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CHEMISTRY
CORE CONCEPTS
SECOND EDITION

BLACKMAN
SOUTHAM
LAWRIE
WILLIAMSON
THOMPSON
BRIDGEMAN
 Dipolar forces 374
Hydrogen bonds 377
Binary hydrogen compounds 380
7.3 Gases 383
Pressure (p) 383
The gas laws 385
The ideal gas equation 387
Determination of molar mass 392
Determination of gas density 395
7.4 Gas mixtures 399
Dalton’s law of partial pressures 400
Describing gas mixtures 401
7.5 Gas stoichiometry 405
Summary of mole conversions 410
7.6 Liquids 414
Properties of liquids 414
Vapour pressure 415
7.7 Solids 417
Magnitudes of forces 417
Molecular solids 418
Network solids 420
Metallic solids 422
Ionic solids 424
Amorphous solids 425
7.8 Phase changes 426
Supercritical fluids 430
Phase diagrams 430
Summary 443
Key concepts and equations 446
Key terms 446
Review problems 448
Acknowledgements 451
CHAPTER 8
Chemical thermodynamics
Chemical enquiry 453
8.1 Introduction to chemical thermodynamics 453
Heat and temperature 455
System, surroundings and universe 456
Units 456
ΔX: the change in X 457
8.2 The first law of thermodynamics 457
Heat capacity 460
The determination of heat 463
8.3 Enthalpy 466
Standard enthalpy change 469
Hess’s law 472
Standard enthalpy of formation 474
Standard enthalpy of combustion 479
vi CONTENTS
Bond enthalpies 481
8.4 Entropy 488
Entropy and probability 488
Entropy and entropy change 490
Factors that affect entropy 490
8.5 Gibbs energy and reaction spontaneity 495
The sign of ΔG 497
Summary 502
Key concepts and equations 504
Key terms 505
Review problems 506
Acknowledgements 513
CHAPTER 9
Chemical equilibria 514
Chemical enquiry 515
9.1 Chemical equilibrium 515
9.2 The equilibrium constant, K, and the reaction
quotient, Q 517
Reactions at equilibrium 517
Reactions not at equilibrium 522
Equilibria involving gases 524
The relationship between Kp and Kc 525
Manipulating equilibrium constant
expressions 528
The magnitude of the equilibrium constant 531
Equilibrium constant expressions for
heterogeneous systems 533
9.3 Equilibrium and Gibbs energy 536
The relationship between Δr G−o and K 536
9.4 How systems at equilibrium respond to
change 540
Le Châtelier’s principle 540
Adding or removing a product or reactant 541
452 Changing the pressure in gaseous reactions 544
Changing the temperature of a reaction
mixture 546
Addition of a catalyst 547
9.5 Equilibrium calculations 551
Calculating Kc from equilibrium
concentrations 551
Calculating equilibrium concentrations from initial
concentrations 556
Summary 570
Key concepts and equations 572
Key terms 573
Review problems 574
Acknowledgements 580
 CHAPTER 10 Summary 677
Key concepts and equations 679
Solutions and solubility 581 Key terms 680
Chemical enquiry 582 Review problems 681
10.1 Introduction to solutions and solubility 583 Acknowledgements 684
10.2 Gaseous solutions 586
10.3 Liquid solutions 587 CHAPTER 12
Gas–liquid solutions 587
Liquid–liquid solutions 592 Oxidation and reduction 685
Liquid–solid solutions 594 Chemical enquiry 686
10.4 Quantification of solubility: the solubility 12.1 Oxidation and reduction 687
product 597 Oxidation numbers 689
The relationship between Ksp and solubility 601 12.2 Balancing net ionic equations for
The common ion effect 604 redox reactions 698
10.5 Colligative properties of solutions 606 Redox reactions in acidic and basic solutions 699
Expressing the concentration of a solution 607 12.3 Galvanic cells 705
Quantifying colligative properties 608 Setting up a galvanic cell 708
Summary 615 Processes in galvanic cells 708
Key concepts and equations 616 12.4 Reduction potentials 714
Key terms 617 Cell and standard cell potentials 714
Review problems 618 Reduction and standard reduction potentials 714
Acknowledgements 620 Spontaneous and nonspontaneous reactions 718
12.5 Corrosion 720
CHAPTER 11 12.6 Electrolysis 724
What is electrolysis? 724
Acids and bases 621 Comparison of electrolytic and galvanic cells 725
Chemical enquiry 622 Electrolysis in aqueous solutions 725
11.1 The Brønsted–Lowry definition of acids and 12.7 Batteries 727
bases 623 The lead storage battery 728
Conjugate acid–base pairs 626 Dry cell batteries 730
11.2 Acid–base reactions in water 632 Modern high-performance batteries 732
The autoprotolysis of water 633 Fuel cells 734
The concept of pH 634 Summary 737
The strength of acids and bases 639 Key concepts and equations 738
11.3 Strong acids and bases 643 Key terms 739
pH calculations in solutions of strong acids and Review problems 741
bases 644 Acknowledgements 746
11.4 Weak acids and bases 646
pH calculations in solutions of weak acids 650 CHAPTER 13
11.5 The molecular basis of acid strength 659
Binary acids 659 Reaction kinetics 747
Inductive effects 659 Chemical enquiry 748
11.6 Buffer solutions 661 13.1 Reaction rates 749
pH calculations in buffer solutions 662 13.2 Factors that affect reaction rates 756
11.7 Acid–base titrations 668 Chemical nature of the reactants 756
Strong acid – strong base and strong base – strong Physical nature of the reactants 756
acid titrations 669 Concentrations of the reactants 757
Weak acid – strong base and weak base – strong Temperature of the system 758
acid titrations 672 Presence of catalysts 758
Acid–base indicators 673 13.3 Overview of rate laws 759

