This is below the detection limit of most
laboratory pH meters.
Buer solutions are very important components of all living organisms.
For example, the pH of human blood is kept within a very narrow range of
7.35–7.45 units by several buer systems that involve hydrogenc arbonate and
hydrogenphosphate ions, c arbon dioxide and proteins.
A simple buer solution c an be prepared from the weak ethanoic acid and its
salt, sodium ethanoate. When these two compounds are dissolved in water, the
following processes take place:
− +
CH COOH(aq) ⇌ CH COO (aq) + H (aq)

3 3
− +

3 3
When a strong acid, such as HCl(aq), is added to this solution, it is neutralized by
the weak conjugate base of the buer system:
+
–
H (aq) + CH COO (aq) → CH COOH(aq)

3 3
strong weak weak
acid conjugate base conjugate acid
Similarly, when a strong base, such as NaOH(aq), is added to this solution, it is
neutralized by the weak conjugate acid of the buer system:
− −
OH (aq) + CH COOH(aq) → CH COO (aq) + H O(l)

3 3 2
strong weak weak
base conjugate acid conjugate base
The neutralization reactions of a strong acid and a strong base by dierent
components of the buer system are known as the buer action. The nature
of the buer action is always the same, regardless of the buer components. In
all c ases, a strong acid reacts with the buer ’s conjugate base and releases the
buer ’s conjugate acid, while a strong base reacts with the buer ’s conjugate
acid and releases the buer ’s conjugate base.
574
LHA
In other words, a strong acid is replaced with a weak acid, and a strong base is
replaced with a weak base. Since weak acids and bases dissociate only to a small
extent, they have very little eect on the solution pH.
An acid–base buer c an work eciently only if both components of its conjugate
pair are weak and present in the solution in sucient concentrations. This c an
usually be achieved when the conjugate acid and the conjugate base originate
from dierent compounds. A solution of a single compound, such as a weak
acid, a weak base or a salt, may contain a high concentration of only one
conjugate, but not both at the same time.
Buer solutions are oen classied according to the acid (or base) and the salt
used for their preparation. For example, the ethanoate buer contains the weak
acid CH COOH(aq) and its anion CH COO (aq), and the ammonia buer
3 3
contains the weak base NH (aq) and its c ation NH (aq). If specic salts, such
3 4
as CH COONa(s) or NH Cl(s), were used for preparing the solutions, the same
3 4
buers are sometimes c alled “a weak acid and its salt” and “a weak base and its
salt”, respectively. Common types of acid–base buers are listed in table11.
Type Example Conjugate acid Conjugate base pK

a
weak acid
ethanoate buer CH COOH(aq) CH COO (aq) 4.76

3 3
and its anion
weak base
+
ammonia buer NH (aq) NH (aq) 9.25

4 3
and its c ation
anions of two phosphate

2
H PO (aq) HPO (aq) 7.20

2 4 4
acid salts buer
anions of an acid salt c arbonate

2
HCO (aq) CO (aq) 10.32

3 3
and a normal salt buer
pTable11 Common acid–base buers
In a laboratory, buer solutions c an be prepared by various methods. For
Practice question
example, the ethanoate buer c an be made as follows:
20. Explain, using ionic equations,
1. solid sodium ethanoate and liquid ethanoic acid are dissolved in water
the buer action of a solution
2. solutions of sodium ethanoate and ethanoic acid are mixed together containing ammonium c ations,
NH (aq), and ammonia,

4
3. excess ethanoic acid is mixed with sodium hydroxide
NH (aq).
3
4. excess sodium ethanoate solution is mixed with hydrochloric acid.
Regardless of the method, the resulting buer will contain the same two
components, the weak acid CH COOH(aq) and its conjugate base CH COO (aq).
3 3
In method 3, the conjugate base will form as follows:
CH COOH(aq) + NaOH(aq) → CH COONa(aq) + H O(l) molecular equation

3 3 2
CH COOH(aq) + OH (aq) → CH COO (aq) + H O(l) net ionic equation

3 3 2
In method 4, the conjugate acid will form as follows:
CH COONa(aq) + HCl(aq) → CH COOH(aq) + NaCl(aq) molecular equation

3 3
CH COO (aq) + H (aq) → CH COOH(aq) net ionic equation

3 3
575
LHA
If the buer solutions prepared by dierent methods contain the same
Activity
concentrations of both the conjugate acid and the conjugate base, the properties
of these buers will also be the same.
Suggest three methods for the
preparation of the ammonia buer.
pH of buer solutions (Reactivity 3.1.17)
The pH of a buer solution depends on the ratio of the components in the
conjugate acid–base pair and the dissociation constant of the weak conjugate.
The acid–base equilibrium in a buer solution containing a weak acid HA(aq) and
its conjugate base A (aq) is characterized by the K of the weak acid:

a
[H ][A ]
+
HA(aq) ⇌ H (aq) + A (aq) K =

a
[HA]
To nd the concentration of H (aq) ions, we need to rearrange the K expression

a
as follows:
+ [HA]
[H ] = K ×
a
[A ]
We c an then take the logarithm of every factor to determine the pH:
+ [HA]
log[H ] = logK + log

a
[A ]
Add a minus sign to every term in the equation:
+ [HA]
−log[H ] = −logK − log

a
[A ]
Finally, subsitute in pH = −log[H ] and pK = −logK , and use the

a a
x y
rule that −log = log :
y x
[A ]
pH = pK + log
a
[HA]
The last equation, known as the Henderson–Hasselbalch equation, c an be used
to c alculate the pH of any buer solution of known composition. Alternatively, it
Practice questions
c an be used to nd the ratio of the concentrations of the conjugate acid and base
in the buer solution at a known pH.
21. C alculate the pH for the buer
solutions containing the

An important consequence from the Henderson–Hasselbalch equation is that
following compounds:
the pH of a buer solution is not aected by dilution. If the solution is diluted by
3
a certain factor, both [A ] and [HA] decrease by the same factor. Therefore, the
a. 0.50 mol dm
[A ]
NaH PO (aq) and
2 4 value of log remains unchanged, and so does the solution pH. However, a
3
[HA]
0.20 mol dm
buer solution c annot be diluted innitely without changing its pH. An innitely
Na HPO (aq)
2 4
diluted aqueous solution of any substance at 298 K will have a pH of 7.00.
b. 0.25 mol dm NH (aq)

3
3
The ability of a buer to resist changes in pH on addition of acids and bases is
and 0.50 mol dm
also limited bec ause the amounts of the weak conjugate acid and base in the
NH Cl(aq).
4
solution are nite. At the point when either of the weak conjugates is used up,
The pK values for conjugate acids

a
the buer ceases to function, and the solution pH changes signic antly on further
are given in table10.

addition of an acid or base.
576
LHA
Worked example 10
3 3
C alculate the pH of an ethanoate buer containing 0.100 mol dm CH COOH(aq) and 0.200 mol dm
3
CH COONa(aq).
3
Solution
The conjugate acid is CH COOH(aq) and the conjugate base is CH COO (aq), which is produced by the dissociation of
3 3
sodium ethanoate:

3 3
All salts are strong electrolytes, so sodium ethanoate dissociates completely, and [CH COO ] = 0.200 mol dm
3
According to table8, pK (CH COOH) = 4.76, so:

a 3
0.200
pH = 4.76 + log = 5.06
0.100
Worked example 11
A buer solution with a pH of 11.00 was prepared by the reaction of methylamine, CH NH (aq), with hydrochloric
3 2
acid, HCl(aq).
a. Identify the conjugate acid–base pair in this buer and state the role of each species.
b. State, with a reason, which of the two reactants was in excess.
c. C alculate the mole ratio of the conjugate acid to the conjugate base in the solution.
Solution
a. The reaction between hydrochloric acid and methylamine proceeds as follows:
CH NH (aq) + HCl(aq) → CH NH Cl(aq) molecular equation

3 2 3 3
+ +
CH NH (aq) + H (aq) → CH NH (aq) net ionic equation

3 2 3 3
The net ionic equation involves two species that dier by a single proton. Therefore, the conjugate acid is
methylammonium, CH NH (aq), and the conjugate base is methylamine, CH NH (aq).

3 3 3 2
Note that the solution contains two more conjugate acid–base pairs, H O (aq)/H O(l) and H O(l)/OH (aq).
3 2 2
However, none of these pairs c an form a buer, as H O (aq) is a strong acid, while OH (aq) is a strongbase.
3
b. A buer must contain both components of the conjugate acid–base pair. If hydrochloric acid were in excess, all
methylamine (weak conjugate base) would be consumed, and the solution could not act as an acid–base buer.
Therefore, methylamine was inexcess.
c. According to table8, pK (CH NH ) = 3.34, so pK (CH NH ) = 14 − 3.34 = 10.66. Substituting pK and pH into
b 3 2 a 3 3 a
[A ]
pH = pK + log gives:
a
[HA]
[CH NH ]
3 2
11.00 = 10.66 + log

+
[CH NH ]
3 3
[CH NH ]
3 2
Rearrange in terms of log :

+
[CH NH ]
3 3
[CH NH ]
3 2
log = 0.34
+
[CH NH ]
3 3
Simplify the expression by making each term the exponential of 10:
[CH NH ]
3 2 0.34
= 10 = 2.19
+
[CH NH ]
3 3
Therefore, [CH NH ]:[CH NH ] = 1 : 2.19. Note that n = c × V, so the mole ratio is equal to the ratio of concentrations.
3 3 3 2
577
Topic review
5. Identify the chemic al formulas of parent acids and bases
for the following salts:
a. C a(NO )
3 2
What happens when protons are transferred?
b. Fe (SO )
2 4 3
c. NH HCO
4 3
6. For each salt from question 5, formulate and balance
2. A solution of acid X has a pH of 1 while a solution of

one molecular equation that produces that salt from the
acidY has a pH of 3. Which statement is correct?

parent acid and base.
A [X] > [Y]
7. Two unlabelled bottles contain solutions of a strong
B Acid X is stronger than acid Y
monoprotic acid, HX(aq), and a weak monoprotic acid,
C [H ] in the solution of X is three times higher than

HY(aq), of the same concentration.
[H ] in the solution of Y
a. Suggest how these acids c an be distinguished
D [OH ] in the solution of X is lower than [OH ] in the

using solid c alcium c arbonate, C aCO (s).
3
solution of Y
b. Formulate molecular and net ionic equations for the
reaction of each acid with c alcium c arbonate.

3. Which pair of species is a conjugate acid–base pair?
A H and OH
8. Deduce the formulas of conjugate acids and bases for
B H O and H O
3 2 each species listed in table12. The rst two rows are
C HCl and NaOH lled for you as examples.
2–
B H CO and CO
2 3 3
Species Conjugate acid Conjugate base

LHA
+ −
4. Which indic ators c an be used for the titration of
H O H O OH
2 3
ammonia, NH (aq), with sulfuric acid, H SO (aq)?

3 2 4 −
Cl HCl does not exist
I Bromocresol green (pK = 4.7)

a
HF
II Methyl red (pK = 5.1)

a
NH
3
III Phenol red (pK = 7.9)

a
(CH ) N
3 3
A I and II only −
HCO
3
B I and III only

−
2
CO
3
C II and III only
pTable12 Conjugate acids and bases
D I, II and III
578
9. 2-Amino acids exist as zwitterions, which have both a positive and a negative charge within the same species:
+ +
+ H + H
H COOH H COO H COO

3 3 2
+ +
+ H + H
R R R
c ation zwitterion anion
Identify two conjugate acid–base pairs involved in these equilibria and state the role of each species.
LHA
10. The K value at 10 °C is 3.47 times lower than that at 16. The pK and pK values for the dihydrogenphosphate
w a b
25 °C. ion, H PO (aq), are 7.20 and 11.88, respectively.

2 4
a. C alculate the pH of pure water at 10 °C. a. Formulate the equations that represent the
acid–base equilibria characterized by K and K

a b
b. Discuss whether pure water at 10 °C is acidic, basic
of the dihydrogenphosphate ion.

or neutral.
b. C alculate the pK value for phosphoric

a
LHA
11. C alculate the pH for the following solutions:
acid, H PO (aq), and the pK value for the

3 4 b
2
3
hydrogenphosphate ion, HPO (aq).
a. 0.015 mol dm HNO (aq) 4
b. 0.010 mol dm H SO (aq)

2 4
17. Formulate the equations for acid–base equilibria in
c. 0.020 mol dm KOH(aq)

aqueous solutions of the following salts:
3 3
a. sodium methanoate, HCOONa
12. A 0.100 dm sample of 0.020 mol dm KOH(aq) was
mixed with 0.900 dm of water. C alculate the pH of

b. potassium iodide, KI
the nal solution. Assume that solution volumes are
c. ammonium cyanide, NH CN
4
additive.
d. trimethylammonium chloride, (CH ) NHCl.

3 3
13. C alculate:
For each solution, predict whether it will be neutral,
a. the pOH of a 0.015 mol dm solution of sodium acidic or basic.
hydroxide, NaOH(aq)
The pK and pK values for weak acids and bases are given
a b
b. the concentration of hydroxide ions in a solution
in table8.
with pOH = 9.50.
18. C alculate the pH values for buer solutions containing
14. A 0.020 mol dm solution of benzoic acid,

the following compounds:
C H COOH(aq), has a pH of 2.95.

