Chemistry in Use

chemistry IN USE
Deb SMITH | Sue MONTEATH | Mark GOULD | Roland SMITH

BOOK 1
Text 2006 McGraw-Hill Australia
Illustrations and design 2006 McGraw-Hill Australia Pty Ltd
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National Library of Australia Cataloguing-in-Publication data:
Chemistry in use. Book 1.
Includes index.
For year 11 students.
ISBN 0 074 71408 2.
1. Chemistry - Textbooks. I. Smith, Debra (Debra Claire).
540

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Acknowledgments ix
About the authors ix
About this book/To the teacher/To the student x
CONTEXTS
Why do we use what we do? 2
Properties make the difference 4
Where do these materials come from? 6
Moving apartseparating substances 8
In the beginning 10
Atomssimilar yet different? 12
Elementswhats the difference? 13
Abundance of elements of the Earth 14
Using materialslooking at properties 16
Organising elementsthe Periodic Table 17
Coming togetherelements making compounds 20
What determines properties? 20
Why compounds? 21
Whats in a name? 23
Using things upkeeping track of atoms 24
Recyclingcounting atoms 27
Using and recycling aluminiuman example 29
Making the aluminium can 30
How much? Chemical quantities! 32
Avoiding wastegreen chemistry 34
CONTENTS
Context 1 Materials: living in a world of materials 1
Water is everywhere 39
Ice and waterthe density phenomenon 40
Watera shapely molecule 42
Molecules in liquid water and ice 42
Water going places in plants 43
Capillary action 43
From roots to leaves 45
Blood is thicker than water 45
Dissolving inorganic salts and ions 45
Water of crystallisation 46
Dissolving organic molecules 46
Changing molecules 47
Dissolving gasesoxygen 49
Dissolving gasescarbon dioxide 50
Dissolving by reacting 51
Effects of solutes upon melting and boiling points of water 51
Getting things in and out of cells 52
A word of warning 54
Replacing water 54
Guidelines for drinking water quality 55
The water cycle 57
Watergood enough to drink? 59
Treating water 59
Why does the aluminium hydroxide form a precipitate 61
Disinfecting water 61
Balancing the treatment 63
To add uoride? 64
Water hard or soft? 64
Water softening 65
Investigating water hardness 66
Scale 66
Bottled water or tap water? 67
Types of bottled water 69
Looking after our water supplies 70
How can water practices on the land affect what happens in the sea? 70
Increased concentration of suspended particles 72
Increased inorganic nutrients 72
Increased organic materials 73
Increased heavy metals 74
Monitoring water quality 75
Temperature tests 75
pH tests 75
Salinity tests 76
Total dissolved solids tests 77
Turbidity tests 77
Nitrate tests 78
Phosphate tests 79
Dissolved oxygen tests 79
Context 2 Water: a unique material 38
iv CHEMISTRY IN USE
Biochemical oxygen demand test 81
Coliforms test 82
Heavy metal tests 82
Using energy 92
The reciprocating internal combustion engine 92
Main systems of the enginefuel and ignition 95
The ignition system 97
Turning chemical energy into mechanical energy 98
Fuels and energy 100
Energy value 101
What a wonderful energy source petrol isor is it? 102
What is petrol and where do we get it? 104
Improving petrols properties 107
Petrol is polluting 116
Greenhouse effect 116
Photochemical smog and acid rain 118
What can we do? 119
Cars, metals and corrosion 122
The composition of airwhat we really breathe 126
Earths air 127
Take a breath 128
Investigating gases of the air 130
Using air 132
Squeezing air 134
The heat is on 135
Calculating how much 137
Mixtures of gases 140
The atmosphere 141
Structure of the atmosphere 142
Main pollutants in our air 143
National air quality standards 145
Monitoring air quality 146
Ozonethe good and the bad 146
Ozone in the stratospherehere today, gone tomorrow 148
Disappearing ozone 150
A closer look at the ozone hole 155
Ozone in the streetshere to stay? 156
Global warminga hot topic 158
Earths energy balance 159
Living in a greenhouse 160
Calculating carbon dioxide 161
Context 3 Transport: a necessary evil 90
CONTENTS v
Context 4 Air: something we all share 125
vi CHEMISTRY IN USE vi CHEMISTRY IN USE
CHEMISTRY
1.1 Solids, liquids and gases 163
1.2 Particle nature of matter 164
1.3 Mixtures and pure substances 166
1.4 Elements and compounds 167
1.5 Atoms and molecules 169
1.6 Symbols for elements 170
1.7 Formulae 170
1.8 Molecules of elements 171
1.9 Separating mixtures 171
1.10 An atoma nucleus and an electron cloud 177
1.11 Some simple atoms 179
1.12 Atomic number and mass number 179
1.13 Isotopes 180
1.14 Relative atomic mass 181
1.15 Physical and chemical changes 183
1.16 Metals and non-metals 185
1.17 The Periodic Table 186
1.18 Electron arrangements in atoms 188
1.19 Stable electron congurations 190
1.20 The Periodic Table and electron conguration 191
2.1 Formation of ions 196
2.2 Ionic bonding and the Periodic Table 198
2.3 Covalent bonding 199
2.4 Covalency and the Periodic Table 200
2.5 Electron-dot structures for ions 201
2.6 Properties of covalent molecular and ionic substances 201
2.7 Covalent network solids 204
2.8 Metallic bonding 205
2.9 Properties of solids summarised 206
2.10 Formulae and names for compounds 208
2.11 Formulae for ionic compounds 208
2.12 Naming ionic compounds 209
2.13 Ions that are not monatomic 210
2.14 Formulae for covalent compounds 211
2.15 Naming covalent binary compounds 212
2.16 Equations for chemical reactions 213
Chapter 1 Classifying substances and exploring atoms 163
Chapter 2 Mainly about compounds 196
3.1 Relative molecular mass (molecular weight) 218
3.2 Relative formula mass (formula weight) 219
3.3 The mole 220
3.4 Moles of gaseous elements 222
3.5 Converting between mass, moles and numbers of atoms or molecules 222
3.6 Per cent composition 225
3.7 Moles and chemical equations 226
3.8 Mass calculations from chemical equations 228
4.1 Structure of water and other simple compounds 232
4.2 Polar covalent bonds 234
4.3 Dipoledipole forces 235
4.4 Hydrogen bonds 236
4.5 Predicting shapes of molecules 239
5.1 Aqueous solutions of ionic compounds 244
5.2 Water of crystallisation and hydrates 245
5.3 Aqueous solutions of molecular substances 246
5.4 Molecular substances that react with water 248
5.5 Solubility summarised 249
5.6 Precipitation reactions 250
5.7 Solubility data 252
5.8 Using the solubility table 253
5.9 Saturated solution, concentration, solubility 255
5.10 Different measures of concentration 255
5.11 Molarity 259
6.1 The element carbon 265
6.2 Double and triple covalent bonds 265
6.3 Carboncarbon bonds 268
6.4 Alkanes 270
6.5 Alkenes 275
6.6 Alkynes 279
6.7 Reactions of alkanes 281
6.8 Reactions of alkenes 282
6.9 Functional groups 284
Chapter 3 Calculations involving chemical formulae and equations 218
CONTENTS vii
Chapter 4 Intermolecular forces 232
Chapter 5 Water as a solvent: aqueous solutions 244
Chapter 6 Hydrocarbons 265
viii CHEMISTRY IN USE viii CHEMISTRY IN USE
7.1 Exothermic and endothermic reactions 288
7.2 Enthalpy 289
7.3 Explaining chemical energy changes 292
7.4 Temperature, quantity of heat and heat capacity 293
7.5 Measuring enthalpy changes for reactions 295
7.6 Heat of combustion 297
7.7 Two basic drives: energy and entropy 299
7.8 Activation energy 302
7.9 Meaning of rate of reaction 303
7.10 Factors inuencing the rate of reaction 306
7.11 Explanations 308
7.12 Temperature effect and activation energy 309
7.13 Catalysts 310
8.1 Pressure and the particle nature of gases 315
8.2 Diffusion 317
8.3 Kinetic theory of gases 318
8.4 Avogadros law 318
8.5 Boyles law 320
8.6 Charles law 322
8.7 Combined gas law 326
8.8 Ideal gas equation 327
8.9 Daltons law of partial pressures 331
Answers to exercises 335
Credits 365
Index 367
Relative atomic masses (atomic weights) of common elements 371
Periodic Table 372
Chapter 7 Energy changes and rates of reaction 287
Chapter 8 Gases 315
The authors wish to thank Judy Gould, Sam Monteath, Sheryl Crofts and
Meryl Smith for support; Cameron Gould, Sheryl Crofts and Jeffrey Smith for
photos; and Ron Heals and Erica McLean for advice.
Deb Smith is an experienced teacher and best-selling author, currently Head of
Department at a large school in Brisbane. She is also the convener of the QSA
sub-committee which developed the new senior Chemistry syllabus.
Mark Gould is an experienced Head of Department and also a member of the
QSA sub-committee. He has worked as a consultant on a number of chemistry
publications for McGraw-Hill Australia.
Sue Monteath teaches Chemistry at a school in Brisbane and is a key member of
the team that developed the new senior Chemistry syllabus.
Roland Smith is a highly respected author whose texts have been used in schools
for nearly two decades. Roland has over 25 years of experience as a science teacher,
CSIRO scientist and university lecturer and researcher.
ACKNOWLEDGMENTS
ABOUT THE AUTHORS
This text was specically designed to make the contextual approach, as mandated
in the new Queensland chemistry syllabus, accessible to any student or teacher by
providing contextual stories clearly linked to chemical concepts.
The contextual stories in the rst half of the book are separated from the
chemical theory in the second half of the book to allow each section to be written in
a style that best suits their separate purpose. Contexts are written in a story format
to maintain readability and interest, while the theory section is written for clarity
and ease of referencing. This structure allows teachers to guide students to chemical
theory as needed and encourages students to review theory to suit their own needs.
Icons
The icons that are used within the four Contexts identify activities, information and
CD material for student or teacher.
indicates activities, based on the content discussed in the preceding text. The
activity may consist of DIY experiments or group experiments, exercises, and
questions. Some of the questions are simple and revise factual knowledge, other
questions are more elaborate and invite you to examine a problem and develop
a theory.
indicates additional information on a particular subject that does not always fall
within a chemistry context but provides very useful background information.
It is often presented in the form of Did you know that boxes, and sometimes as
mini-case studies. Scattered throughout the Contexts they provide highly interesting
and original sources of background information.
ABOUT THIS BOOK
indicates extra material on the CD included with the book
and experiments on the Teacher Resource CD. The material
included on the CDs may be used for revision, extension
work or as additional information.
indicates references to the underlying chemistry in the second
part of the book. Similarly you will nd cross references in
the Chemistry section placing it back into context.
TO THE TEACHER
In a contextual approach to learning chemistry, the starting point must be the
contextthe real-life situation that makes more sense with an understanding of the
chemistry in use.
Students will need to be guided through the contextual stories, taught how to
recognise their learning needs and to use the theory to meet them. New concepts
are indicated in the contexts as they arise, by references to the relevant chemistry
theory sections. Students should be encouraged to use these references to access
the theory and then return to the context as their understanding develops.
Meaningful activities in the text help link concepts to the context and provide
a useful self assessment guide for the students. They also help develop important
thinking skills. Theoretical exercises and useful experiments are supplied on the
student CD to help develop concepts.
Assessment in the new syllabus is signicantly different from previous syllabi,
and pedagogy should reect this change. Students are to be assessed against a
wide range of criteria with understanding chemical concepts only one of the set.
Meaningful tasks associated with the contexts are supplied with further experiments
and worksheets on the teacher resource CD. Establishing a task early in a context
gives students a focus from which they can take control of their learning.
ABOUT THIS BOOK xi
xii CHEMISTRY IN USE
TO THE STUDENT
This chemistry text is divided into two sections. The rst section is about chemistry
in use and describes real-life situations where chemistry is important. You should
read each context, keeping in mind that there will be sections that you wont
understand until you learn the relevant chemistry theory.
When you see a cross reference to the Chemistry section this indicates that new
chemical theory will be needed in the following section of work. Use this reference
to nd the relevant theory to help you understand the new ideas as you come to
them.
Activities give you a chance to test your understanding and develop important
thinking skills. You should try to do all activities. They will help you know what you
need to review.
On the student CD you will nd theoretical exercises and experiments. These
will help you understand the chemical theory. Before you start any experiment, you
should ask yourself several questions.
What do I already know about this?
What do I think should happen and why?
How will I know whether my ideas are possibly right or denitely wrong?
Most importantly let yourself be interested. Chemistry is a fascinating branch of
science that can lead to a wide range of opportunities.
1
CONTEXT 1
Materials: living in a
world of materials
IN THIS CONTEXT
Why do we use what we do? 2
In the beginning 10
Coming togetherelements making compounds 20
Using things upkeeping track of atoms 24
Recyclingcounting atoms 27
2 CHEMISTRY IN USE 2 CHEMISTRY IN USE
Here on Earth we are surrounded by millions of different
materials. Throughout time people have been fascinated
by the materials around them and human history is written
in terms of various materials that dominate a particular
time. The Stone Age, the Bronze Age and the Iron Age
are some examples. Last century could have been called
the Carbon Age and towards its end the Silicon Age when
computers ruled.
People have always made use of the materials of the Earth.
The study of substances, their properties and reactions is
called chemistry. In everything from clothes to computers,
from medicines to machines, from food to fuels, we use a vast
range of materials that have been made by altering the raw
materials of the Earth using chemical processes to suit our
needs and requirements.
Chemistry involves observing, testing and investigating materials in an attempt
to understand them. Explanations and theories have been developed and tested
to try to account for the way material behaves. These explanations and theories
are continually being changed as new evidence is discovered and new ways of
thinking develop.
Everything material is chemical and everything is reacting on one time scale
or another. The chemical reactions that go on in our world are tightly interlocked.
Chemists try to understand how the materials and reactions can be manipulated
to our advantage without creating unforeseen troubles.
All the materials that we currently use have come from the land, seas and
atmosphere of the planet Earth. Space exploration has revealed the uniqueness
of our planet, and how the planets nite resources are a valuable asset for all
living things.
In taking materials (resources) from the Earth it has been greatly altered.
The combined effects of mining, processing industries and using and discarding
raw and generated materials have produced large quantities of waste and caused
environmental damage. As the population of this planet has increased and our
resources recognised as nite, we must learn to use them more effectively and
efciently.
WHY DO WE USE WHAT WE DO?
We live in a material world and every material thing is chemical. The special
characteristics of a material are called its properties and we use a material for
a specic purpose because it has properties that suit it to that purpose.
When there are no available materials that suit a particular purpose, chemists
attempt to create new materials that have the required properties. For example,
in the late 1950s NASA scientists began to develop a material that could be used
inside spacecraft to relieve the enormous g-force experienced by astronauts during
lift-off and in ight. The result was a new kind of foam that yielded to the body
and distributed its pressure evenly around the area of the body in contact with it.
This material has been developed into mattresses, which support the body in its
natural anatomical position, and has been used effectively to relieve back, neck
and joint pains.
CONTEXT 1 MATERIALS 3 CONTEXT 1 MATERIALS 3
Memory Foam, created
by NASA, has been used
to make mattresses and
pillows
Articial spiders silk
Spiders silk is an amazing material, which
scientists are trying to produce synthetically.
The silk is strong enough to bear the weight of a
bungee-jumping spider (it can extend to almost
three times its original length without breaking),
exible enough to withstand the impact of a
ying insect, stable enough to last for days
and insoluble in water.
One of the most thoroughly studied and
strongest known bres is called dragline silk
and is made by the golden orb-weaver spider.
Spiders silk is stronger than any other known
natural or synthetic bre. It is as much as four
times stronger than steel of the same diameter.
Proposals for the possible use of spiders
silk include wear-resistant fabric for clothing,
super-strong reinforcing cables for bridges or
catapult cables on aircraft carriers, bullet-proof
vests and articial tendons and ligaments.
Scientists have determined the DNA sequence
for the genes in spiders that produce the
proteins used to make the silk. By inserting one
of these genes into a species of bacteria, they
were able to get the bacteria to produce the silk
proteins, but only in short chains, resulting in a
much weaker bre.
A biotechnology company has come up with a solution for producing the silk without
the spider. They have implanted spiders silk genes into goats. Spiders silk proteins
are being recovered from the milk of the goats offspring. The company plans to
mass-produce the spiders silk when the goat herd is large enough.
Properties make the difference
Properties can be divided into two groups: macroscopic and microscopic.
The macroscopic properties are the ones that are easily observed or measured.
They include melting point and boiling point, colour, smell, absorbency, density,
hardness, electrical and thermal conductivity, exibility, solubility, transparency
and brittleness. These macroscopic properties also include properties that show
the interaction between materials, such as ability to corrode or resist corrosion
and chemical reaction with acids or with oxygen.
The microscopic properties of a material are the ones concerned with the
arrangement and interaction of the particles that make up the material. These
microscopic properties can be observed only with sophisticated equipment and
include atomic size, shapes and bonding in molecules and electron arrangement
in atoms.
Every day we use a huge variety of materials without really thinking about
their properties and how these inuence their use. Let us investigate some of these
common materials.
ACTIVITY 1.1
Consider the following common objects
you use or come into contact with almost
every day. They include aluminium foil,
plastic wrap, cotton fabric, paper towel,
wood, a rubber band, a tin can, a glass
jar, copper wire, a nail and a plastic soft
drink bottle.
Draw up a table similar to the one
below and complete it for at least ve of
the materials listed above. You may add
other materials if you wish. An example
is provided.
Object
Main material
making up object Use
Important property
or properties in
the use
paperclip steel holding sheets of
paper together
exible, strong
The properties you have listed above are not the only properties of these
materials, merely the ones most relevant to that use. In the next activity, you are to
use procedures to investigate several of the macroscopic properties of the different
objects.
according to its macroscopic properties and the way it is used.
ACTIVITY 1.2
Consider the list of macroscopic properties mentioned earlier. Many of these properties
(colour, smell, transparency, reaction with oxygen (does it burn?) and acids) can be
observed, whereas others require the use of equipment to test or measure the property
(for example, electrical conductivity, exibility, solubility). Choose ve objects made
from different material to compare their macroscopic properties.
The table below offers some suggestions for properties that may be observed and
tested. You may wish to design procedures to test other properties, such as hardness
using Mohs scale with a rock kit or elasticity or bending using weights. You may also
like to consider reaction with other substances such as bases.
Draw a table of properties similar to the one below to record your observations.
Object
Colour
and feel
Stiffness/
exibility
Electrical
conductivity
Ease of
tearing
Water
absorbency
Reaction
with
oxygen
Reaction
with
acids
Here are some suggested tests:
1 Describe the colour and feel (rough/smooth) of each object.
2 Try to bend the object. Does it bend easily or is it resistant to
bending (stiff)?
3 Use conductivity apparatus to test its electrical conductivity.
4 Try to break or tear a small portion of the object. If you
cannot tear it, use a pair of scissors to cut the object.
5 Immerse the object in water for about a minute and compare
the weight before and after immersion. Be sure to dry off any
surface water when you weigh it after immersion.
6 Calculate the percentage water absorbed by dividing the
mass of water absorbed by the original mass of the dry
object and multiply by 100.
7 Hold a small piece of the material with metal tongs in a
Bunsen burner in a fume cabinet (some materials release
poisonous fumes when burnt) and observe what happens.
8 Place a small piece of the material in a beaker containing acid and note if it reacts.
Answer the following questions:
a Group the objects into electrical conductors and non-conductors. What is
common about the group that were conductors? Where might this property
be useful?
b Which of the materials tended to stretch when you tried to tear them?
How might this property be useful?
c Which of the materials displayed the greatest degree of stiffness? Would this
be important if this was to be used as a structural material? Why?
d Classify the materials according to whether they burnt, or melted or didnt
react. Where and why would this property be important?
e Acids are found naturally in citrus fruits, the stomach, and acid rain.
Would any of the material tested be exposed to naturally occurring acids?
Did these materials react?
Where do these materials come from?
All materials that we use today come originally from the Earth. Early Stone Age
humans generally used the materials of the Earth as they were found naturally. They
may have reshaped a piece of wood to create a club or spear but they did not alter
its chemical properties in any way.
With the emergence and growth of the science of chemistry, humans have
become more skilled at using chemical processes to develop new materials from
those resources found naturally on the Earth. As you found in Activity 1.2, materials
can be classied in many different ways depending on the purpose. Another way of
classifying the materials of the Earth is according to their statewhether they are
solids or liquid or gases. Our survival depends on the existence of all three states of
matter. We need solids to give us shelter, tools and food, the gas oxygen to breath
and the liquid water to drink.
To refresh your understanding of the different states of matter and particle

theory, refer to Chemistry Sections 1.1 and 1.2, pp. 1635.
ACTIVITY 1.3
Read the following, then answer the
questions.
Everything on the Earth is made
up of atoms. These atoms can be
manipulated physically and chemically to
suit our needs but what is already here is
all we can use, at least until we begin to
use other celestial bodies. Materially, we
have a virtually closed system, meaning
one that does not receive matter from
anywhere else and does not lose any
matter either. The only signicant amount of matter we gain from space arrives in the
form of meteorites and all the matter that is already here remains here, except for a few
spacecraft that permanently leave Earth and the escape of some atmospheric gases
to space.
Energetically, however, we do not have a closed system. The Earth constantly
receives energy from the sun and constantly releases it to space in the form of heat
radiation. So energy continually ows through the Earths atmosphere and crust.
It is this constant exchange of energy that stirs up the materials of Earth and
makes interesting chemical reactions happen, including reactions that support life.
Life on Earth is possible because the ow of energy at the Earths surface powers
many cycles within our materially closed but energetically open system. The water
cycle is an example of a cycle that involves physical changes of state (that is, changes
between solid, liquid and gas).
Many other cycles, such as the carbon cycle and the nitrogen cycle, involve
complex cycles of chemical change in which specic types of atoms cycle through
many different chemical forms.
a What is meant by the statement, the Earth is a materially closed system?
b If the system is closed, how are new substances formed?
c Give an example of a material cycle.
d What effect do humans have on the Earths closed system, particularly the
material cycles?
only one component of a whole group of materials. The way this is done is
dependent on how the substances have combined to form the material. When
chemists investigate the materials that are found on Earth, they divide them into two
categories: mixtures and pure substances. Pure substances can further be divided
into elements and compounds. Many of the substances we want to use are not the
pure compounds we extract from the Earth but rather substances we make from the
extracted raw materialiron from haematite (iron ore), aluminium from bauxite,
chlorine from salt, salt from salt water, carbon from coal and oil.
Iron ore open cut mine
To learn about elements, compounds and mixtures, refer to

Chemistry Sections 1.3 to 1.8, pp. 16671.
ACTIVITY 1.4
Classify the following common substances as mixtures, compounds or elements:
a air f copper wire
b sea water g milk
c table salt h sugar
d oxygen i nitrogen
e a gold ring
Collecting salt by evaporating sea water
Moving apartseparating substances
Most of the substances found naturally on
the Earth are either mixtures of compounds
or mixtures of elements and compounds or
mixtures of elements. One of the most important
substances, water, is a compound of hydrogen
and oxygen and saltwater is a mixture of salt and
water. You will learn a lot more about water and
its properties in Context 2.
In trying to understand and use the materials
that make up our Earth, chemists separate the
mixtures into their pure components, which
may be elements and/or compounds. They then
investigate the properties of the elements and
compounds that make up that mixture. The
atmosphere is a mixture of gases, predominantly
the elements nitrogen, oxygen and argon.
Lava lampsan interesting mixture
of liquids
Lava lamps have been popular since the
1960s when they were rst marketed.
They are available in a vast number of colour
combinations but essentially consist of a
mixture of different liquids.
The liquid that constitutes the lava is a
substance that does not dissolve readily in
water. The second liquid is either a mixture
of water and a liquid that dissolves readily
on water (to give the colour) or another
water-soluble liquid. The inability of the lava
to dissolve in the water-based liquid means
the two components remain separatethey
are said to be immiscible. The lava forms
the familiar blobs that migrate through the
water-based liquid.
The lava component is slightly more dense
than water at room temperature so it sinks
to the bottom of the lamp when the lamp is
not switched on. A bulb, usually 40 W, and a
small coil of wire at the base of the lamp both
serve as heat sources for the liquids. When
the lamp is switched on and the temperature
of the system increases, both liquids decrease
in density. The lava liquids density changes more dramatically than the water-based
component and, being lighter (less dense), it rises towards the top of the container.
As the lava moves away from the heat source it begins to cool, increasing its density,
and sinks to the bottom of the lamp. The cycle repeats to generate the ever-changing
pattern and motion of the lava.
hydrosphere contains mixtures of compounds dissolved in water whereas
the lithosphere contains an extremely diverse range of mixtures. There are rocks,
sand, dirt, soil, minerals, and coal, crude oil and natural gas mixtures in the Earth.
The resources we need for our everyday life are obtained from the Earth.
Some of the mixtures present in the Earth we use as is, without separating
them into their components. Common ones are shown in Table 1.1.
TABLE 1.1 Common mixtures from the Earth that are used without separation,
and their uses
Mixture Common uses
coal a fuel for heating and generating electricity
sand used for making concrete and glass
granite, marble,
sandstone
surfacing for buildings and for table- or bench-tops, and for carving
statues
various clays making earthenware pots and pipes, china and porcelain ornaments
air compressed into cylinders for use in scuba diving, for lling car tyres
and for spray painting
fresh water often used for domestic, agricultural and industrial purposes without
any separation procedures, but generally subject to some purication
(separation procedure) for domestic use in more developed countries
gypsum (calcium
sulfate with
impurities)
used as mined (pale brown colour) as a soil conditioner in gardens;
it is puried (subjected to separation processes) to make plaster
(pure white) for buildings
Although Table 1.1 gives examples of substances that do not need to be
separated, in reality most substances that we need must be separated from mixtures
of naturally occurring materials.
Chemists have developed many different separation techniques based on the
properties of the materials they want to separate. Table 1.2 summarises some
separation methods and lists the properties these methods depend upon. Because
purication of a substance is removal of unwanted substances (impurities), the
separation methods in the table are also methods of purifying.
TABLE 1.2 Separation methods and the properties they depend upon
Separation method Property used in the separation
sieving particle size
vaporisation
(evaporation
or boiling)
the liquid has a much lower boiling point than the solid
distillation big difference in boiling points
fractional distillation signicant but small difference in boiling points
ltration one substance a solid, the other a liquid or solution
adding a solvent,
then ltration
one substance is soluble in the chosen solvent while the others are
insoluble
using a separating
funnel
components are immiscible liquids
IN THE BEGINNING
chemical processes in Activity 1.2 and in separating a familiar mixture, but have
you ever really considered where all the materials of the Earth originally came from?
Those that are compounds and mixtures are made up of two or more of the hundred
or so elements that have been identied, but where did the elements come from?
Scientists believe elements are born in the stars. The theory of how stars
form was one of the major scientic achievements of the twentieth century. It
was developed through observation of a range of stars at different stages in their
development, studying them as they changed over time.
Most scientic observers agree with the current scientic theory, which says
that the origin of our expanding universethe origin of matter itselfoccurred
915 billion years ago with a cataclysmic event known as the Big Bang. Prior to
the Big Bang the entire matter of the universe was conned within a tiny region
of space, smaller than a grain of sand, at an enormously high temperature. The
explosion of this grainthe Big Bangmarked the moment the universe began.
During the rst second or so after the Big Bang, highly energetic photons
collided and converted their energy into mass, creating protons, neutrons and
electronsthe components of future atoms. As the universe cooled, protons and
neutrons combined to form the nuclei of a few elements, like helium. At this stage
nuclei existed, but it was still too hot for atoms. It took another 300 000 years for the
temperature to cool sufciently to allow electrons to combine with the nucleiand
atoms were born.
To learn about these separation techniques and how they are used, refer to
Chemistry Section 1.9, pp. 1717.
You could do an experiment to try to separate a mixture.

(Refer to Chemistry in Use Book 1 Teacher Resource CD-ROM.)
ACTIVITY 1.5
Using the information you have learnt, complete the following table, giving the
separation method and properties that enable separation.
Example
Separation
method
Property enabling
separation
separating mud from water
separating salt and sand
separating oil and water
obtaining nitrogen and oxygen from liquid air
obtaining fresh water from salt water
entirely hydrogen and helium. Gravity draws the gas molecules together, causing
them to condense and release heat. A star is born when the core temperature
of a GMC reaches 10 million kelvin. Nuclear fusion reactions begin converting
hydrogen nuclei into helium nuclei, releasing huge quantities of energy in the
process.
Our sun releases energy at the rate of 3.9 10
26
J/s. This energy is produced by
the conversion of about 700 million tonnes of hydrogen into about 695 million tons
of helium with about 5 million tonnes of matter being converted into energy every
second.
When the hydrogen fuelling the reaction at the core runs out, gravity again
causes the core to collapse, triggering another round of nuclear fusion reactions.
This time helium atoms in the core begin to fuse together into heavier elements
such as carbon and oxygen. Hydrogen outside the core is also drawn in by gravity,
creating an outer shell where hydrogen is fusing into helium.
If the star is massive enough when the helium in the core runs out, another
round of collapsing and reigniting takes place producing three distinct layers: an
inner core where heavier oxygen and carbon are fusing into a variety of heavier
elements including neon and magnesium, a middle layer where helium is fusing
into heavier elements and an outer layer where hydrogen is fusing into helium.
The pattern of collapsing and reigniting can occur several times, producing
a variety of isotopes of the heavier elements: silicon, phosphorus, sulfur, calcium
and others. The largest nuclei that can be produced in this process is that of iron.
Iron represents the element with the most stable nucleus so no additional energy
can be released in the fusion of iron to heavier elements.
The majority of stars fade away as white dwarfs as all their fuel is used up, but
a very massive star undergoes a different process. When the amount of iron in the
core becomes massive enough, the core of the star collapses under its own weight.
This collapse transforms the core entirely into neutrons as the nuclei and free
electrons fuse. The neutron core is so dense that a teaspoon of its material would
weigh approximately 50 billion tonnes.
Giant molecular cloud
(GMC)
The material of the outer layers of the star is rapidly drawn towards the neutron
core by the immense gravity. When the outer material hits the hard core it bounces
off, causing a supernova. The resultant shock wave blasts the outer core material so
violently that nuclear particles are forced together, creating elements heavier than
iron. These heavier elements are blasted into space where they may eventually be
recycled into new stars.
Astrochemists estimate that hydrogen makes up about 75% and helium about
25% of all matter in the universe today. Although the remaining hundred or so
elements seem abundant here on Earth, they exist in only trace amounts in the
universe as a whole. The hydrogen in our water may have been around since
the Big Bang and the elements that make up our body were probably created
in the core of a star.
ACTIVITY 1.6
Using the information provided above:
a Draw a ow chart, starting with hydrogen, showing how the elements have been
created.
b Draw a diagram showing the layered structure of a star that has collapsed and
reignited three times (not including the original star formation).
Atomssimilar yet different?
Today scientists believe that the naturally occurring elements were formed in stars,
but the idea of atoms has been around for a long time. In about 400 BC two Greek
philosophers, Democritus and Leucippus, suggested that everything is made up
of atoms. They proposed that the atom was the smallest piece of matter capable of
existence and, in fact, the name atom comes from the Greek word atomos, which
means indivisible. Their idea was mostly based on intuition. It was many centuries
before scientists gathered real scientic evidence from quantitative measurements
of chemical reactions, and the results of these experiments led to John Dalton
proposing the rst systematic atomic theory in 1803.
Daltons atomic theory proposed the following:
All matter is composed of atoms.
Atoms cannot be made or destroyed.
All atoms of the same element are identical.
Different elements have different types of atoms in terms of their mass.
Chemical reactions occur when atoms are rearranged.
Compounds consist of characteristic groupings of atoms of the constituent
elements.
Dalton used an elegant set of symbols to represent the elements known at that
time. When Dalton proposed his atomic hypothesis, the mass of an individual atom
could not be measured directly. He tried to work out the relative masses of atoms
using a series of elegant experiments based on the masses of elements that combine
together.
It wasnt until 1879 that the idea of electrons was proposed and in 1911 Ernest
Rutherford proposed the idea that an atom consisted of a small positively charged
nucleus that contained virtually all the mass of an atom, with electrons moving
around the nucleus.
it is accepted that the atom has a structure of its own and is made up of three
fundamental particles known as protons, neutrons and electrons.
Scientists now believe atoms were formed thousands of years after the Big Bang
when a nucleus, containing protons and neutrons, came together with electrons.
The original and lightest elements of hydrogen and helium were formed as a result
of this cataclysmic event. New elements are formed in stars and supernova.
Elementswhats the difference?
If all atoms are made up of the same particles (protons, neutrons and electrons),
why do we have so many different elements? Elements show an enormous variety
of properties, ranging from hydrogen, which is the simplest and most abundant in
the universe, to iron, which is the most abundant part of the whole Earth.
The type of element and all its properties depend on the composition of the
atoms of which it is composed. An atom is described in terms of the number of
protons, the atomic number, Z, and the ZZ mass number, A, which is the total number
of protons and neutrons in its nucleus. Elements are composed of atoms with the
same number of protons. Each element has its own unique symbol and properties.
Although the atoms of an element have the same number of protons, they may
have different numbers of neutrons. When this happens we have an isotope of that
element.
To learn about the structure of the atom and its fundamental particles, refer to
New sub-atomic particles
As our technology has improved, physicists have discovered the existence of other
sub-atomic particles. From as early as the 1950s, scientists have known of the
existence of other sub-atomic particles. They now believe the most fundamental
particle is the quark. Quarks cluster together to create the protons and neutrons found
in the nucleus of an atom. Ever since evidence for their existence was found in the
1960s, when linear and cyclic accelerators were used to bounce electrons off the
quarks, scientists believe they pretty much understand them.
Quarks join together in threes to form the proton and the neutron, or sometimes in
twos forming particles called mesons.
In 2003 a group of scientists reported nding something unusual in their particle
acceleratorsa particle made up of ve quarks bound together. This particle has
been called a pentaquark. Scientists are trying to understand this particle and what
consequences its discovery has on the current understanding of matter.
To learn more about elements, their masses and their isotopes, refer to
Abundance of elements of the Earth
As has been stated earlier, most of the matter in the universe today is hydrogen
and helium. Although the remaining hundred or so elements seem abundant here
on Earth, they exist in only trace amount in the universe as a whole.
Whether naturally occurring or synthetic, all substances found on Earth are
made from the relatively few 115 elements. Of the 115 elements, only 92 are
naturally occurring and just 17 of these make up 99.5% of the Earths crust,
hydrosphere and atmosphere.
TABLE 1.3 Relative abundance of the elements of the Earths biosphere
(crust, hydrosphere and atmosphere)
Element
Percentage
by mass Rank Element
Percentage
by mass
1 oxygen 49.2 10 titanium 0.6
2 silicon 25.7 11 chlorine 0.2
3 aluminium 7.5 12 phosphorus 0.1
4 iron 4.7 13 manganese 0.1
5 calcium 3.4 14 carbon 0.1
6 sodium 2.6 15 sulfur 0.05
7 potassium 2.4 16 barium 0.04
8 magnesium 1.9 17 nitrogen 0.03
9 hydrogen 0.9 all others 0.5
Elements are not uniformly distributed throughout the crust (lithosphere),
hydrosphere and atmosphere. The composition of the atmosphere (a gaseous
mixture) is quite different from that of the hydrosphere (aqueous solutions), which
in turn is different from that of the crust (mainly solids). The composition of living
matter is different again. Table 1.4 shows the differences in the most abundant
elements in each zone of the Earth.
TABLE 1.4 The ve most abundant elements in each zone of the Earth (listed in
decreasing order of abundance)
Rank Biosphere Atmosphere Hydrosphere Lithosphere Living matter
1 oxygen nitrogen oxygen oxygen oxygen
2 silicon oxygen hydrogen silicon carbon
3 aluminium argon chlorine aluminium hydrogen
4 iron hydrogen sodium iron nitrogen
5 calcium carbon magnesium calcium calcium
The gaseous atmosphere consists of the elements nitrogen, oxygen and argon
with variable amounts (0.55%) of water vapour, small amounts of carbon dioxide
and traces of several other gases.
The hydrosphere, the watery part of the Earth, consists of surface water (lakes
and rivers), ground water (stored under the surface of the land) and the oceans.
composition of the hydrosphere is dominated by seawater, which contains 3.5%
dissolved sodium chloride, and smaller amounts of other elements such as
magnesium.
The lithosphere (the Earths crust15 to 50 km skin of the planet and the top
few kilometres of the mantle) is the largest component of the biosphere by mass.
The composition of living matter (plants, animals, fungi, algae and bacteria) is
quite different from that of the non-living parts of the Earth. The basic structural
and functional compounds that make up living things are those of carbon generally
combined with hydrogen and oxygen. However, as the major component of all
living things is water, oxygen becomes the most abundant element in living matter.
The Earth is a closed system materially so the amount of each element present,
shown in Table 1.3, has not changed signicantly since the Earth was formed.
The reason for this is one of the basic laws of nature, the law of conservation
of matter. This law states that:
Matter can be neither created nor destroyed, but merely changed from one form to
another.
This law does not apply to nuclear reactions such as those that occur in stars,
nuclear reactors and nuclear bombs where elements can be converted into other
elements, releasing huge amounts of energy in the process.
Chemistry of cometsthe Rosetta
mission
In January 2003, the European Space Agency (ESA) launched a spacecraft called
Rosetta to intercept and land on the surface of the comet, Wirtanen, to study its
chemistry. It is expected to intercept in 2011.
A study of the elemental isotope ratio of the
comet will provide chemists with information
about the origin of the comet. The formation of the
Earth from a swirl of cosmic dust around the sun
brought with it information stored in an isotope
code for carbon and nitrogen. The question the
Rosetta mission hopes to answer is: Does the
material in the comet have the same isotope code
as that of the Earth?
If the answer to this question is yes, this would
support theories that the oceans on Earth were
formed by collisions with comets, bringing with
them much of the carbon found on Earth.
As a comet, a collection of dust and other
interplanetary debris held together with water,
approaches the sun it melts, producing the
gaseous tail. The centre of the comet, the nucleus,
remains solid and Rosetta will land on this nucleus.
Many experiments will be conducted on the Rosetta mission but the isotope code will
be investigated by an experiment called Ptolemy. This experiment will use various
instruments to analyse cometary ice. It will determine the ratios of stable isotopes
present in certain elements (for example, in H, C, N and O). Carbon-14 or
14
C is a
radioactive isotope of carbon. After a few tens of thousands of years it decays into
stable nitrogen-14 (
14
N), which does not decay any further.
Using materialslooking at properties
In Activity 1.2 you investigated some of the macroscopic properties of different
materials. When we distinguish between materials, we do so on the basis of their
properties. We also use materials because of their properties.
Properties can be divided into two groups: physical and chemical. The physical
properties can be easily observed or measured without altering the chemical
make-up of the material. They include melting point and boiling point, colour,
ACTIVITY 1.7
a Use the data in Table 1.3 on p. 14 to draw a bar graph of the relative abundance
of elements in the biosphere. For the elements use the categories oxygen, silicon,
aluminium, iron, calcium potassium magnesium (as one category) and all other
elements (as one category).
b Consider the information in Table 1.5, comparing the percentages of elements in
the whole Earth with those in the lithosphere.
TABLE 1.5 The percentage of elements in the whole Earth and the lithosphere
Earth Lithosphere
iron 35% oxygen 47%
oxygen 30% silicon 28%
silicon 15% aluminium 8%
magnesium 13% iron 5%
nickel 2.4% calcium 4%
sulfur 1.9% potassium 3%
calcium 1.1% sodium 3%
aluminium 1.1% magnesium 2%
remainder <1% remainder <1%
Account for the difference in abundance of the different elements.
c i State the law of conservation of mass.
ii Why doesnt this apply to nuclear reactions such as those that occur in stars?
It is believed that, after the major planet-forming events of the solar system were
complete, a thin layer of low-boiling point materials was added to the Earths surface
from objects like comets. It is also believed that this process is responsible for much
of the Earths water.
Water is a major constituent of comets and also forms the hydrosphere of the Earth.
It is a molecule made up of two hydrogen atoms and one oxygen atom. Molecules with
a common origin exhibit the same isotopic record so if the Earth and comets are related
this should be evident in the isotopic record. In about ten years time chemists should
have data from Rosetta, enabling them to crack the isotopic code.
Source: Chemistry in the remotest corner of the solar system, Chemistry Review, Vol. 12, No. 3
(February 2003, pp. 225)
If you want further information, check out the website about the Rosetta mission at
www.sci.esa.int/home/rosetta.
solubility, transparency and brittleness. A physical change, such as melting or
boiling at certain temperatures, may also be important. In a physical change the
identity of the substance is not changed.
The chemical properties of a material are described by the materials behaviour
when it reacts with other materials including water, acids and bases and oxygen.
Reactions cause a chemical change in the actual material and lead to the production
of a new material. A chemical change can often be detected by observing the
formation of a new gas or liquid, a colour change, a change in the surface of a solid
material or a temperature change indicating that heat has been absorbed or released.
Organising elementsthe Periodic Table
We have already seen that the percentage of different elements varies quite
considerably when considering the universe, or the Earth or its spheres. We also
know from personal experience that the properties of the different elements, for
example aluminium and oxygen, vary considerably but that there are also some
similarities, for example aluminium and copper, by which we can group elements.
We make many useful
items from substances
obtained from the Earth;
bricks, ceramics, tiles and
clay pots from various
clays, glass from sand,
limestone and sodium
carbonate and plaster
(the white powder) from
gypsum (the pale brown
powder)
To learn more about physical and chemical changes, refer to

ACTIVITY 1.8
In Activity 1.2 you investigated the macroscopic properties of some common materials.
Some of the properties you investigated were physical properties and some were
chemical properties.
a List the physical properties you investigated.
b List the chemical properties you investigated and any chemical changes you
observed.
By the mid-1800s, about 60 elements were known. Five of them are gases at
room temperature hydrogen (H), oxygen (O), nitrogen (N), uorine (F) and
chlorine (Cl). Two other elements are liquidsmercury (Hg) and bromine (Br).
The rest are solids with quite different properties. Chemists of that era tried to
devise a classication system that placed elements with similar properties near
each other on a chart. Dimitri Mendeleev, a Russian chemist, published a table
in 1869 and is credited with the discovery of chemical periodicity (patterns) and
the Periodic Table.
ACTIVITY 1.9
In this activity you are to observe a number of different elements and consider various
different ways of classifying them. You may do this by observing actual samples or
checking out virtual samples on the web.
If you are unable to obtain actual samples, you can see each element on the
Visual Elements website: http://www.chemsoc.org/viselements/.
Another website that provides information about elements is http://www.
webelements.com.
Using large Post-it notes or pieces of paper (one for each element), create element
cards on which you are to record the following information for each element you
investigate.
Name
Appearance
State
Atomic number
Boiling point
Melting point
Atomic radius
Valency
Source
Use
Using your completed cards answer the following questions:
a What is the most common state in which the elements exist?
b What is the least common state? Which elements exist in this state?
c Identify which of the elements are metals and which are non-metals by sorting
them into two groups and colouring a blue dot on the metals and a red dot on
the non-metals. Which is the largest group?
d Which, if any, elements were difcult to classify as metals or non-metals?
e Read through your list of metals and identify any common properties.
f Read through your list of non-metals and identify any common properties.
g What is the main source of metals? Which sphere of the Earth is this?
h Which elements, if any, are found in an uncombined (pure) state?
i Arrange the cards into a Periodic Table using the one in the front cover of this book
to assist you.
j Comment on the position of the metals and non-metals in your arrangement.
Mendeleevcreator of the Periodic Table
Dmitri Ivanovitch Mendeleev was born on 7 February 1834 at Tobolsk, east of the
Ural mountains in Asian Russia. He was the youngest of 14 children; his father was
a teacher and his mother ran a glass factory.
He did very well at university and after leaving taught for a short time in southern
Russia. He had strong academic ambitions and studied in France and Germany.
He spent many years gathering data, which enabled him to
formulate the Periodic Table in 1869. He then spent 37 years
rening it and showing how it was central to chemical
understanding. Although initially other chemists didnt accept
it, they came to see its truth long before Mendeleev died.
Mendeleev listed the elements in order of increasing atomic
weight in rows such that elements with similar chemical
properties kept occurring in the same vertical columnthat
is, periodically. The placement of the elements hinged upon
a correct atomic weight. Sometimes Mendeleev altered the
accepted atomic weight, to make the element t better into
the scheme according to its chemical properties.
Another difference between Mendeleevs table and those of
other chemists of the time was that he left spaces for elements
that at the time were unknown. He made amazingly accurate
predictions of the properties of the missing elements which,
when later discovered, matched his predictions.
He became an advocate for students at the university where he lectured and presented
their protests to the authorities. Shortly after this he left the university but history is
unclear about the reasons. Mendeleev died on 26 February 1907 and at his funeral
procession students carried aloft a Periodic Table.
Mendeleevs Periodic Table, which is a summary of chemical patterns, was achieved
half a century before the discovery of electrons and protons. Today protons and
electrons explain the structure of the Periodic Table, as it is arranged according to
atomic number rather than atomic weight and the properties of elements are explained
in terms of electron arrangements in atoms. The Periodic Table can be found on p. 372.
Dmitri Mendeleev
To learn more about classifying elements and the Periodic Table, refer to
Chemistry Sections 1.16 and 1.17, pp. 1857.
ACTIVITY 1.10
a Compare the relative reactivity of the elements using the following information.
Gold is often found as a free element on the Earth, copper is sometimes found
as a free element on the Earth, but sodium is not.
b From the following list give the element that best matches the purpose:
mercury, tungsten, graphite, aluminium, copper, helium.
i Used in electric light laments ii Used as electrical wires
iii Makes soft drink cans iv Used as a lubricant
v Used in thermometers vi Used to ll weather balloons
c Carbon is commonly found in two different forms or allotropes: graphite and
diamond. Compare their properties and uses.
COMING TOGETHERELEMENTS MAKING
COMPOUNDS
on the Earth. To date chemists have identied over 10 million different compounds
that have been discovered and studied by humans. There are still an unknown
number of compounds that exist without our knowing and understanding them.
What you may not know is that some of the substances that occur on Earth also
exist between the stars.
Molecules, which are two or more atoms joined together, are formed in the
colder parts of the universe when individual atoms meet and bond to each other.
If the two atoms are the same they form a molecule of an element but if they are
different they form a molecule of a compound. Molecules do not exist in stars
because the bonds, which hold the atoms together, cannot survive at the high
temperatures found there. Molecules and their fragments have been detected in
dense gas clouds. Some scientists suggest that the molecules found in these gas
clouds were the building blocks that reacted together to form the molecules that
are the basis of life on Earth.
The properties of a compound are quite different from those of the elements
from which it is formed. Consider the common compounds carbon dioxide and
carbon monoxide. Carbon is a solid found in the common forms of graphite or
diamond. Oxygen is a gas that occurs naturally in the atmosphere. When these two
elements combine together they can form carbon dioxide gas (CO
2
), a compound
containing one atom of carbon and two atoms of oxygen, or carbon monoxide gas
(CO) which has one atom of carbon and one atom of oxygen. (A subscript in a
formula refers to the element immediately preceding it.) The properties of these
compounds are quite different from each other and also from the properties of
the elements that have made them.
What determines properties?
What causes the different reactivities of elements, causing them to make so many
different compounds? As you may have found in the experiment, when elements
come together they produce substances with quite different properties.
Chemists attribute the reactivity of elements and the way in which they form
compounds to the number of electrons in their atoms and how these electrons are
arranged.
You can do an experiment comparing the properties of elements and their

resultant compound. (Refer to Chemistry in Use Book 1 Teacher Resource
CD-ROM.)
To learn more about the organisation of electrons in elements, refer to

Why compounds?
electron congurations. The types of compounds formed by reactions between
different groups of elements are the result of the way in which the different
elements attempt to achieve a noble gas electron conguration.
The properties of compounds are attributed to the type of bonding that
holds the atoms or ions together. When we use the compounds of the Earth or
the compounds chemists have created, we do so because of their properties.
Understanding the properties of compounds is the key to predicting and correlating
the behaviour of materials. This information allows chemists to nd new uses for
materials and to create new chemical compounds to meet specic needs.
Compounds make up
most substances we
commonly use
To understand the different types of bonding and how this affects properties of
a substance, refer to Chemistry Sections 2.1 to 2.9, pp. 196207.
ACTIVITY 1.11
a The following are common compounds. Classify them as ionic, covalent molecular
or covalent lattices.
i sodium chloride ii water
iii carbon monoxide iv copper sulfate
v rust (iron oxide) vi sugar (C
12
H
22
O
11
)
vii quartz (SiO
2
) viii ammonia (NH
3
)
b Why are we warned to keep electrical devices such as heaters and hair dryers away
from water when pure water is not a conductor of electricity?
c A group of students was given an unknown compound and asked to determine the
type of bonding present. Suggest what laboratory tests they should conduct.
ACTIVITY 1.12
Carbon is an amazing element. An entire area of chemistry called organic chemistry is
based on the compounds it forms. More than 90% of all known chemical compounds are
based on carbon including carbohydrates, proteins, fats and DNA (deoxyribonucleic acid).
Carbon also exists in pure forms. Until 1985 it was thought only two pure forms of
carbon occurred; these were diamond and graphite.
In 1985 Harry Krob, Richard Smalley and Robert Curl analysed carbon clusters
produced from the vaporisation of graphite by a powerful laser in an atmosphere
of helium gas. They found many previously unknown carbon molecules; the most
common was a roundish molecule made up of 60 carbon atoms (C
60
). It was named
buckminsterfullerene (often abbreviated to buckyball) after Buckminster Fuller, an
architect who designed the geodesic dome.
Each of these allotropes has quite different properties. As you have learnt,
properties are based on the type of bonding present in elements and compounds.
Using the diagrams and information below along with molecular model kits or
plasticine and straws cut into short pieces, construct a model of each of the three
forms of elemental carbon.
a Graphite forms a planar covalent network structure that consists of at six-membered
rings in which each carbon is bonded to only three other carbon atoms.
Pure forms of
carbondiamond
and graphite

Structure of graphite
Whats in a name?
but they can be divided into two main groups based on their bonding. It would
be impractical to learn the names and formulae of all the different compounds.
Chemists have developed a system in which the name of the compound allows us to
work out the formula and the formula allows us to work out the name.
Because there are two different groups of compounds there are two sets of rules:
one for ionic compounds and one for covalent compounds. It is therefore important
that you are able to distinguish between ionic and covalent compounds.
In general (there are exceptions that it would be worthwhile remembering), an
ionic compound is formed between a positive metal ion and a negative non-metal
ion or non-metal ionic group. Covalent compounds are usually formed between
elements that need to gain electronsthe non-metal elements.
Naming can sometimes become confusing because some compounds, including
water, ammonia and methane, are referred to by their common names rather than
by their systematic names.
b Diamond forms a tetrahedral covalent
network structure with each carbon
bonded to four other carbon atoms.
Using your knowledge, complete the following table.
Substance Bonding type Shape
Electrical
conductivity
graphite
diamond
buckyball
c Use the information and pattern
downloaded from the website
http://www.slb.com/seed/en/lab/buckyball
to construct a C
60
fullerene.
Structure of diamond
Structure of C
60
To learn the rules for naming compounds, refer to Chemistry Sections 2.10 to
2.15, pp. 20813.
USING THINGS UPKEEPING TRACK
OF ATOMS
we travel from place to place. Food we eat vanishes; wood we burn disintegrates and
steel rusts away. Even though the original materials disappear, the atoms of which
they are composed remain because, as you have already learnt, the Earth is a closed
system and the law of conservation of matter applies.
If we count atoms nothing is ever lost. The atoms are simply rearranged into new
compounds that may or may not be of further use. Food has been broken down by our
digestive system, releasing energy and forming new compounds needed by the body.
Sometimes resources can be recycled, as in aluminium cans, plastic containers and
paper. Other times the atoms and molecules are so scattered they cannot be collected
Ban DHMOone of the most
hazardous substances on the planet!
The Coalition to Ban Dihydrogen Monoxide (DHMO) encourages us to support them
in advocating the banning of this dangerous chemical that is freely available for use
by anyone. According to the coalition DHMO can be attributed to many deaths and
millions of dollars in property damage.
DHMO is odourless and tasteless. Inhalation of the liquid form has caused many deaths
while solid DHMO can cause severe and potentially fatal tissue damage. In its gaseous
state it can cause severe, sometimes deadly burns. DHMO dependency pervades all
cultures and substance withdrawal is always fatal.
Other facts about DHMO include that it is a major ingredient in all sorts of deadly poisons
and is often used as an industrial solvent and re retardant, and in chemical weapons
manufacture. It has been discovered in virtually all cancers and tumours, accelerates
corrosion and rusting of metals and causes dangerous electrical short-circuiting.
Widespread DHMO contamination of the environment is evident on every continent.
Vast quantities of DHMO permeate every stream, lake and river with the cleanest
waterways showing the highest concentration.
DHMO causes millions of dollars of property damage every year. Unbelievably, DHMO
continues to be used in many industries as a solvent and coolant. Companies dump
vast quantities of waste DHMO into rivers and oceans.
Governments refuse to take action and ban the production, distribution and use of this
damaging chemical, citing its economic importance to the country.
Answer the following questions:
a What is the formula of DHMO (dihydrogen monoxide)? Give its common name.
b Are the facts given above accurate?
c Give any other facts to support the banning of DHMO.
d If you were asked to argue against the banning of DHMO, what facts would you
use to support your argument?
If you want to nd out more information about the coalition you could access their
web page at:
http://www.netreach.net/~rjones/no_dhmo.org and their research page at
http://www.dhmo.org.
huge amounts of energy, which is used to power vehicles and produce electricity.
Unfortunately, the products of these combustion reactions are dispersed into the
atmosphere where they are beginning to upset delicate natural balances. You will
learn more about these reactions and balances in the Transport and Air contexts.
When we say our resources are used up we are usually talking about non-
renewable resources such as coal, crude oil, natural gas and metals that cannot be
replenished, compared to renewable resources (such as fresh water, air and plants)
that can eventually be replenished by natural processes. These non-renewable
resources become so widely dispersed or changed that it would be very difcult
to gather them back together again.
Using or obtaining a resource often results in producing new, unwanted material.
Burning coal generates corrosive gases that enter the atmosphere. Extracting a metal
from an ore often leaves behind solid wastes that must be discarded.
When we throw away materials such as paper and plastic wrappers, old shoes
and clothes, and food scraps, we do not really get rid of them because at the atomic
level they are still there. The chemical elements found in rubbish may not be useful
in that form, but they are still part of the materials of the Earth.
New materials are formed when substances undergo a chemical reaction.
You were introduced to the idea of chemical properties and chemical reactions in
the Using materialslooking at properties section of this context. Chemists use
balanced chemical equations to describe what is happening when materials undergo
chemical reactions and track atoms. Balanced chemical equations help us represent
on paper how nature accounts for all the atoms in chemical reactions.
The following balanced chemical equation shows what happens when iron rusts:
4Fe(s) 3O
2
(g (( ) gg
2Fe
2
O
3
(s)
This equation tells us that iron reacts with oxygen to produce iron(III) oxide,
which is the chemical formula for the compound rust. It is balanced because there
is the same number of each type of atom on each side of the equation. It also tells us
the state each of the species presents: (s) solid, (l) liquid, ( ll g ) liquid, ( ) liquid, ( ) gas and ( gg aq) aqueous
(dissolved in water).
Burning sugarcane
To learn more about writing and balancing chemical equations, refer to

All living things are alive because
of the thousands, perhaps millions, of
chemical reactions that take place inside
them. Plants rely on photosynthesis
to produce the compounds necessary
for their growth, whereas animals rely
on respiration that occurs in their
cells to produce energy. We are just
one big chemical factory with our
bodies continually breaking apart the
compounds ingested in the food we eat
and reconstructing these basic components
into new compounds to make the building
blocks of our bodies. Most of these
reactions go unnoticed until one or more
of them gets out of control.
Reactions that occur out of place can
often cause problems. If the acidic gastric
juice in your stomach starts reacting with
the stomach lining instead of the food
you have eaten, you may end up with an
ulcer. When the reactions that produce
ozone in the upper atmosphere begin to occur at ground level, the increased ozone
concentrations can cause serious health problems. Research shows that prolonged
exposure to ozone diminishes lung function and increases the risk of respiratory
symptoms like wheezing, chronic phlegm and coughing.
Chemists try to understand what is happening at the atomic and molecular scale
when chemical reactions occur. They can then use this understanding to control
and even alter reactions to change the types and amounts of the various products,
thus improving the materials produced and even developing new ones.
ACTIVITY 1.13
a The reaction of methane (CH
4
) with chlorine (Cl
2
) occurs in sewage water treatment
plants. Common products are chloroform (CHCl
3
) and hydrogen chloride (HCl).
Write a balanced chemical equation for this reaction.
b Balance the following equation showing the combustion of petrol in the engine of
a car:
C
8
H
18
( l ) O
2
(g (( )
CO
2
(g (( ) H
2
O(g O( O( )
c The two following reactions occur in a blast furnace when iron is extracted from
its ore. Balance the reactions.
i C(s C( C( ) O
2
(g (( )
CO(g CO( CO( )

ii Fe
2
O
3
(s (( ) CO(g CO( CO( )
Fe( l ) CO
2
(g (( )
d Why are the phrases using up and throwing away inaccurate from a chemical
viewpoint?
e Considering the law of conservation of matter and resources available, give two
benets of recycling.
f 3.0 g of silver oxide were decomposed into silver metal and oxygen gas. The mass
of silver formed was 2.79 g.
i Write a balanced equation for the reaction.
ii Calculate the mass of oxygen produced.
RECYCLINGCOUNTING ATOMS
Our society faces increasing problems associated with waste. On average each
person in Queensland throws away about 1 kg of unwanted domestic rubbish daily.
Of all this waste 41.7 kg per person is recycled annually.
Taking into account domestic waste, commercial and industrial waste, waste
from construction and demolition and green (plant) wastes, Queenslanders
produce 4.5 million tonnes of waste each year. Approximately 37% of this waste is
recycled while most of the remainder (apart from toxic and hazardous waste) goes
into landll.
Bombadier beetles
Bombardier beetles, like many other plants and animals, are able to produce a chemical
which they use for defence. Stonesh, re coral, stinging nettles, ants, blue bottles and
bees all produce chemicals that discourage predators and that the organism uses for
its defence.
The bombardier beetle is able to eject a hot spray to ward off predators. The hot
solution results when a chemical reaction takes place within the glands in its abdomen.
Within the glands, in a single reservoir it is able to concentrate and store hydrogen
peroxide and hydroquinones.
When a predator disturbs it, it uses muscular contractions to force these liquids into a
second chamber. This chamber contains enzymes that cause the hydrogen peroxide
to be decomposed into water and oxygen gas. The hydroquinones are converted to
quinones. These reactions generate heat, raising the temperature of the solution red
from the beetles abdomen at its predator. Temperatures in the order of 100C are
typically reached so in most cases the predator is effectively discouraged from eating
the beetle.
We extract metals from their ores and transform many different types of natural
materials into useful consumer products. After these products have served their
purpose, they are disposed of and classied as waste. Through this process valuable
non-renewable materials have been lost. The unsystematic disposal of waste has
already led to shortages in some of the less abundant metals such as mercury.
The use of resources is important and affects the whole community since it
concerns most aspects of our lives. As scientists raise awareness of impending
shortages of various natural resources, communities have became more resource
conscious and about 60% of local government councils throughout Australia have
recycling programs.
Recycling involves processing of waste to produce a usable raw material or
product. Recycled material can, in principle, be re-used many times, unlike material
that has been burnt to obtain energy or green waste that has been composted. For
example, most of the gold that has ever been rened is still in use around the world.
The price and availability of virgin raw material have been important incentives
for recycling. Compared with the production from virgin materials, the processing
of recovered materials can lead to less use of energy and less pollution. This is
because the reprocessing starts with a material that is already rened.
Recycling makes good environmental sense. It can avoid some waste materials
entering the natural environment. For example, in Australia about 90% of old car
batteries are recycled, thus avoiding dangerous pollution in landll. Used oils,
solvents and many other chemicals and dangerous substances are treated for further
use. Recycling can reduce greenhouse gases.
Recycling has disadvantages that must be considered. Certain reprocessing
technologies create residues that are difcult to treat but the polluting effect of
using recycled compared to virgin material can only be judged on a case-by-case
basis. For example, the processes involved in de-inking and pulping waste paper
are relatively pollution free using current technology, but de-inking does put salt
in the wastewater efuent.
ACTIVITY 1.14
Table 1.6 shows the total waste generated, recycled and landlled in Queensland for 2003.
TABLE 1.6 Overall waste generation in millions of tonnes for 2003
Waste type
Total quantity
generated
Amount
recycled
Amount
landlled
domestic waste 1.30 0.16 1.14
construction and demolition 1.17 0.49 0.68
green and organic 0.55 0.39 0.16
biosolids 0.29 0.28 0.01
commercial and industrial 0.96 0.21 0.75
regulated waste
a
0.22 0.13 0.09
total
b
4.49 1.66 2.83
Source: The State of Waste and Recycling in Queensland 2003, Queensland EPA
http://www.epa.qld.gov.au
a
Regulated waste includes trackable solid and liquid wastes and 3.3009 tons of oil collected for recycling
by local government. It does not include motor oil.
b
This amount does not include landll cover material of 1.13 10
6
tons or on-site, non-commercial
disposal of waste.
Using and recycling aluminiuman example
recycled is increasing as our awareness of
the impact of our wastes on the environment
grows. Just about any human-made product
could be recycled, given enough time and
money. The materials of greatest concern
as waste are those produced in the largest
amounts. These can be divided into four
general categories: metal (mainly steel and
aluminium), paper, glass and plastics.
According to the Queensland
Environmental Protection Agency, in 2003
the amount of household material recycled
was about 160 000 tonnes compared to a
potential 950 000 tonnes which could have
been recycled (from The State of Waste and
Recycling in Queensland 2003 report).
This amount recycled represents only 17%
of the total possible recyclable.
Queenslanders generate 9000 tonnes of aluminium waste per year,
approximately 2.4 kg per person. However, the recycling rate of aluminium is
quite good with 90% of the population participating in recycling of this material.
Before any material can be recycled it must rst be processed from raw
materials.
a Prepare a bar chart of the total quantity generated, amount recycled and landll
for each type of waste.
b What percentage of total waste was recycled?
c If the population of Queensland was 3 796 800 in 2003, calculate the total quantity
of waste generated per person.
d Use the website http:www.epa.gov.au/environmental_management/waste to nd
out how much waste has been produced this year and compare it with 2003.
Has waste generation improved or worsened? Suggest reasons for this.
e List ve items you used today and discarded.
f Draw up the following table and complete for each of the ve items you have listed.
Item Composition Recyclable
Source/
Renewable
resource
Renewable
or recyclable/
Substitute
material
lunch wrap plastic no crude oil
non-renewable
paper wrap
plastic container
g Prepare a summary list of all items identied by class members in (e). Compare the
number of items made from renewable and non-renewable resources.
Household items made
from aluminium
Making the
aluminium can
of the Periodic Table. It is the third most
abundant element in the Earths crust after
oxygen and silicon. However, whereas
copper, gold, lead and zinc were used by
humans thousands of years ago, aluminium
has only been used for a little over 100 years
because humans did not know until then
how to extract it.
It is the second most used metal (after
iron) as it is very strong, lightweight and
resistant to corrosion. It can be alloyed with
almost any other metal to create material
with a whole range of useful properties.
Uses of aluminium include window frames, parts in cars, kitchen foil and packaging
foil, cans, saucepans and heating and cooling systems.
Aluminium is never found naturally in its pure form. Because of its reactivity
it is found in minerals such as bauxite, which contains aluminium, oxygen and
hydrogen (essentially Al
2
O
3
with variable amounts of water). Australia is the worlds
largest producer of aluminium, mining 40% of the worlds bauxite.
Once mined the aluminium oxide (Al
2
O
3
), commonly called alumina, is
separated from the waste rock by dissolving in caustic soda. The aluminium
is then separated from the oxygen using a process called electrolysis, which
uses large amounts of electricity. This process was discovered by two scientists,
Charles Hall of the United States and Paul Heroult of France, and is now called
the HallHeroult process.
Between 1852 and 1895 the technology for producing pure aluminium was
developed and used. The metal became readily available and, as a result, the price
dropped from US$1090 to US$1 per kilogram.
Mining bauxite for the
production of aluminium
3
AlF
6
). Carbon
rods are placed in the mixture and electricity is passed through the rods, powering
the following chemical reaction:
2Al
2
O
3
(l) 3C(s)
4Al(l) 3CO
2
(g (( ) gg
The molten aluminium, being more dense, settles to the bottom of the tank
and the carbon dioxide bubbles off. The carbon rods are gradually eaten away and
need to be replaced occasionally. The aluminium obtained in this process is more
than 99% pure and can be further rened for special applications to greater than
99.9995% purity.
The advantages of using aluminium as a material are its abundance and relative
ease of preparation. Worldwide, four out of every ve drink cans are made of
aluminium. Although there are plentiful supplies of bauxite the energy requirements
needed to make aluminium are huge. To obtain 1000 kg of aluminium from bauxite
requires the energy equivalent of 120 000 kg of coal. Recycling is an attractive
energy and resource alternative.
About 31% of aluminium produced is recovered for recycling or exported as
scrap. In Australia drink cans are recycled at a rate of 62%one of the highest rates
in the world. Aluminium produced directly from bauxite requires substantial energy
inputs. Smelting of recycled aluminium requires only 5% of the energy needed for
primary production.

Aluminium is obtained
by electrolysing a molten
mixture of alumina and
cryolite; the cryolite is
added to lower the melting
point
Aluminiumonce more precious
than gold
In 1827 German scientist, Friedrich Whler, was the rst person to prepare aluminium
in pure form and to describe its chemical properties. He made aluminium by reacting
aluminium chloride with potassium metal:
AlCl
3
3K
Al 3KCl
Potassium was a costly substance because it had to be separated electrolytically using
an electric current generated from other expensive chemicals in a voltaic cell. By 1845
Whler was making metallic aluminium particles the size of pinheads.
French scientist, Henri St Claire Deville, improved Whlers method and was able to
produce marble-sized lumps of aluminium.
How much? Chemical quantities!
How much aluminium oxide is needed to make one aluminium can? How much
recycled aluminium is needed to make one can?
To answer these questions we need to have an understanding of the chemical
reactions involved and the relationships between reactants and products given in a
balanced chemical equation. For efcient use of substances we need to be able to
calculate the quantities that we should use so as not to waste any.
Consider the balanced equation for the production of aluminium from alumina:
2Al
2
O
3
(l) + 3C(s)
4Al(l) + 3CO
2
(g (( ) gg
This equation tells us that two formula units of aluminium oxide and three
atoms of carbon react to produce four atoms of aluminium and three molecules
of carbon dioxide. This interpretationalthough correctinvolves such small
quantities that the reaction would be completely useless in producing quantities
of the scale needed. It doesnt tell the metal rener how much carbon is needed to
react with the aluminium in quantities that are measurable.
Obtaining answers to the questions posed above requires an understanding
of basic stoichiometry, a study of quantities involved in chemical reactions.
The word stoichiometry comes from the Greek words stoicheon meaning
element and metron meaning measure. It means determining the relative amounts
of materials consumed and produced in chemical reactions using chemical formulae
and equations.
You learnt in the section Elementswhats the difference? that the mass
number of an atom is the sum of the number of protons and neutrons present in
that atom. You also learnt that many elements had isotopes (atoms with different
mass numbers). A term we need for stoichiometric calculations is relative atomic
mass.
Because chemical equations involve compounds as well as individual elements
we need to be able to measure masses of these. Just as each element has a relative
Napoleon III of France was interested in Devilles work and nanced further studies of
aluminium and its preparation as he could see a use for it as a lightweight armour for
his armies. The rst article made from aluminium was a baby rattle for Napoleons son.
Aluminium was too expensive for everyday use but those with enough money had
goods made of it. Napoleon ordered a set of knives, forks and spoons made from
it because it was more precious than gold or silver. He used this cutlery set when
entertaining honoured dignitaries while less important guests had to use gold or
silver sets.
Napoleon III presented his cousin, the King of Denmark, with an aluminium helmet.
The rst view the public had of this precious metal was at a Paris exhibition in 1855
where it was exhibited along with the French crown jewels.
Today aluminium sells for one ten-thousandth of the price of gold.
To learn about relative atomic mass, refer to Chemistry Section 1.14, pp. 1812.
relative molecular mass (for covalent compounds).
Laboratories and factories, however, do not have equipment that will measure
the mass of a few atoms of an element or compound, so chemists needed to devise
a counting unit that was practical for counting out the right number of particles.
Chemists have devised a fundamental counting unit called the mole. A mole is
dened in such a way that 1 mole of any substance contains the same number of
particles (atoms, molecules, ions) as 1 mole of any other substance.
Measuring amounts of chemicals in moles takes into account the fact that
different particles have different masses.
The following examples illustrate the size of a mole. Suppose you had one
mole (6.02 10
23
) of paperclips and strung them together. If you could connect
a million paperclips together every second, it would still take you 190 million
centuries to nish joining them and the string would be able to wrap around the
world 400 trillion (4 10
14
) times.
One mole of 2 cm marbles would form a mountain 116 times the height of
Mt Everest. If 1 mole of Coca-Cola cans were laid end to end they would reach
the sun and back 240 thousand million times.
A mole represents a number of atoms, molecules or formula units large enough
to be conveniently weighed or measured in the laboratory.
One of the great uses of moles is to allow chemists to work out the masses of
different chemicals that will contain equal numbers of atoms, ions or molecules.
To learn how to calculate relative formula mass and relative molecular mass,
refer to Chemistry Sections 3.1 and 3.2, pp. 21820.
To learn more about moles and the relationships between moles, mass and
number of particles, refer to Chemistry Sections 3.3 to 3.6, pp. 2206.
A mole of each of
(clockwise from bottom
left) sulfur (32.1 g), zinc
(65.4 g), copper sulfate
pentahydrate (249.7 g),
mercury(II) oxide
(216.6 g), sodium chloride
(58.5 g), carbon (12.0 g)
and, in the centre, copper
(63.6 g) and ethanol
(46.0 g)
Calculating the right amount for reaction
Now we know the relationship between moles and mass we need to be able to apply
it to chemical reactions. Reactions in which a large proportion of the reactant atoms
end up in waste products contribute to pollution, make ineffective use of resources
and raise the cost of production.
If we do not want to waste chemicals or for expensive chemicals to end up as
waste, we need to be able to calculate the correct amounts of reactants so they are
all used up and none is wasted. We can do this using an understanding of moles
and mass, and apply this using balanced chemical equations.
Consider the question at the beginning of this section:
How much aluminium oxide is needed to make one aluminium can?
The aluminium comes from the aluminium oxide by the chemical reaction:
2Al
2
O
3
(l) 3C(s)
4Al(l) 3CO
2
(g (( ) gg
This reaction tells us the ratios in which the reactants react and the products are
formed. This ratio could be interpreted in atoms, molecules or ions or it could be
interpreted in moles. So 2 mol of aluminium oxide reacts with 3 mol of carbon to
produce 2 mol of aluminium and 3 mol of carbon dioxide.
You can use this equation to answer the question but rst you need to learn
some more about relationships between chemical equations, mass and moles.
To learn about the relationships between chemical equations, moles and mass,
refer to Chemistry Sections 3.7 and 3.8, pp. 22631.
ACTIVITY 1.15
a Using your knowledge of chemical equations and mass, calculate how much
aluminium oxide is needed to produce one aluminium can. Assume the mass
of an aluminium can is 16 g.
b 8.8 10
3
tonnes of aluminium waste was generated in 2003 by Queenslanders.
i If all this waste had been recycled how many cans could have been produced?
ii How much alumina would have been saved?
c You are hired by a company to recover the silver ions in solution produced by the
photographic developing industry. You decide to do this by reacting the silver ions
with copper according to the following reaction:
2Ag
(aq (( ) Cu(s Cu( Cu( )
2Ag(s 2Ag( 2Ag( ) Cu

2
(aq (( )
You are given 150 g of copper metal. How much silver can you recover?
Avoiding wastegreen chemistry
Chemical processes, whether natural or conducted by industry, produce wastes that
can pollute our environment. Chemists are very aware that what chemistry produces
today will have an impact on future generations and they are exploring ways to
reduce pollution by devising new chemical processes that eliminate or signicantly
reduce pollution in the rst place. This movement is called green chemistry.
Green chemistry aims to eliminate pollution by preventing it from happening in
the rst place. One important principle of green manufacturing is atom economy,
which is a simple calculation of how many of the atoms found in the starting
product then they must be going into the waste material.
Counting atoms and understanding the properties and uses of materials are
important in green chemistry if new, more environmentally friendly materials and
processes are to replace those currently in use. These materials and processes must
also be protable for both producers and consumers.
Green chemists work hard to build in manufacturing techniques that have a
high atom economy when creating new products and processes. When a German
pharmaceutical manufacturer designed a new process for making ibuprofen they
nearly doubled the atom economy from 40% to 77%. This green process decreased
the amount of waste chemical by-products and reduced signicantly the amount
of reactants needed, thus conserving valuable resources.
Sometimes the starting material as well as the waste products of chemical
manufacture can be hazardous. Green chemists look for different, safer starting
materials to reduce risks and exposure. The usual starting material for the
manufacture of materials such as nylon, polyurethane and lubricants is adipic acid,
which is typically made using benzene, a known cancer-causing agent. Chemists
have developed a new, greener process using genetically altered bacteria to convert
glucose into adipic acid. The glucose can be derived from cornstarch or the
cellulose found in plant material.
Cornstarch, a renewable resource, is also being used to produce small, puffed,
packaging pellets, which are used to prevent damage to materials shipped in
containers. These pellets are environmentally friendly because they dissolve in water
and are easily digested by micro-organisms. They can replace the more widely used
polystyrene plastic packaging, which is made from petroleum-based chemicals.
Another aspect of green chemistry is the production of fuels from renewable
resources rather than using our dwindling fossil fuels. Biodiesel is diesel fuel made from
renewable resources like oils derived from farm crops such as soyabeans. It can even be
made from recycled vegetable oils like those left over from fast food restaurants and sh
and chip shops. In this process a waste product is converted to a valuable fuel.
Whatever products and materials we use, whether from renewable or
non-renewable sources, they all still have their origin in the resources of the Earth.
We use particular materials because they have specic properties that suit them
to that use, but we should also be aware of the consequences of using particular
materials.
As responsible citizens we should make decisions about the use of materials
based not only on their properties but also on the impact those materials will
have on the resources of the Earth. It is better for the environment and future
generations to use materials that are from renewable resources and materials that
can be recycled.
ACTIVITY 1.16
Is cornstarch packaging as effective as polystyrene packaging?
To investigate this question, obtain some of each of the two types of packaging
materialcornstarch pellets and polystyrene pellets. Design an investigation to test
the effectiveness of the two different materials.
Summary
This context started by looking at the use of materials, which led to investigating the
properties of different materials. All materials have basic components that originated
in stars and the Earth is rich in many materials that are scarce throughout the universe.
In understanding and using the materials of the Earth, it is necessary to understand
their basic components (elements) and the ways in which they are grouped and
classied. When elements combine in chemical reactions, they form compounds
that have their own unique properties, different from the elements of which they
are composed.
The Earth is a closed system and if material is continually used, removed and changed
eventually the resources of the Earth will be exhausted. Chemists keep track of the
elements and compounds through the use of balanced chemical equations and use
the chemical quantity, the mole, to count atoms.
As the amount of waste produced by societies continues to increase, chemists
continue to develop processes through which the waste material can be recycled
or alternative sources of raw material found. Green chemistry attempts to eliminate
pollution by preventing it from happening in the rst place and provides alternative
processes and materials that will benet both the environment and humanity.
GLOSSARY
allotropes different physical forms of the same element, for example graphite and
diamond, ozone (O
3
) and oxygen gas (O
2
)
alumina another name for aluminium oxide (Al
2
O
3
)
atmosphere gaseous layer that surrounds the Earth
atomic number (Z) equal to the number of protons in the nucleus; the same for
every atom of the same element
bauxite an ore of aluminium that contains aluminium oxide
biosphere the part of the Earth in which living organisms live out their lifecycle
carbon cycle the material cycle where carbon atoms are cycled through many
different compounds in the natural environment
chemical change a change in matter resulting in new substances being produced
closed system a system in which no matter may enter or leave
compound substance composed of two or more different elements that cannot
be separated by physical means
element the basic substance from which all matter is composed
formula a group of chemical symbols and numbers representing the composition
of a molecule or compound
hydrosphere mainly water of the Earth found in liquid and solid form
ion an atom or group of atoms that has lost or gained one or more electrons and
thus carries a negative or positive charge
isotopes atoms with the same atomic number (number of protons) but different
mass number (number of neutrons)
lithosphere crust of the Earth mostly composed of rocks and minerals
macroscopic properties those properties that are easily observed
mass number (A) the number of protons plus neutrons in the nucleus
molecules the smallest particle of a substance retaining the properties of the
substance; a particle composed of two or more atoms bonded together
nitrogen cycle the material cycle where nitrogen atoms are cycled through many
different compounds in the natural environment
open system a system in which matter and energy may enter and leave
physical change a change in matter in which the chemical composition of the
substance is not changed, for example melting ice
stoichiometry the study of quantitative aspects of formulae and equations stoichiometry stoichiometry
38
CONTEXT 2
Water: a unique
material
IN THIS CONTEXT
Water is everywhere 39
Ice and waterthe density phenomenon 40
Watera shapely molecule 42
Water going places in plants 43
Blood is thicker than water 45
Getting things in and out of cells 52
Replacing water 54
The water cycle 57
Watergood enough to drink? 59
Treating water 59
Water hard or soft? 64
Bottled water or tap water? 67
Looking after our water supplies 70
Monitoring water quality 75
38 CHEMISTRY IN USE
CONTEXT 2 WATER 39
WATER IS EVERYWHERE
We can nd water almost anywhere on Earthat the poles as ice, in the air as
humidity, in the oceans, rivers and underground. Water denes our planetthe
Earth is known as the blue planet because of water. Currently, about 70% of the
Earth is covered with water but if the Earth were a perfectly smooth sphere and all
the water were in liquid form, it would be covered by a single ocean 2.8 km deep.
Instead, we nd water in different places in varying forms. About 97% of
water is found in the oceans. The polar ice caps and glaciers contain just over
2% of Earths water in the form of solid ice. About 0.6% is under the surface as
groundwater and only 0.017% of all the water on Earth is found in lakes and rivers.
And a mere 0.001% is found in the atmosphere as water vapour.
Water is a very unusual material with lots of peculiar properties. Many scientists
have now concluded that it is an essential component for the development of life.
This is because all organisms are composed of at least 60% water. We use water
to transport substances around our bodiessupplying nutrients to all cells and
removing wastes. We control our body temperature using water. Without water, life
as we know it would not exist. Consequently, scientists searching for life on other
planets always try to establish whether or not water is present in order for life as
we know it to exist.
Lifes need for water is also reected in an Aboriginal story explaining how
life was started in parts of Northern Australia. The story involves Guthi-guthi, the
spirit of the ancestral being calling on Weowie, the water serpent, to come out of
the mountain. But Weowie was trapped in the mountain so Guthi-guthi came down
with a roar like thunder and banged on the mountain. The mountain split open and
the water serpent escaped, making waterholes, streams and depressions. After the
country was created, Guthi-guthi put tribes there to live on the land and Weowie
returned to live in the mountain.
ICE AND WATERTHE DENSITY
PHENOMENON
In fact, one unique property of water allowed life to continue to exist during the
rst ice ages millions of years ago on Earth: if ice didnt oat (have a lower density
than water), the oceans would have frozen from the bottom up, killing all forms
of life.
Water exists as a liquid over an important range of temperature from 0 to
100C. This range allows water to remain as a liquid in most places on the Earth.
Although the average temperature of the Earth is 15C, there are many parts,
particularly at the poles, that have a temperature less than 0C. The liquid water
changes to ice. If this was a regular materialin fact, any other materialthe solid
form would be more dense than the liquid form and so it would sink. However, ice
is less dense than water and oats on the liquid. This unique feature of water is vital
for many marine and freshwater organisms.
ACTIVITY 2.1
Consider the following statements and decide whether each statement is true (T)
or false (F) or needs more information (N).
a Rainwater is the purest form of water.
b Seawater is slightly more basic (the pH value is higher) than most natural
freshwater.
c Water contracts (gets smaller) when it freezes.
d More things can be dissolved in oil than in water.
e Water is unique in that it is the only natural substance that is found in all three
states: liquid, solid and gas.
f Water boils more quickly on Mt Kosciusko than at the Surfers Paradise beach.
g Condensation is water coming out of the air.
h A dairy cow must drink 4 L of water to produce 1 L of milk.
i Your skin is 70% water.
j The water vapour attaches to small bits of dust and forms rain in warm
temperatures and snow or hail in cold temperatures.
k Pure water is tasteless, odourless, and colourless.
l The Celsius temperature scale is based on the melting and boiling temperatures
of water.
ACTIVITY 2.2
Think of an average day when you get up and go to school. How does water inuence
your days existence?
a Brainstorm as many ways as possible that water is used in your daily life.
b Estimate how much water you use in a day. These gures may help: toilet ush
1520 L; shower (10 minutes)100 L; tub bath60 L; automatic dishwashing
40 L; dishwashing by hand35 L; hand washing8 L (with tap running); brushing
teeth10 L (with tap running); outdoor watering35 L/minute; washing machine
225 L.
CONTEXT 2 WATER 41 CONTEXT 2 WATER 41
If solid water sank to the bottom as it froze, lakes and the oceans would freeze
solid from the bottom up. The top surface of the water may evaporate using heat
from the surrounding water, ensuring that it remains cold and perhaps converts into
ice. This means that all the organisms would freeze and die because they lack liquid
water, and they are exposed to temperatures that would cause their bodies to freeze.
Fortunately, however, ice oats. The oating layer of ice insulates the water
below from the cold air, slowing down the freezing process. Once a layer of ice
forms on a body of water, any water below the ice is actually warmed as more and
more layers above it give off heat energy, turning it into a solid. So large lakes rarely
freeze all the way to the bottom (see Fig. 2.1).
At 4C, water that is being cooled begins to expand and become less dense.
In fact, the difference in volume between liquid water and ice can be as much as
9%. The closer it gets to 0C, the less dense it gets, and so a frozen lake actually
has a temperature gradient, with the denser (warmer) layers near the bottom.
The temperature near the bottom stays fairly constant, allowing living organisms
to survive the winter.