CONTENTS vii
 First-order rate laws 762 15.2 Alcohols 907
Second-order rate laws 765 Physical properties 912
Zero-order rate laws 767 Preparation of alcohols 914
13.4 Temperature dependence of chemical 15.3 Reactions of alcohols 917
reactions 769 Acidity of alcohols 917
13.5 Reaction mechanisms and catalysis 774 Basicity of alcohols 918
Catalysts 776 Reaction with active metals 918
Enzyme kinetics 776 Conversion to haloalkanes 919
Summary 782 Acid-catalysed dehydration to alkenes 920
Key concepts and equations 783 Oxidation of primary and secondary alcohols 924
Key terms 784 Ester formation 927
Review problems 785 15.4 Amines 929
Acknowledgements 788 Physical properties 934
Preparation of amines 935
CHAPTER 14 15.5 Reactions of amines 938
Basicity of amines 938
Organic chemistry 1 789 Reaction with acids 943
Chemical enquiry 790 Amide formation 946
14.1 Introduction to hydrocarbons 791 15.6 Carboxylic acids and derivatives 948
14.2 Alkanes 792 Carboxylic acids 948
Conformation of alkanes 795 Acid halides 949
Cycloalkanes 798 Acid anhydrides 949
Conformations of cycloalkanes 800 Esters of carboxylic acids 950
Physical properties of alkanes 809 Amides of carboxylic acids 950
14.3 Alkenes and alkynes 817 15.7 Nomenclature of carboxylic acids and
Shapes of alkenes and alkynes 818 derivatives 951
Nomenclature of alkenes and alkynes 822 Carboxylic acids 952
Physical properties of alkenes and alkynes 841 Acid halides 956
14.4 Reactions of alkanes 844 Acid anhydrides 956
14.5 Reactions of alkenes 847 Esters and lactones 956
Electrophilic addition reactions 848 Amides and lactams 956
14.6 Aromatic compounds 867 Summary 962
The structure of benzene 867 Key concepts and equations 964
Summary 874 Key terms 966
Key concepts and equations 875 Review problems 967
Key terms 876 Acknowledgements 980
Review problems 878
Acknowledgements 884 CHAPTER 16

CHAPTER 15 Biochemistry 981

Chemical enquiry 982
Organic chemistry 2 885 16.1 Carbohydrates 983
Chemical enquiry 886 Monosaccharides 983
15.1 Chirality 887 The cyclic structure of monosaccharides 988
Stereoisomers 887 Disaccharides and oligosaccharides 992
Enantiomerism 891 Polysaccharides 996
Naming stereocentres 900 16.2 Lipids and triglycerides 1000
Molecules with more than one stereocentre 901 Fatty acids 1001
Molecules with two stereocentres 901 Physical properties of triglycerides 1003
Chirality in the biological world 904 Soaps and detergents 1004

viii CONTENTS
16.3 Amino acids 1007 Tertiary structure: supercoiled DNA 1036
Chirality 1008 DNA replication 1037
Protein-derived amino acids 1008 Ribonucleic acid (RNA) 1038
Acid–base properties of amino acids 1011 Ribosomal RNA 1039
16.4 Peptides, polypeptides and proteins 1014 Transfer RNA 1039
The structure of polypeptides and Messenger RNA 1039
proteins 1016 Summary 1044
Protein structure 1017 Key concepts and equations 1046
Enzymes 1023 Key terms 1047
Denaturing proteins 1026 Review problems 1050
16.5 Nucleosides and nucleotides 1028 Acknowledgements 1057
16.6 The chemistry of DNA 1032
Primary structure: the covalent backbone 1032 Appendices 1058
Secondary structure: the double helix 1032 Index 1080

