OCR

A LEVEL
1

CHEMISTRY

John Older
Mike Smith

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 Acknowledgements

Photo credits
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© John Older, Mike Smith 2015
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ISBN 9781471827068

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 Contents

Get the most from this book iv

The questions in this book vi

Module 1 Development of practical skills in chemistry

Chapter 1 Practical skills 1

Module 2 Foundations in chemistry

Chapter 2 Atoms and electrons 10
Chapter 3 Compounds, formulae and equations 28
Chapter 4 Amount of substance – moles in solids and gases 39
Chapter 5 Amount of substance – moles in solution 62
Chapter 6 Types of reaction – precipitation, acid–base and redox 75
Chapter 7 Bonding and structure 89

Module 3 Periodic table and energy

Chapter 8 The periodic table and periodicity 115
Chapter 9 Group 2 and the halogens, qualitative analysis 127
Chapter 10 Enthalpy changes 143
Chapter 11 Rates and equilibria 165

Module 4 Core organic chemistry

Chapter 12 Basic concepts in organic chemistry 184
Chapter 13 Hydrocarbons 202
Chapter 14 Alcohols and haloalkanes 225
Chapter 15 Organic synthesis and analytical techniques (IR and MS) 244
Chapter 16 Maths in chemistry 266
Chapter 17 Preparing for the exam 275
Glossary 281
Index 284
Free online resources 288
The periodic table 290

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 Get the most from this book
Welcome to the OCR A-level Chemistry 1 Student’s Book! This book
covers Year 1 of the OCR A-level Chemistry specification and all content
for the OCR AS Chemistry specification.
The following features have been included to help you get the most from
this book.

Prior knowledge
This is a short list of topics that
you should be familiar with before
starting a chapter. The questions
will help to test your understanding.

Key terms and formulae

These are highlighted in the text
and definitions are given in the
margin to help you pick out and
learn these important concepts.

Tips
These highlight important facts,
common misconceptions and
signpost you towards other
relevant chapters.

Test yourself questions

These short questions, found
throughout each chapter, are useful
for checking your understanding as
you progress.
iv

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 Get the most from this book
Activities
These practical-based activities will
help consolidate your learning and
test your practical skills.

Examples
Examples of questions or
calculations are included to illustrate
chapters and feature full workings
and answers.

Practice questions
You will find Practice questions, including multiple-choice
questions, at the end of every chapter. These follow the
style of the different types of questions with short and
longer answers that you might see in your examination, and
they are colour coded to highlight the level of difficulty.
Challenge questions are also provided.

Dedicated chapters for developing your Maths and Preparing for the exam
can be found at the back of this book.
v

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 The questions in this book
The ‘Test yourself’ questions within the text of each chapter are
designed to check that you have understood the short section of
work that has just been covered. They are intended to be used
during the course but can also be helpful while you are revising.
The ‘Activities’ provide a chance to tackle a more extended
question and also provide a check that you are able to understand
and interpret experiments. The ‘Practice’ questions at the end of
the chapters cover a broader section of work. They include multiple
choice, structured and a smaller number of free response questions.
They also sometimes focus on the evaluation of some experimental
results. They are graded as follows:
Basic questions that everyone must be able to answer
without difficulty within the exam.
Questions which cover work that are a regular feature of
exams and that all competent candidates should be able to
handle.
More demanding questions that sometimes go beyond
the normal requirements of the exam but which the best
candidates should be able to do.
Challenge These are questions for the most able candidates to
test their full understanding and sometimes their ability
to use ideas in a novel situation.
It must be emphasised that although these questions cover the
skills and knowledge required to be successful in the examination,
they are not exam questions as such. Many only cover components
of questions which on the exam paper may come from more than
one section of the specification. When you are confident that your
knowledge base and your understanding is sufficient you must start
practising the past examination questions which are available from
the OCR website. Mark schemes are also available and these are
very helpful in making it clear what points examiners are looking
for and the depth that they expect. The best practice for the exam
is doing past exams.

vi

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 Chapter 1
Practical skills
As part of the full A Level course you must carry out a number of
experiments which are separately assessed and lead to a practical
endorsement. Contained in the chapters of this book you will find
sections to help you understand the correct use of apparatus and the
methods required to carry out these tasks. However, within both the AS
and A Level courses, the written papers may also include questions that
require you to understand the limits of reliability of the techniques that
you have studied. This chapter gives some guidance to help support your
understanding of laboratory work.

The precision of apparatus

Each piece of laboratory apparatus used to measure a quantity has
a limit to its precision. For example, a basic balance may give a
measurement to the nearest gram; greater precision may be achieved
by using a balance capable of reading to one, two, three or even
four decimal places. The volume of a liquid can be measured using a
graduated beaker, a measuring cylinder or volumetric apparatus. Each of
these has a different level of precision. For most measuring equipment,
the manufacturer will give the maximum error that is inherent in using
that piece of apparatus; this is sometimes etched onto the apparatus
but, in other cases, will need to be looked up. Not all experiments
require the quantities measured to be exact, but if a quantitative result
is needed, you should be aware of the limitations of the apparatus used.
The maximum error is an inevitable part of using that piece of
equipment and is distinct from the competence with which the
experiment is carried out. Important decisions are sometimes based on
the results of experiments. For example, titrations are used in health
care, in the food industry and in forensic science. It is crucial that the
people making decisions based on the results obtained understand the
extent to which they can rely on the data from their analysis.

Measuring volumes of liquids

Beakers and conical flasks
Markings on the sides of beakers and conical flasks serve only as a
very rough guide to the volume taken and it is impossible to assess the
maximum error involved in their use; however, it is likely to be large.
Calibrated beakers and conical flasks are not suitable for measuring
volumes reliably.

Measuring cylinders
Unless otherwise indicated, a useful rule of thumb for measuring
cylinders is that they have a maximum error of one-half of the
difference between the graduation marks. If a 25 cm3 measuring
cylinder has graduations every 0.5 cm3, the error is 0.25 cm3. If it is used
1

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 Tip to measure a volume of 20 cm3, then the true volume lies between
19.75 cm3 and 20.25 cm3. This can usefully be expressed as a percentage
In an exam you will be told the error because it can then be carried forward and applied to other results
maximum error that applies to a that are based on the measurement. In this case the percentage error is:
particular piece of apparatus.
0.25
× 100 = 1.25%
20.0
Key term A 100 cm3 measuring cylinder may have graduations every 1 cm3. The
maximum error is, therefore, 0.5 cm3. So, 20 cm3 measured in a 100 cm3
Percentage error is
cylinder is 20 ± 0.5 cm3. The percentage error is:
the maximum error × 100.
actual value 0.5
× 100 = 2.5%
20.0
A 250 cm3 measuring cylinder usually has graduations every 2 cm3. The
maximum error is, therefore, 1 cm3. So, 20 cm3 measured in a 250 cm3
cylinder is 20 ± 1 cm3. This has a large percentage error of 5%.
The difference in the error made in taking these measurements is
considerable.
An increased error arises if both the start and end graduations are used to
measure a volume. For example, if 20 cm3 of water is measured by filling
a 100 cm3 measuring cylinder to the 100 cm3 mark and then pouring off
the water until the 80 cm3 mark is reached, both the start and the end
gradations are subject to a maximum error of 0.5 cm3. It is possible that
the starting volume could be 100.5 cm3 and the end volume 79.5 cm3.
The possible error is therefore 1 cm3 in the 20 cm3 measured, which is 5%
When the pipette is filled, the
(although this is probably greater than the experimental reality).
meniscus of the liquid should
sit on the volume mark on the
neck of the pipette. To do this
Volumetric equipment
reliably requires practice. Volumetric apparatus includes pipettes, burettes and volumetric flasks.
● A pipette is usually selected when a small fixed volume of liquid or
solution is required.
● A burette is used to provide more variable volumes.
● A volumetric flask is used when a larger volume of liquid or solution
is required.
The solution in the pipette
should be allowed to run out
freely. When this is done a
small amount will remain in
Using a pipette
the bottom of the pipette. A pipette is used to deliver a precise volume of solution (see Figure 1.1).
Touch the tip of the pipette The maximum error will vary according to the quality of its manufacture.
on the surface of the liquid
that has been run out and For routine work a 25.0 cm3 pipette with a maximum error of 0.06 cm3 is
then ignore any further often used.
Chapter 1  Practical skills

solution that remains in

the pipette. The percentage error is:
0.06
Figure 1.1 Using a pipette. × 100 = 0.24%
25.0
Tip This is a much smaller error than would occur if a measuring cylinder had
been used. The percentage error using a 25 cm3 measuring cylinder was
Since the solution that is 1.25% (see above), hence the pipette is over 5 times more reliable.
sucked into the pipette may be
poisonous, a pipette filler must Some pipettes are graduated to allow a volume less than the full
always be used. capacity to be dispensed. These are useful but usually have a greater
2 maximum error than a standard pipette.

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 The precision of apparatus
Using a burette
When used correctly a volume measured by a burette has only a small error.
Tip
A funnel should be used to fill a burette so that solution is not spilled
down the outside (Figure 1.2). Care must be taken not to overfill it.
The tap should, of course, be closed during this procedure. However,
before recording a volume, the funnel should be removed and some
solution should be run out so that the space below the tap is filled.

The required volume is measured as the difference between final and

initial readings. It is usual to read from the bottom of the meniscus but,
because two readings are being subtracted, the top of the solution could
be used.
Burettes usually have graduations every 0.1 cm3 and should, therefore,
have a maximum error of 0.05 cm3. The volume delivered is the
difference between two measurements, so the volume obtained has a
potential uncertainty of 0.1 cm3. The percentage error will vary with the
volume that has been measured.