6 5
3 3
a. 0.25 mol dm HCOOH(aq) and 0.50moldm
a. Determine the pK of benzoic acid.

a
HCOONa(aq);
b. Using the pK value from part a, c alculate the pH of 3 3

a
b. 0.50 mol dm CH NH (aq) and 0.20moldm
3 2
a 0.10 mol dm solution of benzoic acid.

CH NH Cl(aq).
3 3
15. C alculate the pH values for the following solutions:

19. Explain, using ionic equations, the buer action of the
3 solutions from the previous question.

a. 0.010 mol dm methylamine, CH NH (aq)
3 2
3 3
b. 2.0 × 10 mol dm ethanoic acid, CH COOH(aq).

3
20. Using table10, identify the most suitable acid–base
Refer to table8.
indic ator for the titration of:
a. methylamine, CH NH (aq), with hydrochloric acid,

3 2
HCl(aq);
b. hydrogen cyanide, HCN(aq), with potassium
hydroxide, KOH(aq).
579
Reactivity 3.2 Electron transfer reactions
What happens when electrons are transferred?
In a reaction where electrons are transferred, one species Some redox reactions are spontaneous and exothermic.
will lose electrons — the species is oxidized — and a If the electron transfer from one species to another is
dierent species will gain electrons — the species is made to occur through a wire, such as in electrochemic al
reduced. It is impossible to have oxidation of one species cells or batteries, the energy released in the process c an
without reduction of another. These reactions are referred be used to power appliances. Other redox reactions are
to as redox reactions. not spontaneous and require energy to occur, such as in
electroplating, or the reduction of aluminium oxide, Al O ,

2 3
to produce aluminium metal.
Understandings
Reactivity 3.2.1 — Oxidation and reduction c an be Reactivity 3.2.10 — Functional groups in organic
described in terms of electron transfer, change in compounds may undergo reduction.
oxidation state, oxygen gain/loss or hydrogen loss/gain.
Reactivity 3.2.11 — Reduction of unsaturated compounds
Reactivity 3.2.2 — Half-equations separate the processes by the addition of hydrogen lowers the degree of
of oxidation and reduction, showing the loss or gain of unsaturation.
electrons.
LHA
+
Reactivity 3.2.12 — The hydrogen half-cell H (aq)
Reactivity 3.2.3 — The relative ease of oxidation and

1
+ e ⇌ H (g) is assigned a standard electrode

2
reduction of an element in a group c an be predicted from 2
potential of zero by convention. It is used in the

its position in the periodic table. The reactions between
measurement of standard electrode potential, E

metals and aqueous metal ions demonstrate the relative
ease of oxidation of dierent metals.
Reactivity 3.2.13 — Standard cell potential,
E , c an be c alculated from standard electrode

cell
Reactivity 3.2.4 — Acids react with reactive metals to
potentials. E has a positive value for a

cell
release hydrogen.
spontaneous reaction.
Reactivity 3.2.5 — Oxidation occurs at the anode and
⦵ ⦵
Reactivity 3.2.14 — The equation ΔG = −nFE

cell
reduction occurs at the c athode in electrochemic al cells.
shows the relationship between standard change in
Reactivity 3.2.6 — A primary (voltaic) cell is an

Gibbs energy and standard cell potential for
electrochemic al cell that converts energy from

a reaction.
spontaneous redox reactions to electric al energy.
Reactivity 3.2.15 — During electrolysis of aqueous
Reactivity 3.2.7 — Secondary (rechargeable) cells involve

solutions, competing reactions c an occur at the
redox reactions that c an be reversed using electric al

anode and c athode, including the oxidation and
energy.
reduction of water.
Reactivity 3.2.8 — An electrolytic cell is an

Reactivity 3.2.16 — Electroplating involves the
electrochemic al cell that converts electric al energy to

electrolytic coating of an object with a metallic
chemic al energy by bringing about non-spontaneous

thinlayer.
reactions.
Reactivity 3.2.9 — Functional groups in organic
compounds may undergo oxidation.
580
Oxidation and reduction (Reactivity 3.2.1)

TOK
Reduction and oxidation c an be dened in several ways:
In chemistry, the same concept
1. in terms of the loss and gain of oxygen
c an be dened in several ways by
2. in terms of the gain and loss of hydrogen drawing on dierent knowledge.
For example, in Reactivity 3.1, you
3. in terms of electron transfer
met three separate denitions of
4. in terms of oxidation state. acids and bases: the Arrhenius,
Brønsted–Lowry, and Lewis
theories. E ach of these theories are

1. Oxidation and reduction in terms of oxygen gain/loss
informed by a dierent aspect of
According to the rst denition, oxidation is a reaction where a substance
a species’ chemistry. What other
combines with oxygen. Examples of this type of oxidation reaction include the
concepts in chemistry c an be
combustion of metals to form metal oxides:
dened in dierent ways?
2Mg(s) + O (g) → 2MgO(s)

2
4Fe(s) + 3O (g) → 2Fe O (s)

2 2 3
During aerobic respiration, oxygen reacts with glucose to form c arbon dioxide
and water. This c an also be described as an oxidation reaction:
C H O (aq) + 6O (g) → 6CO (g) + 6H O(l)

6 12 6 2 2 2
According to the rst denition, reduction is a reaction where oxygen is
removed from a substance. Examples of this type of reduction reaction include
the reduction of nickel(II) oxide by c arbon to produce pure nickel and c arbon
monoxide:
NiO(s) + C(s) → Ni(s) + CO(g)
In all redox reactions, one species is oxidized, and another is reduced. If the
pFigure 1 In the ox i d a t i o n of iron,
substance being oxidized gains oxygen, then the substance being reduced loses
iron(III) ox i d e, or rust, is produce d
oxygen. In the experiment in gure 2, copper(II) oxide is being reduced, losing
oxygen, and hydrogen gas is being oxidized, gaining oxygen:
CuO(s) + H (g) → Cu(s) + H O(g)

2 2
black copper(II) oxide
hydrogen in
heat
pFigure 2 Experimental set-up for the re duction of copper(II) ox i d e by hy d r o g e n
In some c ases, one substance c an be simultaneously reduced and oxidized in
the same reaction. This is known as disproportionation. For example, potassium
chlorate, KClO , decomposes on heating as follows:

3
4KClO (s) → 3KClO (s) + KCl(s)

3 4
In this reaction, some formula units of KClO are reduced to KCl by losing oxygen
3
while other formula units are oxidized to KClO by gaining oxygen.

4
581
2. Oxidation and reduction in terms of hydrogen loss/gain
Oxidation c an also be considered as a loss of hydrogen. For example, in the
reaction between hydrogen chloride and oxygen, hydrogen chloride loses
hydrogen to form chlorine gas:
4HCl(g) + O (g) → 2Cl (g) + 2H O(g)

2 2 2
Reduction c an be considered as the addition of hydrogen to a species. An
example of such a reaction is the hydrogenation of ethene:
C H (g) + H (g) → C H (g)

2 4 2 2 6
The process of heterogeneous This reaction typic ally requires Ni(s) as a heterogeneous c atalyst.
c atalysis is detailed in Structure 3.1
3. Oxidation and reduction in terms of electron transfer
During a reaction, if a species loses electrons, it is oxidized, and if a species gains
electrons, it is reduced. A useful mnemonic for remembering this is OIL RIG:
OIL: Oxidation Is Loss of electrons
RIG: Reduction Is Gain of electrons
Consider the reaction between sodium metal and chlorine gas:
2Na(s) + Cl (g) → 2NaCl(s)

2
This reaction c annot be described in terms of the gain or loss of hydrogen and
oxygen, as these elements are not involved in the reaction. However, we c an
instead describe the oxidation and reduction occurring in terms of the transfer of
electrons between sodium and chlorine.
Sodium metal loses electrons to form sodium c ations, so it is oxidized.
2Na(s) → 2Na + 2e
These electrons are transferred to chlorine gas, reducing it to chloride anions:
Cl (g) + 2e → 2Cl
2
The sodium c ations and chloride anions are held together by ionic bonds in a
three-dimensional lattice structure, NaCl(s) (gure 3).
+ −
Cl
Na Cl Na
2,8,1 2,8,7 2,8 2,8,8
+ −
The formation of ionic lattice NaCl (Na Cl )
structures is detailed in
pFigure 3 Sodium atoms are ox i d i z e d (lose e l e c t r o n s) and chlorine atoms are
Structure2.1
re duce d (g a i n e l e c t r o n s) in the formation of sodium chloride
582
C ase study: Redox reactions in optometry
Optometrists oen prescribe glasses with photochromic lenses. These lenses
darken in the presence of ultraviolet light (from sunlight); this change is based on
a redox reaction.
Ordinary glass is composed of silic ates while photochromic lenses contain
copper(I) chloride, CuCl, and silver chloride, AgCl. The chloride ions are
oxidized to chlorine atoms on exposure to ultraviolet light (hf ).
hf
Cl → Cl + e
Electron transfer then takes place, reducing the silver c ations to silver atoms.
Ag + e → Ag
The silver atoms turn the lenses dark, inhibiting the transmission of light. The
darkening process is reversed by copper(I) chloride allowing the lenses to
become transparent again. When the lenses are no longer exposed to ultraviolet
light, the following reaction takes place:
+
+ 2
Cu + Cl → Cu + Cl
The chlorine atoms formed by the exposure to light are reduced by the Cu ions.
+ +
+ 2 2
In turn, Cu ions are oxidized to Cu ions. These Cu ions then oxidize silver
atoms to Ag ions:
+
2 + +
Cu + Ag → Cu + Ag
As a result, the lenses become transparent again and the silver and chlorine
atoms return to the initial species, Ag and Cl
4. Oxidation and reduction in terms of oxidation state
change
Some redox reactions do not involve a transfer of electrons between species. For
example, in the formation of c arbon disulde, electrons are shared between the
c arbon and sulfur atoms, forming a covalently bonded molecule:
pFigure 4 P hotochromic lenses
C(s) + 2S(s) → CS (l)

2
C arbon disulde has the following Lewis structure:
S C S
We c an describe oxidation and reduction in terms of the change in oxidation
state of the atoms in the reacting species. The oxidation state represents
the charge that an atom would have in a compound if the compound were
composed of ions. In other words, all polar covalent bonds are treated as
ionic, so all shared electrons in each bond are formally transferred to the more
electronegative atom.
You learned the rules for
assigning oxidation states to
A compound is oxidized if the oxidation state of an atom in that compound
atoms in covalent compounds in
increases, and reduced if the oxidation state of an atom in that compound
Structure3.1.
decreases.
583
In the c arbon disulde example, the oxidation state of c arbon increases from
0 in the reactant, C(s), to +4 in the product, CS (l), where c arbon shares four
2
electrons with the more electronegative sulfur. C arbon is therefore oxidized.
Elemental sulfur has an oxidation state of 0. In c arbon disulde, the oxidation
state of each sulfur atom decreases to −2. Sulfur is therefore reduced.
TOK
The underlying assumption when assigning oxidation states is that electrons
are transferred between atoms, not shared. However, oxidation states are
not real bec ause they do not represent the actual charges on the atoms in
a molecule.
If you study the HL course, you learned about formal charges in Structure 2.2.
Formal charges are also articial and do not represent actual charges. When
assigning formal charges, we assume that the electrons in covalent bonds are
shared equally between the atoms involved.
In spite of these simplifying assumptions, oxidation states and formal charges
are both useful tools that help us to explain redox reactions and Lewis
formulas, respectively.
Worked example 1
Sodium chloride, sulfuric acid, and manganese(IV) oxide react according to the following chemic al equation.
4NaCl(s) + 2H SO (aq) + MnO (s) → 2Na SO (aq) + MnCl (aq) + 2H O(l) + Cl (g)
2 4 2 2 4 2 2 2
a. Deduce the change in oxidation states for each atom.
b. State which atom is oxidized, and which atom is reduced.
c. Identify the oxidizing agent and the reducing agent.
Solution
a. First, review the species on each side of the equation and assign oxidation states to each atom:
On the le-hand side On the right-hand side
In NaCl, Na: +1, Cl: −1 In Na SO , Na: +1, S: +6, O: −2

2 4
In H SO , H: +1, S: +6, O: −2 In MnCl , Mn: +2, Cl: −1

2 4 2
In MnO , Mn: +4, O: −2 In H O, H: +1, O: −2

2 2
In Cl , Cl: 0
2
All the oxidation states stay the same, except for manganese, where the oxidation state changes from +4 to +2, and
chlorine, where the oxidation state changes from −1 to 0.
b. The oxidation state of manganese decreases, so manganese is reduced. The oxidation state of chlorine increases, so
chlorine is oxidized.
c. As manganese has been reduced and c aused chlorine to be oxidized, manganese(IV) oxide, MnO (s), is the
2
oxidizing agent. Chlorine has been oxidized and c aused manganese to be reduced. That makes sodium chloride,
NaCl(s), the reducing agent.
584
Worked example 2
Consider the following balanced equation:
Fe(s) + 2HBr(aq) → FeBr (aq) + H (g)