CONTENTS ix
ABOUT THE AUTHORS
Allan Blackman
Allan Blackman is a Professor at the Auckland University of Technology in Auckland, New Zealand.
He obtained his BSc(Hons) and PhD degrees from the University of Otago, New Zealand. He has taught
all levels of undergraduate chemistry, in the areas of inorganic and physical chemistry, for over 24 years.
Allan’s research interests lie mainly in the field of coordination chemistry, where he studies the synthesis,
structure and reactivity of coordination complexes. He has spent research periods in the US (Indiana
University, the University of Minnesota), Australia (the University of Queensland) and France (Universite
Joseph Fourier, Grenoble), and has also given numerous undergraduate lectures at the National University
of Defense Technology, Changsha, China, where he has been appointed a Guest Professor. Allan regularly
appears on TV as a science commentator, and published a monthly newspaper column concerning all
things chemical. Outside science, his interests include music and sport.
Daniel Southam
Dr Daniel Southam is a Senior Lecturer in chemistry at Curtin University and a Fellow of the Royal Aus-
tralian Chemical Institute. He completed his bachelor and PhD degrees in chemistry at the University of
Tasmania, where a passion for chemistry education was sparked. He is the recipient of a number of teach-
ing awards, including the 2014 RACI Chemistry Educator of the Year, and 2017 Australian Awards for
University Teaching Citation for Outstanding Contributions to Student Learning. Daniel teaches across
the chemistry undergraduate curriculum, with a focus on inorganic chemistry. Daniel is a passionate advo-
cate of active learning, and crafts engaging social environments to support student success. His broad
aim is to improve students’ perceptions of their ability to learn chemistry and to develop capacity for real
change in the depth of their understanding and enjoyment of science. Daniel has an interest in the dynamic
relationship between chemistry education research and its application to practice, especially in founda-
tion chemistry classes. To achieve these aims his research explores issues of educational measurement in
different sociocultural contexts, and in inter-disciplines such as forensic science and nanotechnology.
Gwen Lawrie
Gwen Lawrie is an Associate Professor in the School of Chemistry and Molecular Biosciences (SCMB)
at the University of Queensland (UQ) and was the Director, First Year Chemistry (Curriculum & Assess-
ment) between 2012–18. She gained a BSc Applied Chemistry (Hons) from Sheffield Hallam University
(UK) in 1986, a PhD from Cranfield University (UK) in 1990 and a GDipEd (Secondary) from UQ in
2006. Gwen is both a Fellow of the Royal Australian Chemical Institute and a Senior Fellow of the Higher
Education Academy. Gwen teaches introductory chemistry, first-year general chemistry, physical chem-
istry and nanoscience and has received multiple teaching excellence awards including the 2017 RACI
Chemistry Education Division Medal, a 2013 Australian Award for University Teaching and the 2013
Pearson RACI Chemical Educator of the Year Award. Gwen’s research in chemistry education explores
strategies to address student diversity and engagement in very large classes through collaborative inquiry
tasks, blended learning and mechanisms for the provision of formative feedback to support self-regulated
learning. Gwen has published her research in international education journals and multiple book chapters.
Natalie Williamson
Dr Natalie Williamson is an Associate Professor and the First Year Director (chemistry) at the University
of Adelaide. She teaches at all undergraduate year levels, with a particular interest in synthetic organic
chemistry. Natalie enjoys helping students get to that ‘lightbulb’ moment through their own endeavours,
using a mixture of interactive classroom activities, humour and immediate feedback to engage students
in the learning process. She has won a number of teaching awards, including Australian Learning and
Teaching Council/Office for Learning and Teaching Citations for Outstanding Contributions to Student