FIGURE 2.1
The temperature variation
in an ice/water mixture
ACTIVITY 2.3
Half-ll a glass with ice, then ll the remainder of the glass with liquid water.
a Predict what will happen to the uid level as the ice melts. Will it go up, go down
or stay the same?
b Use the data below to plot density of water against the temperature. Draw a
smooth curve through the points.
Temperature (C) 0 5 10 15 20 25
Density (g/mL) 0.9998 1.0000 0.9997 0.9991 0.9982 0.9970
c Use the information obtained from the graph to explain the results of your ice and
liquid water observations.
WATERA SHAPELY MOLECULE
The molecule forms the following bent shape:
Molecules in liquid water and ice
The liquid molecules line up in liquid water. The molecules have some spaces
between them but are free to move; this is a property of liquids.
In the solid water (ice), the molecules form a denite hexagonal pattern of
oxygen atoms; this explains the crystalline nature of ice. The water molecules in ice
are further from each other than they are in liquid water; this shows why ice is less
dense than water.
The bonding within the water molecule and the interaction between the water
molecules causes the molecules to organise themselves in this way.
To revise the information on electron-dot diagrams, refer to

Water molecules in ice
To understand this molecular and intermolecular bonding better, refer to

WATER GOING PLACES IN PLANTS
All organisms take in water and need it to survive. Plants need water to perform
the process of photosynthesischanging sunlight energy into chemical energy.
This process is performed in the leaves of plants and yet the water is absorbed in
the roots. Somehow, the water has to be transported against the force of gravity
up to the leaves, a distance of up to 100 m in tall trees.
This movement of water is called the transpiration stream and is largely
dependent on the cohesive and adhesive properties of water.
ACTIVITY 2.4
Collect a 5 cent coin, a dropper and a beaker of water. Place the 5 cent coin on a at
surface and place drops of water on the coin. Count how many drops can t on the
coin before the water spills over the side. Observe the shape of the surface of the
water as the number of drops increase.
Before the water spills over the side of the coin, the water seems
to bulge like the top of a mufn. This suggests that the molecules
of water are sticking together, defying gravity! These forces of
attraction between the water molecules are called cohesive
forces and can be explained by the polar nature of the bonding
in each water molecule and the hydrogen bonding between the
water molecules.
This activity demonstrates the dipole nature of each water
molecule and the consequent dipoledipole interaction between
the water molecules. This hydrogen bonding helps the water
molecules stick together.
a Draw a diagram of the coin and represent the molecules
of water. Show the dipole nature of the molecule; that is,
represent the charged ends of the molecule, then draw
arrows to represent the dipoledipole interactions between
the molecules of water.
b Predict what would happen if the activity was repeated using
a non-polar liquid like hexane or kerosene. Would you be
able to t more, the same or fewer drops of water on the
coin before it overowed?
c Check your prediction by performing the task and explain
your results.
d Summarise the features of water that contribute to the
cohesive forces demonstrated.
e Explain, with reference to the properties of water, why some
insects can walk on water.
Capillary action
Paper towels rely on the adhesive and cohesive properties of water. The molecules
of water are attracted to the particles in the paper towel. The movement by the
water up the paper towel due to the adhesive forces is called capillary action.
Evidence of capillary action can also be observed by looking at the surface of the
water in a glass container. The slight increase in the water level where the water
meets the glass is called a meniscus (see Fig. 2.2).
The xylem vessels in plants are like capillary tubes. They rely on the attraction
between the water molecules and the cellulose in the walls of the vessels. The xylem
vessels have very narrow diameters to enhance the capillary action.
FIGURE 2.2
The volume of the water
is indicated by the level
of the horizontal water
surface
ACTIVITY 2.5
Select three or four glass tubes of different diameters (ranging from 1 mm to 4 mm).
Put the tubes in a beaker of water coloured with food dye and support them so they
are straight vertically (see Fig. 2.3).
a What is the relationship between the diameter of the tube and the height of the
water level?
b In which tube is the capillary action greatest?
c What forces are acting to cause the water to move up the tube?
FIGURE 2.3
Capillary action of
tubes with different
diameters
ACTIVITY 2.6
Collect a fresh celery branch that still has the leaves attached. Place the end of the
celery branch in a container of water with some red food dye added.
After a few hours (perhaps earlier) the leaves of the celery will have a red
appearance. Closer examination should reveal the red dye is in the veins of the leaves.
Cutting the stem will show the xylem vessels with red dye inside. Compare the diameter
of the xylem vessels to the capillary tubes.
From roots to leaves
Tall trees rely on having xylem vessels with diameters like that found in the celery.
The polar nature of the water molecules, and their ability to form hydrogen
bonds with other substances, mean that the water molecules can be strongly
attracted to substances besides other water molecules, for example to paper and
cellulose in the xylem vessels.
Water transport in trees relies heavily on the unique bonding properties of the
water molecules. Without the strong cohesive and adhesive forces of water, it would
be difcult, if not impossible, to supply the leaves with water.
BLOOD IS THICKER THAN WATER
Human cells are supplied with water in the blood pumped around the body by the
heart. Water is required to help with a number of functions, including maintaining
the volume of blood. The blood contains erythrocytes (red blood cells), leucocytes
(white blood cells) and platelets, all of which are carried in a straw-coloured uid
known as plasma. Plasma is 90% water with the remaining 10% consisting of
dissolved substances.
The dissolved substances (solutes) are nutrients or wastes or substances
that help the body function. They include inorganic salts and ions (bicarbonates,
phosphates, sulphates, chlorides, calcium, potassium, sodium and magnesium),
organic constituents (glucose, fats, amino acids, vitamins, proteins, enzymes and
hormones), and dissolved gases such as oxygen and carbon dioxide.
The range of substances found in blood plasma shows that water is a good
solvent. In fact, water is sometimes called the universal solvent because of the
number and variety of substances that dissolve in it.
Dissolving inorganic salts and ions
Sodium chloride is an essential electrolyte in humans. (Substances that in aqueous
solutions conduct electricity are called electrolytes; electrolytes conduct electricity
because in solution they dissociate into ions.) Sodium ions enable the transmission
of nerve impulses around the body, and the presence of sodium ions is also essential
for the contraction of muscles, including that largest muscle, the heart. Chloride
ions are a component of hydrochloric acid, which helps food digestion in the
stomach. The salinity of blood and other body uids is 0.9% NaCl.
In water, inorganic salts like sodium chloride dissociate. Cations are attracted to
the negative end of the water molecule (the oxygen atom) while anions are attracted
to the positive end of the water (the hydrogen atoms). The separated ions are then
ACTIVITY 2.7
a Identify the solute and solvent in a cordial drink.
b Solutions are considered to be homogeneous mixtures. Interpret this statement.
c Use the example of the cordial drink to clearly illustrate the differences between
a mixture and a compound.
d How would you determine whether a substance is a pure solvent or a solution?
surrounded by water molecules. Individual ions surrounded by water molecules are
said to be hydrated ions.
Water of crystallisation
Sometimes, ionic substances crystallise from aqueous solutions with the molecules
of water still attached. This is called water of crystallisation. If you have broken
a limb, you may have had a plaster cast applied to help support the bone while
it heals. The plaster (of Paris) is the hydrate of calcium sulfate. When water
is added to the plaster of Paris, a hard crystalline compound, calcium sulfate
dihydrate (CaSO
4
.2H
2
O), eventually forms. The water in this solid is called water
of hydration. Heating the solid can drive off the water, leaving the anhydrous
(without water) salt.
Dissolving organic molecules
Organic molecules contain carbon and were once thought to be made only by
living organisms. For example, sugars are made by plants from simple inorganic
molecules (water and carbon dioxide) in the process of photosynthesis. Organic
molecules can now be manufactured synthetically.
Carbon atoms form the backbone of organic molecules. The structure of
the carbon atom enables covalent bonding. Each carbon atom has four valence
electrons that can be shared individually with other atoms (saturated bonds) or
shared in combination (double and triple bonds).
Hydrocarbons are organic molecules consisting of carbon and hydrogen atoms.
These molecules contain bonds that are polar, yet the overall molecule is not polar.
An example is methane, CH
4,
as can be seen in Figure 2.4, which illustrates that
the hydrogen atoms are positioned evenly around the carbon. In fact, each CH bond
in CH
4
is arranged symmetrically forming a tetrahedral shape with all angles 109.5.
This means that the dipoles cancel out resulting in no net dipole for the molecule.
To learn more about dissolving ionic compounds, refer to

To learn more about water of crystallisation, refer to

ACTIVITY 2.8
Collect 2 g of blue copper sulfate. This is the hydrated form of the compound. Weigh
a test tube then put the 2 g in this test tube. Reweigh the combination and then heat
this. Observe the changes. The appearance of the hydrated crystal changes to a white
colour (anhydrouswithout water form) as the water is evaporated away. At the mouth
of the test tube you may observe droplets of liquid water that has condensed. Heat the
mouth of the test tube so this water evaporates away then reweigh the test tube.
a Calculate the weight of the water that was lost and the new weight of the copper
sulfate.
b Use this data to work out the formula for the hydrated copper sulfate.
Hint: Convert the masses to moles.
The non-polar molecule is not attracted to the polar water
molecule. This means that methane and ethane (C
2
H
6
) are
considered insoluble in water. These molecules are termed
hydrophobic.
Changing molecules
Altering the hydrocarbons by the addition of oxygen, for example changing
methane to methanol or ethane to ethanol, causes the molecule to gain polarity.
The OH, or hydroxyl, group enables hydrogen bonding to occur between the O
of the ethanol and the H in the water.
The organic molecules
that will dissolve in water and
therefore in blood (glucose, fats,
amino acids, vitamins, proteins,
enzymes and hormones)
contain groups of atoms that
make the molecule polar. The
polar molecules are able to
have dipoledipole interactions
with the water molecules, and
dissolve.
Groups of atoms that give polarity to the molecule and thus help the molecule
dissolve in water include:
COH
C=O
CNH

FIGURE 2.4
2D and 3D views
of methane
To learn more about how and why some molecular substances dissolve in
water, refer to Chemistry Section 5.3, pp. 2467.

Polar nature of
ethanol
ACTIVITY 2.9
A nutritionally well-balanced diet for an adult includes 2 L of water a day. We also need
vitamins, but in a much smaller amount (330 mg). Fourteen different vitamins have been
shown to be essential for a person to remain healthy. They are needed in trace (small)
amounts to help catalyse many of the biochemical reactions in the body. Vitamins
can be categorised into fat-soluble (non-polar) and water-soluble (polar) molecules.
(Fats are generally non-polar and dissolve non-polar soluteshence the saying, like
dissolves like.)
By examining the structure, we can predict whether a vitamin is fat-soluble
or water-soluble. Water-soluble vitamins are dominated by polar groups whereas
fat-soluble vitamins have very few polar groups.
Figure 2.5 shows the structure of cholecalciferol (vitamin D
3
). Although there is one
hydroxyl group that is polar, most of the molecule is dominated by non-polar groups.
Overall, this molecule is non-polar. Calciferol, vitamin D
2
, has a similar structure; both
of these vitamins are classied as fat-soluble vitamins.
Consider the structural formulas of following vitamins:
a For each vitamin, identify the polar groups.
b Decide whether the overall molecule is polar or non-polar.
c On the basis of polarity, classify each vitamin as likely to be water- or fat-soluble.
FIGURE 2.5
The structure of the
fat-soluble vitamin D
3
,
cholecalciferol

Dissolving gasesoxygen
Two important gases that dissolve in water are oxygen and carbon dioxide. Oxygen
is transported in the blood to cells to enable cellular respiration to take place. The
waste gas from this process must then be removed. The process of respiration
provides the cells with energy to perform the functions that sustain life.
The respiration reaction is as follows:
C
6
H
12
O
6
6O
2
6CO
2
6H
2
O
Oxygen is a non-polar molecule. There are no dipoledipole interactions
attracting the molecules. So the forces between oxygen molecules consist of very
weak dispersion forces. These forces fail to hold the molecules together and so
some oxygen dissolves in water. The solubility of oxygen in water is low compared
to polar gases. In blood plasma, only 0.3 to 0.7 mL of O
2
is dissolved per 100 mL
of plasma.
This amount of dissolved oxygen in blood plasma is insufcient to supply the
oxygen required to all human cells. The quantity of oxygen carried by the blood is
increased because it is chemically bonded to the molecule haemoglobin in the red
blood cell. Haemoglobin can carry approximately 19.7 mL O
2
per 100 mL blood.
This increases the oxygen carried by the blood to 20 mL per 100 mL blood.
A toxic vitamin
The body excretes excess water-soluble vitamins in urine (a solution of water and
dissolved wastes). However, fat-soluble vitamins can be stored in the liver, as the
following incident reveals.
In November 1911, Douglas Mawson and Xavier Mertz participated in an Australasian
Antarctic expedition. After an accident left them without food, they had no choice
but to eat their huskies. The animals were shared between themselves and the
remaining dogs, and no part was wasted. After some weeks of this diet, Mawson
and Mertz noticed strange symptoms, including dizziness, nausea, abdominal pain,
loss of appetite, irrationality and skin, hair and nail loss. These symptoms became
more severe in Mertz, causing increasing irritability, diarrhoea and madness (delirium).
He at one time bit off his little nger, chewed on it and spat it out. Eventually, his death
followed seizures and a coma.
Mawson and Mertz were suffering from the effects of vitamin A toxicity. The vitamin
A was stored in the dogs livers. In fact, 100 g of husky liver contains the toxic dose of
vitamin A for an adult male human. Mertz (who ate more of the liver) died, but Mawson
was able to recover and tell the story after he returned to the base camp. Inuit or native
North American people do not eat the liver of polar bears or seals, so they avoid the
toxic effects of vitamin A.
ACTIVITY 2.10
Haemoglobin is a respiratory pigment found in human blood. Humans have about 15 g
of haemoglobin in 100 mL of blood. Other animals have different respiratory pigments.
a Find out how these molecules work.
b What factors cause them to release oxygen when required? Your search may be
helped by nding out about oxygen dissociation curves.
Dissolving gasescarbon dioxide
The solubility of carbon dioxide in water (6 mL/100 mL plasma) is about twenty
times greater than that of oxygen, but the quantity that can be transported as a
dissolved gas is still not enough to meet human needs. Most of the carbon dioxide
is transported in the form of bicarbonate ions.
This is possible because the carbon dioxide reacts chemically with water.
The reaction is reversible:
CO
2
+ H
2
O s H
2
CO
3
s H
+ HCO
3
The intermediate product in this reversible reaction is carbonic acid, H

2
CO
3
.
Carbonic acid is present in carbonated soft drinks. The amount of carbon dioxide
in carbonated drinks is approximately 150 times its concentration in tap water.
This is possible by passing pressurised carbon dioxide through water. The solubility
is increased because at this higher pressure more CO
2
dissolves compared to
the amount dissolved at standard atmospheric pressure. When the can or bottle
container is opened, the pressure is reduced and the gas comes out of solution,
forming the characteristic bubbles.
You will learn more about dissolved gases in the Air context.
ACTIVITY 2.11
The solubility of carbon dioxide is
inuenced by temperature.
Figure 2.6 shows the solubility
of carbon dioxide as a function of
temperature (with 1 atm pressure
of CO
2
above the solution).
a Use the graph to state the
relationship between the
temperature and the solubility
of carbon dioxide.
b Research the solubility of
oxygen and another gas
with respect to changing
temperature.
c Comment on whether the
same trend exists.
FIGURE 2.6
The inuence of temperature on the solubility of
carbon dioxide
ACTIVITY 2.12
Historically, the rst carbonated water was prepared by adding sodium bicarbonate to
lemonade. A chemical reaction between sodium bicarbonate and citric acid occurred,
creating carbon dioxide. You may like to try this at home. How could you check if the
gas produced is carbon dioxide? Could you write a balanced equation for the reaction?
Many scientists, including Joseph Priestley, investigated how carbonated water
could be made in order to imitate the effervescent water bubbling up from underground
springs. They believed this water was benecial to health.
Investigate whether carbonated water is benecial to health.
Dissolving by reacting
Other substances besides carbon dioxide may also dissolve by reacting with water.
These substances include chlorine and ammonia.
Some chemical reactions taking place inside organisms produce nitrogen
wastes in the form of ammonia. This waste readily dissolves in body uids, forming
ammonium and hydroxide ions. Ammonium solutions are toxic to organisms.
In humans, these wastes have to be converted to a less-toxic form (urea) at the
expense of lots of energy. If humans could continually drink and then eliminate
the water, the removal of ammonia waste could be more straightforward. Fish do
not have to convert the ammonia as they can readily ush out this soluble nitrogen
waste while replacing lost water.
Dissolved substances can change the properties of water. The pH of pure water
is 7. The pH of a substance is a measure of how acidic or basic a substance is. The
pH scale ranges from 0 to 14. Low numbers (less than pH 7) mean that substances
are acidic whereas high numbers (more than pH 7) mean that substances are basic.
A substance that has a pH equal to 7 is said to be neutral. Dissolving HCl or SO
2
in water will decrease the pH. This is evident when sulfur dioxide dissolves in water
and precipitates as acid rain. Plant foliage is detrimentally affected by this type of
rain. This has led to government regulations reducing the allowable quantity of
sulfur in coal burnt at power stations.
The pH of water can affect whether other substances, for example metals, will
react and dissolve in it. Lead is not likely to dissolve in neutral, pure water but may
dissolve in acidic solutions. This has implications for the use of metals in pipes
carrying our drinking water supply and for the pH of the water.
Effect of solutes upon melting and boiling
points of water
The presence of solutes can change some of the properties of water. These include
the melting point and boiling point. The presence of solutes causes a decrease in the
freezing point of water and an increase in its boiling point.
This adjustment of the melting or boiling point can be used to advantage.
Ethylene glycol is added to water in car radiators to increase the boiling point in hot
conditions and to act as antifreeze in cold conditions. The boiling point of water
will increase 0.512C for each 76 g of ethylene glycol (antifreeze) added to 1000 g
of water. The freezing point will decrease 1.86C for each 76 g of ethylene glycol
added to 1000 g of water. This is also why salt is sprayed on roads in cold areasto
reduce the chance of ice forming by lowering the freezing (melting) point.
This property of water can be utilised in the making of ice-cream.
To learn more about substances that react with water, refer to

Chemistry Section 5.4, p. 248.
You might like to make some ice-cream and observe this property of water.
Chemistry Section 5.5, p. 249, provides a summary of the solubilities of

different types of substances in water.
GETTING THINGS IN AND OUT OF CELLS
transports dissolved nutrients like oxygen and sugar to the cells, while taking away
wastes like carbon dioxide.
Once near the cell, nutrients in the extracellular uid (the uid outside the
cell) must pass through a membrane (the outer covering of the cell) into the cell.
Water provides the medium for this to occur. Substances that can pass through the
membrane generally diffuse according to the concentration gradient. This means
that if nutrients like oxygen are in a larger concentration outside the cell compared
to inside the cell, the net result will be that the particles move into the cell. Likewise,
wastes diffuse out of the cell.
Not all substances can diffuse in and out of cells based on the concentration
gradient. This is because the cell membrane is selectively permeable. A selectively
permeable, or semipermeable, membrane allows the movement of some molecules
or ions, but not others. Often solute particles cannot pass through the membrane
but water molecules can and do so in such a way that the concentration gradient is
reduced. This diffusion of the water molecules across a semi-permeable membrane
(because the solute cannot move) is called osmosis.
We can compare solutions (for example, inside and outside a cell) separated
by semipermeable membranes. When the concentrations of the uid inside the cell
and outside the cell are equal, we say the solutions are isotonic. When the solution
surrounding a cell is more concentrated in solutes than the solution inside the cell,
the solution is hypertonic, and when the reverse applies the solution is hypotonic.
The diagrams in Figure 2.7 illustrate how differences in salt concentration affect
the movement of water into and out of cells.
FIGURE 2.7
Isotonic, hypertonic and
hypotonic solutions
Osmolality is an important factor in the design of sports drinks. Osmolality refers
to the particle density of the uid. In blood plasma the particles include sodium
ions, proteins and glucose. Blood has an osmolality of 280330 mOsm/kg. The
unit, milliosmoles per kilogram of water (mOsm/kg), represents a measure of the
capacity of a solute to dissociate in water. One osmole represents the amount of
substance that dissociates in a solution to form one mole of osmotically active
particles. One milliosmole represents one-thousandth of an osmole.
Sports drinks that contain carbohydrate, electrolytes (mineral ions including
sodium), sweeteners and preservatives and have an osmolality of 270330 mOsm/
kg are said to be in balance with the bodys uidthey are isotonic. Isotonic
drinks are more quickly absorbed into the blood and so the athlete is more quickly
rehydrated. Most athletes effectively rehydrate (replace uid lost through sweating)
using isotonic drinks. Gymnasts and jockeys or other athletes who need to be
careful of excess energy intake sometimes use hypotonic drinks (with less sugar)
whereas athletes who exercise for extreme lengths of time (2 hours and longer)
use hypertonic drinks to help replace the sugars used.
The rst sports drink was made at the University of Florida in 1966. It was
developed to help the football team members known as the Gators to rehydrate.
This drink, Gatorade, is now popular in Australia.
Food standards in Australia place restrictions on the formulation of sports
drinks. As a result, sports drinks sold in Australia are very similar in composition
(see Table 2.1).
TABLE 2.1 Carbohydrate and sodium ion concentrations in various sports drinks
Drink Carbohydrate (%) Sodium (mmol/L)
Isosport 6.7 18
Gatorade 6.0 18
Powerade 8.0 10
PB Electrolyte Drink 6.8 25
Energiser 6.0 18
Staminade 5.0 10
Source: http://www.ausport.gov.au/fulltext/2001/ascpub/FactFluid.asp
ACTIVITY 2.13
An effective isotonic drink can be made cheaply if it conforms to the following criteria.
The concentration of the carbohydrate (glucose, sugar or other similar carbohydrate,
such as glucose polymers) should be in the range 48% (that is, between 40 g and 80 g
carbohydrate per litre of water). More than about 8% carbohydrate in your sports drink
will slow down the rate at which the uid empties from your stomach into the intestine
and will therefore interfere with rehydration. Sodium content should be 2030 mmol per
litre (that is, about 12 g of table salt per litre). Added avouring (such as fruit-avoured
cordial concentrate) does not take the carbohydrate level above about 8%.
Make your own isotonic sports drink by mixing 5 tablespoons of table sugar and
1/3 of teaspoon of salt into a litre of water. Compare your sports drink to a commercial
brand.
A word of warning
are low in sodium. This can slow down gastric emptying, and makes these drinks a
less suitable choice, especially for high intensity activity.
Some sports drinks like Red Bull are marketed as energy drinks and contain
the stimulant caffeine. This drug acts as a diuretic (causes the production of urine)
and therefore slows down the rehydration process.
REPLACING WATER
Our bodies are made up of 5060% water; the total amount of water in the body
of an average adult is around 37 litres. We need to replace water that is lost through
breathing, sweat, and urine so that our bodies can continue to function normally.
A 20% loss of water results in death. We must drink water regularly if we are to
function normally and survive.
Table 2.2 shows the average water inputs and outputs of an adult. The quantities
may vary, depending on the level of activity, the weather, and the diet, but all
humans lose water and need to replace the amount lost. (Metabolic water refers
to the water that results from chemical reactions taking place inside the body.)
TABLE 2.2 Input and output for a human during 24 hours
Input Output
drinking 480 g skin 500 g
beverage 580 g expired air 350 g
water in solid food 720 g urine 1100 g
metabolic water 320 g faeces 150 g
total 2100 g total 2100 g
Source: http://www.ausport.gov.au/fulltext/2001/ascpub/FactFluid.asp
ACTIVITY 2.14
Choose another sports
drink and compare its
composition to the drinks
listed. How do they
compare?
Australians live on the driest inhabited continent, yet most take the availability
of safe drinking water for granted. What qualities do you expect in your drinking
water?
Guidelines for drinking water quality
In 1984, the World Health Organisation (WHO) released its Guidelines for Drinking-
water Quality. This publication has become the basis for drinking water standards
around the world. In Australia, the guidelines for drinking water have been prepared
by the National Health and Medical Research Council (NHMRC) and are based
on WHOs standards:
http://www.who.int/water_sanitation_health/dwq/en/
Drinking water providers (local councils or contracted companies) in Australia
try to follow these guidelines. According to these Australian Drinking Water
Guidelines (ADWG):
Drinking water should be safe to use and aesthetically pleasing. Ideally, it
should be clear, colourless, and well aerated, with no unpalatable taste or odour,
and it should contain no suspended matter, harmful chemical substances or
pathogenic micro-organisms.
Source: Australian Drinking Water Guidelines
http://www.health.gov.au/nhmrc/publications/synopses/eh19syn.htm
Generally, people turn on the tap and expect a continuous supply of drinking
water that meets these standardsbut where does this water come from?
ACTIVITY 2.15
Obtain a glass of tap water.
a Describe the appearance, odour and taste of the water. (This activity should be
done at home.)
b Design some criteria (four or ve qualities) to judge whether the water would be
acceptable to drink.
c Identify your criteria that are concerned with the aesthetic qualities of the water
(pleasing appearance, taste and odour).
d How many of your criteria are based on safety?
e After reection, prioritise your criteria.
f Compare and justify your criteria to others.
Perhaps you are a bushwalker or have some experience with camping and trekking.
Sometimes you use the water from nearby available sourcescreeks and streams.
An Australian bushwalker, Roger Cafn, laments:
Once upon a time, long long ago, you could drink from a mountain stream and be
condent you were getting better water than they serve up in the towns and cities.
But not any more: you stand a good chance today of getting some nasty bug or
wog. Sadly, too many of us know this only too well. Why is this so, and what has
gone wrong? Sadly, there are now several dangers lurking in our watercourses
which can harm you.
Source: http://www.bushwalking.org.au/FAQ/FAQ_Water.htm
g What do you think Roger was referring to by the statement, there are now several
dangers lurking in our watercourses which can harm you?
h Consider the criteria you devised to assess tap water. Would this change if you
were a bushwalker considering using creeks and streams for drinking water?
The water source depends on where you live in Australia. Most Australians live
in a catchment or natural drainage area bounded by sloping hills. The water supply
is obtained directly from a river or an articial storage site like a dam or reservoir.
Water is supplied to Brisbane and the surrounding towns from the Somerset and
Wivenhoe dams upstream in the Brisbane River. Adelaide water is piped from the
Murray River, which is part of the MurrayDarling catchment.
Other Australians are not able to rely on catchment water. In the Mutijulu
township near Uluru, rainwater is used for drinking. The rainwater is collected
from a sophisticated catchment system on the roof of each house and stored for
use in tanks.
Some Australians rely on tapping into a water supply that is stored beneath the
ground. Over 50% of the water supplied to the Perth area comes from groundwater
supplies. Groundwater results from rain that percolates down through the soil or
fractures in rock, lling up the pores between sand grains or the ssures in rocks.
Groundwater underlies 60% of Australia (5 226 440 sq. km). The largest source
of ground water is the Great Artesian Basin (Fig. 2.8), which extends through
Queensland, New South Wales and South Australia.
Australians living on Rottnest Island off the coast of Perth originally relied
on rainwater collected in an articial catchment sealed with bitumen (known as
a roaded catchment). When this supply proved inadequate, a drilling expedition
identied freshwater bore supplies. After further expansion of the population,
the locals had to use the bountiful supply of saline groundwater, after desalination
treatment. Water is now collected from three main sources on the island: a rainwater
catchment, an underground freshwater bore eld, and desalination of saline
groundwater. On Kangaroo Island near Adelaide, seawater is processed for
drinking water.

FIGURE 2.8
The Great Artesian Basin
THE WATER CYCLE
Figure 2.9 represents how water is recycled in the environment. For each of the
above-mentioned places in Australia (Brisbane, Adelaide, Mutijulu, Perth, Rottnest
Island), identify on the diagram the water source for drinking water. What is the
source of your drinking water?
Companies that supply water for drinking perform chemical tests on the water
supplied to customers. The tests reveal the quantities of some solutes dissolved
in the water. The quantities of solutes are expressed as a concentration, or a ratio,
of the quantity of solute compared to the quantity of solute (water). There are a
number of ways that concentration can be expressed, including molarity, ppm
(parts per million) and g/L.
Solubility compares the amount of solute to the amount of solvent. The comparison
is the concentration. Concentration may be expressed in a number of different ways.

FIGURE 2.9
The water cycle
ACTIVITY 2.16
Consider the sources for drinking water in Australia: natural catchments, rainwater,
groundwater, and seawater.
Brainstorm a list of all the possible contaminants (or substances that may be in
these water sources, but that you would not like to have in your drinking water). For
each substance describe:
a the substance
b how the substance got into the water source
c why you would not like this substance in your drinking water.
From the brainstormed list, choose three different types of substances and for each
substance propose a method that may be used to eliminate or reduce the quantity of
the substance between the drinking water source and the tap water supply.
To learn more about how solubility is expressed and how to convert from one
unit to another, read Chemistry Sections 5.9 to 5.11, pp. 25563.
ACTIVITY 2.17
The term hydroponics comes from the Greek: hydro = water + ponos = labour.
Hydroponics involves growing plants without soil. This can be done by observing the
following needs of the roots of plants: water, mineral nutrients, oxygen and support.
Plants grown hydroponically can be grown in humid air, in an inert substance with
water around it, or in water infused with air.
Figure 2.10 shows various methods used to set up hydroponic systems. (The support
is provided by non-soil media such as perlite, sand, gravel, rock wool, and sawdust.)
All plants need sixteen elements to grow. These elements are C, H, O, N, P, K, Ca,
Mg, S, Zn, Cu, Fe, Mn, B, Mo and Cl. Some oxygen and the carbon (carbon dioxide) are
absorbed from the atmosphere, but the plants derive most of these elements from the
minerals in the soil.
Hydroponic solutions used for growing plants must contain the correct proportion
of mineral ions. The anions and cations typically needed in large quantities include
nitrates (NO
3
), sulfates (SO
4
2
) phosphates (as dihydrogen phosphate H
2
PO
4
),
calcium (Ca
2
), magnesium (Mg
2
), and potassium (K
).
Table 2.3 represents part of a recipe to prepare a hydroponic solution.
a For each of the chemical compounds, calculate the molarity.
b Calculate the ion concentration for the following elements: magnesium, zinc
and nitrate.
c What is the concentration of copper ions in ppm?
d If a hydroponic solution required a 3.5 millimoles per litre concentration of
potassium ions and the potassium was added in the form of potassium nitrate,
how much potassium nitrate would you add to make a 10 L solution?
TABLE 2.3 Chemicals needed to prepare 1000 L of nutrient solution
Nutrient chemicals Weight in grams
potassium dihydrogen phosphate 263.00
potassium nitrate 583.00
calcium nitrate 1003.00
magnesium sulfate 513.00
copper sulfate 0.39
ammonium molybdate, (NH
4
)
2
MoO
4
0.37
zinc sulfate 0.44
Source: http://www.tre.umn.edu/teaching/Nursery_Management_I/Hydroponics/Hydroponics_Lecture1.htm

FIGURE 2.10
Plants growing
hydroponically
WATERGOOD ENOUGH TO DRINK?
Although three-quarters of the Earths surface is covered with water, about 97% is
too salty to drink. Another 2.5% is either frozen or too far underground to reach,
leaving just 0.5% of the Earths water for drinking, washing, ushing toilets and
watering crops.
In Australia, providers of drinking water try to ensure that the water meets
the Australian Drinking Water Guidelines. People want to be able to drink tap water
without concerns of contamination or poisoning, which can occur in some other
countries.
TREATING WATER
Figure 2.11 shows a representation of how municipal water providers treat the
water.
To get an idea of the relative amounts and availability of all types of water
present on Earth, you can do an experiment. (Refer to Chemistry in Use Book 1
Teacher Resource CD-ROM.)
ACTIVITY 2.18
The bushwalker, Roger Cafn, identies four main classes of possible contaminants
in water:
1 suspended matter such as dirt, vegetable matter, clay and rock dust
2 dissolved but harmless materials like tannins and salt
3 chemicals not included above, such as solvents and agricultural chemicals
4 viruses, bacteria, protozoa, nematodes and the like, also known as bugs.
To avoid drinking contaminated water a bushwalker would generally use several
processes to select and treat the water.
A bushwalker could choose to collect the water from a clear running stream, in
a container covered by a handkerchief. A chemical tablet could then be added to the
water. This water is left for a period of time with the lid off. Alternatively, the water may
be boiled before drinking.
a List the substances that may be removed by these processes.
b How is each substance or the threat of the substance removed?
c Are there any substances that may not be removed by these processes?
ACTIVITY 2.19
Use Figure 2.11 to create a ow chart for the water treatment process.
The process of occulation (and coagulation) is used to help remove ne
suspended solids and colloidal particles. Colloidal solids are particles with a
diameter of less than 0.01 mm. These include ne silts, bacteria and viruses that
might not settle for days, months or even years. These substances make the water
appear cloudy or turbid. Flocculation involves using a chemical coagulant that will
combine smaller particles into larger ones. The larger particles can be ltered out
more readily.
In the coagulation process, a coagulant such as aluminium sulfate, Al
2
(SO
4
)
3
(sometimes called alum), is added to the water and stirred. The alum reacts rapidly
with the carbonates, bicarbonates and hydroxides present in the water. This reaction
produces a gelatinous (jelly-like) precipitate of aluminium hydroxide that entraps
and absorbs impurities. The clump of particles is called a oc.
Al
2
(SO
4
)
3
.14H
2
O 3Ca(HCO
3
)
2
2Al(OH)
3
3CaSO
4
6CO
2
14H
2
O
aluminium sulfate calcium aluminium calcium carbon water
bicarbonate hydroxide sulfate dioxide
After 20 to 30 minutes, the oc particles are usually visible and will look like
tiny tufts of cotton wool, separated by clear water. The water is then ltered to
remove these particles. Generally, the water is ltered through sand that traps the
undissolved particles. Sometimes, this sand can be back-ushed to clean it for
reuse, but the sand must be replaced at regular intervals.
These processes are very effective at removing ne suspended particles that
attract and hold bacteria and viruses to their surface. Research has shown that these
processes alone are capable of removing up to 99.9% of the bacteria and 99% of
the viruses from water supplies. Some of the organic matter washed from soil and
vegetation as water travels into the drinking water source is also removed. This
natural organic matter is often responsible for any brown discolouration in water.
Natural organic matter that is not removed may contribute to the taste and odours
present in some drinking water.

FIGURE 2.11
Water treatment
processes
Why does the aluminium hydroxide form
a precipitate?
Because of the dipole nature of water, most ionic compounds like NaCl are soluble
in water. However, some ionic substances like Al(OH)
3
are not very soluble. This is
because the ionic bonding between the ions is stronger than the attraction between
the ions and the charged ends of the water molecule. Ions that have a greater
attraction for each other than for the water molecules will form a precipitate.
For practical purposes, a salt is considered to be soluble if 1 g or more dissolves
in 100 g of water. If less than 1 g dissolves, the salt is considered to be insoluble.
This does not mean that none of the substance will dissolvejust that the quantity
will be less than 1 g. Solubility rules have been developed experimentally to enable
us to predict salt solubility.
Disinfecting water
In the treatment of water for Brisbane, the water is rst ltered, and then ammonia
and chlorine (in the form of hypochlorous acid, HOCl) are added to form
chloramine, which kills any remaining bacteria and viruses. Chloramine (NH
2
Cl) is
a compound made from chlorine and ammonia. The concentration of chloramine
is maintained in the water to ensure bacteria do not re-grow in the distribution
system.
HOCl + NH
3
s NH
2
Cl + H
2
O
These substances, while safeguarding the water, may cause a slight odour and
can be toxic to aquatic life. For this reason, tap water should not be used directly
in an aquarium. It must be treated to remove all traces of chloramine.
To learn more about precipitation reactions and the solubility of ionic

compounds, refer to Chemistry Sections 5.6 to 5.8, pp. 2504.
ACTIVITY 2.20
Water treatment plants typically clean water by taking water through the following
processes: (1) aeration; (2) coagulation and occulation; (3) sedimentation; (4) ltration;
and (5) disinfection.
Using chemicals and equipment available in the laboratory, design a way of
obtaining drinkable water from a sample taken from your local creek. Evaluate
theoretically the energy expenditure, safety issues, drinkability and efciency of
your proposal.
Disease-causing microbes
The idea that water could contain and transmit disease-causing organisms was
investigated by Dr John Snow in London in 1848. At the time, it was common practice
to have sewage outlets feeding into the drinking water supply. Systematic investigation
by Snow during a cholera outbreak in which at least 53 000 people died demonstrated
the relationship between the disease and infected water supplies. It is now well known
that the bacterium Vibrio cholerae can be transmitted in water and cause cholera, but at
that time few people believed him. Dr Snow addressed this problem by breaking off the
handle of a water pump that was near a sewage outlet, so that people could no longer
use the water from that pump. This reduced the number of people dying from cholera.
A memorial to Dr Snow now marks the place where the pump once stood.
Besides the bacterium that causes cholera, other disease-causing microbes may
be found in water. Cryptosporidium and Giardia are micro-organisms that may
cause gastroenteritis. The organisms are usually spread by contact with pets, farm
animals or people who are already infected. These organisms are both very small.
A Cryptosporidium parasite is 2 to 6 microns (thousandths of a millimetre) in size.
A Giardia parasite is about 8 to 12 microns. The presence of a bacterium called
Escherichia coli (abbreviated to Escherichia coli Escherichia coli E. coli) in drinking water is a sign that the water E. coli E. coli
is contaminated with faeces as this bacteria lives in the digestive tract of animals,
including humans.
Some lters have pores that are small enough to trap disease-causing microbes, but
even water providers that use lters also disinfect the water to ensure the water does
not develop contamination during the distribution.
ACTIVITY 2.21
Chloramines are one way of disinfecting water. Chorine gas is used in Townsville, but
by-products of this procedure are trihalomethanes (THM), for example chloroform.
THMs are formed when free chlorine mixes with organic materials in the water. THMs
are possible carcinogens. The Australian Drinking Water Guidelines suggest maximum
values for a range of by-products formed from the disinfection process (for example,
0.25 parts per million for chloroform-type compounds). Studies comparing the risk of
death due to contamination of microbes in water with the levels of carcinogens in water
have been completed. The ndings suggest that the risk of death from the microbes
is at least 100 to 1000 times greater than the risk from carcinogens. Compared to
chlorine, chloramines have been found to be less likely to react with dissolved organic
matter in the water and so produce fewer disinfection by-products.
The Gold Coast City Council water treatment plant uses chlorine dioxide, which
is about ten times more expensive than chlorine. Its use does not lead to the formation
of THMs.
Noosa Council now use a biological activated carbon (BAC) and ozone system for
the disinfection of the drinking water, while ultraviolet radiation (UV) is being trialled in
other places. The Douglas Shire Council has selected to use the microltration process
to disinfect the drinking water supply of the tourist destination of Port Douglas.
Figure 2.12 illustrates the idea of ltering impurities in order to supply drinking
water. The pore size determines the effectiveness of the ltration. Sufciently small
pores enable microbes to be trapped in the lter. The reverse osmosis ltration can
convert water from the sea into drinking water. This process is used in many remote
areas including the Aboriginal communities of Wujal Wujal in the Daintree rainforests
of Cape York in North Queensland and further north to Bamaga and Yam Island in the
Torres Strait. Gulf countries in the Middle East obtain 95% of their drinking water from
oil-powered units desalinating seawater.
Balancing the treatment
Generally the acidity (pH) needs to be controlled during water treatment. For alum
to form a precipitate pH needs to be about 6 or higher. Often it is necessary to add
slaked lime, Ca(OH)
2
, to raise pH (remove hydrogen ions) before adding alum:
Ca(OH)
2
+ 2H
+
2H
2
O + Ca
2+
Reverse osmosis works by pumping water at a huge pressure through a
membrane (to approximately 6000 kPa). The process takes place because of
the enormous pressure forcing the water through the membrane. The water from
seawater passes through a membrane, which rejects 99% of salt molecules.
The freshwater passing through the membrane is collected. The process is called
reverse osmosis because the movement of the water from a more concentrated
solution (the saltwater) to the freshwater is the opposite of what would naturally
occur (see Fig. 2.13). In Australia, the energy used in this treatment is generally solar.
a Investigate alternative techniques to disinfect water.
b For each system, name the advantages and disadvantages.
c What factors should be considered when deciding how the water should
be disinfected?
FIGURE 2.12
Different types of lters
and the particles they
can trap
FIGURE 2.13
Reverse osmosis lter
set-up
As alum forms a precipitate of Al(OH)
3
it lowers the pH and if too much alum
is added the water becomes acidic. Hence it is often necessary to adjust pH after
ltration (as in Fig. 2.6).
Generally, lime is added before adding alumto give a high enough pH for
Al(OH)
3
to precipitate and the formation of this precipitate brings the pH back
to the neutral range.
When the water is acidic, it is more likely that reactions between water and
the metals in the pipes will take place. Lead metal may change to lead ions, which
are capable of causing health problems. The Australian Drinking Water Guidelines
suggest that concentration of lead ions should be less than 0.01 mg/L. The pH of
drinking water should be between 6.5 and 8.5.
To add uoride?
Fluoride is not added to Brisbanes water but it naturally contains less than
0.1 mg/L. Fluoride in the form of sodium uoride (NaF) is added to most water
supplies (at a concentration of 1 ppm) to help teeth development and maintenance.
In teeth, uoride ions combine with calcium to form a calcium compound called
uorapatite, which improves resistance to dental decay. There is an ongoing debate
in Brisbane as to whether this policy should be changed. Opponents to the addition
of uoride to drinking water cite concerns that uoride may be carcinogenic
(cancer-causing).
The treatment of water ensures that the Australian Drinking Water Guidelines are
met; that is, the water is safe to use and aesthetically pleasing. The water, however,
contains dissolved substances that may affect the taste and usefulness. Removal of
these ions is not necessary for health reasons.
WATER HARD OR SOFT?
Two ions that affect the taste and usefulness of the water are calcium and
magnesium. These ions occur naturally in water sources. The concentration of
the ions varies with the source; for example, water that passes through limestone
rock (CaCO
3
) will generally contain a large quantity of calcium ions. These ions
contribute to the hardness of the water. Water is described as hard when a lather
or suds for washing is more difcult to make.
ACTIVITY 2.22
Blue water (copper corrosion) can appear when water is supplied through and reacts
with copper pipes. The water turns bluegreen in colour as the corroded copper comes
off the inside of the pipes into the water.
Cu (copper metal) 2e
(electrons) Cu
2
(copper ions)
For aesthetic reasons, mainly because of the staining of ttings and tiles, the
copper concentration should be less than 1 mg/L. For health reasons, copper
concentration in drinking water should be less than 2 mg/L. The bitter, metallic taste
of copper can be detected by some people when the concentration is above 3 mg/L.
Design and perform an investigation to determine the properties of water most
likely to cause corrosion of the copper pipes. Consider the variables temperature,
pH and water hardness.
Calcium and magnesium ions can react with soaps and detergents, rendering
them ineffective in cleaning. Instead, an insoluble scum may form in sinks and
bath tubs.
The scum results from a reaction between the calcium ions and the soap
molecule. A soap molecule contains a sodium ion attached to a long hydrocarbon
chain referred to as a stearate ion. The sodium end of the molecule is polar and
dissolves in water. The hydrocarbon end is non-polar and dissolves in fats or grease
(stains on clothing) (see Fig. 2.14).
Calcium or magnesium ions in solution may replace the sodium ions. These ions
are less soluble and form a precipitate with the stearate ion. Visually, this appears as
a scum in the bath.
Water softening
The principle of water softening involves removing the calcium and magnesium
ions. This process can be achieved by ion exchange where the calcium and
magnesium ions are swapped with soluble sodium ions. A substance called zeolite
(Na
2
Z, where Z is an aluminosilicate anionthat is, it contains aluminium, silicon
and oxygen) can be used for this process.
Na
2
Z(s) + Ca
2+
(aq) CaZ(s) + 2Na
+
(aq)
Alternatively, washing soda (sodium carbonate, Na
2
CO
3
) could be added to
the water. The precipitate CaCO
3
can be rinsed away more readily than the scum
precipitate. Other water softeners include sodium tetraborate or borax (Na
2
B
4
O
7
)
and trisodium phosphate (Na
3
PO
4
).

FIGURE 2.14
The structure of sodium
stearate (soap) and the
way the stearate ion
interacts with grease
You can perform an experiment to determine the hardness of your local water
supply. (Refer to Chemistry in Use Book 1 Teacher Resource CD-ROM.)
Investigating water hardness
General descriptions of water hardness are displayed in the following table.
Notice that hardness is reported as the concentration of calcium carbonate.
(The concentration of calcium ions and magnesium ions are added to report this
total gure.)
The average total hardness of Brisbane water is 152 ppm. The National Health
and Medical Research Councils Australian Drinking Water Guidelines suggest a
maximum of 200 ppm for drinking water.
TABLE 2.4 Water hardness scale
Description of water
Hardness
(mg/L calcium carbonate)
soft 050
moderately soft 51100
slightly hard 101150
moderately hard 151200
hard 201300
very hard over 300
Scale
Hard water can also produce
other problems. In hot water
appliances, a scale (precipitate)
of calcium carbonate may build
up on the heating element
(see Fig. 2.15). Scale build-up
in the water heater can slow
the heating process and
increase the energy usage.
This suggests that change in
temperature may alter the
solubility of solutes.
ACTIVITY 2.23
a Water from a particular source was quoted as having a hardness of 54 mg/L.
What hardness classication would be attributed to this concentration?
b Express 54 mg/L as the total moles of calcium and magnesium ions per litre.
c What is the hardness of water in which the calcium and magnesium ions have
concentrations of 3.7 10
4
and 0.9 10
4
moles in 1 litre respectively?
FIGURE 2.15
Scale build-up
You can do an experiment to investigate the relationship between temperature

and solubility. (Refer to Chemistry in Use Book 1 Teacher Resource CD-ROM.)
BOTTLED WATER OR TAP WATER?
Australian tap water is generally considered safe to drink. Unfortunately, this is not
the case in many places around the world, where the water may be contaminated
and unsafe to drink (see Fig. 2.16). People in different countries make choices
about drinking bottled water in preference to tap water (see Table 2.5).
FIGURE 2.16
Access to safe drinking
water
Table 2.5 Per capita consumption of still bottled water
Actual litres Actual litres Forecasted litres Forecasted litres
1997 1998 1999 2000 2001 2002 2003 2004 2005 2006
Australia 6.1 7.1 10 11.1 11.9 12.4 12.8 13.1 13.5 14
New Zealand 1.7 2.2 2.8 3.4 4.0 4.6 5.3 6.0 6.8 7.6
Asia Pacic 3.6 3.5 4.1 4.8 5.7 5.7 7 8.8 11.4 14.6
Western Europe 48.2 50.6 53.7 57.5 61.6 65.3 69 72.7 76.3 80.1
France 97.3 102.2 109 114.4 122.1 128.5 134.8 141 147.2 153.9
UK 8.9 9.1 9.9 11.5 13.4 14.9 16.8 19.6 22.6 26.2
Eastern Europe 3.5 3.8 4.7 5.2 5.9 6.6 7.3 8 8.7 9.5
USA 25.2 28 34 36.5 38.9 40.7 42.1 43.4 44.6 45.6
Source: http://www.softdrink.org.au/html/industry.html
In Sydney in 1998, an incident suggested that the tap water there was not
completely safe. Improvements in technology increased the ability to detect the
presence of Cryptosporidium parvum, an intestinal parasite that can nd its way
into water via infested cattle dung. Many Sydney residents switched to bottled
water after very small quantities of this parasite were shown to be present in the
tap water. That particular event provided the bottled or packaged water industry
with a sustained 30% growth that year and subsequent growth of approximately
10% per year ever since.
In Australia, all major cities and the majority of rural water providers supply
water that meets the Australian Drinking Water Guidelines and consumers can access
information to nd out how the water is treated.
Bottled or packaged water products are regulated by another authority, the
Australia New Zealand Food Authority (ANZFA) under the Australia New
Zealand Food Standard Code. The regulations have some differences; for example,
the recommended limit for bromate in tap water is 0.02 mg/L and 30 mg/L for
bottled water. A study of 30 brands of bottled water sold in Australia conducted by
CHOICE in 2000 showed that 12 contained more bromate than is recommended
for tap water under National Health & Medical Research Council guidelines.
One contained almost twenty times the recommended limit for tap water.
ACTIVITY 2.24
Copy and complete the following table by accessing the websites provided. Comment
on the similarities and differences in the accepted standards.
Australia New Zealand Food Standard Code: http://www.foodstandards.gov.au/
Australian Drinking Water Guidelines :
http://www.health.gov.au/nhmrc/publications/pdf/fs14_15.pdf
Australia New Zealand
Food Standard Code
component
Food Standard Code
maximum concentration
(mg/L)
Australian Drinking
Water Guidelines
(mg/L)
arsenic
barium
borate (calculated as H
3
BO
3
)
chromium (VI)
copper
cyanide (calculated as CN
)
uoride (calculated as F
)
lead
manganese
mercury
nitrate (calculated as NO
3
)
nitrite (calculated as NO
2
)
zinc
Types of bottled water
There are two categories for bottled water. The rst category is spring and mineral
water. This water must come from an underground source. There is no requirement
for approval of the source used to obtain mineral water. Water bottled as natural
spring or natural mineral water has not been treated to remove unwanted chemical
and microbiological components.
ACTIVITY 2.25
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The second category of bottled water is packaged water (other than
mineral water). Packaged water must be from an approved source or prepared
by an approved treatment, or both. Sources include artesian, well and tap
water. Treatment may include carbonating, distilling, deionising, uoridating,
demineralising, ozonation, ultraviolet irradiation, and mineral adjustment. The label
on these packaged water containers must show how they have been treated, for
example carbonated, demineralised or distilled.
An article in the Sydney Morning Herald in 2004 suggested there are more than Sydney Morning Herald Sydney Morning Herald
1000 water brands of bottled water available in Australia. Each year, Australians
consume more than 520 million litres. In Australia it costs less than 0.1 cents to ll
a 1 L bottle from the kitchen tap but generally the cost of an equivalent-sized bottle
of water is more than $1.00. That is more than a one thousand-fold difference in
price. Is bottled water that much better?
LOOKING AFTER OUR WATER SUPPLIES
European settlers in Australia saw endless opportunities to clear land and farm.
Little consideration was given to the differences between the climates (particularly
the volume and reliability of rainfall) of their old and new environments.
Consequently, the sustainability of these practices was not questioned at the time.
Some of the problems with the farming practices are now obvious. Agricultural
practices on the land have been blamed for the degradation in many areas of
Australia, including the Great Barrier Reef.
How can water practices on the land affect
what happens in the sea?
The Great Barrier Reef stretches for more than 2300 km along the north-east
coast of Australia from the northern tip of Queensland to just north of Bundaberg.
It is the biggest system of coral reefs (about 3400 separate groups) in the world.
An estimated 1500 species of sh and more than 300 species of hard, reef-
building corals have been identied and more than 4000 mollusc species and over
400 species of sponges have been collected. Six species of turtle, the dugong, and
more than 240 species of birds also occur in the region. The signicance of this
unique combination of biological diversity and size led to the establishment of
the Great Barrier Reef Marine Park in 1975 by the federal government. This was
followed by the Great Barrier Reef being selected and placed on the UNESCO
World Heritage List in 1981.
In 2001, the Ministerial Council for the Great Barrier Reef noted that activities
in the catchments adjacent to the Great Barrier Reef were affecting the quality of
water owing to the Great Barrier Reef World Heritage Area. The Great Barrier
Reef Marine Park Authority was directed to develop a Great Barrier Reef Water
Quality Action Plan that recommends specic water quality targets for individual
river systems owing to the Great Barrier Reef
Twenty-six major river catchments, comprising approximately 25% of the
land area of Queensland, drain directly into the Great Barrier Reef Marine Park
(see Fig. 2.17). Run-off resulting from land-based agriculture, urban development
and aquaculture has the largest impact, affecting the water quality of the Great
Barrier Reef.
FIGURE 2.17
The Great Barrier Reef and catchment systems
These land-based activities affect the water quality of the rivers in the ways
discussed below.
Increased concentration of suspended
particles
The water around the Great Barrier Reef has increased quantities of suspended
particles which make the water cloudy, decreasing light penetration for aquatic
plants and clogging the gills of sh (see Fig. 2.18). This quality of clarity is referred
to as turbidity. These particles may be added to rivers when the riparian vegetation
(plants growing at the sides of rivers) is removed for sugar farming or other uses.
The soil is no longer held in place by plants and is eroded away into the streams.
It has been revealed that sediment input to Great Barrier Reef catchments has
suffered more than a threefold increase to 28 000 000 tonnes per year since
European settlement.
Increased inorganic nutrients
About 80% of the Great Barrier Reef catchment is actually under agricultural
use. Farmers supply their crops with fertilisers comprised of nitrates (NO
3

) and

phosphates (PO
4
3
), which help plants grow (see Fig. 2.19). Rain and irrigation
can transport these nutrients into rivers and then into the sea. These nutrients
are then used by small single-cell plants called phytoplankton. Elevated nutrient
concentrations affect corals by promoting phytoplankton growth, which in turn
supports increased numbers of lter-feeding organisms such as tubeworms,
sponges and bivalves that compete with coral for space. The algal blooms
(large growths of the plants) may overgrow coral structures, out-competing coral
for space and shading coral colonies to critical levels. The very quick growth or
bloom of the algae is called eutrophication. Prawn farming (a type of aquaculture)
can discharge efuent containing these nutrients and cause eutrophication.
This has occurred in areas close to seagrass beds in the Hinchinbrook Channel
near Townsville. The algae block the light from the seagrass beds, resulting in either
their reduction or disappearance. The animals, for example the dugong, then have
reduced food supply.
FIGURE 2.18
Turbid reef water
Increased organic materials
Naturally occurring organic materials in water result from vegetation, soil, humus
and organisms living in the water. The quantity of organic matter is increased in
rivers when untreated or semi-treated sewage enters the water. Stormwater is the
term used to describe the run-off from rain over an urban catchment. In cities and
towns, stormwater washes across roads and streets, picking up oil, petrol, grease,
sediment, industrial waste, leaf and other litter, and dog droppings on roads, streets
and paths. In rural areas, run-off may include agricultural and livestock waste,
fertilisers and pesticides. The pesticides may directly kill organisms living in the
Reef area.
The sewage, stormwater and run-off all contribute to increased quantities of
organic matter. Generally, the organic matter is broken down by decomposers
(microbes such as bacteria). Excess nutrients lead to increased growth of microbes
that use dissolved oxygen (DO) in the decomposition process. The oxygen
Aquaculture production
ponds in the Great Barrier
Reef catchment
FIGURE 2.19
Graph of nitrogen
and phosphorus for
farmland in the Great
Barrier Reef catchment
Source: http://www.gbrmpa.gov.au/corp_site/key_issues/water_quality/current_issues/wq_report98_aug01.pdf
dissolved in the water is accessed by the microbes and other organisms such as sh.
Increased numbers of microbes feeding on the organic matter result in increased
demand for the oxygen by the organisms in the water. This biochemical oxygen
demand (BOD) may reduce the oxygen supply to a level where the sh and other
aquatic organisms are unable to survive.
Another problem resulting from the growth of the bacteria is the enzymes they
produce to decompose the organic matter. These enzymes may be toxic. Drinking
water supplies are sometimes contaminated by cyanobacteria, otherwise known as
bluegreen algae.
Zoonotic diseases, or zoonoses, are diseases that are naturally transmitted
between vertebrate animals and humans. Mammals in catchments and birds in
service reservoirs are the most common cause of waterborne zoonotic diseases.
For example, Salmonella bacteria entering the water supply from such sources can Salmonella Salmonella
result in waterborne zoonotic disease. Zoonoses can be spread from pets (such
as dogs and cats) and agricultural animals (cattle, sheep and pigs) or from native
or feral animals. It is feared that diseases from land animals may be spread to
organisms living in the Great Barrier Reef via water from the rivers.
There are approximately 4 500 000 beef cattle grazed in Great Barrier
Reef catchments, with the highest stock numbers in the Fitzroy and Burdekin
catchments. The area under sugarcane cultivation in Great Barrier Reef catchments
has also increased steadily over the last 100 years.
Increased heavy metals
Heavy metals are natural constituents of rocks and soils and enter the environment
as a consequence of weathering and erosion. Many metals are biologically essential,
but all have the potential to be toxic to organisms when the concentrations go above
a threshold. The metals affect the organisms by inactivating the enzymes responsible
for normal organism survival and function.
Industries such as mining leads to increased quantities of metals such as
cadmium (Cd), copper (Cu), mercury (Hg), lead (Pb), nickel (Ni), zinc (Zn) and
Zinc metal renery,
Townsville
arsenic(As). Coal production is the major mining operation carried out in the Great
Barrier Reef catchment area, with mines in the region contributing approximately
96% of Queenslands 95 million tonnes of annual black coal production.
Other mining operations close to the coast include shale oil operations north
of Gladstone, silica mining near Cape Flattery and magnesia mining north of
Rockhampton. There is likely to be further expansion of port activities to support
these mines. Expansion of operations at the port of Hay Point are presently
proposed to cater for expanding coal export operations from central Queensland.
MONITORING WATER QUALITY
The quality of the water in catchments entering the Great Barrier Reef is monitored
by measuring the following factors: temperature, pH, salinity, turbidity, nitrates,
phosphates, dissolved oxygen, biochemical oxygen demand and faecal coliforms.
Your local creek, stream or river could be monitored in the same way, using
the following tests, and compared to the data presented on the Waterwatch website
(http://www.waterwatch.org.au) or by the Environmental Protection Agency
(http://www.epa.qld.gov.au/environmental_management/water/).
The Australian and New Zealand Environment Conservation Council
(ANZECC) set Australian Water Quality Guidelines For Fresh and Marine Waters
in 1992. These included standards for rivers and streams, lakes and reservoirs,
estuarine waters and coastal waters. In 2001 the Natural Resource Management
Ministerial Council (NRMMC) (http://www.deh.gov.au/water/quality/nwqms/
index.html) became responsible for those issues previously covered by ANZECC.
Temperature tests
Whats involved
This factor can be measured with a data logger or a
thermometer. The temperature of the water can change
naturally, because of changes in the suns radiation
during the day.
Interpreting the results
The temperature of the water inuences the amount of
dissolved oxygen. Water temperature should be used in
conjunction with other tests to monitor the health of the
waterway because of natural uctuations.
pH tests
Whats involved
pH can be measured with a data logger and pH probe,
universal indicator solution or paper, or a pH meter
(see Fig. 2.20). If using the universal indicator,
comparison with a coloured pH scale provides the
pH value.
FIGURE 2.20
Assessing the pH
of creek water
Most life forms generally tolerate pH in water between 6.5 and 8, but outside
of these ranges many problems begin to occur, especially if the change in pH
is sudden. Few sh can tolerate pH values lower than 5 or greater than 9. The
natural pH of an area can be inuenced by the types of rocks present; for example,
limestone catchment areas have a higher pH between 7.0 and 8.5. Marine waters
normally have a pH close to 8.2. Changes of more than 0.5 pH units from the
natural seasonal maximum or minimum in freshwater and more than 0.2 units in
marine waters should be investigated.
Salinity tests
Whats involved
Salinity, a measure of the amount of dissolved salts, can be assessed using a number
of methods, including one analysis technique called titration and the measurement
of the electrical conductivity.
Titration involves calculating the quantity of chloride ions present. The
concentration of chloride ions can be determined by reacting it with a solution
of silver nitrate (AgNO
3
). This titration procedure involves using a known
concentration of the silver nitrate so the Cl
concentration can be determined.
The main reaction is:

Cl
(aq) Ag
(aq) AgCl(s)
water sample in AgNO
3
white precipitate
Pure rainwater has less than 10 mg/L of dissolved solids. The desirable level in
tap water is less than 500 mg/L. Freshwater rivers may contain between 100 and
1000 mg/L. Brackish water ranges from 1000 to 3000 mg/L. Saline water has more
than 3000 mg/L. Estuarine waters vary, depending upon the amount of freshwater
owing into the system. Seawater contains about 35 000 mg/L or 35 parts per
thousand (ppt).
The ANZECC guidelines (1992) state that adverse biological effects can be
expected in Australian freshwater river and wetland ecosystems if salinity rises
above 1000 mg/L. In estuarine and coastal waters, changes in salinity should not
vary more than 5% from the background level.
Salinity could also be measured by nding the current owing through known
concentrations of salt solutions. A calibration graph could be generated and then the
sample tested. The unknown salinity of the water sample is then calculated by using
the graph. For oceans, electrical conductivity reading is generally 51 500 S/cm.
To understand how concentrations are calculated, refer to

To investigate the salinity of water samples you can do an experiment using

titration. (Refer to Chemistry in Use Book 1 Teacher Resource CD-ROM.)
Total dissolved solids tests
Whats involved
The amount of dissolved solids can be measured by rst ltering the suspended solids
and then evaporating a sample of water to dryness and weighing the solid remaining.
Conductivity is a measure of waters ability to conduct an electric current and
is directly related to the total dissolved salts (TDS) content of the water. Electrical
conductivity is reported in microsiemens per centimetre (S/cm). Most of the
TDS of natural waters is comprised of inorganic compoundsmineral as opposed
to the organic compounds derived from organisms. Although there are at least
traces of many elements, the great majority of the TDS is from four negative
ions (bicarbonate, carbonate, chloride, sulfate) and four positive ions (calcium,
magnesium, sodium and potassium).
When provided with the salinity in S/cm (standardised to 25C), the TDS can
be estimated using the following equation:
TDS (in mg/L or ppm) 0.65 electrical conductivity (in S/cm)
Conductivity probes can be used to measure electrical conductivity and total
dissolved solids (see Fig. 2.21).
The total dissolved solids should be less than
100 mg/L in unpolluted water and may be
over 1000 mg/L in polluted freshwater.
Turbidity tests
Whats involved
Turbidity is a relative measure, usually expressed as nephelometric turbidity units
(NTU). Turbidity can be measured using a turbidity tube (see Fig. 2.22).
FIGURE 2.22
Turbidity tube
FIGURE 2.21 Measurement of total dissolved solids
using a conductivity probe
The turbidity tube is a long, thin, clear, plastic tube, sealed at one end with
a white, plastic disc with three black squiggly lines on it (seen when looking down
the tube). The tube has a scale marked on the side, reading from 10 to 400 NTU.
Drinking water should have a turbidity of 1 or less NTU. Freshwater should be
5 or less NTU. Turbidity levels vary as the rivers move towards the ocean. The
factors that could inuence the turbidity include the silt loads from the catchment,
the strength of the tidal currents and the size of the estuary. Water with a turbidity
reading of greater than 20 would be considered polluted.
Nitrate tests
Whats involved
The most common nitrogen compounds are ammonia (NH
3
), nitrate (NO
3
)
and nitrite (NO
2
). Nitrate is soluble and easily taken up by aquatic organisms;

its concentration in natural water bodies is often measured. Ammonia (NH
3
) is a
product of the decomposition of organic waste and can be used as an indicator of
the amount of organic matter in the waterway. Nitrite (NO
2
) is toxic to humans
and other animals.
Nitrates may be tested using kits designed for
the assessment. First, the nitrates are converted to
nitrites and then reagents are added to produce
a colour change. The colour is interpreted by a
colorimeter or a spectrophotometer (see Fig. 2.23).
These instruments quantitatively measure the light
absorption (or transmittance) by the solution.
The concentration of the nitrates in the solution
is calculated by comparison with standard
concentrations.
The following concentrations can be used to assess
freshwater: 00.3 mg/L (low pollution), 0.350.8 mg/L
(mild pollution), 0.851.6 mg/L (medium pollution),
>1.65 mg/L (high pollution).
To investigate the turbidity of water samples you can do an experiment.


Excess nitrate and

phosphate lead to
eutrophication
FIGURE 2.23
A spectrophotometer
Phosphate tests
Whats involved
Phosphates may also be tested using kits as for nitrates. Spectrophotometers are
used to determine the concentration of phosphates after reactions with reagents to
produce a coloured solution for analysis.
Total phosphate levels higher than 0.03 mg/L may contribute to increased aquatic
plant and algae growth. Desirable rural and urban dry weather water quality is less
than 0.05 mg/L total phosphates.
The ANZECC guidelines (1992) recommend the following range for total
phosphates in different water bodies to prevent eutrophication: rivers and
streams 0.010.1 mg/L, lakes and reservoirs 0.0050.05 mg/L, estuarine waters
0.0050.15mg/L, and coastal waters 0.0010.01 mg/L.
Dissolved oxygen tests
Whats involved
The amount of dissolved oxygen (DO) varies during the day. DO levels are highest
in the afternoon (see Fig. 2.24). Oxygen levels build up during the day as plants
photosynthesise. DO levels are lowest just before dawn. Aquatic plants and animals
use the available oxygen for respiration through the night. No new oxygen can be
produced by plants without daylight. In water where nutrients are available for
excess plant growth (eutrophication), the variation in dissolved oxygen is greater.
Oxygen concentrations are expressed as milligrams per litre (mg/L), but
percentage saturation (% sat., which measures how much oxygen is dissolved
compared to the total possible amount that can be dissolved at the prevailing
temperature) allows direct comparison between results from sites with different
salinity and temperature values (see Fig. 2.25).
You can investigate the presence of phosphate ions using a wet chemistry
experiment. (Refer to Chemistry in Use Book 1 Teacher Resource CD-ROM.)
FIGURE 2.24
Variation of dissolved
oxygen in a river with
much plant growth
compared with a
clear river
Source: Department of Environment and Heritage
In Figure 2.25 a ruler is used, lining up the measured water temperature
(top horizontal line) with the measured oxygen (bottom horizontal line). The ruler
crosses the diagonal line and this point represents the percentage oxygen saturation
for the measured data.
Dissolved oxygen can be measured with a meter and probe. Oxygen is reacted
to produce water and the current produced is proportional to the amount of oxygen
present in the water.
Alternatively, dissolved oxygen can be measured by Winkler titration of water
sample, which is a chemical analysis technique (see Fig. 2.26).

FIGURE 2.25
Converting the oxygen
concentration in mg/L
oxygen to percentage
saturation oxygen
To investigate the quantity of dissolved oxygen using the Winkler titration

method you can do an experiment. (Refer to Chemistry in Use Book 1
Teacher Resource CD-ROM.)
The ANZECC guidelines (1992) recommend that for the protection of freshwater
and marine ecosystems, dissolved oxygen levels should not fall below 8090%
saturation. Results greater than 110% saturation indicate that algal photosynthetic
activity is producing a supersaturation of dissolved oxygen. DO levels below
2 mg/L will not support sh life. DO levels below 3 mg/L are stressful to most
aquatic organisms. At least 56 mg/L are required for sh growth and activity.
Biochemical oxygen demand test
Whats involved
The biochemical oxygen demand (BOD) of a body of water is a measure of the
concentration of dissolved oxygen that is needed for the complete breakdown of the
organic matter in the water by aerobic (oxygen-using) bacteria. Water that contains
lots of sewage will have many bacteria using the oxygen and so the BOD will be high.
The BOD is assessed by carrying out the dissolved oxygen test after 5 days.
The amount of DO on day 5 is subtracted from the amount of DO in the DO
sample bottle on day 1.
Example: DO level on day 1 8 mg/L
DO level on day 5 5 mg/L
BOD level DO on day 1 DO on day 5
8 mg/L 5 mg/L
3 mg/L
FIGURE 2.26
Dissolved oxygen testing kit
To investigate the biochemical oxygen demand (BOD) use the same test for
dissolved oxygen (the Winkler titration method). (Refer to Chemistry in Use
Book 1 Teacher Resource CD-ROM.)
Unpolluted natural waters will have a BOD of 5 mg/L or less. Raw sewage must be
diluted to measure BOD and may have levels of 150 to 300 mg/L. Treated sewage
may have levels of 20 to 30 mg/L. Polluted stormwater run-off from residential
areas may have a BOD reading of 200 to 600 mg/L.
Coliforms test
Whats involved
Faecal coliforms are harmless micro-organisms that colonise the large intestines
of all warm-blooded animals and are excreted in faeces. The presence of faecal
coliforms are an indication of the presence of other more potentially dangerous
pathogens (disease causing organisms) in the water.
Faecal coliform organisms are ltered from the water and cultured in a Petri
dish in an incubator for 24 hours. The higher the count of faecal coliform colonies,
the greater the possibility of dangerous pathogens also being present.
Drinking water must be entirely free of faecal coliforms. Faecal coliform counts
above 150 colonies per 100 mL of water indicate that the water is not safe for
primary contactnot safe to swim in.
Water with 1000 or more faecal coliform colonies per 100 mL is only safe for
secondary contact boating and shing. Less than 1000 colony forming units (CFU)
per 100 mL is desirable, but up to 5000 CFU is permissible for secondary contact
(ANZECC Australian Water Quality Guidelines For Fresh and Marine Waters, 1992).
Heavy metal tests
Whats involved
Heavy metals include the following cations: Pb
2
, Ag
, Hg
2
, Cu
2
, Cd
2
and
As
3
. The presence of these cations can lead to poisoning of organisms. Lead ions
in drinking water are taken in and incorporated into bone material. In humans,
this leads to mental retardation. Mercury (in the form of dimethylmercury) is
a contaminant commonly found in sh, particularly in long-living or predatory
sh. The current maximum permitted level for total mercury in sh (1 mg/kg)
in the Australia New Zealand Food Standards Code has been exceeded in some
individual samples of large sh species such as shark and swordsh. In America,
the Food and Drug Administration (FDA) and the Environmental Protection
Agency (EPA) are advising women who may become pregnant, pregnant women,
nursing mothers, and young children not to eat shark, swordsh, king mackerel or
tilesh because they may contain high levels of mercury.
The test for heavy metals involves using the solubility rules. Recall that suldes
are insoluble except compounds formed with Group 1 and Group 2 elements and
with ammonium. Adding sodium sulde to the sample water reveals that these
heavy metals are present if a precipitate forms.
To investigate the presence of some heavy metal cations you can do an

experiment. (Refer to Chemistry in Use Book 1 Teacher Resource CD-ROM.)
Spectrophotometers may also be used to check for the presence of heavy metals.
The concentration of the metal can also be ascertained using this method.
Concentrations of the heavy metals in mg/kg found in the near-shore subtidal
sediments of the Great Barrier Reef are shown in Table 2.6, along with the low and
median range provided by ANZECC.
TABLE 2.6 Great Barrier Reef heavy metal values (in mg/kg)
Metal
GBR range for
nearshore subtidal
sediments
Australian effects
range low (ERL)
a
(ANZECC 2000)
Australian effects
range median (ERM)
b
(ANZECC 2000)
arsenic 0.720 20 70
cadmium 0.50.7 1.5 10
chromium 5207 80 370
copper 432 65 270
mercury 0.0050.07 0.15 1.0
nickel 590 21 52
lead 239 50 220
zinc 6117 150 410
a
Below the level of Effects Range Low (ERL), contaminants in sediment are not likely to have adverse
effects on animals that live in sediment.
b
Above the level of Effects Range Median (ERM), contaminants in sediment probably have adverse effects
on animals that live in sediment.
Source: http://www.gbrmpa.gov.au/corp_site/key_issues/water_quality/current_issues/wq_report98-aug01.pdf
Some of the properties we have been discussing to assess water quality are
summarised in Table 2.7
TABLE 2.7 Some properties of environmentally clean and polluted
fresh water
Property Typical clean water value Polluted water value
a
turbidity (NTU) <3 >20
total dissolved solids (TDS)
(mg/L)
<100 >1000 (for freshwater)
pH 6.58.5 <6 or >9
dissolved oxygen (DO) (mg/L) 79 <4
biochemical oxygen demand
(BOD) (mg/L)
<5 >10
total phosphate (mg/L) 0.03 >0.05 (lakes and dams)
>0.1 (streams and rivers)
nitrate (mg/L) <0.1 >0.50
faecal coliforms (CFU/100 mL)
(CFU colony forming units)
<5 >200
a
Any one of these values would make the water polluted.
ACTIVITY 2.26
1 a A sample of water contained 5.0 ppm magnesium and 2.0 ppm lead ions.
Express these concentrations in moles of ions per litre.
b Another sample of water contained 1.05 10
4
mol/L sulfate and
3.1 10
4
mol/L dissolved oxygen. Express these concentrations in ppm.
2 An environmental chemist did the analysis shown below on a sample of muddy
river water.
Calculate the percentages of suspended solids and of dissolved solids in the
sample of river water.
3 a Use the data below to draw a graph of dissolved oxygen concentration versus
temperature. Include zero on the temperature scale. Draw a smooth curve
through your points.
Temperature (C) 5.0 10.0 15.0 20.0 25.0 30.0
Dissolved oxygen
concentration (mg/L) 12.6 11.1 9.9 9.0 8.2 7.5
b What is the dissolved oxygen concentration at (i) 22C (ii) 7.0C (iii) 1.0C?
Are any of your answers here less accurate than the others? Explain why or
why not.
c At what temperature is the oxygen concentration (i) 13.5 mg/L (ii) 7.8 mg/L?
d Express your answer to (b)(i) in moles per litre.
4 What is often more important than actual oxygen concentration in assessing water
quality is percentage saturation. Percentage saturation is the actual concentration
of dissolved oxygen expressed as a percentage of the solubility of oxygen at the
prevailing temperature. Using your graph from Exercise 3 calculate the percentage
saturation in water samples in which the concentration of dissolved oxygen and
temperatures are as follows:
a 7.2 ppm at 25.0C c 5.4 ppm at 22.0C
b 7.2 ppm at 8.0C d 8.8 ppm at 13.0C

5 Some measurements on various water samples are shown in the following table.
SAMPLE A B C D E F
TDS
a
mg/L >10
4
900 80 150 >10
4
200
DO
a
(mg/L) 4.6 7.2 8.5 9.2 8.7 6.2
BOD
a
(mg/L) 60 1.6 2.2 2.5 1.8 75
coliforms (CFU/L) 500 0 0 10 0 250
Na
2
S/H
test
a
NR
b
NR
b
NR
b
black ppt NR
b
black ppt
Hardness (mg/L) 280 300 45 120 260 150
a
TDS total dissolved solids; DO dissolved oxygen; BOD biochemical oxygen demand;
Na
2
S/H
test is to add Na
2
S solution to an acidied sample of the water.
b
NR no reaction
Which of these samples would you consider to be:
a (i) sea water (ii) fresh surface water (iii) bore water
b polluted with sewage
c contaminated with one or more heavy metal(s)?
Give your reasons in each case.
Note: the Na
2
S/H
is a test for heavy metals. A precipitate will form when one or

more of the following cations is present: Pb
2
, Ag
, Hg
2
, Cu
2
, Cd
2
, As
3
.
6 A group of students determined the phosphate concentration in some
environmental samples. First they calibrated their colorimeter by making up
solutions of sodium phosphate of known concentration and analysing them
according to a standard procedure and measuring the absorbance with the
colorimeter. Results are shown below. Construct a calibration curve for this
instrument of absorbance versus concentration of phosphate.
Concentration of phosphate (ppm) 0.030 0.060 0.100 0.150
Absorbance 0.07 0.16 0.25 0.41
Four environmental water samples were then put through the same test procedure.
They gave the following absorbances:
Sample A B C D
Absorbance 0.14 0.36 0.48 0.025
Calculate the concentration of phosphate in each of these samples. Does the fact
that two of these absorbances are outside the range of the calibration values make
the results less accurate? Explain.
Summary
Water is distributed widely on the Earth. It can exist naturally in all three states:
solid (ice at the poles), liquid (in the rivers and oceans) and gas (water vapour in the
atmosphere).
Water is unique because the solid state (ice) has a lower density than the liquid form.
This is due to the hydrogen bonding between water molecules. In ice, the molecules
form a regular lattice structure, which means there is more space between the
molecules in ice compared to liquid water. This phenomenon assists organisms living
in large lakes because the ice forms at the surface, insulating the water below.
7 Some test results of water samples taken from seven different streams are listed
below.
SAMPLE A B C D E F G
Turbidity
a
(NTU) 60 30 0.2 14 7 1 10
TDS
a
(mg/L) 620 200 45 450 120 150 180
pH 6.8 8.4 6.5 7.2 6.0 7.2 4.7
DO
a
(mg/L)) 8.1 9.1 8.7 7.8 3.1 9.0 8.3
Phosphate (ppm) 0.06 0.25 0.02 0.5 0.07 0.01 0.04
a
NTU nephelometric turbidity units: less than 1 is very clear water; 30 is quite turbid;
TDS total dissolved solids; DO dissolved oxygen.
a Which stream(s) would you consider to be relatively free of pollution?
b Which sample(s) was(were) taken well downstream from the point where treated
sewage was discharged into the stream?
c Which stream if any has serious soil erosion upstream of the sampling point?
d Which stream if any has suffered damage from acid drainage from a mine site?
e Which stream(s) is(are) susceptible to an algal bloom?
f Which stream is likely to contain very little aquatic life at the sampling point?
Give your reasons for each of your choices.
8 Several water samples were analysed for nitrate content by the method described
on page 78. Results are tabulated below:
Sample W X Y Z
Absorbance 0.429 0.784 0.017 0.086
The colorimeter was calibrated by analysing several solutions of known nitrate
concentration in the same way. From these standards it was determined that:
Nitrate ion concentration (in mg/L) 1.75 Absorbance
up to a concentration of 0.9 mg/L. Above that concentration results became
unreliable.
a Calculate the concentration of nitrate in each of the solutions in the table.
b Are there any results that are suspect because of the limited range over which
the calibration equation is applicable? If so, how would you determine the
nitrate concentration in that(those) solution(s) without that uncertainty?
GLOSSARY
adhesive forces forces of attraction between molecules of different types; for
example water molecules are attracted to glass molecules, which results in
a meniscus
anhydrous without water
BOD biochemical oxygen demand; measures the amount of oxygen used by
bacteria and other micro-organisms during a 5-day period. The BOD is
calculated by subtracting the dissolved oxygen (DO) value after 5 days from
the initial DO value. The reading is given as milligrams per litre (mg L
1
).
capillary action the process whereby water is drawn up a narrow tube, due to the
forces of adhesion between the water molecules and the glass tubing
coagulant a chemical that binds very small suspended particles together.
This process is called coagulation. These particles can then bind to form
larger clumps that include bacteria and viruses. They are then known as ocs.
Coagulants are used in the water treatment process.
Water is a polar molecule, which results in strong cohesive forces. This leads to a
surface tension phenomenon which allows insects to walk on water.
Interactions between water molecules and other materials (for example, paper towel)
contribute to strong adhesive forces. These forces enable capillary action, which helps
explain how water moves from the roots of tall trees to the leaves (the transpiration
stream). These forces also result in the formation of a meniscus where the water meets
the sides of a container.
Water is an essential component of all living cells. The solvent property of water is
utilised as a transport mechanism (for nutrients and wastes) and as a medium for
reactions to take place in. The polarity of the water molecule means that most ionic
compounds and polar molecules dissolve. Water also may dissolve some vital non-
polar substances like oxygen gas. Supplies for drinking water must be chemically
monitored for dissolved substances and treated to ensure that water is safe to drink.
Concentration can be expressed in many forms including ppm, mol/L, and mg/L.
Differences in concentrations of solutes may determine osmosis, the movement
of water through semipermeable membranes. Solutions surrounding a cell may
be isotonic, hypotonic or hypertonic.
Water hardness is caused by excess calcium and magnesium ions. Their presence
results in build-up of scale and the inefcient use of soap and detergents. The scale
and scum (in baths) are precipitates of calcium and magnesium compounds.
The water cycle demonstrates the pathways of water movement and changes of
state. Precipitation and other forms of water may travel across and through soil before
entering streams, rivers and eventually oceans. The potential for unwanted substances
to enter and dissolve in water is clear.
Land use and human activities affect the health of the waterways. For example, soluble
fertilisers applied to crops may run off into nearby streams and rivers.
Monitoring the water quality of local water supplies can help assess the health of
the waterway and identify sources of pollution. Water quality tests involve assessing
temperature, pH, salinity, total dissolved solids, turbidity, nitrates, phosphates,
dissolved oxygen, biochemical oxygen demand, coliforms and heavy metals.
cohesive forces forces of attraction between molecules of the same type; for
example, water molecules are attracted to other water molecules
density mass per unit volume density density
dipoledipole interactions the attraction between molecules that have charged ends
or poles that are attracted to the oppositely charged poles in other molecules
electrolytes substances that separate or dissociate in water to form ions
occulation a process that occurs when chemical reactions bind together particles
suspended in a uid. These large particles, called ocs, can be separated from
the liquid by ltration. The ocs can bind bacteria and viruses together. The
process is used in water treatment.
hydrophobic water-hating; describes the end of the soap molecule that does not
dissolve in water. It is the opposite of hydrophilic (water-loving, describing
the end of the soap molecule that readily dissolves in water)
hypertonic when the solution surrounding a cell is more concentrated than that
inside the cell
hypotonic when the solution surrounding a cell is less concentrated than inside
the cell
isotonic when the concentrations of the uid inside the cell and outside the cell
are equal
meniscus the curvature in a liquids surface where the liquid meets the container
it is in. Water forms an upward curve in a glass container.
organic molecules molecules containing carbon and generally derived from living
organisms, although technology exists to manufacture them
osmosis a process involving two solutions separated by a semipermeable
membrane. The semipermeable membrane allows the passage of the solvent
(usually water), but not the passage of the solute, for example salt. When the
solute concentrations are different (there is a concentration gradient), the water
moves towards the side with the greater salt concentration. Unlike reverse
osmosis, this process does not require energy.
reverse osmosis a process in which high pressure is used to force solvent through a
semipermeable membrane against the concentration gradient; used to desalinate
seawater to a form suitable for drinking; the opposite of osmosis
scale CaCO
3
and/or MgCO
3
caused when Ca(HCO
3
)
2
and Mg(HCO
3
)
2
, both
soluble, are decomposed by heat
semipermeable membrane a membrane or lter that allows some but not all
substances to pass through it
solute the substance that dissolves in a uid or solvent. Salt is the solute in
saltwater.
solution a mixture that contains a solute dissolved in a solvent, for example
saltwater
solvent the substance into which the solute dissolves. Water is the solvent in
a saltwater solution.
spectrophotometer an instrument that uses light to analyse the presence and
generally the concentration of chemicals
TDS total dissolved solids, determined by evaporation to dryness of a known
volume of a ltered sample. The value is converted to parts per million (ppm),
meaning grams of solid per million grams of the mixture.
turbidity cloudiness; it is an indicator of water quality and results from the presence turbidity turbidity
of suspended solids in the water. Water with a high turbidity reduces penetration
of light and decreases photosynthesis, which in turn reduces the oxygen
concentration.
water hardness a measure of the difculty of soap to form a lather with the water.
It is caused by the soap ions reacting with mainly calcium and magnesium ions
present in the water. Hardness in some cases is evident by scale forming in
kettles and scum forming in the bath. The removal of hardness (these ions) is
referred to as water softening. Water hardness is dened in terms of calcium
carbonate (CaCO
3
) and is expressed as the total amount of this compound in
milligrams per litre of water (mg/L).
water of crystallisation ionic substances that crystallise from aqueous solutions
with the molecules of water still attached, for example CaSO
4
.2H
2
O. Such
substances are also known as hydrates.
xylem vessels in vascular plants, the narrow vessels that transport water from the
roots to the leaves
90
CONTEXT 3
Transport:
a necessary evil
IN THIS CONTEXT
Using energy 92
Turning chemical energy into mechanical energy 98
What a wonderful energy source petrol isor is it? 102
Petrol is polluting 116
Cars, metals and corrosion 122
90 CHEMISTRY IN USE
CONTEXT 3 TRANSPORT 91
To drive or not to drive? This is the question for the twenty-rst century. Motorised
transport has only been with us a little over 200 years, and we cannot imagine a
world without it. We are, however, faced with problems of a global scale, including
polluted cities, changed weather patterns and global warming, because of our use
of fossil fuels, much of which is used for transportation.
Another issue that needs to be considered is that fossil fuels have other uses apart
from being fuels. Fossil fuels have become an important source of chemicals for
making new materials; plastics, medicines, fertilisers and many other useful substances
are made from crude oil. It could be said that fossil fuels are just too useful to burn.
A drag racer (left) and an
electric car recharging
(right)
The uses of crude oil

Pollution across the
city sky
USING ENERGY
energy source other than ourselves. energy energy
There is evidence that people have been using animals for transport for over
6000 years and wheeled transport pulled by animals for around 4000 years.
The rst energy converters humans harnessed for transport were probably animals
like horses, bullocks, camels, elephants, dogs and even other humans.
The limitations of animals as converters of energy for transport are:
their unreliability, as animals get tired or sick and can die
the risks, as animals, bite, kick, stomp and gore their handlers
but most importantly
their low power rating.
Power is the rate at which energy can be used to do work. The higher the power
rating, the faster you can use energy to do work for you. One (average) horse can
deliver 1 horsepower (hp) or 746 watts of power, equivalent to 12 average light
bulbs or one average microwave oven.
TABLE 3.1 Power rating of various energy converters for transport
Energy converter Horsepower (hp) Kilowatts (kW)
person 0.2 0.149
dog 0.1 0.075
horse 1 0.746
early internal combustion motor 0.5 0.373
Subaru WRX motor 281 210
diesel truck motor 430 321
dragster motor 500 373
jet engine (gas turbine) 1500 1119
rocket engine (the space shuttle has 3 of this type) 2240 1671
The reciprocating internal combustion engine
While we have steadily improved the efciency and power of car engines over efciency efciency
the last century, the basic process has remained exactly the same. Essentially, the
process is this: fuel is mixed with air, compressed and ignited. The engineering
that makes each step happen is the only thing that varies, apart from the overall
efciency. Generally, the bigger the motor, the more fuel is burned, the more power
is generated and, at the same time, the more pollutants are created.
Most engines are called Otto cycle or four-stroke engines. This means that only
one in every four movements of the piston is a power stroke (see Fig. 3.1). The four
strokes are:
1 intake strokethe piston moves down, and air and petrol in the right
proportions are drawn in
2 compression strokethe piston moves up and compresses the air/petrol
mixture, which is ignited just before the piston reaches the top
3 power strokethe piston is forced down by the expanding hot gases
4 exhaust strokethe piston moves up, pushing out the burnt gases.
CONTEXT 3 TRANSPORT 93 CONTEXT 3 TRANSPORT 93
Engines are designed to suit fuels that have specic combustion characteristics,
including:
heat of combustion (the amount of energy given out when a certain amount of
a substance burns)
standard state of the fuel (solid, liquid or gas at normal temperatures)
volatility (how easy a liquid fuel is to change to vapour, related to boiling point) volatility volatility
ignition temperature (the temperature to which a fuel, or some part of it, has
to be heated before it will begin to burn). Ignition temperature also relates to
octane rating, which will be dealt with later in the chapter in Improving petrols
properties.
FIGURE 3.1
Cutaway of an internal
combustion engine
indicating the four strokes
To review your understanding of stoichiometry, refer to Chemistry Sections

3.7 and 3.8, pp. 22631. To understand energy changes in chemical reactions,
refer to Chemistry Sections 7.1 to 7.3, pp. 28793.
ACTIVITY 3.1
a Fuel is mixed with enough air to make a stoichiometric mixture with the oxygen
in the air. The stoichiometric air to fuel mass ratio for the complete combustion of
petrol is about 15:1 or 15 g of air for every 1 g of petrol. Assuming that petrol is
mostly octane (C
8
H
18
) and air is about 23% oxygen and 76% nitrogen by mass,
conrm this ratio by calculation.
Hints:
1 Write the balanced equation for combustion of the fuel.
2 Calculate the number of moles of oxygen needed for 1 mole of fuel.
3 Calculate the mass of oxygen for each gram of fuel.
4 Calculate the mass of air needed to burn each gram of fuel.
b What would the stoichiometric ratio be for:
i LPG, which is mostly propane (C
3
H
8
)?
ii ethanol (C
2
H
5
OH), made from sugar cane?
ACTIVITY 3.2
a Why is it important for the fuel to be vaporised?
b Use data from Table 3.2 to answer the following question.
If boiling point is a measure of volatility, how hard would it be to keep petroleum
gas as a liquid compared with natural gas? Why?
T
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Main systems of the enginefuel and
ignition
The fuel system
To make a fuel:air mixture that will ignite and burn properly, the fuel and air have
to mix intimately and in the correct proportions. This is the task of the fuel system.
In older vehicles, the mixture is controlled by the carburettor. In modern vehicles,
a fuel injection system, controlled by a microprocessor, is used to create the correct
mixture (see Fig. 3.2). In LPG-fuelled vehicles, a different system is needed
because LPG is a gas in its normal state (see Fig. 3.3).
No matter what the fuel is, the fuel system is designed to deliver a suitable
mixture of fuel and air mixed intimately into the cylinder for burning.
Figures 3.4 and 3.5 illustrate the general relationships between changing air:
petrol ratio and:
power output
fuel consumption, and
pollutant output for a reciprocating internal combustion engine.
A low air:fuel ratio means too much fuel for the air intake and is called a rich
mixturethat is, rich in fuel. A high air:fuel ratio is called a lean mixture; that is,
low in fuel.
ACTIVITY 3.3
a Compare ethanol, methanol, methane and ethane as fuels for cars. What would
make ethanol a more useful fuel compared with the others?
b Why are petrol, propane and diesel the fuels in most common use for automobiles?
c Use a graph to predict the heat of combustion of heptane, then calculate its energy
value per kilogram.
d Would you expect heptane to be a liquid or a gas? Would it make an appropriate
fuel? What were your reasons for your decision?

FIGURE 3.2
Fuel injection and
carburettor fuel systems
FIGURE 3.3
Carburettor and LPG
fuel systems
ACTIVITY 3.4
a The fuel system is described as mixing the fuel and air intimately. What do you
think intimately means in this context and why is it important to combustion?
b From the diagrams and from the properties of petrol and LPG, describe a signicant
difference in the functions of petrol carburettors and LPG carburettors.