Test yourself
1 Figure 1.3 shows four burettes.
A B C D
12 22 9 2

13 23 10 3

Figure 1.2 A burette.

14 24 11 4
Tip
There are different grades of Figure 1.3
burette, so the maximum error in
any reading will vary. In an exam a) Record the readings for each of the four burettes.
the maximum error will be stated b) Calculate the percentage error in each of the burette readings. Assume
if you are required to consider it. the maximum error of each reading to be 0.05 cm3 and give your
answer to 2 decimal places.
c) If the burette reading in A is the initial reading and burette reading in
B is the final reading
i) calculate the titre volume
ii) calculate the percentage error in the titre volume.
Tip
If 250 cm3 were measured using Using a volumetric flask
a 50 cm3 burette filled five times, The mark on the neck of a volumetric flask indicates a specific volume.
the exercise would not only be The maximum error is almost certain to be etched on the flask and is
more tedious, but it would also usually of the order of 0.125%. If a volumetric flask is used to measure
have a greater error because 250.0 cm3, the volume obtained has a maximum error of:
each time the burette was used
0.125
there would be an error in the × 250 = 0.313 cm3
100
volume measured.
This means that the true volume lies between 249.7 cm3 and 250.3 cm3.
3

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 A volume measured in a volumetric flask is very precise. It holds the
specified volume when the bottom of the meniscus of the solution sits
on the engraved marking on the neck of the flask.
If it is necessary to dissolve a solid in water to make the solution to
place in a volumetric flask, care is needed. It is usual to dissolve the
solid first in a container such as a beaker using a volume of distilled
water that is less than that required for the solution. A beaker is used so
that, if necessary, the contents can be warmed to encourage the solid to
dissolve. Once dissolved, the solution must be allowed to cool to room
Tip temperature before being transferred to the volumetric flask, using a
The volume of solution held by a funnel. Any solution remaining in the beaker is washed into the flask.
volumetric flask will depend on Distilled water is added carefully to the flask until the meniscus sits on
its temperature. Do not pour hot the engraved mark on the neck. With the stopper firmly in place, the
solutions into a volumetric flask. flask is inverted a few times to ensure that the solution is completely
mixed. The procedure is illustrated in Figure 1.4.
Dissolve solute in stirring
small amount of rod
solvent, warming
Accurately
if necessary Transfer to
weigh solute paper
wedge standard flask
stirring rod

44.21

Carefully make up
Insert stopper to the mark on
and shake the flask
wash
bottle
Rinse all solution
into flask with
more solvent

Figure 1.4 Preparing a standard solution in a volumetric flask.

Key term Solutions made up in a volumetric flask are sometimes referred to as

standard solutions.
A standard solution is a solution
with a precisely known
concentration.
Measurement of mass
If a balance measures to one decimal place, the mass measured will
normally have a maximum error of 0.1 g (sometimes 0.05 g). For a
balance measuring to two decimal places, the mass will be to within
Chapter 1  Practical skills

0.01 g (sometimes 0.005 g). If carefully maintained and cleaned, a four

decimal place balance will give a reading within 0.0001 g.
So if 1 g is weighed using a balance measuring to two decimal places,
the mass may have an inevitable maximum error of 0.01 g. This means
that the true mass lies anywhere between 0.99 g and 1.01 g.
The percentage error is:
0.01
× 100 = 1%
1
Any result based on this measurement would also have a 1% error. A
4 1% error might be acceptable for most experimental work but weighing

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 The precision of apparatus
1 g using a balance which can measure to four decimal places would
Tip give a percentage error of only
It is worth bearing in mind 0.0001
× 100 = 0.01%
when planning an experimental 1
procedure that it would probably If the mass measured is much smaller, more thought needs to be given.
be inappropriate to use a balance A two decimal place balance used to measure a mass of 0.10 g would
measuring to four decimal places have a large percentage error:
(0.05% accuracy) and then to 0.01
× 100 = 10%
measure a volume with only a 0.10
5% accuracy.
Using a balance accurate to four decimal places to weigh a mass of
0.10 g would give a more acceptable percentage error of 0.10%.

Measurement of temperature
As with equipment used to measure volumes, different thermometers
have different maximum errors in the readings taken. To obtain the
percentage error in the readings, it is best to check the graduations. As
with measuring cylinders, a useful rule of thumb for thermometers is
that they have a maximum error of one-half the difference between
their graduation marks.
In some experiments, thermometers are used to measure small
differences in temperature. Care is needed in assessing the error
resulting from the measurement of temperature change. In order
to determine a temperature difference, both the initial and final
temperatures are measured, which doubles the error.
Table 1.1 shows how the percentage error varies depending on the
actual temperature change.
Table 1.1 Errors in temperature readings. All readings are made using a thermometer
graduated in units of 1 °C.
Initial Final Change in Error/°C % error
temperature/°C temperature/°C temperature/°C
20 22 2 1  1
  × 100 = 50
2
20 60 40 1 1
Tip   × 100 = 2.5
 40 
Don’t assume that digital
readings are necessarily more A digital thermometer should be more precise than a standard
precise. thermometer. It is normal practice with digital equipment to record all
the digits shown, but there is still some inherent error.

Test yourself
2 Calculate the percentage error in measuring a mass of 2.5 g using a
balance with a maximum error of:
a) 0.1 g b) 0.05 g c) 0.001 g.
3 Calculate the percentage error in measuring 50 cm of a solution using:
3

a) a 100 cm3 measuring cylinder with a maximum error of 0.5 cm3

b) a 50 cm3 pipette with a maximum error of 0.1 cm3
c) a 25 cm3 pipette with a maximum error of 0.06 cm3, used twice
d) a 50 cm3 burette where each reading has a maximum error of 0.05 cm3.

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 4 Calculate the percentage error in measuring a temperature rise of 6 °C
using a thermometer with a maximum error of:
a) 0.5 °C
b) 0.1 °C.
5 0.25 g of calcium carbonate is weighed out with a maximum error of
0.05 g to collect the carbon dioxide that it will produce when reacted with
excess hydrochloric acid. The volume of carbon dioxide formed is 60 cm3
and is collected in a syringe with a maximum error of 1 cm3.
a) Why does it matter that the hydrochloric acid is in excess?
b) Calculate whether the balance or the syringe contributes the more
significant error in this experiment.
c) Write the equation for the reaction.
d) Assuming that the volume of 1 mol of gas in the experiment is 24 dm3,
show that the volume of gas collected should be 60 cm3.

Recording results
When recording data, the precision should be indicated appropriately
and the units must always be given. For example, if you use a balance
that reads to two decimal places, the masses recorded should indicate
this. This may seem obvious for a mass of, for example, 2.48 g. However,
you must remember that this applies equally for a mass of, for example,
2.50 g. Here the ‘0’ should be included after the ‘5’ to indicate that this
mass is also precise to two decimal places. Recording the mass as 2.5 g
is incorrect and could be penalised in an exam.
When using a measuring cylinder with a maximum error of 1 cm3 to
measure a volume, the result would normally be recorded without any
decimal places. If you recorded a volume as 224.5 cm3 this would be
considered incorrect.
Burette readings are normally recorded to 0.05 cm3 as this represents
the appropriate maximum error. So a reading of 23.45 cm3 is acceptable,
but 23.47 cm3 is not. The reading should not be recorded as 23.4 cm3
because this implies a maximum error of 0.1 cm3. If the initial reading is
zero, it should be written as 0.00 cm3 because this reading has the same
precision as any other.

Identifying anomalies
If measurements are repeated in an experiment the results should be
examined carefully to identify any that are anomalous. Any that clearly
differ from the general trend should be rejected and excluded if an
Chapter 1  Practical skills

average is taken. For example, if titres obtained had volumes of 23.40 cm3,

23.90 cm3 and 23.50 cm3, the 23.90 cm3 stands out as being inconsistent
with the other readings and should be excluded from the mean titre which
Tip should be given as 23.45 cm3. If a graph is drawn and one result is clearly
inconsistent with the general shape of a line being drawn it should also be
You will not be required to carry rejected and the line should not deviate to pass through that point.
out a detailed analysis. However,
you should be able to identify
the effect of the measurement Overall accuracy of experimental results
with the largest error on the When performing a quantitative experiment it is likely that you will
final answer. use several pieces of apparatus whose maximum errors will vary.
6 For example, a mass might have a percentage error of 0.5%, but a

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 The precision of apparatus
temperature might have an percentage error of 4%. It is important to
consider the appropriate precision of a value calculated using these data.

Significant figures
Errors in measurements and results have been discussed, as has the
importance of using a suitable number of figures when results are recorded, i.e.
the correct number of significant figures. Applied properly, this indicates the
level of precision. Significant figures are explained in more detail in Chapter 16.
Tip
● 0.12 has two digits beyond the decimal point. It has two significant
Remember, if the number is a figures and implies that the accurate number is between 0.11 and 0.13.
decimal less than 1, the number In other words, the final digit is considered to have an accuracy of ± 1.
of significant figures is the number
● 0.120 has three digits beyond the decimal point. Therefore, it has
of digits after the left-hand zeros
beyond the decimal point.
three significant figures and the number lies between 0.119 and 0.121.
● 0.004 has just one significant figure, because the two zeros beyond the
decimal point are not counted. The number is between 0.003 and 0.005.
● 0.0042 has two significant figures. The number lies between 0.0041
and 0.0043.
● 0.004 00 has three significant figures. The two zeros after the ‘4’ do
count, so the number lies between 0.003 99 and 0.004 01.
Tip
A number such as 151.25 suggests a five-figure accuracy; it has five
As well as its importance in significant figures. The true number lies between 151.24 and 151.26.
practical work, examination
questions often expect you to
If 151.25 is rounded to 151, then it has three significant figures. This
give an answer to an appropriate
indicates that the number lies between 150 and 152.
number of significant figures. Writing 150 does not make the meaning clear. This is because when the final
digit is zero it implies that the number is either between 149 and 151 or
between 140 and 160. To get around this difficulty, scientific notation is used:
● 1.50 × 102 indicates that the number lies between 149 and 151
(remember the zero is a significant figure)
● 1.5 × 102 indicates that the number lies between 140 and 160.
Test yourself
6 Using the appropriate number of significant figures, write down the
precision possible of a mass of exactly 14 g measured using:
a) a two decimal place balance
b) a four decimal place balance.
7 A student performed a titration using a burette with a maximum error of
0.05 cm3. The student’s results are recorded in Table 1.2, some of which
are recorded incorrectly.
Table 1.2

Titration Rough 1 2 3
Final volume/cm 3
24.0 23.57 23.9 23.62
Initial volume/cm 3
 0   0.1  0  0
Volume used/cm 3
24 23.47 23.9 23.62

a) Copy this table, but write the results appropriately and to the correct
number of significant figures.
b) State the mean value for the titre that should be used in any
7
subsequent calculation.