x ABOUT THE AUTHORS

Learning (2010 and 2016) and the University of Adelaide Stephen Cole the Elder Award for Excellence
in Teaching (2014). Natalie was also named the Early Career STEM Tertiary Educator of the Year at the
2013 South Australian Science Excellence Awards and the Royal Australian Chemical Institute Chemistry
Educator of the Year in 2015.
Chris Thompson
Dr Chris Thompson is a Senior Lecturer from the School of Chemistry at Monash University, and holds
degrees from the Australian National University and Monash University. Chris has over 50 research
papers to his name, across the fields of spectroscopy, computational chemistry and chemistry education.
He is the Chair of the Victoria RACI Chemistry Education Group, and regular VCE exam author and
vetter. He is also heavily engaged with secondary school outreach, with Monash’s School of Chemistry
hosting over 2000 primary and secondary science students annually. His particular interest is in active
learning in university classrooms, and he is specifically passionate about enabling students to harness
their imagination to visualise chemistry.
Adam Bridgeman
Dr Adam Bridgeman is Director of Educational Innovation in the Deputy Vice Chancellor (Education)
Portfolio and an Honorary Professor of chemistry in the School of Chemistry at the University of Sydney.
He completed his first degree at St Catherine’s College (University of Oxford) and his PhD in theoretical
inorganic chemistry at Trinity Hall (University of Cambridge). After positions at the universities of Cam-
bridge and Hull, he moved to the University of Sydney as Director of First Year Studies in Chemistry.
After being Associate Dean for Learning and Teaching for the Faculty of Science at Sydney, he moved to
his present position in the Educational Portfolio where he leads pedagogical innovation across the cam-
pus. He has received a variety of institutional and national teaching awards in the United Kingdom and in
Australia for his work on electronic resources and personalised education, and support in chemistry and
science. He is currently an Australian National Learning and Teaching Fellow. As a devoted teacher, he
strives to actively engage students in class and online. Alongside his interests in enhancing education and
the student experience, he uses computational approaches to solve chemical problems such as the design
of nanomaterials for applications in medicine.
Lightboard contributors
Throughout the VitalSource digital text there are numerous worked solutions by leading chemistry educa-
tors. These are presented as lightboard videos that help bring to the fore some of the topics that students
can struggle with the most. We thank the following contributors for volunteering time out of their busy
teaching and researching schedules to spend days in the studio, bringing these concepts to life.
r Uta Wille
r Christopher Thompson
r Gwen Lawrie
r Sonia Horvat

ABOUT THE AUTHORS xi

CHAPTER 1

The nature of matter

LEARNING OBJECTIVES

After studying this chapter, you should be able to:

1.1 describe the importance of chemistry across a diverse range of fields
1.2 define atoms, molecules, ions, elements and compounds
1.3 describe the scientific evidence that the atom is the fundamental building block of all matter
1.4 describe the structure of the atom
1.5 explain how the periodic table organises elements into blocks, groups and periods.
Chemical enquiry
Have you ever looked around and wondered ‘why’ or ‘how’? Is there something fascinating that gets
you questioning, hypothesising or even experimenting? The beauty of our human nature is our drive to
observe the natural world, to analyse what our senses tell us, to recognise patterns and to predict the
outcomes of future observations and experiments. We call this enquiry.
It is the ability of our minds to learn through observation, inference and prediction that underpins
science as an inherently creative practice, and it is this innate ability that will enable you to build your
knowledge of chemistry as a core natural science.

Chemistry is often called the study of matter, but what is matter and why is an understanding of matter
so fundamental to every discipline of science? Matter can be thought of as anything that has mass and
volume. This means the entire natural world can be thought of as matter, and chemistry as the study of the
natural world. In chemistry, we often begin with the fundamental building blocks of matter — atoms —
and study the interactions between them.
When we define matter, we often think of its properties in physical terms at a human scale (mass,
volume, colour and so on), in chemical terms at an atomic scale (bonds between atoms and forces between
species), and the link between the two. This chapter establishes a chemist’s definition of matter and
introduces the atom as our fundamental building block. We will then build on this language and definition
in detail during later chapters.
Just as a chemist starts from the smallest building block — the atom — we hope you will learn by
discovering your own building blocks of knowledge and finding the connections between them. To help
you make links between ideas, each chapter in this text will start with a chemical enquiry feature. As we
move through each chapter, you will see the same concepts revisited again and again. These connections
will help you learn and will motivate you in your chemistry studies.
But first, we should be asking the question: why study chemistry?

2 Chemistry core concepts

1.1 Why study chemistry?
LEARNING OBJECTIVE 1.1 Describe the importance of chemistry across a diverse range of fields.
It is likely that you are reading these words because you have enrolled in a first-year chemistry unit
at university. You may be wondering why you are here and how chemistry is relevant to your chosen
degree, your future career or your everyday life. You may not have studied chemistry at university or
school before. Or it may have been a while since you have encountered chemistry. For some, this will
be review; for others this will be completely new. Have a talk with the other people studying in your
chemistry unit and you will discover that your fellow students come from many different backgrounds
and are pursuing a wide variety of degrees. This diversity is a strength of chemistry and can offer you
many different perspectives on learning. Let’s attempt to uncover just some of what might motivate you,
and the students around you, to study chemistry.