2 2
a. Deduce the oxidation states of iron and hydrogen in the reactants and
products.
b. State which species is oxidized, and which species is reduced.
Solution
a.
On the le-hand side On the right-hand side
Fe: 0 Fe in FeBr : +2
2
H in HBr: +1 H in H : 0
2
Br in HBr: −1 Br in FeBr : −1
2
b. The oxidation state of Fe increases, so Fe(s) is oxidized. The oxidation
state of H decreases, so HBr(aq) is reduced.
c. The oxidizing agent is HBr(aq) and the reducing agent is Fe(s)
An oxidizing agent causes another species to be oxidized, with the oxidizing
The use of Roman numerals to
agent itself being reduced in the process. A reducing agent causes another
represent oxidation states of
species to be reduced, with the reducing agent itself being oxidized in the process.
oxyacids and transition element
compounds was covered in
Practice questions
Structure 3.1.
1. Consider the following balanced equation:
Cl (aq) + 2KI(aq) → 2KCl(aq) + I (aq)

2 2
a. Deduce the oxidation states of chlorine and iodine in the reactants
and products.
b. State which element is oxidized, and which element is reduced.
2. Identify the oxidizing agents and the reducing agents in the following
reactions:
a. PbO(s) + H (g) → Pb(s) + H O(l)

2 2
b. 2CuO(s) + C(s) → CO (g) + 2Cu(s)

2
c. Mg(s) + Cl (g) → MgCl (s)

2 2
d. 2KI(aq) + Br (aq) → I (aq) + 2KBr(aq)

2 2
When writing oxidation states, the sign is always placed before the number and
not aer it. In worked example 2, the oxidation state of hydrogen in HBr is +1 and
not1+.
Remember to describe the compounds as being oxidized and reduced, not the
individual atoms in the compounds. This also applies to describing the oxidizing
and reducing agents. In worked example 2, HBr(aq) is reduced and is the
oxidizing agent, not H.
585
Half-equations (Reactivity 3.2.2)
Consider the reaction between sodium metal and chlorine gas, discussed in the
previous section:
2Na(s) + Cl (g) → 2NaCl(s)

2
You saw that the processes of oxidation and reduction could be separated into
two equations:
+ −
Na(s) → Na + e
− −
Cl (g) + 2e → 2Cl
2
These equations are c alled half-equations. Separating a redox process into two
half-equations helps to show the transfer of electrons. Half-equations c an also
make it easier to balance the full equation for the redox reaction. The steps for
writing redox reactions in aqueous solutions are:
1. Identify the species being oxidized and reduced.
2. Separate the equation into an oxidation half-equation and reduction
half-equation.
3. Balance any atoms being oxidized or reduced.
4. For the oxidation half-equation, write the electrons lost on the right-hand
side of the equation. The number of electrons should be equal to the
magnitude of the change in oxidation state of the oxidized species.
5. For the reduction half-equation, write the electrons gained on the le-
hand side of the equation. The number of electrons should be equal to the
magnitude of the change in oxidation state of the reduced species.
6. Balance these half-equations so that the number of electrons lost in oxidation
equals the number of electrons gained in reduction.
7. Add the two half-equations together and c ancel the electrons.
8. If the reaction is occurring in acidic solution, add H O(l) to balance any

2
oxygen atoms and H (aq) to balance any hydrogen atoms.
9. For neutral or basic solutions, add OH (aq) to balance oxygen atoms and
H O(l) to balance hydrogen atoms.

2
10. Finally, add up the charges and check that the sum is equal to zero.
586
Worked example 3
Iron metal, Fe(s), will react with a solution of silver(I) ions, Ag (aq), to form
+
3
aqueous iron(III) ions, Fe (aq), and silver metal, Ag(s).
Write the balanced equation for this redox reaction.
Solution
First, write the unbalanced equation for the reaction:
+
+ 3
Fe(s) + Ag (aq) → Fe (aq) + Ag(s)
The oxidation state of iron increases from 0 to +3, so Fe(s) loses electrons and
is therefore oxidized.
The oxidation state of silver decreases from +1 to 0, so Ag (aq) gains electrons
and is therefore reduced.
Write the oxidation and reduction half-equations, ensuring that the atoms are
balanced:
+
3
oxidation: Fe → Fe
reduction: Ag → Ag
To save time, you c an omit states of reacting species in all steps except the
nal answer.
Add the electrons to make sure that the number of electrons in each half-
equation is equal to the magnitude of the change in oxidation state:
+
3
Fe → Fe + 3e
Ag + e → Ag
Then, multiply the reduction half-equation by three, so that there are three
electrons in each half-equation:
+
3
Fe → Fe + 3e
3Ag + 3e → 3Ag
Add the two half-equations together and c ancel the electrons:
+
+ 3
Fe + 3Ag + → Fe + 3Ag +
+
+ 3
Fe(s) + 3Ag (aq) → Fe (aq) + 3Ag(s)
Finally, check that the charges are balanced: on the le-hand side, there are
three silver(I) ions with a 1+ charge each, and on the right, there is one iron ion
with a 3+ charge. So, the total charge on each side of the equation is 3+ and
therefore the equation is balanced. Do not forget to add states to all species in
the nal equation.
587
Worked example 4
+ − +
2 2 3
Iron(II) ions, Fe (aq), and dichromate(VI) ions, Cr O (aq), react in acidic solution to form iron(III) ions, Fe (aq),
2 7
+
3
and chromium(III) ions, Cr (aq).
Deduce the balanced redox equation for this reaction.
Solution
First, write the unbalanced equation: Add the two half-equations together and c ancel the
electrons:
+ + +
2 2 3 3
Fe (aq) + Cr O (aq) → Fe (aq) + Cr (aq)

2 7
+ + +
2 2 3 3
6Fe + Cr O + → 6Fe + 2Cr +

2 7
The oxidation state of iron increases from +2 to +3,
+ + + +
2 2 2 3 3
therefore Fe (aq) loses electrons and is oxidized. 6Fe + Cr O → 6Fe + 2Cr

2 7
In Cr O (aq), chromium has an oxidation state of +6. The As this reaction is taking place in acidic solution, we need
2 7
oxidation state of chromium decreases from +6 to +3, to balance the oxygen and hydrogen atoms. There are
therefore Cr O (aq) gains electrons and is reduced. seven oxygen atoms on the le-hand side of the equation,
2 7
so add seven moles of water to the right-hand side of the
Write the oxidation and reduction half-equations, ensuring
equation to balance the oxygen atoms:
that all the atoms that change their oxidation states are
+ + +
2 2 3 3
balanced: 6Fe + Cr O → 6Fe + 2Cr + 7H O

2 7 2
+ +
2 3
oxidation: Fe → Fe There are now 14 hydrogen atoms on the right-hand side of
the equation, so add 14 moles of H to the le-hand side of

+
2 3
reduction: Cr O → 2Cr
2 7
the equation to balance the hydrogen atoms:
Add the electrons such that number of electrons in each 2

+
2 + 3
+
3
+
6Fe + Cr O + 14H → 6Fe + 2Cr + 7H O

2 7 2
half-equation is equal to the magnitude of the change in
+
3
oxidation state (remembering that there are two Cr ions Finally, check that the charges are balanced. On the le-
+
2 2 +
in the second half-equation): hand side, there are six Fe , Cr O and 14 H ions:
2 7
+ +
2 3
Fe → Fe + e (6 × 2) + (−2) + (14 × 1) = 24
+ + +
2 3 3 3
Cr O + 6e → 2Cr On the right-hand side, there are six Fe and two Cr ions:
2 7
Then, multiply the oxidation half-equation by six, so that (6 × 3) + (2 × 3) = 24
there are six electrons in each half-equation:
So, the total charge on each side of the equation is 24+
+ +
2 3
6Fe → 6Fe + 6e and therefore the equation is balanced. As usual, do not
forget to add states to all reacting species in the nal

+
2 3
Cr O + 6e → 2Cr
2 7
equation:
+
2 2 +
6Fe (aq) + Cr O (aq) + 14H (aq) →

2 7
+ +
3 3
6Fe (aq) + 2Cr (aq) + 7H O(l)

2
Practice questions
3. Write balanced equations for the following reactions that occur in acidic
solutions:
+
2 2
a. Zn(s) + SO (aq) → Zn (aq) + SO (g)

4 2
+
2
b. MnO (aq) + Br (aq)→ Mn (aq) + BrO (aq)

4 3
c. I (s) + OCl (aq) → IO (aq) + Cl (aq)

2 3
+
2 2 3
d. Cr O (aq) + C O (aq) → Cr (aq) + CO (g)

2 7 2 4 2
588
Oxidation and reduction of metals and
halogens (Reactivity 3.2.3)
Relative ease of reduction of halogens
Halogens c an act as oxidizing agents in redox reactions. In these reactions,
halogens in their elemental state gain electrons, being reduced to singly charged
halogen anions. In Structure 3.1, you learned that the reactivity of halogens
increases going up the group.
increasing reactivity
F Cl Br I
2 2 2 2
This means that uorine is the strongest oxidizing agent among the halogens,
and the most easily reduced, followed by chlorine, and then bromine. For
example, chlorine, Cl , c an oxidize bromide ions, Br :

2
Cl + 2Br → 2Cl + Br
2 2
However, chlorine c annot oxidize uoride ions bec ause uorine is a stronger
oxidizing agent:
Cl + 2F no reaction
2
Instead, the reverse reaction between uorine and chloride ions is possible:
F + 2Cl → 2F + Cl
2 2
Iodine is the weakest oxidizing agent among the halogens, so it c annot be
reduced by the other halogens. However, iodine will oxidize many metals and
other strong reducing agents.
Relative ease of oxidation of metals
Group 1 metals c an act as reducing agents bec ause they lose their valence
electron easily. The reactivity of group 1 metals increases going down the group,
and therefore the relative ease of oxidation increases going down the group.
increasing reactivity
Li Na K Rb Cs
For other metals, you c an deduce their relative ease of oxidation by placing
a pure metal into a solution of ions of a dierent metal. If a reaction occurs,
then the pure metal is more easily oxidized and it is a stronger reducing agent.
If no reaction occurs, then the metal comprising the ionic solution is more
easilyoxidized.
589
zinc Consider the reaction between zinc metal and copper(II) nitrate solution. In
+
2
the copper nitrate solution, there are copper(II) ions, Cu (aq). In this reaction,
copper(II)
zinc metal will dissolve to form a zinc nitrate solution, and copper(II) ions will be
nitrate
reduced to copper metal, which will precipitate out as a solid:
solution
Zn(s) + Cu(NO ) (aq) → Zn(NO ) (aq) + Cu(s)

3 2 3 2
Therefore, zinc is a stronger reducing agent than copper, and is more easily
pFigure 5 Zinc will displace copper in
solution, changing the colour of the solution oxidized. Conversely, this means that copper(II) ions are a stronger oxidizing
from blue to colourless and forming a red agent and are more easily reduced than zinc ions. You c an track the transfer of
copper precipitate
electrons in this reaction using half-equations:
+
2
oxidation: Zn(s) → Zn (aq) + 2e
+
2
reduction: Cu (aq) + 2e → Cu(s)
You c an repeat this experiment with several dierent metals to obtain a reactivity
series. In a reactivity series, the most easily oxidized metal is listed rst and the
least easily oxidized metal is listed last.
Worked example 5
Strips of ve dierent metals, zinc, iron, magnesium, copper and silver, were each added to solutions of their metal
nitrate counterparts. The mixtures were observed for a period of time to see whether a reaction has occurred or not.
These observations were recorded in table 1.
Zn(NO ) (aq) Fe(NO ) (aq) Mg(NO ) (aq) Cu(NO ) (aq) AgNO (aq)
3 2 3 2 3 2 3 2 3
Zn(s) – Yes No Yes Yes
Fe(s) No – No Yes Yes
Mg(s) Yes Yes – Yes Yes
Cu(s) No No No – Yes
Ag(s) No No No No –
pTable 1 S ummary of re actions between metals and metal ion solutions
Use table 1 to deduce the reactivity series of the ve metals.
Solution
M agnesium reacts with all four solutions and is therefore the most easily oxidized and the most reactive. Silver metal
does not react with any solution and is the least easily oxidized. However, Ag (aq) ions are the most easily reduced,
making AgNO (aq) the best oxidizing agent on the list.