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 Errors in experimental procedure
Apart from the limitations imposed by apparatus, experiments also
have errors caused by the procedure adopted. Such errors are difficult
to quantify, but the following checklist might help you to assess an
experiment.
Handling substances
● Can you be sure that the substances you are using are pure? Solids
may be damp and if a damp solid is weighed, the absorbed moisture
is included in the mass.
● Does the experiment involve a reactant or a product that could react
with the air? Remember that air contains carbon dioxide, which is
acidic and reacts with alkalis. Some substances react with the oxygen
present. Air is also always damp.
Heating substances
● If you need to heat a substance until it decomposes, can you be sure
that the decomposition is complete?
● Is it possible that heating is too strong and the product has
decomposed further?
Solutions
● If an experiment is quantitative, can you guarantee that any solution
used is exactly at the stated concentration?
Gases
● If a gas is collected during the experiment, can you be sure that none
has escaped?
● If you collect a gas over water, are you sure it is not soluble?
● The volume of a gas is temperature-dependent.
Timing
● If an experiment involves timing, are you sure that you can start and
stop the timing exactly when required?
Enthalpy experiments
● Heat loss is always a problem in enthalpy experiments, particularly if
the reaction is slow.

Improving experiments
As with limitations resulting from procedure, it is not possible to provide
a comprehensive list of ways to improve experiments. However, it is
Chapter 1  Practical skills

worth emphasising that simple changes are often effective.

Using more precise measuring equipment is only useful if it focuses on
a significant weakness. For example, if the volume of a solution does
not need to be measured precisely, there is no point in using volumetric
equipment.
If a change in the apparatus seems necessary, look for a straightforward
alternative – for example:

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 Errors in experimental procedure
● If the problem is that a gas to be collected over water is slightly
soluble, using a syringe might be an effective remedy.
● If a gas might escape from the apparatus when a reagent is added,
the procedure could be improved by placing one reagent in a
container inside the flask containing the other reagent and mixing
them when the apparatus is sealed.
● If the problem with an enthalpy reaction is that it is too slow, using
powders would help.
It is a mistake to imagine that perfection can be achieved by using
more complicated apparatus if the fault lies in the method that is being
employed.

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 Chapter 2
Atoms and electrons
Prior knowledge
In this chapter it is assumed that you know that:
● elements consist of atoms
● compounds are formed when the atoms of elements combine together
● matter is made up of elements and compounds.

Test yourself on prior knowledge

Explain the difference between:
a) an element and a compound
b) a compound and a mixture
c) an atom and a molecule.

Atoms
Elements are made up of atoms but the ways in which atoms combine
together is very varied and forms the basis of a study of chemistry.
By the end of the nineteenth century scientists began to appreciate
that atoms were not indivisible as had originally been believed but
had an intricate structure made up of different kinds of subatomic
particles. Chemists have largely focused on the three main particles –
protons, neutrons and electrons – although experiments done using the
underground Large Hadron Collider at CERN on the borders of France
and Switzerland have shown that protons and neutrons are made up of
even smaller units.

Protons, neutrons and electrons

● An atom consists of a nucleus that is made up of positively charged
particles called protons and uncharged particles called neutrons.
● Negatively charged particles called electrons orbit the nucleus.
● Protons and neutrons have almost identical masses. Electrons are
much lighter, being approximately 1/2000 of the mass of a proton or
neutron.
Figure 2.1 In the Hadron Large Collider at ● All atoms are neutral. Therefore, the number of electrons is equal to
CERN two beams of high-energy particles
the number of protons.
travelling at speeds close to that of light
are made to collide and the fragments It is worth appreciating that the diameter of the nucleus is only about
created are analysed. In 2013 an analysis
1/100 000 of the total diameter of the atom. So, if the nucleus were
of the results of such an experiment
tentatively confirmed the presence the size of an average bedroom in a house in Birmingham (Figure 2.2),
of a fundamental particle called the the electron would follow roughly an orbit through Blackpool, Swansea,
Higgs boson, whose existence had been London and Skegness. An atom has a large amount of space between its
predicted by Peter Higgs in 1964. nucleus and the outer boundary of electrons.

10

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 Atoms
The actual size of the charge on a proton or an electron
is very small (1.60 × 10 –19 coulombs) and the masses of
protons, neutrons and electrons are equally tiny. A proton
has a mass of only 1.67 × 10 –24 g.
You are not expected to recall these values but it is
important that you remember the relative charges and sizes
as shown in Table 2.1.

Table 2.1 Relative charges and masses of the components of the atom.

Particle Relative charge Relative mass

BLACKPOOL
SKEGNESS Proton (p) +1 1
Neutron (n) 0 1
BIRMINGHAM Electron (e) –1 1/1836 (approx. 1/2000)
SWANSEA
LONDON

Some points to note are:

●   The
atoms of any one element are different from the
Figure 2.2 A geographical illustration of the scale of atoms of all other elements.
an atom. ●   All
atoms of the same element contain the same number
Tip of protons; atoms of different elements contain a different
number of protons.
No one knows the size of an
individual electron. As explained ● The number of protons contained in the atom of an element is called
later, it cannot even be fully its atomic number.
described as a particle. ● The sum of the numbers of protons and neutrons in an atom is
called its mass number. This implies that the protons and neutrons
Key terms supply the total mass of an atom. This is not completely true,
because there are also electrons present but, because electrons
Atomic number is the number of
are so much lighter than protons and neutrons, it is a reasonable
protons in an atom of an element.
approximation.
Mass number is the number
of protons + neutrons in the It is easy to work out the numbers of particles present in an atom using
nucleus of an atom. its atomic number and mass number.
An ion is an electrically charged
particle formed by the loss or gain Example 1
of one or more electrons from an An atom has atomic number 13 and mass number 27. How many protons,
atom or a group of atoms. neutrons and electrons does it contain?

Tip Answer
The atomic number is the number of protons, which is, therefore, 13.
The atomic number is
sometimes referred to as the Since an atom is neutral, the number of electrons is also 13.
proton number. The mass The number of protons plus the number of neutrons is 27. Therefore, the
number is sometimes referred to number of neutrons is 14.
as the nucleon number.
(The element is aluminium and it is usually written as 27
13
Al.)

Tip
Mass Formation of ions
number 27Al Losing or gaining electrons is the process by which many chemical
13
Atomic reactions take place. When atoms do this they form charged particles
number
called ions. An ion has the same atomic number and mass number as
Subtract the bottom number from the top
number to get the number of neutrons.
the atom of the element from which it was made. 11

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 If an atom loses one electron, the number of electrons in the atom
becomes one fewer than the number of protons. Therefore, it has an
electrical charge of +1. For example, a sodium atom loses an electron,
forming an ion that is represented by Na+. A calcium atom can lose two
electrons and, as it then has two fewer electrons than it does protons, it
is written as Ca2+.

Tip If one electron is gained, the atom of the element contains one more
electron than it does protons and, therefore, has an electrical charge
For non-metals, the element of –1. For example, a chlorine atom gains an electron, forming a chloride
and its ion do not have the same ion, which is represented by Cl–. An oxygen atom gains two electrons,
name. A non-metallic ion has forming an oxide ion. This has two more electrons than protons and is
the ending ‘-ide’. For example, written as O2–.
the ion from oxygen is oxide,
from bromine it is bromide and Ions have different properties from those of the atoms of the element
from sulfur it is sulfide. from which they came. For example, sodium metal is extremely reactive
but sodium ions are not.

Example 2
How many protons, electrons and neutrons are present in a sulfide ion, S2–?
Sulfur has atomic number 16 and mass number 32.

Answer
Test yourself Sulfur has atomic number 16, so a sulfur atom contains 16 protons.

1 Use the atomic numbers Since the electrical charge of a sulfide ion is ‘2–’, it contains two more electrons
and mass numbers given to than it does protons. Therefore, the number of electrons is 16 + 2 = 18.
deduce the number of protons, The atomic mass is 32. The number of neutrons is the mass number minus
neutrons and electrons present the number of protons (32 – 16), which is 16.
in the following atoms and
the ion formed from them. Therefore, a sulfide ion contains 16 protons, 16 neutrons and 18 electrons.
a) i) oxygen, O (atomic It is written as 32 S2–.
16
number 8, mass
number 16)
ii) O2–
Example 3
b) i) sodium, Na (atomic How many protons, neutrons and electrons are present in a potassium ion,
number 11, mass K+? Potassium has atomic number 19 and mass number 39.
number 23)
ii) Na+ Answer
c) i) fluorine, F (atomic Potassium has atomic number 19, so a potassium atom contains 19 protons.
number 9, mass Since the electrical charge of a potassium ion is ‘1+’,it contains one more
Chapter 2  Atoms and electrons

number 19) proton than it does electrons. Therefore, the number of electrons is 18.
ii) F–
d) i) calcium, Ca (atomic The atomic mass is 39. The number of neutrons is 39 – 19, which is 20.
number 20, mass Therefore, a potassium ion contains 19 protons, 20 neutrons and 18 electrons.
number 40)
ii) Ca2+ It is written as 39
19
K+.