FIGURE 3.4
Effect of air:petrol ratio
on (a) power output from
an engine and (b) fuel
consumption

FIGURE 3.5
Variations in pollutant
levels with air:petrol
ratio for a car running at
constant speed
Source: Earth, Air, Fire and Water, Vol. 2, 1st edn, 1984, Australian Academy of Sciences.
The ignition system
The role of the ignition
system (Fig. 3.6) is to deliver
a spark to ignite the fuel
at exactly the correct time.
When the fuel:air mixture in
an internal combustion motor
is compressed and ignited, it
explodes and forces the piston
downwards to turn the wheels
(via a clutch and various gears).
The compressed mixture is
usually ignited by a spark
created by a spark plug. The
explosion looks instantaneous,
but actually takes a fraction of
a second.
To allow for this reaction
time the mixture is ignited
just before the piston reaches just before just before
the top of its stroke, called
ACTIVITY 3.5
a To make observations to examine rich and lean as they relate to combustion, ask
your teacher or parents to tie a cotton cloth or handkerchief around a cars exhaust
to collect any particles. Compare the cloth when the car rst starts up (cold) and
when it is warm (after about 15 minutes). Cars usually run rich at start-up and
leaner when warm.
Use Figures 3.4 and 3.5 to answer the following:
b Describe the change in power with changing air:fuel ratio.
c What is the air:fuel ratio at maximum power?
d Is this ratio what you would expect for the highest power? Explain.
e Suggest reasons for the power drop at lean and rich mixtures.
f Describe the change in fuel consumption with changing air:fuel ratio.
g Which air:fuel ratio gives the lowest fuel consumption?
h Explain why this ratio gives the best fuel consumption.
i Suggest reasons for the increase in fuel consumption at both lean and rich
mixtures.
j Describe the change in the three pollutants over the range of mixtures.
k Summarise the change in pollutant levels in Figure 3.5. k
l What anomalies can you nd in the Figure 3.5 graph?
m What do the anomalies tell you about the production of pollutants?
n If oxides of nitrogen are a pollutant and there is no nitrogen in the fuels, then where
does the nitrogen come from?
o Why do oxides of nitrogen peak when they do and decrease at rich and lean mixtures?
To help understand the chemical ideas behind ignition timing, you need to refer
to Chemistry Sections 7.8 to 7.12, pp. 30210.
FIGURE 3.6
A cars ignition system
top dead centre or TDC. The amount of time you allow for the air/fuel mixture to
burn is called the timing of the motor. The fuel should burn and expand at just the timing timing
correct time to begin to force the piston down as it reaches the top of its stroke.
This arrangement extracts the greatest amount of energy from the burning fuel.
If the fuel ignites too early, the explosion tries to push the piston back down while
it is still coming up. This is called pre-ignition and makes a characteristic noise
called pinging or knocking, which can be very damaging to your motor and waste
energy. If the fuel is ignited too late, too much energy is lost as heat and the motor
is even less efcient than normal.
A similar problem results from using a fuel that ignites too easily for your engine
(too low an octane rating). In this case, the fuel auto-ignites when it is compressed,
without the need for a spark. (See Improving petrols properties later in this context.)
Diesel engines do not have spark plugs. They rely on the auto-ignition properties
of diesel fuel to work. The fuel is injected into the cylinder at just the correct time
for it to get hot and explode. Diesel fuel cannot be used in a motor designed for
normal petrol.
TURNING CHEMICAL ENERGY INTO
MECHANICAL ENERGY
Combustion engines are energy converters that turn chemical energy into chemical energy chemical energy
mechanical energy. In essence, there are two types of combustion engine: internal
combustion and external combustion engines. Internal combustion engines include
reciprocating internal combustion engines (ordinary car motors), gas turbines
(including jet engines) and rocket engines. External combustion engines include
steam engines, steam turbines and heat engines (Sterling engines).
Other engines or motors harness mechanical energy besides combustion
engines. These include electric motors and compressed gas motors. For these
motors, the energy is usually generated somewhere else altogether. Electric motors
seem completely pollution-free, until one remembers that the electricity originally
had to be generated in a large power station with its own pollution problems, even
if the electricity itself is then stored in a battery.
Despite the large number of different engines available, almost all cars use
a reciprocating internal combustion engine because this engine is:
relatively efcient (compared to an external combustion engine)
relatively inexpensive (compared to a gas turbine), and
relatively easy to refuel (compared to an electric car).
ACTIVITY 3.6
a On a tile, place about a thimbleful of our and try to burn it with a Bunsen burner.
Does it burn? How quickly? Now take a small amount of our in the palm of your
hand and blow the our into the Bunsen ame. How quickly does this now burn?
Atomised or vaporised fuel particles are many, many times smaller than our
particles. Imagine what this combustion would look like if its rate was increased
again a thousand-fold.
b Find out about the glow plug in diesel engines. What is its purpose?
c Find out about compression ratio. What does it mean? What effect does it have
on motors and the fuel you can use?

This engine combines well-understood materials and technology with low
weight and high power. Its main fuelspetrol, diesel and LPG (liqueed petroleum
gas)are cheap, readily available, reliable and convenient energy sources.
Unfortunately, these engines generate a range of pollutants, and rely on a resource
that is being depleted at an increasing rate and is needed for other tasks.
All combustion engines use the energy stored in fuels to create and pressurise
gases to force wheels to turn. Reciprocating internal combustion engines are only
about 25% efcient. They waste 75% of their energy as follows:
to the cooling system (35%)
as waste heat to the atmosphere (35%)
as heat and sound from friction (5%)
Fuels and energy
All reactions involve energy changes, called the enthalpy change of reaction.
Enthalpy change of reaction can be positive (which means the reaction absorbs
energy), or negative (which means the reaction releases energy).
Fuels are substances that are used to generate energy by reacting with oxygen.
For external combustion engines like steam engines, fuels can be moderately
slow-burning like coal or can be faster burning like gas. For internal combustion
engines, fuels need to react so quickly that they explode. The development of
the internal combustion engine had to wait until a fuel with suitable properties
to combust internally was available. Gunpowder was tried but did not work out.
Gunpowder carburettors are still hard to nd. The rst fuel was really a gascoal
gas generated by heating coal in a pressure vessel or boiler. Later, petrol and diesel
were found to be better because they hold more energy.
TABLE 3.3 A brief outline of the history of the internal combustion engine
1680 Dutch physicist, Christian Huygens, designed (but never built) an internal
combustion engine that was to be fuelled with gunpowder.
1807 Francois Isaac de Rivaz of Switzerland invented an internal combustion engine
that used a mixture of hydrogen and oxygen for fuel. Rivaz designed a car for
his enginethe rst internal combustion powered automobile. However, his
was a very unsuccessful design.
1824 English engineer, Samuel Brown, adapted an old Newcomen steam engine to
burn gas, and he used it to briey power a vehicle up Shooters Hill in London.
1858 Belgian-born engineer, Jean Joseph tienne Lenoir, invented and patented
(1860) a double-acting, electric spark-ignition internal combustion engine
fuelled by coal gas. In 1863, Lenoir attached an improved engine (using
petroleum and a primitive carburettor) to a three-wheeled wagon that managed
to complete an historic 80 km road trip.

1862 Alphonse Beau de Rochas, a French civil engineer, patented but did not build
a four-stroke engine (French patent #52,593, 16 January 1862).
1864 Austrian engineer, Siegfried Marcus, built a one-cylinder engine with a
crude carburettor, and attached his engine to a cart for a rocky 150 m drive.
Several years later, Marcus designed a vehicle that briey ran at 16 kph; a few
historians have considered this to be the forerunner of the modern automobile,
as it was the worlds rst gasoline-powered vehicle.
1866 German engineers, Eugen Langen and Nikolaus August Otto, improved on
Lenoirs and de Rochas designs and invented a more efcient gas engine.
1873 George Brayton, an American engineer, developed an unsuccessful two-stroke
kerosene engine (it used two external pumping cylinders). However, it was
considered the rst safe and practical oil engine.
1876 Nikolaus August Otto invented and later patented a successful four-stroke
engine, known as the Otto cycle.
1876 The rst successful two-stroke engine was invented by Sir Dougald Clerk.
1883 French engineer, Edouard Delamare-Debouteville, built a single-cylinder
four-stroke engine that ran on stove gas. It is not certain if he did indeed
build a car, however, Delamare-Deboutevilles designs were very advanced
for the timeahead of both Daimler and Benz in some ways, at least on
paper.
1885 Gottlieb Daimler invented what is often recognised as the prototype of the
modern petrol engine, with a vertical cylinder and with petrol injected through
a carburettor (patented in 1887). Daimler rst built a two-wheeled vehicle, the
Reitwagen (riding carriage), with this engine and a year later built the worlds
rst four-wheeled motor vehicle.
1886 On January 29, Karl Benz received the rst patent (DRP No. 37435) for a
petrol-fuelled car.
1889 Daimler built an improved four-stroke engine with mushroom-shaped valves
and two V-slant cylinders.
1890 Wilhelm Maybach built the rst four-cylinder, four-stroke engine.
Energy value
The amount of energy released as the fuel burns is called its heat of combustion
or energy value. As can be seen in Table 3.2 on p. 94, the energy value differs
considerably between fuels. On the face of it, hydrogen looks like the best fuel
because it is the fuel with the highest energy value as a liquid. The problem with
this is that hydrogen does not normally exist as a liquid at standard temperature
and pressure, and so has to be liqueed under very high pressure and extremely
low temperatures. This is expensive and difcult to do. Any decision therefore
about choosing a fuel is governed by more than just energy value.
To help understand about heats of combustion and calculations of energy

value, refer to Chemistry Sections 7.4 to 7.7, pp. 293302.
WHAT A WONDERFUL ENERGY SOURCE
PETROL ISOR IS IT?
Australia burn millions of litres of petrol, moving us and our families, goods and
materials from one place to another. In 2001, the Australian Bureau of Statistics
reported that transportation accounted for 37% of all energy use in Australia and
that the number of new private vehicle registrations has increased to over 51 000
each year.
Many people complain about the negative effects of petrol and there is
increasing interest in electric cars. Electric cars are quiet and relatively low in
pollution, and yet there are very few in commercial use in Australia. Most of those
in use are experimental and are not even completely electric vehicles. They are
actually hybrid vehicles, a combination of electric and petrol engines, combining
the energy density (explained below) of petrol with the reduced pollution of the
electric motor.
Electric cars seem ideal, so why arent there many more in use? One problem
with electric vehicles is their cost but that should reduce with high volume
production. The main problem, however, is what is known as energy density.
For electric vehicles, the usual energy source is batteries, whose energy density
is much, much lower than petrol, as you will see below (see Fig. 3.7).
If you had an electric vehicle, you would need to charge the batteries every
night. The energy from your power point would trickle into the car batteries at
a rate of about 60 joules per second (or 60 watts)about the same power rating
as a light bulb. A petrol-powered car, however, can be lled from the petrol pump
at about 1 litre a second, and each litre of petrol can release 35 000 000 joules
(3.5 10
7
Joules) when it is burned.
This means that in about 1 minute, you can load about 2.04 10
9
Joules
of energy. This is equal to about 600 000 times the rate of lling the electric
vehicle. The reverse is also true. You can store much more energy as petrol and
get the energy out of petrol many times faster than you can store and extract it
from batteries, so petrol engines can be more powerful. To store as much energy
as 60 litres of petrol you would need to have about 5000 ordinary car batteries.
This would make your car outrageously heavy and inefcient.
ACTIVITY 3.7
Design and perform an experiment to compare the heat of combustion of different
fuels.
Another way to look at the energy density of petrol is to compare it with a
large power station like the one at Swanbank, Ipswich (see Fig. 3.8). Petrol pumps
deliver about 35 MJs
1
or 35 MW. This power station delivers 960 MW of power.
This is equivalent to just 28 petrol pumps.
FIGURE 3.7
Comparison of energy
characteristics for petrol
and batteries
FIGURE 3.8
Swanbank power station
It is no wonder that petrol is popular. It is a highly concentrated energy source
and relatively cheap and easy to get. In fact, in every way other than availability and
impact on the environment, petrol compares favourably with every other fuel.
What is petrol and where do we get it?
Petrol is a mixture of many different compounds blended to give the most suitable
properties, both physical and chemical. These compounds are obtained from crude
oil using a variety of processes (see Fig. 3.9). Crude oils from different places have
different compositions.
TABLE 3.4 Typical percentage composition by mass of crude oils
Component
of crude oil Uses
Crude from Bass Strait
(Australia) (%)
Crude from the
Middle East (%)
gases LPG and chemical
feedstock
2 2
gasoline petrol 35 15
kerosene aviation fuel 15 15
gas oil diesel and heating oil 20 15
remainder lubricating oil, wax,
tar, asphalt
2530 5055
You will need to learn about carbon chemistry and hydrocarbons to understand
this section. Refer to Chemistry Sections 6.1 to 6.4, pp. 26575.
FIGURE 3.9
Processes involved in
obtaining petrol from
crude oil
The composition of crude oil varies, depending on where it is pumped from.
It contains a range of hydrocarbons that vary in size and structure, including
straight and branched alkanes, alkenes and cyclic hydrocarbons. Most crude oil
also contains some sulfur compounds.
Fractional distillation
The rst process involves separation of these hydrocarbons by fractional distillation
(see Fig. 3.10). In this process, molecules with low boiling points boil move
upwards in a column till they cool enough to condense. The higher up the column,
the smaller the molecule and the lower the boiling point. Gases exit the top of the
column. The various fractions still consist of mixtures of hydrocarbons having
similar boiling points.
FIGURE 3.10
ACTIVITY 3.8
a Distillation can be used for separating solutions of liquids in liquids like crude oil
or for separating solids from liquids in a solution of, for example, salt dissolved in
water. Set up a simple distillation apparatus to distil pure water from saltwater.
b Most geologists believe that oil is formed from fossil plankton that was buried under
sediment millions of years ago, but others believe it is a product of the normal
chemistry of rocks and does not come from fossils at all. Either way, oil takes a
very long time to form. Research the two opposing ideas about the formation of oil.
Present both sides of the argument fairly as an article, report or for a debate.
The need for new energy sourcessoon!
We have become dependent on oil because it is so useful to us. In fact, it is too
important to us than just to burn in cars. It is also an important feedstock for a range feedstock feedstock
of other industries, most importantly the plastics and pharmaceuticals industries.
Most scientists agree that oil is a non-renewable resource and we will run out of
it sooner or later. The latest research says that we have passed the peak production of
oil around the world and it will decline at a faster and faster rate. The generally agreed
amount of oil reserves that are believed to have ever existed is about 2 trillion barrels;
this could mean that there may only be 100 years worth of crude oil left in the ground.

FIGURE 3.11
Estimates of the worlds
initial oil reserves
FIGURE 3.12
The richest years may be
behind us
FIGURE 3.13
Oil discoveries have been
declining
Source: New Scientist, 2 August 2003, Vol. 179, No. 2406, p. 10 (For all the graphs.)
Improving petrols properties
A number of combustion properties are combined into a measure called the
octane rating of a fuel. Octane rating combines rate of reaction, ignition
temperature and other characteristics in a way that allows us to compare fuels by
the way they behave in internal combustion engines. The combustion characteristics
of 2,2,4-trimethylpentane (a branched-chain isomer of octane) was chosen as the
standard and was given an octane rating of 100.
The petrol that comes straight from fractional distillation is called straight-run
petrol. It is mostly composed of straight-chain hydrocarbons with some branched
hydrocarbons. The octane rating is usually too low for commercial use.
Most internal combustion motors need fuel with an octane rating in the 90s.
This allows the motor to run most efciently, extracting maximum energy from
petrol. The main problem with low octane fuels is their tendency to auto-ignite,
meaning that they explode under pressure without a spark. When this
happens, there is less control over the explosion which may occur too
early, trying to force the piston down against its upward motion.
Originally reneries blended in an octane-increasing additive
called tetraethyl lead. This was a cheap and effective way of
raising the octane rating of petrol. Before 1986 there was
standard (octane rating approximately 90) and super
(octane rating 96) petrol, both contained lead.
After 1986 standard petrol was replaced by
unleaded petrol (octane rating 92) so that
catalytic exhausts could be introduced.
Super petrol (containing lead) continued
to be available until late 1999. Lead replacement
petrol (LRP) was used instead; it is also no longer available.
Environmental concerns caused this additive to be
phased out in Australia before 1999. The lead in the exhaust
was not only toxic but ruined the catalytic converters that were
introduced to reduce pollutants in vehicle exhausts.
ACTIVITY 3.9
a Explain what Figure 3.11 tells you.
b Explain what Figure 3.12 tells you.
c Explain what Figure 3.13 tells you.
d Summarise what can be deduced from these three gures.
e Write a letter to the editor of your local paper, arguing why people should purchase
more energy-efcient vehicles and use their cars more carefully to conserve petrol.
Use the graphs to justify your arguments. Clearly state the case that we are running
out of reserves of oil.
f There are other forms of oil not yet in use. Research the pros and cons of these
alternative sources:
i tar sands in Canada and Venezuela
ii shale oil in Australia.

A molecule of
tetraethyl lead
To learn about catalysts, refer to Chemistry Section 7.13, pp. 310312.

Catalytic converters
Catalytic converters were developed to reduce the amount of pollutants coming
from the exhausts of cars and trucks. These pollutants include nitrogen oxides
(NO and NO
2
), unburnt hydrocarbons and carbon monoxide.
Catalytic converters have a relatively simple design (see Fig. 3.14). They are,
however, expensive because of the catalyst material, which is usually an alloy of alloy alloy
platinum and rhodium, both expensive metals.
The platinum in the catalytic converter speeds up reactions with oxygen.
Carbon monoxide is turned into carbon dioxide:
2CO(g 2CO( 2CO( ) gg O
2
(g (( ) gg 2CO
2
(g (( ) gg
and hydrocarbons are turned into carbon dioxide and water:
C
5
H
12
(g (( ) gg 8O
2
(g (( ) gg 5CO
2
(g (( ) gg 6H
2
O(g O( O( ) gg
The rhodium metal in the catalyst helps convert nitrogen oxides into nitrogen
and carbon dioxide:
2CO(g 2CO( 2CO( ) gg 2NO(g 2NO( 2NO( ) gg N
2
(g (( ) gg 2CO
2
(g (( ) gg
When lead is in petrol, it coats the platinum and rhodium until it cannot catalyse
the reactions any more. This is usually called poisoning the catalytic converter.
To use leaded petrol in a car with a catalytic converter is illegal because it results in
more pollution.
When tetraethyl lead became illegal, chemical engineers in oil reneries had to
be more innovative in making petrol with the right octane rating. Now, oil reneries
adjust the composition of the petrol through isomerisation, reforming, cracking and
blending. Catalytic cracking is done primarily to increase the proportion of petrol
that can be obtained from a barrel of crude oilto balance supply and demand for
fuel products. Catalytic reforming was introduced (in the 1960s) to improve the
quality of petrol.
In general, the shorter the alkane chain, the higher the octane rating, so one
way of improving octane rating is to crack the big molecules into shorter ones.
Unfortunately, simply reducing the length of the carbon chain also increases the
volatility, and more of the petrol will vaporise and be lost before it is gets into the
combustion chamber of the engine.
FIGURE 3.14
A catalytic converter
Shapes of hydrocarbons
Hydrocarbonscompounds containing just carbon and hydrogencan be arranged
in a wide variety of molecular shapes. As an example consider hydrocarbons with
six carbons.
Hexane (C
6
H
14
) looks more or less like this:

but can move freely by bending and rotating bonds into:
or
As well as being able to arrange themselves in straight and bent chains, carbon atoms
can form rings, called cyclo compounds.
Cyclohexane (C
6
H
12
) is arranged in a ring like this:

Notice that, because it is joined into a ring, it has two fewer hydrogens.
Carbon atoms also join with double bonds and triple bonds and one arrangement of
double bonds in a ring has special properties. The arrangement of bonds as in benzene
below is called an aromatic bond structure and behaves in unusual ways.
Benzene (C
6
H
6
) looks like this:

To understand ideas about double and triple bonds in hydrocarbons and

shapes of hydrocarbon molecules, refer to Chemistry Sections 6.5 to 6.8,
pp, 27583 and the information box, Shapes of hydrocarbons, below.
Cracking
Cracking involves breaking the larger molecules from the heavier end of the
distillation process into smaller molecules. Although it varies from source to source,
no crude oil naturally has the correct proportion to suit the needs of modern
society. There is usually an excess of larger molecules like tars and other residues,
with smaller molecules like petrol and gases being in short supply (see Fig. 3.15).
Cracking involves heating heavy oils in the presence of a catalyst. This process is
usually called catalytic cracking. The most common catalyst in use is called zeolite.
Zeolites are a family of minerals containing mainly aluminium, silicon and oxygen.
These occur naturally but can also be made synthetically. The uses of the different
types of zeolites depend on the way the atoms arrange themselves in the crystal.
A common feature of zeolites is the large network of interconnecting pores and
channels of different sizes, giving the material a very large surface area. The heavy
oil feedstock is usually made up of molecules containing 25100 carbon atoms.
Catalytic cracking produces a mixture of new hydrocarbons with anything from
four to ten carbon atoms. These hydrocarbons are also more likely to be branched
and to contain double bonds and carbon rings. Some examples of the range of
compounds formed by cracking are shown in Figure 3.16.
FIGURE 3.15
Supply and demand for
different fractions of
crude oil
ACTIVITY 3.10
a Why would oil occur naturally in the proportions shown in Figure 3.15? (Hint Why would oil occur naturally in the proportions shown in Figure 3.15? ( Why would oil occur naturally in the proportions shown in Figure 3.15? ( : Think
of the boiling points of the various fractions and the conditions under which crude
oil occurs underground.)
b Research the petrol properties needed for racing cars and dragsters. Why is their
petrol so expensive?
Cyclic alkanes
Other reactions during the cracking process occur, giving a wide range of smaller,
branched alkanes, straight-chain and branched alkenes, and cyclic alkanes.
A range of different molecules is formed in the cracking process, so the
resultant mixture is once again put through the fractionating column to separate
the different-sized molecules. Alkenes are extracted for use as feedstock in other
important industries. The smaller alkanes are used to blend with the straight-run
petrol to increase the quantity of petrol.
As is always a problem in chemical changes involving carbon, there are a
number of by-products, some of which may cause problems for the reactor. In the
case of catalytic cracking, pure carbon forms on the catalyst, making it inactive.
To reduce the negative impact of this and other problems, chemical engineers
design the processes to minimise any waste of time, energy or materials. In the case
of carbon clogging up the catalyst, the process is designed so that:
the desired products are separated from the clogged catalyst
the coke on the catalyst is burned off
the burning coke heats the catalyst so that it is ready for the next supply of
feedstock.
In this process design, there is no wasted energy, no wasted materials and any
time delay is kept to a minimum.
To keep the volatility of the fuel high enough and still shorten the chain length,
reneries produce more branched chains.

FIGURE 3.16
Examples of uncracked
and cracked
hydrocarbons
Isomerisation
Isomerisation involves heating and decomposing straight-chain alkanes in the
presence of a suitable catalyst so the fragments are more likely to join together as
branched rather than as straight chains. Both pentane (C
5
H
12
) and hexane (C
6
H
14
)
are products of the distillation of crude oil.
Reforming
Reforming is an industrial process used to increase the yield of high octane petrols
from reneries. It involves both isomerisation and cyclisation reactions. In this set
of reactions, naptha, which is mostly straight-chain molecules with 610 carbon
atoms, is heated to about 500
o
C with another catalyst based on platinum. The
straight-chain alkanes are converted to ring compounds and then to aromatic
compounds.
To review the work on isomers and catalysts, refer to Chemistry Sections 6.5,
pp. 2758 and 7.13, pp. 31012.


A number of other branched aromatic compounds such as methylbenzene
(120) are formed as part of the process, raising the octane rating even further.
TABLE 3.5 Octane ratings of various organic compounds
Compound Number of carbon atoms Octane rating
butane 4 94
pentane 5 62
1-pentene 5 91
2-methylbutane 5 93
cyclopentene 5 101
2,2-dimethylpropane 5 96
hexane 6 25
1-hexene 6 85
2-methylpentane 6 71
2,2-dimethylbutane 6 94
cyclohexane 6 83
benzene 6 106
heptane 7 0
1-heptene 7 68
2-methylhexane 7 41
2,2-dimethylpentane 7 89
2,2,3-trimethylbutane 7 113
methylcyclohexane 7 104
octane 8 19
2,2,4-trimethylpentane 8 100
ethylbenzene 8 105
ACTIVITY 3.11
a Draw and name as many isomers of octane as you can. By applying the general
rule, the shorter, the chain the higher the octane rating, which isomers would have
the highest octane rating?
b Most catalytic crackers work on the uidised bed principle. Find out the operation
of the uidised bed.
c Research zeolite and molecular sieves.
d Figure 3.17 is a rough diagram of the isomerisation process but is incomplete.
Fill in the product box with appropriate diagrams and description of the products.
e Cyclohexane (C
6
H
12
) and benzene (C
6
H
6
) are not isomers of hexane yet they both not not
have six carbon atoms. Explain why they are not called isomers.
Blending
Blending involves mixing a range of substances together to get the desirable
characteristics for the cheapest price. The products of cracking, isomerisation
and reforming already discussed are used in the blending process. One other type
of substance is used in petrol, both to increase the octane rating and to reduce
pollution. This group of substances are called oxygenates and include alcohols and
ethers (see Fig. 3.18). Oxygenates reduce pollution by improving the combustion
reaction, making more CO
2
and less CO. CO is poisonous. CO
2
is not.
f Use the data in Table 3.5 to relate octane rating to:
i the number of carbon atoms
ii the features of the molecular structure such as branching, straight-chain
or cyclic, aromatic or aliphatic, the presence of oxygen
iii presence or absence of double bonds.
g Use Table 3.5 to describe how each of the cracking, isomerisation and
reforming processes in rening crude oil changes the octane rating of the
resulting mixture.

FIGURE 3.17
Isomerisation
To understand about functional groups in organic chemistry, you will need to

read Chemistry Section 6.9, pp. 2845.
TABLE 3.6 Octane rating of oxygenates commonly used in petrol blending
(note that straight-run petrol is included for comparison
purposes only)
Name Formula
Type of
compound
Octane
rating
Relative cost per
litre (approx.)
(compared with
straight-run petrol)
straight-run petrol 70 1
methanol CH
3
OH alcohol 114 3
ethanol CH
3
CH
2
OH alcohol 111 5
MTBE CH
3
OC(CH
3
)
3
ether 113 1.5

FIGURE 3.18
Ethanol, ether and MTBE
ACTIVITY 3.12
a Remember how quickly the our burned back in Activity 3.6 when you tried to
burn it in a pile and as atomised powder. Now take a thimbleful of the same
our, mix it with about twice as much potassium nitrate and burn it on a tile.
(Safety note: Wear goggles. (( ) Potassium nitrate is an extreme type of oxygenate
and aids the combustion process. Compare the speed of burning. How would
you explain the difference?
b Burn about 10 mL of petrol in an open dish (like a watch-glass) and 10 mL of
methylated spirits in another open dish. Write a list of observations of the burning
characteristics of these two fuels. Explain the different burning characteristics in
chemical terms if possible. Do not breathe the fumes from either of the fuels or
the combustion products.
c A fuel with the appropriate octane rating could be blended just from straight-run
petrol and methanol. This is not what happens in reality, so there must be other
factors. Make a list of as many factors as you can that could inuence the relative
amounts of substances used in blending petrol.
d Research the role of NOS or nitrous oxide in drag cars.
PETROL IS POLLUTING
water, but, depending on the conditions, the combustion reaction also makes other
products, including highly poisonous carbon monoxide and oxides of nitrogen
that create photochemical smog. Unburnt alkanes, which are poisonous, are also
emitted. In Europe and America, the fuels contain much more sulfur than in
Australia, so an added problem in those places is the emission of oxides of sulfur,
which are responsible for acid rain.
Greenhouse effect
Since carbon dioxide is already present in the atmosphere, it was thought to be
insignicant as a pollutant. The Swedish chemist Arrhenius predicted 100 years
ago that increasing amounts of carbon dioxide in the atmosphere could lead to
warming of the Earth by the greenhouse effect (see Fig. 3.19). Since then, average
temperatures have risen and fallen again, making his prediction of global warming
uncertain. Even now, people who do not want to give up their petrol-driven cars
argue that global warming is not due to the burning of fossil fuels. Although global
warming is unproven and the cause is uncertain, recent measurements of increases
in carbon dioxide and in global temperatures indicate that it is probably very real.
FIGURE 3.19
The greenhouse effect
The consequences of global warming are as uncertain as the fact. Powerful
computer models are used to predict what may happen to the weather. The models
do not all agree but there is general agreement that weather patterns will become
more unpredictable. There will be more droughts, oods, cyclones and hurricanes,
but we just dont know where. Considering that we will run out of fossil fuels and
that burning them creates a number of problems on a global scale, we need to do
something about it now.
ACTIVITY 3.13
Search books, newspapers, magazines and websites on global warming to decide for
yourself whether it is real or not and, more importantly, whether human activity is the
cause. Use the key words global warming, debate, argument.
Models of changing
weather patterns
You will extend your understanding of the greenhouse effect in Context 4 Air,
pp. 15860.
Photochemical smog and acid rain
Photochemical smog is a greybrown haze that occurs around areas of high
pollution. It is a mixture of compounds (some created directly by combustion
reactions) called primary pollutants and some secondary pollutants, created by
further reactions among the primary pollutants under the inuence of ultraviolet
radiation.
Photochemical smog mainly causes haziness and irritation of eyes and
lungs, but for the very young, very old and people with respiratory problems,
photochemical smog can cause severe problems. The ozone in photochemical
smog is a highly reactive substance and attacks chemical bonds in many organic
compounds. It is the main health hazard of photochemical smogfor young
and old.
Acid rain comes mainly from sulfur in fuels burning to become sulfur dioxide,
which dissolves in water to form sulfurous and sulfuric acids. Acid rain has been
responsible for killing large areas of forests in Germany and damaging stone
buildings in Europe and America.
ACTIVITY 3.14
a Refer to Table 3.2. Calculate the mass of CO
2
released for each litre of petrol
burned.
b Does a battery-operated electric car have any negative environmental impacts?
Research an argument against battery-operated vehicles. against against
c Choose one of the pollution problems below to
research in more detail:
i acid rain
ii photochemical smog.
d Burn sulfur in a gas jar in a fume cupboard as in
Figure 3.20. Test the water with pH paper. What
does the result mean? (Caution: Fumes from the
combustion of sulfur will irritate eyes, mucous
membranes and lungs.)
e Brainstorm as many ways as you can imagine
to reduce the pollution problems involved in
transport. Consider all possibilities, including
new fuels, motors, stopping driving and so on.
f Construct a futures map from your ideas, to
test the impact of some of the ideas you came
up with.
FIGURE 3.20
Burning sulfur
You will learn more about ozone and how it is produced in Context 4 Air,
pp. 14658.
What can we do?
Modify existing cars
Existing engine and vehicle technology is undergoing considerable changes.
New materials such as polymers and new alloys based on magnesium mean that
cars can be much lighter, so less fuel is burnt moving them about. Improved
shapes reduce air resistance. New ceramic materials allow engines to run at higher
temperatures, extracting more energy from fuel. Improved engine technology allows
engines to run leaner, resulting in less carbon monoxide and better fuel economy.
Catalytic converters turn carbon monoxide into carbon dioxide and hydrocarbons
into carbon dioxide and water.
Use other fuels
Despite innovative design changes, all hydrocarbon burning engines result in
the production of carbon dioxide and water at the very least. With the enhanced
greenhouse effect (global warming) being one of the greatest challenges to our
planet, there is a powerful need to change from burning hydrocarbons for energy.
Even electric cars that rely on batteries can only be a stop-gap measure, since the
production of electricity is still mostly through burning fossil fuels.
Changing fuels seems to be only way of reducing our real impact on the
environment.
Is there a fuel that when burnt produces a non-polluting product? The only
answer is hydrogen. There is an enormous supply of hydrogen on Earth. Most of
it is tied up in water. The Earths oceans contain millions of tonnes of hydrogen
enough to supply humans need for energy for thousands of years.
At rst glance, hydrogen seems perfect as a fuel. When it burns it yields nothing
more than water and heat as products.
The combustion equation for burning hydrogen is:
H
2
(g (( ) + O gg
2
(g (( ) gg H
2
O(g O( O( ) gg + 285 kJ/mole
TABLE 3.7 The important properties of hydrogen at normal pressures
Chemical
formula
Standard state
at normal
pressures
Boiling
point
(C)
Heat of
combustion
(kJ/mol)
Energy value
as liquid as gas
(MJ/kg) (MJ/L) (MJ/L)
H
2
gas 259 285 141 20.0 0.013
A close look at Table 3.7 shows that, in reality, hydrogen is extraordinarily
difcult to use as a fuel. At normal temperatures and pressures, hydrogen (as a gas)
has a very low energy value. This means to use hydrogen effectively we need to
store it as a liquid or compressed gas or any other method that will pack hydrogen
into a small space and deliver it to the motor fast enough to yield suitable power.
There are a number of experimental ways to get over the problem of
storing hydrogen. The most straightforward is to compress and cool it to a
liquid. Hydrogens properties make this option very difcult; BMW and other
manufacturers have done it successfully, although at great cost. This option requires
considerable energy to compress and cool the hydrogen and keep it that way, and
considerable cost in the materials to prevent it warming up.
Other experimental ways include:
storage in organic molecules, such as methane, methanol, ethanol
storage in inorganic molecules, such as metal hydrides and sodium borohydride,
ammonia
micropore storage.
As well as hydrogen, a number of other fuels are being considered. These
include traditional fuels derived from plants rather than petroleum products, called
biofuels. Biofuels include ethanol from the fermentation of sugar or wheat and
methanol from the fermentation of cellulose, and biodiesel, made from plant oils.
Biofuels still form CO
2
gas when they burn, but because they are products of
photosynthesis they use up CO
2
in their manufacture. The production of biofuels
is more or less a closed cycle:
photosynthesis combustion
CO
2
+ H
2
O biofuel + O
2
biofuel + O
2
CO
2
+ H
2
O
ACTIVITY 3.15
a What would you have to do to hydrogen to keep it as a liquid?
b Most cars store fuel at about 25
o
C. Use Table 3.7 to nd the energy value of
hydrogen (in MJ/L) at this temperature and normal pressure.
c Calculate the ratio of the energy values, in MJ/L at normal temperatures and
pressures, of petrol to hydrogen using data from this table and Table 3.2.
In terms of energy alone, how much better as a fuel source is petrol?
d Hydrogen has the highest energy value per kilogram. It is also relatively
non-polluting. Use the data in Table 3.7 to discuss why hydrogen isnt used
more as a fuel, except in rockets.
e Research the use of hydrogen as a fuel in rockets. Why is it a popular fuel in
this situation?
f Research and report on the various technologies for storing hydrogen:
i storage in organic molecules (for example, methane, methanol, ethanol)
ii storage in inorganic molecules (for example, metal hydrides and sodium
borohydride, ammonia)
iii micropore storage.
g In 2003 in Australia, there was a serious political debate about requiring reneries
to increase the amount of ethanol in petrol to 20%. Find out as much as you can
about the pros and cons of this debate. What do you think Australia should do?
h Think of petrol as simply a way of storing hydrogen, and petrol as mainly octane.
Octane has a formula of C
8
H
18
and has a density of about 0.7 kg/L. If you could
just burn the hydrogen in petrol (and so not make CO
2
), calculate the energy value
of the hydrogen that could be stored per litre of petrol.
ACTIVITY 3.16
Read the article and answer the following questions:
a What type of engine is this hydrogen vehicle using?
b At what temperature is the liquid hydrogen stored?
c List the pros and cons of this current hydrogen-powered car. this current this current
d What is BMW saying will be the future engine for this type of vehicle? Why would
this be their preference?
G
erman luxury carmaker BMW
is looking for partners in the
auto industry and elsewhere in
its bid to bring hydrogen-powered cars
to market. The company is currently
showcasing a eet of ten liquid
hydrogen-powered sedans worldwide,
which are now being tested at a facility
near Los Angeles.
California has some of the most
stringent standards for automobile
emissions worldwide, making it a
rigorous testing ground for BMWs
next-generation cars. These cars
hold the future promise of emitting
nothing but water from a hydrogen
fuel cell rather than the V-12 internal
combustion engine currently exploited
by this eet. This engine can burn
either gasoline or liquid hydrogen
cooled to minus 250 degrees Celsius,
which is stored in insulated 37-gallon
(140-litre) tanks behind the rear seats.
One tank provides a cruising range of
about 217 miles (350 km). The cars do
feature accessory fuel cells instead of
traditional batteries that supply power
for the stereo, air conditioner and other
functions when the engine is off.
The massive cost of storing and
distributing sub-zero liquid hydrogen
is a major hurdle for these cars. Like
typical gasoline power-plants, these
engines still burn some lubricants,
emitting signicant amounts of carbon
dioxide and carbon monoxide and
because they involve combustion some
NO
X
is made. Britains BP Plc, which
produces 1,200 tonnes of hydrogen per
day, is working with BMW on feasibility
studies for a hydrogen-powered car.
Source: www.bmw.com
BMW Looking for Partners to
Make Hydrogen Cars
Articles on other types of biofuels can be found in the Transport context on

the Student CD.
CARS, METALS AND CORROSION
components weaker and unattractive. If the component is critical, rust will make
the car unroadworthy. Most states in Australia have rules regarding rust and
roadworthiness. Rusted components or whole vehicles have to be replaced and
the iron that was used to make them is wasted when they are dumped.
Can rust be stopped? An understanding of metals in general and steel in particular
and the chemistry of rusting is needed before this question can be answered.
If you want to extend this context to learn about cars, metals and corrosion,
refer to the additional material on the Student CD.
Summary
Efcient transportation is an important part of our modern world. It creates wealth but
causes considerable problems.
Engines convert stored chemical energy into mechanical energy, usually depending on
a combustion process to extract the energy.
Fossil fuels such as petrol are an extremely effective source of energy but cause
problems. We are running out of crude oil to make petrol and it seems that its use has
resulted in an increased greenhouse effect. Burning fossil fuels also contributes to other
pollution problems such as acid rain and photochemical smog.
We cannot return to the past but we can learn from it. We can use a variety of methods to
minimise the negative effects of our dependence on mechanised transport. These include:
improving motors to be more efcient
modifying existing fuels to improve their combustion characteristics
using new fuels that are less polluting (such as hydrogen)
using new fuels that are made in a closed cycle with their major pollutants
(such as biofuels, biodiesel), and
designing motors based on new technology (fuel cells and electric motors).
GLOSSARY
alloy a mixture of different metals or a metal with other non-metallic elements alloy alloy
(like carbon)
anomalies odd-looking results; results or observations that are unexpected or do
not match with expected trends
atomise to break a liquid up into a mist of tiny droplets (like y spray or spray
deodorant). In an atomised spray, the particles are still made up of many
molecules. If the boiling point of the liquid is not much more than ambient
temperature, an atomised liquid may vaporise.
auto-ignition a characteristic of a fuel to explode just by heat and compression
(without a spark)
blending the mixing together of different components in a given proportion
catalyst a material that speeds up reactions without getting used up in the process
chemical energy energy that is released (generally as heat) when substances
undergo chemical reactions (such as combustion)
combustion a self-sustaining chemical reaction between a high energy substance
(fuel) and an oxidiser that releases signicant amounts of energy
cracking a process in which large hydrocarbon molecules are split into smaller
molecules
crude oil a black liquid, pumped directly from the ground, that is a mixture of
hydrocarbons
efciency the percentage of the energy taken out of an energy converter in a useful efciency efciency
form compared with the energy that is put in. For example, a car is about 25%
efcient, meaning that only 25% of the energy put into the car (as petrol) is
used to move the car. The other 75% of the energy is wasted as heat, sound
and so on.
energy the capacity to do work
energy converter an object or machine that changes energy from one form into
another more usable form. For example, a loudspeaker converts electrical
energy into sound energy.
energy value the heat of the combustion reaction for fuels, measured in appropriate
units for fuels (for example, joules per gram or kilojoules per litre)
explosion a form of combustion with a very high rate of reaction that creates a
shock wave expanding faster than the speed of sound
feedstock the materials used to supply the basic chemicals needed for chemical feedstock feedstock
processes like rening and cracking
fuel a substance that will react at a reasonable rate with another substance to release
signicant amounts of energy (see chemical energy)
futures map a concept map based on tracing impacts into the future, for example:
using more public transport fewer cars needed less steel needed
fewer jobs unemployment social problems
heat of combustion the energy liberated when 1 mole of a substance undergoes
complete combustion with oxygen at a constant pressure of 1 atm with the nal
products being the completely oxidised forms of the elements in the fuel, usually
carbon dioxide and water
homogenous having no obvious boundaries; for example, a salt solution is
homogenous, where dirty water is heterogeneous
hydrocarbons a group of chemicals made up of carbon and hydrogen
124 CHEMISTRY IN USE
ignition temperature the minimum temperature to which a mixture must be heated
in order for combustion to occur
isomer a molecule with the same molecular formula as another, but with a different
structure
isomerisation rearranging molecules keeping the same molecular formula but a
different structure
mechanical energy energy of movement, kinetic energy mechanical energy mechanical energy
octane rating a number that summarises some of the burning characteristics of
a fuel, especially auto-ignition
oxygenates organic substances used in fuels containing some oxygen in the
formula, for example ethers and alcohols (ethanol, C
2
H
5
OH)
pollutant a substance that has a detrimental effect upon people, other organisms
or the environment generally
power the rate at which energy can be used to do work; usually measured in
watts (W) which is equal to joules per second (J s
1
)
reciprocating repeating backwards and forwards, in and out, or up and down
reforming rearranging the bond structure of organic molecules
standard state the physical state (solid, liquid or gas) of a substance at normal
temperature and pressure
stoichiometry the mathematical relationship between substances in a chemical stoichiometry stoichiometry
reaction. For example, from the equation 2H
2
(g (( ) + O gg
2
(g (( ) gg 2H
2
O(g O( O( ) we gg
know that hydrogen will react with oxygen to make water in the ratio 2 moles
hydrogen:1 mole oxygen:2 moles water, or by weight the ratio will be 4:32:36.
vaporise to turn into a vapour, usually from a liquid (also volatilise)
volatility how easy it is to turn a liquid into a gasmore volatile liquids turn into volatility volatility
gases more easily
125
CONTEXT 4
Air: something
we all share
IN THIS CONTEXT
The composition of airwhat we really breathe 126
Investigating gases of the air 130
Using air 132
The atmosphere 141
Main pollutants of our air 143
Ozonethe good and the bad 146
Global warminga hot topic 155
We can live a few weeks without food, a few days
without water but only a few minutes without air. Air is
the closest and most important biological connection
we have with the rest of the world. We breathe air from
the atmosphere into our bodies every few seconds. Like
it or not, we share the air we breathe with other living
organisms, both plants and animals, as it is constantly
recycled through the atmosphere. To be informed
citizens, we should know about the air we breathe.
Whats in it and the quality of the air surrounding us
affect our very existence.
Air is a complex mixtures of substances; we use
the air and its separate components for many other
purposes apart from breathing. We ll our car and bike
tyres with it and we heat it to cause hot air balloons
to rise. Exploring the chemical concepts related to
the behaviour of gases and their reactions allows us to
understand how and why gases behave as they do.
THE COMPOSITION OF AIRWHAT WE
REALLY BREATHE
ACTIVITY 4.1
Consider the following statements and decide whether or not you think they are true (T)
or false (F). For each statement you think is false, rewrite it to make it true.
a The air is a mixture of gases.
b The main gas in air is oxygen.
c Air is weightless.
d All air on Earth has the same composition.
e All air pollution is caused by human activities.
f Animals need oxygen for respiration while plants need oxygen for photosynthesis.
CONTEXT 4 AIR 127 CONTEXT 4 AIR 127
The composition of the air in our atmosphere has not always been the same.
Studies of the materials of the Earths crust give scientists a glimpse of what the
Earth was like billions of years ago. The oldest known sediments on Earth, found
in Greenland and dated about 3.8 billion years old, contain carbonates, suggesting
there was carbon dioxide in the atmosphere at that time. They also give a hint that
some free oxygen was present.
Beyond 3.8 billion years ago, the nature of the Earths atmosphere is more
difcult to fathom. Scientists hypothesise that the original atmosphere of the Earth
had to be similar to its cosmic source, the sun. Careful studies of the presence of the
noble gases (helium, neon, argon, krypton and xenon) in Earths atmosphere show
they are not as abundant as in the sun. This led to the conclusion that the original
gases associated with the formation of Earth were lost and that the Earths primitive
atmosphere resulted from volcanic out-gassing, thus creating an atmosphere of
ammonia, methane and water vapour. The ammonia (NH
3
) soon broke down into
nitrogen, which currently forms the highest percentage of our current atmosphere,
whereas the hydrogen was lost to space. The methane (CH
4
) was converted to
carbon monoxide and nally to carbon dioxide.
The evolution of the ozone layer is thought to have been signicant in allowing
the development of organisms able to photosynthesise, leading to the gradual
build-up of oxygen in the air. This is because it protected life from the lethal
UV radiation from the sun.
As the oxygen concentration increased and the ozone shield consolidated, life
from the oceans is thought to have crept onto the land. Photosynthesis continued
to ourish. When the oxygen concentration in the atmosphere reached 10%,
organisms needing oxygen for respiration began to evolve. Eventually, the oxygen
concentration of the Earth reached 21%, where it has remained.
The Earths sister planets, Venus and Mars, have quite different compositions
of gases in their atmospheres, even though they were formed at the same time.
The Venusian atmosphere, which is more dense than that of Earth, has 96% carbon
dioxide and 3% nitrogen, with clouds of sulfuric acid. Mars, on the other hand, has
a very thin atmosphere consisting of 95% carbon dioxide and 3% nitrogen.
Earths air
Air is a mixture of many substances. The main four are gases: nitrogen, oxygen,
argon and carbon dioxide. The percentages of these are remarkably constant
throughout the atmosphere. The air also contains water vapour but the percentage
varies considerably. It can be close to 0% in very dry desert air or 56% in a tropical
rainforest. Because of this wide variation, tables such as the one below normally list
the composition of dry air.
ACTIVITY 4.2
Research the composition of the atmosphere of other planets of the solar system and
compare their atmospheric composition with that of the Earth.
TABLE 4.1 The composition of dry air
Major constituents percentage (v/v)
nitrogen 78.08
oxygen 20.95
argon 0.93
carbon dioxide 0.035
Minor constituents (ppm)
nitrous oxide 0.2 carbon monoxide 0.1
neon 18 ozone 0.02
helium 5 NO NO
2
<0.01
methane 1.5 ammonia <0.01
krypton 1 SO
2
H
2
S <0.002
hydrogen 0.5
The concentrations of some of the substances are measured in parts per million
(ppm) by volume. This measure is often used when concentrations involved are
very small; for example, 350 ppm corresponds to a percentage concentration of
0.0350%. Note that ppm is always a volume/volume measure for gases but is a
mass/mass measure for solutions.
In Table 4.1, the composition of the air has been based on volume, so 100 L of
air contains approximately 78 L nitrogen (N
2
), 21 L oxygen (O
2
) and 1 L argon (Ar).
An alternative way to represent composition is in terms of relative amounts of
particles or moles, but because the volume of a gas sample varies with temperature
and pressure, all gas volumes must be measured at the same temperature and
pressure.
Take a breath
When we breathe we inhale all the gases shown in Table 4.1, as well as water
vapour and many solid pollutants. Now consider Table 4.2, which compares the
composition of inhaled and exhaled air.
ACTIVITY 4.3
Use Table 4.1 to answer the following questions:
a Draw a bar graph to show the composition of the main gases.
b How many ppm of argon are there in a typical sample of air?
c In 1 L of dry air, what is the number of molecules of oxygen (O
2
) if 24.5 L contains
1 mole?
TABLE 4.2 Composition of inhaled and exhaled air
Gas Inhaled air (%) Exhaled air (%)
nitrogen (N
2
) 78.0 75.5
oxygen (O
2
) 21.0 14.5
argon (Ar) 0.9 0.9
carbon dioxide (CO
2
) 0.04 4.0
water vapour (H
2
O) 0.0 4.0
Oxygen is needed for respiration. During respiration, glucose (C
6
H
12
O
6
) reacts
with oxygen gas to produce carbon dioxide, water and energy.
Because we continuously exchange millions of molecules with other living
things in any breath (remember 1 mole contains 6.02 10
23
molecules), our lungs
contain 4 10
19
molecules that have been previously breathed by other human
beings and 6 10
8
molecules that have been breathed by some particular person.
It is almost certain that your body contains one molecule that was once in Einsteins
or Newtons last breath.
Table 4.1 tells us some of what we breathe in but our noses are very sensitive
odour detectors and we know air contains trace quantities of other substances not
listed in the table. The main gases in air are odourless, but many other airborne
substances have distinctive odours. Three of the four gases that contribute to air
pollutionozone, sulfur dioxide and nitrogen oxideshave distinctive odours,
whereas carbon dioxide is odourless.
The Buteyko breathing technique
The Buteyko breathing technique, developed by Russian scientist Professor Buteyko,
achieved consistent results in treating diseases such as asthma, sinusitis, snoring
and emphysema. The theory is based on the biological role CO
2
plays in humans.
It has long been recognised medically that hyperventilation (breathing much faster and
deeper than normal) causes a progressive loss of CO
2
, leading to airways and arteries
narrowing. Professor Buteyko proposed that breathing less would open them again.
The human race is believed to have evolved at a time when the carbon dioxide content
of the atmosphere was much higher than it is at present. The problem faced with the
evolving human organism was the depletion of CO
2
in the atmosphere and the increase
in O
2
concentration. The CO
2
concentration has gone from tens of per cent in ancient
times to 0.0367% today.
The human organism coped with this change by the alveoli in the lungs having a
CO
2
concentration of 6.5%. CO
2
is converted into carbonic acid, which is vital in
maintaining the bodys acidbase balance according to the reaction:
CO
2
(aq (( ) + H
2
O(l O( O( ) ll s H
2
CO
3
(aq (( ) s HCO
3
(aq (( ) + H
(aq) ((
You can do an experiment to calculate how much air you breathe in each breath.
INVESTIGATING GASES OF THE AIR
no distinct upper boundary, but disperses gradually into space. At sea level, each
litre of air has a mass of about 1.25 g. Because air has mass, it exerts a pressure on
everything. This pressure is like having a kilogram tub of margarine pushing on
every square cm of every part of the surface of your body all the time. It is caused
by unimaginably large numbers of molecules, moving at hundreds of kilometres
per hour, colliding constantly with each other and every object on the planet.
We tend to forget this pressure is even there, until we need to work with or against it.
A low level of CO
2
strengthens the bond between haemoglobin and oxygen molecules,
so decreasing the dissociation of oxyhaemoglobin and making it difcult for sufcient
oxygenation of the tissues and vital organs.
Hyperventilation and over-breathing, especially in cases of asthma and hypertension,
leads to a decit of CO
2
and imbalance within many of the bodys vital systems.
The aim of the Buteyko method is to correct the patients breathing pattern to rectify
the level of CO
2
in their system. Basically, the Buteyko method involves training
patients to breathe to, on average, 34 L per minute, thus rectifying a shortfall in CO
2
.
ACTIVITY 4.4
a Take a suction cup or
plunger used to clean
drain blockages and place
it on a at surface. Lift it
upit comes off easily.
This time, push the suction
cup rmly to the surface
and try to lift it. Does it
come off easily this time?
Explain why.
b Place a straw in a glass of
milk and suck some milk
into the straw. Quickly place your nger over
the top of the straw and lift it out of the milk.
What happens to the milk in the straw? Why?
What would happen if suddenly there was no
atmosphere?
c Decide whether the following things would work
if there was no atmosphere:
i a vacuum cleaner
ii a siphon
iii an aerosol spray can
iv a match
v lightning
vi a magnet.

The air exerts a pressure of 1 atm or 101.3 kPa. This air pressure varies with
height above sea level and also with temperature. The movement of gases in the air
creates high and low pressure systems that cause the weather.
If air is cooled under pressure it condenses to a liquid at about 200C. This
liquid contains the gases that are in the air, and industrial plants use fractional
distillation to produce liquid and gaseous nitrogen (boiling point 196C) and
oxygen (boiling point 183C), and gaseous argon (boiling point 186C).
In 1883 William Ramsay and his colleagues removed the main components
of air (O
2
, N
2
, H
2
O, CO
2
, pollutants) and found there was still some mixture
remaining. They undertook fractional distillation of the remaining mixture and
discovered the noble gases.
Each of the airs components has distinctive physical and chemical properties.
By preparing oxygen and carbon dioxide and investigating their properties, we can
better understand these two important atmospheric gases. This will help us to better
understand many of the interactions that occur between the components of the
atmosphere.
Oxygen is the most reactive gas in air. Karl Scheele in Sweden rst collected
it in 1773. He recognised that many substances burnt vigorously in this gas and
he called it re air. It was later named oxygne by French scientist, Antoine
Lavoisier.
Carbon dioxide has an important role for all living things, even though it takes
up only a small fraction of the atmosphere. Its existence was rst recognised in
1599 by Belgian chemist, Jean Baptiste van Helmont. The reactivity of carbon
dioxide is quite different to that of oxygen.
ACTIVITY 4.5
You have been asked to write an article for a chemistry magazine about the noble
gases. The article is to be no more than 500 words (not including diagrams and tables)
and is to particularly address the issues of how they were discovered and why their
discovery came so long after the other elemental gases had been discovered.
To understand more about pressure and the scientic explanations of the

nature of gases, refer to Chemistry Sections 8.1, 8.2 and 8.3, pp. 31518.
You can do an experiment to prepare carbon dioxide and oxygen, and

compare their properties. (Refer to Chemistry in Use Book 1 Teacher Resource
CD-ROM.)
USING AIR
we pump it into tanks and use
it when scuba diving, or ying
at high altitudes. The gases of
the air also have many other
uses. Nitrogen is used to protect
products from the atmosphere
and in industrial application where
there is a need to freeze products.
Oxygen is used in medical and
life-support applications, chemical
manufacturing, steel making and
smelting, and pulp and paper
industries. Carbon dioxide is
used in re extinguishers and
carbonated drinks, whereas helium
is used in balloons and argon as a
lling in incandescent light globes.
Unlike solids and liquids, gases
can be compressed. By applying
pressure, the volume of a gas
decreases; this means a greater
mass of gas can be stored in a given container. Tanks of compressed gas are quite
common, and it is important not to overll a compressed gas cylinder as the
container may not be able to cope with the increased pressure.
Did you make the following observations regarding the balloons or syringes?
1 All three occupy the same volume (assuming the same conditions of
temperature and pressure).
2 When the external pressure is increased and the temperature is kept constant,
the balloons shrink in size.
Some products which use components of air
ACTIVITY 4.6
To investigate this relationship between the amount of gas, temperature, volume and
pressure:
1 Obtain three balloons or plastic syringes that can be sealed airtight.
2 Partially ll each balloon with the same amount of air, carbon dioxide or oxygen
(or other gases that are available), so that you have three balloons containing
different gases. If using syringes, ll so the plunger is about halfway out.
3 Draw a line around the middle of each balloon and measure the circumference
or note the reading on the plunger.
4 Squeeze the balloons or push the plunger in. What happens to the volume?
5 Place each of the balloons or plungers in hot water. What happens to the volume?
Check by measuring the circumference of the balloons.
6 Place each of the balloons or plungers in ice water or water containing dry ice.
What happens to the volume?
7 What happens to the volume when some of the gas is allowed to escape?
3 When the temperature is increased or decreased by the same amount for each
balloon and the pressure is kept constant, they all expand or contract the same
amount.
4 When half the gas is removed, they all shrink the same amount (pressure and
temperature kept constant).
This information shows that a balloon lled with the same amount of any gas
expands and contracts exactly the same amount, provided other conditions remain
constant.
These observations support Avogadros law, an idea rst proposed by Italian
chemistry teacher Amadeo Avogadro, in the 1800s. Avogadros law states:
Equal volumes of gases at the same temperature and pressure contain equal numbers
of molecules.
To learn more about the relationship between volume and number of particles,
refer to Chemistry Section 8.4, pp. 31820.
Breathing a liquid
Science ction writers have introduced the
concept of liquid breathing. In the movie
The Abyss by James Cameron, a scientist
investigating deep sea phenomena overcomes
the issue of gas in the blood causing the bends
by breathing an oxygenated liquid. Liquid
breathing has now moved beyond the realms of
science ction into science fact. Since the 1960s,
scientists have been investigating the concept of
liquid breathing.
After experimenting with a number uids
scientists found that peruorocarbons (PFCs),
which are hydrocarbons in which the hydrogen
atoms have all been replaced with uorine, had
properties that made them suitable for liquid
breathing with living creatures.
The Alliance Pharmaceutical Corp. previously
developed a product called LiquiVent
(1-bromoperuorooctane, C
8
F
17
Br) in which both
oxygen and carbon dioxide are easily dissolved
but also readily released. Oxygen is bubbled
into the liquid, which is then warmed and introduced into the lungs where exchange
of oxygen and carbon dioxide occurs. The uid is then breathed out where it is
mechanically recirculated, removing CO
2
and adding more O
2
.
This technique of liquid breathing is being used in hospitals to treat premature babies
and patients with breathing problems and lung disorders. Using the process of liquid
ventilation, the lungs are lled with liquid, which spreads out quickly and evenly, owing
into collapsed or restricted areas where air has not been able to penetrate and so
inates the lungs. The liquid can also clean out debris from the lungs. A small number
of premature babies have been saved by liquid ventilation, although the technique is
still experimental.
A mouse breathing in a liquid-lled jar
Squeezing air
Scuba divers rely on tanks of compressed air for their oxygen when diving.
Because water is much denser than air, the pressure changes are much greater
for a given change in water depth than for the same depth change in air. For every
10 m divers descend, they experience an additional 1 atm pressure. The changes in
pressure experienced are most noticeable on the divers lungs, middle ear and sinus
cavities as they contain air that becomes compressed. Boyles law describes how
these gas volumes respond to changes in pressure. It states:
For a given quantity of gas at a constant temperature, the product of the volume, V,
and the pressure, P, is a constant.
When divers descend without scuba gear, the volume of their body cavities
decreases as the surrounding water pressure becomes greater. When divers are using
scuba gear, the regulator on the air tank delivers air at the same pressure as the
surroundings, so they dont experience the effect of the increasing pressure on their
lungs. However, if they need to make an emergency ascent they must remember to
breathe out steadily as they return to the surface; otherwise the pressure of the air
in their lungs will cause their lungs to expand, rupturing lung tissue.
To see how pressure and volume are related, make and study a Cartesian diver.
To learn more about Boyles law, refer to Chemistry Section 8.5, pp. 3202.
In respiration, Boyles law is the one that relates to the action of the lungs.
As the diaphragm expands, the volume of the lungs increases, resulting in a
decrease of pressure inside the lungs. Atmospheric pressure is higher, so fresh air
will be pushed into the lungs to equalise the pressure. As the diaphragm contracts,
the volume of the lungs decreases, causing an increase in pressure inside the lungs.
Air will now rush out of the lungs to equalise pressure again.
The heat is on
In the above discussion, the temperature was assumed to be constant, but we know
temperature has an effect on the volume of a gas. Hot air balloons rise; a bottle of soft
drink might explode if left in the hot sun; an egg can crack if it is boiled too rapidly.
ACTIVITY 4.7
Use your understanding of pressurevolume relationships to answer the following
questions:
a Why do carbonated drinks pop when the bottle or can is opened?
b Why do tennis balls lose their bounce after many uses? (Hint Why do tennis balls lose their bounce after many uses? ( Why do tennis balls lose their bounce after many uses? ( : Tennis balls contain
gases at high pressure to give a good bounce.)
c A group of students were given the responsibility of inating helium balloons for
the senior formal. They purchased a small tank of helium with a volume of 20 L
at a pressure of 14.4 atm.
i How many 3 L balloons can they ll?
ii What assumptions have you made in answering (i)?
d When a hurricane forms, the wind rushes in to ll an area of low pressure.
As a hurricane approached, the air pressure fell from 101.3 kPa to 79.4 kPa.
i If the volume of your living room was 430 m
3
initially, what volume would the
air in the room change to so that pressure was equalised inside and outside?
ii Why is it suggested that windows are left slightly ajar as a storm approaches?
e The pressure acting on the lungs of an underwater diver at a depth of 20 m is
300 kPa. Atmospheric pressure at the time is 100 kPa. The diver has a lung
capacity of 6 L and is breathing from a scuba tank at a depth of 20 m.
i What volume would the air in the divers lungs occupy at the surface of the
water?
ii What would happen to the divers lungs if she took a deep breath at 20 m,
then swam to the surface without exhaling?
The pump design in sports shoes uses air pumped into an inatable pocket in
the shoe to make it more comfortable and t better. When you pump the pump, air
is forced into a pocket that expands. When the air-lled part of the shoe feels snug,
you stop pumping. As you pump more moles of air into the pocket, the volume
increases. As you run around in the shoes playing sport, you get hot and by the
end of your game your shoes begin to feel uncomfortable. This is because the heat
generated has caused the volume of the gas in the pockets to expand, even though
the number of moles has remained constant, making them tight. You need to release
some of the air or remove the shoes until they have cooled down and the gas has
returned to the original volume.
This and other experiences show us that, as temperature increases, gases
expand. We need to be aware of this when dealing with gases, especially in
potentially explosive situations. We use this information when placing a smoke
detector on the ceiling because hot air (carrying the smoke) becomes less dense
as it expands and so rises.
French chemists Jacques Charles and Joseph Gay-Lussac carried out studies
on the changes in gas volume caused by temperature changes. These scientists
were also hot-air ballooning enthusiasts. Charles stated a relationship between
temperature and pressure that is known as Charles law:
For a xed quantity of gas at constant pressure, the volume increases linearly with
temperature.
The development of a simple mathematical relationship between volume and
temperature only came about when a new temperature scale, Kelvin, was developed
by William Thomson (Lord Kelvin).
Boiling eggs
When an egg is laid, it is warm and, as it cools, its contents contract and a pocket of
air is formed as the inner and outer membranes separate. The eggs shell is porous
so, over time, carbon dioxide and water will diffuse out of the egg and air will enter
to equalise pressure inside and outside. As the egg gets older, the pocket of air gets
bigger. This is why older eggs, which have a large air sac, will oat in water while
fresher eggs, which have a smaller air sac, sink. (This fact is commonly used by cooks
to determine which eggs are the freshest.)
When the egg is placed in rapidly boiling water, the increase in temperature causes the
gas in the air sac to increase in volume. If the temperature increase occurs too rapidly,
the expanding gas doesnt have time to diffuse out through the pores in the shell and
the shell will crack.
ACTIVITY 4.8
The Science centre has just been refurbished and has decided to include a display
relating to gases. They have asked you to help prepare a poster for a section of the
display related to one of the gas law scientistsBoyle, Charles, Gay-Lussac, Avogadro
and Dalton. They want the display to be interesting to the general public so, as well as
their discoveries, the display is to contain information about the scientists themselves
the time they lived, their families, and so on.
To learn about Charles law and the Kelvin temperature scale, refer to
Compared to Boyles law, Charles law is not as important for scuba divers
because the temperature under the water seldom changes enough to seriously
affect air pressure. However, the law is important to keep in mind when lling air
tanks, especially when there is a large difference between air and water temperature.
Suppose a tank holding 25 L of air at a pressure of 202 atm was lled when the air
temperature was 32C. Suppose that tank is taken into water that is 24C. Before
the rst breath is taken, what will the pressure be reduced to?
Scuba shop proprietors know about Charles law, which is why they often ll
tanks in a water bath where the temperature is about the same as where the diving
will take place.
Calculating how much
The most reactive gas in the atmosphere is oxygen. The reaction of oxygen
with fuels is the most common energy-generating reaction, called burning or
combustion. Respiration is an energy-generating reaction important to animals.
This reaction between glucose and oxygen produces 17 kJ of energy for each
gram of glucose burnt. Fat-burning is also a source of energy with 38 kJ of energy
produce for each gram of fat burnt.
The burning of fossil fuels is the most important source of energy in our
society. This combustion provides energy for transport (as discussed in Context 3,
Transporta necessary evil), industry and homes. The amount of oxygen being
consumed and carbon dioxide and other pollutants being produced is enormous.
ACTIVITY 4.9
Use your knowledge of volumetemperature relationships to answer the following
questions:
a Explain why car owners need to add more air to their tyres in winter and release air
from them in summer.
b A 4 L capacity balloon is two-thirds full. If the Kelvin temperature of the gas in the
balloon doubles, what will happen?
c A tank at 300 K contains 0.285 L of gas at 19.2 atm pressure. The maximum
pressure the container is capable of withstanding is 57.6 atm. If the temperature is
doubled and the volume kept constant, what will happen to the pressure?
Petrol reacts with oxygen
to produce the energy to
power cars
Without sufcient quantities of oxygen, these combustion reactions do
not go to completion and poisonous substances such as carbon monoxide and
nitrogen oxides are produced. The pollution being released into the atmosphere by
combustion reactions has serious consequences for the state of the atmosphere and
the environment. Scientists are concerned that the amount of carbon dioxide being
released into the atmosphere is leading to global warming.
Even burning small amounts of fuel can lead to the addition of a substantial
amount of carbon dioxide to the atmosphere.
Whether considering air pollution, balloons, scuba diving or air bags, we
need to be able to understand and apply relationships between volume, pressure,
temperature and moles of gas.
The relationship between all these quantities is called the ideal gas equation:
PV nRT
It describes how pressure (P), volume (V), number of moles of a gas ( VV n) and
temperature (T) are related. R is a constant and called the universal gas constant. RR
Hot air ballooning around the world
Starting on 20 March 1999, the Breitling Orbiter 3 took 20 days to circumnavigate the
globe and became the rst balloon to y non-stop around the world. The balloon was
made up of three sections. The main lift was provided by a central cell lled with helium
that is less dense than air. The greater the volume of helium, the more air it could
displace and the greater the lift.
As the balloon ascended high into the atmosphere, the air pressure dropped and the
volume of the helium cell increased. The temperature of the air outside the balloon
decreased as the balloon went higher. During the day, the sun heated the helium and
the lifting power of the balloon increased whereas during the night the helium cooled,
thus decreasing the lifting power.
To control the lifting power a second, lower compartment was used. This compartment
could be lled with hot air at night and the air allowed to cool during the day, thus
maintaining constant altitude.
Temperature, pressure and number of moles of the gas affected the volume of the
gas in the balloon.
Structure of Breitling Orbiter 3
To learn more about the use and applications of the ideal gas equation, refer to
Chemistry Sections 8.7 and 8.8, pp. 32630.
In anaesthesia, it is important to have an understanding of the gas laws. Oxygen
is stored in gaseous form at room temperature. Consequently, cylinders containing
oxygen obey the gas laws and the pressure gauge on the cylinder directly represents
the amount of gas inside.
Nitrous oxide is used as an anaesthetic and therefore it must be ensured that
there is enough present in a cylinder for the duration of the medical procedure.
Although nitrous oxide (N
2
O) is a gas at room temperature, it can be stored under
pressure as a liquid. Cylinders of nitrous oxide contain both liquid and vapour.
The cylinder is usually 65% lled with liquid, leaving the remaining 35% to be lled
with the vapour. This allows for liquid and gas expansion if the temperature rises;
if there was too much liquid, the cylinder could explode.
The gauge on the cylinder measures only the gaseous vapour pressure. As the
liquid evaporates, it replaces the gas being used up so the pressure remains the same
until almost all the liquid has vaporised. The gauge, therefore, gives no indication of
the total amount of nitrous oxide in the cylinder.
The amount can be estimated by applying the general gas equation. The weight
of the cylinder with nitrous oxide minus the weight of the empty cylinder will give
the amount of liquid inside. If the cylinder contains 2.5 kg of N
2
O, which has a
molar mass of 44 g, the number of moles of N
2
O can be calculated:
n
2500
_____ _____
44

56.8 mol
Knowing the pressure from the gauge and the temperature, the effective volume
of NO
2
gas available can be calculated using PV nRT.
ACTIVITY 4.10
Using your understanding of the ideal gas equation to answer the following:
a Petrol can be represented as C
8
H
18
and has a density of 0.704 g/mL. The equation
for the combustion of petrol is:
2C
8
H
18
25O
2
16CO
2
18H
2
O
What volume of carbon dioxide at 0.96 atm of pressure and 25C will be formed
from the combustion of 5.0 L of petrol?
b You have been given three 5.0 L balloons. One is lled with hydrogen, one with
carbon dioxide and one with air. The average molar mass of air is 29.0 g/mol and
the temperature and pressure of all balloons are 27C and 1.0 atm. Calculate
the mass of gas in each balloon and use this to justify why a balloon lled with
hydrogen rises and one lled with carbon dioxide sinks.
c Canisters that supply oxygen for aircraft are lled with potassium chlorate and
powdered iron. These generate oxygen by an iron-catalysed decomposition
reaction:
2KClO
3
2KCl 3O
2
How many litres of oxygen at 25C and 91 kPa pressure can be generated by
a canister that contains 50.0 g of potassium chlorate?
d The ozone concentration in the upper atmosphere averages 3.0 10
13
molecules
per cm
3
in a region between 15 and 35 km high, at an average pressure of
0.001 atm and temperature of 25C. How thick would the ozone layer be if these
same molecules were at a pressure of 1.0 atm and a temperature of 20C?
Mixtures of gases
Most of the gases we use are actually mixtures of a number of different gases.
Table 4.1 provided the amount of each gas in dry air. According to kinetic theory,
each gas behaves independently of other gases in a non-reacting mixture. All
the molecules in a gas exert pressure so, in a mixture, each gas contributes to
the pressure independently of all other gases. The amount of pressure each gas
contributes depends on the fraction of that gas present. For example, if a mixture
of nitrogen and helium was 90% nitrogen then 90% of the total pressure would be
due to nitrogen and 10% due to helium. We say that each gas in a mixture exerts
its partial pressure.
We have already looked at the how a scuba diver is affected by pressure.
At sea level, the partial pressure of oxygen is 0.21 atm (since the atmosphere is
21% oxygen and the pressure is 1 atm at sea level). At a depth of 100 m under the
oceans surface, the total pressure is about 10 atm. The partial pressure of oxygen
is about 2 atm (0.21 10 atm) for a diver inhaling compressed air, so the diver is
inhaling ten times more oxygen than the normal amount.
Elevated concentrations of oxygen are quite harmful for reasons that are not
well understood. The symptoms of oxygen poisoning include confusion, impaired
vision and hearing, and nausea. For this not to occur, the oxygen must be diluted
by adding another gas. Nitrogen cannot be used because it dissolves easily in the
blood, producing nitrogen narcosis which has an effect similar to overindulging
in alcoholic drinks. Helium is the diluting agent most often used in scuba tanks
because it is inert and has much lower solubility in the blood than oxygen or
nitrogen.
At very high altitudes, mountain climbers must use a supplementary oxygen
supply because the partial pressure of oxygen is too low for normal breathing.
The partial pressure of an anaesthetic gas needed to produce anaesthesia is
called the anaesthetic pressure.
Scuba divers must use
a supplementary oxygen
supply
John Dalton was the rst to form a hypothesis about partial pressures. This has
become known as Daltons law of partial pressures:
The total pressure in a container is the sum of the partial pressures of all gases in the
container.
THE ATMOSPHERE
The atmosphere of the Earth is unique in our solar system. The atmosphere
of other planets varies considerably from that of Earth. Mars and Venus have
atmospheres of mainly carbon dioxide whereas Uranus has mostly methane and
ammonia, and Pluto and Mercury have no atmosphere at all.
Our protective blanket of air sustains life and needs to be protected. Human
activity has released enormous quantities of pollutants into the atmosphere, affecting
the quality of the air. In order to address the problems of air pollution, we need to
have an understanding of the atmosphere and the chemistry involved in air pollution.
To learn more about Daltons law and partial pressures, refer to

ACTIVITY 4.11
Using what you have learnt about partial pressure answer the following:
a A mixture of oxygen and cyclopropane, C
3
H
6
, is sometimes used as an
anaesthetic. In a mixture of these gases the partial pressure of oxygen is 76.0 kPa
and the partial pressure of cyclopropane is 22.7 kPa. Calculate:
i the mole fraction of each gas in the mixture
ii the percentage by mass of oxygen in the mixture.
b Hydrogen is used as a fuel in rockets but oxygen also needs to be present for
the hydrogen to burn. When the hydrogen and oxygen react, water is produced.
A fuel tank was lled with a mixture of hydrogen and oxygen to a total pressure
of 388 kPa. Calculate the mass of each of the hydrogen and oxygen gas that must
be present to ensure complete combustion.
Summary
The air is a mixture of gases and these gases are important to living things. The air
exerts pressure on us in all directions and although we are usually unaware of this
pressure, it is important in everyday applications including straws, syphons, vacuum
cleaners and suction caps. In using gases we need to understand their properties
and the gas laws that apply.
The laws developed by the gas scientists such as Boyle, Charles, Dalton and Avogadro
have enabled the development of many applications of gases such as air conditioners
and air bags. The kinetic theory of gases and the general gas equation need to
be understood by such diverse groups as anaesthetists, scuba divers and hot-air
balloonists as they use gases and apply these laws.
Structure of the atmosphere
In a previous section we considered the composition of the air in the atmosphere.
Now lets look at the structure of the atmosphere.
The atmosphere is made up of four major layers: the troposphere, stratosphere,
mesosphere and thermosphere, as shown in Figure 4.1. The two most chemically
important regions are the troposphere and the stratosphere. The composition of
these layers is different and, in fact, 90% of all the molecules in the atmosphere
are in the troposphere.
As you can see in the gure above, the boundaries between layers are marked
by minima and maxima in the temperature proles. As you move upwards through
the troposphere, the temperature decreases from about 15C to a minimum of
50C. Mixing of gases occurs readily in this layer because hot gases at the lower
altitudes rise while cool gases at higher altitudes fall, creating convection currents
and weather. This mixing means any substances released into the air at ground level
will get mixed through the troposphere and gradually diffuse into the stratosphere.
So, in time, pollutant gases produced naturally or by human activity will spread
throughout the atmosphere.
In the stratosphere, where we nd the ozone layer, the temperature gradually
increases with altitude. The colder, heavier air is at the bottom of this layer while the
warmer lighter air is at the top. This means there is very little mixing, thus giving a
region of high stability. This pattern of temperature fall and rise is repeated through
the next two layers.
FIGURE 4.1
The structure of the
atmosphere
Early morning pollution above Brisbane city
MAIN POLLUTANTS IN OUR AIR
The air we breathe contains a mixture of gases and
small solid and liquid particles (together called
particulates). Some of these gases and particulates are
classied as pollutants. Pollutants are substances which,
when present in high enough concentrations, could
harm the health of humans or animals or could damage
plants or materials. The pollutants that contribute
to air pollution come from both natural and human
sources. Natural sources include smoke from forest
res, wind-blown dust from soil and volcanoes, and
bacteria, fungi and chemicals released from plants
and animals. However, most of these pollutants result
from human activities, including motor vehicles, power
stations, industrial processes, farms and homes.
These pollutants can be carried thousands of miles
across borders and oceans or from one urban area to
another. Compared with cities such as Los Angeles,
Athens and Tokyo, air pollution problems in Australia
are minor. This is partly due to the fact that we are
surrounded by oceans and do not receive masses of
polluted air from other countries. Our oil and coal
contain less sulfur than that of other countries. We also
have fewer sources of pollution and local winds tend to
disperse pollution over our cities. Despite this, Brisbane,
Sydney, Melbourne and other large Australian cities
experience days of high pollution, especially during
summer and autumn.
ACTIVITY 4.12
Atmospheric pressure decreases as altitude increases.
a Use the data below to draw a graph of atmospheric pressure versus altitude.
Note: Atmospheric proles are generally drawn with altitude as the y-axis.
Draw a smooth curve through the points.
Altitude
(km) 0 2.0 5.0 10.0 15.0 20.0 30.0 40.0 50.0
Pressure
(atm) 1.00 0.787 0.518 0.234 0.107 0.045 0.013 0.006 0.002
b The concentration of gas in the atmosphere, c (in mol/L), is given by:
c (12.2 mol L
1
K atm
1
)
p
) )
__
T
where p is pressure in atmospheres and T is temperature in kelvin. Calculate the TT
concentration of atmospheric gas at sea level and at an altitude of 20 km. Use the
pressure from above and a temperature of 293 K at sea level and 220 K at 20 km.
In south-east Queensland, vehicle exhaust emissions are the major source of
human-produced air pollution. They contribute up to 72% of all pollutants. Leaded
petrol was responsible for releasing lead into the air but it is no longer available
in Australia. Industry is responsible for releasing 90% of human-produced sulfur
dioxide and 65% of ne particles into south-east Queenslands air. Landscape
and weather also inuence air pollution in the region. South-east Queensland is
surrounded by hills and ranges that can block and trap pollution at lower altitudes
until it is dispersed by strong winds and rain. The prevailing winds can transport
polluted air around the region.
TABLE 4.3 The major air pollutants, their sources and health effects
Pollutant Source Health effects
carbon monoxide
(CO)
Car exhausts, bush, forest and farm res,
burning fossil fuels
Reduces the amount of oxygen carried in the
blood because it binds to the oxygen-carrying
site on the bloods haemoglobin. It can cause
tiredness, headaches and nausea.
nitrogen oxides
(NO and NO
2
)
coal- and oil-burning power stations, motor
vehicles, gas and wood heaters
Affects the throat and lungs, increasing
susceptibility to respiratory infections and
asthma.
sulfur dioxide
(SO
2
)
burning fossil fuels, smelting of metal ores
containing sulfur
Affects the respiratory tract, the functions of
the lungs and irritates the eyes. Aggravates
conditions such as asthma and chronic
bronchitis.
volatile organic
compounds (VOCs)
industry, solvents, unleaded petrol, plastics
manufacture
Some VOCs such as benzene are
carcinogenic and some are irritants.
airborne lead leaded petrol, lead smelters, lead-based
paint from old house renovations
Absorbed into the blood stream through the
lungs. Continued exposure can affect the
nervous system and the bodys ability to
produce blood.
ozone (O
3
) formed in sunny conditions from the reaction
between nitrogen oxides and hydrocarbons
released by motor vehicles and industry
Attacks the tissue of the throat and lungs and
irritates the eyes. Can cause swelling within
the nasal passages and nasal congestion.
particulates motor vehicles, burning of plant materials,
bushres, mining
Irritates the eyes, nose and throat, causes
coughing and breathing difculty. Some
particles contain cancer-producing materials.
ACTIVITY 4.13
Use the information in Table 4.3 to create a new table listing different sources of
pollution with the type of pollutants they produce.
An example is below.
Motor vehicles Industry
air-borne lead nitrogen oxides
National air quality standards
The gases that cause air pollution are present in relatively small amounts, usually
measured in parts per million (ppm), but even at low concentrations they can be
harmful to humans if they are exposed to them long enough.
In June 1998, the National Environment Protection Measure for Ambient
Air Quality (referred to as Air NEPM) was released. It sets air quality standards
for six pollutants, together with the maximum excedence levels of each standard.
These values are based on scientic studies and are the maximum concentrations
considered safe for the general population. The air quality standards are quite
different in terms of length of exposure:
0.10 ppm per 1 hour for ozone
0.20 ppm for 1 hour for sulfur dioxide
9.0 ppm per 8 hours for carbon monoxide.
The 1 hour, 8 hour and 24 hour averaging times are for the most recent periods
(that is, the latest 1 hour, 8 hour and 24 hour periods).
Table 4.4 gives the current Air NEPM standards.
TABLE 4.4 Current Air NEPM standards
Pollutant Air NEPM standards Averaging time
ozone 0.10 ppm
0.08 ppm
1 hour
b
4 hour
b
nitrogen dioxide 0.12 ppm
0.03 ppm
1 hour
b
1 year
sulfur dioxide 0.20 ppm
0.08 ppm
0.02 ppm
1 hour
b
24 hours
b
1 year
carbon monoxide 9.0 ppm 8 hour
b
particulates 10 m
a
(PM10) 50 g/m
3
24 hour
c
lead 0.50 g/m
3
1 year
a
refers to airborne particles that are greater or equal to 10 m in diameter
b
not to be exceeded more than 1 day per year
c
not to be exceeded more than 5 days per year
ppm: parts per million
g/m
3
: micrograms per cubic metre
Source: http://www.epa.qld.gov.au/environmental_management/air/air_quality_monitoring/national_measures
ACTIVITY 4.14
a Use the data in Table 4.4 to explain the statement, Ozone is twice as hazardous
to breathe than sulfur dioxide.
b In a day a person breathed in 15 m
3
of air that contained 1050 g of particulates.
Does this exceed the Air NEPM standards?
Monitoring air quality
stations around the state that records weather and air pollution data. New data are
uploaded at regular intervals and can be accessed on the EPA website at:
http://www.epa.qld.gov.au/environmental_management/air/air_quality_monitoring
You can log on to the website and obtain the latest air quality data, and you can
obtain data from previous years to determine if the air quality is changing. The air
quality index gives a measure from very good to very poor. It is calculated by
comparing the pollutant concentration with the pollutant goal concentration from
the Air NEPM standards (given in Table 4.4 above). Low values (066) indicate
good air quality while high values (>100) indicate poor air quality.
OZONETHE GOOD AND THE BAD
Ozone is present in the atmosphere in only tiny amounts. It is a molecule containing
three oxygen atoms (O
3
). It has a strong odour and as a liquid is blue in colour. It
was named by its discoverer, German scientist Christian Friedrich Schnbein, from
the Greek word ozein, which means to smell. Out of each 10 million air molecules,
about 2 million are normal oxygen (O
2
) but only three are ozone.
ACTIVITY 4.15
The following readings obtained from the Queensland EPA website show the air quality
index values from the Brisbane CBD monitoring station from 8 a.m. to 9 a.m. on a
certain day of the month for 6-monthly intervals from January 2002 to July 2004.
Month and year
Carbon
monoxide
(ppm)
Nitrogen
dioxide
(ppm)
Ozone
(ppm)
Sulfur
dioxide
(ppm)
Particulate
PM10
January 2002 0 0.001 0.011 0 15.1
July 2002 0.1 0.018 0.008 0.004 21.1
January 2003 0.1 0.005 0.01 0.001 19.8
July 2003 0.1 0.021 0.004 0.002 18.5
January 2004 0.1 0.008 0.003 0 10
July 2004 0.1 0.018 0.007 0.001 4.5
a On the same sheet of graph paper, plot a graph of nitrogen dioxide, ozone and
sulfur dioxide versus time. Alternatively, you may put the above information into
a spreadsheet and plot the graphs electronically.
b Try to identify any patterns in the results either from year to year or season to
season (Januarysummer, Julywinter)
c Can you suggest any reasons for the patterns you identied?
d Log on to the EPA website, obtain data for the Brisbane CBD up to now and
add this to the graph or spreadsheet. Does this data follow any patterns?
e Use the website to nd the data for the monitoring station closest to you.
How does this compare with the Brisbane CBD values?
Ozone (O
3
) is one allotrope of oxygen whereas oxygen gas (O
2
) is the other.
These two molecules have quite distinct properties. Many of the differences in their
properties can be explained in terms of their different bonding. Oxygen gas consists
of a pair of O atoms joined by a double bond; ozone consists of three oxygen atoms
joined together with a double bond and a coordinate covalent bond.
Comparing ozone and oxygen
The electron-dot structures of oxygen and ozone are shown below:
The single bond between the oxygen atoms on ozone is a coordinate covalent bond
because both of the shared electrons came from the one atom.
Although this bond was formed differently from an ordinary covalent bond, once formed
it is identical to any ordinary covalent bond. Figure 4.2 shows models of oxygen and
ozone. Ozone has a bent shape.
TABLE 4.5 Properties of oxygen and ozone
Property Oxygen, O
2
Ozone, O
3
colourless gas condensing to
a pale blue liquid
odourless
essential for all living matter
colourless gas condensing
to a distinctly blue liquid
strong distinctive odour
poisonous
boiling point 183C 111C
density about the same as air about 1.5 times that of air
solubility in water sparingly soluble (9 ppm from air
at 20C)
considerably more soluble
than O
2
stability very stable easily decomposed to O
2
reactivity reacts with most other
elements to form oxides
moderately strong oxidising
agent
much more reactive than
oxygen
very strong oxidising agent
uses widely used medically to
overcome breathing problems
steel-making
oxy-acetylene torches
liquid O
2
used in space
shuttles as an oxidiser for
the fuel
in sterilisers in food shops
and kitchens
purication of water
bleaching agent in paper and
textile making

FIGURE 4.2
Space-lling models of the
O
2
and O
3
molecules
Most atmospheric ozone (about 90%) is
concentrated in a layer in the stratosphere about
1530 km above the Earths surface (see Fig. 4.3).
This layer of ozone is thinnest in the tropics (around
the equator) and denser towards the poles. This ozone
protects all life forms by ltering out short-wavelength
ultraviolet (u.v.) light from the sun that damages
living tissue, and causes various types of skin cancer
and cataracts in animals. The remaining 10% of the
atmospheric ozone is found in the troposphere with
highest concentrations at ground level. This ground level
elevated ozone concentrations is a problem because, as
shown in Tables 4.4 and 4.5, it is considered a pollutant
and can cause health and environmental problems.
Human activity is having a major effect on ozone,
destroying it in the stratosphere where we need it and
producing it at ground level where we dont want it.
Ozone in the stratospherehere today,
gone tomorrow
At any given time ozone molecules are constantly formed and destroyed in the
stratosphere. The amount of ozone per unit area above a point on the Earths
surface is measured in Dobson Units (DU). A Dobson Unit is the amount of ozone
that would correspond to a thickness of pure ozone at 1 atm pressure and 0C of
0.01 mm. Typical amounts of ozone above the Earths surface are about 300 DU.
ACTIVITY 4.16
NASA satellites constantly monitor the level of ozone in the atmosphere. The amount of
ozone overhead can be found on the website:
http://jwocky.gsfc.nasa.gov/teacher/ozone_overhead.html
a Use the website to complete the table below.
Date Ozone amount (DU) Change
yesterday
last week
last month
2 months ago
3 months ago
6 months ago
12 months ago
b Use the information to draw a graph showing ozone concentration versus time.
c At what time of the year was the amount of ozone lowest and highest?
d Using this information write a generalisation relating the amount of ozone to the
time of year.
e Obtain other data from the website to support or refute your generalisation.
Source: http:/www.epa.gov/ozone
FIGURE 4.3
Altitude versus partial
pressure of ozone
Ozone is formed when high-energy solar radiation, with wavelengths of
170195 nanometres (nm) splits ordinary oxygen molecules (O
2
) into oxygen
atoms (see Fig. 4.4). This dissociation requires enough energy to break the
oxygenoxygen double bond, which has bond energy of 498 kJ/mol.
O
2
(g (( ) gg u.v. light 2O(g 2O( 2O( ) gg H 498 kJ/mol Reaction 1
These free oxygen atoms are very reactive and can undergo a number of
different reactions. They can combine with other oxygen molecules to make ozone.
O(g O( O( ) gg O
2
(g (( ) gg O
3
(g (( ) gg H 106 kJ/mol Reaction 2
They can react with ozone:
O(g O( O( ) gg O
3
(g (( ) gg 2O
2
(g (( ) gg H 392 kJ/mol Reaction 3
Ozone is naturally destroyed in the atmosphere. When it absorbs lower-energy
ultraviolet light (210310 nm), it decomposes back into ordinary oxygen. This
reaction is important because it is responsible for the screening effect of the ozone
layerit absorbs the radiation that is responsible for sunburn.
O
3
(g (( ) gg u.v. light O(g O( O( ) gg O
2
(g (( ) Reaction 4 gg
ACTIVITY 4.17
Consider the reactions above.
a Which reactions remove ozone from the atmosphere?
b What is the relationship between reactions 2 and 4?
c Which of the reactions are exothermic?
d Use these reactions to explain why the temperature in the stratosphere is higher
than in the troposphere.
FIGURE 4.4
The cycle of ozone
production and destruction
You can see in Figure 4.3 that ozone is being made and destroyed all the time
as part of the natural cycle. Left to themselves, the rate at which ozone is being
produced and the rate at which it is being destroyed would be equal and the overall
amount of ozone would be stable. This is called a steady state. This situation was
occurring until the last few decades.
When chemists examined the concentration of ozone in the stratosphere over
recent years, they found the concentration was decreasing. This means the rates
at which it is being produced and destroyed were not equal. There are obviously
factors that are increasing the rate of destruction or slowing the rate of production.
Disappearing ozone
Stratospheric ozone concentrations have been measured for the last 80 years
at ground stations spread over the planet and for more than 20 years by
satellite-mounted detectors.
In 1985 a British atmospheric monitoring team in Antarctica noticed a
signicant reduction in ozone concentrations in the atmosphere. The amount of
ozone above the surface of the Earth is measured in Dobson units (DU) and global
average ozone is about 300 DU. Before 1980 ozone levels of less that 200 DU were
rarely seen but in recent years ozone near 100 DU has become normal in Antarctica
in spring.
Figure 4.5 shows the decline in ozone levels near the South Pole. This thinning
of the layer produced areas where the ozone levels were less than 220 DU and this
was dened as the ozone hole.
You can learn about the factors that affect the rate of a chemical reaction in
Chemistry Sections 7.8 to 7.13, pp. 30212. If you have already looked at
factors affecting the rates of chemical reactions, you should revise this section.
ACTIVITY 4.18
The rate of formation and destruction of ozone can be affected by a number of factors.
Some of the reactions require strong sunlight and they all take place in the gaseous
phase.
a Suggest two factors that could affect the rates of these reactions.
b Explain how each factor would alter the rate.
The number above each dot is the minimum reading of DU. The number below
each dot is the date that minimum occurred that year. TOMS means total ozone-
measuring spectrometer (an analytical instrument).
ACTIVITY 4.19
Use the graph above to answer the following questions:
a In which month/months did the minimum values occur?
b What was the lowest value and when was it recorded?
c In 1956 the total ozone was 287 DU. What has been the percentage decrease
from then to 2000?
d If a 1% decrease in ozone is predicted to cause an 8% increase in skin cancers,
what is the total possible percentage increase?
FIGURE 4.5
The variation of minimum
stratospheric ozone in
Antarctica with time.
At the top right of the
diagram is a list of the
satellites that recorded
the data.
Source: http://toms.gsfc.nasa.gov
In the early 1970s, researchers began to investigate the effects of various
chemicals on the ozone layer. A major cause of stratospheric ozone depletion was
discovered by scientists Sherwood Rowland, Mario Molina and Paul Crutzen, who
were awarded the 1995 Nobel Prize for their discoveries.
Their work produced compelling evidence that a group of chemical compounds
called chlorouorocarbons (CFCs) were responsible for the destruction of the
ozone layer. These CFCs do not occur in nature; they are articially produced. They
have been widely used as refrigerants, solvents for oil and grease, foam blowing
agents, sterilisers for surgical instruments and propellants in aerosol cans because
they are stable, low in toxicity, insoluble in water and inexpensive to produce.
The two most widely used chlorouorocarbons are CCl
2
F
2
and CCl
3
F,
commonly known as CFC-12 and CFC-11. By 1985 the combined annual
international production of CFC-11 and CFC-12 was approximately
850 000 tonnes. As the ground level concentration of CFCs has been increasing,
the stratospheric levels of ozone have been decreasing.
Contour map of ozone
using a solar backscatter
ultra violet instrument
(SBUV/2)
CFCs are very stable due to the strong bonds between carbon and chlorine and
carbon and uorine that only exposure to strong u.v. radiation breaks down. This
means that CFCs remain in the atmosphere for many decades and over time they
diffuse into the stratosphere.
Once in the stratosphere, the CFCs are exposed to short wavelength u.v.
radiation which breaks a CCl bond producing a chlorine free radical.
CCl
3
F u.v. light Cl
CCl
2
F
CCl
2
F
2
u.v. light Cl
CClF
2
Similar reactions occur with other CFCs.
The free radical, an atom or molecule with an unpaired electron, Cl
, is very
reactive as it has seven outer shell electrons and has a strong tendency to combine
and share electrons with other atoms to achieve a stable octet.
The chlorine radical pulls an oxygen atom away from the ozone molecule:
Cl
O
3
ClO
O
2
Reaction 5
The ClO
formed is another free radical. The ClO
reacts with free oxygen

atoms to form a molecule of oxygen, O
2
, regenerating a chlorine atom:
ClO
O Cl
O
2
Reaction 6
There are now two competing reactions for the removal of ozone from the
stratosphere:
O(g O( O( ) gg O
3
(g (( ) gg 2O
2
(g (( ) Reaction 3 gg
and reaction 5. The concentration of Cl radicals in the stratosphere is much less
than the concentration of O atoms, but chemists have shown that under conditions
Understanding CFCs
Chlorouorocarbons (CFCs) are compounds containing chlorine, uorine and carbon
only. They contain no hydrogen.
Common CFCs are shown in Table 4.6. CFCs were widely marketed under the trade
name of freonsparticularly freon-11 and freon-12.
TABLE 4.6 Common chlorouorocarbons (CFCs)
a
Structure Systematic name
Common
name
Major use
(before 1996)
Cl
|
ClCF
|
Cl
trichlorouoromethane CFC-11
making foam plastics
(insulation)
Cl
|
ClCF
|
F
dichlorodiuoromethane CFC-12
working uid in
refrigeration and air
conditioning
F F
| |
ClCCCl
| |
Cl F
1,2,2-trichloro-1,1,2-triuoroethane CFC-113
cleaning electronic
circuit boards
a
Production and use of these compounds is now banned by international agreement.
similar to those in the stratosphere the reaction of O
3
and Cl occurs 1500 times
faster than the reaction between O
3
and O atoms. Therefore, the Cl atoms make
a large contribution to the removal of ozone.
The Cl radical has not been used up as shown in reaction 6, so it is able to then
attack another ozone molecule and repeat the process all over again. The chlorine
radical is consumed and regenerated in the cycle, so there is no net change in its
concentration. It is a catalyst in the reaction. On average a single Cl radical can catalyst catalyst
catalyse the destruction of up to 1 10
5
ozone molecules before it is carried back into
the troposphere by winds or removed by other reactions. Only a small amount of CFC
needs to reach the stratosphere for a signicant amount of ozone damage to occur.
Other reactions involving chlorine take place in the atmosphere and remove
it from the ozone destruction cycle. One important reaction is that between the
chlorine atom and methane. This reaction forms hydrogen chloride:
Cl
CH
4
HCl CH
3
This reaction removes chlorine and so prevents it from destroying ozone.