Your degree
Chemistry is often seen as a science that connects everything, and so you may find yourself studying
chemistry without the intention of becoming a chemist. In the not-too-distant past, chemistry was viewed
as a narrowly defined science carried out by men in white coats who inhabited labs filled with flasks
containing all kinds of chemicals, some of them hazardous and used without precaution. Thankfully, this
is no longer the case. Nowadays, the scope of the study and practice of chemistry has expanded, and it
is relevant and accessible to anyone with an interest in, and passion for, science.
Indeed, chemistry now overlaps with many other sciences to the point where the margins between
the different disciplines have become significantly blurred. This is shown by the following observations
concerning the most prestigious award in science, the Nobel Prize. Over the period 2000–2017, many
Nobel Prizes in chemistry were awarded jointly to scientists with degrees in medicine, biological

CHAPTER 1 The nature of matter 3

sciences, engineering and physics. The prizes were awarded for discoveries, insights and innovations as
diverse as:
r how water and other small molecules can pass through the walls of cells
r the mechanisms for protein degradation and DNA repair in cells
r the structure and function of the ribosome
r the discovery and development of a protein in jellyfish that glows green
r the development of methods to determine the structure of large molecules
r the design and synthesis of molecular-scale machines
r the imaging of biochemicals at the atomic level.

Many of these subjects would usually be thought of as the domain of other areas of science and engi-
neering, but their basis is undeniably founded in chemistry. Herein lies the reason that chemistry is a
fundamental part of a large number of degrees at university, especially at an introductory level. The
majority of degrees in science and engineering have some chemistry component because chemistry plays
some role in these disciplines — indeed, you will find chemical names, chemical formulae and chemical
diagrams in almost all science and engineering texts.

Your career
It may be that you’re studying chemistry because you aim to obtain a chemistry degree and become a
chemist. Learning to think as a chemist is a valuable skill in any career, so understanding how chemists
work is valuable even if you’re not planning on being a chemist yourself. Chemists are interested in
many different aspects of matter. Some chemists are primarily concerned with chemical synthesis —
the preparation of new types of matter that have not previously existed. Examples include new drugs
for the treatment of disease; new strong, lightweight materials for use in constructing everything from
yachts to skyscrapers; and plastics that can conduct electricity or emit light. Other chemists are primarily

4 Chemistry core concepts

interested in measuring the properties and amounts of matter; for example, how much heat a particular
material can hold or how much carbon dioxide is in the atmosphere. A growing number of chemists never
even venture into the chemical laboratory, preferring to use computers to predict, with great accuracy,
properties of matter that has yet to be made. These three facets of chemistry — to synthesise, to analyse
and to simulate matter — make chemistry an inherently productive science and mean that chemistry is
an expanding subject.
Health sciences
If you are training for a career in the health sciences, knowledge of chemistry is crucial — we are, after all,
made up of atoms. The human body plays host to a dizzying array of chemical reactions, all of which play
a particular role in a quality that we call ‘life’. We are able to see thanks in part to a molecule called retinal
(see figure 1.1), which undergoes a chemical reaction when it is exposed to light. We maintain a body
temperature of approximately 37 ◦ C primarily due to a molecule called adenosine triphosphate, which
undergoes a chemical reaction in the body that releases energy. Our nerves function as they do because of
the very delicate balance of sodium and potassium ions in the body. Current medical research is not just
about better surgical techniques; it aims to find cures for diseases such as cancer, ALS/MND, HIV/AIDS,
Ebola and Alzheimer’s through an understanding of the molecular basis of such diseases. Health sciences
students must learn about the myriad of processes that enable the human body to function, and appreciate
the role that chemistry plays in many of them.