3
Completing the list by inspection gives the following activity series, from the most easily oxidized to the least easily
oxidized: Mg(s), Zn(s), Fe(s), Cu(s), Ag(s).
590
Redox reactions of acids and metals
(Reactivity 3.2.4)
Reactive metals, such as magnesium, zinc, and iron, are readily oxidized by
strong acids, such as hydrochloric acid, HCl(aq), and sulfuric acid, H SO (aq). In
2 4
dilute solutions, these reactions produce hydrogen gas and a metal salt:
Zn(s) + H SO (aq) → ZnSO (aq) + H (g)

2 4 4 2
Zn(s) + 2HCl(aq) → ZnCl (aq) + H (g)

2 2
In these reactions, the oxidation state of zinc changes from 0 to +2, and the
oxidation state of hydrogen changes from +1 to 0. The electron transfer is shown
by the following half-equations:
pFigure 6 The reaction of metals with
+
2
acids c an be detected by the “pop” test:
oxidation: Zn(s) → Zn (aq) + 2e
the gas released from the reaction mixture
reduction: 2H (aq) + 2e → H (g)

2 is collected in an inverted test tube, and a lit
splint is held close to the test tube opening.
Therefore, in the reaction between a metal and an acid, the metal is the reducing
A small explosion (“pop”) suggests the
agent, and the acid is the oxidizing agent.

presence of hydrogen gas that reacts with
oxygen in the air
Copper and silver are less easily oxidized than magnesium, zinc and iron, so they
do not react with dilute solutions of common acids (gure 7).
potassium most reactive
sodium
calcium
magnesium
aluminium
zinc
iron
tin
lead
(hydrogen)
copper
silver
gold
platinum least reactive
pFigure 7 A reactivity series showing the most easily oxidized metals to the least easily
oxidized. Metals above hydrogen on the list c an react with common acids, those below
c an not
591
ATL Thinking skills
A student investigating the reactivity of zinc and copper noted the following
qualitative observations:
1. Copper wire was placed in dilute sulfuric acid. No change was observed. A
zinc strip was placed in dilute sulfuric acid. Bubbles appeared.
pFigure 8 Gold is at the bottom of
2. Some copper wire was wrapped around one end of the zinc strip. This
the reactivity series of metals, so it is not
oxidized easily. Therefore, it is the most end of the strip and the surrounding copper were placed in dilute sulfuric
likely to be found in its reduced form, with acid. Bubbles evolved quickly on the surface of the copper.
zero oxidation state: elemental gold. It is
3. Strips of copper and zinc were placed in dilute sulfuric acid and
impossible to “pan for lithium” bec ause it is
connected to each other. Bubbles evolved on the surface of the copper.
at the top of the activity series
zinc copper
dilute H SO
2 4
Explain the student’s observations, using your knowledge of metal reactivity,
electron transfer reactions, reactions of acids and metallic bonding.
Write two or three linking questions relating the concepts illustrated by this
experiment.
Redox titration
Iron supplements are used to treat iron deciency. You will determine the iron content in iron tablets by titrating them
with a solution of potassium manganate(VII) of known concentration. M anganate(VII) ions, MnO (aq), are powerful
4
oxidizing agents. In their reaction with iron(II) in acidic solution, purple manganate(VII) ions are reduced to pale pink
+
2
manganese(II) ions, Mn (aq). In this process, iron(II) ions are oxidized to iron(III) ions.
592
Relevant skills 4. In the meantime, review the titration and uncertainty
propagation sections in the Tools for chemistry
• Tool 1: Titration
chapter before starting part B.
Part B Titration against potassium manganate(VII)
• Tool 3: Record and propagate uncertainties
5. Filter the iron tablet extract. Transfer the ltrate into
• Inquiry 2: Assess reliability and validity of results 3
a volumetric ask and make up to the 250 cm mark
with distilled water. Store in a labelled reagent jar.

S afety
6. Fill the burette with 0.020 mol dm potassium

manganate(VII), KMnO (aq).

4
• Sulfuric acid, H SO (aq), is an irritant

2 4
7. Transfer 25.0 cm of iron tablet solution to a clean

• Dilute potassium manganate(VII), KMnO (aq), is an
4
conic al ask. Place this ask on a white tile under the

irritant and will stain skin and fabrics
burette.
Materials
8. Perform a rough titration of the iron tablet solution,
+
2
• iron tablets (or other source of iron(II), Fe (aq), ions)

stopping when the solution in the ask permanently
3
turns pale pink.
• 1.0 mol dm sulfuric acid, H SO (aq)
2 4
• distilled water 9. Repeat the titration several times until you obtain two
concordant values.
3
• 0.020 mol dm potassium manganate(VII) solution,
KMnO (aq)
4
10. Clear up according to the directions given by your
teacher.
• pestle and mortar
• top pan balance Questions
• two 250 cm conic al asks 1. Write the oxidation and reduction half-equations for
thisreaction.
3
3
2. Deduce the redox equation for this reaction.
• 250 cm volumetric ask
• funnel 3. Using your results, determine the mass of iron in one
tablet.
• lter paper
4. Propagate the measurement uncertainties to obtain

• reagent jar
the uncertainty of the mass of iron per tablet.
• burette
5. Compare your result to the iron content reported on

3
• 25 cm volumetric pipette
the tablet packaging. C alculate the percentage error.
• white tile
6. Comment on the reliability and validity of your result.
Instructions
7. Describe at least two sources of systematic error and

Part A Preparation of acidified iron tablet extract
suggest improvements that would minimize these
1. Grind four iron tablets into a ne powder using a
sources of error.
pestle and mortar.
8. Explain why you used four iron tablets in this analysis,
2. Weigh the iron tablet powder and transfer it into a
not just one.
conic al ask.
9. Explain why you le the iron tablet powder in dilute
3 3
3. Add 100 cm of 1.0 mol dm sulfuric acid, H SO (aq),

2 4
acid solution for 24 to 48 hours.
to the tablet powder and leave for 24 to 48 hours.
10. Suggest why redox titrations such as this are said to
be “self-indic ating”.
593
Electrochemic al cells (Reactivity 3.2.5 and
Reactivity 3.2.6)
An electrochemic al cell interconverts electric al and chemic al energy. There are
two types of electrochemic al cell:
1. In primary (voltaic) cells, secondary (rechargeable) cells, and fuel cells the
energy produced by spontaneous chemic al reactions is used to generate
electric al energy.
2. In electrolytic cells, electric al energy is used to drive forward non-
spontaneous chemic al reactions.
In redox reactions, electrons move from the substance being oxidized to
the substance being reduced. Nearly all spontaneous redox reactions are
exothermic, and the energy released in these chemic al changes c an be used
to produce electric al energy. Redox reactions used in primary (voltaic) cells
are irreversible while secondary (rechargeable) cells utilize reversible redox
reactions.
In the 18th century, the Italian scientist Luigi Galvani discovered accidentally
that an electric current could be produced by two dissimilar metals connected
by a moist substance. He noticed that he could c ause an amputated frog leg
to twitch by touching it with two dissimilar metals. Alessandro Volta, another
Italian scientist, doubted that animal legs were integral to produce electricity.
He showed that chemic al reactions c an produce electricity and made the rst
battery
pFigure 9 (a) Galvani’s frog legs experiment (b) Volta’s voltaic pile, the rst modern type
of electric battery
594
Any two dissimilar metals and their ions c an participate in redox reactions. The
one higher in the activity series will oxidize to ions and the one lower in the series
will have its ions reduced to the pure metal. For example, zinc c an be oxidized
+
2
by copper(II) ions, to form zinc ions. The Cu ions get reduced, and act as an
oxidizing agent.
+ +
2 2
Zn(s) + Cu (aq) → Zn (aq) + Cu(s)
Separating this into two half-equations gives:
+
2
Zn(s) → Zn (aq) + 2e
+
2
Cu (aq) + 2e → Cu(s)
These two processes c an occur in separate beakers, c alled half-cells.
Zn
Cu
2+
2+
Zn (aq) Cu (aq)
pFigure 10 The zinc and copper half-cells
The two half-cells c an be connected with a wire to form an electrochemic al cell.
In electrochemic al cells, oxidation always occurs at the anode, and reduction at
the c athode. RED CAT is a useful mnemonic: REDuction at CAThode. Therefore,
in this c ase, Zn(s) is the anode and Cu(s) the c athode. This electrochemic al cell
c an be represented by the following equations:
+ +
2 − 2 −
Zn(s) → Zn (aq) + 2e || Cu (aq) + 2e → Cu(s)
When the half-cells are connected, the electrons produced by the oxidation
of zinc at the anode ow through the wire to the copper half-cell to reduce
copper(II) ions. As a result, the zinc half-cell loses two electrons and now takes
on a slight positive charge while the copper half-cell gains two electrons, taking
on a slightly negative charge. Any further oxidation of zinc is prevented by the
slight negative charge on the copper half-cell, which repels the electrons. The
electrons therefore remain in the slightly positively charged zinc half-cell. The cell
becomes polarized, and the redox reaction stops.
To get around this, a salt bridge is used to connect the solutions in the two
half-cells and complete the electric al circuit. A salt bridge consists of an ionic salt
solution, such as sodium sulfate, Na SO , or potassium nitrate, KNO . It allows

2 4 3
the positive ions (c ations) to ow toward the slightly negatively charged half-cell
with the c athode and negative ions (anions) to ow toward the slightly positively
charged half-cell with the anode.
595
Consider the addition of a sodium sulfate salt bridge to our zinc–copper cell. The
+ 2+
slightly negatively charged copper half-cell attracts Na (aq) and Zn (aq) c ations
through the salt bridge and solution. The slightly positively charged zinc half-cell
2–
attracts SO (aq) anions through the salt bridge and solution. This neutralizes
4
the charge in each half-cell, so the redox reaction c an continue. This is now a
complete primary cell (gure 11). This kind of primary cell is known as the D aniell
cell, named aer its inventor, the British chemist John Frederic D aniell.
e e
– +
+
NO Na
3
Zn anode
Cu cathode
–
NO NO
3 3
uFigure 11 A primary cell consisting of
2+ –
Zn NO
a zinc metal anode (labelled as negative 3
2+
NO Cu
bec ause it is the source of electrons) dipped 3
in ZnSO (aq), a copper metal c athode

4
2+ 2+
Zn(s) → Zn (aq) + 2e Cu (aq) + 2e → Cu(s)
(labelled positive as it attracts electrons)
movement of cations
dipped in CuSO (aq), an electric al
4
connecting wire, a voltmeter and a
movement of anions
salt bridge
As the reaction continues, the blue colour of the copper(II) sulfate solution fades,
the copper bar increases in size as it becomes coated in more copper, and the
+
2
zinc bar gets thinner. Once there is a signic ant build-up of Zn (aq) ions on the
c athode side, the cell ceases to function.
Cell diagrams are used as a short-hand way to represent primary cells. In this
convention, the c athode is always written on the right-hand side and the anode is
always written on the le-hand side. The salt bridge is represented by two parallel
vertic al lines. You c an use the following general template to write cell diagrams
for metal–ion primary cells:
anode being oxidized | product of oxidation || species being reduced | product
of reduction/c athode
Therefore, the cell diagram for the D aniell cell would be written as follows:
+ +
2 2
Zn(s) | Zn (aq) || Cu (aq) | Cu(s)
+
2
The species on the le-hand side, Zn(s) | Zn (aq), represent the anode, with zinc
+ +
2 2
metal being oxidized to Zn (aq). The species on the right-hand side, Cu (aq) |
+
2
Cu(s), represent the c athode, with Cu (aq) being reduced to Cu(s).
596
Worked example 6
M anganese metal reacts with nickel(II) ions to form manganese(II) ions and
nickel metal.
a. Write the redox reaction that occurs between nickel(II) ions and
manganese metal.
b. Assuming that this redox reaction occurs in a manganese–nickel primary
cell, write the half-equations that occur in each half-cell.
c. Write the cell diagram to represent the primary cell for this redox reaction.
d. Sketch a primary cell for this reaction and identify the anode, c athode,
direction of electron ow and direction of ion ow.
Solution
+ +
2 2
a. Mn(s) + Ni (aq) → Mn (aq) + Ni(s)
+
2
b. At the c athode: Ni (aq) + 2e → Ni(s)
+
2
At the anode: Mn(s) → Mn (aq) + 2e
c. You c an use the general template for cell diagrams:
anode being oxidized | product of oxidation || species being reduced |
product of reduction/c athode
This gives:
+ +
2 2
Mn(s) | Mn (aq) || Ni (aq) | Ni(s)
d.
V
anode cathode
( ) (+)
salt bridge
Ni(s)
Mn(s)
2+ 2+
Mn (aq) Ni (aq)
Electrons ow from le to right (from the anode to the c athode) through
+
2
the electric al wire. Mn (aq) and the c ations of the salt in the salt bridge
also ow from le to right through the salt bridge toward the c athode.
The anions of the salt ow from right to le through the salt bridge toward
the anode.
597
Secondary cells (Reactivity 3.2.7)
A battery is a series of two or more electrochemic al cells, typic ally enclosed
in a single container. In a primary electrochemic al cell, ultimately the reaction
materials will be consumed, and the reaction is not reversible. Either the anode,
the electrolyte, or both, need to be replaced, or the battery will be thrown away.
Typic ally, the anode (negative electrode) is oxidized and c an no longer be used.
As previously discussed, the ions travelling through the solution and salt bridge
c an polarize the cell, which c auses the chemic al reaction to stop. Polarization c an
also c ause a build-up of hydrogen bubbles on the surface of the anode. These
c an increase the internal resistance of the cell and reduce its electric al output.
Primary cells do not operate well under high-current demands, such as in ash
photography or electric c ars, but are suitable for low-current household devices.
In a secondary cell, or a rechargeable cell, the chemic al reactions that generate
electricity c an be reversed by applying an electric current to the cell. Secondary
cells c an satisfy higher current demands than primary cells but have a higher rate
of self-discharge. For example, batteries in cell phones are made of secondary
cells that c an be recharged using electric al energy. When you purchase a
replacement battery for a phone, you need to charge it before use bec ause it will
have self-discharged during the storage and transportation.
electron flow (current)
through external circuit
positive plate negative plate
(cathode) (anode)
electrolyte
oxidized
oxidized
positive ions
metal
metal
metal
negative ions
metal or
lower oxide
electrolyte
case
pFigure 12 Structure of an electrochemic al cell. The negative anode is oxidized and the
ow of ions c auses polarization. This process c annot be reversed in a primary cell, but it c an
be reversed in a secondary (rechargeable) battery
598
C ase study: Lead–acid battery
C ar batteries are made of secondary cells. The electric al energy from the battery
is used to power the motor that starts the engine, and to power any electric al
systems in the c ar. This is known as discharge. Some of the chemic al energy from
the combustion in the engine is used to reverse the chemic al reactions that occur
during discharge, therefore recharging the battery. An idling engine runs slowly
and does not provide enough energy to recharge the battery, and so the battery
will gradually discharge.
A typic al c ar uses a lead–acid battery. This battery is composed of a lead anode,
Pb(s), a lead(IV) oxide c athode, PbO (s), and sulfuric acid, H SO (aq). Sulfuric
2 2 4
−
+
acid is a strong acid, so it will ionize into H (aq) and HSO (aq). When the battery
4
is powering the motor and the c ar ’s electric al systems, HSO (aq) will oxidize
4
Pb(s) at the anode, and H (aq) will reduce PbO (s) at the c athode. This gives rise
2
to the following discharge reactions:
−
+ −
anode (oxidation): Pb(s) + HSO (aq) → PbSO (s) + H (aq) + 2e

4 4
−
+ −
cathode (reduction): PbO (s) + 3H (aq) + HSO (aq) + 2e → PbSO (s) + 2H O(l)
2 4 4 2
overall cell reaction: Pb(s) + PbO (s) + 2H SO (aq) → 2PbSO (s) + 2H O(l)
2 2 4 4 2
–
+
Note that the H (aq) and HSO (aq) ions are ultimately produced by the
4
dissociation of sulfuric acid, so in the overall cell reaction they are combined
together and shown as H SO (aq).