The hydrogen chloride formed in this reaction has no effect on ozone and neither
does the CH
3
radical, which undergoes further reactions.

Another important reaction involves removing the ClO
radical:
ClO
NO
2
ClONO
2
The ClONO
2
(chlorine nitrate) does not regenerate Cl
atoms, so the ClO
is
essentially removed from the ozone-destroying reaction.
ACTIVITY 4.20
a Add reactions 5 and 6 to produce the overall reaction.
b Comment on the relationship between the overall reaction and reaction 3.
c What role does the chlorine radical play in the process?
To understand more about catalysts and how they affect the rate of a chemical
reaction, go to Chemistry Section 7.13, pp. 31012.
Stopping ozone destruction
The only way to stop ozone destruction by CFCs is to stop releasing them into the
atmosphere. Replacements have been found and these are now being used.
The rst replacements were HCFCs, hydrochlorouorocarbons, which contain
CH bonds that are susceptible to attack by reactive radicals and atoms in the
troposphere, and so are decomposed there to a signicant extent. This means only a
small proportion are able to reach the stratosphere, so their ozone-destroying capacity
is much less than that of CFCs, but still signicant. HCFCs were only a temporary
substitute for CFCs until a better compound could be found.
HFCs are now widely used as replacements for CFCs. HFCs are hydrouorocarbons
compounds that contain hydrogen, uorine and carbon only. They contain CH bonds,
so undergo some decomposition in the troposphere. They contain no CCl bonds,
so do not form Cl atoms in the stratosphere. This means their ozone-destroying
capacity is zero. The most widely used HFC is HFC-134a; its systemic name is
1,1,1,2-tetrauoroethane. It is now widely used in refrigeration and air conditioning.
A closer look at the ozone hole
You have seen from the information provided in Figure 4.5 about stratospheric
ozone levels in Antarctica that the lowest level of ozone occurs in September and
October, which is spring.
In the previous section you saw that the CFC molecules diffuse into the
stratosphere where u.v. light splits off a chlorine atom, which then destroys ozone
molecules. In Antarctica where winter is a period of continuous darkness, the
situation is changed. Ozone depletion over Antarctica is seasonal and localised.
In winter, a wind pattern called the polar vortex is formed. This pattern stops
Antarctic air mixing with warmer, lower-latitude air and so the stratosphere is
extremely cold. Under these extremely cold conditions, certain solid particles
are able to catalyse a reaction between hydrogen chloride and chlorine nitrate.
HCl ClONO
2
Cl
2
HNO
3
This conversion has no effect on ozone concentrations in winter, but when the
sun comes up in early spring the situation changes dramatically. Sunlight splits
the chlorine molecule into chlorine atoms:
Cl
2
u.v. light 2Cl
These free radical Cl atoms can then destroy ozone in exactly the same way as
chlorine atoms split from CFCs.
So in spring there is an extra source of chlorine atoms and the destruction of
ozone is increased. This means the ozone concentration over the Antarctic is greatly
reduced and the ozone hole is formed.
Figure 4.6 shows the variation in ozone concentration with altitude on two
different days, one in late winter (a normal prole) and one in spring, clearly
showing the ozone hole where about 80% of the ozone has been destroyed.
Only a nite amount of chlorine molecules have been formed during the polar
winter. By early summer they have disappeared, so the rate of ozone destruction
returns to the normal CFC level. The polar vortex breaks up in early summer and
the mixing with the lower-latitude air brings the ozone levels back to normal.
This break-up of the polar vortex has occasionally brought the ozone hole
over Tasmania and parts of Victoria in early summer. Generally, the ozone hole
disappears by about Christmas to mid-January.
FIGURE 4.6
Changes in the ozone prole through the
stratosphere between winter (normal) and
spring (severely depleted).This graph is typical of
those observed from 1985 onwards. The shading
represents the amount of ozone depletionabout
80% in this case.
Ozone in the streetshere to stay?
Although ozone in the stratosphere is good, ozone at ground level can have severe
health effects. Research shows that prolonged exposure to ozone diminishes lung
function and increases the risk of respiratory symptoms like wheezing, chronic
phlegm and coughing.
At ground level, a complicated series of chemical reactions involving the
components of automobile exhausts, sunlight and oxygen occur, producing
photochemical smog of which ozone is a principal component.
Sunbathers and swimmers
should use sunscreen to
protect themselves from
harmful u.v. radiation
Banning CFCs
The initial concern about the ozone layer in the 1970s led to a ban on the use of CFCs
as aerosol propellants in several countries. However, production of CFCs and other
ozone-depleting substances grew rapidly as new uses were discovered.
The rst global agreement to restrict CFCs came with the signing of the Montreal
Protocol in 1987, ultimately aiming to reduce them to half by the year 2000. After the
original protocol was signed, new measurements showed damage to the ozone layer
was worse than expected. In 1992 following the latest scientic assessment, it was
decided to completely end production of the main CFCs from the beginning of 1995.
Because of measures taken under the Montreal Protocol, emissions of ozone-depleting
substances are already falling. Based on measurements of total inorganic chlorine in
the atmosphere, stratospheric chlorine levels peaked in 1997 or 1998 and are now
slowly decreasing.
It was previously anticipated that the natural ozone production would heal the ozone
layer within 50 years of 2000. The World Metrological Organization estimated this would
happen by 2045 but recent investigations suggest the problem is on a much larger
scale than originally anticipated.
Ozone forms when intense sunlight (summer) and high concentrations of
nitrogen dioxide (NO
2
) are present (see Fig. 4.7). The sunlight splits an oxygen
atom from the NO
2
molecule and this combines with an oxygen molecule to
produce ozone.
NO
2
sunlight NO O
3
Reaction 7
O O
2
O
3
Reaction 8
However, NO can destroy ozone:
NO O
3
NO
2
O
2
Reaction 9
The source of nitrogen dioxide isnt hard to nd. Motor cars generate both
nitric oxide (NO) and nitrogen dioxide (NO
2
) when their engines generate
temperatures high enough to cause ordinary oxygen (O
2
) and nitrogen (N
2
)
molecules to undergo a reaction. Nitric oxide is formed initially, and then nitrogen
dioxide forms by the reaction of nitric oxide with oxygen. The mixture of these two
gases emerging from a cars exhaust is about 80% NO. If the ratio of NO
2
to NO
stayed at this value, there would be no harmful build-up of ozone.
Other reactions occurring in the air, involving other substances from the cars
exhaust, convert NO to NO
2
. These other substances are referred to as volatile
organic compounds (VOCs). They are hydrocarbons from unburnt petrol and
their partial combustion products.
NO VOC sunlight NO
2
The production of the NO and VOCs occurs in the morning peak trafc and
produce the photochemical smog. These compounds gradually react over the
morning to produce NO
2
, which reacts with sunlight in the heat of the day to
produce ozone. This means the highest concentrations of ozone normally occur
on summer afternoons (see Fig. 4.8).
FIGURE 4.7
High concentrations of
ozone normally occur on
summer afternoons
Bushres also generate large quantities
of the primary pollutants that form ozone.
In recent years, ozone levels in south-east
Queensland which exceed the pollution
level guidelines have almost always been
associated with bushres or burning-off
events that occur during still weather
conditions.
GLOBAL WARMINGA HOT TOPIC
Climate change, also referred to as global warming or the greenhouse effect,
is a complex topic. On one side is a large group of scientists arguing that human
activities over the last couple of centuries are pushing the environment towards
disaster with increasing global temperatures. On the other side is a smaller, but
equally vocal, group of scientists who believe that the weather conditions we are
experiencing are all within the normal variation seen when climate is viewed over
a long time scale.
However, evidence that supports the view of scientists concerned with the
change in climate is mounting. Many plants and animals are shifting their ranges
towards the Earths poles and to higher altitudes where temperatures are cooler.
Glaciers are melting and oceans are rising. In the northern polar region, Arctic
permafrost is gradually melting.
Over the past century, climate records conrm that the average global surface
temperature has risen by 1C, with more than half that increase in the past 25 years.
Ocean temperatures appear to be rising as seawater absorbs much of the heat.
Over the last 100 years the ve hottest years, in global terms, have all been in the
1990s: in descending order 1998, 1997, 1995, 1990 and 1991.
Scientists use computer climate models to predict the effects of global warming
and these are constantly being rened as new data becomes available. The specic
FIGURE 4.8
Variation in pollutant
concentrations during
a windless, sunny day
ACTIVITY 4.21
a What will be the overall result when the rate of reactions 7 and 9 are the same?
b What factors can affect the rate of these reactions?
c Write the equations for formation of NO and NO
2
.
d Why does afternoon peak hour trafc have much less effect on ozone
concentrations than the morning peak trafc?
You can measure ground level ozone experimentally. (Refer to Chemistry in Use
Book 1 Teacher Resource CD-ROM.)
effects are difcult to predict. Some areas of the world might benet from warming
but in other areas closer to the equator crop yields could be severely reduced and
widespread droughts may occur. Approximately 35% of the Earths natural habitat
could be fundamentally altered. Many plant and animal species may not adapt in
time, becoming extinct.
Earths energy balance
To understand some of the reasons scientists believe global warming is occurring,
we need to know about the Earths energy balance. The main source of the Earths
energy is the sun. About half the radiant energy that strikes our atmosphere is either
reected or absorbed by the greenhouse gases found in the air. These gases ensure
that enough energy remains to keep the temperature right for life. The current
average temperature of the Earth is about 15C which is much higher than the
270C of outer space.
About a third (31%) of the incoming energy gets reected back into space
by clouds, the atmosphere and features such as snow on the Earths surface.
The atmosphere absorbs 20% and Earth itself the remaining 49%. The radiation
that reaches the surface of the Earth is absorbed and so the land and oceans are
warmed. The Earth then releases this absorbed energy as heat (infrared radiation)
into the atmosphere. About 84% of this radiated heat energy is absorbed by the
gases in the atmosphere and then is re-radiated to warm the Earths surface.
This return of energy back to the Earths surface to keep it warm is called the
greenhouse effect. Figure 4.9 shows the Earths energy balance. Because the
total energy coming in from the sun balances the energy re-radiated from the Earth,
a steady state is established and the Earths average temperature remains more or
less constant.
FIGURE 4.9
The Earths energy
balance
Living in a greenhouse
The greenhouse effect is due to gases that occur naturally in our atmosphere and
can absorb infrared radiation. Without the natural greenhouse effect, the average
temperature of the Earth would be 18C and life as we know it would not exist.
To absorb infrared radiation (IR) a bond in a molecule must have polar bonds,
so nitrogen, oxygen and noble gases cannot do this. The gases which do absorb
IR, in order of abundance, are water vapour, carbon dioxide and methane (CH
4
).
These gases are referred to as the greenhouse gases.
Water vapour is constantly recycled in nature and, as its abundance is relatively
constant, so is its contribution to the greenhouse effect. Carbon dioxide is also
recycled in nature. The carbon dioxide produced by animal respiration or by
burning fossil fuels is converted into plant biomass and oxygen by photosynthesis.
Methane is produced by the biological activity of bacteria, in the guts of animals
such as sheep and cattle, the release of natural gas from commercial oil and gas
elds, and vegetation rotting in the absence of oxygen.
Atmospheric measurements show how the atmospheric abundance of these
gases has changed over recent decades. These changes are placed in perspective by
comparing them to the concentrations found in polar ice. Air bubbles in ice cores
go back thousands of years. Changes in concentrations of gases in the atmosphere
from natural causes are observed in these air bubbles. The recent changes in carbon
dioxide and methane are unprecedented in both the rate of increase and the levels
reached for hundreds of thousands of years.
As you can see in Figure 4.10, the
atmospheric abundances of carbon
dioxide and methane have been rising
at an accelerating rate over the last
200 years.
Levels of unnatural greenhouse
gases have also increased in the last
100 years. The most signicant are
nitrogen oxides, sulfur hexauoride
and chlorouorocarbons (CFCs).
Although all these gases contribute to
the greenhouse effect, the main focus
has been on carbon dioxide because
at least half the expected increase
in greenhouse effect due to human
activities is likely to be caused by
carbon dioxide.
ACTIVITY 4.22
a Draw the Lewis structures for H
2
O, CO
2
, CH
4
, N
2
and O
2
.
b Draw the structural diagrams for the above molecules, showing their molecular
shape.
c Which of the molecules have polar bonds and which of the molecules are polar?
If you have forgotten how to do this, refer to Chemistry Section 4.2, pp. 2345 and
Section 4.5, pp. 23942.
Source: http://www.science.org.au/future/etheridge.htm
FIGURE 4.10
Changes in atmospheric
carbon dioxide and methane
in the last millennium
Calculating carbon dioxide
The main increase in atmospheric carbon dioxide has been attributed to the
increasing use of fossil fuels. Over the last 100 years, the amount of fossil fuel
burned has increased by about 4% every year. Since 1860, the CO
2
concentration
has increased from 290 ppm to 370 ppm and the current rate of increase is
1.5 ppm per year. Presently, fossil fuels containing 5 Gt (gigatonnesbillion metric
tonnes) of carbon are burnt annually. Most CO
2
from fossil fuels comes from
power stations, transport and industries, with a small fraction coming from homes
and commercial heating.
ACTIVITY 4.23
A car with typical petrol consumption of about 14 km/L will produce about 0.16 kg of
carbon dioxide per kilometre.
a If the typical annual distance travelled is 20 000 km, how much carbon dioxide will
it produce in a year?
b There are about 1 billion (10
9
) motor vehicles in the world. How many kilograms of
carbon dioxide do they produce per year?
This is a lot of carbon dioxide but how does it compare with the amount of CO
2
in
the atmosphere?
The volume of CO
2
in the atmosphere is approximately 1.8 10
18
L (measured at S.T.P.).
c Assuming the temperature is 0C, calculate the mass of CO
2
in the atmosphere.
d Using your answer from (b) calculate the fraction of CO
2
cars contribute to the
atmosphere.
e If a fully grown tree can take up about 300 kg of CO
2
a year and convert it back
to oxygen, how many trees would there need to be to offset the effects of motor
vehicle CO
2
?
It is thought that by 2080 the amount of carbon dioxide in the atmosphere will
have increased to 570 ppm from its pre-industrial revolution value of 270 ppm,
causing an average temperature rise of about 2C. Taking into account the increase
in other greenhouse gases such as methane, this rise could occur much earlier,
leading to dramatic effects on the global climate.
GLOSSARY
catalyst a chemical that speeds up a chemical reaction without undergoing
permanent change.
Dobson Units a 0.01 mm layer of ozone at 0C and 1 atm pressure
free radical an atom or molecule that contains an unpaired electron
greenhouse effect the process by which atmospheric gases trap the heat radiated
by the Earths surface and return it to the surface
steady state a condition in which a dynamic system is in balance so the loss of
components is equal to the gain
Planes produce CO
2
Although motor vehicles contribute signicantly to CO
2
production so do many other
forms of transport.
A jumbo jet ying from London to New York produces 210 tonnes of carbon dioxide during
that ightthe same amount of CO
2
that would be produced by 280 cars travelling the
same distance. All planes in the world produce about 2 10
9
tonnes of CO
2
per year.
The mass of carbon dioxide you produce in a year is approximately 300 kg, if you were
always at rest. (You might like to use the information from Activity 4.3 to check this
calculation.)
If 60 million (6 10
7
) people each breathe out 300 kg of CO
2
, then the whole population
would breathe out 1.8 10
10
kg or 1.8 10
7
tonnes. So if every time a person was
born a tree was planted, the effect of human CO
2
production would be almost zero.
Summary
In this section the atmospheric problems of pollution, destruction of the ozone layer
and global warming were considered. These problems affect the whole world and
understanding the chemical reactions that take place and the rates of these reactions
in the atmosphere is vital.
Atmospheric pollution is everyones problem as most of the pollutants have serious
health effects. The depletion of ozone is a problem in the stratosphere but the build-up
of ozone is a problem in the troposphere. The reactions for both removing and adding
ozone need to be well understood if a solution is to be found. An understanding of the
role played by CFCs in ozone depletion has resulted in the stopping of production of
these chemicals.
The effect of global warming is occurring in the troposphere and, like ozone, it arises
from the absorption of radiation by gas molecules. The need to understand the sources
and role of carbon dioxide and the need to monitor and detect its concentration is
essential if politicians and the general public are to be fully informed.
We know the composition of the global atmosphere is changing. Human activities are
the main cause. The scientic understanding of the causes is improving, but much is
still to be learnt because the atmosphere is such a complex system.
CHAPTER 1
Classifying substances and
exploring atoms
Solids, liquids and gases
Particle nature of matter
Mixtures and pure substances
Elements and compounds
Atoms and molecules
Symbols for elements
Formulae
Molecules of elements
Separating mixtures
An atoma nucleus and an electron cloud
Some simple atoms
Atomic number and mass number
Isotopes
Relative atomic mass (atomic weight)
Physical and chemical changes
Metals and non-metals
The Periodic Table
Electron arrangements in atoms
Stable electron congurations
The Periodic Table and electron conguration
IN THIS CHAPTER
The rst job of chemists, as they seek to understand the composition and properties
of the vast number of substances that are available on Earth, is to classify them
that is, to divide them into various categories. There are numerous ways of classifying
materials; a simple starting point is to divide substances into solids, liquids and gases.
1.1 SOLIDS, LIQUIDS AND GASES
Substances can exist as solids, liquids or gases; we call these the physical states
of matter. These three physical states of matter have the characteristics shown in
Table 1.1.
It is relatively easy to change a substance from one physical state to another,
for example to vaporise liquid water to gaseous steam, or to melt solid parafn wax
to liquid.
Changes from solid to liquid to gas and vice versa are called changes of state.
The names for the various changes of state are shown in Table 1.1.
163
TABLE 1.1 The three states of matter
Solid Liquid Gas
has a denite volume has a denite volume expands to ll the volume
available to it
has a denite shape (bars or
sheets of Al or Cu) or is made up
of small pieces (crystals) that have
denite shapes (sugar, salt, sand)
takes the shape of the
container it is placed on
takes the shape of the
container it is placed in
difcult to compress difcult to compress easily compressed
After classifying substances and identifying their properties, chemists then try to
nd explanations for these properties. To explain the characteristics (properties) of
solids, liquids and gases, chemists developed a theory that is known as the particle
nature of matter.
1.2 PARTICLE NATURE OF MATTER
All matter is made up of small particles which we often imagine as tiny spheres.
In solids, these particles are packed closely together in an orderly array as shown in
Figure 1.1(a). There are strong forces holding the particles to one another. These
cause solids to have denite shapes and to be relatively hard. In solids the particles
are not stationary as Figure 1.1(a) may suggest, but rather they are vibrating slightly
about their rest positions as shown in Figure1.1(d).
In liquids, the particles are arranged in a much less orderly fashion than in
solids, as shown in Figure 1.1(b), and they move about much more freely. Particles
in liquids possess more motionmore kinetic energy, we sayand the forces
between neighbouring particles are comparatively weaker than in solids. Hence
liquids do not have denite shapes but instead take the shape of the container they
are placed in. Liquids ow and deform easily. The motion of particles in liquids is
not conned to vibration as in solids, but also involves random translation from one
place to another in the bulk of the liquid as Figure 1.1(e) shows.
Because the particles are generally packed more closely together in solids than
in liquids, solids usually have greater densities than liquids, a notable exception
being that water has a greater density than ice.
In gases, the particles are much further apart than in solids or liquids, as shown
in Figure 1.1(c), and they are in very rapid random motion as Figure 1.1(f ) shows.
The particles are so far apart and moving so rapidly that there are no signicant
forces between them. Because the particles are in such rapid random motion, gases
quickly spread out to ll the whole volume available to them.
melting, fusion vaporisation, evaporation, boiling
solid liquid gas
freezing, solidication condensation, liquefaction
sublimation
CHAPTER 1 CLASSIFYING SUBSTANCES AND EXPLORING ATOMS 165 CHAPTER 1 CLASSIFYING SUBSTANCES AND EXPLORING ATOMS 165
We imagine the particles making up matter as being hard and incompressible,
so compressing materials means pushing particles closer together. In solids and
liquids the particles are already quite close to one another. This means that solids
and liquids cannot be compressed very much. In gases there are big spaces between
particles. This means that it is relatively easy to push the particles closer together;
hence gases are easily compressed.
So far we have been talking about the particles that make up substances and
explaining some properties in terms of how close the particles are to one another,
what motions they have, and how strong are the forces of attraction between pairs
of particles. This particle view of matter has easily explained the properties of
solids, liquids and gases shown in Table 1.1. To explain other properties we need to
consider the actual structure of the particles making up substances.
Another classication of substances is to divide them into mixtures and pure
substances and then to divide pure substances into elements and compounds.
FIGURE 1.1
The particle nature of, and
motions in, solids, liquids
and gases
EXERCISES
1 How would you expect the motion of particles in:
a a solid b a liquid
to change as the temperature was increased?
2 1.00 mL of dry ice (solid carbon dioxide) has a mass of 1.2 g. 1.2 g carbon dioxide
gas at standard atmospheric pressure and 25C has a volume of 670 mL. Given
that 1.2 g of solid and of gas each contain the same number of particles, and that
the actual particles have the same total volume both in the gas and in the solid,
calculate the percentage of the total volume of the gas that is empty space. Why is
the gas able to occupy such a large volume (compared to the volume of the solid)?
3 When two gases are brought into contact, they mix more quickly than two liquids
do when brought together. Explain why, in terms of the particle nature of gases and
liquids.
Refer to Context 1 Materials, p. 6.

1.3 MIXTURES AND PURE SUBSTANCES
the meaning of two words used in it should be explained.
Homogeneous means of uniform composition throughout, for example pure
water, sugar, aluminium, petrol or whisky. Heterogeneous means having non-uniform
composition where we can recognise small pieces of the material which are different
from other pieces, for example strawberry jam, wood, or water with ice in it.
Impure substance
An impure substance is one substance contaminated with small amounts of one
or more other substances.
An impure substance is therefore a mixture.
TABLE 1.2 Differences between a mixture and a pure substance
A mixture A pure substance
can be separated into two or more pure substances by
physical or mechanical means such as ltering, boiling or
using a magnet or tweezers
cannot be separated into two or more substances by
physical or mechanical means
may be homogeneous (tap water, air) or heterogeneous
(fruit cake, concrete)
is homogeneous (crystals of sugar, piece of copper)
displays the properties (characteristics) of the pure
substances making it up (different parts of the mixture
show different properties)
has properties (characteristics) such as appearance,
colour, density, melting and boiling points, which are
constant throughout the whole sample
has properties that can change as the relative amounts of
the substances present are changed
has properties that do not change regardless of how it is
prepared or how many times it is subjected to purication
procedures
has a variable composition; that is, the relative amounts of
each pure substance present can be varied
has a xed composition, no matter how it is made or where
it comes from
Examples:
sea water, air, coffee, milk, petrol, whisky, brass, and
silver coins
Examples:
table salt, sugar, copper, aluminium, diamond, gold,
polyethylene and alcohol
Bauxite (left), a mixture,
aluminium oxide (centre),
a compound separated
from it, and aluminium
(right), an element
obtained from the
compound
1.4 ELEMENTS AND COMPOUNDS
Some pure substances can be decomposed into simpler substances while others
cannot. Those that cannot be decomposed are called elements; those that can be
decomposed are called compounds.
An element is a pure substance which cannot be decomposed into
simpler substances.
Some common elements are aluminium, copper, carbon (diamond), oxygen,
gold, nitrogen and mercury.
A compound is a pure substance which can be decomposed into simpler
substances, for example into elements.
Some common compounds are table salt (sodium chloride), sugar (sucrose),
water, sodium carbonate (washing soda), sulfate of ammonia (ammonium sulfate,
a common fertiliser), alcohol (ethanol) and aspirin (painkiller).
A compound:
is made up of two or more elements
always has the elements present in the same ratio by mass
has properties that are quite different from those of the elements that make it up
The elements copper
(centre), sulfur (yellow,
directly below copper)
and carbon (black,
anticlockwise from sulfur),
and some compounds
of copper: (anticlockwise
from carbon) copper
sulfate, copper carbonate,
copper(I) oxide, copper
sulde and copper
chloride
Figure 1.2 shows the classication of matter into mixtures, elements and
compounds.
EXERCISES
4 Classify the following as homogeneous or heterogeneous:
a a diamond d mercury g concrete
b soil e blood h dry ice
c white wine f an orange f i toothpaste
5 a Classify the homogeneous items in Exercise 4 as mixtures or pure substances.
b In terms of mixture or pure substance, what can you say about all the
heterogeneous substances in Exercise 4?
6 Which of the following are pure substances?
a soft drink d aluminium foil g deodorant spray
b a silver pendant e polyethylene wrapping lm h copper pipe
c exhaled breath f a brick f i lead sheeting
7 A 1.00 g sample of a shiny grey solid was heated. At 327C it changed to a silvery
liquid; the temperature did not increase until all the solid had turned to liquid. When
the liquid was cooled, it changed back to a grey solid; the mass was still 1.00 g. Is
this substance an element or a compound? Explain why.
8 When 1.00 g of a particular pale blue solid was heated, it changed to a black solid.
The mass of the black solid was 0.64 g. Suggest why there has been an apparent
loss of mass. Is the original blue solid an element or a compound? Why?
FIGURE 1.2
A classication of matter
Let us now look at some of the particles that make up elements and compounds.
1.5 ATOMS AND MOLECULES
The particles that make up elements are called atoms.
An atom is the smallest particle of an element which is still recognisable as that
element.
This means that if we had a lump of the element copper and kept breaking it
up into smaller and smaller pieces, eventually we would get to the stage where the
individual pieces would be atoms of copper. It is possible to break these atoms into
even smaller pieces but those pieces would no longer be copper (they would be
sub-atomic particles we call electrons, protons, neutronsSection 1.10).
All the atoms of one element are identical (except for some variation in mass
for certain elements), but they are different from the atoms of all other elements.
Compounds consist of two or more elements combined together in denite
proportions by mass. In some compounds the particles which make up the
compound consist of several atoms joined tightly together. We call these particles
molecules. The elements hydrogen and oxygen form the compound water. Water is
made up of molecules. Each molecule of water has two atoms of hydrogen rmly
joined to one atom of oxygen. All the molecules of water are identical. Figure
1.3 illustrates these ideas of atoms and molecules, while Figure 1.4 shows some
common molecules. We dene a molecule as follows:
A molecule is the smallest particle of a substance that is capable of separate
existence.
By this denition the entities shown in Figures 1.3 and 1.4 are clearly molecules.
However, the denition has some consequences for elements as we shall see in
Section 1.8.
Note that only some compounds exist as discrete molecules as described here.
We shall look at the forms in which other compounds exist in Sections 2.1 and 2.7.

FIGURE 1.3
Atoms and molecules
FIGURE 1.4
Some simple molecules

1.6 SYMBOLS FOR ELEMENTS
Chemists talk and write about elements so frequently that they have introduced
a set of symbols to represent the elements. These symbols are a form of chemical
shorthand. They fall into three categories:
1 Some symbols are simply the rst letter of the name of the element (always a
capital letter). These symbols are generally used for very common elements.
B for boron C for carbon F for uorine H for hydrogen
2 Where there are several elements beginning with the same letter, a second
letter is used, frequently though not always the second letter of the name of the
element. The rst letter is a capital (upper case) and the second a small (lower
case) letter.
Ar for argon Al for aluminium As for arsenic
Ca for calcium Cl for chlorine Co for cobalt Cr for chromium
3 For some elements we use a symbol derived from a non-English name of the
element.
Na for sodium (natrium) Ag for silver (argentum)
Cu for copper (cuprum) K for potassium (kalium)
1.7 FORMULAE
Symbols are used for elements. Compounds are made up of elements, so it is
natural that combinations of symbols should be used to denote compounds.
Such combinations of symbols are called formulae.
H
2
O is the formula for water. It is however more than just shorthand. This
formula tells us that:
water is made of the elements hydrogen and oxygen
the water molecule contains two atoms of hydrogen bound to one atom of
oxygen.
A subscript in a formula refers to the element immediately preceding it (as in
water above). Another example is carbon dioxide, CO
2
: each molecule contains two
atoms of oxygen and one atom of carbon. Other formulae are shown in Table 1.3.
TABLE 1.3 Some common formulae and their meaning
Name of
compound Formula One molecule of the compound contains
ammonia NH
3
3 atoms of hydrogen and 1 atom of nitrogen
sulfuric acid H
2
SO
4
2 atoms of hydrogen, 1 atom of sulfur and
4 atoms of oxygen
boric acid B(OH)
3
1 atom of boron, 3 atoms of oxygen and
3 atoms of hydrogen
Note carefully that the subscript 3 refers to all the atoms within the
brackets.
Figure 1.5 shows some common molecules with their formulae.
1.8 MOLECULES OF ELEMENTS
Oxygen is an element. Its symbol is O. However in the atmosphere, oxygen gas
is not present as separate independent atoms. Instead it exists as pairs of atoms
permanently stuck together to form molecules. Or stated differently, in oxygen gas
the small particles moving about randomly are molecules, each molecule being a
pair of atoms chemically bonded together. Hence for oxygen gas the formula is O
2
.
It is a diatomic molecule.
This is true for all the common gaseous elements except the noble gases; the
smallest particle that is able to exist on its own for long periods of time is a molecule
containing two atoms. Nitrogen gas is N
2
, chlorine gas is Cl
2
, and hydrogen gas is
H
2
. Two of these diatomic gaseous molecules are shown in Figure 1.5.
The noble gases, helium, neon, argon, krypton, xenon and radon, exist as
independent atoms.
1.9 SEPARATING MIXTURES
The materials we need for our everyday life are obtained from the Earth. However,
most of the substances we need have to be separated from mixtures of naturally-
occurring materials. Let us therefore look at ways of separating mixtures into their
pure components.
FIGURE 1.5
Some simple molecules
with their formulae
Refer to Context 1 Materials, pp. 67.

Separation of solids of different sizes
Mixtures in which the particles of the different substances have different sizes can
be separated by sieving.
In the home kitchen we often use a sieve (piece of gauze held in a metal or
plastic frame) to separate out lumps from a powdery substance such as our.
Similarly in the laboratory and in industry sieves are used to separate small particles
from large ones. At quarries ne sand, needed for making concrete and mortar, is
separated from the coarser material (sold as gravel) by sieving.
Separating solids and liquids
Mixtures of solids and liquids are commonly separated by ltration as shown in
Figure 1.6. The liquid or solution passes through the paper while the suspended
solid remains on the top of the lter paper. The liquid or solution that passes
through the lter paper is called a ltrate. Sand can be separated from sea water in
this way.
Sometimes if the solid is present as
coarse or very dense particles (such as
coarse sand in water), sedimentation and
decantation can be used. Sedimentation
is the process in which solids settle to
the bottom of a container. Decanting or
decantation is the process of carefully
pouring off the liquid and leaving the
solid undisturbed at the bottom of the
container. Pouring tea off tea leaves is
decantation.
Separating dissolved solids in liquids
When a solid is dissolved in a liquid (that is, when we have a solution), the solid
and liquid can be separated by vaporising off the liquid (called the solvent). We can solvent solvent
do this either by boiling the solution (visible bubbles of vapour form) or by just
evaporating it. Evaporation is a slower process than boiling.
Chemists frequently use the expression evaporate to dryness. This means
heating a solution in an evaporating basin to drive off all the solvent (the liquid),
and is illustrated in Figure 1.7. Evaporating to dryness is a common way of
obtaining a solid from a solution.
Boiling or evaporating off the liquid is effective if it is the solid that we want
(as in getting salt from sea water). However if it is the liquid that we want (as in
getting fresh water from sea water), or if we want both the solid and the liquid,
then we have to use distillation.
FIGURE 1.6
Filtration in the laboratory
FIGURE 1.7
Evaporating a solution to
dryness
Distillation
Distillation is a method of separating two or more liquids from one another or of
separating the liquid from the solids in a solution; this latter process can be thought
of as purifying the liquid.
Distillation is the process in which a solution or mixture of liquids is boiled with
the vapour formed being condensed back to a liquid in a different part of the
apparatus and so separated from the mixture.
The arrangement shown in Figure 1.8 is commonly used for distillation. The
mixture or impure liquid, for example sea water, is placed in the ask and heated
to boiling. The liquid changes to vapour, rises up the neck of the ask and diffuses
down the side arm and into the water-cooled condenser, where the vapour is
cooled and condensed back to a liquid, which is collected in the beaker. The liquid
collected from a distillation is called a distillate.
If the impurities are non-volatile (as is the case with sea water), pure liquid is
collected (pure water from sea water).
Collecting salt by
evaporating sea water.
In Vietnam people do
the hard work while in
Australia we use machines.
Note that the sea water is
not evaporated to dryness:
it is evaporated until a
large proportion of the salt
has crystallised out. In this
way, most of the impurities
stay in the solution
FIGURE 1.8
Simple distillation
apparatus
Separating liquids
A mixture of two or more liquids can be separated by distillation if the boiling
points of the liquids are sufciently different (say by about 40 or 50C).
If we distil a mixture of two liquids (such as alcohol and water) which do not have
greatly different boiling points (78C and 100C), then the distillate is not a pure
substance. Instead it is a mixture, but generally the distillate is richer in the lower boiling
point component.
We often use the word volatile in these contexts: it means able to be converted
to a vapour. The more volatile of two liquids is the one with the lower boiling point:
ethanol is more volatile than water.
If a If If mixture of a volatile liquid with non-volatile impurities (solid or liquid) is
distilled, the distillate is pure liquid. If a mixture of two liquids of comparable
volatility (similar boiling points) is distilled, the distillate is generally richer in the
more volatile liquid.
Despite what has just been said, it is possible to use distillation to separate
liquids with similar boiling points if we use a process called fractional distillation.
To separate liquids by distillation when their boiling points are fairly close together
we have to use many distillation steps. This can be done in specially designed
equipment: the process is called fractional distillation. A typical laboratory
fractionating column is shown in Figure 1.9. This arrangement allows for repeated
condensations and vaporisations up the column, effectively giving many separate
distillations (typically 10 to 100). This means that eventually a pure sample of the
more volatile substance in the original mixture emerges from the top of the column.
FIGURE 1.9
Fractionating column in
the laboratory (commonly
about 400 to 500 mm high)
Fractional distillation is widely used in industry. Examples of this are:
separation of crude oil into various commercial products
separation of ethanol (for use as a fuel additive) from fermented solutions of
sugar molasses or grain mashes
production of liquid nitrogen and argon gas from liqueed air.
Separating immiscible liquids
Two liquids are said to be immiscible if, when they are mixed, they do not form
a homogeneous liquid, but instead stay as drops of one liquid dispersed through
the other liquid. If left standing for some time immiscible liquids separate into two
distinct layers, one on top of the other. Examples are water and kerosene, water and
cooking oil. Liquids that mix to form a homogeneous liquid are said to be miscible.
Alternatively, we say that one liquid dissolves in the other.
Immiscible liquids are generally separated by using a separating funnel. This
pear-shaped piece of apparatus, shown in Figure 1.10 on the next page, tapers to
a narrow tube just above the stopcock. This shape allows us to run out the bottom
liquid without getting it contaminated with any of the top one. A mixture of petrol
and water can be separated in this way.
Separation based on solubility
Mixtures of solids can be easily separated if one solid is soluble in a particular
solvent while the others are not. Sufcient solvent is added to the mixture to
dissolve the soluble component; then the insoluble component(s) is(are) ltered off.
The soluble solid is recovered by evaporating the ltrate (solution of that solid) to
dryness. This is shown in Figure 1.11. A mixture of salt and sand can be separated
this way by adding sufcient water to dissolve the salt, then ltering off the sand.
EXERCISES
9 A careless teacher inadvertently mixed the laboratory supplies of aluminium oxide
and lead pellets. Although small, the lead pellets were larger than the ne crystals
of aluminium oxide. Aluminium oxide is much less dense than lead. Suggest a way
of separating these two substances.
10 Suppose you were given a solution of sucrose (sugar) in water. How would you
separate this mixture if your aim was:
a to obtain pure sucrose b to obtain pure water?
11 a If a mixture of alcohol (ethanol, boiling point 78C) and glycerol (boiling
point 290C) was distilled, what would be the composition of the distillate?
Explain why.
b Would distillation of a solution of acetic acid (boiling point 118C) in water, for
example vinegar, produce a distillate more concentrated or less concentrated
(in acetic acid) than the starting solution? Give your reason.
c If a mixture of chloroform (boiling point 62C) and ethanol (boiling point 78C)
was distilled, the distillate would be richer (than the starting material) in which
substance?
d How would you obtain a pure sample of one liquid from the mixture in (c)?
e If you distilled a mixture of hexane (boiling point 69C) and heptane (boiling
point 98C), what would the distillate be?
Solvents other than water can be used. For example, a mixture of iodine and
charcoal (carbon) can be separated by adding hexane, which dissolves the iodine
but not the carbon.
We will clarify the meaning of some terms before proceeding.
A suspension is a dispersion of particles through a liquid with the particles being
sufciently large that they settle out on standing.
A suspension is heterogeneous in that the dispersed particles can be seen either by
eye or by using a microscope. Examples are sand in water, milk and paint.
A solution is a homogeneous mixture in which the dispersed particles (molecules
or ions) are so small that they never settle out and cannot be seen by a microscope.
Examples are salt or sugar in water, iodine in alcohol, and brandy. In a
solution the substance that is dissolved is called the solute. The liquid that does the
dissolving is called the solvent. Sugar, common salt and caustic soda are solutes that
readily dissolve in the solvent water. As solutes, iodine and cooking oil dissolve in
the solvent hexane.
FIGURE 1.10
(a) Two immiscible liquids
in a separating funnel,
(b) just before all of the
heavier (more dense)
liquid has been run out

FIGURE 1.11
Separating a mixture
by ltration followed
by evaporation
To understand why atoms form the compounds they do and why some atoms
form compounds more readily than other atoms we need to look at the actual
structure of the atom.
1.10 AN ATOMA NUCLEUS AND AN
ELECTRON CLOUD
An atom consists of an extremely small dense nucleus or core which contains the
bulk of the mass of the atom and which carries positive electrical charges. This
nucleus is surrounded by a cloud of rapidly moving extremely light particles
carrying negative electrical charges. These light negative particles are called electrons.
This electron cloud constitutes the bulk of the volume of the atom, but contributes
only very slightly to the mass of the atom. The amount of negative charge carried
by these rapidly and randomly moving electrons is equal to the amount of positive
charge on the nucleus, so that the atom is neutral overall. Figure 1.12 shows the
nucleus and the surrounding electron cloud.
EXERCISES
12 A schools supply of crystalline magnesium sulfate became contaminated with
some barium sulfate. Draw a ow chart for the method you would use to separate
these two substances, ending up with dry pure crystals of each substance.
Magnesium sulfate is soluble in water; barium sulfate is not.
13 Two students were given a mixture of powdered charcoal, kerosene, parafn wax,
sodium sulfate and water. They were asked to obtain pure samples of the charcoal,
kerosene, wax and sodium sulfate from this mixture. A ow chart of the procedure
they followed is shown below.
a Name the separation procedures, 1, 2, 3 and 4, that they used. Draw a diagram
showing how each of these procedures would be performed in the laboratory.
b Identify the solids X and Y and the liquid Z.
c How would you vary their procedure in order to recover a pure sample of water
as well?

The nucleus contains more than 99.95% of the mass of the atom, but its
diameter is less than one ten-thousandth of the diameter of the whole atom.
An electron is an extremely small negatively charged particle with a mass
of 1/2000 of the mass of a hydrogen atom.
Electrons in atoms move very rapidly and randomly around the nucleus.
They do not (repeat, not) move in xed orbits like planets around the sun, but
rather they move so that their distance from the nucleus varies greatly; at one
instant an electron may be close to the nucleus, the next instant far away from it.
Because electrons are extremely small and because the volume available to them
to wander around in is so huge, they are able to move about haphazardly without
ever colliding. It is because we have many electrons moving randomly through the
volume surrounding the nucleus that we use the term electron cloud to describe it.
Here is an illustration of the relative sizes. If the nucleus of an atom were the
size of a cherry stone placed at the centre of the Sydney Olympic stadium, electrons
would be about the size of fruit ies and they would wander through a volume as
big as the whole arena, spectator stands included!
The nucleus is made up of two types of particles. One type carries a positive
charge and is called a proton. The second type is neutral and is called a neutron.
A proton is a small positively charged particle having a mass approximately equal
to the mass of a hydrogen atom and a charge equal in magnitude (but opposite in
sign) to that of an electron.
A neutron is a small neutral particle which has the same mass as a proton.
The properties of electrons, protons and neutrons are summarised in Table 1.4.
As an atom is electrically neutral, the number of electrons in the electron cloud is
equal to the number of protons in the nucleus.
Atoms of different elements contain different numbers of protons and neutrons in their
nuclei and hence different numbers of electrons surrounding the nuclei.
TABLE 1.4 Properties of fundamental particles
Symbol Relative mass
a
Relative charge
b
electron e 1/2000 1
proton p 1 1
neutron n 1 0
a on a scale where the proton is set arbitrarily at unity.
b The actual charge on an electron is 1.602 10
19
coulomb.

FIGURE 1.12
An atom (diameter 0.1 to
0.3 nanometres) consists
of a nucleus and an
electron cloud

1.11 SOME SIMPLE ATOMS
The nucleus of a hydrogen atom consists of one proton only (and no neutrons), so
there is one electron surrounding it. This is consistent with our earlier statements that
the mass of an electron was 1/2000 of the mass of a hydrogen atom and that the mass
of the proton was approximately that of the hydrogen atom.
A helium atom has two protons and two neutrons in its nucleus and two
electrons surrounding the nucleus. Lithium has three protons and four neutrons
in its nucleus and three electrons in its cloud.
Atoms of all the elements are obtained by successively increasing by one the
number of protons in the nucleus. We cannot predict exactly how many neutrons
are present, but for the simpler (lighter) elements, the number of neutrons is
approximately equal to the number of protons. Table 1.5 shows the composition
of the atoms of the rst ten elements. It shows, for example, that a uorine atom
consists of a nucleus containing 9 protons and 10 neutrons and that there are
9 electrons in the electron cloud.
TABLE 1.5 Atomic structure of the rst ten elements
protons
Number of
neutrons
Number of
electrons
Mass number,
A
a
H 1 0 1 1
He 2 2 2 4
Li 3 4 3 7
Be 4 5 4 9
B 5 6 5 11
C 6 6 6 12
N 7 7 7 14
O 8 8 8 16
F 9 10 9 19
Ne 10 10 10 20
a
Mass number, A number of protons number of neutrons.
Atomic number, Z number of protons
1.12 ATOMIC NUMBER AND MASS NUMBER
Atomic number and mass number are two terms frequently used to describe atoms.
The atomic number, Z, of an element is the number of protons in the nucleus of ZZ
an atom of that element.
From Table 1.5 we see that the atomic number of hydrogen is 1, of carbon, 6
and of neon, 10.
The mass number, A, is the number of protons plus neutrons in the nucleus of an
atom of the species concerned.
From Table 1.5 the mass number of helium is 2 2 4 and of carbon,
6 6 12; and of uorine, 19.
1.13 ISOTOPES
(but the same number of protons). For example, for the element chlorine 75%
of the atoms have 18 neutrons while the other 25% have 20, though all atoms all all
of chlorine contain 17 protons: this means that there are two types of atoms for
chlorine, one with mass number 35 and the other with mass number 37. These
different types of atoms of the one element are called isotopes.
Isotopes are atoms of the one element that differ in the number of neutrons in
their nuclei.
We say that there are two isotopes of chlorine. Isotopes are named by their
mass numbers. We talk about chlorine-35 and chlorine-37. Similarly there are
two isotopes of copper, copper-63 (29 protons, 34 neutrons) and copper-65
(29 protons and 36 neutrons).
All atoms of the one element have the same number of protons in their nuclei
that is, the same atomic number.
A symbol commonly used for isotopes is:
A
Z
M
ZZ
where M is the chemical symbol of the element, A is its mass number and Z is its ZZ
atomic number. Some examples are
35
17
Cl,
65
29
Cu,
2
1
H and
16
8
O.
Despite these small differences in mass numbers, the chemical and physical
properties of all isotopes of the one element are virtually identical.
EXERCISES
14 In Figure 1.12 the nucleus has a diameter of approximately 1 mm. If this were a
scale drawing of an atom, what would be the diameter of the whole atom?
15 a A sodium atom consists of 11 protons, 11 electrons and 12 neutrons. What is
its atomic number and mass number?
b Write the
A
Write the Write the
Z
Write the Write the M symbol for silicon with 14 protons and 16 neutrons.
16 Supply the missing numbers in the following table
:
Element
Atomic
number
Mass
number
Number of
protons
Number of
neutrons
Number of
electrons
helium 2 4
oxygen 8 8
boron 11 5
sulfur 32 16
chlorine-35 17
oxygen-18 8
*iodine 53 74
*argon 18 40
*zinc 65 30
Remember that an asterisk in front of an exercise or part of an exercise means that no answer is
provided.
1.14 RELATIVE ATOMIC MASS
(ATOMIC WEIGHT)
Atoms of one element are different from atoms of any other element. Not
surprisingly, then, the atoms of different elements have different masses. However
because atoms are extremely small, it is difcult to measure their individual masses.
Chemists at rst were only able to measure the relative masses of atoms; that is, to
determine for example that a titanium atom had four times the mass of a carbon
atom, that an oxygen atom was 1.33 times the mass of a carbon atom, that a sulfur
atom had twice the mass of an oxygen atom. Hence a scale of relative masses was
devised.
As a start, let us take the relative atomic mass of an element as the mass of an
atom of the element relative to the mass of a carbon atom, taken as exactly 12.
A titanium atom is four times the mass of a carbon atom, so its relative atomic
mass is 4 12 48 (Figure 1.13). An oxygen atom is 1.33 times the mass of a
carbon atom, so oxygen has a relative atomic mass of 1.33 12 16. A sulfur
atom has a mass twice that of an oxygen atom; the relative atomic mass of sulfur is
therefore 2 16 32.
In this way, chemists compiled a table of relative atomic masses of the elements.
Some common ones are given in Table 1.6; a more complete (and more accurate)
list is printed on page 171.
TABLE 1.6 Relative atomic masses (atomic weights) of some common elements
aluminium Al 27 gold Au 197
argon Ar 40 helium He 4
calcium Ca 40 hydrogen H 1
carbon C 12 nitrogen N 14
chlorine Cl 35.5 oxygen O 16
copper Cu 63.5 potassium K 39
uorine F 19 sodium Na 23
Because of the existence of isotopes, we need to be more precise with our
denition of relative atomic mass than the statement above. Isotopes of the one
element have different masses, so in our denition instead of just mass of an atom
we need to say average mass of the atoms in the naturally occurring element.

one carbon atom. Therefore the relative atomic
mass of helium is
1
__
3
12 4
One titanium atom has the same mass as four
carbon atoms. Therefore the relative atomic
mass of titanium is 4 12 48
FIGURE 1.13
Two illustrations of the
meaning of relative atomic
mass (atomic weight)
A further complication is that naturally occurring carbon contains two isotopes:
98.89% of the atoms contain 6 neutrons (and 6 protons, so mass number 12), while
the other 1.11% contain 7 neutrons (mass number 13). The carbon-12 isotope is
used as the standard for relative atomic masses. Hence the strict denition is:
The relative atomic mass (or atomic weight) of an element is the average mass
of the atoms present in the naturally occurring element relative to the mass of an
atom of the carbon-12 isotope taken as exactly 12.
Fortunately, the isotopic composition of each element is virtually the same
throughout the world.
Of 100 atoms of chlorine, 75 have a mass of 35 while 25 have a mass of 37.
The average mass in the above denition is therefore:
75 35 25 37

____________________

100
35.5
Similarly, considering 100 atoms of copper which is 69% copper-63 and 31%
copper-65, the average mass is:
69 63 31 65

____________________

100
63.6
Naturally occurring carbon is 98.89% carbon-12 and 1.11% carbon-13, so its
relative atomic mass is:

98.89 12 1.11 13

_________________________

100
12.01
It is essential to realise that the relative atomic mass (or atomic weight) of an element
is not (repeat, not) the mass of an atom of that element. It is just a relative massrelative
to the mass of a carbon atom. It is not a mass at all, but merely a pure number (that
isit has no units).
Relative atomic mass or atomic weight?
Relative atomic mass is the strictly correct name to use for this term. However when
the term was rst introduced nearly two centuries ago, it was called atomic weight
and this name has been widely used ever since as a synonym for the more correct
name, relative atomic mass.
Before continuing further with our exploration of atoms, we need to return
to the other theme of this chapter, namely classifying things, in particular the
distinction between physical and chemical changes and the differences between
metals and non-metals.
Refer to Context 1 Materials, pp. 13 and 32.

1.15 PHYSICAL AND CHEMICAL CHANGES
Many of the changes that we can make to materials involve:
changing the state of a substance (melting lead, boiling water)
changing the physical appearance (grinding big lumps of limestone into ne
powder, rolling blocks of copper into sheets or drawing into wires)
dissolving a solid in a liquid (iodine in hexane, sugar in water)
separating mixtures (separating sea water into solid salt and liquid water,
ltering sand from water).
In these changes no new substance has been formed.
A change in which no new substance is formed is
called a physical change.
By contrast there are changes in which new substances are
formed. Examples are:
heating green copper carbonate to form a black solid and a
colourless gas
burning silvery magnesium ribbon to form a white powder
heating a mixture of grey iron lings and yellow sulfur to
form a homogeneous black solid.
A change in which at least one new substance is
formed is called a chemical change.
Chemical changes are also called chemical reactions.
Common ways of deciding that a chemical change
(reaction) has occurred are:
1 if a gas is evolved, for example zinc granules dropped into hydrochloric gas is evolved gas is evolved
acid solution
2 if a solid (called a precipitate) is formed when two solutions are mixed; for solid (called a precipitate) is formed solid (called a precipitate) is formed
example when silver nitrate and sodium chloride solutions are mixed, a
white solid (silver chloride) forms
3 if there is a change in colour; for change in colour change in colour
example when purple potassium
permanganate solution is added
to hydrogen peroxide, the mixture
becomes colourless (Fig. 1.14)
4 if there is a signicant change
in temperature of the mixture; in temperature in temperature
for example when magnesium
is burnt, the metal becomes
very hot
5 if there is disappearance of a solid
which is not merely physical
dissolution of the solid in the
solvent; for example white
magnesium hydroxide powder
added to hydrochloric acid
produces a clear solution
The sublimation and
condensation of iodine
(solid gas solid)
are physical changes
FIGURE 1.14
Purple potassium
permanganate solution
undergoes a chemical change
when mixed with colourless
hydrogen peroxide solution
6 if an odour is produced; for example when sodium odour is produced odour is produced
hydroxide is added to a warm solution of ammonium
chloride, the sharp smell of ammonia is detected.
In a chemical reaction the starting substances are called
reactants and the substances that are formed are called
products.
Table 1.7 summarises the differences between chemical reactions and physical
changes.
TABLE 1.7 Differences between chemical and physical changes
Physical change
at least one new substance is formed no new substance is formed
difcult to reverse (hard to un-boil an egg) easily reversed (melt a solid: freeze it again)
generally a large input or output of energy
(burn natural gas)
relatively small energy changes involved
(evaporate alcohol, dissolve sugar in water)
Physical and chemical properties
Properties of substances that relate to physical changes, such as melting and boiling
points, are called physical properties. Other common physical properties are
appearance, density, electrical conductivity, and hardness.
Properties that relate to the chemical reactions that substances undergo are
called chemical properties. Common chemical properties are ease of decomposition
by heat, effect of light, and reactivity with other substances such as oxygen, chlorine
and sulfur.
Colourless solutions
of potassium iodide
and lead nitrate
react chemically to
produce a yellow
precipitate
EXERCISES
17 Classify each of the following as a physical or chemical change:
a tarnishing of copper d melting wax
b dissolving sugar in water e evaporating sea water to dryness
c burning a candle f rusting of iron f
18 When a silvery granule of zinc is dropped into a pale blue solution of copper sulfate,
a reddish brown solid deposits on the zinc and the solution loses its blue colour. Is
this a physical or chemical change? Give your reasons.
1.16 METALS AND NON-METALS
Chemists have found it convenient to classify the elements into what are called
metals and non-metals.
Metals are elements which:
are solids at room temperature
have a shiny or lustrous appearance
are good conductors of heat and electricity
are malleable (able to be rolled into sheets) and ductile (able to be drawn
into wires).
Most other elements are called non-metals.
On this basis, aluminium, cobalt, copper, gold, iron, lead, magnesium, nickel,
potassium, sodium, silver, tin and zinc are clearly metals. Argon, bromine, chlorine,
hydrogen, iodine, nitrogen, oxygen, phosphorus and sulfur are non-metals.
Common metals:
left of the left-hand photo)
gold, aluminium, zinc,
magnesium, copper,
iron; and non-metals:
left of right-hand photo)
carbon, phosphorus,
iodine, sulfur
19 Decide whether the changes in a and b are physical or chemical. Explain your
reasoning.
a When 1.00 g of a certain white solid was mixed with 20 mL of water, a clear
solution resulted. When this solution was evaporated to dryness, 1.41 g of
white solid was recovered. The original white solid remained as a solid when
heated to 400C; the recovered white solid melted at 360C.
b When 1.00 g of a different white solid was mixed with 20 mL of water, a clear
solution resulted. When this solution was heated to evaporate off the water,
1.00 g of white solid was recovered. The white solid had the same melting point
as the starting solid.

There are however some problem elements. Mercury has a shiny appearance
and is a good conductor of electricity, but it is a liquid. We choose to classify
mercury as a metal because, on balance, its properties are closer to those of the
other metals than the non-metals. Carbon in the form of graphite is a fair conductor
of electricity and is a solid. Despite this we classify it as a non-metal because,
considering all its properties, it resembles the non-metals more closely than the
metals.
As with any classication into two categories, there are some elements which are
difcult to classify as metals or non-metals because they have some properties of
both classes. Boron, silicon, germanium, arsenic, antimony and tellurium do not fall
clearly into either category. We therefore call them semi-metals.
This classication of the elements into metals and non-metals is useful because
very frequently, as we shall nd in later chapters, the metals have one property
while the non-metals have a different one.
Finally, in our survey of classifying substances we turn to the most useful of
all chemical classications, the Periodic Table.
1.17 THE PERIODIC TABLE
Because there are so many elements (more than 90) with such a wide variety of
properties, chemists have devised a chart which organises the elements into groups
with similar properties. It is called the Periodic Table. A typical Periodic Table is
shown on p. 372.
In this table the elements are arranged so that those with similar properties fall
into the same vertical column. Lithium, Li, sodium, Na, potassium, K, rubidium,
Rb, and caesium, Cs, all have very similar properties; they fall into the extreme
left-hand column of the table. Beryllium, Be, magnesium, Mg, calcium, Ca,
strontium, Sr, and barium, Ba, have similar properties; they fall into another vertical
columnthe one second from the left. Fluorine, F, chlorine, Cl, bromine, Br, and
iodine, I, have similar properties; they are also in the same vertical column, the
one second from the right.
The vertical columns are called groups. The main groups of the table, the ones
with at least ve elements in them, are numbered from 1 to 7 with the right-hand
group being numbered either 0 or 8. Group 1 contains Li, Na, K, Rb, Cs. The
elements Be, Mg, Ca, Sr and Ba belong to Group 2, while F, Cl, Br and I belong
to Group 7. The ten groups of elements between Groups 2 and 3 are not normally
numbered. The elements in these groups are called transition elements. The other
elements (in Groups 1 to 7 and 0) are called main-group elements.
The horizontal rows are called periods and they too are numbered from 1 to 7.
Period 1 contains only two elements, hydrogen, H, and helium, He. Periods 2
and 3 each contain eight elementslithium, Li, to neon, Ne, and sodium, Na,
to argon, Ar, respectively. Periods 4 and upwards contain larger numbers of
elements (because they contain transition elements).
There is often a gradual change in properties as we go across any one period.
While periods are useful for seeing trends in properties, they are less useful than
the groups for working out actual properties of particular elements.
A big advantage of the Periodic Table is that it allows us to deduce the
properties of elements we may not be familiar with. For example, if we know
nothing about rubidium, Rb, we note that it occurs in the same group of the table
as sodium, Na. Hence the properties of rubidium and the compounds it forms are
very similar to those of sodium. If we know that sodium reacts with water, then the
table tells that rubidium also reacts with water.
Similarly we can use the table to deduce that strontium will undergo the same
reactions as magnesium and calcium, or that bromine and iodine will form the
same type of compounds as chlorine.
As our study of chemistry progresses, we will see that the Periodic Table
provides much more information than this. For present purposes it is sufcient
to appreciate that the table tells us which elements have similar properties; that is,
those that are in the same group.
Metals and non-metals in the Periodic Table
On the Periodic Table the non-metals occur near the top and right of the table.
Most of the other elements are metals. A diagonal band of semi-metals separates
the metals from the non-metals. This division is shown in Table 1.8.
TABLE 1.8 Division of the elements into metals and non-metals

Elements to the left of the blue shaded zone are metals; elements to the right (in the pink
shaded zone) are non-metals. Elements within the blue shaded zone have properties
intermediate between metals and non-metals and are therefore hard to categorise; they
are called semi-metals. Hydrogen is usually classed as a non-metal.
The Periodic Table shows that there are groups of elements that have very
similar properties, and that the properties of one group can be quite different from
those of other groups. Having made observations such as these, chemists try to
nd explanations for them. It turns out that the explanations arise from the way
in which electrons are arranged in the atoms, so let us take at look at this.

1.18 ELECTRON ARRANGEMENTS IN ATOMS
discrete energy levels which we call the rst,
second, third energy level and so on. Each electron in the rst energy level has a
certain constant amount of energy; each electron in the second energy level also has
a xed amount of energy but it is greater than that possessed by electrons in the rst
energy level. Similarly, the electrons in the third energy level have larger amounts of
energy still.
Each of these energy levels can accommodate only a certain maximum number
of electrons as shown in Figure 1.15(a). The rst energy level can accommodate
only two electrons, the second can hold eight and the third eighteen; in general the
nth energy level can accommodate 2n
2
electrons. Electrons must be in one energy
level or anotherthey cannot have energies that are intermediate between two
levels.
In atoms, the electrons tend to be in the lowest energy levels possible consistent
with not over lling the levels.
We work out the arrangement of electrons in any given atom by feeding the
electrons into the energy levels starting at the lowest, and remembering that each
level can hold only a certain maximum number.
For hydrogen (one electron only) we put the electron in the lowest energy level.
For helium (two electrons) we put both electrons in the rst level. Lithium has three
electrons, two of which go into the rst level with the third going into the second level.
We write this as (2, 1). Beryllium with four electrons is (2, 2), and boron with ve is
(2, 3). Neon with ten electrons is (2, 8). The second energy level is now full (Figure
1.15(a)), so for sodium (eleven electrons) the last one goes into the third level to give
(2, 8, 1).
The arrangement of electrons in energy levels is called the electron
conguration of the atom. What is being described in this chapter is a simple
form of electron conguration. It is perfectly adequate for our present purpose
which is to understand chemical bonding. Table 1.9 presents the simple form
electron congurations for the rst 22 elements, plus a few more.
FIGURE 1.15
(a) Energy levels for
electrons in atoms
(b) The sequence for
lling them
As we proceed from sodium (2, 8, 1) to argon which has 18 electrons, each
additional electron goes into the third level, so that argon is (2, 8, 8).
As the third energy level can accommodate 18 electrons, we should expect
potassium (19 electrons) to be (2, 8, 9), but it is not! What we nd is that after there
are eight electrons in the third level, the next two go into the fourth level. Potassium is
(2, 8, 8, 1) and calcium (2, 8, 8, 2). This happens because these congurations are
more stable than (2, 8, 9) and (2, 8, 10), although an explanation for them being
more stable requires a more detailed picture of atomic structure than presented
here.
Having put two electrons in the fourth level, we now go back and complete
the lling of the third level. Scandium (21 electrons) is (2, 8, 9, 2), titanium
(22 electrons) is (2, 8, 10, 2), and zinc (30 electrons) is (2, 8, 18, 2). The third
level is now completely lled and further electrons go into the fourth level. Gallium
(31 electrons) is (2, 8, 18, 3) and krypton (36 electrons) is (2, 8, 18, 8).
The sequence of feeding electrons into energy levels is shown in Figure 1.15(b).
Sometimes the term energy shells is used instead of energy levels. The two
terms have exactly the same meaning.
TABLE 1.9 Electron congurations for simple elements
Element
Atomic
number
a
Electron
conguration Element
Atomic
number
Electron
conguration
hydrogen 1 1 chlorine 17 2, 8, 7
helium 2 2 argon 18 2, 8, 8
lithium 3 2, 1 potassium 19 2, 8, 8, 1
beryllium 4 2, 2 calcium 20 2, 8, 8, 2
boron 5 2, 3 scandium 21 2, 8, 9, 2
carbon 6 2, 4 titanium 22 2, 8, 10, 2
nitrogen 7 2, 5
oxygen 8 2, 6
uorine 9 2, 7 zinc 30 2, 8, 18, 2
neon 10 2, 8 gallium 31 2, 8, 18, 3
sodium 11 2, 8, 1 germanium 32 2, 8, 18, 4
magnesium 12 2, 8, 2
aluminium 13 2, 8, 3 bromine 35 2, 8, 18, 7
silicon 14 2, 8, 4 krypton 36 2, 8, 18, 8
phosphorus 15 2, 8, 5 rubidium 37 2, 8, 18, 8, 1
sulfur 16 2, 8, 6 strontium 38 2, 8, 18, 8, 2
a
number of electrons number of protons atomic number
1.19 STABLE ELECTRON CONFIGURATIONS
increasing atomic number, as in Table 1.9, we can make some deductions about
the relation between chemical reactivity and electron congurations.
First we notice that the so-called noble gases which (with a few minor
exceptions) undergo no chemical reactions correspond to completely lled or
semi-lled energy levels (semi-lled means lled to eight electrons). These gases
are helium, neon, argon, krypton (and xenon and radon which are not shown):
they are shaded pink in Table 1.9.
The electron congurations of these noble gases, then, must be extremely stable
ones as the substances having them have virtually no tendency to undergo chemical
reaction.
Our second major observation is that the so-called alkali metals, lithium,
sodium, potassium, rubidium (and caesium which is not shown in Table 1.9), which
all have very similar properties, all have electron congurations that have one more
electron (in the next energy level) than the nearby noble gases. These elements are
shaded yellow in Table 1.9.
The alkali metals all have similar chemical properties because they all tend to
lose one electron to obtain the electron conguration of the nearby noble gas.
A further observation is that the halogens, uorine, chlorine, bromine (and
iodine which is not shown in Table 1.9), which all have very similar properties, all
have one electron less than the nearby noble gases. These elements are shaded green
in Table 1.9.
The halogens have similar chemical properties because each tends to gain one
electron to obtain the electron conguration of the nearby noble gas.
From these and other similar observations we are able to make the following
generalisation:
All elements, except the noble gases, tend to undergo chemical reactions and to
form compounds in order to obtain the electron congurations of the nearby
noble gases.
A consequence of this general principle that atoms tend to become like the
nearby noble gases is that a group of elements that differ from their nearby noble
gases in the same way will have very similar chemical propertiesthey will form
a family of elements.
EXERCISES
20 Without consulting any table or diagram, give the electron conguration of the
following elements (atomic number in brackets): B (5), O (8), P (15), Ar (18), Ca (20),
Mn (25), Se (34), Kr (36), Rb (37).
21 Atoms cannot have the following electron congurations:
a (1, 3) c (2, 9, 2) *e (2, 8, 14, 1) *g (3, 8, 8, 2)
b (2, 7, 4) d (2, 18, 8, 2) *f (2, 8, 20, 4) *f *h (2, 8, 8, 4)
For each, give the reason why not. Assuming that the total number of electrons is
correct, suggest the correct electron conguration for each of these elements.
Because of this tendency of atoms to gain or lose electrons to obtain noble gas
congurations, it is the electrons in the highest energy level (outermost energy shell)
that are most important in determining properties and reactivities of the elements.
We give these electrons a special name.
The electrons in the incompletely lled highest energy level (outermost energy
shell) are called valence electrons. The outermost energy level is called the
valence shell.
Since the noble gases have their highest energy levels lled or semi-lled to the
stable conguration (8), we consider that they have no valence electrons.
We have just seen that there are families of elements that have the same number
of valence electrons and similar properties. These families correspond to groups
of the Periodic Table as described in Section 1.17. This strongly suggests that the
layout of elements in the Periodic Table must be related to electron conguration.
1.20 THE PERIODIC TABLE AND ELECTRON
CONFIGURATION
Now that we have looked at electron congurations we can describe the Periodic
Table somewhat differently from how it was described in Section 1.17.
The Periodic Table is a chart in which the elements are listed in order of
increasing atomic number, with elements having similar electron congurations
(and therefore similar chemical properties) arranged to fall vertically underneath
one another. Having similar electron congurations means showing similar
relationships to the nearby noble gases.
A typical Periodic Table is shown on p. 372. The noble gases, helium, neon, argon,
krypton, xenon and radon, fall in a vertical column at the extreme right of the table.
Those elements that have one electron fewer than these gases are the halogens
uorine, chlorine, bromine and iodine; they fall in a column just to the left of the
noble gases. The elements with one electron more than the noble gases are the alkali
metalslithium, sodium, potassium, rubidium and caesium; they fall in a column at
the extreme left of the table.
The transition elements or transition metals (Section 1.17) arise from converting
a semi-lled level to a completely lled level (8 to 18 electrons). The sequence,
scandium to zinc, is our rst transition series.
Hydrogen is often placed a little separate from the other elements in the
Periodic Table because its chemical properties are quite different from those of
members of any of the groups in the table. This arises because hydrogen can form
stable electron congurations both by losing an electron to become a bare proton
or hydrogen ion, H
+
, and by gaining an electron to become like helium. It is the
only element with this option and therefore has unique properties.
The relationship between the layout of the Periodic Table and the lling of
electron energy levels (shells) for the rst four periods of the table is shown in
Figure 1.16.
Valence electrons and position in the
Periodic Table
Because of the way the Periodic Table has been constructed:
elements in the same group have the same number of valence electrons
the number of valence electrons is equal to the group number (if the groups are labelled
as in this book).
Oxygen (2, 6) and sulfur (2, 8, 6) have six valence electrons; selenium and
tellurium are in the same group, so they also have six valence electrons. Arsenic,
antimony and bismuth are in the same group as nitrogen (2, 5) and phosphorus
(2, 8, 5), so they also have ve valence electrons.
These are very useful observations because they mean we do not have to work
out the full electron conguration of an atom in order to determine how many
valence electrons it has.
The Periodic Table is a basic tool of chemistry. Chemists always have it
readily available and frequently refer to it because they can deduce much useful
information about any particular element just by noting its position in the table.
FIGURE 1.16
The relationship between
the Periodic Table and
the sequence of lling
electron energy levels
EXERCISES
22 Give the electron conguration of N (atomic number 7), Al (13), S (16), and Ca (20).
For each of these elements decide whether the atoms tend to gain or lose electrons
in reactions, and if so how many.
23 Underline the valence electrons in the congurations you wrote in Exercise 20.
Answer Exercise 24 without consulting a Periodic Table.
24 a Magnesium has two valence electrons; strontium and barium belong to the
same group. How many valence electrons do strontium and barium have?
b Carbon (atomic number 6), germanium and lead are all in the same group.
How many valence electrons do they each have?
atom (p. 169)
atomic number, (Z atomic number, ( atomic number, ( ) (p. 179)
atomic weight (p. 182)
changes of state (p. 163)
chemical change (p. 183)
chemical properties (p. 184)
chemical reaction (p. 183)
compound (p. 167)
decanting (decantation) (p. 172)
diatomic molecule (p. 171)
discrete energy levels (p. 188)
distillate (p. 173)
distillation (p. 173)
electron (p. 178)
electron cloud (p. 178)
electron conguration (p. 188)
element (p. 167)
energy shells (p. 189)
evaporate to dryness (p. 172)
ltrate (p. 172)
ltration (p. 172)
formulae (p. 170)
fractional distillation (p. 174)
groups (p. 186)
homogeneous (p. 166)
heterogeneous (p. 166)
immiscible (p. 175)
impure substance (p. 166)
isotope (p. 180)
main-group elements (p. 186)
mass number, (A mass number, ( mass number, ( ) (p. 179)
metals (p. 185)
miscible (p. 175)
mixture (p. 166)
molecule (p. 169)
neutron (p. 178)
noble gases (p. 190)
non-metals (p. 185)
nucleus (p. 177)
Periodic Table (p. 186)
periods (p. 186)
physical change (p. 183)
physical properties (p. 184)
products (p. 184)
proton (p. 178)
pure substances (p. 167)
reactants (p. 184)
relative atomic mass (p. 182)
sedimentation (p. 172)
semi-metals (p. 186)
separating funnel (p. 175)
sieving (p. 172)
solute (p. 176)
solution (p. 176)
solvent (p. 176)
states of matter (p. 163)
suspension (p. 176)
symbols (p. 170)
transition elements (metals ) (p. 186)
transition series (p. 191)
valence electrons (p. 191)
valence shell (p. 191)
vaporising (p. 172)
IMPORTANT NEW TERMS
You should know the meaning of the following terms:
25 Using the Periodic Table, how many valence electrons do the following elements
have:
a tin (Sn) b iodine (I) c caesium (Cs) d indium (In)?
Explain your reasoning.
26 The electron congurations of some elements are A (2, 7), B (2, 8, 8, 2), C (2, 5),
D (2, 8, 18, 8, 1), E (2, 8, 8). What conguration would you expect each of these
elements to tend towards when they undergo chemical reaction? Which, if any,
of these elements would you expect to be unreactive? Why?

TEST YOURSELF
1
above.
2 What names do we give to the following changes of state: solid to liquid, liquid
to gas, liquid to solid, gas to liquid?
3 Name four substances that are homogeneous and four that are heterogeneous.
4 Name four substances that are mixtures and four which are compounds.
5 List ten elements for which the symbol is just the capital of the rst letter of the
name.
6 Give three elements and their symbols for which the symbol is two letters starting
with:
a B b C c N.
7 Why do we say oxygen gas is O
2
and not just O?
8 List four gaseous elements that exist as diatomic molecules and give their
formulae.
9 What mixtures can you separate by sieving? Upon which physical property does
sieving depend?
10 Explain how sedimentation and decanting can be used to separate a mixture:
give a specic example.
11 Describe one specic example of using the procedure of evaporating to dryness
to separate one substance out of a mixture.
12 How would you separate two liquids having boiling points of:
a 88C and 175C respectively and b 110C and 122C respectively.
Draw the apparatus you would use for a.
13 Explain how you would separate two solids if one was soluble in water while the
other was insoluble. Give full details and include a diagram.
14 How would you separate a mixture of cooking oil and water? Name and draw
the apparatus you would use.
15 Describe the structure of an atom. What are the main particles that make up an
atom? Where is virtually all the mass located? What occupies most of the volume
of an atom?
16 Why do we use the term electron cloud in describing an atom?
17 Describe the relative mass and charge of protons, neutrons and electrons.
18 What particles are present in the nucleus of an atom?
19 A neutral carbon has an atomic number of 6 and a mass number of 12. How many
protons, neutrons and electrons does it have?
20 A uorine atom consists of nine protons, ten neutrons and nine electrons. What is
its mass number and atomic number?
21 How do atoms of one element differ from atoms of other elements?
22 How do isotopes of the one element differ from each other?
23 Krypton atoms are seven times as heavy as carbon atoms. What is the atomic
weight of krypton?
24 Describe four physical changes and four chemical changes.
25 List ve observations that can be used to decide whether a change is a chemical
or physical one.
26 How do you distinguish between metals and non-metals?
27 Where do non-metals appear in the Periodic Table? Where do the semi-metals
appear?
28 Where in the Periodic Table would you nd:
a the noble gases b the alkali metals c the halogens?
29 Do all electrons within the one atom have the same amount of energy? Explain.
30 What is the maximum number of electrons which can exist in each of the rst,
second, third and fourth energy levels?
31 Give the electron congurations of Li, C, Ne, Mg, Al, Cl and S.
32 What common feature is there about the electron congurations of:
a the noble gases (He, Ne, Ar, Kr, Xe, Rn)
b the alkali metals (Li, Na, K, Rb, Cs)
c the halogens (F, Cl, Br, I)
33 What is the driving force behind chemical reactivity? (That is, when atoms react
what stable states are they trying to achieve?)
34 What principles are used in drawing up the Periodic Table of elements?
35 In the Periodic Table, what name is given to
a the vertical columns of elements
b the horizontal rows of elements?
36 Why are we particularly interested in valence electrons?
37 How can you determine the number of valence electrons in an atom without
working out its full electron conguration?
CHAPTER 2
Mainly about compounds
Formation of ions
Ionic bonding and the Periodic Table
Covalent bonding
Covalency and the Periodic Table
Electron-dot structures for ions
Properties of covalent molecular and ionic substances
Covalent network solids
Metallic bonding
Properties of solids summarised
Formulae and names of ionic compounds
Formulae and names of binary covalent compounds
Equations for chemical reactions
IN THIS CHAPTER
196
We have seen that there is a huge number of compounds in the world around us
and that they have a wide range of different properties. To try to see why there are
so many compounds and why they have the properties they do, we shall now look
at the structure of compoundsthat is, at how elements are joined together to form
compounds. This general topic is called chemical bonding.
We shall also look at how to write formulae for compounds and how to name
them and nally at how to write chemical equations.
2.1 FORMATION OF IONS
The formation of ions and the ionic bonding that it leads to are best explained by
considering a specic example.
Sodium chloride
Sodium and chlorine combine to form the compound, sodium chloride.
The sodium atom, with electron conguration (2, 8, 1) (see Table 1.9 on
p. 189), has a tendency to lose one electron to become like neon (2, 8); the chlorine
atom, with electron conguration (2, 8, 7), tends to gain one electron to become
like argon (2, 8, 8). Hence one electron is transferred from a sodium atom to
a chlorine atom. When the neutral sodium atom loses one electron it becomes
positively charged: we call it a positive ion. When the neutral chlorine atom gains an
electron, it becomes negatively charged: it is a negative ion. We call it the chloride ion.
Schematically:
Na (2, 8, 1j
Cl (2, 8, 7j
1 electron
+
-
Na
+
(2, 8j
Cl
-
(2, 8, 8j
CHAPTER 2 MAINLY ABOUT COMPOUNDS 197
Ions are positively or negatively charged particles. The simplest ions form when
atoms lose or gain electrons (as with sodium and chlorine here).
There is strong electrostatic attraction between positive and negative ions. This
is what holds the ions together in ionic bonding. Sodium chloride is therefore NaCl
(one sodium atom per chlorine atom, because that is the way to balance charges).
Crystals of sodium chloride consist of sodium ions and chloride ions packed in
an orderly fashion. The electrostatic attraction between pairs of oppositely charged
ions extends throughout the whole crystal. This is shown in Figure 2.1. There are
no separate molecules of NaCljust an extremely large array of positive and negative ll
ions held tightly together.
Ionic bonding is that type of chemical bonding which involves the outright
transfer of electrons from one atom to another. The bonding consists of
electrostatic attraction between the positive and negative ions formed by this
transfer of electrons.
Note carefully that in ionic compounds there are no discrete moleculesjust an
innite array of positive and negative ions.
Meaning of the formula of an ionic
compound
For an ionic compound, the formula (for example NaCl) species the ratio in which
the atoms (or ions) are present, not the composition of discrete molecules. Such a
formula that gives the ratio by atoms of elements in a compound rather than the
actual numbers of atoms in a molecule is called an empirical formulae. Formulae
for ionic compounds are therefore always empirical formulae (because there are
no molecules).
Cations and anions
Positive ions are called cations. Negative ions are called anions.

FIGURE 2.1
Ionic substances consist
of orderly arrays of
positive and negative ions:
(a) a two-dimensional
array of ions,
(b) a portion of a sodium
chloride crystal
2.2 IONIC BONDING AND THE
PERIODIC TABLE
Elements that can attain noble gas electron congurations by losing or gaining one
or two electrons commonly form ions. This means that we can use the Periodic
Table to predict which elements will form ionsgenerally those that are only one
or two elements away from a noble gas. In particular:
1 Group 1 metals (Li, Na, K, Rb, Cs) all tend to lose one electron and therefore
form singly charged positive ions: Li
+
, Na
+
, K
+
, Rb
+
, Cs
+
.
2 Group 2 metals (Be, Mg, Ca, Sr, Ba) tend to lose two electrons and therefore
form doubly charged positive ions:
Be
2+
, Mg
2+
, Ca
2+
, Sr
2+
, Ba
2+
.
3 Group 7 elements (non-metals, F, Cl, Br and I) all tend to gain one electron and
therefore they form singly charged negative ions: F
, Cl
, Br
, I
.
4 Group 6 elements (non-metals, O, S, Se, Te) tend to gain two electrons and thus
form doubly charged negative ions: O
2
, S
2
, Se
2
, Te
2
.
However while Groups 1 and 2 form only ionic compounds, as we shall see below,
Groups 6 and 7 also form covalent compounds.
5 The transition metals all lose electrons to form positive ions (for example Cr transition metals all lose electrons to form positive ions transition metals all lose electrons to form positive ions
3+
, Fe
2+
,
Cu
2+
, Ag
+
, Zn
2+
), but it is not possible from a simple look at the Periodic Table to
predict just how many electrons any particular atom will lose.
6 Elements that are three places away from a noble gas may form ions: aluminium
generally does (Al
3+
), boron never does, nitrogen and phosphorus do so on rare
occasions.
Another generalisation is that metals generally form positive ions while non-metals
(when they form ions) form negative ions.
Beryllium is exceptional in that it forms some covalent compounds.
Remember that an asterisk in front of an exercise or part of an exercise means that no answer is provided.
EXERCISES
1 Show (in terms of electron congurations of the atoms involved and the ions
formed) how the following pairs of elements form ionic compounds. Deduce the
formulae of the compounds formed:
a potassium and uorine *c
sodium and oxygen

b calcium and bromine *d magnesium and oxygen
2 Explain why:
a potassium bromide is KBr and not K
2
Br or KBr
2
*b barium chloride is BaCl
2
and not Ba
2
Cl or BaCl
3
3 Which of the following elements would you expect to form positive ions and which
negative ions and which not form ions at all? What charge would you expect each
ion to carry? Si, Rb, I, Mg, S, Ga, K, C, Br, Ar, Se, B, P, Ba, Cs, F
4 a Give the electron conguration of the following atoms and ions, taking atomic
numbers from the Periodic Table if necessary:
i magnesium atom, magnesium ion *iii chlorine atom, chloride ion
ii sulfur atom, sulde ion *iv potassium atom, potassium ion
b What do you expect for the formula of each of the following compounds?
i magnesium sulde iii magnesium chloride
*ii potassium chloride *iv potassium oxide
CHAPTER 2 MAINLY ABOUT COMPOUNDS 199 CHAPTER 2 MAINLY ABOUT COMPOUNDS 199
2.3 COVALENT BONDING
Covalent bonds are formed between pairs of atoms by the atoms sharing electrons.
Again the nature of this type of bonding is best explained by considering specic
examples.
Chlorine gas
Two chlorine atoms combine to form a chlorine molecule.
A chlorine atom, with electron conguration (2, 8, 7) (see Table 1.9 on p. 189),
tends to gain one electron to acquire the conguration of argon (2, 8, 8). Two
chlorine atoms can combine to form a chlorine molecule, Cl
2
, by sharing a pair of
electrons with each atom contributing one electron to the shared pair. Each atom
considers that it owns the shared pair and thus counts both members of the pair
to determine that it has a noble gas conguration.
Cl (2, 8, 7) + Cl (2, 8, 7) Cl (2, 8, 6) + shared pair + Cl (2, 8, 6)
This shared pair of electrons occupies a volume of space that surrounds both
atoms. By moving around both nuclei these electrons hold the atoms together and so
form a chemical bond. This is illustrated in Figure 2.2. The rest of the electrons (that
is, the unshared ones) remain in volumes of space that surround one nucleus only.
Each chlorine atom in the chlorine molecule now considers that it has the
conguration (2, 8, 8) and is therefore satised. This bonding which results from
sharing pairs of electrons is called covalent bonding. Each pair of shared electrons
is called a covalent bond and is denoted by a dash. Molecular chlorine has the
structure:
ClCl
We call it a covalent molecule.
A common way of describing covalent bonding is to use what are called
electron-dot structures (or diagrams). These are symbols or formulae of elements
or compounds with the valence electrons (outer energy level electrons) shown as
dots. The electron-dot formula for the chlorine atom is:

(The completely lled rst and second main levelsthe 2, 8are ignored and
just the seven valence electrons are shown.) We can then denote the pairing up
of electrons by drawing:

which we write as ClCl (above).