Isotopes and mass spectra

Most elements are made up of more than one type of atom. Although
these atoms contain the same number of protons they differ in the
number of neutrons that are present. Potassium, for example, consists
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 Isotopes and mass spectra
Key term of three different types of atom. All have 19 protons and most have 20
neutrons but a few have 22 neutrons and a very small number have 21.
Isotopes are atoms of the same These variations are called isotopes of the element.
element that have different
masses. The isotopes of an Evidence for the existence of isotopes was obtained by using an
element have the same number instrument called a mass spectrometer. Although you will not be
of protons (and electrons), but expected to have knowledge of a mass spectrometer in an exam it is
different numbers of neutrons. useful for you to understand the general principle by which it works.
A gaseous sample of the substance is bombarded with high-energy
electrons, which knock off electrons from the edge of an atom to create
positive ions. These are separated according to their charge and those
with a 1+ charge are selected. After being accelerated by an electric
field, a focused stream of these ions is then passed at constant speed
through a magnetic field. Here, the ions are deflected and the degree of
the deflection depends on the mass of the ion. A detector is calibrated to
record the degree of deflection and interpret this in terms of mass. The
key features are summarised in Figure 2.3. In order to avoid interference
from gases in the air, the spectrometer is evacuated using a pump.
electron gun ions are
detected
atoms or molecules enter
ions are accelerated through
an electric field

they are ionised

(turned to positive
ions after being
hit by a stream ions are deflected by a
of electrons) magnetic field according
to their mass
to a pump, which
maintains lighter ions will bend more,
magnet heavier ones less
low pressure

Figure 2.3 A representation of a mass spectrometer.

A mass spectrometer analyses positive ions only. Do not confuse these
ions with the ions that are formed under normal laboratory conditions.
The conditions employed in the apparatus are such that it is impossible
to create negative ions. An alternative version is the ‘time of flight
(TOF)’ mass spectrometer. In this spectrometer ions are accelerated
so that those of the same charge have the same kinetic energy. The
velocity of the ion then depends only on its mass with those of greater
mass moving more slowly. The time taken for ions to move across a
fixed distance to a detector is then measured and this is interpreted to
obtain an accurate mass of the particle.
Tip
Although you will not be
Mass spectra of elements
asked to describe a mass The mass spectrometer provides information about the masses of every
spectrometer in an exam, you particle that has been formed inside the machine and how often this
need to understand how the particle has been detected. For an atom, a typical print-out from a mass
results obtained from a mass spectrometer looks like a ‘stick-diagram’. Each ‘stick’ shows the presence
spectrometer are used. of an ion formed from an isotope and the height of the ‘stick’ represents
its abundance. 13

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 100 The mass spectrum for boron is shown in Figure 2.4.
Relative abundance
The x-axis is labelled ‘m/z’, which means mass/charge. However,
since the charge is 1+ it is effectively the relative mass of
50
the ions that is recorded. A mass spectrometer is calibrated
so that the isotope carbon-12 is given a value of exactly 12.
This is the standard used universally for the comparison of
0
5 6 7 8 9 10 11 12 the masses of atoms (see page 40). The y-axis records relative
m/z abundance, which is the number of times an ion of that mass
Figure 2.4 The mass spectrum of boron. has been detected.

Tip
The word ‘relative’ is used
because the figures are the
masses of the isotopes based on
a comparison with the mass of
carbon, which is given a mass of
12 (see Chapter 4 page 40).
Figure 2.5 A mass spectrometer.

Tip The mass spectrum of boron has two lines. They are both a result of
Strictly, it is better to use the the formation of B+ ions. One line is equivalent to a mass of 10 and
expression ‘weighted mean the other to a mass of 11. This occurs because boron consists of two
relative atomic mass’ rather isotopes, the atoms of one isotope containing five neutrons and the
than ‘relative atomic mass’. other containing six neutrons. The relative abundance of these two
The average of 10 and 11 isotopes is shown by the heights of the lines – they are in the ratio of
is 10.5. However, here the 23 (boron-10) to 100 (boron-11). Knowing this ratio allows the mean
Chapter 2  Atoms and electrons

numbers of atoms of each relative atomic mass to be determined.

isotope are considered and, in Consider a total of 123 boron particles. 23 will be boron-10 and 100 will
these circumstances, the word be boron-11. Therefore, the atomic mass has a contribution of (23/123)
‘weighted’ is included which takes from boron-10, which is (23/123) × 10 = 1.87, and a contribution of
account of the fact that there (100/123) from boron-11, which is (100/123) × 11 = 8.94.
are more atoms of boron-11 than
there are of boron-10. The relative atomic mass of boron is 1.87 + 8.94 = 10.81 (or 10.8 to
1 decimal place).
In some problems the percentage abundances obtained from a mass
spectrum may be supplied. The following example shows how the
atomic mass is then obtained.

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 Isotopes and mass spectra
Tip Example 4
It is good practice to give the Silver has two isotopes: 51.35% of the atoms are silver-107 and 48.65% of
answer to a calculation using the atoms are silver-109. Calculate the relative atomic mass of silver.
the same number of significant
figures as used in the quantities Answer
given in the question. The fraction that is 107Ag+ is 51.35/100; the fraction that is 109Ag+ is 48.65/100.
   48.65 
weighted mean relative atomic mass = 51.35 × 107 + × 109 = 107.97
 100   100 
or 108.0 to 1 decimal place

Activity
Finding the relative atomic mass of neon
Look carefully at the mass spectrum of neon in Figure 2.6.

100
90
80
70
Relative abundance

60
50
40
30
20
10
0

18 19 20 21 22 23 24
m/z

Figure 2.6 The mass spectrum of neon.

1 How many isotopes does neon contain?

2 What are the relative masses of the isotopes of neon?
3 What are the relative amounts of the isotopes of neon?
4 Start a spreadsheet program (e.g. Excel) on your computer and open up a new spreadsheet for your results.
a) Enter the relative masses of the isotopes of neon in column 1 and the relative amounts of these isotopes in
column 2.
b) Enter a formula in column 3 to work out the contribution of each isotope to the overall relative atomic mass of
neon. (Hint: Look at the calculation of the relative atomic mass of boron or silver in the section above.)
c) Finally, enter a formula in column 4 to calculate the relative atomic mass of neon.

(If you do not have access to a computer with a spreadsheet program, calculate the relative atomic mass of
neon yourself.)
5 Pure samples of the isotopes of neon have different densities.
a) Why is this?
b) Which isotope of neon will have the highest density?
6 Isotopes of the same element have different physical properties but the same chemical properties. Why is this?
7 Samples of neon collected in different parts of the world have slightly different relative atomic masses. Why is this?

15

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 Test yourself
2 Rubidium consists of two isotopes. Rb-85 has an abundance of 72.2%;
Rb-87 has an abundance of 27.8%.
Calculate the relative atomic mass of rubidium.
3 Neon consists of three isotopes. The percentage composition is Ne-20,
90.48%; Ne-21, 0.27%; Ne-22, 9.25%.
Calculate the relative atomic mass of neon.
4 Copper has a relative atomic mass of 63.6. It contains two isotopes. One
isotope has a relative mass of 63 and an abundance of 69%.
Deduce the relative mass of the other isotope.
5 The mass spectrum of the element gallium is shown below.
Calculate the relative atomic mass of gallium.

60.2%
Relative abundance

39.8%

60 62 64 66 68 70 72 74 76
m/z

Key term Mass spectra of compounds

A molecular ion peak is the peak The mass spectrometer is also used to analyse compounds. This is
corresponding to the relative because bombardment by electrons causes the molecule to break up and
molecular mass of the compound. each of the fragments obtained registers on the detector. This can be an
(It is sometimes referred to as the advantage, as it is sometimes possible to obtain details of the molecule’s
parent ion peak.) structure as well as its overall molecular mass (see Chapter 15).

100 Mass spectrum of propane

29
The mass spectrum of propane, C3H8, is shown in Figure 2.7.
80
The relative molecular mass of propane is 44. The peak
Relative abundance

28 furthest to the right of the spectrum represents the

60
ion [C3H8]+. This is called the molecular ion peak. The
Chapter 2  Atoms and electrons

molecular ion is produced by the removal of an electron

40
from the molecule within the mass spectrometer:
44
20 H3C–CH2–CH3(g) → [H3C–CH2–CH3]+(g) + e–
15
However, under the bombardment of electrons, the
0 molecular ion is unstable and breaks down to ion fragments
0 10 20 30 40 50
m/z of the molecule, which are also detected. Some examples
Figure 2.7 Mass spectrum of propane, C3H8.
are labelled on Figure 2.7. The peak at m/z 29 occurs
because a C–C bond in the CH3CH2CH3 chain of the
molecular ion is broken, producing two fragments. One of
the fragments has a positive charge and the other is neutral:
[H3C–CH2–CH3]+(g) → [CH3 –CH2]+(g) + CH3(g)
16

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 Isotopes and mass spectra
In this case, the ion [CH3CH2]+ is then detected with a peak at m/z = 29.
The peak at m/z 15 represents a [CH3]+ ion. Again, a C–C bond in the
CH3CH2CH3 chain is broken, producing one fragment with a positive
charge and one fragment that is neutral:
[H3C–CH2–CH3]+(g) → [CH3]+(g) + CH3 –CH2(g)
A fragment can be identified for all other peaks in the spectrum. It is
because of this fragmentation that the set of peaks is often described as a
fingerprint of the molecule.
100
Mass spectrum of ethanol, CH3CH2OH
80 The mass spectrum of ethanol is shown in Figure 2.8.
Relative abundance

The molecular ion is represented by the line at m/z 46.