2 4
Worked example 7
Determine the reactions that occur at the anode and c athode in a c ar battery
cell, and the overall cell reaction, when the engine is charging the battery.
Solution
The charging reactions are the reverse of the discharge reactions:
−
+ −
anode: PbSO (s) + H (aq) + 2e → Pb(s) + HSO (aq)

4 4
−
+ −
c athode: PbSO (s) + 2H O(l) → PbO (s) + 3H (aq) + HSO (aq) + 2e

4 2 2 4
overall cell reaction: 2PbSO (s) + 2H O(l) → Pb(s) + PbO (s) + 2H SO (aq)
4 2 2 2 4
The continual charging of a lead–acid battery tends to produce hydrogen and
oxygen from water. Therefore, non-sealed c ar batteries occ asionally need to be
topped up with distilled water.
tFigure 13 A lead–acid battery consists
of a series of secondary cells with lead(IV)
oxide plates, lead plates, and sulfuric acid
electrolyte
599
C ase study: Lithium-ion batteries
Lithium-ion rechargeable batteries use lithium atoms embedded in a lattice of
graphite electrodes, rather than pure lithium metal for the anode. The c athode
is a lithium–cobalt oxide complex, LiCoO . The lithium atoms are oxidized to

2
lithium ions during discharge.
During charging, the opposite process occurs: the lithium ions in the complex
migrate through the battery medium to the anode, where they accept electrons
and are reduced to lithium atoms. These atoms become embedded in the
graphite lattice. The battery medium must be completely non-aqueous, usually
a polymer gel, as lithium reacts vigorously with water. Table 2 summarizes
thesereactions:
Electrode Discharging reaction Charging reaction
+ − + −
anode Li(s) → Li + e Li + e → Li(s)
+ − + −
c athode Li + e + CoO (s) → LiCoO (s) LiCoO (s) → Li + e + CoO (s)

2 2 2 2
pTable 2 Anode and c athode reactions in the lithium-ion battery
The overall cell reaction during discharge is Li(s) + CoO (s) → LiCoO (s).
2 2
flow of electrons
e
anode
during discharge
Li
Li
+
Li Li
Li
Li
Li
Li
Li
Li
Li
Li
Li
cathode anode
cathode
pFigure 14 Structure of a typic al
lithium-ion rechargeable battery. The

When the lithium-ion battery is in use, electrons ow from the anode to the
battery consists of a series of secondary

c athode through the external circuit while lithium ions ow from the anode to
cells composed of c athodes and
the c athode through the polymer gel inside the cell. When no more lithium ions
anodes with a layer of polymer (yellow)
are le on the anode, the battery is at. To recharge it, the process is reversed,
separating them
transferring lithium ions back to the anode.
600
Practice questions
4. During the discharge of a nickel–c admium battery, the following reactions
occur in the cells:
anode: Cd(s) + 2OH (aq) → Cd(OH) (s) + 2e

2
c athode: NiO(OH)(s) + H O(l) + e → Ni(OH) (s) + OH (aq)

2 2
a. Write the overall equation for the cell.
b. Write the cell diagram.
c. Determine the charging reactions that occur in the cell.
Fuel cells
Fuel cells are a type of electrochemic al cell that convert hydrogen, methanol,
or ethanol and oxygen into water, c arbon dioxide and heat. They c ause little
pollution and are very ecient. Like primary cells, they are not rechargeable,
but unlike primary cells, they require a steady supply of fuel and oxygen, so the
reactions in the cell c an continue indenitely.
For example, in a hydrogen fuel cell, hydrogen gas is supplied to the anode
while oxygen gas is supplied to the c athode. The following reactions occur in a
hydrogen fuel cell:
anode: H (g) → 2H (aq) + 2e

2
c athode: O (g) + 4H (aq) + 4e → 2H O(l)

2 2
overall cell equation: 2H (g) + O (g) → 2H O(l)

2 2 2
In a direct methanol fuel cell (DMFC), methanol is supplied to the anode. The
following reactions occur in a DMFC:
anode: CH OH(l) + H O(l) → CO (g) + 6H (aq) + 6e

3 2 2
3
+
c athode: O (g) + 6H (aq) + 6e → 3H O(l)

2 2
overall cell equation: CH OH(l) + O (g) → CO (g) + 2H O(l)

3 2 2 2
A typic al fuel cell has the following key components:
• Electrolyte or separator: this keeps components from mixing. For example, a
proton exchange membrane (PEM) is a polymer that allows H ions to diuse
through but prevents the diusion of other ions, electrons or molecules.
• Electrodes: The electrodes are made of a c atalyst that allows for the
chemic al reactions to occur. There is an oxidizing electrode (anode) and
reducing electrode (c athode).
• Bipolar plate: This conducts the electric al current from cell to cell and
ensures uniform distribution of the fuel gas.
601
external circuit
fuel H
2 O (air)
2
+
heat
fuel
air and H O
2
recirculated
gas diffusion
catalyst catalyst
gas diffusion
electrode (cathode)
electrode (anode)
proton exchange
membrane (PEM)
pFigure 15 In a hydrogen fuel cell, H (g) is oxidized at the anode and O (g) is reduced at the c athode. The proton exchange membrane
2 2
(PEM) allows H ions to diuse but prevents the diusion of other ions, molecules and electrons
Hydrogen fuel cells use hydrogen gas as the fuel. These cells do not produce
greenhouse gases. The heat formed in the exothermic reaction 2H (g) + O (g) →
2 2
2H O(l) c an be utilized, increasing the eciency of the cell. The oxygen gas c an
2
be obtained from the air.
The c atalysts used for the electrodes are oen made of platinum or other
expensive metals, which makes fuel cells expensive to run on a commercial
sc ale. The hydrogen gas used must be very pure to prevent the poisoning of the
c atalyst and therefore the reduction of the cell electric al output. There are two
main sources of hydrogen gas:
Practice question 1. Clean hydrogen c an be produced by the electrolysis of water. Solar cells
or wind generators provide the cleanest form of energy for powering the
5. O utline the function of the
electrolysis.
proton exchange membrane
(PEM) in fuel cells. 2. Hydrogen gas c an also be obtained by the reaction of hydroc arbons,
especially methane, with steam: CH (g) + H O(g) ⟶ 3H (g) + CO(g)

4 2 2
DMFC s have the advantage of not needing to extract hydrogen gas bec ause they
The eect of greenhouse gases
use methanol as the fuel. However, they produce c arbon dioxide, CO (g), which
2
on atmospheric temperatures is
is a greenhouse gas.
602
Electrolytic cells (Reactivity 3.2.8)
An electrolytic cell is an electrochemic al cell that converts electric al energy to
chemic al energy. The oxidation and reduction reactions in an electrolytic cell are
non-spontaneous, so they require an external source of electricity to bring about
the chemic al changes. This process is known as electrolysis.
An electrolytic cell consists of a single container lled with an electrolyte. The
electrolyte c an be a solution of an ionic salt, or a molten ionic salt, composed of
free-moving c ations and anions. Two electrodes (the c athode and the anode) are
dipped in the electrolyte, and a direct current (DC) power source is connected to
the electrodes.
DC power
e e
source
electrolyte
electrodes
pFigure 16 The structure of an electrolytic cell
In a closed circuit, electrons ow from the negative terminal to the positive
terminal of the DC power source. The negative terminal of the DC power source
is connected to the c athode. Therefore, electrons ow to the c athode and
reduce the c ations in the electrolyte. The anions in the electrolyte ow to the
anode and undergo oxidation, releasing electrons. The electrons ow to the
positive terminal of the DC power source to complete the circuit. The ow of
electrons and ions in an electrolytic cell comprises electric current
Consider the electrolysis of molten sodium chloride, NaCl(l), shown in gure 17.
ammeter to
DC power source
measure current
+ – A
– –
e e
anode cathode
oxidation reduction
occurs here occurs here
– – + –
2Cl + 2e Na + e
2
– +
Cl Na
tFigure 17 The electrolysis of molten sodium chloride
heat
603
In the electrolytic cell, molten sodium chloride is the electrolyte, which contains
sodium c ations, Na , and chloride anions, Cl . Electrons ow to the c athode,
reducing the sodium c ations in the electrolyte to form molten sodium metal. The
reduction half-equation is as follows:
Na + e → Na(l)
At the anode, chloride anions are oxidized, producing chlorine gas and electrons
to complete the circuit. The oxidation half-equation is as follows:
2Cl → Cl (g) + 2e
2
The overall equation for reactions in the electrolytic cell is:

Practice question
2NaCl(l) → 2Na(l) + Cl (g)

2
6. Write the half-equations, and
full equation, for the electrolysis
This electrolytic cell is therefore useful for the production of sodium metal and
of molten lead bromide, PbBr

2
chlorine gas.
Reactive metals, such as lithium, magnesium, aluminium, and sodium are all
obtained by electrolysis of their molten salts. These metals react with oxygen, so
the electrolysis must take place in an inert atmosphere.
Oxidation of organic compounds
(Reactivity 3.2.9)
Some functional groups in organic compounds c an undergo oxidation under
certain conditions. For example, in the presence of an oxidizing agent, the
hydroxyl group in secondary alcohols c an be oxidized to a c arbonyl group,
forming a ketone:
OH O
[O]
R C R C + H O
2
R
R
secondary alcohol ketone
The symbol [O] is used to indic ate the oxidizing agent, which provides a source
of oxygen atoms. In this oxidation reaction, two hydrogen atoms are lost from
the compound, forming water with an oxygen atom from the oxidizing agent. An
additional bond forms between c arbon and oxygen.
Primary alcohols c an be oxidized to c arboxylic acids in a two-step reaction.
In the rst step, the hydroxyl group is oxidized to a c arbonyl group, forming an
aldehyde:
OH O
The denitions of primary,
[O]
secondary and tertiary alcohols
R C H C + H O
2
are given in Structure 3.2.
R
H
Namingcompounds with
hydroxyl, c arboxyl and c arbonyl
primary alcohol aldehyde

functional groups is also covered in
Structure 3.2
Like in the oxidation of a secondary alcohol, two hydrogen atoms are lost and an
additional bond forms between c arbon and oxygen.
604
In the second step, the c arbonyl group is oxidized to a c arboxyl group, forming
a c arboxylic acid:
O O
water
[O] out
C C
condenser
R
H
aldehyde c arboxylic acid
In this oxidation reaction, the aldehyde gains an oxygen atom.
water in
The oxidation of a primary alcohol to a c arboxylic acid, or a secondary alcohol
to a ketone, c an be accomplished by reux. Reux involves heating the reaction
mixture with a reux condenser, which cools any vapours produced and returns
them back to the reaction mixture (gure 18). An oxidizing agent, such as
potassium dichromate(VI), K Cr O , and a concentrated acid are also added to

2 2 7
the reactionmixture.
alcohol + excess
oxidizing agent
For the oxidation of a primary alcohol to a c arboxylic acid, the oxidizing agent
+ concentrated acid
is present in excess to ensure complete two-step oxidation, rather than partial
oxidation to an aldehyde aer the rst oxidation step.