FIGURE 1.1 Retinal is used by the body to assist us to see. It is one of the many molecules that helps our body to
function.

all–trans-retinal

Biochemistry
Biochemistry and genetics are mainly concerned with huge molecules such as DNA, RNA and proteins.
The importance of chemistry in these disciplines is self-evident. To understand how these molecules
function, biochemists and geneticists need knowledge of chemical principles such as acid–base chem-
istry, electrochemistry, intermolecular forces and molecular recognition, as well as an appreciation of the
fundamentals of methods used for structural determination of these molecules.
Biochemical applications in forensic science, most notably DNA fingerprinting, have significant chem-
istry components; samples must be kept scrupulously clean to avoid contamination, and highly pure
reagents and stringently controlled techniques must be used to obtain usable evidence. People’s lives
depend on the skill and understanding of the person carrying out these analyses.
Public health
Of current interest in the area of public health is the question of fluoridation of water supplies to reduce
the incidence of tooth decay, particularly in young children. What are the risks and what are the benefits?
What is the role of fluoride in reducing tooth decay? What form of fluoride is added to city water supplies?

CHAPTER 1 The nature of matter 5

Scientists who work in the areas of public health and health promotion need to have an understanding of
this issue, and this understanding is underpinned by a fundamental knowledge of chemistry.
Environmental science
The chemistry of the environment continues to increase in importance as we grow to appreciate the
significant impacts that humans are having on the Earth. Recognition and confirmation of the damaging
consequences of increasing amounts of greenhouse gases in the atmosphere, for example, are due to
careful and painstaking measurements by scientists all around the globe. Because of this, we now use
terms such as ‘carbon footprint’ and ‘food miles’, which were unheard of only two decades ago. Likewise,
chlorofluorocarbons (CFCs) have now been all but banned because of their capacity to destroy the ozone
layer, a fact recognised as a result of experiments in the chemistry laboratory. It is because of this work
that the ozone hole in the vicinity of Australia and New Zealand has slowed its growth and is showing
some signs of recovery.
It is certain that we will run out of accessible fossil fuels at some stage, possibly in your lifetime; what
we ultimately need is not more efficient use of this dwindling resource but an entirely new source of
energy. Both Australia and New Zealand are perfectly situated to exploit solar power. Chemists are at the
forefront of research in this area and are developing new materials that can cleanly and efficiently convert
sunlight to electricity (figure 1.2). Again, those of you studying environmental science or ecology will
learn about these subjects and the chemistry behind them.

FIGURE 1.2 Scientist examining a silicon wafer. Chemists are researching new materials to effectively harness
energy from the sun.

Law
Chemistry also crops up in quite unexpected places — law, for example. Scientific discoveries with any
commercial potential are usually immediately patented, and this process is carried out by patent attorneys.
Given that many of the most valuable patents concern drugs, it is obviously vital that the patent attorneys
involved have an appreciation of chemistry, and graduates who trained in both patent law and chemistry
are currently in great demand. Similarly, an understanding of both chemistry and commerce is a major
advantage in manufacturing industries, and a significant number of commerce students now opt to include
some science units in their degrees.

6 Chemistry core concepts

Your everyday life
Look around you and think ‘What roles have chemistry and chemists played in advances in humanity?’,
‘What part might you play in exploring and extending these advances?’ And how might chemistry help
you achieve this? Whether you are studying chemistry out of interest, because you need to be informed
by chemistry in your future career, or you have a passion to study chemistry further, this text will guide
you through this amazing field of study. We sincerely hope you find it a useful resource, feel inspired as
you explore the world of chemistry, and appreciate the relevance to your studies, career and life.
Let’s begin.

REVIEW QUESTIONS

1.1 Consider the Nobel Prizes awarded for chemistry to date by searching the web and reading the
titles of the awards. What other sciences have played a role in these discoveries?
1.2 Think of the molecule retinal, found in your eye. Explain which chemical process — synthesis, ana-
lysis, or simulation — is being used when:
(a) a biologist develops a computer model to recognise the synaptic process of sight at a cellular
level.
(b) an ophthalmologist receives a result giving the quantity of retinal found in human tissue.
(c) a biochemist develops a catalyst that produces retinal from beta-Carotene.
1.3 What role does:
(a) chemistry play in your chosen career?
(b) your discipline have in shaping chemistry?

LEARNING CHECK

Can you:
 define
– synthesis
– analysis
– simulation
 describe the importance of chemistry across a diverse range of fields
 explain the relevance of chemistry to your chosen course?

1.2 Introduction to matter

LEARNING OBJECTIVE 1.2 Define atoms, molecules, ions, elements and compounds.
Chemistry is the study of matter. Matter is composed of various chemical entities. Before we embark
on our study of chemistry, we will define some terms used to describe these entities. This will aid our
understanding of the material in this chapter. It is important that we carefully define these terms, as they
have specific meanings to a chemist and are important in communicating our understanding of the atomic-
scale world. We will look at these concepts again, in greater detail, in subsequent chapters. To illustrate
these definitions we will use one of the most fundamental chemical building blocks of human life: water.
As you read the following, refer to figure 1.3, which describes the chemical species that come together
to make water.
Atoms are discrete chemical species comprising a central positively charged nucleus surrounded by
one or more negatively charged electrons. Atoms are always electrically neutral because the number of
electrons is equal to the number of positively charged protons in the nucleus. Elements are collections of
one type of atom only. Figure 1.3a presents atoms of the elements hydrogen, H, and oxygen, O. At the
time of writing, 118 elements are known.