60
This is the line furthest to the right, but it is not the
highest peak. The height of the line represents the relative
40
amount of that ion formed from the sample. It is often
the case that a molecule breaks down readily, rather than
20
surviving as the molecular ion. The peak at m/z 45 is due
to the loss of H from the –OH group, resulting in the
0
0 10 20 30 40 50
ion [CH3CH2O]+(g). The most abundant peak is at m/z 31,
m/z which corresponds to the ion [CH2OH]+(g), formed by the
Figure 2.8 Mass spectrum of ethanol, CH3CH2OH
fragmentation of ethanol by breaking the C–C bond.

Tip Lines due to isomers

The precision of a mass spectrometer is such that lines formed from
Remember that it is positive
different isotopes can be observed (though these have been excluded
ions that are detected by a mass
from Figures 2.7 and 2.8). These lines have small peak heights. One
spectrometer and you must
characteristic is the presence of such small peaks beyond the molecular
include the positive charge if you
ion peak. These are usually the result of small numbers of ions containing
are asked to identify any of the
the isotope 13C, although other isotopes may contribute. These peaks
fragments.
do not usually need to be considered when using a mass spectrum to
identify a compound.

The accuracy of mass spectrometers

Whereas the original machine designed by Francis Aston was large
and only moderately accurate, today’s instruments are much smaller
and the results are accurate to 4 decimal places. This precision means
that, for example, a mass spectrometer can distinguish between carbon
monoxide, nitrogen and ethene even though to a first approximation
each has a mass of 28. The accurate figures are: carbon monoxide, CO,
28.0101; nitrogen, N2, 28.0134; ethene, C2H4, 28.0530.
A mass spectrometer uses very small samples of gaseous molecules
and, today, can be operated remotely. This makes it a useful piece of
equipment for analysing samples in remote locations. For example, the
equipment on board the Mars space probe included a mass spectrometer
that analysed samples of gas and returned the results to Earth. The mass
spectrometer also plays an important role in forensic science. Chemicals
are separated and a mass spectrum is obtained and the fragmentation
pattern is matched by computer to a database. This type of analysis is
used extensively in sport for detecting the use of illegal substances.
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 Test yourself
6 The mass spectrum below is of a compound containing only hydrogen
and carbon.
a) State which peak is the molecular ion peak.
b) Give the molecular formula of the hydrocarbon.
c) Suggest the formulae of each of the labelled fragments.
100
55

80

Relative abundance
60 70
41
40 29

20 15

0
10 20 30 40 50 60 70
m/z

Electrons
Key term You may be familiar with a picture of atoms based on a model
suggested by the Danish scientist, Niels Bohr. Each atom has electrons
The ground state of an atom in orbits that are outside the nucleus and are of increasing size. The first
shows how it naturally exists shell can accommodate two electrons, the second eight electrons, and
with its electrons in their lowest so on. Such diagrams show what is known as the ground state of the
energy position. atom. This means that its electrons are in positions that are as close
as allowable to the nucleus of the atom. These diagrams are useful as
a basic representation of atomic structure and help us to understand
Tip the nature of chemical bonding (see Chapter 7). However, their use is
If you are asked to give the limited to atoms with relatively few electrons. Electrons can however
electron configuration of an move from one orbit to another within an atom. If the electrons are in a
element you should give the position of higher energy they are said to be excited.
ground state for that element.
Ground states of some elements
The simplest atom is hydrogen. With atomic number 1, an atom of
hydrogen contains one proton and hence one electron. The next atom,
helium, has atomic number 2. Therefore, there are two protons in its
nucleus. The first shell can accommodate two electrons only and it is
Chapter 2  Atoms and electrons

therefore completely filled. An atom of lithium has three protons in its

nucleus. The third electron is in a new, larger shell.
Table 2.2 shows the arrangement of the electrons for the first three
elements.
Table 2.2 Electron arrangement for the ground state of the first three elements.

Atomic number/ number of protons 1 2 3

Symbol H He Li
Arrangement of electrons

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 Electrons
The second shell can accommodate eight electrons. As the atomic
number increases, the electrons progressively fill this shell. This is
illustrated by beryllium and carbon. Beryllium, 4Be, has four electrons
arranged 2, 2; carbon, 6C, has six electrons arranged 2, 4.

Be C

Tip Neon, element 10, contains the maximum eight electrons in the second
The shells are also referred to as shell. The next element, sodium, 11Na, utilises a third shell. Its electrons
electron orbits. are arranged 2, 8, 1.

Na

Chlorine and argon are further examples of elements with electrons in

the third shell.

Cl Ar

When an element forms an ion, the electrons are also accommodated in

the appropriate shells.
So, for example, an oxide ion, 8O2– contains 10 electrons which between
them will fill both the first and second shell.
2−

Key terms
The 1st ionisation energy is the
energy required to remove 1 Test yourself
electron from each atom in 1 7 Draw the electrons in their shells for each of the following elements:
mole of gaseous atoms to form 1 a) nitrogen (atomic number 7)
mole of gaseous 1+ ions. b) magnesium (atomic number 12)
The 2nd ionisation energy is the c) chloride ion, Cl– (atomic number 17)
energy required to remove 1 d) calcium ion, Ca2+(atomic number 20).
electron from each 1+ ion in 1
mole of gaseous 1+ ions to form
1 mole of gaseous 2+ ions. Ionisation energies
The nth ionisation energy is the Some evidence for the existence of electron shells can be obtained
energy required to remove 1 by plotting the energy required to remove electrons, one by one,
electron from each (n – 1)+ ion from a gaseous atom. These energies can be measured and are called
in 1 mole of gaseous (n – 1)+ ionisation energies.
ions to form 1 mole of gaseous
n+ ions. For example, when successive ionisation energies are plotted for chlorine
the graph has the shape shown in Figure 2.9.

19

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 Large jumps in ionisation energy after the
seventh and the fifteenth ionisation energy

The large jumps

in ionisation
energy indicate

Ionisation energy
a new electron
shell closer to
the nucleus

7 8 2

This indicates 7 electrons in the outer shell,

8 in the next and 2 in the inner shell

Successive ionisation energy

Figure 2.9 Successive ionisation energies of chlorine, 17Cl.

Chlorine has 17 electrons, arranged 2, 8, 7. There is a steady increase

in the energy required to remove the electrons. This is to be expected
because, as each electron is removed, the nucleus exerts an increasing
pull on the remaining electrons (see page 120 for more details on
ionisation energies). There is a noticeable jump in the energy required
after the seventh and the fifteenth electrons have been removed. This is
because at these two stages the electron is now being removed from a
shell nearer to the nucleus.

Evidence for the existence of sub-shells

Knowing the basic structure of the atom is helpful in understanding
the way that atoms behave and you will use these ideas as your
knowledge of chemistry develops. However, there are some aspects of
the behaviour of electrons that cannot be explained by assuming they
are in shells. Further research during the twentieth century revealed
that electrons are more complicated than just small particles revolving
around a central nucleus. There is experimental evidence to suggest that
each shell is made up of sub-shells.
He
By studying the first ionisation energy (the
Ne
filling up the energy required to remove the first electron
Chapter 2  Atoms and electrons

Ar from an atom), it is found that the first 20

First ionisation energies

p-subshell
filling up the elements show a more complex pattern than
p-subshell
might be expected (Figure 2.10). Trends in the
H
ionisation energies of the elements are looked
Li
half-filled at in detail in Chapter 8. For now, notice
p-subshell half-filled that, although there is a general increase in
s-subshell p-subshell
Na ionisation energy until each shell is filled, the
K
s-subshell
trend is not quite uniform. There are several
s-subshell small peaks and troughs. These peaks and
Atomic number troughs are repeated in each shell and provide
some evidence that the arrangement of
Figure 2.10 The pattern of ionisation energies gives evidence for the
existence of sub-shells. electrons involves sub-shells.
20

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 Electron energy levels and orbitals
Electron energy levels and orbitals
Energy levels
Tip Apart from the evidence obtained from the patterns of ionisation energies,
other research, particularly the mathematical description developed by
The numbers 1, 2, 3, etc. are Erwin Schrödinger, led to the conclusion that instead of focusing on the
called principal quantum position of electrons in terms of shells, it is more accurate to assign them
numbers which are then divided energy levels. These energy levels are numbered 1, 2, 3, etc. and correspond
into the various sub-shells s, p, broadly to the shells. All but level 1 are subdivided and given letters that
d, and f. characterise them in more detail. The letters used are s, p, d and f.
The lowest electron energy level in an atom is called ‘1s’. This is the only
Tip option for shell 1. Stepping upwards in energy, the next energy level is
It may seem strange to use the ‘2s’. However, shell 2 has a further energy subdivision called a sub-shell
letters s, p, d and f, but they and labelled ‘2p’. Level 3 has 3s, 3p and also 3d sub-shells. Level 4 has
relate to the appearance of the 4s, 4p, 4d and 4f sub-shells.
lines in the emission spectra of An energy level labelled ‘p’ is of higher energy than the equivalent ‘s’
alkali metals which result from level. Therefore, 2p has higher energy than 2s; 3p has higher energy
small bursts of energy emitted than 3s and so on.
when electrons jump from one
energy level to another: It is important to know the order of increasing energy of the electron
levels because this indicates the electron configuration of the element in
s = sharp its ground state (i.e. the lowest energy state that it can achieve). These
p = principal energies do not always follow the sequence you might expect, but
d = diffuse fortunately there is an easy way of remembering the order (Figure 2.11).
f = fundamental.
Follow the arrows to obtain the order that the electrons
fill the orbitals. Start with the red and follow with
Tip 1s the orange, yellow, green etc. to give the sequence,
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p etc.
You will not be expected to 2s 2p
remember the order of filling
3s 3p 3d
electrons into the energy levels
for elements with an atomic 4s 4p 4d 4f
number greater than 36.
5s 5p 5d 5f 5g