A dash equals one shared (bonding pair) of electrons or one covalent bond.
FIGURE 2.2
In a covalent bond
the shared pair of
electrons occupies a
volume of space that
surrounds both nuclei
Water
Oxygen (2, 6) needs to gain two electrons to become like neon (2, 8) (see
Table 1.9 on p. 189). Hydrogen needs to gain one electron to become like helium.
Hence covalent bonds are formed between one oxygen atom and two hydrogen
atoms to form the covalent molecule water:

achieved the noble gas conguration (because each atom counts both electrons
in the shared pair).
The actual appearances of the two covalent molecules in these examples is
shown in Figure 2.3. While strong covalent bonds bind the atoms together within
each molecule, the molecules are able to move about more or less independently
of one another as described in Section 1.2.
Substances (elements or compounds) that are made up of simple covalent
molecules as in Figure 2.3 are called covalent molecular substances or sometimes
just molecular substances (to distinguish them from covalent lattices which will be
treated in Section 2.7).
2.4 COVALENCY AND THE PERIODIC TABLE
Covalent bonding occurs when both of the elements forming the compound need
to gain electrons to attain noble gas congurationsin the above two examples,
chlorine and chlorine, hydrogen and oxygen.
Elements in the centre and to the right of the Periodic Table tend to form
covalent compoundselements such as carbon, silicon, nitrogen, phosphorus,
oxygen, sulfur, uorine, chlorine (though the last four commonly form ionic
compounds also).
The number of covalent bonds an atom forms is the number of electrons that
an atom needs to gain to acquire a noble gas congurationone for hydrogen and
chlorine, two for oxygen (as in the above examples), three for nitrogen and four
for carbon.
The position of an element in the Periodic Table tells us how many electrons the
atom needs to gain to attain a noble gas conguration and so it tells us how many
covalent bonds the atom will form.
Nitrogen (Group 5) needs another three electrons so it forms three covalent
bonds (for example in ammonia, NH
3
). Carbon (Group 4) needs another four
electrons so it forms four covalent bonds (for example in methane CH
4
).
Refer to Context 2 Water, p. 42.

FIGURE 2.3
Simple covalent molecules
2.5 ELECTRON-DOT STRUCTURES FOR IONS
While electron-dot structures are particularly useful for describing the bonding in
covalent compounds, they can be used for ions as well. For example the chlorine
and sulfur atoms and the chloride and sulde ions would be:

The electron-dot structure for a simple metal ion will not have any dots
(for electrons) because these ions have no valence electrons:

of ions.
2.6 PROPERTIES OF COVALENT MOLECULAR
AND IONIC SUBSTANCES
Table 2.1 contrasts the common properties of covalent molecular and ionic
substances. Note that ionic substances are always compounds, whereas covalent
molecular substances can be elements (e.g. iodine, phosphorus and sulfur) as well
as compounds.
EXERCISES
5 Draw electron-dot diagrams and give molecular formulae for the covalent
molecules formed between:
a hydrogen and chlorine *c nitrogen and hydrogen
b two bromine atoms *d sulfur and uorine
6 Explain why:
a the compound formed between uorine and oxygen is F
2
O and not FO
2
or FO
*b ammonia is NH
3
and not NH
2
or NH
4
7 Decide the formula you would expect, and give your reasons, for the compound
formed between:
a sulfur and chlorine *c silicon and hydrogen
b hydrogen and iodine *d phosphorus and uorine
8 a Draw electron-dot structures for the bromide ion and the oxide ion.
*b In a very small number of compounds nitrogen exists as the nitride ion.
Draw an electron-dot structure for this ion.
c Draw electron-dot structures for barium and caesium atoms and the ions
they form.
TABLE 2.1 Contrasting properties of covalent molecular and ionic substances
Ionic substances Covalent molecular substances
solids at room temperature at room temperature, generally gases (N
2
,
SO
2
, NH
3
) or liquids (H
2
O, CCl
4
, methanol
CH
3
OH); a few are solids (I
2
, PCl
5
, CBr
4
)
high melting points (typically above 400C)
and high boiling points (typically over
1000C)
low melting points (generally below 200C)
and low boiling points (generally below
400C)
hard and brittle when solid they are soft
as solids they do not conduct electricity not not pure covalent substances do not conduct
electricity either as solids or as liquids electricity electricity
when molten or when in aqueous solution
they do conduct electricity.
in aqueous solution do not conduct
electricity (unless they actually react with electricity electricity
water to form ions)
These properties can be explained by the nature of the two types of bonding.
Properties of ionic substances
Melting an ionic solid means breaking up the orderly arrangement of ions shown in
Figure 2.1. As the electrostatic forces between ions are strong, much energy (and
therefore a high temperature) is needed to do this. Boiling an ionic substance means
producing a vapour that consists of well-separated ion pairs. This requires an even
greater amount of energy and so an even higher temperature is needed.
The strong electrostatic attraction between pairs of ions makes ionic substances
hard. If the orderly array of ions is disturbed by applying a strong force, then ions
of the same charge come close together as in Figure 2.4. They then repel each other
and this causes the crystal to shatter. This means that ionic crystals are brittle.
Solid ionic compounds do not conduct electricity because in the solid the ions
are tightly bound into an orderly array and so are unable to move towards a charged
electrode. However when ionic substances melt, the orderly arrangement of ions
is broken up and the ions can move about relatively freely. They can then migrate
towards a charged electrode; so molten ionic substances conduct electricity.
Similarly, when ionic substances are dissolved in water, the crystals are
completely broken up and the solutions consist of individual ions moving randomly
about through the water. These freely moving ions can migrate towards oppositely
charged electrodes; so solutions of ionic substances conduct electricity.

FIGURE 2.4
Ionic substances are
brittle because distorting
the crystal brings like
charges together and
they repel one another:
this causes the crystal
to break
Properties of covalent molecular substances
While the bonding forces holding atoms together within a covalent molecule are
very strong, the forces between one molecule and its neighbours are quite weak.
These weak forces between pairs of molecules are called intermolecular forces.
Their nature will be discussed in Sections 4.2, 4.3 and 4.4.
Figure 2.5 shows a sample of bromine liquid. There is a strong covalent bond
holding the two bromine atoms together within each bromine molecule, Br
2
. There
are only weak intermolecular forces (the dotted lines) between pairs of bromine
molecules.
Boiling involves separating molecules from one another. This means that boiling
overcomes intermolecular forces: it does not break any covalent bonds. Because the
intermolecular forces holding the bromine molecules to one another in the liquid
are weak, bromine has a relatively low boiling point of 58C; that is, not much
energy is required.
Similarly in solid bromine, the intermolecular forces holding the molecules
to one another are relatively weak (compared with covalent bonds). Melting just
involves disrupting the orderly arrangement of molecules; that is, melting, like
boiling, only overcomes weak intermolecular forces. Therefore bromine has a
relatively low melting point (7C).
Bromine is typical of all covalent molecular substances; there are only weak forces
holding the molecules to one another and so they have low melting and boiling
points.
However the strength of the intermolecular forces does vary from one molecular
compound to another. We nd that:
the stronger the intermolecular forces in molecular compounds, the higher are
the melting and boiling points.
Because these weak intermolecular forces are easily overcome, it is easy to
distort a solid covalent molecular substance. This means that such solids are soft.
Because covalent molecules are neutral species, they cannot conduct electricity
either as pure substances or in solution (for example iodine, sucrose or urea in
water). However, some covalent substances when mixed with water actually react
with the water and form ions; these solutions do conduct electricity. Examples
are hydrogen chloride and sulfuric and nitric acids which will be discussed in
Section 5.4.
In liquid bromine there

are weak intermolecular
forces (dotted lines)
between each bromine
molecule and its
neighbours. Boiling
overcomes these relatively
weak forces; it does not
break the strong covalent
bonds holding pairs of
bromine atoms together
as molecules
Other types of solids
solid, namely:
metals, and
covalent network solids (or covalent lattice solids or just covalent lattices).
2.7 COVALENT NETWORK SOLIDS
Covalent network solids are solids in which the covalent bonding extends
indenitely throughout the whole crystal.
Covalent network solids are sometimes called covalent lattice solids or just covalent
lattices.
The word lattice is used to mean an innite orderly array of particles. Ionic
solids are sometimes called ionic lattices.
Carbon in the form of diamond is an example of a covalent network solid.
As we expect from the Periodic Table, each carbon atom is covalently bonded to
four other atoms, and since we are talking about an element it can only be to four
other carbon atoms. This is shown in Figure 2.6: (a) is an exploded view of part
of the crystal, showing atoms as spheres and using lines to represent the covalent
bonds. The lines have no physical reality: in the actual diamond crystal the atoms
are overlapping one another. (b) is the structure chemists usually draw for diamond:
each dash or line represents a covalent bond. Literally billions of atoms are bonded
together in this way to form what we call a covalent network solid.
Silica (silicon dioxide or quartz, SiO
2
) is another example. From the Periodic
Table we see that silicon wants to form four covalent bonds while oxygen wants to
form two. Therefore in silica each silicon atom is covalently bonded to four oxygen
atoms, and each oxygen atom is bonded to two silicon atoms to form an innite
network of covalent bonds as shown in Figure 2.7.
As with ionic lattices (Section 2.1), the chemical formula for a covalent lattice
compound represents the ratio in which the atoms are present in the compound.
EXERCISES
9 Phosphorus trichloride is a liquid with a boiling point of 74C; it does not conduct
electricity. Calcium chloride is a solid with a melting point of 772C; when molten it
conducts electricity. Explain, in terms of bonding, why these two compounds have
such different properties.
10 The boiling points of the uorides of the elements of Period 2 of the Periodic Table
are: LiF (1720C), BeF
2
(1175C), BF
3
(101C), CF
4
(128C), NF
3
(120C),
OF
2
(145C) and F
2
(188C). Explain why the boiling points of lithium and
beryllium uorides are so much higher than the others.
11 Calcium and arsenic both form hydrides. Calcium hydride is a solid with a melting
point of 600C, while the hydride of arsenic, called arsine, is a gas at room
temperature.
a What do these facts imply about the bonding in the two compounds?
b What do you expect the formulae of these compounds to be?
Hence SiO
2
for quartz. Because this formula represents a ratio, it is an empirical
formula (Section 2.1).
When covalent lattices melt, the one big covalent crystal breaks up into many
smaller pieces, which are able to move about relative to one another. Hence melting
covalent lattices involves breaking many covalent bonds that are very strong. This
process requires a lot of energy and thus only occurs at high temperatures.
Covalent lattices Covalent Covalent have extremely high melting points, typically well above 1000C
(diamond > 3550C, silica 1700C).
Except for graphite covalent network solids do not conduct electricity. This is
because they do not contain any ions and all the electrons are tied up either being
held by individual atoms or being shared by pairs of atoms; none are free to roam
around as in metals (next section).
2.8 METALLIC BONDING
Metals, with the exception of mercury, are solids at room temperature. Most have
relatively high melting points and are fairly hard. They are all good conductors of
electricity. Properties of metals were described in Section 1.16 on p. 185.
These properties of metals arise because a metal consists of an orderly
three-dimensional array of positive ions held together by a mobile sea of
delocalised electrons. The valence electrons break away from their atoms, leaving
behind positive ions. These free electrons, called delocalised because they no longer
belong to particular atoms, move randomly through the lattice and, by being shared
FIGURE 2.6
The structure of diamond
FIGURE 2.7
The structure of silica,
SiO
2
. To its right an
aggregate of quartz
(silica) crystals.
by numerous positive ions, provide the chemical bonding that holds the crystal
together. This is shown in Figure 2.8.
It is the ability of these delocalised electrons to move freely through the lattice
that causes metals to be good conductors of electricity. Electric current through
a metallic wire is a ow of electrons.
Metals can be bent, rolled into sheets, and drawn into rods and wires. These
processes are possible because when the orderly array of positive ions is sheared,
the mobile electrons are able to adjust to the new arrangement of positive ions and
again provide the glue to hold the whole assembly together as shown in Figure 2.9.
This contrasts with ionic or covalent lattices; when these are sheared they shatter
(Figure 2.4).
Ionic and covalent lattices are hard but brittle. Metals (generally) are also hard
but by contrast they are malleable (able to be rolled into sheets) and ductile (able to
be drawn into wires).
2.9 PROPERTIES OF SOLIDS SUMMARISED
The common types of solids and the properties generally used to identify them are
summarised in Table 2.2.
Note that the key physical properties for distinguishing between types of solids
are melting points, electrical conductivity, hardness, malleability and ductility.
Malleability and ductility are sometimes jointly referred to as workability.

FIGURE 2.8
A metal is a three-
dimensional lattice of
positive ions immersed
in a sea of delocalised
electrons. For clarity just a
two-dimensional slice is
shown here
FIGURE 2.9
The mobile electrons are
able to hold the positive
ions of metals together
even when the metal is
distorted. This explains
the malleability and
ductility of metals

TABLE 2.2 Types of solids and their properties
Molecular
solids
Lattice solids
metallic ionic covalent network
a
covalent network covalent network
melting and boiling
points
low variable high high
conduct electricity? no yes as solid, no
molten, yes
no
hardness and/or
workability
soft variable hardness;
malleable and ductile
hard and brittle hard and brittle
forces holding particles
together in the solid
intermolecular delocalised electrons
(metallic bonding)
electrostatic covalent bonding
throughout the crystal
a
sometimes called covalent lattice solids
EXERCISES
12 Silicon carbide, SiC, is a covalent lattice. Draw its structure. How does this explain
why it is widely used as an abrasive (carborundum)?
13 Silicon dioxide and carbon dioxide have similar formulae, SiO
2
and CO
2
, yet one is
an extremely hard solid while the other is a gas at room temperature. Explain why
they are so different.
14 The melting points and electrical conductivities of seven elements are as follows:
Element A B C D E F G
Melting point (C) 113 650 3550 1280 2030 1083 44
Conductivity
a
10
20
23 10
17
29 10
10
58 10
15
a
of a 1 metre cube in megohm
1
a Which elements are metals?
b Which elements are made up of discrete small covalent molecules?
c Which elements are covalent lattices?
d Explain why each of these three classes of elements has the properties given in
the table.
15 Melting points, densities and electrical conductivities of the Group 4 elements are
given in the table below. What conclusions can you draw about the bonding in
these elements? Give your reasons.
Element C Si Ge Sn Pb
Melting point (C) 3550 1410 937 232 327
Density (g/mL) 3.51 2.33 5.32 7.30 11.4
Conductivity
a
10
17
10
9
10
3
8.5 4.8
a
of a 1 metre cube in megohm
1

2.10 FORMULAE AND NAMES FOR
COMPOUNDS
As we have already seen, there is a huge number of compounds in existence. It
would be impractical to have to memorise formulae for all of these. What we need
is a system in which the name of a compound lets us work out its formula, and
the formula of a compound allows us to write down its name. This avoids much
confusion and minimises memory work.
For writing formulae and names different rules apply for ionic and covalent
compounds, so we have to take each in turn.
2.11 FORMULAE FOR IONIC COMPOUNDS
We saw in Section 2.2 that for many elements we can deduce the charge on the ions
they form from their position in the Periodic Table. This cannot be done for other
elements such as lead and tin and the transition metals, particularly as most of these
can form ions of more than one charge type (e.g. Fe
2+
and Fe
3+
). The ions formed
by the common elements are therefore summarised in Table 2.3, opposite. We need
to memorise these charges so that we can write formulae of ionic compounds.
Remember (from Section 2.1) that positive ions are called cations, and negative
ions are called anions.
To write the formula for an ionic compound we use the basic principle that such
compounds are overall neutral. This means that:
When ionic compounds are formed, the ions are present in ratios such that
the total number of positive charges is equal to the total number of negative
charges.
Sodium chloride is NaCl, one positive charge with one negative charge. In
magnesium chloride we need two singly charged Cl
ions to balance the double
charge on magnesium, Mg
2+
. Hence magnesium chloride is MgCl
2
. In general:
To determine the values of x and xx y in the formula yy A
x
AA B
y
of an ionic compound, we
choose the smallest values of x and xx y that make yy
x (magnitude of charge on A) = y (magnitude of charge on B) (2.1)
Aluminium oxide contains the ions Al
3+
and O
2
. If we write the formula as
Al
x
O
y
then
yy
x 3 = xx y 2 yy
Therefore x = 2 and xx y = 3, giving the formula Al yy
2
O
3
.
A term which is commonly used in these contexts is valence.
Valence or valency
The valence or valency of an element is a number that measures the combining
power of the element when it forms compounds.
When an element forms ionic compounds, the valence of the element is the
charge that the ion of the element carries.
Valencies of the common elements forming ionic compounds are shown in
Table 2.3.
2.12 NAMING IONIC COMPOUNDS
All the compounds in the previous section consist of two elements only. They are
called binary compounds.
Ionic binary compounds are named by giving the positive ion rst, then the negative
ion; the positive ion has the same name as the element (sodium, calcium), while
for the negative ion the ending of the element name is changed to -ide as shown in ide ide
Table 2.4. Hence sodium chloride, magnesium oxide, and potassium sulde.
TABLE 2.4 Names of negative ions formed from single atoms
Element Negative ion formed Example
Cl chlorine Cl
chloride ZnCl
2
zinc chloride
Br bromine Br
bromide AgBr silver bromide

I iodine I
iodide MgI
2
magnesium iodide
O oxygen O
2
oxide CaO calcium oxide
S sulfur S
2
sulde K
2
S potassium sulde
H hydrogen H
hydride LiH lithium hydride

TABLE 2.3 Ions formed by common elements
Charge Valence
one type of ion only +1 Group 1
a
(Li
+
, Na
+
, K
+
, Rb
+
, Cs
+
), Ag
+
+1
+2 Group 2
a
(Be
2+
, Mg
2+
, Ca
2+
, Sr
2+
, Ba
2+
), Zn
2+
+2
+3 Al
3+
+3
1 Group 7
a
(F
, Cl
, Br
, I
1
2 Group 6
a
(O
2
, S
2
)
2 2
2
more than one type of ion +1 and 1 H
+
and H
+1 and 1
+1 Cu
+
+1
+2 Cu
2+
, Fe
2+
, Pb
2+
, Sn
2+
+2
+3 Fe
3+
+3
+4 Pb
4+
, Sn
4+
+4
a
of the Periodic Table
For those metals which display variable valencies (Table 2.3), the valence of the
metal in the compound being named is indicated either by:
1 putting the valence as a capital Roman numeral in brackets after the
name of the metal, as in iron(II) chloride, FeCl
2
; iron(III) chloride, FeCl
3
;
copper(I) oxide, Cu
2
O; copper(II) oxide, CuO; or
2 using special endings: -ous for the lower valence state, and -ic for the higher ic ic
valence statesometimes with a Latinised name for the metal. Hence cuprous
sulde, Cu
2
S; cupric sulde, CuS; ferrous chloride, FeCl
2
; ferric chloride,
FeCl
3
.
The rst method (using Roman numerals) is preferred.
Compounds of copper(I) and lead(IV) are fairly rare. Hence chemists
frequently drop the (II) when writing compounds of copper and lead with a valence
of 2. We frequently see copper sulfate instead of copper(II) sulfate and lead iodide
instead of lead(II) iodide. If the valence is not given we always assume it is the more
common valence. On the other hand, Cu
2
S and PbO
2
must always be written as
copper(I) sulde and lead(IV) oxide.
When both valencies are equally common, as with iron, we must always include
the valence in the nameiron(II) chloride, iron(III) oxide.
2.13 IONS THAT ARE NOT MONATOMIC
So far all the ions considered have been monatomic. We need to include some other
ions that commonly occur. These are shown in Table 2.5.
Although made up of two or more atoms, each of these ions acts as a separate
entity when it forms compounds. Sodium sulfate Na
2
SO
4
is two Na
+
ions and one
SO
4
2
ion: the S and O atoms do not split up. Ions such as OH
2 2
are called
diatomic
ions while ions such as SO
4
2
are called
2 2
polyatomic ions (because they consist of
three or more atoms).
TABLE 2.5 Some common polyatomic ions and their charges
Name of the ion Formula Valency Example
ammonium NH
4
+
+1 ammonium sulde, (NH
4
)
2
S
hydroxide OH
1 calcium hydroxide, Ca(OH)

2
nitrate NO
3
1 potassium nitrate, KNO

3
sulfate SO
4
2
2 sodium sulfate, Na
2
SO
4
carbonate CO
3
2
2 calcium carbonate, CaCO
3
phosphate PO
4
3
3 sodium phosphate, Na
3
PO
4
Formulae for compounds involving these ions are written in the same way
as for monatomic ions (using Equation 2.1). For example calcium phosphate is
Ca
3
(PO
4
)
2
because 3 2 = 2 3.
2.14 FORMULAE FOR COVALENT
COMPOUNDS
As with ionic compounds, the valence or valency of an element in a covalent
compound is a measure of its combining power. It is the number of covalent bonds
that the element can form. As explained in Sections 2.3 and 2.4, this can generally
be deduced from position in the Periodic Table. However, several elements can
display more than one valence in covalent compounds. Valencies shown by common
elements in covalent compounds are therefore summarised in Table 2.6 on the
next page.
We need to memorise the usual valencies of the common elements so we can
work out the formulae of the binary compounds they form.
To determine the values of x and xx y in the formula yy A
x
AA B
y
of a covalent compound, we
choose the smallest values for x and xx y that make yy
x valence of A = y valence of B (2.2)
EXERCISES
16 Write the formulae for the following ionic compounds:
a potassium bromide e lithium sulde *i tin(II) bromide
b zinc oxide *f barium chloride *j copper(I) sulde
c sodium oxide g aluminium uoride *k lead(IV) chloride *k
d calcium hydride *h lead uoride *l iron(III) oxide
17 Name the compounds, CaH
2
, Li
2
S, AlBr
3
, *ZnO, *CuCl
2
, *Ag
2
S.
18 Give the formulae of:
a sodium nitrate c potassium phosphate *e iron(III) hydroxide
b lithium carbonate *d zinc nitrate *f ammonium carbonate
19 Give the names of:
a ZnSO
4
c Fe(OH)
2
*e Sn(NO
3
)
2
b (NH
4
)
2
CO
3
d Al(NO
3
)
3
*f Fe
2
(SO
4
)
3
20 For each of the ionic compounds in the following lists:
a State the valence of the element, M.
i MCl
2
iii M
2
O
3
v MH
2
*vii M
2
O
ii M
2
S iv MS
2
*vi MF
4
*viii MBr
3
b State the valence of the element, X.
i CaX iii AlX
3
v Ag
2
X *vii Fe
2
X
3
ii Na
2
X iv AlX *vi ZnX
2
*viii SnX
4
TABLE 2.6 Valencies of common elements in covalent compounds
Fixed valencies Variable valencies
1 H, F, Cl
a
, Br
a
, I
a
2 S
2 O
b
3 N
d
, P
4 C
c
, Si 4 S
5 N
d
, P
6 S
a
except in some compounds with O or with H and O where these three elements can have valencies
greater than 1
b
except in H
2
except in H except in H O
2
and a few other compounds where it is 1
c
except in carbon monoxide where it is 2
d
in compounds with O, N can display valencies of 1, 2 and 4 as well
dd
When phosphorus reacts with oxygen, two compounds are possible: one in
which phosphorus has a valence of 3 and the other in which phosphorus has a
valence of 5. For the rst compound the formula is P
2
O
3
, because:
2 3 = 3 2
valence of P valence of O
2.15 NAMING COVALENT BINARY
COMPOUNDS
In covalent compounds many elements show variable valencies (Table 2.6), so an
indication of valency is needed in the names of compounds. We therefore name
covalent compounds differently from ionic ones.
To name covalent binary compounds:
Use the normal element name for the rst element and an -ide name for the ide ide
second, for example hydrogen sulde and phosphorus trichloride.
The rst element named is the one which occurs further to the left in the
Periodic Table (nitrogen dioxide, boron triuoride).
If both elements occur in the same group, the one lower down the group is
named rst (sulfur dioxide, bromine chloride).
An exception to the above two rules is that oxygen is named last in compounds
with Cl, Br and I (chlorine monoxide, Cl
2
O, iodine pentoxide, I
2
O
5
)
The number of atoms of each type is given by using the prexes mono-,
di-, tri-, tetra-, penta-, hexa-, in front of each part of the name (though
mono- is usually omitted from the rst-named element and occasionally other
prexes are omitted from it also).
Some examples will illustrate:
CO carbon monoxide
CO
2
carbon dioxide
NO
2
nitrogen dioxide
N
2
O
5
dinitrogen pentoxide
SCl
2
sulfur dichloride
SF
6
sulfur hexauoride
P
2
O
5
phosphorus pentoxide (more correctly diphosphorus pentoxide)
Cl
2
O chlorine monoxide (more correctly dichlorine monoxide)
Several non-metallic hydrides have special names: CH
4
, methane; NH
3
,
ammonia; H
2
O, water. Others are named in the systematic way: H
2
S, hydrogen
sulde (more correctly dihydrogen sulde); HF, hydrogen uoride (and similarly
HCl, HBr, HI).
Now that we have seen how to work out formulae for compounds, we can turn
to the matter of writing equations for chemical reactions.
2.16 EQUATIONS FOR CHEMICAL REACTIONS
Chemists use equations to describe what happens in chemical reactions. To start
with we write word equations. An example is:
Solid phosphorus reacts with yellow-green chlorine gas to form a colourless liquid,
phosphorus trichloride:
phosphorus + chlorine phosphorus trichloride
Phosphorus and chlorine are the reactants; phosphorus trichloride is the product.
Before we can write a word equation we need to know all the reactants and all
the products of the reaction.
We then convert word equations into symbolic equationsequations that
use symbols and formulae for the elements and compounds involved. Symbolic
equations are often just called chemical equations. To do this we need to know,
EXERCISES
21 Write the formulae for the following compounds:
a sulfur diuoride e sulfur dioxide
b nitrogen trichloride *f silicon tetrachloride
c carbon tetraiodide *g phosphorus pentabromide
d boron trichloride *h dinitrogen trioxide
22 Name the following compounds:
a SiCl
4
, CS
2
, N
2
O, Cl
3
N, H
2
S, *PBr
3
, *SiC
b P
2
O
5
, N
2
O
4
, Cl
2
O, F
2
O, *Cl
2
O
3
, *SO
3
, *S
2
F
2
23 Give the name and formula of the compound formed between:
a nitrogen and hydrogen *c hydrogen and iodine
b silicon and bromine *d phosphorus and bromine
(two compounds)

or be able to work out, the formulae of all the substances involved in the reaction.
For the phosphorus plus chlorine reaction the rst step is:
P + Cl
2
PCl
3
In chemical reactions mass is conserved and the number of each type of atom
involved is conserved also. This means that:
a chemical equation must have the same number of atoms of each element on
each side of the arrow.
We say that chemical equations must be balanced. To do this we put numbers in
front of the formulae until the number of atoms of each type on both sides of the
equation are equal:
2P + 3Cl
2
2PCl
3
The nal thing we need to include in our equation is the physical state for each
species present: (s) for solid, (l ) for liquid, (g ) for liquid, ( ) for liquid, ( ) for gas (and ( gg aq) for a substance
present in an aqueous solution):
2P(s) + 3Cl
2
(g (( ) gg 2PCl
3
(l )
This equation now reads, two atoms of solid phosphorus react with three
molecules of chlorine gas to form two molecules of liquid phosphorus trichloride.
This is called a balanced equation.
The numbers in front of the formulae or symbols are called the coefcients of
the equation (sometimes the stoichiometric coefcients).
Figure 2.10 shows a symbolic equation and what it means in terms of molecules.
The steps for writing a chemical equation are summarised below.
HOW TO WRITE A BALANCED CHEMICAL EQUATION
1 Write a word equation that includes all reactants and products all all
2 Write the formulae for all substances involved (to make an unbalanced equation).
3 Balance the equation by putting numbers in front of symbols or formulae. Start with
elements that occur in one place only on each side of the equation.
4 Add symbols for the physical states, (s states, ( states, ( ), (l ), ( ), ( ), ( ll g ), ( ), ( ), (aq ), ( ), ( ).
Step 1 may be omitted when you have gained more experience.

The equation for the
reaction between
hydrogen and chlorine to
form hydrogen chloride
EXERCISES
24 Write word equations and symbolic equations that convey the same information
as the following statements:
a Two molecules of gaseous ethane, each of which contains two carbon and
six hydrogen atoms, react with seven molecules of gaseous oxygen, each
containing two oxygen atoms, to form four molecules of carbon dioxide gas,
each containing one carbon atom and two oxygen atoms, and six molecules
of liquid water (H
2
O).
*b One molecule of dinitrogen pentoxide gas, which contains two nitrogen atoms
and ve oxygen atoms, reacts with one molecule of liquid water to form two
molecules of aqueous nitric acid, each containing one hydrogen, one nitrogen
and three oxygen atoms.
25 Write in words all the information conveyed by each of the following equations
(in a similar style to that used in Exercise 24):
a C
4
H
8
( g) + 6O
2
( g) 4CO
2
( g) + 4H
2
O(l O( O( ) (C
4
H
8
is called butene.)
*b Fe
2
O
3
(s (( ) + 3CO( g) 2Fe(s 2Fe( 2Fe( ) + 3CO
2
( g)
26 a The equation for combustion of butane, the fuel in handy-pack fuel cans, is:
2C
4
H
10
(g (( ) + 9O
2
(g (( ) 8CO
2
(g (( ) + 10H
2
O(g O( O( )
b The equation for the reaction between potassium permanganate, hydrogen
peroxide and sulfuric acid is shown in Figure 1.14 on p. 183:
2KMnO
4
(aq (( ) + 5H
2
O
2
(aq (( ) + 3H
2
SO
4
(aq (( )
K
2
SO
4
(aq (( ) + 2MnSO
4
(aq (( ) + 5O
2
(g (( ) + 8H
2
O(l O( O( ) ll
For each of these equations, how many atoms of each type are there on each side
of the arrow? Are these equations balanced? Explain why or why not.

anions (p. 197)
balanced equations (p. 214)
binary compounds (p. 209)
cations (p. 197)
chemical bond (p. 199)
chemical equations (p. 213)
coefcents (of an equation) (p. 214)
covalent bonds (p. 199)
covalent molecular substances (p. 200)
covalent molecule (p. 199)
covalent lattices (solids) (p. 204)
covalent network solids (p. 204)
delocalised electrons (p. 205)
diatomic ions (p. 210)
electron-dot diagrams (structures)
(p. 199)
empirical formulae (p. 197)
intermolecular forces (p. 203)
ionic bonding (p. 197)
ionic lattices (p. 204)
ions (p. 197)
lattice (p. 204)
metallic bonding (p. 205)
polyatomic ions (p. 210)
stoichiometric coefcients (p. 214)
symbolic equations (p. 213)
valence (valency) (p. 209)
word equations (p. 213)
IMPORTANT NEW TERMS
TEST YOURSELF
1
2 When atoms combine to form compounds, what electron congurations do they
strive to achieve? In what two general ways do they do this?
3 Give two examples to illustrate formation of ions.
4 What holds ions together in ionic compounds? Why do they say there are no
molecules in ionic compounds?
5 Give two examples of covalent bonding.
6 Draw electron-dot diagrams for hydrogen chloride and water.
7 What type of compound, ionic or covalent, does carbon always form?
8 What type of compound, ionic or covalent, is usually formed by:
a alkali metals (Group 1) c halogens
b alkaline earth metals (Group 2) d oxygen and sulfur?
9 Give three common properties of ionic compounds.
10 How do melting points and boiling points of covalent compounds compare with
those of ionic compounds? Explain why.
11 Based on structure we can divide pure solids into four classes. What are they?
12 Draw a structure of one covalent network solid; give its name and empirical
formula.
13 Give three properties of covalent lattices that are consequences of the chemical
bonding involved.
14 Draw a diagram to illustrate metallic bonding.
15 What properties of a metal are a direct consequence of this type of bonding?
16 Complete the following table, using the terms given below the table. If any property
is inapplicable, put a dash.
17 What is the basic rule for working out the formula of an ionic compound?
18 What is the formula of (and the charge carried by) the ammonium, hydroxide,
sulfate, carbonate, nitrate and phosphate ions?
19 Which elements generally have xed valencies in covalent compounds and what
are they? Name three important elements that show variable valencies and state
what their common valencies are.
Substance
Physical state
a
(at 25C)
Melting
point
b
Electrical conductance
c
Pure In aqueous solution Hardness
d
Example
ionic lattice
covalent molecule
metallic lattice
covalent lattice
a
solid, liquid or gas
b
low, high, very high
c
zero, low, high
d
of the solid if applicable: hard or soft
dd
20 What is the basic rule for working out the formula of a covalent compound?
21 In naming covalent binary compounds, how do we decide which element is
named rst?
22 In naming covalent compounds, what prexes do we use to denote 1, 2, 3, 4, 5,
6 atoms of a particular type?
23 What do we mean by conservation of atoms in a chemical reaction?
24 What qualitative and quantitative information does the following chemical equation
tell you?
N
2
(g (( ) + 3H
2
(g (( ) 2NH
3
(g (( )
25 State in words the complete information conveyed by the chemical equation in
Figure 2.10.
26 What is wrong with the following equation?
2AgNO
3
(s (( ) Ag
2
O(s O( O( ) + 2NO
2
(g (( ) + O
2
(g (( )
CHAPTER 3
Calculations involving chemical
formulae and equations
Relative molecular mass
(molecular weight)
Relative formula mass (formula weight)
The mole
Moles of gaseous elements
Converting between mass, moles and numbers of atoms
or molecules
Per cent composition
Moles and chemical equations
Mass calculations from chemical equations
IN THIS CHAPTER
218
It is important to keep track of the quantities of materials used in various reactions
and processes to ensure waste is minimised. Chemical formulae and chemical
equations allow us to calculate the amounts of reactants and products involved
in various chemical reactions. The study of quantative aspects of formulae and
equations is called stoichiometry. The calculations involved are called stoichiometric
calculations.
In Section 1.14 on p. 181 we saw that atoms of different elements had different
masses, and a measure of those masses was introduced there, the relative atomic
mass (atomic weight). There is a similar term to express the mass of compounds.
3.1 RELATIVE MOLECULAR MASS
(MOLECULAR WEIGHT)
While we talk about relative atomic masses of elements, for compounds we refer
instead to relative molecular masses.
The relative molecular mass (or molecular weight) of a compound is the mass
of a molecule of the compound relative to the mass of an atom of the carbon-12
isotope taken as exactly 12.
It follows then that:
The molecular weight of a compound is the sum of the atomic weights of the
atoms as given in the molecular formula.
In this book the shorter name, molecular weight, will generally be used instead
of the more correct but longer name, relative molecular mass.
CHAPTER 3 CALCULATIONS INVOLVING CHEMICAL FORMULAE AND EQUATIONS 219
Using the Periodic Table:
the molecular weight of water, H
2
O, is 2 1 + 16 = 18
the molecular weight of nitrogen dioxide, NO
2
, is 14 + 2 16 = 46 and
the molecular weight of sulfuric acid, H
2
SO
4
, is 2 1 + 32 + 4 16 = 98.
Again, the molecular weight is not the mass of a molecule: it is a pure number
that merely expresses the relative mass of the moleculerelative to the mass of the
carbon atom.
We generally use atomic weights rounded off to one decimal place, except for
hydrogen where we start with two, though the answer can only have one decimal
place.
3.2 RELATIVE FORMULA MASS
(FORMULA WEIGHT)
As we saw in Chapter 2, many compounds, particularly ionic ones, do not exist as
discrete molecules. Instead they exist as an orderly array of ions or atoms bound
tightly to one another with no recognisable molecules (Figs 2.1, 2.6, 2.7 on pp. 197
and 205). We still use chemical formulae for these compounds, but instead of
representing the composition of discrete molecules, these formulae describe the
ratios in which the elements are present in the compounds. Sodium chloride is a
typical example: we cannot recognise any discrete NaCl molecules. The formula
NaCl instead tells us that in this compound, sodium and chlorine atoms are present
in the ratio 1:1. Similarly, in calcium uoride, CaF
2
, there are no discrete CaF
2
molecules; instead the formula tells us that throughout the sample of calcium
uoride there are two uorine atoms for every calcium atom present. For such
compounds, it is more correct to talk about the relative formula mass (or formula
weight) instead of the molecular weight.
The relative formula mass (or formula weight) of a compound is the sum of
the atomic weights of the atomic species as given in the stated formula of the
compound.
Again using the Periodic Table:
the formula weight of sodium chloride, NaCl, is 23.0 + 35.5 = 56.5
the formula weight of calcium uoride, CaF
2
, is 40 + 2 19 = 78.
EXAMPLE 1
Calculate the molecular weight of table sugar, sucrose, which has the formula
C
12
H
22
O
11
.
Molecular weight = 12 A
C
+ 22 A
H
+ 11 A
O
(where A is the atomic weight of the indicated element)
= 12 12.0 + 22 1.01 + 11 16.0
(taking atomic weights from page 371)
= 342.2
Formula weight is sometimes called molecular weight. While you are urged to
use the more correct term, you should not be unduly worried about the loose use
of molecular weight in many textbooks.
3.3 THE MOLE
Eventually chemists were able to measure the mass of individual atoms and
molecules. It was found that the mass of the carbon atom was 1.99 10
23
grams.
Expressed differently, there are 6.02 10
23
atoms in 12 grams of carbon.
Now if 6.02 10
23
atoms of carbon have a mass of 12 grams, then for
titanium (atomic weight 48), 6.02 10
23
atoms (each of which is four times
as heavy as a carbon atom) must have a mass of 4 12 = 48 grams. For sulfur
6.02 10
23
atoms (each of which is 32/12 = 2.67 times the mass of a carbon
atom) must have a mass of 2.67 12 = 32 grams. In general:
If for If If any element we take the mass which in grams is numerically equal to the
atomic weight, then it contains 6.02 10
23
atoms.
63.6 grams of copper contain 6.02 10
23
atoms. 108 grams of silver contain
6.02 10
23
atoms.
EXAMPLE 2
Calculate the formula weight of calcium phosphate, Ca
3
(PO
4
)
2
, commonly called rock
phosphate and used to make superphosphate fertiliser.
Formula weight = 3 A
Ca
+ 2 (A + 2 ( + 2 (
P
+ 4 A
O
)
(where As are atomic weights)
= 3 40.1 + 2 (31.0 + 4 16.0)
(taking atomic weights from the table on page 371)
= 310.3
Note carefully that the subscript 2 refers to everything inside the brackets.
EXERCISE
1 Calculate the molecular weight (or formula weight) of:
a potassium bromide, KBr i ammonium nitrate, NH
4
NO
3
b carbon dioxide, CO
2
j glucose, C
6
H
12
O
6
c magnesium chloride, MgCl
2
k calcium hydroxide, Ca(OH) k
2
d sodium sulde, Na
2
S l copper nitrate, Cu(NO
3
)
2
e iron(III) oxide, Fe
2
O
3
m ammonium sulfate, (NH
4
)
2
SO
4
f diphosphorus pentoxide, P
2
O
5
n aluminium sulfate, Al
2
(SO
4
)
3
g calcium sulfate, CaSO
4
o sodium carbonate decahydrate,
h sodium carbonate, Na
2
CO
3
Na
2
CO
3
.10H
2
O

CHAPTER 3 CALCULATIONS INVOLVING CHEMICAL FORMULAE AND EQUATIONS 221 CHAPTER 3 CALCULATIONS INVOLVING CHEMICAL FORMULAE AND EQUATIONS 221
The argument also extends to compounds. The molecular weight of water
is 18. This means a water molecule is 1.5 times the mass of a carbon atom.
Hence 6.02 10
23
molecules of water must have a mass of 1.5 times the mass
of 6.02 10
23
atoms of carbon, that is 1.5 12 = 18 grams.
If for If If any compound we take the mass which in grams is numerically equal to the
molecular weight, then it contains 6.02 10
23
molecules.
46 grams of nitrogen dioxide, NO
2
, contain 6.02 10
23
molecules. 98 grams
of sulfuric acid, H
2
SO
4
, contain 6.02 10
23
molecules. 342 grams of sucrose,
C
12
H
22
O
11
, contain 6.02 10
23
molecules.
We call this quantitythis 6.02 10
23
atoms or moleculesa mole. To dene
terms:
A mole of a substance is that quantity which contains as many elementary units
(e.g. atoms, ions or molecules) as there are atoms in exactly 12 grams of the
carbon-12 isotope.
The Avogadro constant (for which we use the symbol N
A
NN
AA
) is the number of
AA
atoms in exactly 12 grams of the carbon-12 isotope.
N
A
NN = 6.02 10
AA
23
particles per mole
It follows then that the Avogadro constant is the number of atoms or molecules
in a mole of any substance.
A mole of an element is the mass that in grams is numerically equal to the atomic
weight. A mole of a compound is the mass that in grams is numerically equal to
the molecular weight.
Stated less precisely, a mole of a substance is simply the atomic or molecular
weight in grams. A mole of copper (atomic weight 63.6) is 63.6 grams. A mole
of nitrogen dioxide (molecular weight 46) is 46 grams.
Figure 3.1 shows a mole of each of several common substances.
FIGURE 3.1
A mole of each of
left) sulfur (32.1 g), zinc
(65.4 g), copper sulfate
pentahydrate (249.7 g),
mercury(II) oxide
(216.6 g), sodium chloride
(58.5 g), carbon (12.0 g)
and, in the centre, copper
(63.6 g) and ethanol
(46.0 g)
A mole of silver (atomic weight 108) is 6.02 10
23
atoms of silver or 108
grams of silver. A mole of sucrose (molecular weight 342) is 6.02 10
23
molecules
of sucrose or 342 grams of sucrose.
The accepted abbreviation for mole is mol, as in 3.9 mol of zinc or 4.3 10
3
mol of carbon. The word molecule is always written in full (to avoid any
confusion).
A commonly used term is molar mass.
The molar mass is the mass of a mole of the substance. It can be used for both
elements and compounds.
Molar mass has unitsmass per mole, most commonly grams per mole, usually
written as g mol
1
or g/mol. The molar mass of copper is 63.6 g/mol. The molar
mass of nitrogen dioxide is 46 g/mol.
3.4 MOLES OF GASEOUS ELEMENTS
When we talk about a mole of oxygen (atomic weight 16), do we mean 16 grams
or 32 grams? (Oxygen gas is O
2
with a molecular weight of 32.) This highlights
another factor involved in using moles. Sometimes to avoid ambiguity we need to
specify which elementary units (atoms, ions or molecules) we are talking about.
A mole of oxygen atoms is quite clearly 16 grams. A mole of oxygen molecules
is 32 grams. This mole of oxygen molecules contains 2 moles of oxygen atoms
because each molecule of oxygen contains two atoms. Similarly, a mole of chlorine
gas (that is molecules) is 2 35.5 = 71 grams, whereas a mole of chlorine atoms
is 35.5 grams.
3.5 CONVERTING BETWEEN MASS,
MOLES AND NUMBERS OF ATOMS
OR MOLECULES
We often need to calculate the number of moles present in a given mass of a
substance (element or compound). At other times we want to calculate the number
of atoms or molecules in a sample. Even if our nal goal is the number of atoms or
molecules, we must rst convert mass to number of moles and then go on to atoms
or molecules.
Mass to moles
The key equation for converting mass into number of moles
is:
Number of moles =
mass
_______________

mass of one mole

=
mass
__________
molar mass

}
(3.1)
=
mass

________________________________

atomic or molecular weight in grams

Schematically:
Moles to number of atoms or molecules
To convert number of moles to number of atoms or molecules we use the Avogadro
constant:
number of atoms of of aattoommss uu bbee of of aattoo of of aattoommss
or molecules
mmss
=
number of nu nu ber of ber of
moles
ber of ber of
the Avogadro Avogadro Avogadro

Avogadro Avogadro
constant
Avogadro Avogadro
(3.2)
Again schematically:
To go from mass to number of atoms or molecules (or vice versa) we need to
go through number of moles; that is, we have to use both Equations 3.1 and 3.2.
Schematically:
Some examples will illustrate the use of these important equations.
Strictly speaking we should use amount of substance ( amount of substance amount of substance in moles) instead of number of moles, because
mass in grams divided by molar mass in grams per mole gives the answer in moles. A number should
not have any units. However, number of moles makes the meaning quite clear and is easier to say and
write, so it will be used throughout this book, despite its lack of precision.

EXAMPLE 3
How many atoms are there in a pure copper coin weighing 2.56 g? The atomic weight
of copper is 63.6.
From Equation 3.1:
Number of moles of copper =
2.56
_____
63.6

= 0.0403 mol
Now from Equation 3.2:
Number of atoms of copper = 0.0403 6.02 10
23
= 2.43 10
22
EXAMPLE 4
What is the mass of 10
12
molecules of sulfur dioxide, SO
2
(a pollutant formed when
copper is extracted from sulde ores)?
First we need to convert from number of molecules to number of moles (using the
Avogadro constant and Equation 3.2), then we can use Equation 3.1 to calculate the
mass.
Number of moles =
10
12
____________

6.02 10
23

= 1.66 10
12
Molar mass of SO
2
= 32.1 + 2 16.0 = 64.1 g/mol
Mass of SO
2
= 1.66 10
12
64.1
= 1.1 10
10
g
= 0.11 ng (ng = nanogram = 10
9
g)
EXERCISES
2 How many moles are there in:
a 13 g zinc c 15 g sulfur
b 0.50 g gold d 5.0 kg iron
3 What is the mass of:
a 3.0 mol copper b 0.044 mol sulfur c 2.3 10
3
mol magnesium?
4 How many atoms are there in each of (a) to (d) of Exercise 2?
5 Calculate the mass of one atom of:
a zinc b gold c helium
6 A one carat diamond (pure carbon) weighs 0.10 g. How many atoms does it
contain?
7 Using results from Exercise 1, calculate the number of moles in 20 g of:
a sodium sulde b diphosphorus pentoxide c copper nitrate
8 Use your results for Exercise 1 to calculate the mass of:
a 0.037 mol calcium sulfate b 6.5 10
4
mol ammonium nitrate
3.6 PER CENT COMPOSITION
The chemical formula of a compound tells us directly the ratios in which the atoms
are present. In aluminium oxide, Al
2
O
3
, the Al and O atoms are present in the
ratio 2:3. In sulfuric acid, H
2
SO
4
, the H, S, O atoms are present in the ratio 2:1:4.
Sometimes we need to know the ratio by mass in which the elements are present,
that is the per cent composition by weight.
Knowing the per cent composition, an industrialist can determine how much
aluminium can be extracted from a tonne of aluminium oxide, or a farmer can
decide which of several fertilisers contains the most nitrogen per kilogram of
compound.
Calculating per cent composition from
a chemical formula
The method of calculating per cent composition from a chemical formula is best
illustrated by an example.
9 How many molecules are there in 10 g of:
a chlorine gas, Cl
2
b phosphorus pentachloride, PCl
5
c nitric acid, HNO
3
?
10 What is the mass of:
a 5.18 mol nitrogen gas
b 0.082 mol argon gas
c 6.24 10
2
mol hydrogen gas?
11 How many molecules are there in 7.0 g of nitrogen gas, N
2
? How many nitrogen
atoms are there in this sample?
12 Consider 0.374 g aluminium chloride, AlCl
3
. It contains how many moles of:
a aluminium chloride b aluminium c chlorine?
EXAMPLE 5
Calculate the percentage of iron in the common ore, haematite, Fe
2
O
3
. Atomic weights
are Fe, 55.9 and O, 16.0.
One mole of Fe
2
O
3
is 2 55.9 + 3 16 g = 159.8 g.
One formula unit of Fe
2
O
3
contains two atoms of iron. Hence one mole of Fe
2
O
3
contains 2 moles of iron. Two moles of iron is 2 55.9 g = 111.8 g. Hence 159.8 g
Fe
2
O
3
contains 111.8 g Fe.
Fraction of Fe
2
O
3
which is Fe =
111.8
______
159.8

= 0.700
% iron in Fe
2
O
3
= 70.0%
This example illustrates the general method for calculating per cent
composition:
% A in a compound =
mass of A in 1 mole of the compound mass of A in 1 mole of the compound mass of A in 1 mole of the compound
_________________________________
mass of A in 1 mole of the compound mass of A in 1 mole of the compound
mass of one mole of the compound
mass of A in 1 mole of the compound mass of A in 1 mole of the compound
100
or more specically,
in the compound of formula A
w
B
y
C
z
:
%A =
w (atomic weight of A) 100

______________________________

molecular weight of A
w
B
y
C
z
(3.3)
3.7 MOLES AND CHEMICAL EQUATIONS
We have already seen that the chemical equation:
4P(s) + 5O
2
( g) gg 2P
2
O
5
(s) (3.4)
tells us that:
1 qualitatively, solid phosphorus reacts with oxygen gas to form solid
diphosphorus pentoxide
2 four atoms of phosphorus react with ve molecules of oxygen to form two
molecules of diphosphorus pentoxide
Because atoms and molecules have such small masses, we usually have to work with
very large numbers of them in order to have masses that we can conveniently weigh
in the laboratory. Since Statement 2 above is true, then multiplying through by the
Avogadro constant we can say:
3 four moles of phosphorus react with ve moles of oxygen to form two moles of
diphosphorus pentoxide.
That is, chemical equations can be read in terms of moles as well as in terms of
atoms and molecules.
EXERCISES
13 a Calculate the percentage of sulfur in sodium sulfate, Na
2
SO
4
.
b Calculate the percentage of barium in barium hydroxide, Ba(OH)
2
.
14 Calculate the percentage of each element in:
a silver nitrate, AgNO
3
b ammonium phosphate, (NH
4
)
3
PO
4
15 Calculate the percentage of nitrogen in:
a ammonium sulfate, (NH
4
)
2
SO
4
b urea, CH
4
ON
2
Both of these compounds are used as nitrogen fertilisers. Which is better on a yield
of nitrogen per gram of fertiliser basis?
16 The explosive, TNT, has the molecular formula, C
7
H
5
N
3
O
6
. Calculate the
percentage of nitrogen in the compound.

Equations in terms of masses
We can convert a moles statement about an equation into a mass statement. We saw
above that Equation 3.4 can be read as:
Four moles of phosphorus react with ve moles of oxygen to form two moles of
diphosphorus pentoxide.
Using the fact that a mole is the atomic or molecular weight in grams, we can
convert this moles statement into a grams one:
4 31.0 grams of phosphorus react with 5 32.0 grams of oxygen to form
2 (2 31.0 + 5 16) grams of diphosphorus pentoxide.
That is, 124.0 g P react with 160.0 g O
2
to form 284.0 g P
2
O
5
.
A chemical equation tells us the ratios by mass in which substances react or are
formed in a reaction.
EXAMPLE 6
a How many moles of oxygen are needed to react with 1 mole of aluminium
(to form Al
2
O
3
)?
First we need a balanced equation:
4Al(s 4Al( 4Al( ) + 3O
2
( g) 2Al
2
O
3
(s (( )
From this equation we see that 4 moles of Al react with 3 moles of O
2
, so we can
write:

number of moles of O
2
required

_____________________________

number of moles of Al given
=
_____________________________ _____________________________
3
__
4

So number of moles of O
2
required = 0.75 mol (for 1 mol Al)
b Acetylene burns with oxygen (in oxyacetylene torches for cutting and welding
metals) to form carbon dioxide and water. How many moles of CO
2
are formed
when
i 1 mol ii 0.25 mol acetylene burns?
The balanced equation is:
2C
2
H
2
( g) + 5O
2
( g) 4CO
2
( g) + 2H
2
O(l O( O( )
From this equation:

number of moles of CO
2
formed

_____________________________

number of moles of C
2
H
2
used
=
_____________________________ _____________________________
4
__
2

In i number of moles CO
2
formed =
4
__
2
1
__ __
= 2 mol O
2
In ii number of moles CO
2
formed =
4
__
2
0.25
__ __
= 0.5 mol O
2
If we wish to calculate the mass of diphosphorus pentoxide formed from 0.25 g
phosphorus, we rst write the equation (3.4 above), then say:
4 moles of P 2 moles of P
2
O
5
or writing it another way:
number of moles of P
2
O
5
produced

_______________________________

number of moles of P used
=
_______________________________ _______________________________
2
__
= =
4

mass of P used = 0.25 g
number of moles of P used =
0.25
____
number of moles of P used = number of moles of P used =
31.0

= 0.0081
number of moles of P
2
O
5
produced =
2
__
produced = produced =
4
0.0081
__ __
= 0.0040
mass of P
2
O
5
produced = 0.0040 (2 31.0 + 5 16.0)
= 0.57 g
That is, 0.25 g P produces 0.57 g P
2
O
5
.
3.8 MASS CALCULATIONS FROM CHEMICAL
EQUATIONS
The basic ideas explained above for the phosphorusoxygen reaction can be used
to calculate:
1 the mass of one reactant needed to react completely with a given mass of
another reactant, or
2 the mass of a product that can be formed from a given mass of a reactant.
EXAMPLE 7
The rst step in extracting magnesium from one of its ores, magnesite (magnesium
carbonate), is to dissolve the ore in hydrochloric acid. Calculate the mass of
hydrochloric acid needed to dissolve 5.0 g of magnesium carbonate.
First we write the equation in skeletal form:
MgCO
3
+ HCl MgCl
2
+ CO
2
+ H
2
O
Then we balance it:
MgCO
3
(s (( ) + 2HCl(aq ) + 2HCl( ) + 2HCl( ) MgCl
2
(aq (( ) + CO
2
( g) + H
2
O(l O( O( ) ll
From the balanced equation one mole MgCO
3
reacts with 2 moles HCl,
or expressed differently:

number of moles of HCl required

_______________________________

number of moles of MgCO
3
given
=
_______________________________ _______________________________
2
__
1
(3.5)
That is, number of moles HCl required = 2 (number of moles of MgCO
3
given)
An example will illustrate.
This method of doing what we call massmass calculations is summarised
in the box below and shown schematically in Figure 3.3. It is illustrated again in
Example 8.
HOW TO PERFORM A MASSMASS CALCULATION
1 Write a balanced chemical equation.
2 Calculate the number of moles of the given substance (from Equation 3.1).
3 Use the chemical equation to write an expression for:
number of moles of required substance number number

____________________________________

number of moles of given substance number number
This is simply equal to the ratio of the stoichiometric coefcients in the equation as
shown in Examples 7 and 8.
4 Use this ratio to calculate the number of moles of the required substance number of number of .
5 Calculate the mass of the required substance mass of the required mass of the required from rearranged Equation 3.1.
Hence we need to calculate the number of moles of magnesium carbonate given.
To do this we rst want:
Molar mass of MgCO
3
= 24.3 + 12.0 + 3 16.0
= 84.3 g/mol
From Equation 3.1:
number of moles of MgCO
3
given =
5.0 g
______
84.3 g

= 0.059
number of moles of HCl needed = 2 0.059
= 0.118
As Equation 3.1 can be rearranged to:
mass = number of moles mass of one mole (3.6)
mass of HCl = 0.118 (1.01 + 35.5)
= 4.3 g
That is, we need 4.3 g HCl to react completely with 5.0 g MgCO
3
.
mass of the given substance
mass of the required substance
number of moles of
given substance
number of moles of the
required substance
divide by its
multiply by its
molar mass
molar mass
use the chemical equation
FIGURE 3.3
Steps for a massmass
calculation involving a
chemical reaction
EXAMPLE 8
Calculate the amount of iron needed to react with oxygen to produce 3.5 grams of
iron(III) oxide, Fe
2
O
3
. The equation is:
4Fe(s 4Fe( 4Fe( ) + 3O
2
( g) 2Fe
2
O
3
(s (( )
Step 1: The equation is given.
Step 2: no. of moles of iron oxide produced =
mass of iron(III) oxide

_________________________

molar mass of iron(III) oxide

=
3.5 g

_____________________

(2 55.9 + 3 16.0)

=
3.5
______
159.8

= 0.0219
Step 3:

number of moles of iron needed

_________________________________

number of moles of Fe
2
O
3
produced
=
_________________________________ _________________________________
4
__
2

Step 4: number of moles of iron needed =
4
__
2
0.0219
__ __
= 0.0438
Step 5: mass of iron required = 0.0438 55.9
= 2.5 g
EXERCISES
17 a Ethane (C
2
H
6
, a minor constituent of natural gas) burns in oxygen to form
carbon dioxide (CO
2
) and water. How many moles of oxygen are needed to
react with one mole of ethane? How many moles of:
i CO
2
ii water
are produced?
b Octane (C
8
H
18
, a constituent of petrol) burns in air to form CO
2
and H
2
O.
How many moles of oxygen are needed to react with 10 moles of octane and
how many moles of water are produced?
18 a Nitrogen and hydrogen combine to form ammonia, NH
3
. How many moles of
hydrogen are needed to form 40 moles of ammonia?
b Sulfur dioxide, SO
2
, reacts with oxygen to form sulfur trioxide, SO
3
. How many
moles of oxygen are needed to form 0.6 mole of sulfur trioxide?
19 a What mass of zinc is formed when 0.2 mole zinc oxide reacts with excess
carbon?
b What mass of magnesium hydroxide, Mg(OH)
2
, is precipitated from solution
when excess sodium hydroxide is added to a solution containing 0.050 mol
magnesium ion? This reaction can be used to extract magnesium from sea
water.
20 Calcium carbonate, CaCO
3
, when heated decomposes to calcium oxide (CaO) and
carbon dioxide. Calculate the mass of calcium oxide formed when 2.0 g calcium
carbonate is decomposed.
21 What mass of hydrogen gas is produced when 1.3 g zinc reacts with excess
hydrochloric acid, HCl? How much zinc chloride, ZnCl
2
, is produced?
22 Sodium reacts with water to form hydrogen and sodium hydroxide solution.
What mass of water is decomposed by 1.32 g sodium and what mass of hydrogen
is formed?
23 The rst step in extracting aluminium oxide from bauxite is to dissolve it in sodium
hydroxide solution. The reaction is:
Al
2
O
3
(s (( ) + 2NaOH(aq ) + 2NaOH( ) + 2NaOH( ) + 3H
2
O(l O( O( ) ll 2Al(OH)
4
(aq (( ) + 2Na
+
(aq (( )
What mass of sodium hydroxide is needed to react with 12.7 g aluminium oxide?
24 To extract copper from cuprite, Cu
2
S, the ore is roasted in air: copper and sulfur
dioxide form. What mass of sulfur dioxide is produced per tonne of copper by this
reaction?

Avogadro constant (p. 221)
formula weight (p. 219)
massmass calculations (p. 229)
molar mass (p. 222)
mole (p. 221)
molecular weight (p. 218)
per cent composition (p. 225)
relative formula mass (p. 219)
relative molecular mass (p. 218)
stoichiometry (p. 218)
stoichiometric calculations (p. 218)
IMPORTANT NEW TERMS
TEST YOURSELF
1 Explain the meaning of each of the items in the Important new terms section
above.
2 How is molecular weight of a compound calculated from atomic weight?
3 What is the difculty with using the term molecular weight for compounds such
as sodium chloride and magnesium oxide? What term should be used?
4 The atomic weight of copper is 63.6. What is the mass of a mole of copper?
5 How do you calculate the number of moles in a sample of a compound, given
its mass and molecular weight?
6 What is unclear about the phrase a mole of nitrogen?
7 How do you convert:
a a mass to a number of moles
b a number of moles to a number of molecules
c a mass to a number of molecules?
8 Explain how you would calculate the percentage of sulfur in aluminium sulfate,
Al
2
(SO
4
)
3
.
Refer to Context 3 Transport, p. 93.

CHAPTER 4
Intermolecular forces
Structure of water and other simple
compounds
Polar covalent bonds
Dipoledipole interactions
Hydrogen bonds
Predicting shapes of molecules
IN THIS CHAPTER
232
In Sections 2.3 and 2.4 we saw how atoms combine to form covalent molecules.
In Section 2.6 it was simply stated that there are forces of attraction between pairs
of molecules (Figure 2.5). In this chapter we shall look at the nature and strength of
these intermolecular forces, as they are called, largely because they strongly affect the
properties of water which in turn inuence the whole living world of which we are
a part. To do this we shall start with the structures of some simple molecules.
4.1 STRUCTURE OF WATER AND OTHER
SIMPLE COMPOUNDS
The water molecule has an oxygen atom covalently bonded to two hydrogen atoms;
the electron-dot structure is shown in Figure 4.1. Some other simple covalent
molecular compounds are ammonia, NH
3
, methane, CH
4
, and hydrogen sulde,
H
2
S. Their electron-dot structures are also shown in Figure 4.1. Remember that
the number of valence electrons on an atom is the group number from the Periodic
Table, meaning 5 for N, 4 for C and 6 for S. Hence there are covalent bonds to 3 H
atoms in ammonia, to 4 H atoms in methane and to 2 H atoms in hydrogen sulde
(to make up eight valence electrons around the central atom).
Electron-dot structures do not tell us anything about the shape of molecules;
they just tell us how valence electrons are arranged and how many covalent bonds
FIGURE 4.1
Electron-dot structures for
(a) water
(b) ammonia
(c) methane and
(d) hydrogen sulde
(aj
H H O
( j
H H
H
N
(Cj
H
H
H
H
C
(Dj
H H b
CHAPTER 4 INTERMOLECULAR FORCES 233
are formed. The four molecules in Figure 4.1 have the shapes shown in Figure 4.2.
By shape we mean the geometrical arrangement of atoms in the molecule. Water
and hydrogen sulde have a bent shape with the HOH and HSH angles
being about 110. Ammonia has a pyramidal shape and methane is tetrahedral.
The melting and boiling points of these four substances are shown in Table 4.1.
Methane, ammonia and hydrogen sulde are gases at room temperature, while water
is a liquid.
TABLE 4.1 Melting and boiling points for water, ammonia, methane and
hydrogen sulde
H
2
O NH
3
CH
4
H
2
S
Molecular weight 18 17 16 34
Melting point (C) 0 78 183 86
Boiling point (C) 100 33 162 60
Although water, ammonia and methane have similar molecular weights, they have
very different melting and boiling pointsmethane very low, ammonia quite low, and
water much higher. Hydrogen sulde has a higher molecular weight than water, so we
should expect it to have higher melting and boiling points but in fact they are much
lower.
Electron-dot structures do not explain the differing melting and boiling points
of these compounds, because as we saw in Section 2.6 melting and boiling points
depend upon the strength of intermolecular forces, not upon the strength of the
covalent bonds within the molecules.
Before considering intermolecular forces we need an understanding of what
are called polar covalent bonds.

FIGURE 4.2
Shapes of the water,
ammonia, methane
and hydrogen sulde
molecules
4.2 POLAR COVALENT BONDS
2
, Cl
2
and N
2
,
they are shared very evenly. However in many heteroatomic molecules such as
HCl, H
2
O and NH
3
, the electron pairs are unevenly shared: the electrons spend more
time near one nucleus than the other. In hydrogen chloride, HCl, the shared pair
of electrons spends more of its time near the chlorine atom than near the hydrogen
atom. This means that the chlorine end of the molecule is slightly negative (more
electrons on average around it than protons in the nucleus), while the hydrogen end
is slightly positive. We write this as:
+
H Cl

where (delta) means small amount of . These delta charges are much smaller
than whole electron or proton charges.
Covalent bonds Covalent Covalent in which the electrons are unequally shared are called polar
covalent bonds.
The HCl bond above is a polar covalent bond. Similarly, the HF, HBr,
HI bonds are polar as are the OH, NH and SH bonds.
A pair of equal and opposite charges separated in space as in the HCl molecule
is called a dipole. Polar molecules are molecules that have a net dipole.
Diatomic molecules that have a polar covalent bond are polar molecules.
However for polyatomic molecules (more than two atoms), the presence of polar
covalent bonds does not guarantee that the molecule will be polar. This is because
two or more dipoles in the one molecule may cancel each other out. The shape of
the molecule determines whether dipoles cancel out or add up to give a net dipole.
The two
OH
+
polar bonds in water combine to give a net dipole as shown
in Figure 4.3. Similarly the three polar
NH
+
bonds in ammonia combine
to give a net dipole (also in Figure 4.3). This makes water and ammonia polar
molecules. In hydrogen sulde also, the two polar bonds combine to produce
a polar molecule.
Sometimes the shape of the molecule is such that the individual dipoles cancel
out. Boron triuoride, BF
3
, is a at moleculeit has what is called a trigonal
planar shape: the three bonds are at angles of 120 to one another in the one plane
(Figure 4.3). Each bond is polar but the three cancel one another out, so that this
molecule is non-polar. Contrast the effect of this planar shape with ammonias
pyramidal (non-planar) shape.
In the tetrahedrally shaped methane molecule, each of the four CH bonds
is slightly polar, but when they combine together, they cancel one another out.
This means that methane is a non-polar molecule.

FIGURE 4.3
Dipoles add up in water
and ammonia but cancel
out in boron triuoride and
in methane. The arrows
point from the positive end
to the negative end of the
dipoles.
CHAPTER 4 INTERMOLECULAR FORCES 235 CHAPTER 4 INTERMOLECULAR FORCES 235
A particular covalent bond between two atoms will be polar if one atom has
a greater electron-attracting power than the other. Electron-attracting power is
measured by a property called electronegativity: electronegativity increases from
left to right across the Periodic Table and decreases from top to bottom. For the
common elements the order in decreasing electronegativity is:
F > O > N Cl > Br > C S I > P H > Si (4.1)
Common polar bonds are therefore HO, HN, CO and CCl, with the
rst-named atom in each bond being the positive end. Some non-polar bonds are
NCl, CS and PH. The CH bond is very slightly polar, but for all practical
purposes we regard it as non-polar.
In summary, to decide whether a particular molecule is polar or not:
use electronegativities to decide whether it contains any polar bond(s), then
use the shape of the molecule to decide whether the polar bonds cancel out
(to produce a non-polar molecule) or combine to produce a net dipole
(polar molecule).
Whether a molecule is polar or not affects the strength of intermolecular forces.
4.3 DIPOLEDIPOLE FORCES
Because polar molecules have positive and negative ends, they are able to line
up so that the positive end of one molecule attracts the negative end of another
molecule as in Figure 4.4. Therefore electrostatic attraction holds the molecules to
one another more strongly than would be the case for non-polar molecules. These
electrostatic attractions are called dipoledipole forces.
Dipoledipole forces are present in hydrogen sulde, ammonia and water but
not in (non-polar) methane. Hence intermolecular forces are stronger in the rst
three substances than in methane, and so those rst three compounds have higher
melting and boiling points than does methane.
There are intermolecular forces in methanejust as there were in bromine
(also non-polar) in Section 2.6 (Figure 2.5). They are called dispersion forces.
Dispersion forces are weak intermolecular forces that are always present
between pairs of molecules. They arise from the attraction of the nucleus of
one molecule for the electron cloud of a neighbouring molecule. This attraction
is opposed by the repulsion between the electron clouds of the neighbouring
molecules, so the force of the attraction is quite small. However, the strength of
the dispersion forces does increase as the number of electrons in the electron cloud
increases (which is also as the number of positive charges on the nuclei increases,
because the molecules are electrically neutral). This means that:
dispersion forces increase as molecular weight increases
This shows up most clearly in the molecular elements chlorine (gas, molecular
weight 71), bromine (liquid, molecular weight 160) and iodine (solid, molecular
weight 254). It is also the reason why boiling points of alkanes (Chapter 6) increase
as molecular weight increases.

FIGURE 4.4
Dipoledipole forces in
polar covalent substances.
intermolecular forces such as dipoledipole forces are also present. The combination
of dipoledipole forces plus dispersion forces is stronger than dispersion forces alone
would be in that substance.
However, these dipoledipole forces plus dispersion forces do not explain why
the higher molecular weight hydrogen sulde has lower melting and boiling points
than do water and ammonia.
This is because there is another type of intermolecular force involved in water
and ammonia, called hydrogen bonding.
provided.
4.4 HYDROGEN BONDS
The third and strongest type of intermolecular force is what is called a
hydrogen bond.
A hydrogen bond is a type of intermolecular force that involves a hydrogen atom
bonded to an O, N or F atom in one molecule becoming attached to an
O, N or F atom in a different molecule.
Water and ammonia display hydrogen bonding as shown in Figure 4.5.
EXERCISES
1 Draw electron-dot diagrams and give molecular formulae for the covalent
molecules formed between:
a hydrogen and bromine *c
oxygen and uorine

b phosphorus and hydrogen *d carbon and bromine
2 Using Relationship 4.1 if necessary, indicate what partial charges (if any) you would
expect in the following covalent bonds:
FO, ClO, NCl, NH, SH, CS, *CO, *PO, *PCl, *CH, *CCl.
3 a Which of the molecules in Exercise 1 contain polar bonds? Show the direction
of the dipole (by drawing an arrow pointing towards the negative end) of each
bond that is polar. State whether the molecule has a net dipole and, if so, show
its direction (again with an arrow). The shapes of the molecules are
(a) linear, (b) pyramidal, (c) bent, (d) tetrahedral.
b Do the same for the following molecules. The shapes of the molecules which
are not diatomic are given in brackets.
i molecular chlorine *v nitrogen trichloride (pyramidal)
ii boron trichloride (trigonal planar) *vi iodine chloride
iii silicon tetrachloride (tetrahedral) *vii phosphorus tribromide (pyramidal)
iv sulfur diuoride (bent) *viii trichloromethane, CHCl
3
(tetrahedral)
4 The gases helium, neon and hydrogen all have boiling points below 180C, while
the gases sulfur dioxide, hydrogen iodide and dichlorodiuoromethane, CCl
2
F
2
, all
have boiling points between 0C and 50C.
a What do you conclude about the relative strengths of the intermolecular forces
(if any) in the two groups of gases?
b If there are any intermolecular forces, what do you expect their nature to be?
O, N and F atoms have very strong electron-attracting powersthey are
the three most electronegative elements (Relationship 4.1). This means that the
bonding electrons in OH, NH and FH bonds are strongly attracted to the
O, N and F atoms respectively, giving those atoms signicant negative charges with
the H atom becoming positively charged. In addition, the small size of the H atom
means that two adjacent molecules can get close together: the positive H atom,
bonded to the O, N or F atom in one molecule, forms a strong attraction to an O, N
or F atom on the adjacent molecule and so there is a strong attractive intermolecular
force. This is shown schematically in Figure 4.6.
Hydrogen bonds are much stronger than ordinary dipoledipole forces. Their
relative strength arises from the facts that the hydrogen nucleus (a bare proton only)
is extremely small and that the F, O and N atoms are strongly electron-attracting.
The strength of a hydrogen bond is typically about one-tenth that of a normal
covalent bond.
Hydrogen bonding explains why water and ammonia in Table 4.1 have
much higher melting and boiling points than the much higher molecular weight
compound hydrogen sulde.
The effect of hydrogen bonding is illustrated in Figure 4.7. Normally when
we compare sets of similar compounds, we nd that boiling point increases as
we go down a group of the Periodic Table; that is, for similar compounds boiling
point increases as molecular weight increases. This is what we observe for the
hydrides of carbon, silicon, germanium and tin. However, for the hydrides of the
FIGURE 4.5
Hydrogen bonding in
water and ammonia.
Dashed lines are hydrogen
bonds, solid lines are
covalent bonds. The O
atom of a water molecule
can hydrogen bond to two
other molecules, though
for clarity this has been
shown for only one of
the molecules here.
FIGURE 4.6
The hydrogen bond
in more detail
nitrogen and oxygen groups, we nd that the boiling point of the lightest member
is anomalously high. This is due to hydrogen bonding.
While H
2
O and NH
3
are the classic examples of substances that display
hydrogen bonding, it also occurs in many other compounds in which hydrogen is
attached to O or N; some examples are hydrogen peroxide (H
2
O
2
), sulfuric acid
(H
2
SO
4
), methanol (CH
3
OH) and other alcohols, carbohydrates (sugars), amino
acids and proteins.
The relative strengths of the various intermolecular forces are summarised in
Table 4.2.
TABLE 4.2 Strengths of intermolecular forces in small molecules
a
(relative to a covalent bond arbitrarily set at 100)
hydrogen bond 10
dipoledipole forces plus dispersion forces 1 to 3
dispersion forces alone 0.1 to 1
(numbers are very approximatechosen to illustrate order of magnitude only)
a
When the total number of electrons becomes largesay over 100dispersion forces can be much
stronger than indicated here (e.g. in I
2
and C
16
H
34
).
Hydrogen bonding has explained the high melting and boiling points of water:
it is also the key to understanding many other properties of water.
Boiling points for hydrides

of Groups 4, 5 and 6
We saw in Section 4.2 that in order to predict whether or not a molecule is polar
we need to know its shape as well as the polarity of its bonds. Let us now turn to the
question of predicting shapes of molecules.
4.5 PREDICTING SHAPES OF MOLECULES
There are a variety of experimental techniques available for determining the shapes
of simple moleculesthat is, the geometrical arrangement of the atoms in the
molecules. By comparing these experimental shapes with electron-dot structures
chemists have deduced a very useful principle:
Pairs (or sets) of valence electrons around an atom in a molecule arrange
themselves spatially so as to get as far away from one another as possible,
and this determines the shape of the molecule.
EXERCISES
5 Use the data below to plot boiling point against period number of the Periodic Table
for each of the two series of compounds. Draw a curve or series of straight lines,
whichever is appropriate, through the points of each set. Identify any anomalous
compound, explaining why you think it is anomalous. Offer some explanation for
its behaviour.
CH
4
SiH
4
GeH
4
SnH
4
Compound HF HCl HBr HI
6 The table below presents melting points of hydrides from three groups of the
Periodic Table. On the one graph plot melting point against period number for each
set of compounds. Draw curves or series of straight lines through the points for
each set. Does this graph present any evidence for hydrogen bonding and, if so,
for which compounds? Explain fully.
Compound CH
4
SiH
4
GeH
4
SnH
4
Melting point (C) 183 185 165 150
Compound NH
3
PH
3
AsH
3
SbH
3
Compound H
2
O H
2
S H
2
Se H
2
Te
7 In which of the following pure liquids would you expect there to be hydrogen bonding?
a phosphorus trichloride d dichloromethane, CH
2
Cl
2
b hydroxylamine, HONH
2
e bromomethane, CH
3
Br
c tetrauoromethane, CF
4
f nitrous acid, HONO
For those with hydrogen bonding, draw diagrams which show it. (Include at least
three molecules.)
This is called the electron-pair repulsion theory. Sometimes it is more precisely
called the valence shell electron-pair repulsion theory. This is because only valence
electrons are involved in it.
Having the electron pairs (or sets) as far away from one another as possible is
the most stable ( most stable most stable or lowest energy) arrangement for the valence electrons around the
nucleus.
In beryllium chloride, BeCl
2
(which unlike most beryllium compounds is
covalent), there are only two pairs of electrons around the beryllium atom. The
most stable arrangement for two pairs of electrons is to be diametrically opposite
each other which gives rise to a linear molecule: linear linear

Boron trichloride, BCl
3
, has the following electron-dot structure:

It is an unusual molecule in that the B atom has only six electrons (three pairs)
around it instead of the normal eight (four pairs).
The most stable arrangement for three pairs of electrons is for them to be planar
and pointing to the corners of an equilateral triangle, that is, at an angle of 120 to each and pointing to the corners of an equilateral triangle, that is, at an angle of 120 and pointing to the corners of an equilateral triangle, that is, at an angle of 120
other. This explains why boron trichloride is planar. It is frequently called trigonal
planar.
In methane, there are four pairs of valence electrons around the carbon atom
(Figure 4.1); the most stable arrangement for these is for them to be pointing to
the corners of a tetrahedron which has the carbon atom at its centre:
Hence methane has a tetrahedral shape with each HCH angle being the normal tetrahedral tetrahedral
tetrahedral angle of 109.5.
Now, in ammonia, nitrogen also has four pairs of valence electrons around
it (Figure 4.1)the three bonding pairs and one other pair not used in bonding
which we call a lone pair. These four pairs of electrons, as in methane, point to the
corners of a tetrahedron. Three of these pairs have a hydrogen attached while the
fourth does not:
If we draw the shape dened by the four atoms, we have a pyramid. The existence
of the lone pair of electrons explains why ammonia, with three covalent bonds, has
a different shape from that of boron trichloride which also has three covalent bonds.
It is the total number of pairs of valence electrons which is the key factor in deciding shape.
In water, the oxygen atom also has four pairs of valence electrons around it
(Figure 4.1)two bonding pairs and two lone pairs. Again, these four pairs are
directed towards the corners of a tetrahedron, but only two of them have hydrogen
atoms attached:
If we draw the shape dened by the three atoms, we get a bent molecule. bent bent
The shapes just discussed are summarised in Table 4.3 and Figure 4.8.
Structures with ve and six electron pairs around a central atom are included for
completeness, though we shall not go into details here.
TABLE 4.3 Electron pairs and shapes of molecules
Total number
of electron
pairs (sets)
Arrangement
of electron
pairs (sets)
Bonding
pairs (sets)
Lone
pairs
Shape of
molecule Examples
2 linear 2 0 linear BeCl
2
, HCN
3 trigonal planar 3 0 trigonal BCl
3
, CH
2
O
4 tetrahedral 4
3
2
0
1
2
tetrahedral
pyramidal
bent
CH
4
, SiF
4
NH
3
, PCl
3
H
2
O, SCl
2
5 trigonal
bipyramidal
5 0 trigonal
bipyramidal
PCl
5
6 octahedral 6 0 octahedral SF
6
FIGURE 4.8
Some common shapes
for molecules
Compounds with double and triple bonds
(Defer reading this sub-section until you understand what is meant by double and
triple bonds: they are introduced in Chapter 6.)
When a double or triple bond is involved, the shape of the molecule is deduced by
considering the multiple bond as a set of electrons that stay together; that is, we consider
a double or triple bond as if it were a single bond.
This is the reason for the phrase or sets in the original statement of the
electron-pair repulsion theory given at the start of this section. We will illustrate
this now.
In carbon dioxide,

, we consider that around the carbon atom
there are only two sets of electrons (each set being a double bond or two pairs of
electrons). As in BeCl
2
(p. 240), two sets arrange themselves to be diametrically
opposite each other. Hence CO
2
is a linear molecule:

Similarly in hydrogen cyanide,
, we consider that around the carbon

atom there are only two pairs (sets) of electronsa triple bond and a single bond.
Hence the shape of this molecule will also be linear:
In methanal, CH
2
O, for which the structure is:
we consider that there are three sets of electrons around the carbon atom (counting
the double bond as one set). They form a trigonal planar shape as in boron trigonal planar trigonal planar
trichloride. The above structure thus gives a good picture of the geometry around
the carbon atom.

EXERCISE
8 Name and draw the shape you would expect for each of the following molecules:
a oxygen diuoride f sulfur dichloride
b silane, SiH
4
g arsine (compound of As and H)
c boron tribromide h carbon tetrachloride (tetrachloromethane)
d nitrogen trichloride i hydrogen peroxide, HOOH
e iodine chloride, ICl j hypobromous acid, HOBr
dipole (p. 234)
dipoledipole forces (p. 235)
dispersion forces (p. 235)
electronegativity (p. 235)
electron-pair repulsion theory (p. 240)
heteroatomic (p. 234)
hydrogen bond (p. 236)
lone pair (p. 240)
polar covalent bonds (p. 234)
polar molecules (p. 234)
IMPORTANT NEW TERMS
TEST YOURSELF
above.
2 Draw electron-dot structures for water, ammonia, methane and hydrogen sulde.
3 Intermolecular forces are strongest in which state of mattersolid, liquid or gas?
4 Name three types of intermolecular forces.
5 In which of the substances listed in 2 are there:
a dispersion forces
b dipoledipole forces
c hydrogen bonds?
What are the consequences for melting and boiling points? Explain why.
6 What is the experimental evidence for believing that there is hydrogen bonding in
water, ammonia and hydrogen uoride?
7 What basic principle can be used to work out the shapes of covalent molecules?
8 What are the shapes of the molecules listed in 2?
9 Deduce the shapes of molecules of:
a beryllium chloride
b boron triuoride
c nitrogen trichloride
d carbon tetrabromide
CHAPTER 5
Water as a solvent:
aqueous solutions
Aqueous solutions of ionic compounds
Water of crystallisation and hydrates
Aqueous solutions of molecular substances
Molecular substances that react with water
Solubility summarised
Precipitation reactions
Solubility data
Using the solubility table
Saturated solution, concentration, solubility
Different measures of concentration
Molarity
IN THIS CHAPTER
244
Water is the most widely used solvent both by humans and by nature. In all living
matter, most of the chemical reactions responsible for life occur in water solutions,
or aqueous solutions as they are called.
Many, but not all, substances dissolve in water. In this chapter we shall look at
which substances dissolve and the nature of the solutions they form, then consider
some simple reactions that occur in aqueous solutions and nally explore some of
the methods that are used to report concentrations of solutions.
To start, recall that when one component is present in a much larger amount
than the other(s), we call the major component the solvent and the other(s) the
solute(s).
We say that the solvent dissolves the solute to form a solution.

The nature of the solution formed depends upon the type of substance
dissolved in the solvent, so let us consider the solutions formed by some different
classes of compound.
5.1 AQUEOUS SOLUTIONS OF IONIC
COMPOUNDS
Most ionic compounds are soluble in water.
When ionic substances such as common salt (sodium chloride, NaCl), baking
soda (sodium hydrogen carbonate, NaHCO
3
), or Epsom salts (magnesium sulfate,
MgSO
4
) dissolve in water, they break up into their basic structural units which are
ions. These ions then move freely and independently of one another through the
solution, as shown in Figure 5.1.
In some solutions two components are present in comparable amounts. Examples are gin and
whisky (nearly 50% of each water and ethanol) and brass (a solid solution of 45% to 65% copper
with 55% to 35% zinc). For such solutions it is inappropriate to use the terms solvent and solute.
CHAPTER 5 WATER AS A SOLVENT: AQUEOUS SOLUTIONS 245
The reason why most ionic compounds dissolve in water is that polar water
molecules have a strong attraction for charged ions: the negative end of the water
molecule (the O atom) attaches to positive ionsseveral water molecules per
ionwhile the positive ends (the H atoms) attach to negative ionsagain several
molecules per ion. We say that the ions become hydrated. Figure 5.2 shows this.
If the attractive forces between water and the ions are stronger than the attractive
forces between the positive and negative ions, then the ionic solid dissolves in water.
Water is called a polar solvent. This is because it consists of polar molecules.
5.2 WATER OF CRYSTALLISATION AND
HYDRATES
Sometimes ionic substances crystallise from aqueous solution with the molecules of
water still attached to the ions.
Water that becomes bound to a pure substance during crystallisation is called
water of crystallisation.
Copper sulfate crystallises with ve water molecules per ion pair (formula
unit). We write this as CuSO
4
.5H
2
O. The 5H
2
O tells us that there are ve water
molecules attached to each copper sulfate ion pair. A dot is used to separate the
compound from its water of crystallisation. Some other substances that crystallise
with water of crystallisation are:
sodium carbonate (washing soda) Na
2
CO
3
.10H
2
O
magnesium sulfate (Epsom salts) MgSO
4
.7H
2
O
calcium sulfate (gypsum) CaSO
4
.2H
2
O
barium hydroxide Ba(OH)
2
.8H
2
O
Salts that contain water of crystallisation are called hydrates. The term
anhydrous is used to describe forms of salts that do not contain water of
FIGURE 5.1
A solution of an ionic
substance (such as
sodium chloride). The
separated ions are
dispersed throughout the
whole solution. Their size
is greatly exaggerated in
this diagram
FIGURE 5.2
Polar water molecules
readily attach to ions. This
is why most ionic solids
are soluble in water
Refer to Context 2 Water, pp. 456.

crystallisation. Anhydrous copper sulfate is CuSO
4
, while hydrated copper sulfate
is CuSO
4
.5H
2
O. Anhydrous barium hydroxide is Ba(OH)
2
; hydrated barium
hydroxide is Ba(OH)
2
.8H
2
O.
The name for hydrated copper sulfate is copper sulfate pentahydrate, penta
meaning ve. Similarly Ba(OH)
2
.8H
2
O is called barium hydroxide octahydrate.
The other common prexes are di- for two, tri- for three, tetra- for four, hexa- for six,
hepta- for seven and deca- for ten. So the other compounds in the above list are sodium
carbonate decahydrate, magnesium sulfate heptahydrate and calcium sulfate dihydrate.
5.3 AQUEOUS SOLUTIONS OF MOLECULAR
SUBSTANCES
Most molecular substances such as hexane, kerosene, parafn wax and chloroform are
insoluble in water. However, some very important molecular substances, such as
sugars, are soluble.
When a substance such as sugar (sucrose) or urea (a common fertiliser)
dissolves in water, the crystals of the solid break up and disperse throughout the
solvent, and they break up right down to the molecular level. So a solution of
sucrose or urea in water consists of individual sucrose or urea molecules dispersed
throughout the solvent water. This is shown schematically in Figure 5.3.
A molecular substance
only dissolves in water if
water can form stronger
attachments to the molecules
than the intermolecular forces
in the molecular substance.
Generally the only molecular
substances which dissolve in
water are ones that have very
polar molecules or ones that
can form hydrogen bonds with
water. Common sugars such as
sucrose, glucose and fructose
contain many OH groups.
FIGURE 5.3
Dissolution of a crystal
of a molecular substance
such as sucrose in water
(the size of molecules is
greatly exaggerated)
Many substances used
in the home are aqueous
solutions
CHAPTER 5 WATER AS A SOLVENT: AQUEOUS SOLUTIONS 247 CHAPTER 5 WATER AS A SOLVENT: AQUEOUS SOLUTIONS 247
Water can hydrogen bond to these and so sugars (carbohydrates) are soluble in
water. Urea and the amino acids have NH groups and exposed O atoms; these
can form hydrogen bonds to water, so these compounds are soluble in water.
Most molecular substances are neither strongly polar nor do they form
hydrogen bonds with water. This is why most molecular substances are not soluble
in water.
However, some non-polar molecular substances such as oxygen and nitrogen
gases and iodine are slightly soluble in water. The solventsolute interactions are
weak dispersion forces (Section 4.3 on p. 235). Because these interactions are weak,
the solubilities of such substances are quite low.
Non-aqueous solutions of non-polar
substances
A non-polar solvent is a liquid which consists of non-polar molecules.
Hexane (C
6
H
14
) and carbon tetrachloride (CCl
4
) are non-polar solvents.
Many molecular substances dissolve in non-polar solvents such as hexane
or carbon tetrachloride. A common example is a solution of iodine in hexane.
This solution consists of individual iodine molecules dispersed uniformly through
the solvent. As with sugar in water, for a solution to form, the solventsolute
molecular interactions must be stronger than the solutesolute ones. In this case
the interactions are just dispersion forces.
Covalent lattices and big molecules
Covalent lattices such as diamond and silicon dioxide are insoluble in water.
This is because water is not able to break up the strong covalent bonds between
the particles (atoms) in these lattice solids.
In living matter there are many large covalent molecules, typically with
molecular weights into the hundreds of thousands. Common examples are cellulose
(stems of plants, wood, cotton) and structural proteins (skin, hair, wool, silk).
There are discrete molecules of these substances, but they are so large, and held
to one another in such orderly fashions by hydrogen bonds, that water is not able
to separate them from one another and so they are insoluble.
Synthetic plastics (more correctly called polymers) such as polyethylene
(polyethene or polythene) and polyester similarly consist of very large molecules,
and for the same reason these are insoluble in water.
On the other hand, there are many proteins (including enzymes) and some
carbohydrates (amylose, a type of starch, and glycogen, used for energy storage in
animals) which are soluble in water, even though they have large molecular weights.
These molecules have very complex structures that do not pack together neatly into
crystals, so water is able to separate molecules and form solutions (again with much
hydrogen bonding).
As this discussion shows, the most important factors for causing solubility in
water are the highly polar nature of the water molecule and the ability of water to
form hydrogen bonds with other molecules.
Refer to Context 2 Water, pp. 467.