CHAPTER 1 The nature of matter 7

 FIGURE 1.3 Definitions of chemical species. The representations of the atom-level components of water illustrate
how the differing connections at this level dictate the words we use to describe them. The white
spheres represent hydrogen atoms. The red spheres represent oxygen atoms. When these spheres
are touching, this represents a chemical bond.

chemical species

elements compounds

atoms molecules molecules ions

hydrogen, H hydrogen, H2 hydronium cation, H3O+

water, H2O

oxygen, O oxygen, O2 hydroxide anion, OH−

(a) (b) (c) (d)

Chemists regard the atom as the fundamental building block of all matter, so it may surprise you to
learn that individual atoms are rarely of chemical interest. Free atoms (with the exception of the elements
helium, neon, argon, krypton, xenon and radon) are usually unstable or highly reactive. Of much greater
interest are molecules, which are collections of atoms with a definite structure held together by chemical
bonds. The smallest molecules contain just two atoms, while the largest can consist of literally millions.
Most gases and liquids consist of molecules, and most solids based on carbon (organic solids) are also
molecular. Like atoms, molecules are electrically neutral and are, therefore, uncharged. Molecules are
held together by covalent bonds, which involve the sharing of electrons between neighbouring atoms.
These molecules may be:
r elemental, containing just one type of atom (e.g. oxygen and hydrogen are most stable as molecules of
two atoms, i.e. O2 and H2 respectively, shown in figure 1.3b), or
r compounds, comprising more than one type of atom (e.g. water, H O, which is a combination of hydro-
2
gen and oxygen atoms, shown in figure 1.3c).
Ions are chemical species that have either a positive or negative electric charge (because they have
differing numbers of electrons compared to the neutral atom or molecule). Those with a positive charge
are called cations; those with a negative charge are called anions (respectively designated by a + or − ).
Ions can be formally derived from either atoms or molecules by the addition or removal of one or more
electrically charged entities. Examples of such entities are a hydrogen ion, H+ , and an electron, e− .

8 Chemistry core concepts

For example, in any sample of pure water, there will be small amounts of the hydroxide anion, OH− ,
which has one more electron than it has protons, and the hydronium ion, H3 O+ , which has one fewer
electron than it has protons (see figure 1.3d). The presence of OH− and H3 O+ forms the basis of the
study of acids and bases, which we will encounter later in this text.
Compounds are defined as substances containing two or more elements in a definite and unchanging
proportion. Compounds may be composed of molecules, ions or covalently bonded networks of atoms.
We have already seen how hydrogen atoms and oxygen atoms combine to form molecules of water.
Note, however, that in an ionic compound such as sodium chloride, NaCl, we do not have individual
‘molecules’. Rather, NaCl simply represents the smallest repeating unit in an enormous three-dimensional
array of Na+ ions and Cl− ions. We sometimes call the smallest ratio of ions in an ionic compound
the formula unit, in this example NaCl. The same applies to certain covalently bonded structures. For
example, quartz, which is composed of an ‘infinite’ three-dimensional network of covalently bound Si
and O atoms, has the chemical formula SiO2 , which refers not to individual SiO2 ‘molecules’ but to the
smallest repeating unit in the network.

Classifying matter
Matter is often classified on the basis of its physical (or measurable) properties. These properties allow
us to relate observations at the human scale with what we infer is happening at the atomic scale. The
three familiar states of matter — solid, liquid and gas — are differentiated by their volume and shape,
and how these properties respond to temperature and pressure. Returning to our chemical building block
of life, water, we can observe its three different states of matter and zoom in to a representation of the
molecular structure of each state, as shown in the lower portion of figure 1.4.

FIGURE 1.4 The three states of matter: (a) solid — water molecules are held together rigidly and are very close to
each other (b) liquid — water molecules are close together but are free to move around and slide
over each other (c) gas — water molecules are far apart and move freely and randomly.

solid (ice) liquid (water) gas (water vapour)

(a) (b) (c)

Solids have a fixed volume and shape that does not respond to compression, as shown for solid H2 O
(ice) in figure 1.4a. The reason for this is evident when we view ice at the molecular level — the molecules
are in close proximity and arranged in a regular pattern.