Key term 6s 6p 6d 6f 6g 6h

An orbital is a region around the Figure 2.11 Key to remembering the order in which energy levels are filled.
nucleus of an atom that can
hold up to a maximum of two Note that the 4s fills up before the 3d; likewise, the 5s fills up before the 4d.
electrons.
Electron orbitals
Tip Chemists have used complex mathematics to develop a description of
how electrons look in the various energy levels. It will seem strange
Spin is a complex factor and when you first meet it, but the idea of an electron as a particle is
all you need to know is that replaced by a description based on the electron as a cloud of negative
electrons with opposing spins charge. This charge is spread like a mist around the nucleus of the
have an attraction sufficient to element. The mist varies in its density at different distances from
allow them to occupy the same the nucleus. These regions of ‘electron mist’ are called orbitals and
orbital. correspond to the energy levels used by an atom. Each orbital can hold
one or two electrons and has a density of charge that depends on the
energy level being described. If the orbital has two electrons the two
electrons will differ in the direction in which they spin.
21

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 In Figure 2.12, the plot is darkest where the electron charge density
is greatest and lightest where the electron charge density is less.

s-orbitals
The simplest type of orbital to describe is the orbital corresponding
to an ‘s’ energy level. It consists of a spherical volume of
negative charge with the nucleus at its centre. All s-orbitals have
this shape. The difference between a 1s-orbital and a 2s-orbital is
the distance from the nucleus to where the major density of charge
is concentrated. In the 1s-orbital, the electron density is closer to
the nucleus. As the levels (principal quantum numbers) increase, the
radius at which the charge is most dense becomes further away from
the nucleus. For example, a 4s-orbital is larger than a 3s because
the point at which the 4s-orbital has its greatest density of negative
Figure 2.12 A 1s orbital. charge is further from the nucleus than it is for the 3s-orbital.
z

p-orbitals
z x The p-orbitals are more complex and harder to visualise
x (Figure 2.14). They have an elongated dumbbell shape and a
variable charge density, with the area of greatest concentration
increasing with the distance from the nucleus as the principal
y y quantum number increases. For each principal quantum number
there are three p-orbitals. They are identical and have the same
energy, differing only in their orientation in space. They are
1s-orbital 2s-orbital
labelled ‘x’, ‘y’ and ‘z’ to correspond to the three principal axes.
Figure 2.13 The shape of 1s- and 2s-orbitals.
z z z

y y y

Tip x x x

Orbitals that have the same pz-orbital

px-orbital py-orbital
energy are said to be degenerate.
Figure 2.14 The shape of 2p-orbitals.

Tip Representing the electron configuration of the

For each principal quantum elements
Chapter 2  Atoms and electrons

number of 3 and above there are Electron energy levels can be represented in ‘box’ diagrams, as shown in
five d-orbitals. It is not necessary Figure 2.15.
to know their shapes at this stage.
4d
5s
Tip 4p Note that the
3d 5s-orbital is at
The reasons why the orbitals are a lower energy
4s
Energy

filled in this order are complex 3p Note that the level than the 4d
and you will not be asked to 3s
4s-orbital is at
provide any explanation. a lower energy
level than the 3d
2p
2s
22 1s
Figure 2.15 Energy-level diagram.

9781471827068_OCR_A_Level_Chemistry.indb 22 30/03/15 2:43 PM

 Electron energy levels and orbitals
Each box represents an orbital and each orbital can contain a maximum
of two electrons.
Some examples of electron configurations using ‘electrons in box’
diagrams are given in Figure 2.16. It has been mentioned that where an
orbital contains two electrons they differ in their direction of spin. To
distinguish between the two electrons they are shown with an upward
arrow (↑) and a downward arrow (↓).

x y z x y z
2p 2p

Energy

Energy

Energy
2s 2s 2s

Tip 1s 1s 1s

In diagrams of this kind you can

also represent the electrons Lithium Boron Carbon

using half arrows. Figure 2.16 ‘Electrons in box’ diagrams for the electron configurations of lithium, boron
and carbon.

Box diagrams are a useful visual way of showing how electrons are
distributed but it is often more helpful to identify the orbitals using the
orbital names. The system for doing this is as follows.
● An atom of hydrogen has one electron, which in its ground state is in
the 1s-orbital. It is represented as 1s1. (You would say this as ‘one s one’)
● An atom of helium has two electrons that occupy the 1s-orbital. Its
electron configuration is represented as 1s2. (You would say this as
‘one s two’)
● An atom of lithium has three electrons and its electron structure is
represented as 1s22s1.
● The electron structure of beryllium is 1s22s2.
● An atom of boron has five electrons and the next highest energy
orbital, 2p, is used. The electron configuration is represented as
1s22s22px1, although the subscript x is not really necessary because
any of the three 2p-orbitals could be used as they all have the same
energy. The label x has no direct meaning until the y- and z-orbitals
are also occupied. Labelling is only necessary to distinguish between
orbitals of equivalent energy.
Each orbital of equivalent energy is occupied by one electron before
the second electron is added. The reason for this is that two electrons
within the same orbital experience a degree of repulsion that makes the
pairing of electrons slightly less favourable.
● Carbon, atomic number 6, therefore has the ground state
1s22s22px12py1.
● Nitrogen, atomic number 7, has the ground state 1s22s22px12py12pz1.
After nitrogen, the electrons in the p-orbitals pair up:
● oxygen is 1s22s22px22py12pz1
● neon is 1s22s22px22py22pz2.
23

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 Tip Once the 2p-orbitals have been filled, the 3s-orbital and the 3p-orbitals
are occupied in a similar way so that, for example, the ground state of
The valency corresponds to silicon (14 electrons) is 1s22s22p63s23px13py1 and that of chlorine with 17
the charge on the ion that is electrons is 1s22s22p63s23px23py23pz1.
obtained when the atom loses
or gains electrons. So sodium is Note that once the 3p-orbitals have been filled, the next orbital to be
Na+, oxygen becomes O2− and occupied is the 4s (not the 3d). Therefore, the ground state of potassium
NO3 is an ion NO3−. (19 electrons) is 1s22s22p63s23p64s1.
The 3d-orbitals are filled in the atoms of scandium (21 electrons) to zinc
Tip (30 electrons). These elements have a number of properties in common
It is conventional to write
and are called d-block elements. For example, scandium would be
the electron configuration as
written as 1s22s22p63s23p64s23d1 or 1s2, 2s2, 2p6, 3s2, 3p6, 3d1, 4s2.
1s22s22p63s23p63d14s2 (i.e. with ‘Electrons in box’ representations of the electron ground states of some
the 4s and 3d energy levels elements are given in Figure 2.17.
reversed) for all elements with
both 4s and 3d electrons. Number of
Element electrons 1s 2s 2p 3s 3p 3d 4s 4p 5s
Hydrogen 1
Tip Helium 2
Lithium 3
Where an atom has a large
Carbon 6
number of electrons, its
Neon 10
structure is often abbreviated Sodium 11
by using the symbol of a group Sulfur 16
18 element to provide its inner Argon 18
electron configuration. It is then Potassium 19
only necessary to provide details Scandium 21
of its outermost electrons. Iron 26
For example scandium can be Zinc 30
abbreviated to [Ar] 4s2, 3d1 or Bromine 35
vanadium to [Ar] 4s2, 3d3. Krypton 36
Strontium 38

Figure 2.17 The electronic ground states of some elements.

Test yourself
8 Copy and complete the following information for the quantum shell with
principal quantum number 3.
a) Total number of sub-shells =
b) Total number of orbitals =
c) Number of different types of orbital =
Chapter 2  Atoms and electrons

d) Maximum number of electrons in the shell =

9 Give the electron orbital configuration for the ground state of the
following atoms or ions:
a) Na
b) K
c) N
d) O2–
e) Ca2+
f) Al3+
g) Cl–
h) P3–

24

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 Practice questions
Practice questions
Multiple choice questions 1–10 6 When sulfur, 32
16
S is bombarded with neutrons 01n,
1 Which one of the following has more neutrons two particles are formed.
than electrons and more electrons than protons? One of them is a hydrogen atom, 11H and the
A 199F– other is an element, X.

B 37
Cl–
32
16
S + 10n → 11H + X
17
Which one of the following correctly represents X?
C 9
4
Be
A 32
15
S
D 9
4
Be2+
B 32
15
P
2 Successive ionisation enthalpies of an element C 33
16
S
X in kJ mol–1 are as follows:
578, 1817, 2745, 11 578, 14 831, 18 378 D 33
15
P
Which one of the following is X? 7 Chlorine has two isotopes, 35Cl and 37Cl. Bromine
A boron has two isotopes, 79Br and 81Br.
B carbon How many lines would you expect to observe on
C aluminium the mass spectrum of the molecule ClBr?
D silicon A 5 B 6
3 Which one of the rows giving information about C 7 D 8
the fourth period of the periodic table is correct? Use the key below to answer Questions 8, 9 and 10.