heat
pFigure 18 The experimental set-up

The oxidation of a primary alcohol to an aldehyde c an be accomplished by
for a reux reaction. Reux allows vapours

distillation. Distillation allows the aldehyde to be isolated before it undergoes
to condense back to the boiling reaction

further oxidation to c arboxylic acid (gure 19). In this c ase, the alcohol, not the
mixture for further oxidation
oxidizing agent, is used in excess.
water out
condenser
primary alcohol
in excess +
oxidizing agent
water in
+ concentrated
acid
anti-bumping granules
heat
tFigure 19 The experimental set-up for
the distillation of an aldehyde obtained by
aldehyde
the oxidation of a primary alcohol
605
Worked example 8
Write the equations for the following oxidation reactions, showing
displayed formulas:
a. oxidation of ethanol to an aldehyde
b. oxidation of propan-1-ol to a c arboxylic acid
c. oxidation of propan-2-ol.
Use [O] to symbolize the oxidizing agent. In each equation, state which
reacting species is in excess and suggest which experimental procedure,
reux or distillation, must be used.
Solution
a.
H H H
[O]
C C C + H O
2
H H H
ethanol ethanal
ethanol in excess
distillation
b. H H H H H
[O]
H C C C C
OH
H H H H H
propan-1-ol propanoic acid
oxidizing agent in excess
reux
c.
H H H H H
[O]
H C C C + H O
2
H OH H H O H
propan-2-ol propanone
oxidizing agent in excess
reux
606
In both primary and secondary alcohols, oxidation of the hydroxyl group to a H
c arbonyl group involves the removal of the hydrogen atom connected to the
H C H
c arbon with the hydroxyl group. Tertiary alcohols do not have this hydrogen
H H
atom, so they c annot be oxidized in the same way as primary and secondary
alcohols (gure 20).
H C C C H
H H
Reduction of organic compounds
OH
(Reactivity 3.2.10)
pFigure 20 2-methylpropan-2-ol is a
C arboxylic acids c an be reduced to primary alcohols via a two-step reaction tertiary alcohol, so it c annot be oxidized by
involving an aldehyde intermediate, and ketones c an be reduced to secondary reux or distillation in the presence of an
oxidizing agent
alcohols. The reactions are the opposite of the corresponding oxidation
reactions.
In the presence of a reducing agent, the c arbonyl group in a ketone c an be
reduced to a hydroxyl group, forming a secondary alcohol:
O OH
[H]
C R C
R
R R
ketone secondary alcohol
The symbol [H] is used to indic ate the reducing agent, which provides hydrogen
atoms. In this reduction reaction, the ketone gains two hydrogen atoms and one
of the bonds between c arbon and oxygen is broken.
C arboxylic acids c an be reduced to primary alcohols in a two-step reaction. In
the rst step, the c arboxyl group is reduced to a c arbonyl group, forming an
aldehyde:
O O
[H]
C C
R OH R H
c arboxylic acid aldehyde
In this reduction reaction, the c arboxylic acid loses an oxygen atom.
In the second step, the c arbonyl group is reduced to a hydroxyl group, forming a
primary alcohol:
O OH
[H]
C R C
H
R H
aldehyde primary alcohol
Like in the reduction of a ketone, two hydrogen atoms are gained and one of the
c arbon–oxygen bonds is broken.
In the reduction of c arboxylic acids, the aldehyde is produced as an intermediate
product, but in most c ases it c annot be isolated.
607
A common reducing agent used in all the reactions above is lithium aluminium
hydride, LiAlH . Aldehydes and ketones (but not c arboxylic acids) c an also be
4
reduced by sodium borohydride, NaBH

4
Vincent van Gogh used lead and chromium paints to Chemists, art historians and conservators work together
create many of his colourful and well-known paintings. to explore and understand these changes, as well as to
Redox reactions have c aused some of the colours to fade devise possible preservation methods. Where else does
over time. chemistry intersect with the world of art?
pFigure 21 The yellow paint used in Van Gogh’s Bedroom at Arles was probably made from lead chromate, PbCrO (right)
4
Reduction of alkenes and alkynes
(Reactivity 3.2.11)
Alkenes and alkynes are unsaturated compounds. Alkenes have a c arbon–c arbon
double bond, and alkynes have a c arbon–c arbon triple bond. Unsaturated
compounds c an be reduced by the addition of hydrogen to the multiple bond.
In the presence of a suitable c atalyst, such as deactivated palladium, Pd(s),
alkynes c an be reduced by hydrogen gas to alkenes:
H H
C + H H C C
R R
alkyne hydrogen gas alkene
In this equation, the symbol R represents either an alkyl group or a
hydrogenatom.
608
Alkenes are reduced by hydrogen gas to alkanes:
H H
R R
C C + H H R C
C R
R'' R'''
R'' R'''
alkene hydrogen gas alkane
This reaction also requires a transition metal c atalyst, such as Ni(s) or Pt(s). The
same c atalysts c an be used to reduce alkynes directly to alkanes using excess
hydrogen gas:
R–C≡C–R’ + 2H–H → R–CH –CH –R’

2 2
alkyne excess alkane
hydrogen
Reduction of alkynes and alkenes decreases the degree of unsaturation of these
compounds.
ATL Thinking skills
In this task, you will create a concept map to summarize the material covered
in this unit and identify the connections between various aspects of electron
transfer reactions. You will need a large sheet of paper and several sticky
notes. This task is based on a Harvard Project Zero Visible Thinking Routine
known as Generate-Sort-Connect-Elaborate.
• M ake a list of the key words in this unit and write them on sticky notes.
These are the nodes of your concept map.
• Write the title “Electron transfer reactions” at the centre of a large sheet of
paper.
• Arrange the nodes (sticky notes) on the paper around the title, from
general to more specic.
• Draw lines between pairs of nodes to represent the connections between
them.
• Write a brief statement along each connecting line to describe how the
key words are linked.
• Share your concept map with your class and expand it once you have
received feedback.
Practice questions
7. Predict the products of the reaction of excess hydrogen gas with:
a. propene
b. pent-1-yne.
Write the full equations, including displayed formulas, for these reactions.
609
LHA
Standard electrode potentials
(Reactivity 3.2.12)
The ease of oxidation and reduction of a species in an electrochemic al cell c an
be described numeric ally using a standard electrode potential, or standard
reduction potential, E . Standard electrode potentials are dened relative to a
hydrogen-based half-cell where the following reaction occurs:
1 ⦵
+
H (aq) + e ⇌ H (g) E = 0 V
2
This half-cell is known as the standard hydrogen electrode (SHE) and is assigned
a standard electrode potential of zero. An inert platinum electrode is used in the
SHE bec ause the reduced species is hydrogen gas and not a metal.
Species with a more negative standard electrode potential will have greater ease
of oxidation, and greater tendency to reduce other species. They will be higher
in the reactivity series. Species with a more positive standard electrode potential
will have greater ease of reduction and greater tendency to oxidize other
species. They will be lower in the reactivity series. Of all the elements, lithium has
the greatest ease of oxidation and uorine has the greatest ease of reduction.
The reactivity series and the
corresponding standard electrode
Standard electrode potentials are measured in volts (V). They are correct for
potentials are given in section 19 of
standard temperature and pressure (SATP) conditions (temperature = 298 K,
the data booklet. SATP conditions
pressure = 100 kPa). All aqueous species present in the half-cell equation must
are provided in section 4.

3
also have a concentration of 1.0 mol dm
Practice question
8. The standard electrode potentials of four metals are given in table 3.
Metal E / V
tin, Sn(s) −0.14
c alcium, C a(s) −2.87
lithium, Li(s) −3.04
aluminium, Al(s) −1.66
pTable 3 E values for selected metals
Order these metals according to their ease of oxidation, with the most
readily oxidized rst.
610
LHA
Standard cell potentials (Reactivity 3.2.12)
The voltage of an electrochemic al cell depends on the identity of the electrodes
in each half-cell. The further apart the species are on the reactivity series, the
greater the voltage. This voltage, known as the standard cell potential, E ,
cell
c an be c alculated by nding the dierence between the standard electrode
potentials of the half-cells:
⦵ ⦵ ⦵
E = E (reduced species) – E (oxidized species)

cell
For a reaction in an electrochemic al cell to be spontaneous, E must have

cell
a positive value. In that c ase, the reduction will occur at the electrode with
the more positive value of E (the c athode) and the oxidation will occur at the
electrode with the more negative value of E (the anode). In other words:
⦵ ⦵ ⦵
E = E (c athode) − E (anode)
cell
+ +
2 2
Consider an electrochemic al cell composed of Fe | Fe and Cu | Cu half-cells.
The data booklet states the half-cell reduction reactions and their standard
electrode potentials as follows:
+ ⦵
2 −
Fe (aq) + 2e ⇌ Fe(s) E = −0.45 V
+ ⦵
2 −
Cu (aq) + 2e ⇌ Cu(s) E = +0.34 V
⦵ +
2
The copper electrode has the more positive value of E , so Cu (aq) will be
reduced to Cu(s), and the half-equation at that electrode will proceed in the
forward direction.
The iron electrode has the more negative value of E , so Fe(s) will be oxidized
+
2
to Fe (aq), and the half-equation at that electrode will proceed in the reverse
direction to that stated above:
+
2 −
Fe(s) ⇌ Fe (aq) + 2e
Now you c an determine the overall standard potential of the cell:
⦵ ⦵ ⦵
E = E (reduced species) − E (oxidized species)

cell
= (+0.34 V) − (−0.45 V)
= 0.79 V
To nd the overall equation for the electrochemic al cell, add the two half-
equations together, c ancelling the electrons and ensuring that the equation is
balanced:
+ +
2 2
Fe(s) + Cu (aq) ⇌ Fe (aq) + Cu(s)
This reaction is described as being spontaneous in the forward direction. You
c an therefore use E data to predict which direction will be spontaneous for a
reversible redox reaction in an electrochemic al cell.
611
LHA
Worked example 9
+
2
An electrochemic al cell composed of a Zn | Zn half-cell and a standard hydrogen electrode (SHE) half-cell is shown
in gure 22. The redox reaction in the cell c an be written as follows:
+
+ 2
2H (aq) + Zn(s) ⇌ Zn (aq) + H (g)

2
voltmeter
e e
H gas zinc

at 1 bar
salt bridge
ZnSO (aq)
4
latinm (1 mol dm )
electrode
Hl(aq)
3
(1 mol dm )
standard hydrogen electrode standard zinc half-cell
+
2
pFigure 22 The electrochemic al cell with a SHE half-cell and a Zn | Zn half-cell. The voltmeter
is set up to measure the overall cell potential
a. State which half-cell contains the anode and which contains the c athode.
b. Predict whether the forward or backwards reaction is spontaneous.
c. Show that the standard cell potential, E , is +0.76 V using section 19 of the data booklet.
cell
Solution
a. First, write the half-cell reduction reactions and Before you add the half-equations together, you rst
standard electrode potentials from the data booklet: need to double the stoichiometric coecients in the
hydrogen half-equation to ensure that there is an equal

+ ⦵
2
Zn (aq) + 2e ⇌ Zn(s) E = −0.76 V
number of electrons in each half-equation:
1 ⦵
+
H (aq) + e ⇌ H (g) E = 0.00 V

2
2 + −
2H (aq) + 2e ⇌ H (g)
2
The SHE half-cell has the more positive value of E , so it
Now add the half-equations together, c ancelling the

will involve a reduction reaction and therefore contains
electrons:
the c athode.
⦵ +
+ 2
The zinc half-cell has the more negative value of E , 2H (aq) + Zn(s) → Zn (aq) + H (g).
2
so it will involve an oxidation reaction and therefore
Therefore, the reaction will be spontaneous in the
contains the anode.
forward direction for the equation given in the
b. Reduction occurs at the SHE half-cell, so its half- question.
equation will proceed in the forward direction as given

⦵ ⦵ ⦵
c. E = E (reduced species) − E (oxidized species):

cell
Oxidation occurs at the zinc half-cell, so its half-

(0.00 V) − (−0.76 V)
equation will proceed in the reverse direction:
= 0.76 V
+
2 −
Zn(s) ⇌ Zn (aq) + 2e
612
LHA
Worked example 10
+
2 +
An electrochemic al cell comprises a Cu | Cu half-cell and an Ag | Ag
half-cell.
a. State which half-cell contains the anode, and which contains the
c athode.
b. Write the spontaneous reaction that occurs in the electrochemic al cell.
c. C alculate the standard cell potential, E .

cell
Solution
a. Copy the half-equations and standard reduction potentials for each half-
cell from the data booklet:
⦵
+ −
Ag (aq) + e ⇌ Ag(s) E = +0.80 V
+ ⦵
2 −
Cu (aq) + 2e ⇌ Cu(s) E = +0.34 V
The silver half-cell has the more positive value, so it contains the c athode, and
the copper half-cell contains the anode.
b. The silver half-cell has the more positive E value, so reduction occurs
in this half-cell and the half-equation is already shown in the correct
direction. Oxidation occurs in the copper half-cell, so the half-equation
needs to be reversed:
+
2 −
Cu(s) ⇌ Cu (aq) + 2e
Before you add the half-equations together, you rst need to double the
stoichiometric coecients in the silver half-equation to ensure that there is an
equal number of electrons in each half-equation:
+ −
2Ag (aq) + 2e ⇌ 2Ag(s)
Now add the half-equations together, c ancelling the electrons:
+
+ 2
2Ag (aq) + Cu(s) → 2Ag(s) + Cu (aq)
⦵ ⦵ ⦵
c. E = E (reduced species) − E (oxidized species):

cell
= (+0.80 V) − (+0.34 V)
= 0.46 V
It is important to note that the half-cell voltage for silver electrode is not
multiplied by two. The electrons lost and gained need to be balanced,
but the potential of the cell only depends on the chemic al nature of the
species involved in the half-equation, and not on the way the half-equation is
balanced.
613
LHA
Gibbs energy and standard cell potentials
(Reactivity 3.2.14)
The standard change in Gibbs energy, ΔG , over the course of a chemic al
This equation and the value of

reaction occurring in an electrochemic al cell, c an be determined from the
the F araday constant are given ⦵
standard cell potential, E :

cell
in sections 1 and 2 of the data
⦵ ⦵
booklet. Change in Gibbs energy, ΔG = −nFE

cell
ΔG, c an also be dened in terms
where n is the number of electrons transferred in the balanced redox equation,
of the enthalpy change, entropy
4 1
and F is the F araday constant, 9.65 × 10 C mol
change and temperature, as
⦵
described in Reactivity 1.4 (AHL).
You know that an electrochemic al reaction will be spontaneous if E is positive.
cell
As the right-hand term in the equation above has a negative sign, a reaction will
be spontaneous if ΔG is negative.
F has units of coulombs per mole, C mol , where coulomb is the SI unit of
⦵ ⦵
charge. E has units of volts, V. When the n, F and E terms are multiplied
cell cell
together, the resulting value has units of C V mol . One volt is equivalent to one
unit of energy per unit charge; in other words, one joule per coulomb: 1 V =
1 1
1 J C . Substituting this into C V mol gives:
1 1 1
C J C mol = J mol
⦵ ⦵
1 1
Therefore, the units of ΔG are J mol , or more oen ΔG is converted to kJ mol
by dividing by 1,000.
Worked example 11
⦵ +
+ 2
In worked example 9, E for the reaction 2H (aq) + Zn(s) → Zn (aq) +

cell
H (g) was c alculated to be +0.76 V. C alculate ΔG for this reaction.