CHAPTER 1 The nature of matter 9

 Liquids also have a fixed volume that does not respond easily to compression, but they have a variable
shape — they take the shape of the container in which they are stored. As we can see in figure 1.4b, as
a liquid, H2 O molecules are still close together, but they are not organised in a tight arrangement.
Gases are easily compressible. Unlike liquids, gases do not have a fixed volume. They will expand to
fill the container in which they are stored. Like liquids, they take the shape of their container. Figure 1.4c
shows that H2 O molecules in water vapour are far apart and are free to move independently of each other.
Each state is sometimes called a phase, and converting between states is called a phase change. Solids
and liquids are sometimes called ‘condensed phases’ because of their fixed volume and limited compress-
ibility. Liquids and gases are sometimes called fluids, because of their variable shape. The properties we
have discussed are summarised in table 1.1.

TABLE 1.1 Physical properties of states of matter

Physical property

State Volume Shape Compressibility

Solid Fixed Fixed None
Liquid Fixed Variable Very low
Gas Variable Variable Very high

Matter can be further classified as either a pure substance or a mixture, as shown in figure 1.5. Pure
substances are compounds or elements and are called pure because only one chemical species is present.
Mixtures contain two or more chemical species and can be separated into pure substances by physical
means. Mixtures can be either homogeneous (only one phase present) or heterogeneous (two or more
phases present).

FIGURE 1.5 Pure substances and mixtures

matter
anything with measurable
mass and volume

pure substances mixtures

matter made of a single matter containing two
chemical species or more chemical species

elements compounds homogeneous heterogeneous

matter made of a single matter made of more than all chemical species are chemical species are
type of atom one type of atom found in a single phase found in different phases

Interconverting matter
Matter can be converted through either physical or chemical change. A physical change alters just the
physical state of a sample of matter without changing its chemical composition. In chemistry, the most
important physical changes involve changes between the solid, liquid and gaseous forms of a sample of
matter. As noted earlier, we call these processes phase changes; for example, the melting of ice to produce
liquid water is a phase change.

10 Chemistry core concepts

 Chemical changes involve a substance being changed into new chemical species as a result of a chem-
ical reaction. All of the chemical species discussed earlier (atoms, molecules, ions, elements and com-
pounds) may be involved in chemical reactions. A chemical reaction is a process in which one or more
chemical species (which we call reactants) undergo transformations, generally involving the breaking
and/or making of chemical bonds. This usually results in the formation of different chemical species
(which we call products). Burning a piece of paper or reacting a metal with acid are chemical changes. It
is not a simple matter (and often not possible) to return a substance to its original chemical species after
a chemical change.

WORKED EXAMPLE 1.1 Classifying matter

Problem Petrol is a liquid that contains many different hydrocarbons. Each hydrocar-
bon contains carbon and hydrogen chemically bound together in different
ways. When we burn petrol the hydrocarbon reacts with oxygen in the atmo-
sphere and forms carbon dioxide and water.
Using the information above answer the following questions.
(a) Are hydrocarbons elements or compounds?
(b) Is petrol a pure substance, a heterogeneous mixture or a homogeneous
mixture?
(c) Is burning petrol a chemical or physical change?
Analyse To answer the questions, we will need to determine:
1. whether hydrocarbons are made of one type of atom or more than one
type
2. whether petrol contains only one chemical species, or if a mixture of
species, then whether they are all in the same phase or in different phases
3. what type of change occurs when petrol is burned.
Solve Step 1
We learned above that a chemical species that consists of more than one
element is a compound. The problem tells us that a hydrocarbon contains
the elements carbon and hydrogen chemically bound together. Therefore a
hydrocarbon must be a compound.
Step 2
The problem tells us that petrol is a mixture of different hydrocarbons. It
therefore cannot be a pure substance. The problem also tells us that petrol is
a liquid, so the hydrocarbons are all present in the same phase. Petrol must
therefore be a homogeneous mixture.
Step 3
The problem says that new chemical species (carbon dioxide and water)
are formed when the hydrocarbon reacts with oxygen. This is therefore a
chemical change.

Answer In summary, a hydrocarbon is a compound. Petrol is a homogeneous mixture

of hydrocarbons. The burning of petrol is a chemical change.
Reflect At this stage, it is important to memorise the fundamental definitions of
various types of matter, along with how matter may be classified and the
difference between a chemical and a physical change.

CHAPTER 1 The nature of matter 11

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