Total The Maximum A B C D

number of number of number of 1, 2 & 3 correct 1, 2 correct 2, 3 correct 1 only correct
orbitals different electrons in
types of the shell 8 Which of the following elements have atoms that
orbital contain only one unpaired p-orbital electron?
A 4 2 8 1 phosphorus, 15P
B 9 2 18 2 bromine, 35Br
C 9 3 8 3 aluminium, 13Al
D 9 3 18 9 Which of the following statements is true for
4 Chlorine exists as two isotopes, 35 Cl with an elements in the third period of the periodic table?
17
abundance of 75.5% and 17Cl with an abundance
37 1 They all have electrons in at least six
of 24.5%. different orbitals.
Phosphorus has only one isotope, 31 P. 2 They all have some p-orbitals in their
15
The mass spectrum of PCl3 has four lines electron structures.
at m/z = 136, 138, 140 and 142. 3 Only two of the elements have electron
Which one these lines will have the smallest height? structures with all of their orbitals containing
A 136 B 138 pairs of electrons.
C 140 D 142 10 Which of the following has the sum of the
5 Antimony has two isotopes Sb and Sb.
121 123 number of neutrons and the number of electrons
The relative atomic mass of a naturally occurring equal to 12?
sample of antimony is measured as 121.75. 1 three helium atoms (42He)
Which one of the following is the best 2 two lithium ions (73Li+)
approximate estimate of the percentage of 121Sb 3 six hydrogen molecules (11H2)
present in the naturally occurring sample? 11 Give the numbers of protons, neutrons
A 20% and electrons present in each of the
C 60% following atoms.
B 40% a) 40 Ar b) 127 I c) 127 –
I
18 53 53
D 80%
d) 197
79
Au e) 197
79
Au+ f) 52
24
Cr3+
(6)
25

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 12 This question concerns the following five species: 17 The first five successive ionisation energies in
O2–
16
F
19 20
Ne Na
23 25
Mg2+ kJ mol–1 of an element X are 578, 1817, 2745,
8 9 10 11 12
11 578 and 14 831.
a) Which two species have the same number
a) How many electrons are there in the outer
of neutrons?
shell of X?
b) Which two species have the same ratio of
b) Explain how you obtained your answer. (3)
neutrons to protons?
c) Which two species do not have 10 electrons? 18 Give the electron orbital configuration for the
d) What do the numbers 16, 8 and 2– ground state of the following atoms or ions:
represent in the symbol 168O2–? (6) a) 5B
13 The isotopes in naturally occurring silicon – b) 13
Al
28
14
Si, 29
14
Si and 30
14
Si – can be separated by mass c) 4Be2+
spectrometry.
d) 16
S2–
a) Explain what you understand by the term
isotope. e) 21
Sc3+ (5)
b) Copy and complete the table below to show 19 The element, thallium, Tl, has two isotopes, 203Tl
the composition of isotopes 28 14
Si and 30
14
Si. and 205Tl, and the relative atomic mass is 204.37.
Isotope Protons Neutrons Electrons Calculate the percentage of each isotope present
28
Si in a naturally occurring sample of thallium. (6)
14
30
Si 20 The first five ionisation energies of an element
14
are 738, 1451, 7733, 10 541 and 13 629 kJ mol–1,
c) Why do samples of silicon extracted from respectively. Explain why the element cannot
different samples of clay have slightly have an atomic number less than 12. (4)
different relative atomic masses? (5)
21 a) Explain what you understand by the word
14 The element rhenium (Re) has two main isotopes, ‘orbital’ as applied to electrons.
185
Re with an abundance of 37.1% and 187Re with b) Draw an s- and a p-orbital.
an abundance of 62.9%. c) How does a 1s-orbital differ from a
a) Calculate the weighted mean atomic mass of 2s-orbital?
rhenium. d) Place the following orbitals in order of
b) Why is the atomic mass described as increasing energy: 2p, 3d, 3s, 2p, 4p and 3p.
‘relative’? (3) e) How many electrons are there in:
15 Antimony has two main isotopes, 121Sb and 123Sb. i) a 3d-orbital
A forensic scientist was asked to help a crime ii) orbitals with a principal quantum
investigation by analysing the antimony in a number of 3? (7)
bullet. This was found to contain 57.3% of 121Sb 22 Bromine exists as a molecule with two bromine
and 42.7% of 123Sb. atoms combined together. Bromine has two
a) Calculate the relative atomic mass of the isotopes: bromine-79 and bromine-81.
sample of antimony from the bullet. Write a) A molecule of bromine containing two atoms
Chapter 2 Atoms and electrons

your answer to three significant figures. of bromine both with a mass number of 79
b) State one similarity and one difference can be written as 79 Br . Write the formulae for
35 2
between the isotopes in terms of the two other possible molecules of bromine.
subatomic particles. (5) b) The mass spectrum of molecules of bromine is
16 Draw the electrons in their orbits for each of the shown on the next page.
following elements: i) Explain why these peaks are observed.
a) 12
6
C ii) The peaks at 79 and 81 are the same
b) 19
F height. What does this tell you about the
9
relative abundances of the two isotopes?
c) 27
Al3+
13
iii) Explain why the peak at 160 is twice the
d) 12 2–
16
S (4) height of the peaks at 158 and 162. (7)

26

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 Practice questions
100
160

80
Relative abundance

60
158 162

40

20
79 81

0
80 100 120 140 160
m/z

a) Deduce the total number of electrons that can

Challenge
be held in the fourth and fifth shells.
23 Chlorine exists as a molecule with two chlorine b) The extra numbers of electrons are possible
atoms combined together. Chlorine has two because level 4 has f-orbitals and level 5 has
isotopes: chlorine-35 and chlorine-37. f- and g-orbitals. How many different f- and
The mass spectrum of chlorine is shown below. g-orbitals are there?
In November 1952, the first large thermonuclear
explosion was carried out in the Pacific Ocean. It
was codenamed ‘Mike’ and was the prototype of
Relative abundance

the ‘hydrogen bomb’.

In the fallout of that event, a new transuranic
element was identified. The element is called
einsteinium and has the symbol Es. It took until
1961 before enough of the element – 0.01 mg
– had been made to study its properties. It was
found that its atomic number was 99 and it had
at least two isotopic forms, with mass numbers
10 20 30 40 50 60 70
m/z 253 and 254. Since then, it has been established
that einsteinium has 14 isotopes.
a) The peak at 35 is three times as high as the
c) Give the numbers of protons, neutrons
peak at 37. Calculate the relative atomic mass
and electrons found in an atom of the
of chlorine.
einsteinium-253 isotope.
b) Explain why peaks are observed at 70, 72 and 74.
d) What is the difference in the number
c) The heights of the peaks at 70, 72 and 74 are
of particles present in the atoms of
in the ratio 9 : 6 : 1. Explain why the heights are
einsteinium-253 and einsteinium-254?
in this ratio.  (9)
e) Use your answer to part (a) to decide how
24 You have already learned that s-, p- and d-orbitals many 5f electrons there are in an atom of
can hold two, six and ten electrons respectively. einsteinium.
You might have noticed that there is a pattern to All elements with such high atomic numbers have
the total number of electrons that can be held in nuclei that break down spontaneously. This is the
the orbitals of each shell. For example, when n = cause of radioactivity. Usually this breakdown
1, only the 1s energy level is possible and it holds (known as decay) occurs in several steps,
two electrons. When n = 2, there are the 2s and 2p ultimately producing the element lead. In the
energy levels, so level 2 can hold a total of eight first step of its decay einsteinium releases alpha
electrons. Level 3 has the 3d-orbitals, which means radiation, which consists of particles containing
that level 3 can hold a total of 18 electrons. The two protons and two neutrons.
total number of electrons that can be held at the f) Suggest what happens to an atom of
various shells is given by the formula 2n2. einsteinium when it loses an alpha particle. (16)

27

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 Chapter 3
Compounds, formulae
and equations
Prior knowledge
In this chapter it is assumed you will be able to:
● recall the symbols and the charges carried by the ions of elements in

Groups 1, 2, 16 and 17
● recall the symbols and the charges carried by the ions of aluminium (3+),

zinc (2+), iron (both 2+ and 3+), copper (2+) and silver (1+)
● write the formulae of simple compounds based on the elements above
● recall the formulae H O, CO , H , O , N , Cl , Br , I , NH .
2 2 2 2 2 2 2 2 3

Test yourself on prior knowledge

Write the formula for each of the following compounds:
a) sodium chloride b) calcium oxide c) potassium oxide
d) zinc bromide e) magnesium bromide f) iron(iii) chloride
g) silver iodide h) sodium sulfide i) iron(ii) oxide
j) aluminium oxide k) nitrogen l) ammonia.

Formulae
Many experiments in chemistry require precise quantities of reagents to
be used. It is important to understand how these quantities are decided.
This involves first being able to write the correct formulae for simple
compounds, and then using these formulae to produce balanced equations
for chemical reactions. An equation does more than provide information
about what reacts together and what is produced; it gives exact details of
the numbers of particles – atoms, molecules or ions – that are involved.
This chapter should be studied carefully because much of what follows
in this book depends on your ability to apply the ideas met here. The
final section, covering ionic equations, can be studied now or left until
the work on structure and bonding (Chapter 7) has been completed.
The approach taken in this book uses the word ‘valency’ but you do not
need to know a definition or use the word in an exam. It is introduced
here as a helpful way to make sure the formulae you write are correct. If
you have learnt to obtain the formulae using another method this does
not matter: it is not the method you use but the answers that you obtain
that is important. You may be already familiar with the work covered in
this section of the book but it is of such importance that you should make
absolutely certain that this really is the case.
Although you may be able to write the formulae of the simple
compounds given in the ‘Test yourself’ section above you must also be
able to construct the formulae of a range of other compounds.
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 Formulae
The extensive range of compounds containing carbon is the basis of
organic compounds that are studied in later chapters of this book. Other
compounds based on metals are considered here.
Metal atoms usually lose electrons; non-metals usually gain or share
electrons. The number of electrons involved is a characteristic property
of the element known as its valency. For example, an atom of sodium
can lose only one electron, so sodium has valency 1. An atom of oxygen
can gain two electrons, so oxygen has valency 2.
A valency can also be given to groups of atoms. For example, a nitrate
group (NO3) consists of one nitrogen atom and three oxygen atoms
combined together and this whole unit has valency 1.
Valency does not specify whether electrons are gained or lost, but it is a
Tip helpful concept that can be used to generate correct formulae.