2
Solution
Two electrons are transferred in this redox reaction, so n = 2.
⦵ ⦵
ΔG = −nFE
cell
4 1 1
= −2 × (9.65 × 10 C mol ) × 0.76 J C
5 1 1
= −1.47 × 10 J mol or −147 kJ mol
Practice questions
⦵
1
9. The standard change in Gibbs energy, ΔG , is –152 kJ mol for the
following electrochemic al reaction:
Fe(s) + CuSO (aq) → FeSO (aq) + Cu(s)

4 4
a. State whether the reaction will occur spontaneously.
b. C alculate the value of E . Compare the value obtained with the

cell
2+ 2+
dierence in standard reduction potentials of Fe /Fe and Cu /Cu
electrodes, which are given in section 19 of the data booklet.
614
LHA
Measuring standard cell potentials
The displacement reaction between zinc and copper(II) • 50 cm beakers
ions is as follows:
• filter paper
+ +
2 2
• tweezers
Zn(s) + Cu (aq) → Cu(s) + Zn (aq)
• high-resistance voltmeter
If the oxidation and reduction processes are separated
• crocodile clips
into two half-cells connected by an external wire and
• connecting wires
salt bridge, chemic al energy from the spontaneous
redox reaction is converted into electric al energy. In this
Instructions
practic al, you will measure the cell potential of a zinc–
−3
copper cell and use this to determine ∆G for the reaction.
1. Prepare a 1.0 mol dm copper(II) sulfate solution and
transfer 5.0 cm of it into a weighing bottle.

3
You will be using 1.0 mol dm solutions, which require
−3
2. Prepare a 1.0 mol dm zinc sulfate solution and

large quantities of the corresponding hydrated salts. To
transfer 5.0 cm of it to a second weighing bottle.

minimize waste, very small volumes of the electrolytes will
be used. Once nished, you are encouraged to recover

3. S and the two electrodes to remove any surface
the electrolyte solutions instead of disc arding them, as

contaminants.
they c an be used for other experiments.
4. Prepare a small volume of saturated potassium
chloride solution. Cut a strip of filter paper to use as

Relevant skills
a salt bridge between the two half-cells. Dip the strip
• Tool 1: Measuring potential difference
into the potassium chloride solution.
• Tool 1: Constructing electrochemic al cells

5. Construct the voltaic cell:
• connect the two solutions in weighing bottles

• Tool 3: C alculate percentage error
with the salt bridge
• connect the electrodes to the voltmeter using the
crocodile clips and connecting wires

S afety
• dip the electrodes into their corresponding
solutions in weighing bottles.
• Copper(II) sulfate and zinc sulfate are harmful and
6. Measure the potential difference.

irritant. Avoid contact with eyes and skin
7. Clear up according to the directions given by your
• Copper(II) sulfate and zinc sulfate are toxic to the
teacher.
environment and must be disposed of safely
Questions
Materials
1. C alculate the theoretic al standard cell potential for
• copper(II) sulfate pentahydrate, CuSO •5H O

4 2
your zinc–copper cell, using the standard electrode
• zinc sulfate heptahydrate, ZnSO •7H O potentials in the data booklet.

4 2
• distilled water
2. Compare your experimental result to the theoretic al
value and c alculate the percentage error.

• zinc electrode
• copper electrode 3. Suggest at least two reasons why your measured
value differs from the theoretic al value.

• potassium chloride
4. C alculate ∆G from your measured cell potential.

• two weighing bottles (or other small wide-mouth
containers)
5. Research the relationship between E and ∆G under
cell
• sandpaper non-standard conditions. Use this to briefly outline two
research questions related to voltaic cells, E and ∆G

cell
615
LHA
Electrolysis of aqueous solutions
(Reactivity 3.2.15)
We have discussed the electrolysis of molten ionic salts where c ations are
reduced and anions are oxidized. The electrolysis of aqueous solutions of
ionic salts introduces oxidation and reduction reactions involving water, which
compete with the redox reactions of the anions and c ations of the salt at the
anode and c athode.
The reduction of water c an proceed as follows:
1 ⦵
H O(l) + e → H (g) + OH (aq) E = −0.83 V

2 2
If the standard electrode potential of the salt c ation is more negative than
−0.83 V, then water will be preferentially reduced over the salt c ation and
hydrogen gas will be formed at the c athode.
The other possible competing reaction is the oxidation of water. In the data
booklet, the reduction of oxygen is given as follows:
1 ⦵
+
O (g) + 2H (aq) + 2e → H O(l) E = +1.23 V

2 2
Reversing the equation gives the half-equation for the oxidation of water. The
reduction potential has to be reversed as well, giving an oxidation potential:
1 ⦵
+
H O(l) → O (g) + 2H (aq) + 2e E = −1.23 V

2 2
If the oxidation potential of the salt anion is more negative than −1.23 V, then
water will be preferentially oxidized over the salt anion and oxygen gas will be
formed at the anode.
For example, consider two electrolytic cells: one composed of molten sodium
chloride, NaCl(l), and one composed of an aqueous sodium chloride, NaCl(aq).
In the electrolysis of NaCl(l), electric al energy is provided to the cell, resulting
in the reduction of sodium ions to form sodium metal at the c athode and the
oxidation of chloride ions to form chlorine gas at the anode:
c athode: Na + e → Na(l)
anode: Cl → Cl (g) + e
2
overall cell equation: 2NaCl(l) → 2Na(l) + Cl (g)

2
In the electrolysis of aqueous sodium hydroxide, NaCl(aq), the two competing
oxidation and reduction reactions involving water are introduced. There are now
two species that c an potentially be reduced at the c athode: sodium ions from the
salt, and water. The two competing reduction reactions are as follows:
⦵
+
Na (aq) + e → Na(s) E = −2.71 V
1 ⦵
−
H O(l) + e → H (g) + OH (aq) E = −0.83 V

2 2
The reduction potential of water is less negative than that of sodium, so water is
more easily reduced than the sodium ions. Therefore, the only product formed
at the c athode will be hydrogen gas, H (g). The sodium ions, Na (aq), and
2
hydroxide ions, OH (aq), will stay in the solution.
616
LHA
The chloride ions from the salt and water also compete to be oxidized at the
anode. The half-equations and standard electrode potentials involving the
oxidation of chloride ions and water are shown below.
1 ⦵
Cl (g) + e → Cl (aq) E = +1.36 V chlorine gas hydrogen gas

2
1 ⦵
+
O (g) + 2H (aq) + 2e → H O(l) E = +1.23 V sodium

2 2
chloride
The equations need to be reversed to reect the oxidation of these species:

solution
1 ⦵
Cl (aq) → Cl (g) + e E = −1.36 V

2
1 ⦵
+
H O(l) → O (g) + 2H (aq) + 2e E = −1.23 V

2 2
The chloride ions have a more negative oxidation potential than water, so we c an
expect water to be oxidized preferentially compared to chloride ions. However,
the dierence between the two oxidation potentials is small, so in solutions with
high concentration of Cl (aq) ions the main product formed at the anode will be
chlorine gas, Cl (g) (gure 23).

2
The overall cell equation is as follows:
1 1
+ +
Na (aq) + Cl (aq) + H O(l) → H (g) + Cl (g) + Na (aq) + OH (aq)

2 2 2
carbon rod carbon rod

2 2 +
as positive as negative
or
electrode ( +) electrode ( )
1 1
NaCl(aq) + H O(l) → H (g) + Cl (g) + NaOH(aq)

2 2 2
pFigure 23 The electrolysis of aqueous

2 2
sodium chloride
Doubling the stoichiometric coecients gives the nal equation:
2NaCl(aq) + 2H O(l) → H (g) + Cl (g) + 2NaOH(aq)

2 2 2
In dilute solutions of NaCl(aq), the concentration of Cl (aq) ions is low, so water
is oxidized along with chloride ions. In that c ase, a mixture of oxygen gas and
chlorine gas is produced at the anode. In very dilute solutions, oxygen gas will be
the only product at the anode.
Worked example 12
Deduce the products of the electrolysis of aqueous copper(II) sulfate,
CuSO (aq), with inert electrodes. Write the overall cell equation.
4
Solution
First, write the half-equations and standard electrode potentials involving the
reduction of copper(II) ions and water.
+ ⦵
2
Cu (aq) + 2e → Cu(s) E = +0.34 V
1 ⦵
H O(l) + e → H (g) + OH (aq) E = −0.83 V

2 2
The reduction potential of copper(II) ions is more positive than that of water,
so copper(II) ions will be reduced to copper metal at the c athode.
The two competing species for oxidation at the anode are sulfate ions, SO
4
(aq), and water. In this c ase, the sulfate ions c annot be oxidized bec ause sulfur
is in its highest oxidation state of +6. Therefore, removing any more electrons
from sulfate would result in an impossible electron conguration for sulfur.
617
LHA
This means that water will be oxidized at the anode and oxygen gas will be
released, with hydrogen ions staying in solution:
1
+
H O(l) → O (g) + 2H (aq) + 2e

2 2
Practice question
2
The overall cell equation is therefore:
10. Deduce the products of
the electrolysis of aqueous + 1

2 2 + 2
Cu (aq) + SO (aq) + H O(l) → Cu(s) + O (g) + 2H (aq) + SO (aq)

4 2 2 4
2
potassium dichromate,
K Cr O (aq), with inert or

2 2 7
electrodes.
1
CuSO (aq) + H O(l) → Cu(s) + O (g) + H SO (aq)

4 2 2 2 4
Doubling the stoichiometric coecients gives the nal equation:
2CuSO (aq) + 2H O(l) → 2Cu(s) + O (g) + 2H SO (aq)

4 2 2 2 4
Electroplating (Reactivity 3.2.16)
The electrolysis of aqueous copper(II) sulfate described in worked example12
uses inert c arbon electrodes (gure 24, le). However, if the electrodes are
made from a reactive metal, the electrolysis of an aqueous solution of an ionic salt
will add material to the c athode and take material away from the anode. These
processes are known as plating and eroding, respectively.
For example, consider an electrolytic cell containing a solution of copper
sulfate, CuSO (aq), with the anode and the c athode each made of copper metal
4
(gure24, right). When the electric current is applied, the copper anode will
+
2
erode to form Cu (aq) ions while the same ions will be reduced at the c athode
to form Cu(s). This process c an be used to purify a sample of impure copper
metal. The impure copper is used as the anode, which will be eroded to produce
+
2
Cu (aq) ions. These ions will then be reduced at the c athode and plated there
as pure copper metal. The impurities will either stay on the anode (if they are less
readily oxidized than copper metal) or remain in the solution (if their ions are less
readily reduced than copper(II) ions).
+ A + A
inert electrodes
copper electrodes
e e
(Pt or graphite)
(+) ( ) (+) ( )
copper deposited
+
2
oxygen evolved Cu + 2e Cu copper deposited
+ +
2
2H + 4e Cu + 2e Cu
2
copper dissolves
+ O
2
+
CuSO (aq) 2 CuSO (aq)
4 + 2e 4
solution loses blue colour solution retains blue colour
pFigure 24 Electrolysis of copper(II) sulfate with inert electrodes Electrolysis using copper electrodes c auses the copper anode to
reduces copper(II) ions at the c athode and oxidizes water, dissolve and copper metal to deposit on the c athode. The amount of
producing oxygen gas at the anode. The blue colour of the solution copper(II) ions in the solution remains constant, so the blue colour of
fades as copper(II) ions are replaced with hydrogen ions. the solution does not fade
618
LHA
Electroplating involves coating an object with a thin layer of pure metal by +
electrolysis. A metal anode is oxidized to form c ations in the solution. The c ations
travel through the solution to the c athode, where they are reduced to form a thin
layer of metal on the c athode.
For example, in an electrochemic al cell comprising a copper anode, a steel
c athode, and copper(II) sulfate solution, the steel c athode will be plated with a
steel ring
copper
thin layer of copper (gure 25).
cathode ( )
anode ( +)
to be plated
with copper
Observations
copper(II) sulfate
solution
Scientists make inferences from their observations. Observation involves use
of the senses. Our knowledge of the behaviour of matter then allows us to infer pFigure 25 In copper electroplating,
copper(II) ions are reduced at the c athode

conclusions from observed data. For example, you can observe gas bubbles
to form a thin layer of Cu(s) on the surface of

being generated at an electrode during electrolysis, and you can infer the
the c athode (in this c ase, a steel ring)

identity of the gas from your knowledge of the composition of the electrolyte.
Similarly, you may observe a brownish-red solid being deposited at the cathode
during the electrolysis of aqueous copper(II) sulfate and, from that, infer that
copper is reduced at that electrode. What “counts” as an observation in science?
Worked example 13
Deduce the half-equations at each electrode in the electroplating of a steel
electrode with copper in a copper(II) sulfate solution, CuSO (aq).