5.4 MOLECULAR SUBSTANCES THAT REACT
WITH WATER
So far we have had molecular substances that:
dissolve in water by forming hydrogen bonds (such as glucose)
and those that
dissolve slightly via dispersion forces (O
2
and I
2
)
and others that
are insoluble in water (carbon tetrachloride, olive oil, parafn wax).
In addition, there are some polar molecular substances that dissolve in water by
chemically reacting with it. An example is hydrogen chloride; this is a covalent gas.
It dissolves readily in water to form hydrogen and chloride ions:
HCl( g) + H gg
2
O(l ) H
3
O
+
(aq) + Cl
(aq)
This hydrogen ion, H
3
O
+
, is often called the hydronium ion. We call the solution
hydrochloric acid.
While it is often convenient to write the hydrogen ion as H
+
, it is more
accurately described as H
3
O
+
, an H
+
attached to a water molecule. Free H
+
does
not exist in aqueous solution. When we say that an acid is a substance that in
solution produces hydrogen ions, we really mean that it produces H
3
O
+
ions.
Our other common acids, sulfuric acid and nitric acid, are covalent molecular
liquids. They dissolve in water by reacting with it, again to form hydrogen ions.
For nitric acid:
HNO
3
(l ) + H
2
O(l ) H
3
O
+
(aq) + NO
3
(aq)
where NO
3
is called the
nitrate ion.
Other polar covalent molecules dissolve in water by reacting with it to form the
hydroxide ion, OH
. An example is ammonia, which as we saw in Section 4.1 on

page 232 is a covalent gas:
NH
3
( g) + H gg
2
O(l ) NH
4
+
(aq) + OH
(aq)
The NH
4
+
ion is called the ammonium ion.
Substances that dissolve in or react with water to form hydroxide ions are called
alkalis; the solutions formed are called alkaline solutions.
Ammonia is an alkali and its solution in water is alkaline.
The reactions described here, in which covalent molecular substances react with
water to form ions, are called ionisation reactions. We say that nitric acid ionises to
form hydrogen ions and nitrate ions, that ammonia ionises to form ammonium ions
and hydroxide ions.

5.5 SOLUBILITY SUMMARISED
Solubilities of different classes of substances in water are summarised in Table 5.1.
TABLE 5.1 Solubility in water and bonding type
Bonding type Solubility in water Examples
ionic most are soluble NaCl, MgSO
4
, Cu(NO
3
)
2
polar molecular soluble if H bonds possible
soluble by reacting with it
otherwise insoluble
ethanol, glucose
HCl, HNO
3
, H
2
SO
4
, NH
3
ether, dichloromethane
non-polar molecular some are slightly soluble
most are insoluble
I
2
, O
2
CCl
4
, benzene, parafn wax
very large molecules insoluble if highly structured
a few soluble
cellulose, structural proteins,
synthetic polymers
starch, glycogen, enzymes
covalent lattices insoluble diamond, SiO
2
metals insoluble
unless they react with water
Al, Zn, Fe
Li, Na, K, Ca, Ba
About solubility more generally
Another generalisation about solubility (not restricted to just water as the solvent) is:
Like dissolves like.
Or stated more fully, polar (including ionic) substances dissolve in polar solvents
such as water and do not dissolve in non-polar solvents such as hexane. Non-polar
substances dissolve in non-polar solvents but do not dissolve in polar ones.
Covalent lattices (network solids) do not dissolve in any solvents.
EXERCISES
1 Which of the following compounds would you expect to be soluble in water?
Explain why.
HBr, SiO
2
, MgCl
2
, CS
2
, BF
3
, ZnBr
2
, H
2
SO
4
, hexachloroethane (C
2
Cl
6
), silicon
tetrachloride (SiCl
4
), hydrogen peroxide (H
2
O
2
), fructose (a sugar, C
6
H
12
O
6
),
octane (C
8
H
18
), urea (NH
2
CONH
2
), boron
2 a Iron(II) sulfate, FeSO
4
, crystallises with seven molecules of water per ion pair
of iron(II) sulfate. Write the formula for the hydrate.
b Magnesium nitrate, Mg(NO
3
)
2
, crystallises as a hexahydrate. Write its formula.
*c
Calcium nitrate, Ca(NO

3
)
2
, crystallises with four molecules of water per ion pair
of calcium nitrate. Write a formula for the hydrate and name it.
*d Lithium bromide, LiBr, crystallises as a dihydrate. Write its formula.
*3 Hydrogen bromide and methane are small covalent molecules. Hydrogen bromide
readily dissolves in water whereas methane does not. Explain why.
Having considered the nature of ionic solutions, we can now look at some reactions
involving ions in solution. In particular let us look at what are called precipitation
reactions.
5.6 PRECIPITATION REACTIONS
Sometimes when clear solutions of two ionic substances are mixed, they react to
produce a nely divided solid.
A solid produced by reaction between two clear solutions is called a precipitate.
Such reactions are called precipitation reactions.
The verb, to precipitate, means to fall outsolids fall out of solution. Common
examples of precipitation reactions are as follows:
1 When colourless solutions of potassium chloride and silver nitrate are mixed,
a white precipitate of silver chloride is formed.
2 When a colourless solution of sodium hydroxide is added to a clear blue
solution of copper sulfate, a blue precipitate of copper hydroxide forms.
3 Colourless solutions of sodium iodide and lead nitrate react to form a bright
yellow precipitate of lead iodide.
4 Yellow iron(III) chloride solution and colourless sodium hydroxide solution
when mixed react to form a dark brown precipitate of iron(III) hydroxide.
Figure 5.4 shows these precipitates.
Recall that in a chemical reaction the starting substances are called reactants
and the substances formed, products. In 1 potassium chloride and silver nitrate are
the reactants while silver chloride is a product.
The nature of ionic solutions provides an explanation of how and why precipitates
form when certain solutions are mixed. As we saw in Section 5.1, a solution of
an ionic compound consists of positive and negative ions moving randomly and
independently throughout the whole volume of water they are present in.
When solutions of zinc sulfate and magnesium nitrate are mixed, the resulting
solution consists of Zn
2+
, SO
4
2
, Mg
2+
and NO
3
ions all moving randomly
throughout the whole volume of the liquid. This mixed solution is identical with
4 a For soluble ionic compounds such as sodium chloride and magnesium sulfate,
what can you say about the relative strengths of the forces between the ions
and water in the solution and the forces between ions in the solid? Explain.
b Not all ionic compounds are soluble in water. For example, lead sulfate and zinc
hydroxide are insoluble. Suggest an explanation for these compounds being
insoluble.
5 Pure sulfuric acid is a covalent liquid. It dissolves in water by reacting with it.
Write an equation for the reaction.
provided.
one formed by mixing solutions (of appropriate concentrations) of zinc nitrate and
magnesium sulfate. Both mixed solutions contain the same four types of ion moving
freely around.
However if we mix barium nitrate and zinc sulfate solutions, a heavy white
precipitate forms. In solution, barium nitrate consists of separated Ba
2+
ions and NO
3
ions, while in zinc sulfate solution there are separated Zn

2+
and SO
4
2
ions. Now
2 2
barium sulfate is insoluble, so when Ba
2+
and SO
4
2
ions collide, they stick together
2 2
to form solid barium sulfate which falls out of (precipitates from) solution:
Ba
2+
(aq) + SO
4
2
(aq) BaSO
4
(s) (5.1)
This precipitation reaction can be written in two other ways:
Ba(NO
3
)
2
(aq) + ZnSO
4
(aq) BaSO
4
(s) + Zn(NO
3
)
2
(aq) (5.2)
Ba
2+
+ 2NO
3
+ Zn
2+
+ SO
4
2
BaSO
4
(s) + Zn
2+
+ 2NO
3

(5.3)
As the nitrate and zinc ions are not actually involved in the reaction, we call
them spectator ions. Equations such as 5.1 are called net ionic equations: they only
show the ions that actually react. Equation 5.3 is called a complete ionic equation:
it shows all the ions in the mixed solutions. Equation 5.2 is called a neutral species
equation: it shows the actual (neutral) compounds that were in the solution.
The driving force behind a precipitation reaction is the formation of an
insoluble substance. When solutions of two ionic substances are mixed,
precipitation occurs if one type of positive ion present can combine with one
type of negative ion present to form an insoluble substance.
Barium ions combine with sulfate ions to form a precipitate of barium sulfate,
regardless of what spectator ions are involved. Mixing solutions of:
1 barium chloride and sodium sulfate
2 barium hydroxide and potassium sulfate
3 barium bromide and sulfuric acid
all result in precipitation of barium sulfate. Reaction 5.1 occurs in every case, though
we can write each reaction in other ways if we wish. For example, for 1 we can write:
BaCl
2
(aq) + Na
2
SO
4
(aq) BaSO
4
(s) + 2NaCl(aq)
Ba
2+
+ 2Cl
+ 2Na
+
+ SO
4
2
BaSO
4
(s) + 2Na
+
+ 2Cl
FIGURE 5.4
Precipitates of silver
chloride, copper
hydroxide, lead iodide and
iron(III) hydroxide
Lead iodide is an insoluble substance; it precipitates out when we mix
solutions of:
1 lead nitrate and potassium iodide
2 lead acetate (ethanoate) and magnesium iodide
3 lead nitrate and hydroiodic acid.
In all cases the essential reaction is described by the net ionic equation:
Pb
2+
(aq) + 2I
(aq) PbI
2
(s)
though we can write the individual reactions as neutral species equations:
1 Pb(NO
3
)
2
(aq) + 2KI(aq) PbI
2
(s) + 2KNO
3
(aq)
2 Pb(CH
3
COO)
2
(aq) + MgI
2
(aq) PbI
2
(s) + Mg(CH
3
COO)
2
(aq)
3 Pb(NO
3
)
2
(aq) + 2HI(aq) PbI
2
(s) + 2HNO
3
(aq)
or as complete ionic equations (for 1 and 2):
1 Pb
2+
+ 2NO
3
+ 2K
+
+ 2I
PbI
2
(s) + 2K
+
+ 2NO
3
2 Pb
2+
+ 2CH
3
COO
+ Mg
2+
+ 2I
PbI
2
(s) + Mg
2+
+ 2CH
3
COO
This latter form emphasises that K

+
and NO
3
in
1 and Mg
2+
and CH
3
COO
in 2 are spectator ions; they are not actually involved in the reaction.
Since precipitation occurs through the formation of insoluble substances, we
need to know which substances are soluble and which are insoluble. We need a table
of solubility data.
5.7 SOLUBILITY DATA
By taking solutions of a soluble compound of each of the cations (positive ions)
we are interested in, and systematically mixing samples of these with solutions of
the anions (negative ions) we are interested in, we can establish experimentally
which substances are soluble and which are insoluble. We can then summarise the
results of these experiments into a table of solubility data. This table can then be
used to predict what, if any, precipitation reactions will occur when solutions of
other substances are mixed.
Table 5.2 opposite summarises the solubility of common ionic compounds.
The cations covered by this table are Group 1, Group 2, NH
4
+
, Al
3+
, Cr
3+
, Mn
2+
,
Fe
3+
, Fe
2+
, Co
2+
, Ni
2+
, Cu
2+
, Ag
+
, Zn
2+
, Cd
2+
, Pb
2+
, Sn
2+
.
Soluble means that the compound dissolves to more than 10 g/L; insoluble
that it dissolves to less than 1 g/L. Some substances have solubilities in the range
1 to 10 g/L and are often classed as sparingly soluble. Common sparingly soluble
compounds (included in Table 5.2) are silver acetate, lead chloride, calcium sulfate,
silver sulfate and calcium hydroxide.
Sometimes when only a small amount of a precipitate is formed, it does not
settle to the bottom of the test tube as an obvious solid, but stays in suspension and
makes the mixture look cloudy or turbid. We need to distinguish between a colourless
solution (completely transparent or clear), a coloured solution (still transparent)
and a turbid suspension (can be coloured but is not fully transparent). Examples are
shown in Figure 5.5. If mixing two clear (coloured or colourless) solutions produces
turbidity (cloudiness), then a precipitate has been formed. We need to recognise that
cloudiness signals the formation of a precipitate.
TABLE 5.2 Solubility of ionic compounds
Compounds that are soluble Compounds that are insoluble
Group 1 and NH
4
+
compounds
nitrates
acetates (ethanoates)
chlorides, bromides and iodides
(exept Ag
+
and Pb
2+
)
sulfates (except Ag
+
, Pb
2+
,
Ba
2+
, Sr
2+
, Ca
2+
)
carbonates
sultes
phosphates
hydroxides
oxides
suldes
}
}
(except Group 1 and NH
4
+
compounds)
(except Group 1, NH
4
+
, Ba
2+
,
Sr
2+
, Ca
2+
)
(except Groups 1, 2 and NH
4
+
)
5.8 USING THE SOLUBIL ITY TABLE
Table 5.2 can be used to predict what will happen when solutions of particular
substances are mixed, as the following examples illustrate.
FIGURE 5.5
Solutions and
suspensions. From left
to right: a colourless
solution of sodium chloride
(clear), a white precipitate
(suspension) of silver
chloride (turbid), a yellow
solution of potassium
chromate (clear), a yellow
precipitate (suspension)
of lead iodide (turbid), a
coloured solution of copper
sulfate (clear), and a blue
precipitate (suspension) of
copper hydroxide (turbid)
EXAMPLE 1
What precipitate (if any) will form when aqueous solutions of sodium bromide and lead
nitrate are mixed?
In solution, there will be Na
+
, Br
, Pb
2+
and NO
3
ions moving freely around. We could

possibly form sodium nitrate, NaNO
3
, and lead bromide, PbBr
2
. From Table 5.2 sodium
nitrate is soluble, but lead bromide is insoluble. Hence lead bromide precipitates out:
Pb
2+
(aq (( ) + 2Br
(aq (( ) PbBr
2
(s (( )
EXAMPLE 2
What reaction (if any) will occur when a solution of potassium carbonate is added to a
solution of zinc chloride?
By changing partners the cations could form potassium chloride and zinc carbonate.
From Table 5.2 KCl is soluble, but zinc carbonate is insoluble, so it will precipitate out:
2K
+
+ CO
3
2
+ Zn
2+
+ 2Cl
ZnCO
3
(s (( ) + 2K
+
+ 2Cl

EXAMPLE 3
When solutions of ammonium chloride and magnesium nitrate are mixed, what,
if anything, will precipitate?
By a change of partners we could form ammonium nitrate and magnesium chloride, but
both NH
4
NO
3
and MgCl
2
are soluble, so nothing happens. This mixed solution merely
has NH
4
+
, Cl
, Mg
2+
and NO
3
ions moving randomly around throughout its whole

volume; it is in no way different from the mixture formed from solutions (of appropriate
concentration) of magnesium chloride and ammonium nitrate.
EXAMPLE 4
Does sodium hydroxide solution react with nickel chloride solution? If so what is
formed?
We note that a change of partners could form sodium chloride and nickel hydroxide.
From Table 5.2 Ni(OH)
2
is insoluble so that:
Ni
2+
(aq (( ) + 2OH
(aq (( ) Ni(OH)
2
(s (( )
EXERCISES
6 Which of the following substances are soluble in water?
a copper sulde f copper nitrate k ammonium sulde k
b magnesium sulfate g calcium bromide l sodium phosphate
c aluminium chloride h potassium iodide m magnesium hydroxide
d iron(II) sulde i iron(II) hydroxide n silver bromide
e zinc hydroxide j lead sulfate o barium hydroxide
7 Write the formulae for the substances in Exercise 6.
8 Mixed solutions (of suitable concentrations) of what pairs of substances would be
identical to solutions containing mixtures of:
a sodium sulfate and magnesium nitrate
b barium hydroxide and potassium chloride?
9 Name and give the formula of the precipitate (if any) that forms when solutions of
the following pairs of substances are mixed.
a lead nitrate and ammonium sulfate
b zinc sulfate and potassium carbonate
c sodium chloride and magnesium sulfate
d iron(II) chloride and sodium hydroxide
*e copper sulfate and hydrogen sulde
*f nickel sulfate and cadmium chloride
*g potassium bromide and lead nitrate
*h sodium sulde and iron(III) sulfate
10 Which solutions would you mix to produce a precipitate of:
a barium carbonate b silver bromide *c aluminium hydroxide?
11 Write net ionic equations for all the reactions in Exercise 10.

5.9 SATURATED SOLUTION,
CONCENTRATION, SOLUBILITY
We nd that we can only dissolve a certain amount of a particular substance in a
given volume of a solvent (at a particular temperature). If we try to dissolve more,
the extra solute just remains undissolved at the bottom of the container. We say
such a solution is saturated. Thirty-six grams of sodium chloride can be dissolved in
100 millilitres of water at room temperature, but if we add more than this, the extra
does not dissolve no matter how hard or long we shake the mixture.
A saturated solution is one in which no more of the particular solute can
be dissolved in a given quantity of the solvent at the specied temperature.
A solution which contains less than this maximum amount of solute is called
an unsaturated solution.
A solution containing 36 g NaCl/100 mL water at 25C is a saturated solution;
a solution containing 20 g NaCl/100 mL is an unsaturated one.
The concentration of a solution is the amount of solute present in a specied
amount of solvent or solution.
Concentration can be given in a variety of units, for example as 36 grams NaCl
per 100 mL of water; 360 grams per litre of water; 36 g/100 g water; 360 grams per
kilogram of water; or 0.36 grams per gram of water. We shall look at other measures
of concentration in the next section.
The solubility of a substance in a particular solvent is the concentration of its
saturated solution at the specied temperature. It is the maximum amount of the
substance that will dissolve in a given amount of the solvent at that temperature.
Since the amount of solute which can be dissolved in a given quantity of solvent
varies as temperature is changed, it is essential to state the temperature to which
a particular solubility value applies. Hence we say that the solubility of sodium
chloride in water at 25C is 36 g/100 g; or the solubility of potassium nitrate is
37 g/100 g water at 25C and 245 g/100 g at 100C.
5.10 DIFFERENT MEASURES OF
CONCENTRATION
In the previous section concentration was dened as the amount of solute in a
specied amount of solvent or solution. This can be expressed in many ways.
Some of the more common are:
mass of solute per 100 mL or 1 L of solvent
mass of solute per 100 mL or 1 L of solution
volume of solute per 100 mL or 1 L of solvent
volume of solute per 100 mL or 1 L of solution
convenient for solid solutes,
such as sodium chloride
convenient for liquid convenient convenient
solutes, such as ethanol
}
}
%(w/v) standing for per cent, weight, volume (should be m/v, mass, volume),
which means mass of solute per 100 mL of solution
%(v/v) standing for per cent, volume, volume, meaning volume of solute per
100 mL of solution.
All the above measures are in terms of volume of solvent or solution. This is
generally the most convenient way of making solutions. However we can express
concentration in terms of mass of solvent or solution. Common ones are:
%(w/w), per cent by weight, meaning mass of solute per 100 g solution, and
ppm, standing for parts per million, meaning grams of solute per million grams
of solution.
If % is used on its own, it generally means %(w/w), mass of solute in 100 g of solution.
Why different measures of concentration?
Several ways of expressing concentration are used because each method has
advantages for particular situations. In commerce, industry and shopping, where
the main concern is with how much solute is present, then mass per unit volume is
very convenient. If we want a desired mass of the solute, we can then just measure
out the necessary volume of the solution. It is usually easier to measure out volumes
than masses.
If the solute is a liquid, then volume per unit volume is often preferred because
we generally think in terms of volumes of liquids rather than masses.
In environmental contexts concentrations are usually quite low. Masses per unit
volume or per cent compositions generally lead to very small numbers, so ppm
gives more manageable numbers. For example, 1.5 ppm is more convenient to say
and write than 0.000 15% or 0.0015 g per litre (a litre of water or dilute aqueous
solution is approximately a kilogram).
When we want to measure quantities in chemical reactions, we will nd
(in the next section) that another measure of concentration in terms of moles
is more convenient.
Using concentrations
Some examples will illustrate how we use concentrations.
This is the denition for liquid solutions; in mixtures of gases (such as the atmosphere), ppm means
volume per million volumes, which is equal to molecules per million molecules.
EXAMPLE 5
a 1.32 g potassium permanganate, KMnO
4
, was dissolved in water and the volume
made accurately to 250 mL. Calculate the concentration of this solution in
i g/100 mL and ii g/L of solution.
We have 1.32 g KMnO
4
in 250 mL of solution.
i Mass of KMnO
4
in 100 mL solution =
100
____
250
1.32
____ ____
= 0.528 g/100 mL
ii Mass of KMnO
4
in 1 L (= 1000 mL) =
1000
_____
250
1.32
1000 1000
_____ _____
= 5.28 g/L
b 13.6 g copper sulfate was dissolved in 500 mL water. Calculate the %(w/w) copper
sulfate in this solution. Assume that the mass of 500 mL of water is 500 g.
Total mass of the solution = 13.6 + 500
= 513.6 g
Percentage CuSO
4
in this solution =
13.6
______
513.6
100
______ ______
= 2.65%(w/w)
Dilution
Frequently we need to dilute a solution from one concentration to a lower one.
We do this by measuring out a volume of the original solution and adding water to
make the new volume. The volume to dilute the solution to is calculated from the
fact that the amount of solute (or the number of solute particles) in the diluted solution is
the same as was in the volume of the original solution that was taken (because the only
thing that was done was to add water). Figure 5.6 illustrates this. Now:
amount of solute in original solution = original concentration original volume

amount of solute in diluted solution =
concentration of
nal volume
diluted solution
amount of solute in diluted solution = amount of solute in diluted solution =
Because the amount of solute is the same:
(
concentration of concentration of concentration of concentration of concentration of concentration of concentration of
diluted solution
)
nal volume =
(
original original original

original original original original
concentration
)
original volume (5.4)
This equation can be written in symbols as:
c
2
V
2
VV = c
1
V
1
VV
Equation 5.4 can be used to calculate c
2
or V
2
VV when the other three quantitites
are known. An example will illustrate.
EXAMPLE 6
a What mass of sodium chloride has to be dissolved in 250 mL water to make a
0.90%(w/v) solution (the common saline solution in hospitals)? Assume that the
solution has a volume of 250 mL.
A 0.90%(w/v) solution contains 0.90 g NaCl in 100 mL of solution.
In 250 mL of solution we require
250
____
100
0.90 =
____ ____
2.3 g
b What volume of alcohol (ethanol) is present in 750 mL of a 14%(v/v) solution
of alcohol in water (a red wine)?
In 100 mL there are 14 mL of alcohol, so:
volume of alcohol in 750 mL =
750
____
100
14 =
____ ____
105 mL
c A solution contained 500 ppm mercury(II) ion. Express this as a %(w/w).
500 ppm means 500 g mercury(II) ion per 10
6
g solution.
%(w/w) means grams per 100 g solution, so:
mass of mercury(II) ion in 100 g =
100
____
10
6
500
100 100
____ ____
= 0.050 g
Therefore the solution is 0.050%(w/w).
FIGURE 5.6
Dilution: the same number
of solute particles in a
larger volume of solvent
EXAMPLE 7
a
diluted to 500 mL (using a pipette and volumetric ask). What is the concentration
of the diluted solution?
Using Equation 5.4:
concentration of diluted solution =
original concentration original volume

_____________________________________

nal volume

=
84.1 25
__________
500

= 4.21 g/100 mL
Alternatively, using basic principles instead of Equation 5.4:
mass of solute taken =
25
____
100
84.1
____ ____

= 21.03 g
This mass ends up in 500 mL of solution, so:
concentration of diluted solution =
21.03
______
500
100
21.03 21.03
______ ______

= 4.21 g/100 mL
b To what volume should 50 mL of a 30 g/100 mL solution of potassium nitrate be
diluted to make a solution which is 6.0 g/100 mL?
Using Equation 5.4:
nal volume =
original concentration original volume

_____________________________________

concentration of diluted solution

=
30 50
________
6.0

= 250 mL
If we only wanted an approximate dilution, we would measure out 50 mL of the
starting solution in a small measuring cylinder, transfer it to a larger one and make
the volume to 250 mL. If we wanted an accurate dilution, we would use a pipette
to transfer 50 mL of the original solution into a 250 mL volumetric ask, then add
water to bring the volume to exactly 250 mL (meniscus sitting on the mark on the
neck of the ask).
An intuitive approach to dilution problems is this: if you want to dilute a solution
by a factor of x, then you need to increase the volume by a factor of x. To dilute
a solution by a factor of 5, dilute 50 mL to 250 mL (or 10 mL to 50 mL).
EXERCISES
12 a 7.3 g sodium sulfate was dissolved in 75 mL water. Calculate the concentration
of this solution in i g/100 mL of solution ii g/L of solution iii %(w/v).
Assume that the volume after dissolution is still 75 mL.
b 15 mL ethanol (which has a mass of 11.9 g) was dissolved in 80 mL water.
Assuming that the nal volume is 95 mL, calculate the concentration of the
solution in i mL/100 mL of solution ii g/100 mL of solution
iii mL/L of solution iv %(v/v).
Let us now turn to a more convenient measure of concentration to use when
chemical reactions are involved.
5.11 MOLARITY
As explained in Section 3.7 on pp. 2268, when we want to calculate quantities
involved in chemical reactions, the basic unit is the mole. We read chemical
equations in moles, not in grams. Therefore it is convenient to have a measure
of concentration in terms of moles: it is called molarity.
The molarity of a solution is the number of moles of solute per litre of solution.
A molarity of 0.020 mol/L (alternatively written mol L
1
) means 0.020 moles
of solute in one litre of solution.
molarity =
number of moles of solute

__________________________

volume of solution in litres

}
(5.5)
=
number of moles of solute 1000

_________________________________

volume of solution in millilitres

To calculate the number of moles of solute in a particular volume of solution:
number of moles of solute = molarity volume in litres
=
molarity volume in millilitres

______________________________

1000
}
(5.6)

These important equations, along with Equation 3.1 on p. 223:
number of moles =
mass
____________

molar mass
(3.1)

are essential for calculations using molarities as the following examples will show.
13 a What mass of potassium nitrate do you need to dissolve in 50 mL water to
make a 2.5%(w/v) solution?
b What mass of glucose do you need to dissolve in 200 g water to make a
7.0%(w/w) solution?
c What mass of mercury(II) nitrate should be dissolved in 500 mL water to make
a 750 ppm solution? 500 mL water is approximately 500 g.
14 a How would you make 250 mL of an aqueous solution of ammonium chloride
having a concentration of 3.5 g/100 mL of solution?
b How would you make 500 mL of an aqueous solution of ethanol having a
concentration of 15.0 mL ethanol per 100 mL solution?
c How would you make 250 mL of a 8.0%(w/v) solution of sodium carbonate?
15 a Some environmentalists wanted a 2.0 ppm solution of lead ions to use as a
standard in some pollution monitoring. What mass of lead nitrate would they
need to dissolve in exactly 1 litre (1 kg) of water to make such a solution?
b What is the problem in making the solution in this way? Suggest a better way
of making the required solution.
EXAMPLE 8
17.54 g of pure barium hydroxide was dissolved in water and made up to 500 mL
(0.5000 L) in a volumetric ask. Calculate the molarity of the solution.
Molar mass of Ba(OH)
2
= 137.3 + 2 (16.0 + 1.0)
= 171.3 g/mol
Number of moles of Ba(OH)
2
used =
17.54
______
171.3

= 0.1024
From Equation 5.5:
molarity =
0.1024
_______
0.500

= 0.2048 mol/L
EXAMPLE 9
What mass of pure sulfuric acid, H
2
SO
4
, must be dissolved in water and made up to
250 mL in a volumetric ask to make a 0.550 mol/L solution?
Molar mass of sulfuric acid = 2 1.0 + 32.1 + 4 16.0
= 98.1 g/mol
From Equation 5.6:
number of moles of H
2
SO
4
required = 0.550 0.250
= 0.138
mass of H
2
SO
4
required = 0.138 98.1
= 13.5 g
EXAMPLE 10
How many a moles b grams of NaCl are there in 45.3 mL of 0.148 mol/L sodium
chloride solution?
By Equation 5.6:
a number of moles = 0.148
45.3
_____
1000

= 6.70 10
3
mol
b molar mass of NaCl = 23.0 35.5
= 58.5 g/mol
By Equation 3.1 (rearranged):
mass of NaCl = 6.70 10
3
58.5
= 0.392 g
These three examples illustrate how to convert from mass or moles to molarity
and vice versa. Now let us see how to calculate quantities from a reaction.
The molarities of these
everyday solutions are:
NaCl in sea water,
0.60 mol/L; ammonia,
1.1 mol/L; hydrochloric
acid, 8.2 mol/L; acetic acid
in vinegar, 0.67 mol/L;
chlorine in bleach,
0.56 mol/L; and ethanol
in wine, 2.4 mol/L
EXAMPLE 11
What mass of lead iodide is formed when 25 mL (from a pipette) of a 0.492 mol/L
solution of potassium iodide is added to a solution containing excess lead ions?
First we write the equation for the reaction:
Pb
2+
(aq (( ) + 2I
(aq (( ) PbI
2
(s (( )
Number of moles of potassium iodide used = 0.492
25
_____
1000

= 0.0123
From the chemical equation:

number of moles of PbI
2
formed

_____________________________

number of moles of KI provided
=
_____________________________ _____________________________
1
__
2

Therefore number of moles of PbI
2
formed =
1
__
2
0.0123
__ __
= 6.15 10
3
molar mass of PbI
2
= 207.2 + 2 126.9
= 461.0 g/mol
mass of PbI
2
formed = 6.15 10
3
461.0
= 2.84 g
The phrase containing excess lead ions is a chemists shorthand way of saying that
the solution contains more than enough lead ions to react with all the iodide added.
EXERCISES
16 Calculate the molarity of the solutions made by dissolving the following amounts of
solute in water and making up to the stated volumes:
a 0.20 mole NaCl in 100 mL d 31.8 g sodium carbonate in 250 mL
b 1.5 mole KNO
3
in 2.0 L e 5.04 g barium hydroxide in 500 mL
c 0.51 mole Na
2
SO
4
in 250 mL f 11.9 g silver nitrate in 100 mL
17 In each of the following, how many moles of the named solute do you need to
make the volume of solution indicated?
a hydrochloric acid to make 2.00 L 0.400 mol/L solution
b potassium bromide to make 250 mL 0.500 mol/L solution
c copper sulfate to make 250 mL 2.50 10
3
mol/L
18 In each of the following, what mass of solute is needed to make the stated solution?
a hydrochloric acid to make 5.00 L 0.200 mol/L solution
b sodium hydroxide to make 0.250 L 1.50 mol/L solution
c sodium carbonate to make 2.0 L 7.25 10
2
mol/L solution
19 State how many moles of solute there are in:
a 25 mL 0.106 mol/L NaOH c 50 mL 0.055 mol/L MgCl
2
b 7.2 mL 0.048 mol/L NaNO
3
d 1.83 L 0.36 mol/L NaI
20 How many grams of solute are there in (a) and (c) of Exercise 19?
21 a How many moles of:
i calcium chloride ii calcium ions iii chloride ions
are there in 17.7 mL 0.0330 mol/L calcium chloride solution?
b How many moles of:
i sodium sulfate ii sulfate ion iii sodium ion
are there in 38.4 mL 0.110 mol/L sodium sulfate solution?
22 The volumes of solutions given in Column A in the following table were accurately
diluted to the volumes in Column B. Calculate the molarity of the diluted solutions.
Column A Column B
a 50 mL 0.106 mol/L NaCl 500 mL
b 25 mL 0.223 mol/L KOH 1 L
c 100 mL 0.304 mol/L Na
2
SO
4
250 mL
d 10 mL 1.52 mol/L HNO
3
500 mL
23 The solutions listed under Solution A in the table below are provided and it is
required to prepare between 250 mL and 2 L of accurately diluted solutions having
the concentrations given in Column B. Using only standard-sized volumetric
glassware, what volumes of Solutions A should be diluted to what volumes to give
the required concentrations?
Solution A Column B
a 0.143 mol/L 0.0143 mol/L
b 1.260 mol/L 0.0315 mol/L
c 2.00 mol/L 0.400 mol/L
24 How many moles of Substance A below would be formed when an excess of a
solution of the substance in Column B was added to the solution in Column C?
Substance A Column B Column C
a barium sulfate sodium sulfate 50 mL 0.326 mol/L barium chloride
b lead bromide lead nitrate 25 mL 0.509 mol/L sodium bromide
c iron(III) hydroxide iron(III) nitrate 75 mL 0.087 mol/L NaOH
25 What mass of Substance A is formed in a and c in Exercise 24?
26 To measure the concentration of magnesium ion in a solution an analyst took 50 mL
of the solution and added sodium hydroxide solution until no further precipitate (of
magnesium hydroxide) formed. The precipitate was ltered off, dried and weighed:
it had a mass of 1.72 g.
a What was the molarity of magnesium ion in the original solution?
b How many grams of magnesium ion were there per litre in the original solution?
27 What was the molarity of:
a silver ion in a solution, 50 mL of which produced 1.87 g silver chloride when
excess sodium chloride solution was added to it
b lead ion in a solution, 25 mL of which produced 3.19 g lead iodide when excess
potassium iodide was added to it?
28 What was the concentration of lead ions in g/100 mL of solution in b of Exercise 27?
Refer to Context 2 Water, pp. 57 and 76.

alkaline solutions (p. 248)
alkalis (p. 248)
anhydrous (p. 245)
complete ionic equation (p. 251)
concentration (p. 255)
dilution (p. 257)
hydrates (p. 245)
hydronium ion (p. 248)
ionisation reactions (p. 248)
molarity (p. 259)
net ionic equations (p. 251)
neutral species equation (p. 251)
non-polar solvent (p. 247)
parts per million, ppm (p. 256)
per cent by weight, %(w/w) (p. 256)
polar solvent (p. 245)
precipitate (p. 250)
precipitation reactions (p. 250)
saturated solution (p. 255)
solubility (p. 255)
spectator ions (p. 251)
unsaturated solution (p. 255)
water of crystallisation (p. 245)
IMPORTANT NEW TERMS
TEST YOURSELF
1 Explain the meaning of each of the items in the Important new terms section.
2 Draw a diagram to show hydrogen bonding in aqueous solutions of:
a ammonia
b methanol, CH
3
OH
3 What do chemists mean when they say that ions in solution are hydrated?
4 Write the formula for copper sulfate pentahydrate. Name MgSO
4
.7H
2
O.
5 Name two substances that react with water as they dissolve and write equations
for the reaction.
6 Summarise the solubility in water for most of the compounds in each of the
following classes: ionic substances, polar covalent molecules, non-polar covalent
molecules and covalent lattices.
7 Why do precipitates form?
8 Write net ionic equations for two precipitation reactions.
9 How can you tell whether a solution is saturated?
10 List eight methods of giving the concentration of a solution.
11 15 g sodium chloride was dissolved in 50 g water. What is the concentration
a in g/100 g water
b %(w/w)?
12 How do you calculate the molarity of a solution?
13 How do you calculate the number of moles in a given volume of solution of
known molarity?
CHAPTER 6
Hydrocarbons
The element carbon
Double and triple covalent bonds
Carboncarbon bonds
Alkanes
Alkenes
Alkynes
Reactions of alkanes
Reactions of alkenes
Functional groups
IN THIS CHAPTER
265
People use large amounts of energy and most of it comes from fossil fuels, which are
predominantly compounds of carbon. In order to identify the compounds present in
fossil fuels we need to understand the structure and naming of these compounds so
we start with the simpler classeshydrocarbons.
6.1 THE ELEMENT CARBON
The element carbon belongs to Group 4 of
the Periodic Table. With atomic number 6,
its electron conguration is 2, 4. This means
that it has four valence electrons. We saw in
Section 4.1 on pp. 2323 how carbon forms
covalent bonds to each of four hydrogen
atoms to form methane, CH
4
(Figures 4.1
and 4.2). In addition, we saw in Section 2.7
on pp. 2045 how carbon formed the covalent
network solid, diamond, by each carbon
atom making covalent bonds to each of four
other carbon atoms (Figure 2.6, which is
reproduced here as Figure 6.1).
6.2 DOUBLE AND TRIPLE COVALENT BONDS
In all the examples of covalent bonding considered so far (Sections 2.3 on
pp. 199200 and 4.1 on pp. 2323), just one pair of electrons has been shared
between a particular pair of atoms. We call such bonds single bonds.
Sometimes, in order to attain noble gas electron congurations, it is necessary
for pairs of atoms to share more than one pair of electrons. In order to form carbon
FIGURE 6.1
The structure of diamond
dioxide, carbon (2, 4), which needs to gain four more electrons, and oxygen (2, 6),
which needs to gain two more electrons, pair up their electrons as follows:

Between the carbon atom and each oxygen atom there are two shared pairs of
electrons. In this way, carbon considers that it has eight outer electrons (counting
all of the shared electrons), and each oxygen atom considers that it too has eight
outer electrons. Because there are two shared pairs of electrons between carbon and
each oxygen atom, we call these double bonds. Remember in Section 2.3 on p. 199
it was stated that a dash is used to represent a pair of bonding electrons. Because
there are two shared pairs between C and each O, we draw two dashes as in the
right-hand diagram above (called a structural formula).
Similarly for ethene, C
2
H
4
, there is a double bond between the carbon atoms
(and single bonds between each carbon atom and the hydrogen atoms):

to form nitrogen molecules, it is necessary for pairs of atoms to share three pairs of
electrons to form what we call a triple bond:

Similarly in ethyne (acetylene), C
2
H
2
, a triple bond is formed between the
carbon atoms in order to satisfy the bonding drives of all four atoms. Again three
dashes are used to represent a triple bond (three shared pairs of electrons).

Other ways of drawing electron-dot
structures
While the type of electron-dot structure being drawn in this book makes it easy to
see which electrons have been paired up, to check that each atom has the required
number of valence electrons (two or eight) and to count the number of covalent
bonds, there are three other forms of electron-dot structure that are much more
widely used. These just put the bonding electrons between the atoms they are
joining without any loops or balloons; they represent the electrons in different ways:
1 dots are used for all electrons:

2 dots are used for the electrons from one atom with crosses for those from the
other atom:

3 different coloured dots are used for the electrons from different atoms:

CHAPTER 6 HYDROCARBONS 267 CHAPTER 6 HYDROCARBONS 267
Electron-dot structures in these three styles for methane and the three other
molecules just discussed are:
These types of structures are often called Lewis electron-dot structures or just
Lewis structures after the person who introduced them in the 1920s.
Structural formulae
So far we have used two types of drawings to show chemical bonding:
1 electron-dot structures, which show valence electrons and how they combine
to form chemical bonds, and
2 drawings in which dashes are used to indicate bonding pairs of electrons.
These diagrams are called structural formulae. They show the way atoms are
held to one another in molecules. The structural formulae of the compounds
discussed in Sections 2.3 on pp. 199200 and 4.1 on pp. 2323 are shown in
Table 6.1 along with the corresponding molecular formulae. The diagrams to
the right of the electron-dot structures on the page opposite for carbon dioxide,
ethene, nitrogen and ethyne are structural formulae.
Structural formulae are sometimes drawn to show the geometrical arrangement
of bonds but are often drawn with all dashes at right angles for printing convenience
(as in Table 6.1).
TABLE 6.1 Structural and molecular formulae for compounds in Sections 2.3 and 4.1
Chlorine Water Ammonia Methane
Hydrogen
sulde
structural formula ClCl HOH HN H
|
H
H
|
HCH
|
H
HSH
molecular formula Cl
2
H
2
O NH
3
CH
4
H
2
S

6.3 CARBONCARBON BONDS
As the structure of diamond shows, carbon can also form carboncarbon single
bondsnot just in diamond but in many compounds as well. The simplest
compound containing a carboncarbon single bond is ethane, C
2
H
6
. It has three
hydrogen atoms attached to each carbon atom with the two carbon atoms joined
together. Its electron-dot structure and structural formula are:
We often need to consider the shape of molecules, or in other words, the
geometric arrangement of bonds around a central atom. For example, in Section 4.2
on p. 234 we saw that shape was an important factor in determining whether
a molecule was polar or not. As mentioned in Section 4.1 on pp. 2323, when
drawing electron-dot structures we do not attempt to include the shape of the
molecule. With simple molecules as in Section 4.2 on p. 234, structural formulae
can be drawn to show molecular shape. However, with more complicated molecules
there is often difculty in showing shape on such structures. What are more useful
are different types of molecular models.
Structural formulae and molecular models
The best description of the physical appearance of molecules is given by so-called
space-lling models as shown in Figures 1.4 on p. 169 and 1.5 on p. 171. However,
these models do not show the nature of the chemical bonding very clearly, and
therefore chemists often use ball-and-stick models which represent molecules as
balls (atoms) held together by sticks (bonds).
A comparison of these two types of models with structural formulae is shown
in Figure 6.2. In ball-and-stick models, the balls are best regarded as nuclei of atoms
with the sticks merely indicating the type and geometry of the bonding; such models
are really skeletons. We have to imagine the electron clouds superimposed upon
them to esh out the skeletons into real molecules: the sticks have no physical reality.
FIGURE 6.2
Ball-and-stick models,
structural formulae and
space-lling models of
methane, ammonia and
ethene
Shapes of simple carbon molecules
We saw in Section 4.1 on pp. 2323 that the four single bonds in methane were
tetrahedrally arranged about the carbon atom. This is true in all molecules in
which carbon forms only single bonds. In ethane, the four bonds around each
carbon atom are tetrahedrally arranged. This gives the molecule the shape shown
in Figure 6.3. Note that it is the ball-and-stick model that shows the shape most
clearly. When a carbon atom forms a double bond and two single bonds as in
ethene, the atoms are planar. In ethene, all six atoms lie in the one plane as
Figure 6.2 shows. When the carbon atom forms two double bonds as in carbon
dioxide, the arrangement of atoms is linear (Figure 6.3). These shapes are
summarised in Table 6.2.
TABLE 6.2 Geometrical arrangement of bonds around carbon atoms
Bonds around the C atom
Geometrical
arrangement
of the bonds Example
four single bonds
tetrahedral methane (Fig. 6.2)

one double and two single
planar (angle between

bonds 120)
ethene (Fig. 6.2)
two double bonds

linear carbon dioxide
(Fig. 6.3)
one triple and one single linear ethyne (Fig. 6.3)

Ball-and-stick and
space-lling models for
carbon dioxide, ethane
and ethyne
The huge number of carbon compounds
than of any other element, except hydrogen (but that is because carbon compounds
almost always contain hydrogen). In fact the vast majority of compounds known to
chemists are carbon compounds. This is because:
carbon readily forms carboncarbon bonds
these bonds can be single, double or triple, and
carbon readily forms cyclic compounds (rings) as well as straight and branched
chain compounds.
And in all of these carboncarbon compounds carbon always forms four covalent
bonds (4 single, 1 double plus 2 single, 2 double, or 1 triple plus 1 single as in
Table 6.2).
Many of the compounds of carbon contain only carbon and hydrogen.
These are called hydrocarbons.
Let us now look more closely at some hydrocarbons.
6.4 ALKANES
Hydrocarbons in which all the bonds are single bonds are called alkanes.
The simplest alkanes are methane, CH
4
, and ethane, C
2
H
6
(Figures 6.2 and
6.3). The next two alkanes are propane, C
3
H
8
, and butane, C
4
H
10
. Models and
structural formulae are shown in Figure 6.4.
Although the structural formulae in Figures 6.2, 6.3 and 6.4 have been drawn
at and with bonds at right angles to one another, this is not the true shape of
these molecules. The four bonds around each carbon atom are tetrahedrally arranged,
regardless of whether the bonds join to hydrogen atoms or to other carbon atoms. The
true shape of these molecules is best appreciated by examining models of the types
depicted in Figures. 6.2, 6.3 and 6.4.
EXERCISES
1 Carbon disulde has two sulfur atoms attached to a central carbon atom. Draw
an electron-dot structure and structural formula for it. What shape do you expect
for this molecule? Why? Do you expect carbon disulde to be polar or non-polar?
Explain why.
2 Draw electron-dot diagrams and structural formulae for:
a formaldehyde (systematic name methanal), H
2
CO (H and O atoms all attached
to the C atom)
b nitrosyl chloride, ClNO (Cl and O atoms attached to a central N atom)
c hydrogen cyanide, HCN (H and N atoms attached to a central C atom)
3 a What shape do you expect for the molecules of formaldehyde and hydrogen
cyanide in Exercise 2?
b Nitrosyl chloride has a bent shape. Which (if any) of the three molecules in
Exercise 2 do you expect to be polar and which (if any) non-polar? Explain
your reasoning.
There is a whole family of alkanes made up of different numbers of carbon
atoms joined together to form a single chain. They are called straight-chain
alkanes, meaning that all the carbon atoms are joined in the one continuous
string. Names and structures of the rst eight straight-chain alkanes are given in
Table 6.3 on the next page. Straight-chain alkanes are a sub-group of straight-chain
hydrocarbons: we will meet other sub-groups in Sections 6.5 and 6.6.
Although we call them straight-chain alkanes, the chain is not really straight
at all, but rather it is zig-zagged or twisted up, because the CCC angle is the
normal tetrahedral angle of 109.

Figure 6.5 illustrates how a carbon chain can be roughly linear or all curled
up into a ball. In both cases all the CCC, CCH and HCH angles are still 109.
Straight-chain alkanes have all carbon atoms joined together in the one string
so that no carbon atom is joined to more than two other carbon atoms. In addition
there are branched-chain alkanes with carbon skeletons such as:

In branched-chain compounds, at least one carbon atom is attached to more
than two other carbon atoms.
When drawing structures of actual molecules, we must always include all the
hydrogen atoms. The H atoms have been left off the red structures above in order
to show more clearly the nature of the carbon chains.

FIGURE 6.4
Models and structural
formulae for propane,
C
3
H
8
, and butane, C
4
H
10
TABLE 6.3 The rst eight straight-chain alkanes
Name
Molecular
formula
Boiling point
(C)
a
Physical
state
b
Structural formula
methane CH
4
162 gas
H
|
HCH
|
H
ethane C
2
H
6
89 gas
H H
| |
HCCH
| |
H H
propane C
3
H
8
42 gas
H H H
| | |
HCCCH
| | |
H H H
butane C
4
H
10
0.5 gas
H H H H
| | | |
HCCCCH
| | | |
H H H H
pentane C
5
H
12
36 liquid
H H H H H
| | | | |
HCCCCCH
| | | | |
H H H H H
hexane C
6
H
14
69 liquid
H H H H H H
| | | | | |
HCCCCCCH
| | | | | |
H H H H H H
heptane C
7
H
16
98 liquid
H H H H H H H
| | | | | | |
HCCCCCCCH
| | | | | | |
H H H H H H H
octane C
8
H
18
126 liquid
H H H H H H H H
| | | | | | | |
HCCCCCCCCH
| | | | | | | |
H H H H H H H H
a
at standard atmospheric pressure.
b
at normal atmospheric pressures and temperatures.
Homologous series
The molecular formulae in Table 6.3 are all special cases of the general formula
C
n
H
2n+2
where n can be 1, 2, 3, 8,
A family of compounds which can be represented by one general molecular
formula is called an homologous series.
Table 6.3 presents the rst eight members of the homologous series called
alkanes. Alkanes have the general formula C
n
H
2n+2
. Alkanes having up to 30 and
40 carbon atoms per molecule are quite common. Alkanes are hydrocarbons in
which all the carboncarbon bonds are single ones; there are no double or triple
bonds (Section 6.2).
In carbon chemistry there are many families of related compounds with very
similar physical properties and reactionsthat is, many homologous series. Hence
the study of this branch of chemistry is the study of structure and properties of
families of compounds rather than of individual substances.
Naming alkanes
Because there are so many carbon compounds, we need a systematic method of
naming them. With systematic names, the name allows us to work out the structure
of the molecule, and the structure allows us to work out the name. This avoids
having to memorise long lists of names and structures.
The name for a carbon compound consists of a stem, which tells us the length
of the carbon chain, and a sufx (ending), which tells us the family the compound
belongs to; for example the alkanes have the ending ane. The stems for the rst
eight members of the series are:
C
1
meth C
4
but C
7
hept
C
2
eth C
5
pent C
8
oct
C
3
prop C
6
hex
Combination of these stems with the sufx ane leads to the names in Table 6.3.
While it may seem difcult to have to memorise these eight stem names, it is
essential because they keep recurring in all the families we shall be dealing with.
FIGURE 6.5
Space-lling models of
octane showing how the
molecule can be stretched
out or curled up while
keeping all the bond
angles at the tetrahedral
value of 109
Systematic names are sometimes called IUPAC nomenclature, because IUPAC,
the International Union of Pure and Applied Chemistry, is the body that draws
up the rules for systematic naming of compounds. Systematic naming was only
introduced in the 1930s and the use of the pre-existing non-systematic names,
called trivial names, was so entrenched in the chemical industry that many of
them continue to be used and some of these are now the preferred IUPAC names.
Examples are ethylene (for ethene) and acetic acid (for ethanoic acid). Trivial
names such as the two just mentioned do not give any indication of the structure
of the compound they refer to.
Physical properties
As Table 6.3 shows, the simplest alkanes (C
1
to C
4
) are gases at room temperature.
Alkanes with 5 to about 18 carbon atoms per molecule are colourless liquids, while
compounds with 20 or more carbon atoms per molecule are waxy solids. Parafn
wax and Vaseline are mixtures of alkanes with about 30 carbon atoms per molecule.
In other words:
the melting and boiling points of alkanes increase as molecular weight increases
(that is as the number of C atoms per molecule increases).
The densities of both liquid and solid alkanes are signicantly less than that of
water (1.00 g/mL). Alkanes are insoluble in water and, as expected for molecular insoluble in water insoluble in water
compounds, they do not conduct electricity.
We can explain these properties in terms of molecular structure.
In Section 4.2 on pp. 2345 we saw that CH bonds were slightly polar, but that
in symmetrical structures such as methane the small dipoles cancel out to produce
non-polar molecules. Even though not all alkanes are strictly symmetrical, alkanes
are non-polar molecules. This is because CC bonds are non-polar, CH bonds are
only slightly polar, and the geometry usually cancels out much of this small polarity.
This lack of polarity accounts for alkanes being insoluble in water (a polar solvent).
Being non-polar, the only intermolecular forces between alkane molecules are
dispersion forces (Section 4.3 on p. 235). These are quite weak intermolecular
forces so it is easy to separate alkane molecules from one another. This means that
alkanes have relatively low boiling and melting points.
Dispersion forces arise from the attraction of the nuclei of one molecule for the
electron cloud of a neighbouring molecule. This attraction is of course opposed
by the repulsion between the electron clouds of the neighbouring molecules, so
the force of attraction is quite small. However, dispersion forces do increase as
the number of electrons in the electron cloud increases. This means that:
dispersion forces increase as molecular weight increases.
This is the reason why boiling points of alkanes increase as molecular weight
increases.
The volatility of a substance is the ease with which it can be converted to
a vapour. Volatility increases as boiling point decreases. So for alkanes, volatility
decreases as molecular weight increases.
6.5 ALKENES
Hydrocarbons which contain a double bond between a pair of carbon atoms are
called alkenes.
The simplest alkene is ethene, C
2
H
4
:

Its structure was discussed in Section 6.2. You will recall that a double bond
consists of two pairs of electrons being shared by the two carbon atoms. A
consequence of this is that the molecule is planar (Section 6.3): each HCH
and HCC angle is 120. Models of ethene were shown in Figure 6.2.
There is a whole family or homologous series of alkenes with general formula,
C
n
H
2n
, with n > 1. The rst three members are ethene (above), propene, C
3
H
6
,
and butene, C
4
H
8
.
Refer to Context 3 Transport, pp. 1047.

EXERCISES
4 What would be the molecular formula and molecular weight of the alkane
containing the following numbers of carbon atoms?
a 9 b 13 c 24
5 Give the name and molecular formula for each of the following compounds:
a b
6 Write the structural and molecular formulae for:
a hexane b octane
7 Do hexane, C
6
H
14
, and cyclohexane, C
6
H
12
, belong to the same homologous
series? Explain.
8 For the alkanes in Table 6.3 (except for methane) plot boiling point against number
of carbon atoms in the molecule. Draw a suitable curve through the points and
summarise how boiling point depends upon number of carbon atoms in the
molecule. Keep this graph for Exercise 19.

*
Structures (2), (3) and (4) are different ways of representing propene.
(2) tries to show the planar geometry about the double bond, and the tetrahedral
arrangement about the other carbon atom. (3) shows the geometry about the
double bond but leaves it to the reader to infer the tetrahedral shape about the
H
3
C carbon. (4) is the simplest way of writing propene: it makes no attempt to
show geometry. (2) is a full structural formula. (4) is called a condensed structural
formula, while (3) is an intermediate type.
Names, structures and boiling points for seven members of the homologous
series of alkenes are shown in Table 6.4. It uses condensed structural formulae.
TABLE 6.4 Formulae and boiling points of common alkenes
Name Formula Boiling point (C)
ethene CH
2
CH
2
103.7
propene CH
3
CHCH
2
47.7
1-butene CH
3
CH
2
CHCH
2
6.3
1-pentene CH
3
CH
2
CH
2
CHCH
2
30.0
1-hexene CH
3
CH
2
CH
2
CH
2
CHCH
2
63.5
1-heptene CH
3
CH
2
CH
2
CH
2
CH
2
CHCH
2
93.6
1-octene CH
3
CH
2
CH
2
CH
2
CH
2
CH
2
CHCH
2
121.3
A condensed structural formula is a cross between a molecular formula and a
full structural formula. It provides enough detail for a full structural formula to be
written if required, but writes common groups of atoms (for which the reader can
be assumed to know the full structural arrangement) in molecular formula form.
For comparison with the condensed structural formula given in Table 6.4, the full
structural formula of 1-hexene is:
As you gain prociency in carbon chemistry you will nd yourself using

condensed structural formulae more frequently, although at this stage it is probably
best to stick with full structural formulae or perhaps the intermediate type such as
(3) above.
Isomers
For the straight-chain alkene with four carbon atoms there are two possible structures:
(5) CH
3
CH
2
CHCH
2
(6) CH
3
CHCHCH
3
Structure (5) has the double bond between the rst and second carbon atoms
(counting from the right end) while (6) has it between the second and third carbon
atoms. Both of these structures exist. They are quite distinct compounds with
different boiling points and densities.
Boiling point (C) Density (g/mL)
CH
3
CH
2
CHCH
2
6.3 0.589
CH
3
CHCH CH
3
+3.7 0.615
There are actually two compounds with this structure. The other one has a boiling point of 0.9C
and a density of 0.598 g/mL. Can you work out the structural difference between them?
These two compounds are called isomers.
Isomers are sets of different compounds that have the same molecular formula
(but different structural formulae).
The two compounds in the above table have different structural formulae
(double bond in different places) but are both C
4
H
8
.
Similarly, a straight-chain compound with ve carbon atoms and one double
bond gives rise to two isomers of C
5
H
10
:
(7) CH
3
CH
2
CH
2
CHCH
2
(8) CH
3
CH
2
CHCHCH
3
At rst sight structure (9)
(9) CH
3
CHCHCH
2
CH
3
looks to be another isomer. However it is actually just (8) written the other way
round: the double bond is still between the second and third carbon atoms along
the chain. The best way to convince yourself that (8) and (9) are identical is to build
models and compare them.
This existence of isomers raises the question of how to name these compounds.
Naming alkenes
To name straight-chain alkenes:
take the usual stem name (but-, pent- hex-, etc) to denote the number of carbon
atoms in the chain, then add the ending -ene to denote a compound containing a ene ene
double bond
then show the location of the double bond by putting in front of the name the
number of the carbon atom at which the double bond starts
begin the numbering of the carbon chain from the end of the molecule that
minimises the number for the double bond.
Compound (5) above is 1-butene (not 3- or 4-butene), while (6) is 2-butene
(not 3-butene). Compound (7) is 1-pentene while (8) and (9) are different ways
of writing 2-pentene (not 3-pentene).
C
2
H
4
and C
3
H
6
are called ethene and propene: no 1- is used with these
compounds, because no isomers are possible.
Physical properties
The straight-chain alkenes have similar physical properties to the alkanes. The
C
2
to C
4
alkenes are gases while the C
5
to C
17
ones are liquids with boiling point
increasing as molecular weight increases. Boiling points of alkenes are slightly lower
than those of corresponding alkanes (compare Tables 6.3 and 6.4). Densities are
similar to those of corresponding alkanes. Alkenes are insoluble in water and do not
conduct electricity.
These properties arise because alkenes contain only CC and CC bonds which
are non-polar, and CH bonds which are just slightly polar. This means that alkene
molecules, like alkanes, are non-polar so that the only intermolecular forces are weak molecules, like alkanes, are non-polar molecules, like alkanes, are non-polar
dispersion forces. This explains their low boiling points and their insolubility in water.
EXERCISES
9 Write the molecular formulae for the alkenes in Table 6.4.
10 a Draw a complete structural formula for 1-pentene.
b Draw condensed structural formulae for heptane and 3-heptene.
11 What are the molecular formulae for alkenes containing the following numbers of
carbon atoms?
a 9 b 13 c 18
12 Do 1-butene and 3-hexene belong to the same homologous series? Justify your
answer.
13 Name the following compounds and give their molecular weights:
a CH
3
CH
2
CHCHCH
2
CH
3
b CH
3
CHCHCH
2
CH
2
CH
2
CH
2
CH
3
14 Draw the structural formula for and name an isomer of each of the compounds (a)
and (b) in Exercise 13.
15 Draw structural formulae for:
a 2-hexene b 3-heptene
16 What is wrong about the following names? Give the correct names.
a 5-octene b 3-pentene c 1-propene
17 Which of the following compounds are pairs or sets of isomers? Which (if any) are
structures that represent the same compound?
a CH
3
CHCHCH
2
CH
3
b CH
2
CHCH
2
CH
3
c CH
3
CCCH
3
| |
33
H H
d H H
| |
CH
3
C CCCH
3
| |
33
H H
e CH
3
CH
2
CHCHCH
2
CH
3
f CH
3
CH
2
CH
2
CHCHCH
3
g H H H H H
| | | | |
HCCCCCCH
| | | | |
H H H H H
18 Name the compounds in Exercise 17 and give their molecular formulae.
19 On the same graph you used in Exercise 8, plot boiling points of the alkenes in
Table 6.4 against number of carbon atoms in the molecule. Use a different symbol
for these points so they are clearly distinguishable from the alkane points. Draw
a suitable line through the points and summarise the way that boiling points of
alkenes depend upon number of carbon atoms. In addition, what can you say
about boiling points of alkenes compared with those of alkanes?

6.6 ALKYNES
There is a homologous series of hydrocarbons containing triple bonds. The general
formula for the series is C
n
H
2n2 nn
(again with n > 1). They are called alkynes. The
simplest member is ethyne, C
2
H
2
. It is commonly called acetylene and widely used
in oxyacetylene torches (Fig. 6.6) for cutting and welding. Its structure is:
HCCH
It was described in Sections 6.2 and 6.3. Models of it were shown in Figure 6.3.
Ethyne is a linear molecule. In the other alkynes the two bonds either side of the
triple bond lie in a straight line with the triple bond. The next three members of the
alkyne family are:
(10) CH
3
CCH (11) CH
3
CH
2
CCH
(12) CH
3
CH
2
CH
2
CCH
As with alkenes, isomerism is possible in straight-chain alkynes with four or
more carbon atoms. Compounds (13) and (14) are isomers of (11) and (12)
respectively:
(13) CH
3
CCCH
3
(14) CH
3
CH
2
CCCH
3
Naming alkynes
To name straight-chain alkynes:
take the usual stem name (but-, pent- hex-, etc) to denote the number of carbon
atoms in the chain then add the ending, -y atoms in the chain then add the ending, - atoms in the chain then add the ending, - ne, to denote a compound containing
a triple bond
then show the location of the triple bond by putting in front of the name the
number of the carbon atom at which the triple bond starts
begin the numbering of the carbon chain from the end of the molecule which
minimises the number for the triple bond.
Compound (11) is 1-butyne, (12) is 1-pentyne, (13) is 2-butyne and (14) is
2-pentyne.
Numbers are not used with ethyne and propyne because they have no isomers.
FIGURE 6.6
Oxy-acetylene torches
are widely used for cutting
and welding steel
Properties
insoluble in water.
Saturated and unsaturated compounds
Alkenes and alkynes are called unsaturated hydrocarbons. This means unsaturated
with respect to hydrogen, because it is possible to attach more hydrogen to the
molecule by breaking the double or triple bond and forming single bonds to extra
hydrogen atoms (for example to convert C
2
H
2
or C
2
H
4
to C
2
H
6
). Alkanes are
called saturated hydrocarbons, because they contain the maximum number of
hydrogen atoms that the particular carbon skeletons can accommodate.
Vegetable oils such as
olive and peanut contain
unsaturated CC
bonds. Polyunsaturated
margarine is made by
converting some of these
CC bonds to single
bonds. A saturated fat
or cooking margarine
contains only single
CC bonds.
EXERCISES
20 What are the molecular formulae of alkyne molecules containing the following
numbers of carbon atoms?
a 7 b 11 c 16
21 A particular hydrocarbon has the molecular formula C
6
H
10
. Could this hydrocarbon
be an alkyne? Explain.
22 How many straight-chain alkynes are there with the molecular formula C
7
H
12
? Draw
their structures.
23 a Name the following alkynes:
i CH
3
CCCH
2
CH
2
CH
3
i CH
3
CH
2
CH
2
CH
2
CCCH
2
CH
3
b Draw structural formulae for:
i 2-pentyne ii 3-heptyne
24 How many atoms of hydrogen need to be added to molecules of:
a 2-pentene b 2-hexyne
to convert them to saturated compounds? What would be the names of the
saturated compounds so formed?
6.7 REACTIONS OF ALKANES
For alkanes there are only two important reactions:
1 Alkanes burn in air to form carbon dioxide and water. In doing so they liberate Alkanes burn in air Alkanes burn in air
large amounts of heat, for example:
For propane: C
3
H
8
(g (( ) + 5O gg
2
(g (( ) gg 3CO
2
(g (( ) + 4H gg
2
O(g O( O( ) gg
For octane: C
8
H
18
(g (( ) + 12O gg
2
(g (( ) gg 8CO
2
(g (( ) + 9H gg
2
O(g O( O( ) gg
It is this combustion reaction that makes alkanes useful to us as fuels.
2 Alkanes react with chlorine and bromine when the mixtures are exposed to ultraviolet
(u.v.) light, for example: (u.v.) light (u.v.) light
For methane: CH
4
(g (( ) + Cl gg
2
(g (( ) gg CH
3
Cl(g Cl( Cl( ) + HCl( gg g ) + HCl( ) + HCl( ) gg
(chloromethane)
For hexane: C
6
H
14
(l) + Br ll
2
(soln) C
6
H
13
Br(soln) + HBr(soln)
(bromohexane)
A reaction such as these in which an atom in a molecule is replaced by
another atom or group of atoms is called a substitution reaction.
A variety of other products can be formed by these reactions, depending
upon the conditions used, but for our present purposes the key point to note is
that alkanes do not react with (decolorise) chlorine or bromine solutions in the
absence of u.v. light but that they do react (quite slowly for the liquid ones) in
the presence of u.v. light. This contrasts with the behaviour of alkenes.
EXERCISES
25 Write equations, using molecular formulae, for the combustion of:
a butane b hexane *c
octane
26 Write equations for the reaction of butane with chlorine in the presence of ultraviolet
light. How many monosubstituted chloro-compounds (that is, compounds with only
one Cl atom per molecule) can be formed? Draw their structures.
27 a When ethane is reacted with bromine in the presence of u.v. light, under
certain conditions compounds having two Br atoms per molecule are formed.
Draw structures to show that two such compounds (isomers) are possible.
b Under other conditions compounds with three Br atoms per molecule are
possible. How many isomers with three Br atoms are possible from ethane?
provided.
6.8 REACTIONS OF ALKENES
The presence of the double bond in alkenes makes them very reactive. There are
many substances which react with alkenes by opening out the double bond to form
two single bonds: these are called addition reactions. The general form of addition
reactions is
(6.1)
where XY is a molecule such as Cl

2
, Br
2
, H
2
, HCl, HBr, HOH (H
2
O) and where
R
a
, R
b
, R
c
and R
d
represent the rest of the alkene moleculeeither H atoms or
what are called alkyl groups.
An alkyl group is an alkane molecule with one hydrogen atom missing: it does not
exist on its own, but is part of another molecule.
Alkyl groups are named by deleting the -ane from the parent alkane and adding
-yl -- . The simplest alkyl groups and their parent alkanes are shown in Table 6.5.
TABLE 6.5 Names and formulae of simple alkyl groups
Alkane Name Alkyl group Name
CH
4
methane CH
3
methyl
CH
3
CH
3
ethane CH
3
CH
2
ethyl
CH
3
CH
2
CH
3
propane CH
3
CH
2
CH
2
propyl
CH
3
CH
2
CH
2
CH
3
butane CH
3
CH
2
CH
2
CH
2
butyl
Two addition reactions that are often used in the laboratory to distinguish alkenes
from alkanes are:
the reaction of chlorine or bromine in a non-aqueous solvent such as chloroform
or hexachloroethane, for example chlorine with 2-pentene:
CH
3
CH=CHCH
2
CH
3
+ Cl
2
CH
3
CHCHCH
2
CH
3
| |
33 22 33 22 33
Cl Cl
(2,3-dichloropentane)
the reaction of chlorine or bromine in aqueous solution, for example bromine
water with 3-hexene:
Br
2
+ H
2
O sHOBr + Br
+ H
+
CH
3
CH
2
CH=CHCH
2
CH
3
+ HOBr CH
3
CH
2
CHCHCH
2
CH
3
| |
33 22 22 33 33 22
OH Br
(4-bromo-3-hexanol)
In both of these reactions the alkene decolorises the pale yellow chlorine solution or
the brown bromine solution. Alkanes do not react with these reagents and so do not
decolorise the solutions.
Addition reactions of alkenes are summarised in Figure 6.7. Although ethene is
used as the alkene (for simplicity), all alkenes undergo these reactions. all all

EXERCISES
28 Write balanced equations for the combustion (in excess oxygen) of:
a propene b 1-pentene *c 1-octene
Use molecular formulae for all substances involved.
29 Write equations for the reaction of (i) hydrogen (using a catalyst) (ii) chlorine
(iii) bromine water, with each of the alkenes
a propene b 2-butene *c 1-pentene
Use structural formulae for the carbon compounds.
30 Write equations for the reaction of hydrogen chloride with:
a propene b 1-butene *c 3-hexene
If two products are possible, give both.
31 Write equations for the reaction of aqueous acid solution with
a propene *b 2-butene
If two products are possible, give both.
32 Draw structural formulae for the products of the following reactions:
a 1-butene with
i bromine ii hydrogen bromide iii water (with H
+
catalyst)
b 2-pentene with
i bromine water ii hydrogen (with Ni catalyst)
33 a When a few drops of a solution of bromine in chloroform were added to a
certain compound A and the mixture shaken, there was no apparent reaction.
When a solution of bromine in water was added to another sample of the same
compound, again after shaking the mixture there was no apparent reaction.
What do you conclude about the compound?
b When similar tests were performed on a different compound, B, this compound
decolorised both of the bromine solutions. What do you conclude about
compound B?
c The same two tests were performed on compound C on a sunny patio outside
the laboratory. Compound C slowly decolorised both bromine solutions.
When the tests were repeated inside the laboratory in very subdued light,
neither solution was decolorised. Explain these results and draw a conclusion
about the nature of compound C.
FIGURE 6.7
Common addition reactions
of alkenes (examples of
Reaction 6.1)

6.9 FUNCTIONAL GROUPS
a double bond is introduced, the molecule becomes much more reactive, but the
reactivity is associated with the double bond, not with the rest of the molecule.
Similarly, when a halogen atom, OH group or NH
2
group replaces a hydrogen atom
in an alkane, the molecule becomes much more reactive, again with the reactivity
centred around the halogen atom, the OH group or the NH
2
group. Hence we use
the term functional group, to describe the centre of reactivity in a carbon compound. centre of reactivity centre of reactivity
In alkenes, the functional group is the double bond. The functional group is where
the action is.
Carbon compounds may be considered as relatively unreactive alkyl groups
(see p. 282), attached to functional groups which are the reactive centres of the
molecules. Figure 6.8(a) shows two alkenes with the functional group and the
alkyl groups identied.
Another family of carbon compounds is the alkanols of which ethanol
(common alcohol) is the best known member. Alkanols contain the functional
group COH called the alcohol functional group (or hydroxyl group).
Figure 6.8(b) shows two alkanols with the functional group and the alkyl groups
identied.
All molecules with a particular functional group react very similarly, regardless
of which carbon, hydrogen chain(s) is(are) attached. Therefore the study of carbon
compounds is really the study of the reactions of the various functional groups.
(a)
(b)
FIGURE 6.8
Functional groups
and unreactive alkane
fragments (alkyl groups)
(a) for two alkenes (b) for
two alkanols (with the
alcohol functional group)
Functional groups are used for naming compounds. Each functional group has
its own particular ending (sufx) which is added to the usual stem. Compounds
containing the double bond functional group have names ending in ene (butene,
hexene, etc); compounds containing the CC functional group have names ending
in yne in in . The alcohol group gives rise to the ending -ol as in ethanol, butanol, etc. ol ol
We will meet other functional groups later.
addition reactions (p. 282)
alkanes (p. 270)
alkenes (p. 275)
alkyl group (p. 282)
alkynes (p. 279)
ball-and-stick models (p. 268)
branched-chain alkanes (p. 271)
condensed structural formula (p. 276)
double bonds (p. 266)
functional group (p. 284)
homologous series (p. 273)
hydrocarbons (p. 270)
isomers (p. 277)
IUPAC nomenclature (p. 274)
Lewis electron-dot structures
(Lewis structures) (p. 267)
saturated hydrocarbons (p. 280)
single bonds (p. 265)
space-lling models (p. 268)
straight-chain alkanes (p. 271)
structural formulae (p. 267)
substitution reaction (p. 281)
systematic names (p. 273)
triple bond (p. 266)
trivial names (p. 274)
unsaturated hydrocarbons (p. 280)
volatility (p. 274)
IMPORTANT NEW TERMS
TEST YOURSELF
above.
2 Draw electron-dot structures for a carbon atom, carbon dioxide, ethene, nitrogen
gas and ethyne (acetylene).
3 Sketch space-lling and ball-and-stick models of ethene.
4 Write the molecular and structural formulae for methane. State clearly the spatial
arrangement of the bonds in the molecule.
5 Name two homologous series of hydrocarbons.
6 Name the rst eight alkanes and give their molecular formulae.
7 What is the general formula for the alkanes?
8 Give the structural and condensed structural formulae for hexane.
9 For straight-chain alkanes, how does boiling point vary with the number of carbon
atoms in the molecule? How does volatility vary?
10 Give the name and molecular and structural formulae of the simplest alkene, and
describe the shape of the molecule.
11 Name the rst seven straight-chain alkenes and give their molecular formulae.

12 Give the general formula for the alkenes.
13 Give an example of isomerism in straight-chain alkenes. Name the compounds
used.
14 Draw structural formulae for three isomers of C
6
H
12
and name them.
15 How do the boiling points of alkenes compare with those of alkanes (with the same
numbers of carbon atoms per molecule)?
16 What are the functional groups (if any) in propene, propane and 1-butyne?
17 What is the general formula for the alkynes?
18 Give the molecular and structural formula for the simplest alkyne and describe the
shape of its molecule. What are its systematic and trivial name?
19 Write molecular formula for and name the following:
a C
3
H
4
b C
6
H
10
c C
8
H
14
20 Draw all possible straight-chain isomers of C
5
H
8
and give their systematic names.
21 How do the boiling points of alkynes compare to those of alkanes and alkenes (with
the same numbers of carbon atoms per molecule)?
22 What is the difference between a saturated and unsaturated compound?
23 What are the two major reactions of alkanes? Write equations for a specic
example of each.
24 Write an equation for the reaction of butane with Br
2
.
25 List ve addition reactions of alkenes. Write an equation for a specic example of
each, using either propene or a butene as the alkene.
26 Name and give the formulae of the rst six alkyl groups.
27 Describe a test for distinguishing between an alkane and an alkene.
CHAPTER 7
Energy changes and
rates of reaction
Exothermic and endothermic reactions
Enthalpy
Explaining chemical energy changes
Temperature, quantity of heat and
heat capacity
Measuring enthalpy changes for reactions
Heat of combustion
Two basic drives: energy and entropy
Activation energy
Meaning of rate of reaction
Factors inuencing the rate of reaction
Explanations
Temperature effect and activation energy
Catalysis
IN THIS CHAPTER
287
In the Transport context we saw that our main sources of energy today are
fossil fuels. We obtain energy from these fuels by burning themin a process
called combustion.
Combustion is a process in which a self-sustaining chemical reaction occurs
at temperatures above those of the surroundings. More simply, combustion is
burning. Explosions are also forms of combustion.
Some common combustion reactions are the burning of coke (carbon), petrol
(for example, octane) and natural gas (methane). The reactants are oxygen from the
air and the greyish-black solid (coke), the colourless liquid (octane) and the colourless
gas (methane). Each of these burns with a bluish ame to form colourless carbon
dioxide gas and colourless water vapour.
Chemical reactions have occurred here (rather than just physical changes) because:
light and much heat have been emitted
completely new substances have been formed (CO
2
and H
2
O)
the processes cannot easily be reversed.
The chemical equations for the combustion reactions just described are:
For coke: C(s) + O
2
( g) gg CO
2
( g) gg
For methane: CH
4
( g) + 2O gg
2
( g) gg CO
2
( g) + 2H gg
2
O( g) gg
For octane: C
8
H
18
(l ) + 12O
2
( g) gg 8CO
2
( g) + 9H gg
2
O( g) gg
The amounts of heat released in the above reactions are 393 kJ/mol for coke,
890 kJ/mol for methane and 5460 kJ/mol for octane.
All combustion reactions liberate large amounts of heat. They are what we call
exothermic reactions.
7.1 EXOTHERMIC AND ENDOTHERMIC
REACTIONS
As we saw in Chapter 2, in most chemical reactions signicant amounts of energy
are either released or absorbed. We use special terms to describe this release or
absorption of energy:
Reactions that release heat are called exothermic reactions.
Reactions that absorb heat are called endothermic reactions.
Examples of exothermic chemical reactions (apart from combustion)
are:
direct combination reactions
(Mg + O
2
, Cu + S, H
2
+ Cl
2
, P + Cl
2
)
eg. 2Mg(s) + O
2
(g (( ) gg 2MgO(s)
reactions of metals with water and acids
( Na + H
2
O, Mg + HCl)
eg. Mg(s) + 2HCl(aq) MgCl
2
(aq) + H
2
(g (( ) gg
reactions of acids with bases
(HCl + NaOH, H
2
SO
4
+ CuO, HNO
3
+ NH
3
)
eg. CuO(s) + H
2
SO
4
(aq) CuSO
4
(aq) + H
2
O(l) ll
Examples of endothermic chemical reactions are:
decomposition reaction of CaCO
3
(to form CaO and CO
2
)
formation of synthesis gas (CO + H
2
) for industry by reacting CH
4
or C with steam
some precipitation reactions such as MgCl
2
+ Na
2
CO
3
.
There are far more exothermic reactions than endothermic ones.
When we carry out an exothermic reaction in a test tube, the test tube gets hot.
This is because as the reaction occurs there is a decrease in chemical energy and
the lost chemical energy is released as heat, which warms up the test tube and
its contents. When an endothermic reaction occurs, the test tube gets cold. This
is because the reaction as it occurs needs to take in heat (to convert to chemical
energy). The only place the reaction can
get this heat is from the test tube and its
contents and so they get cold.
Unfortunately the heat released or
absorbed during a reaction depends to
some extent on the conditions under which
the reaction is carried out, in particular
upon whether it is performed at constant
volume (in a closed vessel) or at constant
pressure (in a container open to the
atmosphere). This is particularly true for
reactions involving gases. When we compare
heats from different reactions, we should
do so using constant conditions. Hence we
introduce a new term called enthalpy.
Combustion of methane
(natural gas) is an
exothermic reaction that
is widely used for cooking
in homes
CHAPTER 7 ENERGY CHANGES AND RATES OF REACTION 289 CHAPTER 7 ENERGY CHANGES AND RATES OF REACTION 289
7.2 ENTHALPY
Enthalpy is a measure of the total energy possessed by a substance or group of
substances. We can think of enthalpy as being mainly the chemical energy stored
in a substance. Unfortunately we cannot measure this total energy or enthalpy of
a substance; all we can do is measure changes in it.
The change in enthalpy for a chemical reaction, in enthalpy H, is dened as the heat HH
absorbed (per mole of specied reactant or product) when the reaction occurs
at constant pressure.
Since most experiments we shall be dealing with occur at constant pressure (open
to the atmosphere), the heat absorbed or released will be a direct measure of H. HH
By change in enthalpy we mean the increase in enthalpy in going from
reactants to products:
H = enthalpy of products enthalpy of reactants HH (7.1)
in front of a symbol means change in, and it always means nal state minus
initial statealways products minus reactants. Since H is dened as heat absorbed HH
in going from reactants to products:
for endothermic reactions, H is positive HH
for exothermic reactions, H is negative HH
Figure 7.1 shows graphically the relation between enthalpies of products and
reactants, and H for endothermic and exothermic reactions. HH
The denition of H above includes the term HH per mole of specied reactant or
product, because it is often possible to write the reaction in more than one way. product product
Refer to Context 3 Transport, pages xxx.

FIGURE 7.1
Graphical representation
of enthalpy changes
For example, the statement that H for the formation of water from hydrogen HH
and oxygen is 572 kJ is ambiguous because it does not make clear whether the
reaction concerned is:
2H
2
( g) + O gg
2
( g) gg 2H
2
O(l )
or H
2
( g) + O gg
2
( g) gg H
2
O(l )
Ambiguity is removed by saying:
H = 572 kJ per mole of oxygen HH
or H = 286 kJ per mole of water (or of hydrogen) HH
Alternatively, the reaction referred to can be specically written, for example:
H
2
( g) + O gg
2
( g) gg H
2
O(l ) H = 286 kJ/mol HH (7.2)
Here, per mole means per mole of the reaction as written, in this case per mole of
hydrogen or per mole of water.
We put per mole in the units of H to show that the value is not a per HH
molecule one, because as we saw in Section 3.6 equations can be read in terms of
molecules or moles.
H depends upon the physical state (solid, liquid, gas or solution) of the HH
reactants and products, and therefore in chemical energy contexts, we always indicate
the physical state of the substances involved in chemical equations.
Equation 7.2 is the usual way of writing the enthalpy change for a chemical
reaction: we write the equation in the normal way, then put a H = expression after HH
it. For the combustion of methane:
CH
4
( g) + 2O gg
2
( g) gg CO
2
( g) + 2H gg
2
O( g) gg H = 890 kJ/mol HH
H is sometimes loosely referred to as the HH heat of reaction.
Examples will illustrate ways that enthalpy changes are determined and used.
EXAMPLE 1
When 3.4 g ethanol, C
2
H
5
OH, was burnt in excess oxygen, 101 kJ of heat was
released. Write the equation for the reaction and calculate the molar enthalpy change,
H, for it.
The equation is
C
2
H
5
OH(l OH( OH( ) + 3O
2
( g) 2CO
2
( g) + 3H
2
O(l O( O( )
We need to calculate the heat released per mole of ethanol used.
Molar mass of ethanol = 2 12.01 + 6 1.01 + 16.0
= 46.1 g/mol
Number of moles of ethanol burnt =
3.4
_____
46.1

= 0.074 mol
Heat released by 0.074 mol = 101 kJ
Heat released per mole =
101
______
0.074

= 1370 kJ/mol
When a reaction releases heat (as here), we say that the heat absorbed is minus the
quantity of heat released (in this case, 1370 kJ/mol). Because H is dened as heat HH
absorbed,
H = 1370 kJ/mol HH
EXAMPLE 2
The molar enthalpy change for the reaction of butane, C
4
H
10
, with oxygen is
2880 kJ/mol. How much heat is absorbed or released (state which) when 1.5 g
butane is burnt in excess oxygen?
Molar mass of butane = 4 12.01 + 10 1.01
= 58.1 g/mol
Number of moles of butane used =
1.5
_____
58.1

= 0.026 mol
H is negative so heat is released when butane burns.
Heat released by 0.026 mol = 0.026 2880
= 74 kJ
EXERCISES
1 Which of the following reactions are exothermic and which are endothermic?
a 2SO
2
( g) + O
2
( g) 2SO
3
( g) H = 198 kJ/mol
b CH
4
( g) + H
2
O( g) CO( g) + 3H
2
( g) H = +206 kJ/mol
c NH
3
(aq (( ) + HCl(aq ) + HCl( ) + HCl( ) NH
4
+
(aq (( ) + Cl
(aq (( ) H = 52 kJ/mol
d Ag
+
(aq (( ) + I
(aq (( ) AgI(s AgI( AgI( ) H = 112 kJ/mol

e NiCl
2
(aq (( ) + Na
2
CO
3
(aq (( ) NiCO
3
(s (( ) + 2NaCl(aq ) + 2NaCl( ) + 2NaCl( ) H = +59 kJ/mol
If reactions (c), (d) and (e) were carried out in thermally insulated containers, for
which ones would the temperature increase as reaction proceeded and for which
would it decrease?
2 When ammonia and hydrochloric acid solutions are mixed in a test tube, the tube
gets warm. When solutions of potassium carbonate and nickel sulfate are mixed
in a test tube, a precipitate forms and the tube gets cold. Write equations for the
reactions that occur. Which reaction (if either) is endothermic and which (if either)
is exothermic? Explain how you decided this from the information given.
3 Write the chemical equation and calculate H for the reaction that occurs in each
of the following:
a when 0.50 g magnesium is burned in air, 12.4 kJ of heat is released
b when 1.1 g zinc is dissolved in excess hydrochloric acid, 2.6 kJ of heat is
liberated
c when an aqueous solution containing 18.0 g magnesium chloride is added
to an excess of sodium carbonate solution, 9.2 kJ of heat is absorbed
(temperature falls)
4 Given the H values in Exercise 1, calculate the amount of heat released or
absorbed (stating whether released or absorbed) when:
a 5.0 g sulfur dioxide reacts with excess oxygen
b 5.0 g nickel chloride is added to excess sodium carbonate solution
c 25 mL 0.20 mol/L HCl is added to 50 mL of a solution containing excess
ammonia
7.3 EXPLAINING CHEMICAL ENERGY
CHANGES
The question of why there are energy changes when chemical reactions occur
warrants consideration.
The reason why decomposition reactions require an input of energy is because
energy is needed to break chemical bonds. Conversely, energy was liberated when
atoms form molecules because making chemical bonds releases energy. That is:
Energy must be supplied to break chemical bonds.
Making chemical bonds releases energy.
In other words, breaking bonds is endothermic while making bonds is exothermic.
In many chemical reactions, some bonds (in reactant molecules) are broken
and new bonds are formed to make the product molecules. Two examples are:
1 When hydrogen burns in oxygen to form water, effectively HH bonds in
hydrogen gas and OO bonds in oxygen gas break and HO bonds form
to make water. The reaction does not actually occur by each reactant breaking
up completely into atoms with the atoms then recombining to form product
molecules, but that is the net effect.
2 When methane burns in oxygen to form carbon dioxide and water, CH
bonds in methane and OO bonds in oxygen gas are broken and CO and
HO bonds are formed to make carbon dioxide and water respectively.
The enthalpy change for a reaction, H, will be the energy required to break HH
the necessary bonds in reactant molecules minus the energy released when the
new bonds are formed:
H = HH
energy to break
energy to make

{
energy to break energy to break
bonds in reactants
}
energy to break energy to break

{
energy to make energy to make
bonds for products
}
(7.3)
This equation is illustrated in Figure 7.2 for the two reactions:
2H
2
( g) + O gg
2
( g) gg 2H
2
O( g) gg (7.4)
N
2
( g) + O gg
2
( g) gg 2NO( g) gg (7.5)
For Reaction 7.4, the energy required to break the HH and OO bonds is
less than the energy released when HO bonds form, so the reaction is exothermic
(H negative). On the other hand, for Reaction 7.5 the energy required to break HH
NN and OO bonds is greater than the energy released when NO bonds
form, so the reaction is endothermic (H positive). HH
Energy diagrams for

forming H
2
O and NO
(Equations 7.4 and 7.5)
In order to calculate energy changes for chemical reactions from experimental
data, we need the concepts of quantity of heat and heat capacity.
7.4 TEMPERATURE, QUANTITY OF HEAT
AND HEAT CAPACITY
Humans have the physiological sensation of hotness or coldness. The physical
quantity used as a measure of this sensation is temperature.
Temperature is a measure of the degree of hotness or coldness of an object or
substance. The hotter the object, the higher its temperature.
If two objects or samples of material are brought into contact, heat will ow from
the hot object to the cold one until the temperature of the two objects is equal. When the
temperature is uniform throughout both objects or samples of material, we say that
thermal equilibrium has been reached.
Quantity of heat
Amount of heat (or quantity of heat) is different from temperature: two objects can be
at the same temperature but contain very different amounts of heat. Consider a red-hot
pin and a red-hot horseshoeboth have the same temperature but they contain very
different quantities of heat. This is demonstrated by the experiments in Figure 7.3.
Three well-insulated beakers each contain 100 g of water at 25.0C. To the rst
is added 10 g of water at 100C, to the second is added 20 g of water at 100C, and
to the third is added 20 g of copper at 100C. After mixing, the nal temperatures
are 32.0C, 37.5C and 26.5C respectively.
EXERCISES
5 Ammonia is made from nitrogen and hydrogen gases. Write an equation for the
reaction. It is an exothermic reaction. What bonds have to be broken and what
bonds made for the reaction to occur? Draw a diagram similar to those in Figure 7.2
for this reaction.
6 a Hydrazine, H
2
NNH
2
, burns in oxygen to form nitrogen gas and water.
Write an equation for the reaction. The reaction is exothermic. Draw an energy
diagram showing the reaction as occurring by breaking hydrazine and oxygen
into atoms and then the atoms forming products.
b The energies required to break all the bonds in hydrazine, oxygen, nitrogen gas
and water are 1722, 498, 945 and 926 kJ/mol respectively. Use these data with
your energy diagram from (a) to calculate H for the reaction.
FIGURE 7.3
Experiment demonstrating
that quantity of heat
depends upon mass,
(a) and (b), and nature
of substance, (b) and (c)

Since the nal temperature in (b) is greater than in (a) of Figure 7.3, we
conclude that the 20 g of water contains more heat than the 10 g of water.
More rened experiments show that:
the amount of heat energy is proportional to the mass of the substance involved.
Comparison of (b) and (c) in Figure 7.3 shows that the 20 g of water contains
more heat than the 20 g of copper. This and other experiments show that:
the amount of heat energy contained in equal masses of different substances
depends upon the nature of the substances involved.
These observations lead to the following denition:
The specic heat capacity, C, of a substance is the amount of heat required to CC
raise the temperature of unit mass of the substance by 1C (or through 1 kelvin).
Specic heat capacity is therefore measured in joules per kelvin per gram,
J K
1
J K J K g
1
. Specic heat capacities of some common liquids are shown in Table 7.1.
TABLE 7.1 Specic heat capacities of some common pure liquids
Substance
Specic heat
capacity
(J K
1
(J K (J K g
1
) Substance
Specic heat
capacity
(J K
1
(J K (J K g
1
)
water 4.18 acetic acid 2.03
hydrogen peroxide 2.62 ethyl acetate 1.94
ethanol 2.44 toluene 1.68
ethylene glycol 2.39 carbon disulde 0.99
octane (in petrol) 2.22 chloroform 0.96
acetone 2.17 gallium ( l, >30C) 0.37
mercury 0.14
High specic heat capacity of water
Tables 7.1 shows that water has a much higher specic heat capacity than other
common liquids. Consequences of this are that:
water plays an important role in regulating the temperature of organisms and
the environment of Earth generally, and
water is widely used to measure energy changes in chemical reactions.
Calculating quantities of heat
Specic heat capacities allow us to calculate the quantities of heat that ow from
one object or substance to another.
From the above denition of specic heat capacity, when an object or a sample
of a substance undergoes a change in temperature, the quantity of heat involved q is
given by:
q = m C T TT (7.6)
where m is the mass, mm C the specic heat capacity and CC T is the change in temperature: TT
T = nal temperature initial temperature TT
If temperature increases (T positive), TT q is positive, which means that the object
has gained heat. If temperature falls (T negative), TT q is negative which means that
the object has lost heat.
Let us illustrate this equation for quantity of heat with an example.
7.5 MEASURING ENTHALPY CHANGES
FOR REACTIONS
Example 4 will illustrate how enthalpy changes for many chemical reactions can
be measured. Reactants (pure or in solution) at the same known temperature are
mixed in a well-insulated container of low heat capacity and the temperature after
complete reaction is noted.
EXAMPLE 3
Calculate the quantity of heat needed to raise the temperature of 155 g water from
17.0C to 35.5C.
We use Equation 7.6 along with the specic heat capacity in Table 7.1:
amount of heat required = 155 4.18 (35.5 17.0)
(for temperature changes, 1C = 1 K)
= 1.20 10
4
J (= 12.0 kJ)
EXERCISES
7 What quantity of heat is needed to heat 1.00 kg water from 20C to 100C?
8 Using data from Table 7.1, calculate the amount of heat needed to increase the
temperature of:
a 25 g acetone from 18C to 55C d 150 g chloroform from 25C to 50C
b 25 g mercury from 18C to 55C e 3.5 g ethanol through 47 K
c 250 g water through 36C f 1.5 kg ethylene glycol through 54C
9 A small electrical immersion heater was used to heat 125 g ethanol from 18.0C to
23.6C. The heater provided 1.73 kJ of energy. Calculate the specic heat capacity
of ethanol. Assume that all the energy was used to heat the ethanol and that there
were no losses to the surroundings.
EXAMPLE 4
1.62 g lithium was added to 150 g water at 17.4C in a well-insulated container of very
low heat capacity (disposable polystyrene coffee cup) as shown in the diagram on
the next page. The mixture was stirred with the thermometer until all the lithium had
reacted. The nal temperature was 37.2C. Write a balanced chemical equation for the
reaction and calculate the molar enthalpy change for it. Take the specic heat capacity
of the nal solution as that of water, namely 4.2 J K
1
of the nal solution as that of water, namely 4.2 J K of the nal solution as that of water, namely 4.2 J K g
1
.
The general procedure for calculating molar enthalpy changes from
experimental data is summarised below.
HOW TO CALCULATE H FOR HH A REACTION AA
1 Calculate the amount of heat released or absorbed, generally by using
q = m CT
2 Calculate the number of moles that reacted from the number of the number of
number of moles =
mass
___________

molar mass

3 Calculate heat released or absorbed per mole from
total heat released or absorbed

_____________________________

number of moles that reacted

4 H is plus the heat absorbed or minus the heat released.
The equation for the reaction is:
2Li(s 2Li( 2Li( ) + 2H
2
O(l O( O( ) 2LiOH(aq 2LiOH( 2LiOH( ) + H
2
( g)
We use Equation 7.6 to calculate the amount of heat released. In this case
m is 150 + 1.62 = 152 g, C is 4.2 J K
1
is 4.2 J K is 4.2 J K g
1
and T is 37.2 17.4 = 19.8C. TT
Therefore:
heat released = 152 4.2 19.8
= 1.26 10
4
J
This heat was released by the reaction of 1.62 g lithium. Because of the equation we
have written, we want the heat released by two moles of lithium.
Molar mass of lithium = 6.9 g/mol
Number of moles of lithium used =
1.62
_____
6.9

= 0.235 mol
Heat released by 2 moles of lithium =
2 1.26 10
4

___________________
0.235

= 107 kJ/mol
Hence we can say heat absorbed = 107 kJ/mol
and because H is heat absorbed,
for the reaction written H = 107 kJ/mol HH
7.6 HEAT OF COMBUSTION
Our main concern in this chapter is energy and extracting it from fuels by
combustion. A useful quantity in this context is the heat of combustion, or more
precisely the molar heat of combustion.
The molar heat of combustion of a substance is the heat liberated when 1 mole
of the substance undergoes complete combustion with oxygen at standard
atmospheric pressure with the nal products being carbon dioxide gas and
liquid water.
As thus dened, the molar heat of combustion is minus the enthalpy change for the
combustion process because H is dened as heat HH gained.
Combustion (or burning) is always exothermic. This means that heat is always
given out, so H for combustion processes is always negative. This difference in HH
signusing a positive value for heat of combustion while the enthalpy change for
the reaction is negativecan be a trap when working problems. Remembering that
combustion reactions are always exothermic, regardless of the sign of the value given,
helps avoid any confusion. Enthalpy change for combustion is sometimes abbreviated Enthalpy change for combustion Enthalpy change for combustion
to enthalpy of combustion. In summary:
molar heat of combustion (= heat released) is positive released released
enthalpy change for a combustion process
enthalpy of combustion
}
(= heat absorbed) is negative absorbed absorbed
EXERCISES
In Exercises 10 and 11, make the approximations:
the heat capacity of all solutions is that of water (4.2 J K
1
the heat capacity of all solutions is that of water (4.2 J K the heat capacity of all solutions is that of water (4.2 J K g
1
)
the heat capacity of the container (beaker) is negligible
there are negligible heat losses to the surroundings
the density of all solutions is 1.0 g/mL.
10 When 25 mL 0.20 mol/L sodium hydroxide solution at 23.2C was added to excess
hydrochloric acid present in 50 mL of solution at the same temperature in a light
plastic beaker, the temperature of the mixture rose to 24.1C. Calculate the heat
released and hence the enthalpy change for the reaction.
11 50 mL 0.20 mol/L lead nitrate solution is added to excess potassium iodide
contained in 30 mL of solution. Both solutions are initially at 19.6C. After mixing,
the temperature rose to 22.2C. Calculate the enthalpy change (per mole of Pb
2+
)
for the reaction.
12 For the reaction
2SO
2
( g) + O
2
( g) 2SO
3
( g) H = 198 kJ/mol
What is H for each of the reactions below?
a SO
2
( g) + O
2
( g) SO
3
( g)
b 2SO
3
( g) 2SO
2
( g) + O
2
( g)
Sometimes molar heat of combustion is just called heat of combustion. The
per mole in the units makes it clear that it is molar heat. molar molar
The molar heat of combustion of propane (a major constituent of liqueed
petroleum gas, LPG) is 2220 kJ/mol. This means that for the reaction:
C
3
H
8
( g) + 5O gg
2
( g) gg 3CO
2
( g) + 4H gg
2
O(l ) H = 2220 kJ/mol HH
Some other heats of combustion are shown in Table 7.2.
TABLE 7.2 Molar heats of combustion
a
for some common substances
Molar heat of
combustion
(kJ/mol) Substance
Molar heat of
combustion
(kJ/mol)
hydrogen, H
2
285 ethyne, C
2
H
2
1300
carbon, C 393 octane, C
8
H
18
5460
carbon monoxide, CO 280 toluene, C
7
H
8
3910
methane, CH
4
890 dodecane, C
12
H
26
8080
ethane, C
2
H
6
1560 ethanol, C
2
H
5
OH 1360
propane, C
3
H
8
2220 sucrose, C
12
H
22
O
11
5650
a
Molar heat of combustion is minus the enthalpy change for the combustion process with CO
2
(g) and
H
2
HH O(l) being the nal products
EXERCISES
13 The heat of combustion of hexane is 4160 kJ/mol. What is H for the reaction?
Draw an enthalpy diagram similar to Figure 7.1 showing reactants and products
and H. Let the up the page direction be positive.
14 a Calculate the heat released per gram from the combustion of each of the
following fuels (heats of combustion in kJ/mol are given in brackets):
i hydrogen (285) iv propane (2220)
ii ethanol, C
2
H
5
OH (1360) v sucrose, C
12
H
22
O
11
(5650)
iii ethyne (acetylene), C
2
H
2
(1300) vi octane (5460)
15 Arrange the fuels from Exercise 14 in decreasing order of heat released per gram.
What can you say about the heat released per gram for hydrocarbons? What is the
effect of having oxygen in the fuel molecule?
16 a Using data in Exercise 14, calculate the amount of heat released by 1.0 L petrol
(taken as pure octane with a density of 0.70 g/mL). Do the same calculation for
LPG (taken as pure liquid propane with a density of 0.49 g/mL).
b If petrol sells at 95 cents per litre, what would the price of LPG need to be for
it to have an equivalent price in cents per kilojoule as petrol?
7.7 TWO BASIC DRIVES: ENERGY AND
ENTROPY
Our everyday experience is that systems always tend towards a state of lower
energy: stones roll down hills, water falls from the top of a cliff to the bottom, a
metallic spring unwinds. The stones, the water and the spring all move from a state
of high potential energy to one of lower potential energy. There is a natural tendency
for systems or objects to move towards states of lower energy.
The occurrence of exothermic reactions accords with this general concept.
The chemicals move from a state of higher chemical energy to one of lower chemical
energy (and energy is released, generally in the form of heat, as this process occurs).
However there are endothermic reactions which occur spontaneously:
carbon reacts with steam
C(s) +H
2
O(g O( O( ) gg CO(g CO( CO( ) + H gg
2
(g (( ) gg H = 131 kJ/mol HH (7.7)
limestone decomposes (at high temperatures)
CaCO
3
(s) CaO(s) + CO
2
(g (( ) gg H = 178 kJ/mol HH (7.8)
sodium thiosulfate readily dissolves in water
Na
2
S
2
O
3
.5H
2
O(s) Na
2
S
2
O
3
(aq) H = 46 kJ/mol HH (7.9)
In addition liquids evaporate
C
2
H
5
OH(l) ll C
2
H
5
OH(g OH( OH( ) gg H = 43 kJ/mol HH (7.10)
All of these processes absorb heat as they occur. This means that the systems are
moving naturally towards states of higher energy. This suggests that there must be higher higher
some other natural tendency in addition to our drive towards lower energy.
We nd that in nature, in addition to a drive towards lower energy, there is a drive
towards increased chaos or increased randomness.
In chemical systems it is generally the drive towards minimum energy which
predominates. This is why exothermic reactions are much more common than
endothermic ones. However, there are some reactions where the drive towards
maximum randomness is stronger than the energy drive. And if the drive towards
increased randomness is in the opposite direction to the energy drive, then the
reaction will be endothermic. The four processes described above occur as written
because the drive towards increased randomness is stronger than the drive towards
lower energy.
In chemical contexts, then, what does randomness or chaos mean?
As explained in Chapter 1, a solid has a very orderly arrangement of atoms
or ions. When a solid changes to a liquid, the arrangement of the particles is less
ordered; the particles are able to move around more freely. We say that there is more
randomness or more chaos in the liquid than in the solid. When a liquid is converted
to a gas, there is again an increase in the randomness of the system; in the gas the
particles are well spread out and they are moving rapidly in a quite random manner.
Randomness or chaos increases as we change from solid to liquid to gas.
In Reaction 7.7 one mole of solid and one mole of gas are converted to two
moles of gas; effectively one mole of solid has been converted to one mole of gas.
This results in a considerable increase in randomness. The energy drive is in the
opposite direction (from H
2
+ CO to C + H
2
O) but it is not particularly strong, so
the drive towards chaos wins out. The reaction goes as written.
Similarly in Reaction 7.8 one mole of solid is converted to one mole of solid
plus one mole of gas. Effectively one mole of gas has been created, so there has been
a great increase in randomness. This drive towards chaos is stronger than the energy
drive (which is in the opposite direction) and so the reaction occurs as written, that
is in the endothermic direction.
In Process 7.10 one mole of liquid has been converted to one mole of gas; this
corresponds to a great increase in randomness. Hence the drive towards chaos is
stronger than the drive towards minimum energy (gas to liquid), and so the process
goes as written.
When solid and pure liquid are mixed to form a solution, there is an increase
in randomness. This is because the orderly arrangement of particles (molecules or
ions) in the solid has been replaced by a random arrangement or mixing of these
particles throughout the solvent molecules. Hence Reaction 7.9 corresponds to
an increase in randomness.
Randomness or chaos is measured by a physical quantity called entropy.
We shall not go into details about how entropy is measured, but merely note the
following:
For a given substance entropy increases as the substance changes from a solid
to a liquid to a gas.
Although different solids have different values for their entropies (per mole),
these differences are quite small compared with the differences in entropy
(per mole) between a solid and a liquid or between a liquid and a gas. Similarly,
the difference in entropies for any two liquids or any two gases is much smaller
than the difference between entropies of a substance as a liquid and as a gas.
It follows then that to estimate qualitatively the entropy change for a chemical
reaction, all we need to do is consider the change in number of moles of solid, liquid
or gas in the reaction.
EXAMPLE 5
Do you expect the entropy changes for the following reactions to be positive or
negative:
a NH
4
Cl(s Cl( Cl( ) NH
3
(g (( ) + HCl(g ) + HCl( ) + HCl( )
b CaO(s CaO( CaO( ) + H
2
O(g O( O( ) Ca(OH)
2
(s (( )
c N
2
(g (( ) + 3H
2
(g (( ) 2NH
3
(g (( )
d CuSO
4
.5H
2
O(s O( O( ) CuSO
4
(s (( ) + 5H
2
O(g O( O( )
In (a) 1 mole of solid is converted into 2 moles of gas. We have already seen that the
entropy change for converting 1 mole of solid into 1 mole of gas is positive. Hence the
entropy change for this reaction is positive (and quite large).
In (b) 1 mole of solid and 1 mole of gas are replaced by 1 mole of solid. Effectively
1 mole of gas has disappeared. Gases have quite high entropies. Hence for Reaction (b)
the entropy change is negative.
In (c) 4 moles of gas are converted into 2 moles of gas. Effectively 2 moles of gas have
disappeared. Hence the entropy change for Reaction (c) is negative.
In (d) effectively 5 moles of gas have been formed, so the entropy change is positive
(and quite large).
To summarise then:
In chemical reactions there are two drives, a drive towards minimum energy
and a drive towards maximum entropy. If both of these drives are in the one
direction, then the reaction goes in that direction. If these drives are in opposite
directions, then the reaction goes in the direction of the stronger drive.
EXAMPLE 6
The four reactions in Example 5 all go in the direction written. Reactions (a) and (d) are
endothermic while (b) and (c) are exothermic. What conclusions can you draw about the
direction and relative strengths of the energy and entropy drives in these reactions?
In (a) and (d) the entropy drives are in the forward direction (entropy changes are
positive, as decided above). The energy drives are in the reverse direction, because for
each reaction the reverse direction is the one corresponding to a decrease in energy.
Because the reactions go as written we conclude that the entropy drives are stronger
than the energy drives for these two reactions.
In (b) and (c) the energy drives are in the forward direction (because that direction
corresponds to a decrease in energy). The entropy drives are in the reverse direction,
because for both of these reactions we decided above that the entropy changes (for the
forward directions) were negative. Because these reactions go in the forward direction,
the energy drive must be greater than the entropy drive.
EXERCISES
17 Consider the reactions:
(i) PCl
3
(l (( ) + Cl ll
2
(g (( ) PCl
5
(s (( )
(ii) N
2
O
4
(g (( ) 2NO
2
(g (( )
(iii) C
2
H
5
OH(l OH( OH( ) + 3O ll
2
(g (( ) 2CO
2
(g (( ) + 3H
2
O(g O( O( )
(iv) 2SO
2
(g (( ) + O
2
(g (( ) 2SO
3
(g (( )
(v) (NH
4
)
2
SO
4
(s (( ) + 2NaOH(s ) + 2NaOH( ) + 2NaOH( ) Na
2
SO
4
(s (( ) + 2NH
3
(g (( ) + 2H
2
O(g O( O( )
All of these reactions occur in the direction written. Reactions (ii) and (v) are
endothermic while the others are exothermic. For each reaction:
a Estimate whether the entropy change is positive or negative.
b Indicate the direction (forward or reverse) of each of the energy and entropy
drives.
c Decide, if possible, which of these two drives is the stronger. Explain how you
reached your decision or why a decision is not possible.
18 When crystals of hydrated barium hydroxide and ammonium thiocyanate are mixed
in a ask and placed on a very wet piece of board, the ask cools so much that it
sticks to the board (because it freezes the water to ice). The reaction occurring is:
Ba(OH)
2
.8H
2
O(s O( O( ) + 2NH
4
SCN(s SCN( SCN( ) 2NH
3
(g (( ) + 10H
2
O(l O( O( ) + Ba ll
2+
(aq (( ) + 2SCN
(aq (( )
a Is the reaction exo- or endothermic? Explain why.
b From the fact that the reaction goes in the direction written, what do you
conclude about the sign of the entropy change for the reaction?
c Does your conclusion in b conform with your understanding of entropy as
a measure of randomness? Explain fully.
A convenient property of common fuels is that they do not react with oxygen
at room temperature. They react only if we ignite them; that is, set re to them.
A heap of coal does not spontaneously burst into ames. We can expose petrol to
the air without any reaction occurring, and natural gas ows out of an open tap
without burning. We need to heat the coal in a ame, strike a match near the petrol
or apply a heated electrical lament to the natural gas to get them all to burn (react
with oxygen). Let us look for a reason for this.
7.8 ACTIVATION ENERGY
The reason why many reactions do not occur spontaneously, but need some sort of
a prod to get them going, is that there is often an energy barrier between reactants
and products. We therefore have to give the reactant molecules sufcient energy
to scale this energy barrier. Once an exothermic reaction gets going, it releases
sufcient energy to activate further reactant molecules and so the reaction becomes
self-sustaining. We call this energy barrier an activation energy.
The activation energy, E
a
EE , of a reaction is the minimum amount of energy
reactant molecules must possess in order to form products.
It is generally expressed in kilojoules per mole, kJ/mol. This energy barrier exists
for both exothermic and endothermic reactions as Figure 7.4 shows.
For exothermic reactions (such as combustion of common fuels), once we get
them going they generate enough energy to become self-sustaining. However, for
endothermic reactions we have to supply energy continuously. For example, the
reaction between nitrogen and oxygen (Equation 7.5) occurs only at temperatures
above about 1000C and only while we supply energy to maintain that temperature.
If we stop supplying energy, the reaction stops (which is just as well, otherwise we
would lose our precious atmosphere!).
We shall see in Section 7.12 that there are many reactions that occur at room
temperature even though they have a signicant activation energy. However,
the reactions of our common fuels with oxygen have much higher activation
energies and so there is no signicant reaction at room temperature: we have
to ignite them.
FIGURE 7.4
Energy diagrams showing
activation energy E
a
EE and
enthalpy change H
for both exothermic and
endothermic reactions

The activation energy determines how quickly the rate of reaction increases
as temperature increases. If the activation energy is high, the reaction proceeds
extremely slowly at room temperature but its rate increases dramatically as
temperature is increased; if the activation energy is small, the reaction proceeds
at a moderate rate at room temperature and its rate increases steadily (but not
dramatically) as temperature increases. Let us take a closer look at what we mean
by rate of reaction.
7.9 MEANING OF RATE OF REACTION
By rate of reaction we mean the rate at which reactants disappear or, alternatively,
the rate at which products form. A specic example will illustrate. Nitric oxide
reacts with oxygen to form nitrogen dioxide:
2NO( g) + O gg
2
( g) gg 2NO
2
( g) gg (7.11)
Nitric oxide is colourless whereas nitrogen dioxide is brown. We can follow
the progress of this reaction by measuring the increasing intensity of the brown
colour. This allows us to construct a graph of concentration of nitrogen dioxide
as a function of time after mixing oxygen and nitric oxide; this is shown in
Figure 7.5(a).
EXERCISES
19 Sketch energy diagrams for reactions having:
a H = 80 kJ/mol and E
a
EE = 40 kJ/mol
b H = 30 kJ/mol and E
a
EE = 120 kJ/mol
20 The diagrams below show energy proles for two reactions. What is the activation
energy and the enthalpy change for each of these reactions?
21 For the combustion reactions of two fuels, A and B, enthalpy changes and
activation energies are:
Fuel A: H = 200 kJ/mol, E
a
EE = 100 kJ/mol
Fuel B: H = 70 kJ/mol, E
a
EE = 250 kJ/mol
Draw energy proles for these reactions on the one set of axes, clearly identifying
each reaction. Use the same energy position for both sets of reactants.
In terms of heat released per mole, which of A or B would be the better fuel?

rate of reaction is the rate of change of concentration with time.
Alternatively the average rate of reaction over a small time interval is the change
in concentration divided by the time taken for the change to occur.
Average rate =
change in concentration

_____________________
Average rate = Average rate =
time taken

If the concentration is c
1
at time t
1
and c
2
at t
2
a short time later, then
Average rate =
c
2
c
1
_______
t
2
t
1

Or if we use for change in,
Average rate =
c
___
t
where c = cc c
2
c
1
and t = tt t
2
t
1
.
In terms of a concentration versus time graph, the rate of reaction at any
particular time is the slope (gradient) of the curve at that time.
In Figure 7.5(a) we see that as the reaction proceeds, the slope of the curve
decreases (curve gets less steep). This means that the rate of reaction is decreasing
as the reaction proceeds.
Figure 7.5(a) presented the concentration of NO
2
, the reaction product, as a
function of time. Alternatively we could plot the concentration of NO, the reactant,
as a function of time, as in Figure 7.5(b). The rate of reaction is now the rate of
change in concentration of NO. It is still the slope (gradient) of the curve except
that we always take the rate of reaction as positive, so in Figure 7.5(b) the rate of the
reaction is the magnitude of the slope (i.e. minus the actual slope because that slope
is negative).
In Figure 7.5(b) the magnitude of the slope decreases as reaction proceeds,
so the rate of reaction is still decreasing as reaction proceeds (as we expect from
Figure 7.5(a)).
The shapes of the curves (a) and (b) in Figure 7.5 are typical for products
and reactants respectively. These curves show that:
Reaction rate decreases as reaction proceeds.
This is by far the most usual situation. An explanation will emerge in the
next section.

FIGURE 7.5
Concentrations of (a)
nitrogen dioxide and (b)
nitric oxide as functions
of time after mixing nitric
oxide and oxygen. Initial
concentrations were
4.1 10
3
mol/L for O
2
and 5.0 10
4
mol/L
for NO.
The key point from this discussion is that:
the rate of a reaction is the magnitude of the slope (gradient) of the concentration
versus time curve.
EXERCISES
22 In order to determine whether or not the concentration of hydrochloric acid affected
the rate of the reaction between magnesium and dilute hydrochloric acid, a chemist
reacted 5.0 cm lengths of cleaned magnesium ribbon with 50 mL portions of
hydrochloric acid solution and collected the hydrogen formed by displacement of
water in an inverted burette. The volume of hydrogen was recorded at various times
after the start of the reaction. Results are given in the following table.
Experiment A (0.20 mol/L HCl)
Time (s) 0 40 70 100 140
Volume of H
2
(mL) 0 11 19.5 28 39
Experiment B (0.60 mol/L HCl)
Time (s) 0 20 35 50
Volume of H
2
(mL) 0 16.5 29 41
a On the one piece of graph paper plot volume of hydrogen versus time for each
experiment and draw smooth lines through the points for each experiment.
b Which experiment has the greater rate of reaction? Explain how you decided
this.
c In what way, if any, is the rate of this reaction affected by concentration of
hydrochloric acid?
23 For Exercise 22 calculate the average rate of reaction (in mL H
2
per s) over the rst
40 s for Experiment A and over the rst 20 s for Experiment B.
24 Aqueous ammonium nitrite solutions
decompose to form nitrogen gas:
NH
4
NO
2
(aq (( ) N
2
( g) + 2H
2
O(l O( O( ) ll
In two separate experiments, using different
initial concentrations of reactant, the volume
of nitrogen formed (at 25C and standard
atmospheric pressure) was measured as a
function of time. The results are plotted in
the graph.
a Which experiment, A or B, has
the greater initial rate of reaction?
Give your reasoning.
b Which experiment would you expect to
correspond to the higher initial reactant
concentration? Justify your choice.


7.10 FACTORS INFLUENCING THE RATE
OF REACTION
Experimentally, we nd that increasing the concentration of a reactant generally
increases the rate of the reaction. This explains the shape of the concentration versus
time curves in Figures 7.5(a) and (b). As reaction proceeds, the concentrations of
the reactants decrease and so the rate of reaction continuously decreases; that is, the
magnitude of the slope decreases as time increases.
For most reactions, the rate increases as the temperature is increased. This increase
is often quite marked: for some reactions a 10C increase can double the rate of
reaction.
Sometimes the rate of a reaction is increased by the presence of a substance
which is not even involved in the stoichiometric equation for the reaction. For
example, the reaction of sulfur dioxide with oxygen to form sulfur trioxide:
2SO
2
( g) + O gg
2
( g) gg 2SO
3
( g) gg
is quite slow. However if some nitrogen dioxide is added to the reaction mixture,
reaction proceeds much more rapidly.
Substances that increase the rate of a reaction without undergoing permanent
chemical change in the reaction are called catalysts.
Nitrogen dioxide is a catalyst for the SO
2
+ O
2
reaction.
The two reactions which we have been considering so far in this section,
NO + O
2
and SO
2
+ O
2
, involve species that are all in the gas phase, and the
reaction occurs uniformly throughout the whole gaseous mixture. Such reactions
are called homogeneous reactions. Reactions that occur uniformly throughout
a solution are also homogeneous reactions. An example is the reaction between
colourless hydrogen peroxide and acidic iodide solutions to form brown iodine
solution:
H
2
O
2
(aq) + 2I
(aq) + 2H
+
(aq) I
2
(aq) + 2H
2
O(l )
In summary:
FACTORS INFLUENCING THE RATE OF HOMOGENEOUS REACTIONS ARE:
1 concentration of reactants (in solution or in the gas phase)
2 nature and concentration of any catalyst present
3 temperature
There are many reactions, some extremely important industrially, that occur
at the interface between two phases; such reactions are called heterogeneous
reactions. Some common examples are:
reaction of zinc metal with hydrochloric acid (to form hydrogen gas and zinc
chloride)
decomposition of hydrogen peroxide in solution (to form oxygen and water)
occurring on the surface of various solids such as manganese dioxide
hydrogenation of alkenes and vegetable oils (to form alkanes and margarine,
respectively) on the surface of nely divided nickel metal
cracking of high molecular weight compounds from crude oil (gas oil fraction)
to lower molecular weight ones (for use as petrol).
The rates of heterogeneous reactions, as well as depending upon the three
factors listed above, also depend upon two other factors:
EXTRA FACTORS INFLUENCING THE RATE OF HETEROGENEOUS
REACTIONS ARE:
4 the state of division of the solid
5 the rate of stirring which is used
For example, 1 g of nely crushed limestone, CaCO
3
, added to
1 L hydrochloric acid solution causes carbon dioxide to be produced at a much
greater rate than does one solid lump of the same mass added to a similar
hydrochloric acid solution. Also, the reaction will be faster if the mixture is stirred
continuously to keep the crushed limestone dispersed throughout the solution
instead of letting it settle to the bottom of the ask. Both these effects are due
to the fact that reaction is occurring on the surface of the solid.
For some reactions, the rate depends upon the intensity (brightness) of visible or
ultraviolet light shining upon the reactants.
Ozone, O
3
, is decomposed by ultraviolet light:
2O
3
( g) gg 3O
2
( g) gg
This reaction occurs in the stratosphere and lters out the harmful ultraviolet
radiation from sunlight.
A large lump of calcium
carbonate reacts with a
solution of hydrochloric
acid more slowly (left test
tube) than the same mass
crushed into small pieces
(right test tube)
7.11 EXPLANATIONS
For a reaction to occur the reactant particles (atoms, molecules or ions)
must collide.
Anything that increases the rate at which collisions occur will increase the rate
of reaction. Increasing the concentration of reactants, state of division of a solid
reactant, or rate of stirring increases the rate of collision and so increases the rate
of reaction. The explanations are as follows:
Concentration measures the number of particles of the particular substance
per unit volume. Increasing the concentration puts more particles in unit
volume and so increases the chance of collision between particles of one
reactant and those of another reactant, which increases the reaction rate.
Breaking big lumps of solid into smaller pieces increases the surface area of
the solid (Exercise 27 below). In a reaction between a solute in solution and
a suspended solid or between a gas and a solid, the reaction rate depends upon
the rate of collision between the solute or gas particles and the solid. The greater
the area of the solid, the more collisions that can occur in a given time, so
reaction rate increases.
EXERCISES
25 Which of the following reactions are homogeneous and which are heterogeneous?
a Ca(OH)
2
(aq (( ) + 2HNO
3
(aq (( ) Ca(NO
3
)
2
(aq (( ) + 2H
2
O(l O( O( ) ll
b C(s C( C( ) + H
2
O( g O( O( ) CO( g CO( CO( ) + H
2
( g (( )
c BaO(s BaO( BaO( ) + 2HCl(aq ) + 2HCl( ) + 2HCl( ) BaCl
2
(aq (( ) + H
2
O(l O( O( )
d NO( g NO( NO( ) + O
3
( g (( ) NO
2
( g (( ) + O
2
( g (( )
e 2NaOH(aq 2NaOH( 2NaOH( ) + H
2
SO
4
(aq (( ) Na
2
SO
4
(aq (( ) + 2H
2
O(l O( O( ) ll
f Zn(s Zn( Zn( ) + CuSO
4
(aq (( ) Cu(s Cu( Cu( ) + ZnSO
4
(aq (( )
26 In the reaction of bromoethane with aqueous sodium hydroxide solution to form
ethanol:
C
2
H
5
Br(aq Br( Br( ) + OH
(aq (( ) C
2
H
5
OH(aq OH( OH( ) + Br
(aq (( )
the concentration of hydroxide was
measured as a function of time in
two experiments at different
temperatures. The same reactant
concentrations were used in both
experiments. The results are shown
in the accompanying graph.
a In which experiment, A or B, is the
rate of reaction greater? Why?
b Which experiment was performed
at the higher temperature? Explain
your reasoning.
*c
Copy graph B on to your work pad and sketch on it the curve you would expect
for an experiment using double the reactant concentrations at that temperature.
Label this curve clearly and explain why it has the shape you have given it.
provided.
Stirring has two effects. First it keeps the solid suspended in the solution or
gas and so exposes the maximum surface area of the solid to the solute or gas.
Secondly for reactions in solution, stirring quickly replaces solution in which
the reactant has been used up with fresh solution, so ensuring that there is always
plenty of solute for the solid to react with. In these two ways stirring increases the
rate of collision between reactant particles and so increases the rate of reaction.
7.12 TEMPERATURE EFFECT AND
ACTIVATION ENERGY
As temperature increases, the average kinetic energy (and so the speed) of particles
increases. This means that the rate of collision will increase, which will cause an
increase in reaction rate. However, this effect alone does not explain the very rapid
increase in rate that we observe when temperature increases. There is another more
important factor involved.
We saw in Section 7.8 that there is an energy barrier separating reactants from
products: we call this the activation energy. Although our common fuels need
to be heated above room temperature before they will start to react with oxygen
(Section 7.8), there are many reactions with signicant activation energies which
proceed at appreciable rates at room temperature. These get faster as the temperature
rises. This is due to the activation energy. The explanation is as follows.
In order for a reaction to proceed, it is necessary not only for the reactant
molecules to collide, but also for the colliding molecules to possess a certain
minimum amount of kinetic energy so that they can reach the top of the energy
barrier. Once they reach the top they easily roll down the other side of the hill and
fall apart to products (Figure 7.4). If the colliding molecules have insufcient energy,
they just bounce apart and stay as reactants. Kinetic energy is energy of motion: the
faster particles are moving, the higher is their kinetic energy.
In a sample of reactant molecules at room temperature, the average kinetic
energy possessed by the molecules may be relatively low. However, a small fraction
of the molecules will have kinetic energies very much higher than this average
and some, in fact, may have enough to reach the top of the energy barrier and so
these molecules will react. Because this fraction of the molecules having enough
kinetic energy is small, the reaction rate is low (but still signicant). If the sample
is heated, not only is the average kinetic energy of the molecules increased, but also
the fraction of the molecules having more than enough kinetic energy to scale the
energy barrier is quite markedly increased, so that the reaction rate increases.
Figure 7.6 shows the distribution of kinetic energy for a sample of gas molecules
at 300 K and at 500 K. At 300 K only
a very small fraction of the molecules
in the sample has kinetic energy
greater than the activation energy,
E ' (the darker orange-shaded area
in the gure). Therefore the reaction
rate is quite small. At 500 K a much
greater fraction of the molecules (both
orange-shaded areas) has kinetic energy
greater than E '. This means that the
reaction rate increases quite markedly.

FIGURE 7.6
Distribution of kinetic
energy for particles in a
gas at 300 K and at 500 K
If we compare two different reactions at the one temperature, then generally
speaking the one with the greater activation energy will have the smaller reaction
rate. In addition the higher the activation energy, the more rapidly the reaction rate
increases as temperature increases.
Many reactions have quite small activation energies and so proceed quite
rapidly at room temperature.
7.13 CATALYSIS
As was shown in Section 7.10, for many reactions the rate can be increased by using
a catalyst. Catalysts may be homogeneous or heterogeneous.
Homogeneous catalysts
Homogeneous catalysts work throughout the bulk of the reaction mixture (gas or
solution). As mentioned above, nitrogen dioxide is a homogeneous catalyst for the
reaction between sulfur dioxide and oxygen. As another example, hydrogen peroxide
reacts fairly slowly with acidic iodide in aqueous solution to form iodine:
H
2
O
2
(aq) + 2I
(aq) + 2H
+
(aq) I
2
(aq) + 2H
2
O(l ) ll
EXERCISES
27 What is the surface area of a cube with a side of 1 cm? Suppose this was cut into
1000 cubes each with a side of 0.1 cm. What would be the total surface area of the
solid now? This illustrates how crushing a lump of solid into small pieces increases
the surface area.
28 The diagram opposite shows how
the rates of two reactions increase
as temperature is increased. Which
reaction, A or B:
a has the higher rate at room
temperature
b has the higher activation energy?
Give your reasoning.
29 Energy proles for four reactions are
shown below.
a Which reactions are endothermic and which exothermic?
b Which reaction has the greatest activation energy and which the least?
c Which reaction would you expect to show the greatest percentage increase in
rate for a 30 K increase in temperature, and which the least? Give your reasoning.

Adding about 10
4
mol/L sodium molybdate to the reaction mixture makes the
reaction very fast (complete in a few seconds). The molybdate ion, MoO
4
, is
a homogeneous catalyst for this reaction.
Heterogeneous catalysts
A heterogeneous catalyst provides a surface on which the reaction occurs more
rapidly than it does in the bulk of the reaction mixture. Finely divided nickel
catalyses the reaction between alkenes and hydrogen to form alkanes (for example
C
2
H
4
+ H
2
C
2
H
6
on p. 283). The nickel is a heterogeneous catalyst. The
reaction occurs between gaseous hydrogen and liquid or gaseous alkene on the
surface of the solid nickel particles.
Heterogeneous catalysts are of tremendous practical importance. Some
examples of their use are:
synthesis of ammonia for fertiliser from N
2
and H
2
(using an iron catalyst)
sulfuric acid synthesis (using a vanadium pentoxide catalyst for the
SO
2
+ O
2
step; NO
2
is no longer used industrially)
hydrogenation of liquid vegetable oils into semi-solid fats for use in margarine
(using a nickel catalyst); the reaction adds hydrogen across some or all of the
double bonds in the oil to form single bonds (the alkene alkane reaction
mentioned above)
How catalysts work
Catalysts are particularly useful when the uncatalysed reaction has a very high
activation energy (and is therefore very slow). The catalyst usually provides a
pathway of lower activation energy; this is shown schematically in Figure 7.7.
For example the direct reaction:
2SO
2
( g) + O gg
2
( g) gg 2SO
3
( g) gg (7.12)
is extremely slow (very high activation energy). However, in the presence of NO
2
the following two reactions occur fairly rapidly (both have relatively low activation
energies):
SO
2
( g) + NO gg
2
( g) gg SO
3
( g) + NO( gg g) gg
2NO( g) + O gg
2
( g) gg 2NO
2
( g) gg
A combination of these two reactions (twice the
rst reaction added to the second) is effectively
Reaction 7.12, and the combination occurs much
more rapidly than the direct reaction. Note that
there is no net consumption of NO
2
.
Although catalysts decrease the activation energy
of reactions, they have absolutely no effect upon
H, the enthalpy change for the reaction. HH
Figure 7.7 shows this. The reason for this is that
the reactants and products are exactly the same for
both the catalysed and the uncatalysed reactions.
FIGURE 7.7
Energy proles for
catalysed and uncatalysed
paths of the one reaction
The way that heterogeneous catalysts work is as follows. Reactant particles
(molecules or ions) adsorb (stick) onto the surface of the catalyst; in doing this
some chemical bonds are broken or at least considerably weakened. In some
reactions, gaseous or solute particles collide with these adsorbed particles with
broken or weakened bonds, and so reaction occurs, with product particles
desorbing (coming off) from the catalyst surface. For other reactions both reactants
are adsorbed, and reaction occurs between neighbouring adsorbed reactant particles
(Fig. 7.8).
FIGURE 7.8
The reaction between
ethene and hydrogen to
form ethane occurring
on the surface of nickel.
Hydrogen adsorbs as
atoms which then react
with adsorbed ethene
molecules.
Refer to Context 3 Transport, pp. 107 and 11213.
Refer to Context 4 Air, pp. 14850 and p. 154.

EXERCISES
30 Copy the diagram for Reaction A in Exercise 29 onto your work paper. A good
catalyst is available for this reaction. Sketch the energy prole you would expect
for the catalysed reaction. Clearly label the original and catalysed reactions.
31 A certain chemical reaction used in industry has the same rate at room temperature
using a catalyst as it has at 75C without a catalyst. Why is it more efcient
energy-wise to carry out the reaction using the catalyst?
32 a Sulfur dioxide and oxygen molecules react very slowly in the gas phase.
However, solid vanadium pentoxide is a very effective heterogeneous catalyst
for the reaction. Suggest a way that this reaction could be brought about by
using the surface of the solid.
b Nitrogen and hydrogen molecules do not react in the gas phase. However, they
do react (to form ammonia) on an iron surface. Suggest how this reaction could
be brought about by the surface.
33 Hydrogen peroxide decomposes to oxygen gas quite slowly at room temperature.
However, the reaction proceeds rapidly when nely divided solid manganese dioxide
is added to the solution. How would you determine that the manganese dioxide was
catalysing the reaction and not undergoing a separate reaction to produce oxygen
gas?
*
*
activation energy (p. 302)
adsorb (p. 312)
average rate of reaction (p. 304)
catalysts (p. 306)
change in enthalpy (p. 289)
combustion (p. 287)
endothermic reactions (p. 288)
enthalpy (p. 289)
entropy (p. 300)
exothermic reactions (p. 288)
heat of combustion (p. 298)
heat of reaction (p. 290)
heterogeneous catalysts (p. 311)
heterogeneous reactions (p. 306)
homogeneous catalysts (p. 310)
homogeneous reactions (p. 306)
molar heat of combustion (p. 297)
quantity of heat (p. 293)
rate of reaction (p. 304)
specic heat capacity (p. 294)
temperature (p. 293)
thermal equilibrium (p. 293)
IMPORTANT NEW TERMS
TEST YOURSELF
above.
2 Write equations for three combustion reactions.
3 What is the sign of the enthalpy change, H, for exothermic and endothermic
reactions?
4 If a reaction is carried out in a test tube and the tube gets cold, is the reaction
exothermic or endothermic? Explain.
5 What are the units for H for a chemical reaction?
6 In chemical energy contexts, why must we always specify the physical states of
reactants and products in chemical equations?
7 How is H for a combustion process related to the heat of combustion?
8 Explain in terms of structure of molecules why energy is released in some reactions.
Use a diagram for a specic reaction to illustrate your explanation.
9 How do you calculate the quantity of heat from temperature change and specic
heat capacity?
10 Explain how you would measure experimentally the heat of reaction, for example
for sulfuric acid solution plus sodium hydroxide solution.
11 Draw energy proles for an exothermic and an endothermic reaction clearly
labelling the activation energy and the enthalpy change for the reaction.
12 Sketch the most usual type of curve for the dependence of concentration of a
reactant upon time of reaction. Sketch the corresponding curve for concentration
of a product.
13 For most reactions, does the rate increase, decrease or remain the same as
reaction proceeds? Explain why.
14 List three factors which inuence the rate of homogeneous reactions.
15 Give two additional factors which affect the rate of heterogeneous reactions.
16 Explain why some molecules in a reactant sample can undergo reaction even
though the average energy of reactant molecules is much less than the activation
energy.
17 Explain how increasing the temperature causes reaction rate to increase.
18 Explain the difference between a homogeneous catalyst and a homogeneous catalyst homogeneous catalyst heterogeneous
catalyst. Give an example of each.
19 In what way, if any, does a catalyst affect the activation energy and the enthalpy
change for a reaction?
CHAPTER 8
Gases
Pressure and the particle nature of gases
Diffusion
Kinetic theory of gases
Avogadros law
Boyles law
Charles law
Combined gas law
Ideal gas equation
Daltons law of partial pressures
Summary
IN THIS CHAPTER
315
Gases are an important part of the environment; without oxygen and carbon
dioxide, we and all the other living organisms of the Earth could not exist.
However, gases often go unnoticed, because they are less obvious than solids
and liquids. On the other hand, in some aspects of our daily lives gases are very
noticeablefrom carbon dioxide adding zz to soft drinks to LPG (liqueed
petroleum gas) for fuelling barbecues and motor vehicles to natural gas for heating
water, cooking and warming our homes to the propellant in aerosol deodorants.
In this chapter we shall survey some of the common properties of gases.
8.1 PRESSURE AND THE PARTICLE NATURE
OF GASES
We saw in Section 1.2 and Figure 1.1(c) and (f ) on pp. 1645 that gases consist of
particles that are well separated in space and in continual random motion. Because
of the rapid motion, gases always expand to ll the total volume available to them;
because the particles are well separated in space, gases are easily compressed into
smaller volumes.
We often recognise the presence of a gas from the pressure it exerts.
Pressure
Pressure is dened as force per unit area. The systematic unit for pressure is the
pascal, Pa, which is a newton (unit of force) per square metre, N m
2
.
This is quite a small pressure, so we frequently use kilopascal, kPa. Standard
atmospheric pressure is 1.103 10
5
Pa or 101.3 kPa.
Another common unit for pressure is the atmosphere. It is dened as:
1 atmosphere (atm) = 101.3 kPa
Atmospheric pressure is not always exactly 1.00 atmosphere; it varies with weather
conditions. While chemists and physicists generally use pascals (or kilopascals) or
atmospheres, meteorologists generally use the hectopascal, hPa (= 100 Pa) though hectopascal hectopascal
sometimes the older units, the bar (= 10
5
Pa) and millibar (= 100 Pa), are used
.
Standard atmospheric pressure is 1013 hectopascals or 1013 millibars.
Effect of temperature and pressure on
volumes of gases
If we have a sample of gas in a hypodermic syringe that is tted with a well-
lubricated and easily moving plunger and that has the needle outlet sealed off as in
Figure 8.1(a), then the pressure exerted by the gas upon the walls and plunger of
the syringe is equal to the pressure the atmosphere is exerting upon the barrel and
plunger of the syringe. The gas pressure arises because the particles of the gas are
continuously hitting the walls of the container and exerting a force (and hence a
pressure) upon them.
If we push the plunger in by exerting a force upon it (that is, by increasing
the pressure applied to the gas), the gas compresses (that is, its volume becomes
smaller). The gas volume decreases until the pressure exerted by the gas becomes
equal to the applied external pressure. The collisions of gas particles with the walls
of the syringe are spread out over a smaller area and hence force per unit area
(pressure) increases as shown in Figure 8.1(b). If we release the plunger so that the
external pressure on it falls back to atmospheric, the compressed gas expands and
pushes the plunger back until the gas pressure also falls to atmospheric again.
The volume of gas is very dependent upon the pressure acting upon it. In fact
doubling the pressure halves the volume.
If the syringe in (a) with atmospheric pressure acting on the plunger is
immersed in a beaker of boiling water, the volume increases considerably: 20 mL
of gas at 20C would expand to 25 mL at 100C. By contrast 20 mL water at 20C
heated to 100C (without being vaporised) would expand to only 20.8 mL. Gases
expand to a far greater extent than do solids or liquids.
The explanation is this: as we heat the gas, we increase the kinetic energy of
the particles (molecules) so they move faster and strike the walls and plunger
FIGURE 8.1
Compression of a gas
increases the number of
collisions per unit area
and hence pressure
The unusual prex hecto (= 100) was used when meteorologists converted to systematic units in
order to keep the numerical value of the pressure in new units equal to the value in the old unit,
millibars.
CHAPTER 8 GASES 317 CHAPTER 8 GASES 317
more frequently and with more force, and so at constant volume would exert
greater pressure; because the pressure acting on the plunger is atmospheric, this
greater pressure pushes the plunger out until the number of (more forceful)
collisions per unit area decreases sufciently to bring the pressure exerted by the
gas back to the external pressure acting on the plunger (atmospheric pressure).
Because the volume of a sample of gas depends upon both the temperature and the
applied pressure, it is essential when reporting gas volumes to state the temperature and
the pressure of the measurement. Hence we talk about 10 L of oxygen at 20C and
1.00 atm pressure, or 50 mL of hydrogen at 100C and 220 kPa.
Gas volumes are frequently given for conditions called standard temperature
and pressure, STP.
Standard temperature is 0C.
Standard pressure is exactly 1 atmosphere (atm).
Hence we frequently talk about 2.0 L of gas at STP or 400 mL of nitrogen at STP.
8.2 DIFFUSION
Diffusion is the process in which one substance becomes mixed with another
substance.
Consider a gas jar of brown nitrogen dioxide placed in contact with another
gas jar containing colourless nitrogen as in Figure 8.2. When the coverslip is
removed, the two gases quickly diffuse into each other and within a few seconds the
combined volume is seen to contain a gaseous mixture of uniform colour (the same
composition throughout). This diffusion of gases occurs much more quickly than
does diffusion of liquids or solids.
The much slower diffusion of liquids or solutions can be demonstrated as
follows. If a test tube is half-lled with a purple solution of potassium permanganate
solution, and if water is carefully poured on top of it (pouring it slowly down the
side of a slanted test tube), then diffusion will be seen to occur as the purple colour
spreads upwards into the clear water, but it will take a few minutes before the colour
is uniform (mixing is complete).
Solids diffuse even more slowly. A block of copper can be clamped to a block
of aluminium for many years before there is signicant diffusion of copper into the
aluminium.
Rapid diffusion of gases can be explained in terms of the particle nature of
gases. Because the particles of a gas are well separated from one another and
because they are in continuous rapid motion, particles of one gas easily penetrate
the space occupied by another gas and vice versa. The particles move such distances
between collisions that they rapidly mix together.
FIGURE 8.2
An experiment to
demonstrate rapid
diffusion of gases
8.3 KINETIC THEORY OF GASES
The explanations given for the experimental observations in the preceding two
sections are part of what is called the kinetic theory of gases.
The kinetic theory of gases proposes that:
1 Gases consist of molecules (small particles) that are in continual random
motion.
2 The actual volume of all the molecules present in a sample of gas is negligible
compared to the total volume they occupy.
3 Intermolecular forces are negligible.
4 Pressure is due to collision of the particles with walls of the container.
5 Temperature is a measure of the average kinetic energy (or speed) of the gas
molecules.
The kinetic theory can be used to explain many properties of gases other than
those we have just considered.
8.4 AVOGADROS LAW
From what we have just seen about diffusion of gases and the way volumes of gases
depend upon pressure and temperature, it appears that the properties of gases
depend more upon the number of particles (molecules) present than upon their
chemical nature. It is not surprising then that we nd that:
Equal volumes of different gases, measured at the same temperature and
pressure, contain the same number of molecules.
EXERCISES
1 A sample of gas is enclosed in a syringe as in Figure 8.1(a). If the plunger is pushed
in (by exerting an increased pressure on it), how would you expect the number
of molecules per millilitre to changeto increase, decrease or remain the same?
If the syringe and the gas it contained were then heated, what would happen to the
number of molecules per millilitre if the volume was kept constant? Why would it
be necessary to apply a greater pressure to the syringe plunger to keep the volume
constant as the gas was heated?
2 When two gases are brought into contact, they mix more quickly than do two
liquids similarly brought together. Explain why in terms of the particle nature of
gases and liquids.
3 a Convert the following pressures to atmospheres:
i 50.7 kPa ii 3.68 10
3
Pa iii 986 hectopascals
b Convert the following pressures to kPa:
i 2.34 atm ii 0.52 atm iii 1072 hectopascals
Refer to Context 4 Air, pp. 1301.

This is known as Avogadros law or Avogadros hypothesis, after the person who
rst proposed it in 1811.
At constant temperature and pressure 50 mL of oxygen, O
2
, contains the same
number of molecules as does 50 mL of nitrogen, N
2
, or 50 mL of ammonia, NH
3
.
Since helium and argon are monatomic gases (the molecules are atoms, Section 1.8
on p. 171), the number of molecules (atoms) in 50 mL of helium or argon is the
same as the number of molecules in 50 mL of oxygen.
We saw in Section 3.3 on pp. 2202 that a mole was a xed number of particles.
Hence we can rephrase the above statement as:
Equal volumes of different gases, measured at the same temperature and
pressure, contain the same number of moles.
Or turning the statement around:
Measured at the same temperature and pressure, 1 mole of any gas has the same
volume as 1 mole of any other gas.
We call this the molar volume of a gas. Its value at STP (0C and 1.00 atm) is
22.4 L.
It follows then, that if 1 mole of oxygen gas at STP has a volume of 22.4 L, then
3 moles of chlorine gas at STP has a volume of 67.2 L and 0.5 mole of helium has a
volume of 11.2 L at STP.
EXERCISES
4 a How many moles of i carbon dioxide ii helium are present in 375 mL of the gas
at STP?
b What volume container would you need to store 0.095 mol of i argon
ii ammonia at STP?
5 In order to verify Avogadros law a group of students performed the following
experiment. They sealed (with silicone adhesive) two glass tubes into a clean empty
drink can as in the diagram below.
They lled the can with helium gas by
connecting a helium cylinder to tube A
and ushing out the can (gas leaves via
tube B), then sealing off the two tubes
with pieces of Blue Tack: this leaves
the can containing atmospheric pressure
of the gas being used. They weighed
the can plus gas. They repeated the
procedure with several other gases,
being careful to use the same pieces
of Blue Tack each time and not losing
any of it. Results are shown below.
Gas helium methane oxygen
carbon
dioxide
sulfur
dioxide
Mass of can 81.41 81.58 81.81 81.95 82.29
plus gas (g) 41

Avogadros law tells us that at constant temperature and pressure, volume of
a gas is proportional to n, the number of moles present, and is independent of the
nature of the gas; that is:
V = kn (8.1)
Let us now try to quantify the dependence of volumes of gases upon pressure
and temperature.
8.5 BOYLES LAW
By measuring the pressures and volumes of many samples of different gases at
constant temperature, Robert Boyle in 1662 rst made the following observation:
For a given quantity of gas at a constant temperature, the product of its volume,
V, and its pressure VV P, is constant. This is known as PP Boyles law.
The following experiment demonstrates the validity of this law. 25 mL of air
is drawn into a graduated gas-tight syringe and a pressure gauge is attached to
it as shown in Figure 8.3. The plunger of the syringe is pushed in and the new
pressure and volume recorded; this is repeated twice. Then the plunger is released
so pressure reduces back to the starting value, and then the plunger is pulled out
to increase the volume and two more sets of pressure and volume values recorded.
The results are shown in Table 8.1. We see there that the product PV is constant PV PV
(within experimental error). This shows the validity of Boyles law.
They then measured the mass of the can (without any gas in it, not even air) by
rst measuring the volume of water needed to ll the can and the tubes (using
volumetric asks and burette for accuracy), then weighing the can (with Blue Tack
plugs) lled with water.
Volume of water to ll the can = 332 mL
Mass of can plus water = 412.7 g
Temperature of the water = 20.2C
Density of water at 20.2C = 0.998 g/mL
a Use these results to determine the mass of the empty can (that is, without any
water, air or other gas in it).
b Combine the mass of the empty can with the results in the table to calculate
the number of moles of each gas in the can. Comment upon whether or not
the results conrm Avogadros law.

TABLE 8.1 Measurements showing the validity of Boyles law
Volume, V (mL) VV 25 21 18 16 30 39
Pressure, P (kPa) PP 102 118 134 164 82 66
10
3
PV 2.55 2.48 2.41 2.62 2.46 2.57
Average = 2.5 0.1
No matter what gas was used, providing temperature was constant during the
experiment, the product of pressure and volume was always constant (as in our
example in Table 8.1). Boyles law, like all scientic laws, is a summary of a large
number of experimental observations.
We can write Boyles law as:
PV = PV PV k (8.2)
where k is a constant. We say that volume is inversely proportional to pressure: if
pressure is doubled, volume is halved, or if pressure decreases to one-fth of its
initial value, volume increase to ve times its initial value.
An alternative statement of Boyles law is:
For a given quantity of gas at a constant temperature, the volume is inversely
proportional to the pressure.
A very useful alternative form of Equation 8.2 is:
P
2
PP V
2
VV = P
1
V
1
VV (8.3)
(since each of the products, P
2
PP V
2
VV and P
1
V
1
VV , is equal to the same constant, k). The
following example illustrates the use of this equation.
FIGURE 8.3
Device for testing
Boyles law
EXAMPLE 1
A sample of gas originally had a volume of 1.5 L at 1.0 atmosphere (atm). What volume
would it have at 4.0 atm pressure at the same temperature?
Let us call the initial conditions P
1
and V
1
VV ; P
1
= 1.0 atm, V
1
VV = 1.5 L. The nal
conditions are P
2
and V
2
VV ; P
2
= 4.0 atm and V
2
VV is what we want to nd.
By equation 8.3:
(4.0 atm) V
2
VV = 1.0 x 1.5 atm L
V
2
VV =
1.5
___
4.0

atm L
______
atm

= 0.38 L
In using Equation 8.3, we can use any units we like for pressure and volume, provided
we use the same units on both sides of the equation.
8.6 CHARLES LAW
experiments in the following law:
For a xed quantity of gas at constant pressure, the volume increases linearly
with temperature.
(Temperature is dened in terms of a mercury-in-glass thermometer on what
we now call the Celsius scale.)
We can demonstrate the validity of Charles law by modifying our previous
apparatus as shown in Figure 8.4(a). The syringe is connected to the pressure
gauge by a bent capillary tube (very small volume) and the body of the syringe
is immersed in a beaker of water, which can be heated over a Bunsen burner or
cooled by adding ice to it. Initially, the gas in the syringe is at atmospheric pressure
and room temperature; the volume and temperature are recorded. The water (and
so the gas) is heated; the plunger of the syringe is slowly withdrawn to maintain
the pressure at its initial value. Three sets of temperature and volume values are
recorded. Then the hot water is replaced by cold water and cooled by adding ice,
and again constant pressure is maintained (now by pushing the plunger in); sets
of temperature and volume values are recorded. Results are shown in Table 8.2.
EXERCISES
6 In the table below, P
1
and V
1
VV are the initial pressures and volumes, and P
2
and V
2
VV
the nal pressures and volumes, of samples of gases at constant temperatures.
Calculate the missing entry in each line.
P
1
V
1
VV P
2
V
2
VV
a 3.4 atm 500 mL 0.82 atm
b 87 kPa 4.6 L 6.5 L
c 2.2 atm 1.5 L 80 kPa
d 130 kPa 2.3 L 700 mL
7 73.3 kPa pressure of gas in a 2.5 L ask is expanded into a total volume of 6.3 L at
constant temperature. Calculate the nal pressure.
8 In order to measure the volume of a piece of apparatus, a chemist lled a 750 mL
ask with 93.3 kPa pressure of gas, then expanded it into the apparatus. The nal
pressure was 29.9 kPa. Calculate the total volume occupied by the gas, and hence
the volume of the apparatus being measured.
Refer to Context 4 Air, p. 134.

TABLE 8.2 Volume as a function of temperature for a sample of gas at constant
pressure (using the apparatus in Figure 8.4(a)
Temperature (C) 4 25 50 72 95
Volume (mL) 23 25 27 29 31
In Figure 8.4(b), volumes are plotted against temperatures (in degrees
Celsius, C). A straight line with positive intercept results.
When more sophisticated apparatus is used, it is possible to make measurements
over a wider range of temperature, and the results shown in Figure 8.5(a) for four
different samples of gas are obtained.
FIGURE 8.4
(a) Apparatus for testing
Charles law
(b) A graph of results from
the apparatus in (a)

FIGURE 8.5
Volumes of samples of
gas at constant pressure
versus (a) Temperature
in C, (b) Absolute
temperature, K
An interesting feature emerges from these plots. If we extrapolate all the lines to
lower temperatures, we nd that they all intersect the temperature axis at 273C
(273.15C using more exact methods). This is true for all samples of gas that have
been studied.
Consequently, a new scale of temperature is introduced, called the absolute
scale of temperature, or the Kelvin scale of temperature, or the thermodynamic
scale of temperature. It is dened as follows:
273.15 K = 0C
373.15 K = 100C
which means that 0 K = 273.15C
The unit of temperature on this new scale is called the kelvin, symbol K.
One advantage of this Kelvin scale of temperature is that all physically accessible
temperatures have positive values. 0 K is the absolute zero of temperature: we
cannot get any lower.
If the data of Figure 8.5(a) are replotted using absolute temperatures instead of
Celsius temperatures, then Figure 8.5(b) results. All the lines now pass through the
origin of the graph. We can write:
V = VV kT (8.4)
where k is constant (but not the same constant as in Equation 8.2). If y = yy kx, we
say that y is proportional to yy x. Hence:
At constant At At pressure, the volume of a xed quantity of gas is proportional to its
absolute (or Kelvin) temperature.
Equation 8.4 can be written as:

V
__
T
=
__ __
k (at constant pressure) (at (at (8.5)
An alternative and more practical form of this equation is:
V
2
VV
___
T
2
TT
=
___ ___
V
1
VV
___
= =
T
1
TT
(8.6)
since each of the quotients,
V
2
VV
___
since each of the quotients, since each of the quotients,
T
2
TT
and
___ ___
V
1
VV
___
and and
T
1
is equal to the same constant
___ ___
k
(of Equation 8.5). The use of this equation is easily demonstrated.
EXAMPLE 2
A sample of gas at 1.0 atm pressure had a volume of 2.5 L at 100C. What would its
volume be at 0C at the same pressure?
Let the initial conditions be V
1
VV and T
1
TT . Hence V
1
VV = 2.5 L and T
1
TT = 100 + 273.2 = 373.2 K.
(Caution: In Equation 8.6, temperature must be in kelvin.) Let the nal conditions be V
2
VV
and T
2
TT . Hence T
2
TT = 0 + 273.2 = 273.2 K and V
2
VV is what we want to nd.
By Equation 8.6

V
2
VV
________
273.2 K
=
________ ________
2.5
______
373.2

L
__
K

V
2
VV =
2.5 273.2

___________
373.2

L K
____
K

= 1.8 L
EXERCISES
9 In the table below, V
1
VV and (temp)
1
are the initial volume and temperature and V
2
VV
and (temp)
2
are the nal volume and temperature of samples of gas at constant
pressures. Calculate the missing entry in each line of the table.
V
1
VV (temp)
1
V
2
VV (temp)
2
a 500 mL 200 K 400 K
b 1.5 L 350 K 2.2 L
c 250 mL 22C 80C
d 500 mL 180C 1.3 L
10 A sample of gas had a volume of 1.7 L at 25C and 1 atm pressure. What would its
volume be at 250C (at the same pressure)? To what temperature would it need to
be cooled to have a volume of 900 mL?
11 To test Charles law, a sample of dry nitrogen gas was trapped in a capillary tube
tied to a small ruler as shown in the diagram below. This assembly was then
immersed in a series of liquids at different temperatures and the length of the gas
sample measured:
i methanol cooled to dry ice temperature 78C, 22 mm
ii ice water, 0C, 31 mm
iii room temperature water, 20C, 33 mm
iv boiling water, 100C, 42 mm
v heated ethylene glycol, 151C, 48 mm
Show
a graphically and b numerically
that these results obey Charles law.
12 The volume of gas in a constant-pressure gas thermometer was 61.0 mL at 280 K.
When it was immersed in a liquid of unknown temperature, its volume increased to
73.3 mL. What is the temperature of the liquid?
Refer to Context Air, pp. 1356.

8.7 COMBINED GAS LAW
For a xed quantity of gas,

PV
___
T
=
___ ___
k* (a constant) (8.7)
Another form of Equation 8.7 is:

P
2
PP V
2
VV
_____
T
2
TT
=
_____ _____
P
1
V
1
VV
_____
= =
T
1
TT
(8.8)
This equation is true because each side of it is equal to the same constant k*.
However, this equation is only true if temperature is in kelvins (as also was the case
with Equation 8.6). An example will illustrate the use of Equation 8.8.
EXAMPLE 3
A certain quantity of gas had a volume of 1.3 L at 1.0 atm pressure and 80C.
What pressure is needed to compress it to 500 mL at 30C?
Let the initial conditions be P
1
, V
1
VV , T
1
TT ; hence P
1
= 1.0 atm, V
1
VV = 1.3 L,
T
1
TT = 80 + 273.2 = 353.2 K. Let P
2
, V
2
VV , T
2
TT be the nal conditions;
V
2
VV = 500 mL = 0.5 L (units of V
2
VV must be the same as those for V
1
VV ) and
T
2
TT = 30 + 273.2 = 303.2 K. Hence by Equation 8.8:

P
2
0.50 L

___________
303.2 K
=
___________ ___________
1.0 1.3
________
353.2

atm L
______
K

P
2
=
1.3 303.2

____________

353.2 0.50

atm L K
________
K L

= 2.2 atm
EXERCISES
13 In the table below, P
1
, V
1
VV and (temp)
1
are the initial pressure, volume and
temperature, and P
2
, V
2
VV and (temp)
2
are the nal pressure, volume and temperature
of samples of gas. Calculate the missing item in each line.
P
1
V
1
VV (temp)
1
P
2
V
2
VV (temp)
2
a 101.3 kPa 1.5 L 300 K 53.3 kPa 450 K
b 1.3 atm 500 mL 280 K 1.2 L 500 K
c 1.0 atm 250 mL 25C 106.6 kPa 0.60 L
d 100 kPa 1.3 L 80C 3.5 10
5
Pa 271C
e 1.0 atm 20 L 250C 5.0 L 422C
f 53 kPa 23 mL 17C 3.0 atm 0.015 L
14 A gas, initially at 292 K, enclosed in a bulb of volume 15.1 mL at a pressure
of 90.2 kPa, was rst expanded into a reaction vessel so that the volume was
182.2 mL and then heated to 423 K. What is the nal pressure in the vessel?
8.8 IDEAL GAS EQUATION
When dealing with gases in many real-life situations such as scuba diving and
in using anaesthetics, all of the conditions of pressure, temperature, volume and
quantity of gas can be varied. To handle such situations we need to combine Boyles
and Charles laws with Avogadros law (in the form of Equation 8.1) to get:

PV
___
nT
= constant
PV PV
___ ___
(8.9)
Part of Avogadros law is that at constant P, PP T and TT n, the volume is constant for
all gases; this means that the constant in Equation 8.9 is the same for all gases: H
2
,
He, O
2
, N
2
, Ar, CO
2
and so on. We use the symbol R for this constant and call it the RR
universal gas constant.
Hence
PV
___
Hence Hence
nT
=
___ ___
R (8.10)
or PV = nRT (8.11)
This is called the ideal gas equation or the general gas equation.
This equation is called the ideal gas equation because real gases deviate slightly ideal ideal
from it, particularly at high pressures and low temperatures.
The value of R can be calculated from the molar volume of a gas at STP, RR
namely 22.4 L. Hence putting P = 1.00 atm, PP V = 22.4 L, VV n = 1.00 mol and
T = 273.2 K into Equation 8.10 gives: TT
R = RR
1 22.4
___________
= =
1 273.15

atm L
______
mol K

that is R = 0.0820 L atm K RR
1
= 0.0820 L atm K = 0.0820 L atm K mol
1
(or 0.08206 using a more precise value for V). VV
This value of R uses a non-systematic unit for pressure, namely the atmosphere. RR
To obtain R in proper units, we put RR P = 1.013 10 PP
5
N m
2
(that is, pascals,
15 A steel capsule of volume 25 mL contains carbon dioxide at a pressure of
5000 kPa; the contents are allowed to expand into an empty glass vessel of volume
1 L. In so doing, the temperature of the gas falls from 295 K to 282 K. Calculate the
nal pressure in the vessel.
16 Some balloons for upper atmosphere research are designed so that their shapes
can alter in order to change their volumes, and as a result, the pressure inside the
balloon is always equal to the outside atmospheric pressure. Such a balloon had
a volume of 10 m
3
at 1.0 atm pressure and 20C. What would its volume be in the
upper atmosphere where the pressure was 0.050 atm and the temperature 50C.
17 A chemist measured the pressure of a sample of nitric oxide in a cylinder of
constant volume at several temperatures. The results are given below.
*a Determine graphically the relation which exists between the pressure and
temperature.
b Is this what you expect from the combined Boyles and Charles law? Explain.
Temperature (C) 0 25 72 100 156
Pressure (atm) 1.05 1.15 1.33 1.44 1.65
using the conversion factor at the bottom of p. 315) and put volume in cubic
metres, that is, V = 22.4 10 VV
3
m
3
(because 1 m
3
= 10
3
L).
Hence:
R = RR
1.013 10
5
22.4 10
3

___________________________
= =
1 273.15

N m
2
m
3
_________
mol K

= 8.31 N m K
1
= 8.31 N m K = 8.31 N m K mol
1
Using more precise values for P and PP V, the value is 8.314. VV
Now a newton metre, N m, is a joule, J (the unit of work or energy), so that:
R = 8.314 J K RR
1
= 8.314 J K = 8.314 J K mol
1
The following examples illustrate the use of the ideal gas equation.
The only difculty in using Equation 8.11 is getting the units right. A foolproof
approach is to appreciate that a symbol such as P, PP V or VV T represents a physical TT
quantity and that the value of a physical quantity consists of a number and a unit: and and
P is not just 10 PP
5
but 10
5
Pa; V is not 2.3 but 2.3 L. Hence when we substitute a VV
value for a symbol, we should put in both the number and the unit. If this is done
for all physical quantities in an equation, then the units should cancel or combine
to give a suitable unit for the physical quantity being calculated. This practice has
been followed in Examples 1 to 4 above. You are strongly urged to adopt it too. If an
inconsistent set of units is inadvertently fed into an equation, then the units will
not cancel or combine to give sensible units for the answer, and the error is quickly
recognised.
The use of systematic units is strongly recommended:
P in pascals, Pa (= N m
2
)
V in cubic metres, m
3
T in kelvins, K
We then use R = 8.314 J K RR
1
= 8.314 J K = 8.314 J K mol
1
= 8.314 N m K
1
= 8.314 N m K = 8.314 N m K mol
1
EXAMPLE 4
What volume will 2.50 moles of carbon dioxide occupy at 400 kPa pressure and 100C?
As we are given P, T and TT n, and we have to nd V, Equation 8.11 is required.
P = 400 kPa PP
= 4.00 10
5
Pa (Pa = N m
2
)
T = 100 + 273.2 TT
= 373.2 K
n = 2.50 mol
R = 8.314 J K
1
= 8.314 J K = 8.314 J K mol
1
(and J = N m)
Hence V = VV
nRT
____
P

=
2.50 8.314 373.2

_____________________

4.00 10
5

mol N m K
1
mol N m K mol N m K mol
1
K

___________________

N m
2

= 1.94 10
2
m
3
Or to put in more familiar units:
V = 19.4 L VV
It is perhaps worth noting that P in kilopascals and PP V in litres is equivalent to VV P
in pascals and V in cubic metres, because: VV
1 kPa 1 L = 1 10
3
Pa 1 10
3
m
3
= 1 Pa m
3
Hence an alternative to putting P in pascals and PP V in cubic metres is to put VV P in PP
kilopascals and V in litres. VV
The key to handling units in the ideal gas equation is to recognise that:
Pa m
3
= J
or kPa L = J or or
Although in systematic units R is always given as: RR
R = 8.314 J K RR
1
= 8.314 J K = 8.314 J K mol
1
you may like to translate that into:
R = 8.314 Pa m RR
3
K
1
K K mol
1
or to R = 8.314 kPa L K RR
1
= 8.314 kPa L K = 8.314 kPa L K mol
1
If R is available in litre atmosphere units (that is RR R = 0.0820 L atm K RR
1
= 0.0820 L atm K = 0.0820 L atm K mol
1
)
and if pressure is given in atmospheres, it is quicker to work the problem in
atmospheres rather than convert to pascals.
EXAMPLE 5
Calculate the molar mass of a gas for which 8.79 g is needed to ll a 2.55 L ask to
a pressure of 1.30 atm at 21.2C.
In order to calculate the molar mass, we need to know how many moles there are in
8.79 g, that is how many moles are in the ask. Hence we use the ideal gas equation
to calculate n.
P = 1.30 atm, PP V = 2.55 L, VV T = 21.2 + 273.2 = 294.4 K TT
From Equation 8.11:
n =
PV
___
RT

=
1.30 2.55

_______________

0.0820 294.4
atm L

_________________

L atm K
1

L atm K L atm K mol
1

K
= 0.137 mol
That is, 8.79 g is 0.137 mol.
Hence 1 mol =
8.79
______
0.137

= 64.1 g
The molar mass is therefore 64.1 g/mol.
Most our discussion of gases so far has concerned single pure gases. Let us now
look at mixtures of gases.
EXERCISES
18 Pressure, volume, temperature and number of moles of different samples of gases
are listed in the table. Calculate the missing entry in each line.
P V Temperature n
a 20 10
3
Pa 5.0 L 300 K
b 304 kPa 450 K 0.20 mol
c 0.010 m
3
292 K 0.055 mol
d 5.33 10
4
Pa 500 mL 0.030 mol
e 2.026 kPa 2.0 L 26C
f 350 Pa 35C 0.010 mol
19 What pressure in kilopascals will 2.0 g argon exert when placed in a 500 mL
cylinder at 18C?
20 What mass of nitric oxide, NO, is present in a 2.5 L ask in which the pressure is
6.67 10
4
Pa at 310 K?
21 What volume is needed to store 0.800 g sulfur dioxide at a pressure of 101.3 kPa
at 17C?
22 To what pressure must a piece of equipment be evacuated in order that there be
only 10
8
molecules per mL at 25C?
23 5.0 g of an unknown gas produced a pressure of 19.4 kPa in a 10.0 L ask at 25C.
Calculate the molar mass of the gas.
24 A chemist measured the pressure generated at 80C in a cylinder of xed
volume by different masses of different gases. The results are given below.
Show graphically that these results are in accord with the ideal gas equation.
Gas used SO
2
NO HCI CO
2
NH
3
Mass of gas (g) 3.2 2.40 3.65 5.72 3.06
Pressure (kPa) 54 89 109 145 197
25 A gas exerts a pressure of 0.33 atm in a 1.7 L ask at 28C. How many moles are
there in the ask?
26 What pressure (in atm) will be exerted by 87.6 g ammonia in a 5.2 L steel cylinder
at 24.2C?
27 A steel cylinder of volume 50 L is lled with argon to a pressure of 105 atm at 19C.
What mass of gas is in the cylinder?
28 Some chemists, trying out a new technique for synthesis, prepared a pure gaseous
compound containing sulfur and uorine only. They collected a sample of their
compound in a small ask of volume 25.7 mL. At 27.2C the sample exerted a
pressure of 0.50 atm and had a mass of 0.0772 g. Which of the compounds SF
2
,
SF
4
or SF
6
had they prepared? Explain your answer fully.

8.9 DALTONS LAW OF PARTIAL PRESSURES
In the early 1800s, John Dalton made the observation which is now called Daltons
law of partial pressures:
If two If If or more gases are present in the same container, the total pressure exerted
is the sum of the pressures each gas would exert if it alone occupied the container.
P
tot
PP =
tot tot
P
A
PP + P
B
PP +
BB
P
C
PP +
CC
(8.12)
where P
tot
is the total pressure and
tot tot
P
A
PP , P
B
PP , P
C
, are what are called partial
pressures of gases A, B, C CC
The partial pressure of a gas in a mixture of gases is the pressure which that gas
would exert if it alone were present in the container. An alternative statement of the law
of partial pressures is:
The total pressure in a gas mixture is the sum of the partial pressures of the
individual gases.
If 0.10 mole of nitrogen and 0.050 mole of chlorine are present in a 2.0 L ask
at 20C, the partial pressure of nitrogen, P
N
PP , is calculated by putting n = 0.10 mole, nn
T = 293.2 K, TT V = 2.0 10 VV
3
m
3
into Equation 8.11:
P
N
PP =
0.10 8.314 293.2

_____________________
= =
2.0 10
3

mol Pa m
3
K
1
K K mol
1
K

_____________________

m
3

= 1.22 10
5
Pa
The partial pressure of chlorine, P
Cl
PP , is similarly calculated:
P
Cl
PP =
0.050 8.314 293.2

______________________
= =
2.0 10
3

mol Pa m
3
K
1
K K mol
1
K

_____________________

m
3

= 6.09 10
4
Pa
The total pressure, P
tot
, is the sum of these partial pressures:
P
tot
=
tot tot
P
Cl
PP + P
N
PP
= (0.61 + 1.22) 10
5
Pa
= 1.83 10
5
Pa
As this illustration shows, the law of partial pressures means that in a mixture, the
gas equation can be applied to each gas separately to calculate the partial pressure of gas, i,
in terms of n
i
, the number of moles of gas, i, present; alternatively the gas law can be used
to calculate the total pressure of all the gases in the container, provided that n, in that case,
is the total number of moles present.
That is, in a mixture of gases:
P
i
PP V = VV n
i
RT
ii
(8.13)
where P
i
PP is the partial pressure of gas,
ii
i, and ii n
i
is the number of moles of gas,
ii
i, ii
and P
tot
PP =
tot tot
n
tot
RT
tot tot
(8.14)
where P
tot
is the total pressure and
tot tot
n
tot
is the total number of moles of gas.
tot tot
We can use the ideal gas equation in whichever form is more convenient for
the problem at hand. In the illustration just discussed we used it in the form of
Equation 8.13. Let us now illustrate the use of Equation 8.14.
EXAMPLE 6
If 4.0 g carbon dioxide and 5.0 g carbon monoxide are placed in a 5.0 L ask at 15C,
what is the total pressure of the gas mixture?
To use the gas law, we need the total number of moles of gas. The molecular weights of
CO
2
and CO are 44 and 28 respectively. Hence:
total number of moles =
4.0
___
44
+
4.0 4.0
___ ___
5.0
___
28

= 0.27 mole
Putting n = 0.27 mole, T = 288.2 K, TT V = 5.0 10 VV
3
m
3
into Equation 8.14:
P =
nRT
____
P = P =
V

=
0.27 8.314 288.2

_____________________

5.0 10
3

mol Pa m
3
K
1
K K mol
1
K

_____________________

m
3

= 1.3 10
5
Pa
= 130 kPa
EXERCISES
29 Two small asks with closed stopcocks are attached by short tubes to a large ask.
The large ask and connecting tubing is well evacuated. One small ask, of volume
25 mL, contains oxygen at a pressure of 101.3 kPa, while the other, of volume
75 mL, contains helium at a pressure of 70.9 kPa. The stopcocks of the small asks
are opened so that the two gases mix and expand into the evacuated volume. The
total volume of the whole apparatus is 10.0 L. Calculate the partial pressures of
oxygen and helium and the total pressure.
30 A 5.0 L cylinder containing hydrogen at a pressure of 500 kPa is connected to
a 3.0 L cylinder containing argon at a pressure of 300 kPa, and sufcient time is
allowed for complete mixing. Calculate the partial pressures of hydrogen and argon
and hence the total pressure in the joined cylinders.
31 0.5 g carbon dioxide and 0.7 g neon were placed in a 2.0 L ask. Calculate the
partial pressures at 25C and the total pressure.