4
Solution
At the anode, copper metal is oxidized to copper(II) ions:
+
2
Cu(s) → Cu (aq) + 2e
At the c athode, the reverse reaction occurs:
+
2
Cu (aq) + 2e → Cu(s)
Practice question
11. A nickel spoon is used in a silver electroplating experiment as shown below.
silver
nickel spoon
to be plated
(cathode)
silver nitrate solution
a. Write the half-equation for the reaction occurring at the:
i. c athode ii. anode.
pFigure 26 The trophy for the top prize
b. Describe and explain what would happen to the concentration of the
at the Berlin International Film Festival, the
silver(I) nitrate electrolyte.
Golden Bear, is made of bronze coated with
c. Describe and explain the mass changes at each of the two electrodes. a thin layer of gold by electroplating
619
7. The following reaction occurs in a voltaic cell.
Topic review
+ 2+
2Ag (aq) + Cu(s) → 2Ag(s) + Cu (aq)

What reaction occurs at each electrode?
C athode Anode
What happens when electrons are transferred?
+ 2+
A. Ag (aq) → Ag(s) + e Cu(s) → Cu (aq) + 2e
+ 2+
Exam-style questions B. Ag (aq) + e → Ag(s) Cu(s) + 2e → Cu (aq)
+ 2+
C. Ag (aq) + e → Ag(s) Cu(s) → Cu (aq) + 2e

2+ +
D. Cu(s) → Cu (aq) + 2e Ag (aq) + e → Ag(s)

2. Which species contains nitrogen with an oxidation state
of +5?
8. Which of the following classes of compound c an be
A. N
reduced?
2
B. N O
I alkene
2
C. NO
II c arboxylic acid
2
D. HNO
III aldehyde
3
A. I and II only
3. Which element is reduced in the following reaction?
B. I and III only

2MnO (aq) + Br (aq) + H O(l) →
4 2
C. II and III only

2MnO (s) + BrO (aq) + 2OH (aq)
2 3
D. I, II and III
A. Mn
B. O
9. Which class of compound is formed when a secondary
C. Br
alcohol is oxidized?
D. H
A. aldehyde
B. ether
4. Which of the following is not a redox reaction?
C. ketone
A. 2H O → 2H O + O
2 2 2 2
D. c arboxylic acid
B. CH COOH + LiOH → CH COOLi + H O
3 3 2
C. C H + Br → C H Br
10. Hydrogen c an be added to ethene to produce ethane.
3 6 2 3 6 2
D. Na + Cl → 2NaCl
C H (g) + H (g) → C H (g)
2
2 4 2 2 6
Which of the following is correct for this reaction?

5. Which pair reacts most vigorously?
A. Li and Br
2
Degree of Species that undergoes
B. Li and F unsaturation reduction

2
C. K and Br
A. increases ethene
2
D. K and F
2 B. decreases ethene
6. What are the products of the electrolysis of molten C. increases hydrogen
lead(II) bromide, PbBr ?

2 D. decreases hydrogen
LHA
C athode product Anode product

11. Consider the standard reduction potentials:
2+ ⦵
Cd (aq) + 2e ⇌ Cd(s) E = –0.40 V

A. lead bromine
3+ ⦵
Cr (aq) + 3e ⇌ Cr(s) E = –0.74 V

B. lead bromide
Which is the strongest oxidizing agent?
C. lead(II) bromine
2+
A. Cd
D. lead(II) bromide
3+
B. Cr
C. Cd
D. Cr
620
LHA
12. What are the major products of the electrolysis of 16. a. Write an equation for the complete combustion
concentrated sodium chloride solution, NaCl(aq)? of ethanol. [1]
b. i. Deduce the oxidation state of c arbon in

Negative electrode Positive electrode
c arbon dioxide. [1]
O
A. Na
2
ii. Deduce the mean oxidation state of c arbon
H O
B.
2 2
in ethanol. [1]
Cl
C. Na
2
iii. State and explain, with reference to oxidation
H Cl
D. states, whether c arbon is oxidized or reduced
2 2
when ethanol undergoes complete
Extended-response questions combustion. [1]
2– c. Ethanol c an also be oxidized when reacted with

13. The reaction between ethanedioate ions, C O and
2 4
acidied potassium dichromate(VI).

manganate(VII) ions, MnO , in acidic solution is a redox
4
i. Draw the structural formulas and state the names

reaction. The incomplete equation for this reaction is
of the two possible organic products of this

shown below:
2– 2+ reaction. [2]
C O + MnO → CO + Mn
2 4 4 2
ii. State the methods used to isolate each of the

a. Deduce the oxidation state of c arbon in the
2– substances in your answer above. [1]

ethanedioate ion, C O . [1]
2 4
b. The oxidation half-equation is:

17. A student c arries out the following reactions between
2–
C O (aq) → 2CO (g) + 2e

three unknown metals (X, Y and Z) and several dilute
2 4 2
Deduce the reduction half-equation, solutions. The following results were obtained:
including state symbols. [2]
Reactants Observations
c. Deduce the full redox reaction. [1]
Y + Z(NO ) (aq) Y is a shiny grey metal. Z(NO ) (aq) is

3 2 3 2
14. Sodium chloride is found in table salt. a clear blue solution. When reacted
together, a red-brown solid appeared

a. Describe how bonding occurs in sodium
on the surface of the metal. O ver

chloride. [2]
time, the solution’s blue colour faded.
b. Explain why sodium chloride is not an electric al
X + Y(NO ) (aq) No reaction

conductor when solid but c an conduct electricity
3 2
when molten. [1]

Z + X(NO ) (aq) No reaction
3 2
c. Molten sodium chloride c an be electrolysed.

Z + HCl(aq) No reaction
Identify the half-equation for the reaction that takes
a. List metals X, Y and Z, in order of increasing
place at the
reactivity. [1]
i. c athode [1]
b. Suggest, with reference to two observations,
ii. anode. [1]

which metal, X, Y or Z, could be copper. [2]
LHA
d. Deduce the half-equation for the oxidation reaction

c. A standard nickel–copper voltaic cell is set up.
that takes place when dilute aqueous sodium
i. Draw the cell diagram for this voltaic cell and
chloride is electrolysed. [1]
label the following:
e. A student prepares a concentrated sodium
- ions in each solution
chloride solution and adds a few drops of
- c athode
phenolphthalein. The student then electrolyses the
- anode
solution. Describe two observations made by the
- direction of travel of electrons in the external
student during the electrolysis. [2]
circuit
15. a. Li + e → Li(s) is a reaction occurring at one of the

- direction of travel of c ations in the salt
electrodes in a lithium-ion battery. State at which

bridge. [2]
electrode (anode/c athode) this reaction occurs

ii. Deduce the equation, including state symbols,
and whether this is the charging or discharging

for the spontaneous redox reaction that occurs
reaction. [2]
in this cell. [2]
b. Identify the reaction at the opposite electrode. [1]

LHA
d. C alculate the standard cell potential, in V, for the
c. Explain why lithium-ion batteries must be sealed. [1]

redox reaction. Refer to section 19 of the data
booklet. [1]
621
Reactivity 3.3 Electron sharing reactions
What happens when a species possesses an unpaired electron?
When an atom or polyatomic species has an unpaired electron, it is c alled a radic al. When a covalent bond between two
atoms breaks through the process of homolytic ssion, the two electrons involved in the bond move onto the separate
atoms. The radic als are highly reactive and c an combine with other radic als to form more stable covalent molecules.
Understandings
Reactivity 3.3.1 — A radic al is a molecular entity that has Reactivity 3.2.3 — R adic als take part in substitution
an unpaired electron. R adic als are highly reactive. reactions with alkanes, producing a mixture of products.
Reactivity 3.3.2 — R adic als are produced by homolytic
ssion, e.g. of halogens, in the presence of ultraviolet (UV)
light or heat.
Introduction to radic als (Reactivity 3.3.1)
Organic reaction mechanisms are detailed descriptions of the conversion of
reactants to products. These mechanisms are a means of explaining which bonds
are broken and formed, and how electrons move over the course of the reaction.
One type of chemic al species involved in such mechanisms are radic als.
A radic al is a chemic al entity that has an unpaired electron. R adic als are dierent
from charged species (such as ions) in that a radic al c an exist independently
of any other species. In contrast, c ations and anions will always have a
corresponding counter-ion. A radic al species is indic ated by a dot (•). There are
two common types of radic al:
• a single atom, such as a halogen radical, for example the chlorine radical, Cl•
• a polyatomic species, for example the methyl radic al, •CH , and the hydroxyl
3
radic al, •OH.
When the radic al consists of several atoms, the dot in the chemic al formula is
placed next to the atom with the unpaired electron. For example, in the methyl
radic al, the dot is placed next to c arbon, as c arbon has the unpaired electron:
C H
Due to their high reactivity, radic als are usually formed as intermediates in a
reaction, that is, they are not the ultimate reaction products. Two radic als c an
react with each other to form a new covalently bonded compound with no
unpaired electrons. This process is known as termination. However, radic al
species c an also react with non-radic al species to create further radic al species.
This process is known as propagation.
622
Reactivity 3.3 Electron sharing reactions
Hypotheses
Scientists make provisional explanations for the patterns they observe. A
universal observation that has puzzled humans for a long time is ageing. All
living things deteriorate physic ally over time. The free radic al hypothesis of
ageing (also known as the free radic al theory of ageing) was proposed in the
mid-20th century and has been widely accepted. R adic als are produced in
mitochondria (gure 1) as a by-product of metabolic processes.
0.5 μm
pFigure 1 The structure of a mitochondrion
The gradual accumulation of these radic al species over time is associated
with the oxidation of DNA, proteins and other biomolecules. The free radic al
hypothesis suggests that ageing is c aused by the “oxidative stress” that arises
from the build-up of radic als. Correlations have been observed between age,
mitochondrial radic al production and oxidative damage.
However, critics of this hypothesis challenge the c ausality of the relationship.
The free radic al hypothesis of ageing is therefore an area of ongoing research.
What other aspects of nature of science are hypotheses connected to?
Formation of radic als (Reactivity 3.3.2)
Curly arrows are used to illustrate the movement of electrons in reaction
mechanisms, as bonds are broken and made. A double-barbed arrow shows the
movement of a pair of electrons (gure 2).
pFigure 2 The double-barbed arrow represents the movement of an electron pair
A single-barbed, or sh hook, arrow is used to show the movement of a single
electron (gure 3).
pFigure 3 The sh hook arrow represents the movement of a single electron
623
When you draw mechanisms using curly arrows, pay attention to the following:
• The base of the arrow must start at the origin of the moving electrons.
• The arrowhead must nish at the exact destination of the electrons.
• The arrow starts at an electron-rich region and ends at an electron-poor
region of the molecule or other species.
Fish hook arrows are commonly used in the reactions involving radic als. A radic al
is formed when a molecule undergoes homolytic ssion. The two electrons of a
covalent bond are split evenly between two atoms resulting in two radic als that
each have a single electron. Halogen radic als are formed this way, where the
halogen bond in a diatomic halogen molecule is broken homolytic ally.
+ Cl
pFigure 4 Homolytic ssion of chlorine, Cl

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(https://alum.mit.edu/www/toms/images/boltzmann); p443(b):M ariyana M/

Gary Horner: To my friends and colleagues for their support throughout my

Shutterstock; p452:SCIENCE PHOTO LIBRARY; p453:Reprinted (adapted) with

Society;p460:Richard Liu; p468:sciencephotos / Alamy Stock Photo; p470(l):Heritage

Image Partnership Ltd / Alamy Stock Photo; p470(r):The Granger Collection

their loving memory.

/ Alamy Stock Photo; p477(l):MAXIMILIAN STOCK LTD / SCIENCE PHOTO

Elisa Jimenez Grant: To Miljan.

PHOTO LIBRARY; p497:Kenneth Brown / EyeEm; p499:dpa picture alliance / Alamy

Stock Photo; p509:bluesnote/Shutterstock; p513:CHARLES D. WINTERS / SCIENCE

PHOTO LIBRARY; p538:CHARLES D. WINTERS / SCIENCE PHOTO LIBRARY; p543:SCI-

ENCE PHOTO LIBRARY; p553:ANDREW LAMBERT PHOTOGRAPHY / SCIENCE PHOTO

Cendrella Kettaneh, Astha Acharya, Natalie Parker, Chandan Bhosale, Deepa

LAMBERT PHOTOGRAPHY / SCIENCE PHOTO LIBRARY; p581:Judy Kennamer/

Shutterstock; p583:MARTYN F. CHILLMAID / SCIENCE PHOTO LIBRARY; p591:MARTYN

LIBRARY;p599:Dorling Kindersley/Getty Images; p608(l):© Corbis; p608(r): ggw/

Photo;p637:ANDREW LAMBERT PHOTOGRAPHY / SCIENCE PHOTO LIBRARY.

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