8.10 SUMMARY
This chapter has shown how to calculate one of the properties of a gas (pressure,
volume, temperature, number of moles) from known values of other properties and
how to calculate the change in one property when other properties are changed.
In this regard the key equations are 8.8 (of which 8.3 and 8.6 are special cases) and
8.11. The key to success in using these equations is using correct or consistent units.
When mixtures are involved, we use Daltons law of partial pressures,
Equation 8.12, and its consequences, Equations 8.13 and 8.14.
TEST YOURSELF
above.
2 State the basic postulates of the kinetic theory of gases.
3 What is the systematic unit for pressure?
4 How is the absolute or Kelvin scale of temperature dened? What is its relationship
to the Celsius scale?
5 What is meant by STP?
6 Describe an experiment for demonstrating the validity of Boyles law.
7 Describe an experiment that could be performed to test Charles law.
8 Explain the following:
a The pressure in bicycle tyres increases on a hot day.
b A weather balloon increases in volume as it rises.
9 Two asks of equal volume are lled with nitrogen and helium respectively to the
same pressure at the same temperature. Compare the two samples in terms of:
a the number of molecules present
b the mass of gas present.
10 What experimental fact can be used to calculate a value of the universal gas
constant, R?
11 By volume the atmosphere is 20% oxygen, 79% nitrogen and 1% argon. On a day
when atmospheric pressure is 100 kPa, what are the partial pressures of these gases?
absolute scale of temperature
(Kelvin scale) (p. 324)
atmosphere (unit of pressure) (p. 315)
Avogadros law (hypothesis) (p. 319)
Boyles law (p. 320)
Charles law (p. 322)
combined gas law (p. 326)
Daltons law of partial pressures (p. 331)
diffusion (p. 317)
ideal gas equation (general gas equation)
(p. 327)
Kelvin scale of temperature (absolute
scale) (p. 324)
kinetic theory of gases (p. 318)
molar volume of a gas (p. 319)
partial pressure (p. 331)
pascal (Pa) and kilopascal (kPa) (p. 315)
pressure (p. 315)
standard temperature and pressure
(STP) (p. 317)
thermodynamic scale of temperature
(p. 324)
universal gas constant, R (p. 327)
IMPORTANT NEW TERMS
CONTEXT 1 ANSWERS 335
ACTIVITY 1.3
a Materials do not enter or leave the Earththe amount of matter is constant.
b New substances are formed by the recombination of atoms in existing substances.
c carbon cycle, nitrogen cycle, water cycle
d Humans can send material into space, causing loss and they also interfere with the
cycles causing build-ups in some areas and depletion in others.
ACTIVITY 1.4
a mixture
b mixture
c compound
d element
e mixture
f element
g mixture
h compound
i element
ACTIVITY 1.5
Example Separation method
Property enabling
separation
separating mud from water ltration difference in particle size
separating salt and sand dissolve in water and lter difference in solubility in
water and particle size
separating oil and water using a separating funnel liquids do not mix, oil oats
on water (immiscible)
obtaining nitrogen and
oxygen from liquid air
fractional distillation difference in boiling point
obtaining fresh water from
salt water
distillation large difference in boiling
points
ANSWERS
Materials
ACTIVITY 1.6
a helium heavier elements such as carbon and oxygen heavier
elements including neon and magnesium silicon, phosphorus, sulfur, calcium and
others iron (supernova) elements heavier than iron
b

ACTIVITY 1.7
a
b When the whole Earth is considered the mantle and core must be considered.
These are composed of different materials. The mantle is mainly iron, magnesium and
silicates, whereas the core is mainly iron and nickel. The lithosphere is composed of
mostly different minerals which contain a variety of elements, primarily oxygen, silicon
and aluminium.
c i Law of conservation of matter: matter cannot be created or destroyed, merely
changed from one form to another.
ii Nuclear reactions involve the combining together (fusion) or the breaking apart
(ssion) of nuclei during which some matter is converted to energy.
ACTIVITY 1.8
a Physical properties include colour, feel, electrical conductivity, ease of tearing, water
absorbency, solubility, hardness, elasticity.
b Chemical properties include reaction with oxygen, reaction with acids, reaction with
bases. Chemical change could be identied by production of a gas, colour change,
new solid formed, signicant change in temperature, disappearance of a solid, odour
produced.
ACTIVITY 1.10
a Gold is very unreactive so will exist in its pure state because it tends not to combine
with other substances; copper is slightly more reactive than gold so may be found in
both combined and uncombined states; sodium is very reactive so will not be found
in its pure state.
b i tungsten
ii copper
iii aluminium
iv graphite
v mercury
vi helium
c diamondhard, crystalline, sparkling, non-conductor of electricity, graphiteelectrical
conductor, soft, dull grey, slippery
CONTEXT 1 ANSWERS 337 CONTEXT 1 ANSWERS 337
ACTIVITY 1.11
a i ionic
ii covalent molecular
iii covalent molecular
iv ionic
v ionic
vi covalent molecular
vii covalent network
viii covalent molecular
b Water from the tap has lots of ions from dissolved ionic compounds and so is a good
conductor of electricity.
c Tests could include solubility in water; electrical conductivity of the compound,
solution (if soluble) and molten compound; ease of melting.
ACTIVITY 1.13
a CH
4
(g (( ) + 3Cl
2
(g (( ) CHCl
3
(g (( ) + 3HCl(g ) + 3HCl( ) + 3HCl( )
b 2C
8
H
18
(l (( ) + 25O
2
(g (( ) 16CO
2
(g (( ) + 18H
2
O(g O( O( )
c i 2C(s 2C( 2C( ) + O
2
(g (( ) 2CO
2
(g (( )
ii 2Fe
2
O
3
(s (( ) + 6CO(g ) + 6CO( ) + 6CO( ) 4Fe(l 4Fe( 4Fe( ) + 6CO
2
(g (( )
d Using up and throwing away imply materials are lost but atoms are merely rearranged
into new substances so are never really lost.
e Matter is still available for reuse, matter can be converted to new materials.
f i 2Ag
2
O(s O( O( ) 4Ag(s 4Ag( 4Ag( ) + O
2
(g (( )
ii Mass O
2
= 0.21 g
ACTIVITY 1.15
a 30.2 g
b i 5.5 10
8
cans
ii 1.8 10
7
g
c 5.2 10
2
g
ACTIVITY 2.1
a
b T
c F
d F
e T
f T
g T
h T
i T
j T
k T
l T
ACTIVITY 2.2
Answers vary according to usage.
ACTIVITY 2.3
The graph shows a peak at 5C. The density decreases with increasing temperature
except between 0C and 5C. This shows why ice is less dense and oats in water.
The water should reduce its level as the ice melts as the liquid water takes up less volume
because it is less dense.
ACTIVITY 2.4
a

b Prediction should be that fewer drops will t on the coin before it overows.
c Non-polar molecules do not have the attractive dipoledipole forces of water
molecules. Fewer drops will t on the coin. The liquid will not bulge to the same extent
as water.
ANSWERS
Water
d
and helps to hold the water together (cohesion).
e At the surface of the water the water molecules exhibit forces of attraction (cohesion)
which are stronger than the forces of penetration into the water due to the insects
weight.
ACTIVITY 2.5
a There is an inverse relationship between the height the water rises and the diameter
of the tubeas the diameter decreases in size, the water moves higher in the capillary
tubing.
b The capillary action is greatest in the tube with the smallest diameter.
c Forces of adhesion between the glass and the water molecules attract the water up
the tube.
ACTIVITY 2.6
The size of the xylem vessel diameter should be similar to that of the narrow capillary
tubes.
ACTIVITY 2.7
a The solvent is water and the solutes include sugars, avourings and preservatives.
b A homogeneous mixture consists of two or more substances that are evenly
distributed but not chemically combined. This means that the dissolved substance
particles are spread out evenly between the water molecules.
c No chemical formula can be written for the cordial, which is a mixture. This is because
the proportion of water to the sugars is not xed. The water in the cordial is a
compound and always has a ratio of two hydrogen atoms to one oxygen atom.
d One way of determining whether the substance is a pure solvent or solution would
be to evaporate the substance. Evaporating a pure solvent would leave no substance
behind, whereas evaporating a solution would leave the solute behind.
ACTIVITY 2.8
The formula for the copper sulfate hydrate is CuSO
4
.5H
2
O. This means there are ve
molecules of water for every unit of copper sulfate.
ACTIVITY 2.9
The polar and thus water soluble molecules are vitamin B2 and vitamin C. The non-polar
and thus fat-soluble molecules are A and E.
ACTIVITY 2.10
Students own research required.
ACTIVITY 2.11
a As the temperature increases the solubility of the carbon dioxide in water decreases
(provided the pressure remains constant).
c Other gases like oxygen exhibit the same trend.
ACTIVITY 2.12
ACTIVITY 2.13
ACTIVITY 2.14
ACTIVITY 2.15
ACTIVITY 2.16
Possible answers are in the table below.
Substance
How the substance
got into the water
source
Why you would not
like this substance
in your drinking
water
Method that
may be used to
eliminate or reduce
the quantity
dissolved minerals Dissolve in water as
it passes though the
soil/ground.
Affects the taste of
the water.
Chemicals may
be used to react
with the solutes to
form precipitates
removed by ltering.
organic wastes Manure and other
wastes ow into
catchments with
rainwater.
Affects the
taste, smell and
appearance of the
water.
Some may be
removed by ltering.
bacteria Spores land and
feed on organic
wastes.
May make you sick. Disinfect the water.
undissolved/
suspended particles
Wastes ow into
catchments with
rainwater.
Affects the
taste, smell and
appearance of the
water.
Some may be
removed by ltering.
poisonspesticides Wastes ow into
catchments with
rainwater.
May make you sick,
e.g. cause cancer.
Disinfect the water/
react with chemicals
for removal.
ACTIVITY 2.17
The table below represents part of a recipe to prepare a hydroponic solution.
Chemicals needed to prepare 1000 L of nutrient solution
Nutrient chemicals Weight in grams
potassium dihydrogen phosphate 263.00
potassium nitrate 583.00
calcium nitrate 1003.00
magnesium sulphate 513.00
copper sulphate 0.39
ammonium molybdate 0.37
zinc sulphate 0.44
a KH
2
PO
4
= 1.93 10
3
mol/L
KNO
3
= 5.77 10
3
mol/L
Ca(NO
3
)
2
= 6.11 10
3
mol/L
MgSO
4
= 4.26 10
3
mol/L
CuSO
4
= 2.44 10
6
mol/L
(NH
4
)
2
MoO
4
= 1.89 10
6
mol/L
ZnSO
4
= 2.73 10
6
mol/L
b Mg
2+
= 4.26 10
3
mol/L, Zn
2+
= 2.73 10
6
mol/L, NO
3
= 1.80 10
2
mol/L
c Cu
2+
= 0.156 ppm
d 3.54 g
ACTIVITY 2.18
a The substances that may be removed include the decaying matter and suspended
substances and some microbes.
b Collecting the water through a handkerchief will lter some undissolved particles,
including some microbes. The chemical tablet contains an ingredient to kill the
microbesgenerally a chlorine compound, which is converted to hypochlorous acid
(HClO), a powerful oxidising agent (Cl
2
+ H
2
O HClO + H
+
+ Cl
). Boiling the water
will improve the chances that the microbes are destroyed.

c Chemicals that dissolve in water like salts will remain in the water. Heavy metal ions
like arsenic would still remain a risk.
ACTIVITY 2.19
Answers may vary, but should reect all processes shown in the diagram.
ACTIVITY 2.20
Student designs should follow the investigation model used in the Queensland Studies
Authority Chemistry Syllabus Design.
ACTIVITY 2.21
Answers depend on student research.
ACTIVITY 2.22
Student designs should follow the investigation model used in the Queensland Studies
Authority Chemistry Syllabus Design.
ACTIVITY 2.23
a This water would be considered to be moderately hard.
b 5.4 10
4
mol/L
c 46 mg/L
ACTIVITY 2.24
Food Standard Code
Component
Food Standard Code
(mg/L)
Australian Drinking
Water Guidelines
(mg/L)
arsenic 0.05 0.007
barium 1.0 0.7
borate (calculated as H
3
BO
3
) 30 0.02
chromium (VI) 0.05 0.05
copper 1.0 2.0
cyanide (calculated as CN

) 0.01 0.08
uoride (calculated as F

) 2.0 1.5
lead 0.05 0.01
manganese 2.0 0.5
mercury 0.001 0.001
nitrate (calculated as NO
3

) 45 50
nitrite (calculated as NO
2

) 0.005 3
zinc 5.0 3.0
Some substances have the same standards, for example levels of mercury and
chromium(VI); other standards are similar, for example nitrates; while other standards show
quite a discrepancy, for example borate and nitrite. It is difcult to understand why such
discrepancies exist.
ACTIVITY 2.25
a The components appear to be in a similar range, but are different. This is probably
due to the waters exposure to different rocks and soils on the way to the underground
source.
b The low value of bicarbonates suggests that this substance may have been decreased
compared to the original value. The other values seem similar.
c Microlters may have removed some silt, sand and micro-organisms. Ozonation will kill
some of the microbes present.
d Tap water appears to contain greater concentrations of substances, for example
sodium and chloride ions.
e The packaged water is provided for drinking and should meet the same levels required
by the Australian Drinking Water Guidelines.
ACTIVITY 2.26
1 a 2.1 10
4
mol/L; 9.7 10
6
mol/L
b 10.1 ppm; 9.9 ppm
2 1.13% suspended solids; 7.6 10
2
% dissolved solids
3 b i 8.7 mg/L
ii 12.0 mg/L
iii 14.1 mg/L
(iii) is less accurate than (i) or (ii) because it involves an extrapolation whereas the
others involve interpolation
c i 2.5C
ii 28.5C
d 2.7 10
4
mol/L
4 a 88% saturation
b 62%
c 62%
d 85%
5 a i A and E
ii C and D (though D is somewhat polluted:
see (c))
iii B (all three based on TDS)
b A and F (based on BOD and DO)
c D and F (based on Na
2
S test)
6 A (0.054 0.002) ppm; B (0.136 0.004) ppm; C (0.182 0.006) ppm;
D (0.010 0.001) ppm; no; because the calibration curve is linear, there are no extra
errors in extrapolating to the small extents involved here
7 a The stream that would be considered relatively free of pollution would be
stream C, as this stream meets the criteria for healthy water (turbidity of 5 or less
NTU, TDS less than 100 mg/L, pH in water between 6.5 and 8, dissolved oxygen
at least 56 mg/L and phosphate 0.010.1 mg/L). Stream F has TDS of 150 mg/L,
higher than the criteria for healthy water but it is still drunk by many Australians.
b A stream that may have had a sample taken well downstream from the point where
sewage was discharged into the stream would be stream D, as the dissolved
oxygen reduced possibly because of bacterial demand for oxygen.
c Streams that may have had serious soil erosion include A, because of the
increased levels of turbidity and TDS.
d A stream that may have suffered damage from acid drainage could be stream G,
because of the low pH.
e A stream susceptible to algal bloom could be streams B and D, because of the
increased phosphate level.
f Streams likely to contain very little aquatic life at the sampling point would be E
(because of the low pH and dissolved oxygen).
8 a (in ppm) W, 0.751; X, 1.37; Y, 0.030; Z, 0.151
b X; quantitatively dilute the sample (e.g. 25 mL to 100 mL) to bring the
concentration within the reliability range and re-do the analysis
CONTEXT 3 ANSWERS 343
ACTIVITY 3.1
a C
8
H
18
+ 12
1 __
2
O
2
8CO
2
+ 9H
2
O
1 mole octane = 114 g, 1 mole oxygen = 32 g
Therefore mass ratio = 114g: 12
1 __
2
32 g
= 114:400
= approx 1:3.5
Since air is only 23% O
2
, fuel to air ratio = 1:15.2
LPG 1:15.8
ethanol 1:9.1
ACTIVITY 3.2
a Since reactions can occur only when particles collide, the fuel needs to be vaporised
so that oxygen particles can get to all of the fuel particles quickly.
b Natural gas has BP = 164
o
C, petroleum gas has BP = 42
o
C, so natural gas would
be much more difcult to keep as a liquid (it is more volatile because it boils much
more easily).
ACTIVITY 3.3
a Students should relate to properties such as whether it is a liquid or gas at room
temperature, boiling point, how hard the fuels are to ignite, how much energy is obtained
per gram and per litre of fuel, and how hard each fuel would be to store and transfer.
b Petrol, diesel and propane are all derived from crude oil so are relatively cheap.
Methane is cheap, but is not easy to store and transfer because it is hard to liquefy.
c Hint: Use only alkanes in the graph.
heat of combustion of heptane = 4811 kJ/mole
heptane = C
7
H
16
, MM = 100 g/mol
heat of combustion = 481 kJ/g
d liquid
ANSWERS
Transport

ACTIVITY 3.4
a
as many particles of the fuel in contact with oxygen particles as possible, to increase
the rate of the combustion reaction.
b Petrol carburettors have to atomise the liquid fuel to ensure rapid burning, then mix it
with air in the correct proportions. LPG carburettors only have to mix the gas with air in
the correct proportions.
ACTIVITY 3.5
a Observations would include more soot or unburned petrol caught in the handkerchief
when the car is cold than when it is warm.
b At low and high air:fuel ratios the power is low. Power peaks at around 12.7:1
c 12.7:1
d This is a lower air:fuel ratio than expected. Power would be expected to be highest at
the stoichiometric ratio of around 15:1.
e At rich mixtures there is not enough air to burn all of the fuel so less power is obtained.
At lean mixtures there is not enough fuel for the air. The low power output is most likely
due to problems maintaining the explosion reaction without enough fuel.
f Fuel consumption is very high at rich mixtures, lowest at about 15:1 and begins to
increase again at lean mixtures.
g 15:1
h This is around the stoichiometric ratio for complete combustion.
i Answer is similar to part e.
j For both CO and hydrocarbons the pollution is highest for the rich mixtures. Unburned
hydrocarbons begin to rise again for lean mixtures. CO continues to decrease to
a minimum at about 16:1, then continues low. Hydrocarbon pollution is minimum
at about 16:1, then increases again. Oxides of nitrogen are lowest at lean and rich
mixtures and highest at 15.5:1.
k CO and hydrocarbon pollution are lowest around the stoichiometric ratio. Oxides of kk
nitrogen are highest at the stoichiometric ratio.
l One anomaly is that hydrocarbon pollution increases again for lean mixtures. It would
be expected to stay low since there is plenty of oxygen for combustion. Another
anomaly is that the oxides of nitrogen graph are the reverse of the other pollutants.
m Production of pollutants is not simply a matter of incomplete combustion.
n Nitrogen comes from the air.
o Oxides of nitrogen come from combustion of nitrogen in the air, which occurs only
at high temperatures, so the pollutant will peak when the motor is burning most
efciently.
ACTIVITY 3.6
a Generalisations would be similar to that the more intimate the contact of smaller
particles with air the faster the combustion.
b The glow plug in a diesel engine is a wire that glows red hot in the cylinder. Its purpose
is to help diesel fuel ignite when the engine is rst started and cold, heating the fuel:air
mixture above the ignition temperature.
c Compression ratio means the ratio by which the fuel:air mixture is compressed.
For example, if the volume of each cylinder changes from 500 mL when the piston
is down to 50 mL when the piston is up, the compression ratio is 10:1. The higher
the compression ratio, the more energy can be extracted from the fuel when it is
combusted. Also the higher the compression ratio, the hotter the air:fuel mixture gets
when it is compressed, so the more chance it has of igniting just from the heat of
compression processes.
ACTIVITY 3.7
a Refer to teacher.
ACTIVITY 3.8
a Refer to teacher.
b Refer to teacher.
ACTIVITY 3.9
a Figure 3.9 tells you that no one is certain of total reserves, and that we can make
a best case estimate of about 3 trillion barrels and a worst case estimate of about
2 trillion barrels.
b Figure 3.10 tells us that even the best case scenario shows that we will begin to run
out of oil very soon and very quickly.
c Figure 3.11 tells us that we are unlikely to discover much more oil in the future.
d The three graphs indicate that oil is running out very quickly as a resource.
e Refer to teacher.
f Refer to teacher.
ACTIVITY 3.10
a The proportions would change depending on the time since the living material was
buried, the temperature and pressure at that place, the structure of the rock, and so
on. The higher temperature after the oil is formed, the more the lower boiling point
fractions might vaporise and leave heavier fractions behind.
b Many responses are possible.
ACTIVITY 3.11
a 2,3,4-trimethylpentane would have the highest octane rating.

b Refer to teacher.
c Refer to teacher.
d


e Cyclohexane and benzene are not isomers of hexane because they do not have the
same formula. Cyclohexane = C
6
H
12
, benzene = C
6
H
6
, hexane = C
6
H
14
f i More C atoms lower octane rating.
ii Double bonds increase the octane rating.
iii Branching increases the octane rating.
g Each of the processes increases the octane rating of the petroleum products.
ACTIVITY 3.12
a The reaction is much faster because potassium nitrate breaks down with heat into
oxygen (and by-products) which can then react with the our particles. More oxygen
in more intimate contact means a faster reaction.
b Petrol burns with a sooty, yellow ame, indicating incomplete combustion. A yellow
ame indicates particles of soot being heated and emitting a yellow light. Ethanol
burns with a clean, blue or nearly invisible ame, indicating complete combustion.
The oxygen in ethanol reduces its need for external oxygen from the air, so improving
combustion. It may burn more slowly than petrol, allowing the oxygen particles to
collide with the fuel particles. (This could be tested by seeing how long the same
amount takes to burn under similar conditions.)
c Cost, availability, toxicity, volatility, ash point (how easy it is to make a fuel explode).
d NOS or nitrous oxide is a source of oxygen for race cars that gives more oxygen more
quickly than air. There are other combustion benets to be researched.
ACTIVITY 3.13
a Refer to teacher.
ACTIVITY 3.14
a Assuming petrol is mostly octane. The energy values as a liquid tells you that the
density of octane is
33.7
/
47.9
kg/L = 0.70 kg/L.
1 L petrol = 0.70 kg = 700 g
700 kg =
700
/
114
moles
= 6 moles petrol
6 moles petrol gives 8 6 moles CO
2
48 moles CO
2
= 48 44 g CO
2
Therefore 1 L of petrol makes 2100 g of CO
2
= 2.1 kg of CO
2
b Refer to teacher.
c Refer to teacher.
d The gas forms an acid in water.
e Refer to teacher.
f Refer to teacher.
ACTIVITY 3.15
a Compress and cool it.
b 0.013 MJ/L
c Petrol = 33.7 MJ/L at normal temperature and pressure. Hydrogen = 0.013 MJ/L at
normal temperature and pressure. Therefore, ratio of energy of petrol to hydrogen is
about 2600:1 at normal pressure and temperature.
d Answers should focus on the cost or difculty of maintaining hydrogen in a liquid or
concentrated form for storage.
e Refer to teacher.
f Refer to teacher.
g Refer to teacher.
h Calculate the number of moles of hydrogen in 1 L of petrol
(18/2 6.14 = 13.8 moles H = 55.3 moles H
2
)
Calculate the energy value of the hydrogen in 1 L of petrol
(55.3 285 = 15750 kJ or 15.75 MJ)
Therefore if you could just burn the hydrogen in petrol the energy value would be
15.75 MJ/L or just under half of what you get when you burn petrol normally.
ACTIVITY 3.16
a internal combustion engine
b 250C
c

Pros Cons
Hydrogen is in plentiful supply. Takes a lot of energy and expensive
technology to keep the hydrogen as a
liquid.
Hydrogen is available from a variety of
biological and mineral sources.
Still makes NO
x
pollution because it burns
the fuel.
The main by-product of hydrogen is water.
This type of car uses well-understood
technology.
The internal combustion motor is
acceptable to a wider range of consumers.
d The future engine will be a fuel-cell-powered electric vehicle.
ACTIVITY CD3.1
a annealing: to toughen metal by heating to correct temperature and cooling slowly.
b quenching: to cool hot metal quickly by dipping in cold water or oil.
c work-hardening: to make a metal harder and more brittle by bending and shaping
it during the manufacturing process.
ACTIVITY CD3.2
Refer to teacher.
ACTIVITY CD3.3
a Refer to teacher.
b Refer to teacher.
c For 9-carat gold: of 24 g, 9 g will be gold and 15 g will be copper.
% gold is 9/24 = 37.5. Therefore 9-carat gold is 37.5% gold, 62.5% copper
For 18-carat gold: of 24 g, 18 g will be gold and 6 g will be copper.
% gold is 18/24 = 75. Therefore 18-carat gold is 75% gold, 25% copper.
d i The melting point of solder alloys decreases as the percentage of tin increases,
until around 70% when it begins to increase again.
ii approximately 250C
iii approximately 7% tin
iv From the graph, any value between 320C and 400C would be acceptable.
According to the Handbook of Chemistry and Physics, 63rd edition, the melting
point of pure tin is 232C.
e Refer to teacher.
ACTIVITY CD3.4
a i Cu Cu
2+
+ 2e
Cl
2
+ 2e

2Cl
Cu is oxidised.
Cl
2
is reduced.
ii Fe Fe
2+
+ 2e
2H
+
+ 2e
H
2
Fe is oxidised.
H
+
is reduced.
iii S
2
S + 2e
I
2
+ 2e
2I
S
2
in H
2
S is oxidised.
I
2
is reduced.
b In reaction (i) elemental Cl is the oxidant and is reduced to Cl
.
In reaction (ii) H
+
is the oxidant and is reduced to elemental H.
In reaction (iii) elemental I is the oxidant and is reduced to I
.
c In reaction (i) elemental Cu is the reductant and is oxidised to Cu
2+
.
In reaction (ii) elemental Fe is the reductant and is oxidised to Fe
2+
.
In reaction (iii) elemental S
2
is the reductant and is oxidised to elemental S.
d i Ba(s Ba( Ba( ) + H
2
(g (( ) BaH
2
(s (( )
2K(s 2K( 2K( ) + H
2
(g (( ) 2KH(s 2KH( 2KH( )
ii Ba Ba
2+
+ 2e
H
2
+ 2e
2H
+
K K
+
+ 1e
H
2
+ 2e
2H
+
ACTIVITY CD3.5
a

Use
Properties
i ii iii iv v vi vii viii
a reector for a radiator X X X
a lament in a light bulb X X X
a saucepan X X X X X
a manhole cover X X
the blade of a knife X X X X
b Refer to teacher.
c Quenching carbon steel changes its structure and softens it. Quenched steel will bend
easily and have no spring. Allowing it to cool slowly hardens it and it becomes brittle
and snaps easily. Heating to a lower temperature and cooling it is called annealing
and leaves steel springy but still tough.
d Refer to teacher.
ACTIVITY CD3.6
The smell is probably hydrogen sulde. The main reaction is:
2Al(s 2Al( 2Al( ) + 3Ag
2
S(s S( S( ) + 6H
2
O 6Ag(s 6Ag( 6Ag( ) + 2Al
2
(OH)
3
(s (( ) + 3H
2
S(aq S( S( )
ACTIVITY CD3.7
a At the zinc electrode the reaction will be Zn(s At the zinc electrode the reaction will be Zn( At the zinc electrode the reaction will be Zn( ) Zn
2+
(aq (( ) + 2e
.
At the copper electrode the reaction will be Cu
2+
(aq (( ) + 2e
Cu(s Cu( Cu( ).

b At the lead electrode the reaction will be Pb(s At the lead electrode the reaction will be Pb( At the lead electrode the reaction will be Pb( ) Pb
2+
(aq (( ) + 2e
.
At the silver electrode the reaction will be Ag
+
(aq (( ) + 1e
Ag(s Ag( Ag( ).

c At the iron electrode the reaction will be Fe(s At the iron electrode the reaction will be Fe( At the iron electrode the reaction will be Fe( ) Fe
2+
(aq (( ) + 2e
.
At the tin electrode the reaction will be Sn
2+
(aq (( ) + 2e
Sn(s Sn( Sn( ).

d At the aluminium electrode the reaction will be Al(s At the aluminium electrode the reaction will be Al( At the aluminium electrode the reaction will be Al( ) Al
3+
(aq (( ) + 3e
.
At the nickel electrode the reaction will be Ni
2+
(aq (( ) + 2e
Ni(s Ni( Ni( ).

ACTIVITY CD3.8
a i
ii
iii
b Au
+
+ 4e
Au(s Au( Au( )

Cu
2+
+ 2e
Cu(s)
Ag + 1e
Ag(s)
ACTIVITY CD3.9
a Refer to teacher.
b Gold can be found as pure nuggets of gold because it is on the most easily reduced
end of the activity series. Gold is stable as a pure element.
c Refer to teacher.
d Refer to teacher.
e Refer to teacher.
f All three methods involve putting extra electrons on the metal to be protected.
g Tin is more easily reduced (more stable) than iron, so actually causes iron to oxidise.
Tin protects iron only by sealing out oxygen and water. As soon as the tin is scratched
the iron will oxidise quickly. Galvanising iron coats it with zinc. Zinc is more easily
oxidised than iron so the iron is kept in a reduced form. The zinc coating still protects
the iron even when scratched.
h Tin is used in food containers because the tin is stable. Tin will not dissolve into the
food and change its avour. Foods often contain acids that would attack zinc coatings.
As long as the tin can is sealed once it is made, it will not start corroding. Tin forms a
smoother, more attractive surface and can be overcoated with plastic seals easily to
improve its protection.
ACTIVITY 4.1
a
b F. The main gas in the air is nitrogen.
c F. Air has weight.
d F. The composition of the atmosphere varies in amount of pollutants in different
locations.
e F. Most air pollution is caused by human activities, but some is from natural sources
such as volcanoes, bush res and animals.
f F. Both plants and animals need oxygen for respiration and plants need carbon dioxide
for photosynthesis.
ACTIVITY 4.3
a bar graph
b 9300 ppm
c 5.15 10
21
molecules
ACTIVITY 4.4
a hard to remove because pressure inside is lower than pressure outside so air pressure
pushing down holds cup in place
b Milk stays in the straw because of air pressure.
c would not work: (i), (ii), (iv), (v)
would work: (iii), (vi)
ACTIVITY 4.7
a Carbon dioxide is sealed in the bottle or can under pressure. When the container is
opened the gas expands and rushes out due to decreased external pressure.
b The gas in the tennis ball is under pressure and tiny pores in the material of the ball
allow the gas to leak out.
c i 96 balloons
ii temperature constant, no gas is lost
d i 548 m
3
ii If the windows remained closed the sudden expansion of the air might cause the
windows to blow out.
e i 18 L
ii He could rupture lung tissue due to the expansion of the air in his lungs.
ANSWERS
Air
ACTIVITY 4.9
a In winter the temperature drops so the volume of air in the tyres decreases, and so
more air must be added to maintain correct tyre pressure. In summer the temperature
increases, so the air in the tyre expands and some gas must be released to maintain
the correct tyre pressure.
b The air in the balloon will double its volume to 5.3 L and the balloon will burst.
c The pressure will double to 38.4 atm.
ACTIVITY 4.10
a 6.3 10
3
L carbon dioxide
b 5.9 g air, 8.9 g CO
2
, 0.41 g H
2
. The hydrogen is less dense than air so will oat, but the
carbon dioxide is more dense so will sink.
c 16.7 L
d 2.5 10
5
km
ACTIVITY 4.11
a i O
2
0.77 mol, C
3
H
6
0.23 mol
ii 70.9%
b 517.3 g H
2
, 4139 g O
2
ACTIVITY 4.12
a bar graph
b at sea level: 0.0416 mol/L; at 20 km: 2.50 10
3
mol/L
ACTIVITY 4.14
a From the table it can be seen that the 1 hour ozone exposure has approximately half
the number of ppm limits compared to the 1 hour exposure for sulfur dioxide, making
it twice as hazardous.
b 1050/15 = 70 g/m
3
, which exceeds the standard of 50 g/m
3
ACTIVITY 4.17
a reactions 3 and 4
b They are the reverse of each other but energy is absorbed and released in different
forms.
c reactions 2 and 3
d The Suns energy is most intense at the top of the stratosphere so the u.v. radiation is
absorbed there and so reactions 1 and 4 would occur. Reactions 2 and 3 release heat
energy so the stratosphere would heat up.
ACTIVITY 4.18
a Concentration of the gases, amount of sunlight, temperature
b Increasing concentration increases the rate, more sunlight increases the rate, increase
in temperature increases the rate.
ACTIVITY 4.19
a September and October
b 88 DU, 28 September 1994
c 65.9%
d 527.8%
ACTIVITY 4.20
a overall reaction: O(g overall reaction: O( overall reaction: O( ) + O
3
(g (( ) 2O
2
(g (( )
b They are the same reaction.
c Cl radical causes the reaction but is regeneratedit is a catalyst.
ACTIVITY 4.21
a The rate of production of ozone and the rate of destruction will be the same so the
concentration of ozone will be constant.
b The amount of car emissions producing NO
2
, NO and VOCs, the amount of sunlight,
whether bushres and burning off are occurring.
c NO
2
+ sunlight NO + O
3
NO + VOC + sunlight NO
2
N
2
+ O
2
2NO
d Intense sunlight is necessary for the reaction that produces ozone. In the afternoon the
sunlight is much less intense and because production takes place over a longer period
the sun has set.
ACTIVITY 4.22
a

c
2
O, CO
2
, CH
4
have polar bonds whereas H
2
O is a polar molecule.
ACTIVITY 4.23
a 3200 kg
b 3.2 10
9
tonnes
c 3.5 10
12
tonnes
d 1 10
3
e 1.1 10
10
trees
ANSWERS CHEMISTRY CHAPTERS 353
CHAPTER 1
1 a more vigorous vibrations
b more vigorous vibrations and more rapid translational motion
2 99.85% empty space; particles are moving very rapidly, with only weak attractive
forces between them, so they spread out to ll the space available.
3 There is much more empty space in gases than in liquids and the particles move more
rapidly and travel longer distances between collisions in gases than in liquids.
4 homogeneous: a, c, d, h; heterogeneous: b, e, f, g, i
5 a Mixture: c; pure substances: a, d, h
b All the heterogeneous substances are mixtures.
6 b, d, e, h, i
7 cannot tell; all elements and some compounds melt and re-solidify without
decomposing.
8 Blue solid decomposed into black solid plus a colourless gas: the gas is the missing
0.36 g. Compound; because it can be decomposed into two simpler substances.
9 use a sieve; alternatively add water, stir and decant the suspension of aluminium oxide
in water: the lead pellets are so heavy that they remain on the bottom.
10 a evaporate to dryness
b distil the mixture and collect water as the distillate
11 a pure ethanol; it has the lower boiling point and the difference in boiling points is
quite large.
b less concentrated in acetic acid (boiling points are too close to get a complete
separation)
c chloroform
d use fractional distillation
e pure hexane
12 Your ow chart should show (a) adding water and stirring to dissolve magnesium
sulfate, (b) ltering to separate off the insoluble barium sulfate, (c) drying the barium
sulfate, (d) evaporation to dryness to recover the magnesium sulfate.
13 a 1 is ltration, 2 is using a separating funnel, 3 distillation, 4 evaporation to dryness.
b X is charcoal, Y is sodium sulfate, Z is kerosene.
c use distillation at 4. For diagrams: Figures 1.6 for (1), 1.10 for (2), 1.8 for (3) and
1.7 for (4)
14 10 m
15 a Z = 11, ZZ A = 23
b
30
14
Si
ANSWERS
Chemistry Chapters 18
16 helium: 2 4 2 2 2
oxygen: 8 16 8 8 8
boron: 5 11 5 6 5
sulfur: 16 32 16 16 16
chlorine-35: 17 35 17 18 17
oxygen-18: 8 18 8 10 8
17 physical: b, d, e chemical: a, c, f
18 chemical: a new substance appearsthe reddish-brown solidand another
substance disappearsthe one responsible for the blue colour.
19 a chemical; a new substance is formed: the nal white substance is different from the
starting substance (different melting point). The increase in mass suggests that the
original substance reacted with water to form the new substance.
b physical; the original white substance was recovered at the end (same mass and
melting point).
20 for B, O, P, Ar, Ca, see Table 1.9. Mn 2, 8, 13, 2; Se 2, 8, 18, 6; Kr 2, 8, 18, 8;
Rb 2, 8, 18, 8, 1
21 a Must ll the rst level before starting the second; 2, 2.
b Must ll the second before starting the third; 2, 8, 3.
c Cannot have more than 8 electrons in the second level; 2, 8, 3.
d Cannot have more than 8 electrons in the second level, but can have 18 in the
third; 2, 8, 18, 2.
22 N 2, 5; Al 2, 8, 3; S 2, 8, 6; Ca 2, 8, 8, 2; N tends to gain 3 electrons, Al tends to lose 3,
S tends to gain 2, Sr tends to lose 2.
23 for Exercise 20: B 2, 3; O 2, 6; P 2, 8, 5; Ar 2, 8, 8 (no valence electrons); Ca 2, 8, 8, 2;
Mn 2, 8, 13, 2; Se 2, 8, 18, 6; Kr 2, 8, 18, 8 (no valence electrons); Rb 2, 8, 18, 8, 1
24 a 2 b 4
25 a 4 b 7 c 1
d 3. Number of valence electrons equals the Group number.
26 A to 2, 8; B to 2, 8, 8; C to 2, 8; D to 2, 8, 18, 8; E has no reactions as it is already a EE
stable conguration.
CHAPTER 2
1 a K (2, 8, 8, 1) donates one electron to F (2, 7) to form K
+
(2, 8, 8) and F
(2, 8); KF
b Ca (2, 8, 8, 2) donates one electron to each of two Br atoms (2, 8, 18, 7) to form
Ca
2+
(2, 8, 8) and Br
(2, 8, 18, 8); CaBr

2
2 a Stable ions are K
+
(2, 8, 8) and Br
(2, 8, 18, 8) so KBr. To form K

2
Br would need
Br
2
(2, 8, 18, 8, 1) which is not a stable conguration; similarly KBr
2
would require
K
2+
(2, 8, 18, 7) which also is not a stable conguration.
3 positive ions: Rb, +1; Mg, +2; Ga, +3; K, +1; Ba, +2; Cs, +1; negative ions: I, 1; S, 2;
Br, 1; Se, 2; F, 1; no ions: Si, C, Ar, B, P
4 a i Mg, 2, 8, 2; Mg
2+
, 2, 8
ii S, 2, 8, 6; S
2
, 2, 8, 8
b i MgS
iii MgCl
2
5 a b

6 a O (2, 6) needs to gain two electrons; F (2, 7) needs to gain one. To satisfy both
drives two F atoms combine with one O atom:

For FO and FO
2
at least one atom would have only 7 electrons and so would not be
stable:

7 a SCl
2
; S needs to gain 2 electrons, Cl needs to gain 1, so we need two Cls for
each S.
b HI; each atom needs to gain just 1 electron.
ANSWERS CHEMISTRY CHAPTERS 355 ANSWERS CHEMISTRY CHAPTERS 355
8 a

c Atoms: Ions: Ba
2+
Cs
+
9 PCl
3
is covalent, CaCl
2
is ionic.
10 They are ionic compounds whereas the others are covalent.
11 a Calcium hydride is ionic whereas arsenic hydride is covalent.
b CaH
2
, AsH
3
12

Widely used as an abrasive because the covalent bonding extends throughout the
whole crystal and so it is extremely hard (like diamond).
13 CO
2
exists as small discrete molecules with only weak intermolecular forces between
any one molecule and its neighbours. SiO
2
is a covalent lattice with strong covalent
bonding extending throughout the whole crystal.
14 a B, D, F
b A, G
c C, E
d Metalsstrong bonds within metal lattice give high melting point while loosely
held electrons give good conductivity; covalent molecularweak bonds between
molecules mean low melting point, no charged particles so low conductivity;
covalent latticestrong bonds between atoms in the lattice extending throughout
the whole crystal mean high melting point, but no charged particles so low
conductivity.
15 Ccovalent network
Sisemi-metallic, meaning that it is a network solid, but with the electrons in the
covalent bonds easily able to be lifted into a delocalised sea as in a metal; hence its
conductivity, which is considerably higher than that of the non-metal, C
Gesemi-metallic (though closer to a metal than Si is; the bonding electrons in Ge are
more easily delocalised)
Snmetallic
Pbmetallic
16 a KBr c Na
2
O e Li
2
S
b ZnO d CaH
2
g AlF
3
17 calcium hydride, lithium sulde, aluminium bromide
18 a NaNO
3
b Li
2
CO
3
c K
3
PO
4
19 a zinc sulfate c iron(II) hydroxide
b ammonium carbonate d aluminium nitrate
20 a i 2 ii 1 iii 3 iv 4 v 2
b i 2 ii 2 iii 1 iv 3 v 2
21 a SF
2
b NCl
3
c CI
4
d BCl
3
e SO
2
22 a silicon tetrachloride, carbon disulde, dinitrogen monoxide, nitrogen trichloride,
hydrogen sulde (though strictly it should be dihydrogen sulde)
b diphosphorus pentoxide, dinitrogen tetroxide, dichlorine oxide (though often called
chlorine oxide), oxygen diuoride
23 a ammonia, NH
3
b silicon tetrabromide, SiBr
4
24 a ethane + oxygen carbon dioxide + water
2C
2
H
6
( g) + 7O
2
( g) 4CO
2
( g) + 6H
2
O( g)
25 a
reacts with 6 oxygen molecules (each containing 2 oxygen atoms) to form
4 molecules of carbon dioxide (each containing one carbon atom and 2 oxygen
atoms) and 4 water molecules (each containing 2 hydrogen atoms and 1 oxygen
atom).
26 a left of arrow: 8 C, 20 H, 18 O
right of arrow: 8 C, 20 H, 26 O
not balanced because not enough O on left
b left: 2 K, 2 Mn, 30 O, 16 H, 3 S
right: 2 K, 2 Mn, 30 O, 16 H, 3 S
balanced
CHAPTER 3
1 a 119.0 e 159.8 i 80.0 m 132.1
b 44.0 f 142.0 j 180.2 n 342.3
c 95.3 g 136.2 k 74.1 kk o 286.1
d 78.1 h 106.0 l 187.6
2 a 0.20 b 2.5 10
3
c 0.47 d 89
3 a 1.9 10
2
g b 1.4 g c 0.056 g
4 a 1.2 10
23
b 1.5 10
21
c 2.8 10
23
d 5.3 10
25
5 a 1.09 10
22
g b 3.27 10
22
g c 6.64 10
24
g
6 5.0 10
21
7 a 0.26 mol b 0.14 mol c 0.11 mol
8 a 5.0 g b 0.052 g
9 a 8.5 10
22
b 2.9 10
22
c 9.6 10
22
10 a 145 g b 3.3 g c 0.126 g
11 1.5 10
23
; 3.0 10
23
12 a 2.80 10
3
b 2.80 10
3
c 8.40 10
3
13 a 22.6% b 80.1%
14 a 63.5% Ag, 8.2% N, 28.3% O
b 28.2% N, 8.1% H, 20.8% P, 43.0% O
15 a 21.2% b 46.7%; urea
16 18.5%
17 a 3.5; i 2 ii 3
b 125; 90
18 a 60 b 0.3
19 a 13 g b 2.92 g
20 1.1 g
21 0.040 g; 2.7 g
22 1.03 g; 0.057 g
23 9.96 g
24 0.50 t
CHAPTER 4
1 a

b

FO
+ +
ClO

NCl (none)

NH
+
SH
+
CS (none)
3 a a, c, d; HBr OF CBr;

net dipole: HBr and OF
2
b i bond and molecule non-polar

ii polar bond BCl; molecule is non-polar

iii polar bond SiCl; molecule is non-polar

iv polar bond SF; molecule is polar

4 a Intermolecular forces are greater in sulfur dioxide, hydrogen iodide and CCl
2
F
2
.
b In He, Ne, H
2
dispersion forces; in SO
2
, HI, CCl
2
F
2
dispersion forces plus
dipoledipole attractions.
5 CH
4
, SiH
4
, GeH
4
, SnH
4
show the normal trend of boiling point increasing with
molecular weight. In the HF, HCl, HBr, HI series HF is anomalous in that its
boiling point is +19C whereas the trend line suggests it should be about 100C.
Explanation: there is hydrogen bonding in HF.
6 Presents evidence for hydrogen bonding in H
2
O and NH
3
.
7 b and f

8 a OF
2

bent
b SlH
4

tetrahedral
c BBr
3

B
Br Br
Br
trigonal planar
d NCl
3

pyramidal
e ICl ICl linear
f SCI
2

bent
g AsH
3

pyramidal
h CCl
4

tetratredral
i
2
O
2

bent
j HOBr

bent
CHAPTER 5
1 HBr and H
2
SO
4
(both polar and react with water); MgCl
2
and ZnBr
2
(both ionic); H
2
O
2
,
fructose and urea (polar and form hydrogen bonds with water)
2 a FeSO
4
.7H
2
O b MgSO
4
.6H
2
O
4 a NaCl and MgSO
4
are both soluble in water, so the attraction between the positive
and negative ions in each of the compounds is less than the attraction between
those ions and the polar water molecules.
b These compounds are insoluble because the attraction between the positive and
negative ions in the compound is greater than the attraction between each of
these ions and water.
5 H
2
SO
4
(l (( ) + H
2
O(l O( O( ) H
3
O
+
(aq (( ) + HSO
4
(aq (( )
(or H
2
SO
4
(l (( ) + 2H
2
O(l O( O( ) 2H
3
O
+
(aq (( ) + SO
4
2
(aq (( ))
6 soluble: b, c, f, g, h, k, l, o
7 a CuS e Zn(OH)
2
i Fe(OH)
3
m Mg(OH)
2
b MgSO
4
f Cu(NO
3
)
2
j PbSO
4
n AgBr
c AlCl
3
g CaBr
2
k (NH kk
4
)
2
S o Ba(OH)
2
d FeS h KI l Na
3
PO
4
8 a sodium nitrate and magnesium sulfate
b barium chloride and potassium hydroxide
9 a lead sulfate, PbSO
4
b zinc carbonate, ZnCO
3
c no precipitate
d iron(II) hydroxide, Fe(OH)
2
10 a barium chloride and sodium carbonate (or barium nitrate and potassium
carbonate)
b silver nitrate and potassium bromide (or sodium bromide)
11 a Ba
2+
+ CO
3
2
BaCO
3
(s (( )
b Ag
+
+ Br
AgBr(s AgBr( AgBr( )

12 a i 9.7 g/100 mL ii 97 g/L iii 9.7%(w/v)
b i 16 mL/100 mL ii 12.5 g/100 mL iii 160 mL/L iv 16%(v/v)
13 a 1.3 g b 14 g c 0.38 g
14 a Dissolve 8.8 g ammonium chloride in water and make up to 250 mL in a volumetric
ask.
b Mix 75 mL ethanol with water and make the volume to 500 mL; 25 mL pipette for
ethanol (ll 3 times), 500 mL volumetric ask for the solution.
c Dissolve 20 g sodium carbonate in water and make volume to 250 mL.
15 a 2.0 10
3
g
b It is hard to measure this small mass accurately. Make a 200 ppm solution by
dissolving 0.32 g in exactly 1 L then dilute it by 100: 10 mL pipette into a 1 L
volumetric ask.
16 a 2.0 mol/L c 2.04 mol/L e 0.0588 mol/L
b 0.75 mol/L d 1.20 mol/L f 0.700 mol/L
17 a 0.800 mol b 0.125 mol c 6.25 10
4
mol
18 a 36.5 g b 15 g c 15.4 g
19 a 2.65 10
3
mol c 2.8 10
3
mol
b 3.5 10
4
mol d 0.66 mol
20 a 0.106 g c 0.26 g
21 a i 5.84 10
4
mol ii 5.84 10
4
mol iii 1.17 10
3
mol
b i 4.22 10
3
mol ii 4.22 10
3
mol iii 8.45 10
3
mol
22 a 0.0106 mol/L c 0.122 mol/L
b 5.58 10
3
mol/L d 0.0304 mol/L
23 a 25 mL to 250 mL b 25 mL to 1000 mL
c 50 mL to 250 mL or 100 mL to 500 mL
24 a 0.0163 mol b 6.36 10
3
mol c 2.18 10
3
mol
25 a 3.80 g b 0.232 g
26 a 0.590 mol/L b 14.3 g/L
27 a 0.261 mol/L b 0.277 mol/L
28 5.74 g/100 mL
CHAPTER 6
1

non-polar, because CS bonds are non-polar (C and S have similar electronegativities)
2 a

b

c

3 a
hydrogen cyanide, linear (same arrangement as around each C of ethyne)
b all 3 are polar; the CO bond in formaldehyde, the NO and ClN bonds in
ClNO and the CN bond in HCN are all polar and there is no cancelling out of
identical bonds
4 a C
9
H
20
, 128.3 b C
13
H
28
, 184.4
c C
24
H
50
, 338.7
5 a pentane, C
5
H
12
b heptane, C
7
H
16
6 a

C
6
H
14

b

C
8
H
18

7 no; they cannot both be represented by the one general formula

9 C
2
H
4
, C
3
H
6
, C
4
H
8
, C
5
H
10
, C
6
H
12
, C
7
H
14
, C
8
H
16
10 a

b heptane: CH
3
CH
2
CH
2
CH
2
CH
2
CH
2
CH
3
3-heptene: CH
3
CH
33 2
CHCHCH
2
CH
2
CH
3
11 a C
9
H
18
b C
13
H
26
c C
18
H
36
12 Yes; their molecular formulae C
4
H
8
and C
6
H
12
can be represented by the same general
formula C
n
H
2n
13 a 3-hexene, 84.2 b 2-octene, 112.2
14 a
3
CHCHCH
2
CH
2
CH
3
; 2-hexene
(or CH
2
CHCH
2
CH
2
CH
2
CH
3
; 1-hexene)
b CH
2
CHCH
2
CH
2
CH
2
CH
2
CH
2
CH
3
; 1-octene (or 3- or 4-octene)
15 a see 14(a)
b CH
3
CH
2
CHCHCH
2
CH
2
CH
3
16 a does not number C atoms from the end that gives the smaller number; 3-octene
b same error; 2-pentene
c number is not necessary because there is only one propene; propene
17 Isomers: b and c; e and g or e and f
Same compound: a and d; f and g
18 a and d 2-pentene e 3-hexene
b 1-butene f and g 2-hexene
c 2-butene
19 Boiling point of alkenes increases as number of C atoms in the molecule increases
(as it did for alkanes). Boiling points of alkenes are slightly lower than those of the
corresponding alkanes.
20 a C
7
H
12
b C
11
H
20
c C
16
H
30
21 yes, if the molecular formula were C
6
H
10
22 3, HCCCH
2
CH
2
CH
2
CH
2
CH
3
CH
3
CCCH
2
CH
2
CH
2
CH
3
CH
3
CH
2
CCCH
2
CH
2
CH
3
23 a i 2-hexyne ii 3-octyne
b i CH
3
CCCH
2
CH
3
ii CH
3
CH
2
CCCH
2
CH
2
CH
3
24 a 2; pentane b 4; hexane
25 a 2C
4
H
10
+ 13O
2
8CO
2
+ 10H
2
O
b 2C
6
H
14
+ 19O
2
12CO
2
+ 14H
2
O
26 C
4
H
10
+ Cl
2
+ u.v. C
4
H
9
Cl + HCl
two monosubstituted products:

27 a BrCH
2
CH
2
Br

b two; CBr
3
CH
3
and CHBr
2
CH
2
Br
28 a 2C
3
H
6
+ 9O
2
6CO
2
+ 6H
2
O
b 2C
5
H
10
+ 15O
2
10CO
2
+ 10H
2
O
29 a i CH
3
CHCH
2
+ H
2
CH
3
CH
2
CH
3
ii CH
3
CHCH
2
+ Cl
2
CH
3
CHCH
2
Cl

Cl
iii CH
3
CHCH
2
+ HOBr CH
3
CHCH
2
Br

OH
or CH
3
CHCH
2
OH

Br
b i CH
3
CHCHCH
3
+ H
2
CH
3
CH
2
CH
2
CH
3
ii CH
3
CHCHCH
3
+ Cl
2
CH
3
CHCHCH
3

Cl Cl
iii CH
3
CHCHCH
3
+ HOBr CH
3
CHCHCH
3

OH Br
(only one possibility)
30 a CH
3
CHCH
2
+ HCl CH
3
CH
2
CH
2
Cl and
CH
3
CHCH
3

Cl
b CH
3
CH
2
CHCH
2
+ HCl CH
3
CH
2
CH
2
CH
2
Cl and
CH
3
CH
2
CHCH
3

Cl
31 a CH
3
CHCH
2
+ H
2
O CH
3
CH
2
CH
2
OH (1-propanol) and
CH
3
CHCH
2
(2-propanol)

OH
32 a i CH
3
CH
2
CHCH
2
Br

Br
ii CH
3
CH
2
CH
2
CH
2
Br or
CH
3
CH
2
CHCH
3

Br
iii CH
3
CH
2
CH
2
CH
2
OH or
CH
3
CH
2
CHCH
3

OH
b i CH
3
CHCHCH
2
CH
3
or CH
3
CHCHCH
2
CH
3

Br OH OH Br
ii CH
3
CH
2
CH
2
CH
2
CH
3
33 a It is not an alkene.
b It is an alkene.
c It is an alkane.
CHAPTER 7
1 exothermic: a, c, d endothermic: b, e
increase: c, d decrease: e
2 NH
3
(aq (( ) + HCl(aq ) + HCl( ) + HCl( ) NH
4
Cl(aq Cl( Cl( ) exothermic
K
2
CO
3
(aq (( ) + NiSO
4
(aq (( ) NiCO
3
(s (( ) + K
2
SO
4
(aq (( ) endothermic
The fact that the test tube became warm in the NH
3
+ HCl reaction shows that the
reaction must have liberated the heat that warmed up the test tube: if the reaction
liberated heat, then by denition it is exothermic. In the second reaction the test tube
got cold: that means that heat was taken away from the solutions, so the chemical
reaction must have absorbed (taken in) heat: reactions that absorb heat are called
endothermic.
3 a 2Mg(s 2Mg( 2Mg( ) + O
2
( g) 2MgO(s 2MgO( 2MgO( )
H = 1.2 10
3
kJ/mol (for 1 mol O
2
)
b Zn(s Zn( Zn( ) + 2HCl(aq ) + 2HCl( ) + 2HCl( ) ZnCl
2
(aq (( ) + H
2
( g)
H = 154 kJ/mol
c MgCl
2
(aq (( ) + Na
2
CO
3
(aq (( ) MgCO
3
(s (( ) + 2NaCl(aq ) + 2NaCl( ) + 2NaCl( ) H = +49 kJ/mol
4 a 7.7 kJ released b 2.3 kJ absorbed c 0.26 kJ released
5 N
2
( g) + 3H
2
( g) 2NH
3
( g); need to break NN and HH bonds and make NH bonds;
diagram should look like the left-hand one in Figure 7.2.
6 a
2
H
4
( g) + O
2
( g) N
2
( g) + 2H
2
O(l O( O( ) ll

b 577 kJ/mol
7 3.3 10
2
kJ
8 a 2.0 10
3
J c 3.8 10
4
J e 4.0 10
2
J
b 1.3 10
2
J d 3.6 10
3
J f 1.9 10
5
J
9 2.47 J K
1
J K J K g
1
10 H = 57 kJ/mol
11 87 kJ/mol
12 a 99 kJ/mol
b +198 kJ/mol
13 4160 kJ/mol; should be like Figure 7.1(b)
14 a i 142.5 iii 50.0 v 16.5
ii 29.5 iv 50.3 vi 47.8 all in kJ/g
15 hydrogen, propane, ethyne, octane, ethanol, sucrose; its approximately the same;
increasing oxygen content decreases the energy released per gram
16 a 33 MJ/L; 25 MJ/L b 72 c/L
17 a i ve ii +ve iii +ve iv ve v +ve
b i energy forward, entropy reverse ii energy reverse, entropy forward
iii energy forward, entropy forward iv energy forward, entropy reverse
v energy reverse, entropy forward
c The stronger drive is
i energy ii entropy
iii cannot tell because both are in the same direction
iv energy v entropy
18 a endothermic; energy is absorbed from the surroundings.
b The entropy change must be positive
c yes, (g yes, ( yes, ( ) (l ) ( ) ( ) (aq ) ( ) ( ) more random than (s ) more random than ( ) more random than ( )
19 a b

20 a E
a
EE = 40 kJ/mol; H = 30 kJ/mol
b E
a
EE = 45 kJ/mol; H = +15 kJ/mol
21

Fuel A would be the better fuel.

22 b experiment B, because the slope (gradient) of the curve is greater
c increasing the concentration of HCl increases the rate
23 0.28 mL s
1
for Experiment A; 0.83 mL s
1
for Experiment B
24 a A; it has the steeper slope
b A, because increasing reactant concentration generally increases the rate of
a reaction
25 homogeneous: a, d, e heterogeneous: b, c, f
26 a greater in B; magnitude of the slope is greater
b B; reaction rate generally increases when temperature is increased
27 6 cm
2
; 60 cm
2
28 a A
b B, because the rate increases more rapidly as temperature increases than in A
29 a endothermic: C; exothermic: A, B, D
b greatest C; least D
c greatest C; least D; the higher the activation energy the more rapidly does the
reaction rate increase as temperature increases
31 Because we do not need to provide energy to maintain the temperature at 75C.
33 Add a measured mass of manganese dioxide; then after the reaction is complete, lter
it off, dry and weigh it. If it is a catalyst, then the mass recovered will be the same as
the mass initially added (within experimental error), but if the manganese dioxide is a
reactant in a separate reaction, the recovered mass will be signicantly less than the
starting mass.
CHAPTER 8
1 Increase, stay the same as temperature increased. Gas molecules move more rapidly,
exert greater pressure when they hit the walls.
2 Lots of empty space in gases; molecules move rapidly and travel long distances
between collisions.
3 a i 0.500 atm ii 0.0363 atm iii 0.973 atm
b i 237 kPa ii 52.7 kPa iii 107.2 kPa
4 a i 0.0167 mol ii 0.0167 mol
b i 2.128 L ii 2.128 L
5 a 81.36 g
b number of moles of: He, 0.0103; CH
4
, 0.0138; O
2
, 0.0141; CO
2
, 0.0134;
SO
2
, 0.0145
The results show (within experimental error) that the same number of moles of different
gases occupy a xed volume at constant temperature and pressure; that is, they
conrm Avogadros law.
6 a 2073 mL b 62 kPa c 4.2 L d 427 kPa
7 29 kPa
8 2.34 L, 1.59 L
9 a 1000 mL b 513 K c 299 mL d 1178 K or 905C
10 2.98 L; 158 K (115C)
11 a Plot length (proportional volume) against temperature, and a straight line results.
Using C the line has a positive intercept and using K, the line passes through the
origin. The latter plot shows Charles law is obeyed.
b The quotient, length/temperature in K is constant at 0.113 0.001 mm Hg K.
12 336 K
13 a 4.28 L b 0.97 atm c 753 K (480C) d 0.57 L
e 5.31 atm f 1085 K (812C)
14 10.8 kPa
15 119 kPa
16 152 m
3
17 Pressure is linear with temperature in C or proportional to temperature in K. This is
what is expected; if volume is constant, then from Equation 8.7

P
__
T
=
k* kk
__
V
= constant or P = kT
18 a 0.0401 mol b 2.46 L c 13.4 kPa d 107 K
e 0.00163 mole f 73 L
19 242 kPa
20 1.94 g
21 298 mL
22 4.1 10
7
Pa
23 64 g/mol
24 Plot pressure versus number of moles. A straight line through the origin results; this
shows that at constant volume and temperature p is proportional to n and independent
of the nature of the gas.
25 0.023 mol
26 24.2 atm
27 8.76 kg
28 molecular weight is 147, hence compound is SF
6
29 Partial pressures are: O
2
, 0.25kPa; H
2
, 0.53kPa; P
TOT
= 0.78kPa
TOT TOT
30 313 kPa H
2
; 113 kPa Ar; 425 kPa total
31 14 kPa CO
2
; 43 kPa Ne; 57 kPa total
CREDITS 365
PHOTOGRAPHS
Zefaimages: cover image
Auscape International: p. 1 (far left), p. 126 (top), p. 3 (bottom), p. 6, p. 7 (top), p. 30 (bottom)
Tempur-Pedic, Inc.: p. 3 (top), reproduced by permission of Tempur-Pedic, Inc.
Debra Smith: p. 1 (left, right and far right), p. 4, p. 5, p. 8, p. 22, p. 25, p. 26, p. 35,
p. 125, p. 130, p. 132, p. 134, p. 135, p. 137, p. 143, p. 156, p. 157, p. 161
Photolibrary.com: p. 7 (bottom), p. 19, p. 30 (top), p. 66, p. 90 (left), p. 91 (top left and
right), p. 117, p. 126 (bottom), p. 140, p. 166 (left), p. 205
Digital Vision: Astronomy and Space: p. 11, p. 15
Roland Smith: p. 17, p. 21, p. 29, p. 33, p. 77 (left), p. 90 (right), p. 108, p. 166
(centre and right), p. 167, p. 173, p. 183, p. 184, p. 185, p. 221, p. 246, p. 251, p. 253,
p. 261, p. 273, p. 288, p. 307
Newspix: p. 27
Sue Monteath: p. 38, p. 39, p. 43, p. 54, p. 75, p. 77 (right), p. 81
Great Barrier Reef Marine Park Authority: p. 71, p. 72, p. 73, p. 74
Greg Heath, courtesy Land & Water Australia: p. 78
Australian Picture Library: p. 90 (far right), p. 91 (centre), p. 279
Mark Gould: p. 90 (far left), p. 103, p. 122
Digital Vision: Globes and Maps: p. 2
Alliance Pharmaceutical Corp.: p. 133
National Oceanic and Atmospheric Administration (NOAA): p. 152
Miriam Marcx: p. 280
TEXT, FIGURES, GRAPHS AND TABLES
p. 3 Spiders silk: Spinning a strong thread, by Steve Miller, Chematters, February 2001
p. 15 Chemistry in the remotest corner of the solar system, Chemistry Review, Vol. 12,
No. 3 (February 2003, pp. 225). Reproduced by permission Philip Allan Updates
p. 28 Table 1.6Reproduced with the permission of the Environmental Protection Agency
Queensland. The copyright in the reproduced material belongs to the State of Queensland.
Credits
p. 41 Figure 2.1The temperature variation in an ice/water mixture. Adapted from:
www.wcsscience.com
p.57 Figure 2.9The water cycle diagram Erich Roeckner, Max Planck Institute for
Meteorology; reproduced by permission.
p. 58 Figure 2.10Adapted. www.tre.umn.edu
p. 60 Figure 2.11Adapted from Investigating Freshwater. A resource book for National
Science Week 2003, Australian Science Teachers Association, p. 22
p. 63 Figures 2.12 and 2.13Adapted. www.waterquality.crc.org.au/consumers/
consumersp9.htm
p. 69 Table from Drinking water from different sources, FSANZ Guidelines for Drinking
Water and Bottled Water; Food Standards Australia New Zealand reproduced by
permission.
p. 73 Graph of nitrogen and phosphorousreproduced by permission of the Great Barrier
Reef Marine Park Authority
p. 79 Graph of dissolved oxygenDepartment of Environment & Heritage.
Commonwealth of Australia 2005, reproduced by permission
p. 83 Table showing GBR metal valuesReproduced by permission of the Great Barrier
Reef Marine Park Authority
p. 93 Figure 3.1Illustration adapted. www.howstuffworks.com
p. 95 Figure 3.2Illustrations adapted. www.howstuffworks.com
p. 96 Figure 3.3Illustration (top) adapted. www.howstuffworks.com
p. 97 Figure 3.6Illustration adapted. www.howstuffworks.com
p. 99 Illustrations adapted from: www.howstuffworks.com
p. 116 Figure 3.19www.epa.gov/ozone, courtesy NASA GSFC
p. 138 Structure of a Rozier balloonChemistry Review, Vol 12, No 3, (February 2003,
p. 20). Reproduced by permission Philip Allan Updates
p. 142 Figure 4.1Salters Advanced Chemistry: Chemical Storylines, Burton G. et al,
(2000) University of York Science Education Group. Reprinted by permission of Harcourt
Education.
p. 145 Current Air NEPM Standards. Reproduced with the permission of the Environmental
Protection Agency Queensland. The copyright in the reproduced material belongs to the
State of Queensland.
p. 149 Figure 4.4www.epa.gov/ozone Courtesy NASA GSFC
p. 160 Changes in atmospheric carbon dioxide and methane. Reproduced by permission
Dr David Etheridge, Atmosphere & Earth Observation, CSIRO Atmospheric Research
The following material used in the Contexts section was taken from McGraw-Hill
publications: Tables 1.1 (p. 9), 1.3 (p. 14) and 1.4 (p. 14)Roland Smith, Conquering
Chemistry Preliminary Course 3e; Tables 1.2 (p. 9) and 3.4 (p. 104), Figures on pp. 22
and 23 (left) and 3.10 (p. 105) Roland Smith, Conquering Chemistry Preliminary Course
4e; Tables 4.1 (p. 128) and 4.5 (p. 147), Figures 2.6 (p. 50), 4.2 (p. 147), 4.6 (p. 155),
4.8 (p. 158), Activities on pp. 84-6 and 143Roland Smith, Conquering Chemistry HSC
Course 3e; Table 2.7 (p. 83)Roland Smith, Conquering Chemistry HSC Course 4e;
Figure on p. 31 Roland Smith, Exploring Chemistry.
The material used in the Chemistry section (chapters 18) was taken from the following
McGraw-Hill publications: Roland Smith, Conquering Chemistry Preliminary Course 4e;
Roland Smith, Conquering Chemistry HSC Course 3e; Roland Smith, Exploring Chemistry.
INDEX 367
Index
Aboriginal story of the water
serpent, 39
absolute scale of temperature,
324
acid rain, 118
acids, in water, 248
activation energy, 3023,
30912
addition reactions, 2823
adhesive forces, 43, 45
adsorbtion, catalysis and, 312
aeroplanes, 162
agriculture, effect on the sea,
70, 724
air, 12562, see also
atmosphere; gases; ozone
layer
composition of, 12631
uses of, 13241
air pollution, 1436, see also
greenhouse effect; ozone
layer
from combustion, 92, 108,
11621
national air quality
standards, 1456
ozone at street level, 1445,
1568
air:fuel ratios, 956
alcohol functional group, 284
alkali metals, 190
alkaline (basic) solutions, 248
alkanes, 2705, 2801
cyclic, 111
naming, 2734
alkanols, 284
alkenes, 2758, 280, 284
isomers, 2767
naming, 277
reactions of, 2823, 31112
alkyl groups, 282, 284
alkynes, 27980
allotropes of carbon, 223
alumina, 301
aluminium hydroxide, 61
aluminium sulfate, 63
aluminium use and recycling,
2931
ammonia, 2323, 237, 240,
268
water quality tests, 78
ammonium ion, 248
amount of heat, see quantity
of heat
anaesthetic gases, 13940
anhydrous salts, 46, 245
anions (negative ions), 197,
209
Antarctic, ozone depletion,
1502, 155
ANZECC guidelines, 756,
79, 81, 83
aquaculture, 723
aqueous solutions, 24464
ionic compounds, 2445
molarity, 25961
molecular substances, 2467
reactions in, 248, 2502
solubility, 249, 2529
water as universal solvent, 45
argon, 1289
aromatic compounds, 11213
Arrhenius, Svante, 116
atmosphere, 8, 1413, see also
air
atmospheric pressure, 1301
composition of, 14, 12631
atmospheres (units of
pressure), 31516
atom economy, 346
atomic number (Z), 13, 179
atomic theory, 1213
atomic weight, see relative
atomic mass (weight)
atoms, 1213, 169, 1779, see
also electron conguration
conversion from moles to
number of, 223
formation after the Big
Bang, 13
keeping track of, 246
Australia New Zealand Food
Authority, 68
Australian Drinking Water
Guidelines, 55, 59, 62, 64,
66, 68
auto-ignition, 98
average rate of reaction, 304
Avogadros constant, 221
Avogadros law (hypothesis),
133, 31820, 327
balanced chemical equations,
25, 214
ball-and-stick models, 2689
basic (alkaline) solutions, 248
batteries, car, 1023
bauxite, 3031
benzene, 109, 112
Big Bang, 1012
binary compounds, 209,
21113
biochemical oxygen demand,
74, 812
biofuels, 120
biosphere, elements in, 1415
blood plasma, 45, 52
BMW, research on hydrogen
as a fuel, 119, 121
BOD (biochemical oxygen
demand), 74, 812
boiling eggs, 136
boiling points, 51, 233, 2378
bombardier beetles, 27
bonding, 203, 292, see also
covalent bonding; ionic
bonding
carboncarbon, 26870
double, 242, 266, 2767
hydrogen, 23638
metallic, 2056
single, 2656
triple, 242, 266
bottled water, 6770
Boyles law, 1345, 3201
combined gas law, 326
ideal gas equation, 327
branched-chain alkanes, 271
breathing, 1289, 12930, 133
bromine, 203, 2812
burning, see combustion
bushres, ozone levels and,
158
butane, 2701, 272
1-butene, 276
Buteyko breathing technique,
12930
butyl groups, 282
calcium carbonate (scale), 66
calcium, in water supplies,
645
calculations, 324, 21831, see
also equations
gases, 1379
quantity of heat, 2945
capillary action, 434
carbon, 223, see also organic
compounds
carboncarbon bonding,
26870
valence electrons, 265
carbon cycle, 6
carbon dioxide, 269
atmospheric, 1279, 131,
1612
Buteyko breathing and,
12930
dissolving, 50
greenhouse effect from, 116,
138, 160, 162
uses of, 132
carbon monoxide pollution,
1445
carbonic acid, 50
carburettor systems, 956
cars, see also reciprocating
internal combustion
engine; transport
batteries, 1023
corrosion, 122
electric, 102, 119
emissions, 144
catalysis, 108, 306, 31012
CFCs in ozone destruction,
154
catalytic converters, 108
catalytic cracking, 108, 11011
catalytic reforming, 108,
11213
cations (positive ions), 197
cell membranes, 52
centres of reactivity, 2845
CFCs, see chlorouorocarbons
change in enthalpy, see
enthalpy change of
reactions
changes of state, 163
chaos, see entropy
Charles law, 1367, 3224
chemical bonding, see bonding
chemical energy, 292, see also
enthalpy
conversion to mechanical,
98102
chemical equations, see
equations
chemical properties, see
properties of materials
chemical reactions, see
reactions (changes)
chloramines, 612
chlorine, 62, 199, 2812
chlorouorocarbons (CFCs),
1526, 160
classifying substances, see also
Periodic Table
elements and compounds,
1678
mixtures and pure
substances, 166
states of matter, 1634
climate change, 11617,
see also global warming
closed systems, 6
clouds of electrons, 1778
coagulation (occulation), 60
coefcients (of an equation),
214
cohesive forces, 43, 45
coke, combustion of, 287
coliforms, in water quality
tests, 82
collisions (particles), 3089,
316
combustion (burning), 93,
281, 2878, 302
heat of combustion, 2978
pollution from, 11618,
1378
comets, 1516
complete ionic equations,
2512
compounds, 7, 167, 196
214, see also covalent
compounds; ionic
compounds; organic
compounds
binary, 209, 21113
made from elements, 20
naming, 23
with double and triple
bonds, 242
compressed air, 132
compressed gases, 1345, 137,
13940, 316
concentration, 2558
rates of reactions and, 306,
308
condensed structural formulae,
276
conductivity, 77, 206
corrosion of cars, 122
covalent bonding, 199200
double and triple, 2656
polar, 2346
covalent compounds, 23,
21112
naming, 21213
covalent molecular substances,
199200
aqueous solutions of, 2467
non-polar solvents of, 247
properties of, 2013, 207
reactions with water, 248
covalent network solids
(covalent lattices), 2045
non-polar solvents, 247
properties of, 207
cracking, catalytic, 108,
11011
crude oil, 104, 106, see also
petrol
source of chemicals, 91, 105
crystallisation, water of, 46
cyclic alkanes, 11112
cyclohexane, 109, 112
Dalton, John, 1213, 141,
3312
decanting (decantation), 172
delocalised electrons, 2056
density, of water and ice, 402
diagrams, see electron-dot
structures; structural
formulae
diamond, 2045, 265
diatomic ions, 210
diatomic molecules, 171
diffusion, 317
dihydrogen monoxide
(DHMO), campaign to
ban, 24
dilution, 2578
dipole, 234
dipoledipole forces, 47,
2356, 238
discrete energy levels, 188
diseases, 62, 74
disinfecting water, 61
dispersion forces, 2356
dissolution and, 247
hydrocarbons, 274, 278
relative strength, 238
dissolution (dissolving), 457,
246, 249
gases, 4950
by reacting, 51
dissolved oxygen, in water
quality tests, 7981
dissolved salts (salinity), 76
dissolved solids, 77, 172
distillates, 173
distillation, 105, 1735
Dobson Units, 148
double bonds, 242, 266, 2767
drinking water, 546
bottled versus tap, 6770
quality and sources, 556, 67
drinks, sports and cordials,
534
driving, see transport
drying, 172, 176
Earth
air, see atmosphere
as a closed system, 6
elements in biosphere, 1415
energy balance of, 159
water, see hydrosphere
eggs, boiling, 136
electric cars, 102, 119
electric motors, 98
electrical conductivity, 77, 206
electrolysis, 301
electrolytes, 45
electron clouds, 1778
electron conguration, 1889
Periodic Table and, 1912
reactivity of elements and,
201
stable, 18991
electron-dot structures
(diagrams), 199, 201,
2667
electron-pair repulsion theory,
2401
electronegativity, 235
electrons, 1778, see also
electron conguration
elements, 7, 13, 167, see also
Periodic Table
abundance on Earth, 1415
compounds made from, 20
rst ten, 179
ions formed from, 209
molecules of, 171
origin in the stars, 1012
relative atomic mass, 323,
1812
symbols for, 170
emissions, 144
empirical formulae, 197
endothermic reactions, 288,
292, 299, 302
energy, see also activation
energy; chemical energy;
fuels; kinetic energy
conversion, 92, 98102
energy density, 1023
entropy and, 299301
need for new sources of,
1057
tendency to minimum,
299301
use of, 923
energy levels (shells), 1889,
192, see also valence shells
energy value (heat of
combustion), 934, 101,
2978
engines, efciency of, 92, see
also reciprocating internal
combustion engine
enthalpy, 28991
enthalpy change of reactions,
100, 28990, 292
catalysis no effect on, 311
exothermic and endothermic
reactions, 302
heat of combustion and,
2978
measuring, 2956
entropy, 299301
equations, 25, 21314, see also
calculations
calculations involving,
21831
mass and, 2279
moles and, 2268
ethane, 26970, 272
ethanol, 284
as a fuel, 115, 120
ethene (ethylene), 268, 2746
reaction with hydrogen,
31112
ethyl groups, 282
ethyne (acetylene), 269, 279
eutrophication, 72, 79
evaporating to dryness, 172,
176
exhaled air, 129
exothermic reactions, 288, 292,
297, 299, 302
expansion of gases, 316
explosions, in ignition systems,
97
external combustion engines,
98, 100
faecal coliforms, 82
families of compounds, see
homologous series
families of elements, 1901
farming, effect on the sea, 70,
724
fat-soluble vitamins, 478
feedstocks, for industry, 105
lters, 63
ltrates, 172
ltration, 172, 176
occulation (coagulation), 60
uoride, added to water, 64
formula weight (relative
formula mass), 33, 21920
formulae, 23, 1701
calculations involving,
21831
condensed structural, 276
covalent compounds,
21112
covalent lattice solids, 2045
derived from names of
compounds, 208
empirical, 197
homologous series, 273, 275,
279
ionic compounds, 197,
20810
structural, 2678
fossil fuels, 91, 161, see also
fuels
four-stroke (Otto cycle)
engines, 923, 101
fractional distillation, 105,
1745
fractionating columns, 174
free radicals, CFCs and, 1534
freons, 153
fuel systems (engines), 957
fuel:air ratios, 956
fuels, 915, 161, see also
combustion; crude oil;
hydrocarbons; petrol
alternatives to petrol, 119
combustion engines, 100
energy value, 101
fuel injection systems, 95
renewable, 35
require ignition to react, 302
functional groups, 2845
fundamental particles, 178,
see also electrons
fusion reactions, in stars, 11
futures maps, 118
gases, 1635, 31533, see also
air
Avogadros law, 31820
calculations, 1379
diffusion, 317
dissolving, 4950
expansion, 316
kinetic theory of, 140, 318
mixtures, 1401, 3312
moles of gaseous elements,
222
partial pressures, 1401,
3312
summary, 333
temperature and pressure
and, 1356, 31517,
3204, 3267, 3312
volumes of, 31620
general (ideal) gas equation,
3279
giant molecular clouds
(GMCs), 11
global warming, 11617, 138,
15862
Great Artesian Basin, 56
Great Barrier Reef, 705, 83
green chemistry, 346
greenhouse effect, 11617,
138, 15862
greenhouse gases, 160, see
also chlorouorocarbons
(CFCs)
groundwater, 56
groups (Periodic Table), 186
Guidelines for Drinking-water
Quality, 55
gunpowder carburettors, 100
halogens, 190
hard water, 646
HCFCs, 154
heat, 288, see also quantity of
heat
of combustion, 934, 101,
2978
of reaction, 290, 2956
specic heat capacity, 294
heavy metals, water quality
tests for, 745, 823
hectopascals (hPa), 316
helium, 1112, 132
heptane, 272
1-heptene, 276
heteroatomic molecules, 234
heterogeneous catalysts,
31112
heterogeneous reactions,
3067
heterogeneous substances, 166
hexane, 109, 112, 272, 281
1-hexene, 276
HFCs, 154
INDEX 369 INDEX 369
homogeneous catalysts,
31011
homogeneous reactions, 306
homogeneous substances, 166
homologous series, 273, 275,
279
hot air ballooning, 136, 138
hydrates, 46, 2456
hydrocarbons, 26586
catalytic cracking and,
11011
in crude oil, 1045
saturated and unsaturated,
280
shapes of, 109
straight-chain, 2712, 2767,
279
hydrochloric acid, 248
hydrochlorouorocarbons, 154
hydrouorocarbons, 154
hydrogen
as a fuel, 11921
in Periodic Table, 191
in stars, 1112
reaction with ethene, 31112
hydrogen bonding, 2368
hydrogen sulde, 2323
hydronium ions, 248
hydrophobic molecules, 47
hydroponics, 58
hydrosphere, 9, 1415, 39,
see also water
hypertonic solutions, 523
hypotonic solutions, 523
ice, density of, 402
ideal gas equation, 138, 3279
ignition of fuels, 934, 302
ignition systems (engines),
978
immiscible liquids, 8, 1756
impure substances, 166
infrared radiation, 15960
inhaled air, 129
inorganic salts and ions, 456,
723
insolubility, see solubility
intermolecular forces, 203,
23243, see also bonding
internal combustion engines,
928, 1002
ionic bonding, 1968
ionic compounds, 23
aqueous solutions of, 2445
formulae for, 197, 20810
naming, 20910
properties of, 2012, 207
ionic lattices, 204
ionisation reactions, 248
ions, 21, 197
in aqueous solutions, 244
from common elements, 209
electron-dot structures for,
201
formation of, 1967
polyatomic, 210
isomers of hydrocarbons, 107,
112, 114, 2767, 279
isotonic solutions, 523
isotopes, 11, 1802
IUPAC nomenclature, 274
jet engines, 99
Kelvin temperature scale (K),
136, 324
kilopascals (kPa), 315
kinetic energy, 309, 31617
kinetic theory of gases, 140,
318
lattices, 204, 207, see also
covalent network solids
lava lamps, 8
lead, air pollution from, 1445
Lewis electron-dot structures,
267
liquid breathing, 133
liquids, 1635
lava lamps, 8
separation, 1725
specic heat capacity of, 294
lithosphere, 9, 1415
living things, see also organic
compounds
abundance of elements in,
1415
chemical reactions in, 26
large molecules, solubility
of, 247
organic matter in water
bodies, 734
water in the human body,
546
water movement in plants,
435
lone pairs (electrons), 240
LPG carburettors, 96
macroscopic properties, 4
magnesium, in water supplies,
645
main-group elements, 186
mass
conversions, 223, 2289
equations in terms of, 2278
moles and, 222
mass number (A), 13, 179
materials, see substances
(materials)
mechanical energy, from
chemical energy, 98102
melting points, 51, 233
Memory Foam, in mattresses,
12
Mendeleev, Dmitri, 19
meniscus, 434
mercury, water quality tests
for, 823
mesosphere, 142
metallic bonding, 2056
metals, 1856
corrosion in cars, 122
heavy, water quality tests for,
7475, 823
in Periodic Table, 187
properties of, 207
solubility, 249
variable valency, naming
and, 210
methane, 268, 270, 272, 281
combustion, 2878
greenhouse effect, 160
structure of, 2323, 240
methyl groups, 282
microscopic properties, 4
mineral water, 69
mining, 745
miscible liquids, 175
mixtures, 166
gases, 1401, 3312
separation, 1717
molar heat of combustion,
2978
molar mass, 222
molar volume of a gas, 31920
molarity, 25961
molecular formulae, see
formulae
molecular substances, see
covalent molecular
substances
molecular weight, see relative
molecular mass (weight)
molecules, 20, 169
conversion from moles, 223
molecular models, 2689
of elements, 171
predicting shapes of, 23942
moles, 334, 2203
conversions, 223
equations and, 2268
of gaseous elements, 222
Montreal Protocol, 156
motorised transport, 90124,
see also cars
motors, 98, see also engines
naming, 208, 2734
compounds, 23, 20910,
21213
functional groups and, 285
hydrocarbons, 2734, 277,
279
national air quality standards,
1456
natural resources, recycling
and, 28
negative ions (anions), 197,
209
nephelometric turbidity units
(NTUs), 778
net ionic equations, 2512
neutral species equations,
2512
neutrons, 178
newton metres (N m), 328
newtons per square metre
(pascals), 315
nickel catalysts, 31112
nitrates, 78, 248
nitrogen, 1279, 132
nitrogen cycle, 6
nitrogen oxides, 1445, 157
noble gases, 1279, 1312
stable electron
congurations, 18991
nomenclature, 274
non-metals, 1857
non-polar molecules, 2345
hydrocarbons, 274, 278, 280
non-renewable resources, 25,
279
crude oil, 105
nuclei (of atoms), 1778
nutrients in waterways, 724
octane, 2723, 281, 287
octane ratings, 93, 98, 1078,
113, 115
1-octene, 276
oil, crude, see crude oil
open systems, 6
organic compounds, see also
carbon
dissolving, 467
octane ratings, 113
shapes of, 26970
volatile, as air pollutants,
144, 157
water quality and, 734
osmolality, 53
osmosis, 52
Otto cycle (4-stroke) engines,
923, 101
oxygen, see also ozone
in air, 1279, 131
allotropes of, 147
biochemical oxygen demand,
74, 812
breathing, in gas mixtures,
140
combustion reactions, 1378
dissolved, in water quality
tests, 7981
dissolving, 49
properties of, 147
uses of, 132
oxygenates, 11415
ozone, 307
properties of, 147
street level air pollution,
1445, 1568
ozone layer, 127, 14854
CFCs and, 1526
contour map of, 152
ozone hole in Antarctica,
1501, 155
steady state in, 150
packaged water, 70
partial pressures, Daltons law
of, 1401, 3312
particle nature of matter,
1645, 31517
particles, moles and, 222
particulates, in air, 1435
parts per million (ppm), 256
pascals (Pa), 31516
pentane, 112, 272
1-pentene, 276
per cent by weight (%(w/w)),
256
per cent composition, 2256
peruorocarbons (PFCs), 133
Periodic Table, 1718, 1867,
372
boiling points and, 238
covalent bonds and, 200
created by Mendeleev, 19
electron conguration and,
1912
electronegativity, 235
ionic bonds and, 198
metals and non-metals in,
187
periods (Periodic Table), 186,
372
petrol, 10115, see also crude
oil; fuels
blending of, 11415
from crude oil, 104
energy density, 1023
improving properties of,
1078
pollution from, 11621
pH scales, 51
pH, water quality tests, 756
phosphates, water quality tests,
79
photochemical smog, 118,
1567
physical changes, 1834
physical properties, 1617, 184
hydrocarbons, 274, 2778
physical states of matter, 1634
planar arrangement, 240
plants, water movement in,
435
polar covalent bonds, 2346
polar molecules, 2346
organic, 47
solubility, 2459
polar solvents, 245
polar vortex (wind pattern),
155
pollution, see air pollution;
water quality
polyatomic ions, 210
polymers, solubility of, 247
polyunsaturated margarine,
280
positive ions (cations), 197
power, 92, 96
energy density and, 1023
precipitates, 2503
precipitation reactions, 2503
pressure, gases and, 31517,
3201, 3312
standard pressure, 317
units of, 31516
products of chemical reactions,
184
products (of chemical
reactions), 250
propane, 2702, 281
propene, 276
properties of materials, 4,
1617, 201, 184
propyl groups, 282
proteins, 247
protons, 178
pure substances, 166
purifying substances, 9,
see also separation
quantity of heat, 2935
quarks, 13
quartz, 2045
Queensland
air pollution in, 144
Great Barrier Reef, 705, 83
rainwater, 56
randomness, see entropy
rates of reactions, 3039,
see also catalysis
activation energy and, 310
energy changes and,
287312
reactants, 184, 250
reactions (changes), 6, 1834
atom economy, 346
calculations, 324
collisions needed, 3089
dissolving by, 51
enthalpy, see enthalpy change
of reactions
equations for, see equations
exothermic and
endothermic, 288, 292,
297, 299, 302
heterogeneous and
homogeneous, 3067
of hydrocarbons, 2813,
31112
ionisation, 248
in living things, 26
precipitation, 2503
rates of, see rates of reactions
reactivity of elements, 201,
see also functional groups
reciprocating internal
combustion engine, 928
advantages and
disadvantages of, 98, 100
car engine diagram, 99
fuel systems (engines), 957
ignition systems, 978
recycling, 279, 31
reforming, catalytic, 108,
11213
relative atomic mass (weight),
323, 1812
relative formula mass (weight),
33, 21920
relative molecular mass
(weight), 33, 21819
resources, 25, 356
reverse osmosis, 623
rivers, water quality and, 702
rocket engines, 99
Rosetta mission, 1516
rusting of cars, 122
Rutherford, Ernest, 12
salinity, water quality and, 76
salt, collecting from sea water,
173
salts (hydrates), 2456
saturated hydrocarbons, 280
saturated solutions, 255
scale (precipitate), 66
scuba diving tanks, 1345,
137, 140
sea of electrons, 2056
sea water, separation of, 173
sedimentation, 172
semi-metals, 1867
semipermeable membranes, 52
separating funnels, 1756
separation, 810, 1717
shapes of molecules, 23942,
2689
sieving, 172
silica, 2045
single bonds, 2656
smog, 118, 1567
soaps, hard water and, 65
sodium chloride, 45, 1967
soft water, 646
solar radiation, 159
solids, 1635, 2067
separation, 172
total dissolved solids, 77
solubility, 245, 249, 255
data on, 2524
separation based on, 1756
solutes, 176
in blood, 45
dilution, 2578
effect on melting and boiling
points, 51
measures of, 2556
solutions, 176
dilution, 2578
measures of concentration,
2556
molarity, 25961
separating solids from
liquids, 172
solvents, 176
dilution, 2578
measures of concentration,
256
water as, 45, 24464
South Pole, ozone depletion at,
1502, 155
space-lling models, 2689
spectator ions, 2512
spectrophotometers, for water
quality tests, 789
speed of particles (kinetic
energy), 309
spiders silk, 2
sports drinks, 534
spring water, 69
stable electron congurations,
18991
standard state, of fuels, 934
standard temperature and
pressure, 317
stars, origin of elements in,
1012
states of matter, 1634, 299
steam engines, 99
stems (systematic names), 273
stirring, rates of reactions and,
307, 309
stoichiometry, 32, 218
stoichiometric coefcients,
214
stormwater, 73
STP (standard temperature
and pressure), 317
straight-chain hydrocarbons,
2712, 2767, 279
stratosphere, 142, see also
ozone layer
structural formulae, 2678
condensed, 276
sub-atomic particles, 13
substances (materials), 137
classifying, see classifying
substances
from the Earth, 67, 9
properties of, 4, 1617, 201
separating, 810, 1717
uses of, 17
substitution reactions, 281
sufxes (systematic names),
273
sulfur dioxide, 1445
surface area, in reactions,
3078, 311
suspensions, 72, 176, 2523
symbolic equations, see
equations
symbols for elements, 170
systematic names, 273, see also
naming
systematic units (ideal gas
equation), 3289
TDS (total dissolved solids),
77
teeth, uoride and, 64
temperature, 2934
absolute scale of (K), 324
activation energy and,
30910
gases and, 1356, 31617,
3224, 3267
kinetic energy and, 309
rates of reactions and, 306
standard temperature, 317
water quality, 75
tetraethyl lead, in petrol, 107
thermal equilibrium, 293
thermodynamic temperature
scale (K), 324
thermosphere, 142
total dissolved solids, 77
transition elements, 186, 1912
transpiration stream, 43
transport, 90124
trigonal planar, 240, 242
triple bonds, 242, 266
trivial names, 274
troposphere, 142, 148
turbidity, 72, 778, 2523
ultraviolet light, in reactions,
281, 307
ozone and, 1489, 153
units, in ideal gas equation,
3289
universal gas constant, 138,
327
universe, origins of, 1012
unsaturated hydrocarbons, 280
unsaturated solutions, 255
valence electrons, 1912
valence shell electron-pair
repulsion theory, 240
valence shells, 191, 240, see also
energy levels (shells)
valence (valency), 20912
predicting shapes of
molecules using, 23940
vaporising, 172
vegetable oils, 280
vehicles, see cars
vitamins, 479
volatile organic compounds
(VOCs), 144, 157
volatility, distillation and, 174
volumes of gases, 31617
Avogadros law, 31820
Boyles law, 3201
Charles law, 3224
STP (standard temperature
and pressure), 317
waste management, 346
tons of waste generated,
279
water, 3889, see also
hydrosphere
ban DHMO campaign, 24
bottled versus tap, 6770
covalent bonds, 200
density compared with ice,
402
effect of solutes on melting
and boiling point, 51
hardness of, 646
human requirements for,
546, 6770
hydrogen bonding in, 237
molecular shape, 42
movement in plants, 435
reactions with molecular
substances, 248
as a solvent, see aqueous
solutions
structure of, 2323, 241
vapour, in air, 127, 129
water catchments, 56, 705
water cycle, 57
water of crystallisation, 46,
2456
water of hydration, 46
water quality, 7586
Cryptosporidium, 62, 68
heavy metals, 745, 83
inorganic nutrients, 723
organic materials, 734
water-soluble vitamins, 478
water treatment, 5964
desalination, 56
disease-causing microbes,
62, 68
uoride addition, 64
Waterwatch website, 75
weather changes, 11617,
see also global warming
word equations, 213
World Health Organisation,
guidelines for drinking
water, 55
xylem vessels, 44
zeolites, 110
zoonotic diseases, 74
RELATIVE ATOMIC MASSES OF COMMON ELEMENTS 371
RELATIVE ATOMIC MASSES (ATOMIC
WEIGHTS) OF COMMON ELEMENTS
(arranged alphabetically by element name)
Element
Relative
atomic mass Element
Relative
atomic mass
aluminium Al 26.98 neon Ne 20.18
antimony Sb 121.75 nickel Ni 58.71
argon Ar 39.95 niobium Nb 92.91
arsenic As 74.92 nitrogen N 14.01
barium Ba 137.34 osmium Os 190.2
beryllium Be 9.01 oxygen O 16.00
bismuth Bi 208.98 palladium Pd 106.4
boron B 10.81 phosphorus P 30.97
bromine Br 79.90 platinum Pt 195.09
cadmium Cd 112.40 potassium K 39.10
caesium Cs 132.91 radium Ra 226.03
calcium Ca 40.08 rhenium Re 186.2
carbon C 12.01 rhodium Rh 102.91
cerium Ce 140.12 rubidium Rb 85.47
chlorine Cl 35.45 ruthenium Ru 101.07
chromium Cr 52.00 scandium Sc 44.96
cobalt Co 58.93 selenium Se 78.96
copper Cu 63.55 silicon Si 28.09
uorine F 19.00 silver Ag 107.87
gallium Ga 69.72 sodium Na 22.99
germanium Ge 72.59 strontium Sr 87.62
gold Au 196.97 sulfur S 32.06
hafnium Hf 178.49 tantalum Ta 180.95
helium He 4.00 technetium Tc 98.91
hydrogen H 1.01 tellurium Te 127.60
indium In 114.82 thallium Tl 204.37
iodine I 126.90 thorium Th 232.04
iridium Ir 192.22 tin Sn 118.69
iron Fe 55.85 titanium Ti 47.90
krypton Kr 83.80 tungsten W 183.85
lanthanum La 138.91 uranium U 238.03
lead Pb 207.2 vanadium V 50.94
lithium Li 6.94 xenon Xe 131.30
magnesium Mg 24.31 yttrium Y 88.91
manganese Mn 54.94 zinc Zn 65.38
mercury Hg 200.59 zirconium Zr 91.22
molybdenum Mo 95.94
P
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Deb SMITH | Sue MONTEATH | Mark GOULD | Roland SMITH

To refresh your understanding of the different states of matter and particle

To learn about elements, compounds and mixtures, refer to

You could do an experiment to try to separate a mixture.

To learn more about physical and chemical changes, refer to

You can do an experiment comparing the properties of elements and their

To learn more about the organisation of electrons in elements, refer to

To learn more about writing and balancing chemical equations, refer to

CO(g CO( CO( )

(aq (( ) Cu(s Cu( Cu( )

2Ag(s 2Ag( 2Ag( ) Cu

To revise the information on electron-dot diagrams, refer to

To understand this molecular and intermolecular bonding better, refer to

To learn more about dissolving ionic compounds, refer to

To learn more about water of crystallisation, refer to

CONTEXT 2 WATER 49 CONTEXT 2 WATER 49

The intermediate product in this reversible reaction is carbonic acid, H

To learn more about substances that react with water, refer to

Chemistry Section 5.5, p. 249, provides a summary of the solubilities of

To learn more about precipitation reactions and the solubility of ionic

You can do an experiment to investigate the relationship between temperature

concentration can be determined.

The main reaction is:

To understand how concentrations are calculated, refer to

To investigate the salinity of water samples you can do an experiment using

). Nitrate is soluble and easily taken up by aquatic organisms;

To investigate the turbidity of water samples you can do an experiment.

Excess nitrate and

To investigate the quantity of dissolved oxygen using the Winkler titration

To investigate the presence of some heavy metal cations you can do an

CONTEXT 2 WATER 85 CONTEXT 2 WATER 85

is a test for heavy metals. A precipitate will form when one or

The uses of crude oil

To review your understanding of stoichiometry, refer to Chemistry Sections

100 CHEMISTRY IN USE 100 CHEMISTRY IN USE

To help understand about heats of combustion and calculations of energy

To learn about catalysts, refer to Chemistry Section 7.13, pp. 310312.

To understand ideas about double and triple bonds in hydrocarbons and

CONTEXT 3 TRANSPORT 113 CONTEXT 3 TRANSPORT 113

To understand about functional groups in organic chemistry, you will need to

Articles on other types of biofuels can be found in the Transport context on

To understand more about pressure and the scientic explanations of the

You can do an experiment to prepare carbon dioxide and oxygen, and

Structure of Breitling Orbiter 3

To learn more about Daltons law and partial pressures, refer to

formed is another free radical. The ClO

reacts with free oxygen

This reaction removes chlorine and so prevents it from destroying ozone.

radical, which undergoes further reactions.

atoms, so the ClO

Refer to Context 1 Materials, p. 6.

170 CHEMISTRY IN USE 170 CHEMISTRY IN USE

Refer to Context 1 Materials, pp. 67.

Refer to Context 1 Materials, pp. 810.

Refer to Context 1 Materials, pp. 1213.

Refer to Context 1 Materials, pp. 13 and 32.

Refer to Context 1 Materials, pp. 1617.

Refer to Context 1 Materials, pp. 1719.

Refer to Context 1 Materials, p. 20.

Beryllium is exceptional in that it forms some covalent compounds.

sodium and oxygen

which we write as ClCl (above).