A copy of the periodic table is Table 3.1 is a list of the valencies that you should learn. The groups
provided in the examination. referred to in the table are those of the periodic table (page 116). Notice
that some metals can have more than one valency.

Table 3.1 Valencies of elements and groups of elements.

Valency Element/group losing electrons Element/group gaining electrons

1 All Group 1 elements, hydrogen (H), silver (Ag), All Group 17 elements, hydroxide (OH), nitrate (NO3),
ammonium (NH4), copper (Cu) hydrogencarbonate (HCO3)
2 All Group 2 elements, iron (Fe), copper (Cu), zinc (Zn), Oxygen (O), sulfur (S), sulfate (SO4), carbonate (CO3)
lead (Pb)
3 All Group 13 elements, iron (Fe)
4 Lead (Pb)

Tip Writing formulae

You can use the groups of the The second column in Table 3.1 contains electron givers (but also
periodic table (see Chapter 8) including ammonium). Electron givers make compounds with the electron
to help you remember some of receivers (non-metals or groups of non-metals) listed in the third column.
these valencies correctly. If each has the same valency, they combine directly. For example, the
formula of potassium bromide is KBr (both potassium and bromine have
valency 1) and the formula of barium oxide is BaO (both barium and
oxygen have valency 2).

Tip If the valencies differ, the numbers of the components have to be balanced
until each of their valencies is satisfied. For example, sodium has valency
Elements with valency 1 are 1 and oxygen has valency 2. In sodium oxide, the valency of oxygen must
called univalent. Those with be satisfied by the use of two sodium. The formula is Na2O. The subscript
valency 2 are divalent and 2 indicates that two sodiums are required for each oxygen. This balancing
those with valency 3 are called of valencies is essential. Sodium cannot form a compound of formula NaO.
trivalent. In terms of the electrons that are involved, each oxygen can react only by
receiving two electrons and each sodium can provide only one electron.
Therefore, it is necessary to have two sodiums for each oxygen.
Some further examples of using the valency table are given below.
● The formula of aluminium oxide is Al2O3. Aluminium has valency
3 and oxygen has valency 2 and to balance the valencies requires two
aluminium and three oxygen. Each then has a total valency of 6. In terms
29

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 of electrons, each of two aluminium atoms provides three electrons (total
six) and each of three oxygen atoms receives two electrons.
● The formula of magnesium nitrate is Mg(NO3)2.
Notice the use of brackets in the formula for magnesium nitrate.
Magnesium with valency 2 requires two nitrate units of valency 1. The
whole nitrate unit must be kept intact and brackets are used to make
this clear. They are essential to avoid the ambiguity of writing MgNO32.
Some elements can have more than one valency – for example, iron can
have a valency of 2 or 3 (Table 3.1). The name given to the compounds
reflects the valency of the element: for example, iron(ii) chloride indicates a
compound containing iron with valency 2; iron(iii) sulfate contains iron with
valency 3. The formulae are, therefore, FeCl2 and Fe2(SO4)3 respectively.
Once you have obtained the correct formulae you must understand
that metallic compounds are composed of ions. The charge on metal
ions is always positive and the size of the positive charge can often be
predicted using the Periodic Table on page 116.
Group 1 metals have a charge of 1+, whilst group 2 and 3 metals have
charges of 2+ and 3+ respectively. You will also have to recall the
names and formulae of the ammonium ion, NH4+ and the transition
metal ions Cu2+, Zn2+ and Ag+.
The charge on non-metallic ions is always negative. The size of the
negative charge can also often be predicted using the periodic table.
Group 17 ions have a charge of 1- whilst the charge of group 16 ions is
2-. You will also have to recall the names and formulae of nitrate, NO3−,
carbonate, CO32−, sulfate, SO42− and hydroxide, OH−.
The formulae you generate are such that they always have the
positive and negative charges of the ions in balance making the overall
compound neutral. For example magnesium nitrate is Mg(NO3)2 because
the magnesium has a charge of 2+ (Mg2+) whilst the nitrate ion has
a charge of 1- (NO3−), so two nitrate ions are required to balance the
charge on the magnesium ion. Ammonium sulfate is (NH4)2SO4 because
the ammonium has a charge of 1+ (NH4+) whilst the sulfate ion has a
Chapter 3  Compounds, formulae and equations

charge of 2- (SO42−), so two ammonium ions are required to balance the

charge on the sulfate ion.

Test yourself
1 Select the correct formula for the following 3 Write the correct chemical formula for each of the
compounds and explain your choice. following compounds and state the ions that each
a) calcium hydroxide: CaOH, CaOH2, Ca(OH)2 contains.
b) sodium sulfate: NaSO4, (Na)2SO4, Na2SO4, a) silver b) sodium c) zinc
Na2(SO)4 sulfate carbonate nitrate
c) iron(iii) chloride: Fe3Cl, FeCl3 d) iron(ii) e) iron(iii) f) aluminium
2 Use the data in Table 3.1 to answer the following bromide oxide sulfate
questions. 4 Write the formula for each of the following:
a) The formula of strontium bromide is SrBr2. a) lead(iv) b) tin(ii) c) iron(iii)
Deduce the valency of strontium. oxide chloride sulfate
b) The formula of sodium phosphide is Na3P. Deduce 5 Name the following compounds:
the valency of phosphorus. a) Fe2O3 b) PbO c) PbO2
d) Sn(NO3)2 e) PbI4 f) SnI4
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 Equations
Equations
Being able to state the correct formulae for substances is essential
when writing equations for chemical reactions. An equation includes the
reactants used and the products obtained and also indicates the number
of particles of each substance required. The following examples illustrate
the procedure involved.

Example 1
Write a balanced equation for the reaction of magnesium and oxygen to
make magnesium oxide.

Answer
First, write the correct formulae for the reactants and products:
Mg + O2 → MgO
Now examine the formulae to decide what numbers of each particle are
required and how much product is formed.
Oxygen is O2 (not ‘O’) and the formula of magnesium oxide is MgO, so two
particles of MgO are made. Therefore, the balanced equation is:
2Mg + O2 → 2MgO
When balancing an equation, you must not alter the formulae of the reactants
or products. These are fixed by the valency rules and must not be changed.
The equations can also be written using fractions to balance the equation.

Example 2
Write a balanced equation for the reaction between sodium hydroxide and
sulfuric acid to form sodium sulfate and water.

Answer
The unbalanced equation is:
NaOH + H2SO4 → Na2SO4 + H2O
Balancing is required, as follows:
2NaOH + H2SO4 → Na2SO4 + 2H2O
The formula of sodium sulfate indicates that 2NaOH are required.

Example 3
Write a balanced equation for the reaction between aluminium oxide and
sulfuric acid to form aluminium sulfate and hydrogen.

Answer
The unbalanced equation is:
Al2O3 + H2SO4 → Al2(SO4)3 + H2O
Balancing this equation is trickier. Note that to form the aluminium sulfate,
2Al are required and 3H2SO4 are needed to provide the sulfate. The balanced
equation is:
Al2O3 + 3H2SO4 → Al2(SO4)3 + 6H2O 31

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 In summary, the procedure to be adopted in balancing equations is:
● Use valencies to determine the correct formula of each reactant
and product.
● Write down the unbalanced equation with the reactants on the left-
hand side of the arrow and the products on the right-hand side.
● Make sure that the number of each atom on the left-hand side equals
the number on the right-hand side.
hydroxyde de potassium
(alcali fixe végétal pur)

acide sulfurique
+
(acide vitriolique pur)

+
hydroxyde de baryum
(terre pesante pur)

+
acide chlorhydrique
+
(acide marin pur)

eau
(eau)

Figure 3.1 A representation of a chemical equation from A dissertation of Elective

Attractions by Torben Bergman published in 1775.

State symbols
Equations can be made more informative by including state symbols.
The equation for the reaction between silver nitrate and potassium
bromide is as follows:
AgNO3 + KBr → AgBr + KNO3
Chapter 3  Compounds, formulae and equations

This is correctly balanced, but it does not indicate that the reaction
Tip occurs only if the silver nitrate and potassium bromide are both in
aqueous solution. Nor does it give the useful information that mixing
‘Aqueous solution’ means the solutions produces solid silver bromide. The physical state of the
dissolved in water. substances in the equation can be shown by including state symbols:
AgNO3(aq) + KBr(aq) → AgBr(s) + KNO3(aq)

Tip The symbol (aq) indicates aqueous solution; (s) indicates that the silver
bromide is a solid.
State symbols can often be
used to show what you expect There are four state symbols:
to observe in a reaction. In this ● (s) for a solid
case the calcium carbonate solid
reacts and disappears and you ● (l) for a liquid
would also see bubbles of gas ● (g) for a gas
given off.
● (aq) for an aqueous solution.

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 Ionic equations
The equation for the reaction of calcium carbonate with dilute
hydrochloric acid uses all four state symbols:
CaCO3(s) + 2HCl(aq) → CaCl2(aq) + CO2(g) + H2O(l)

Test yourself
6 Balance the following equations:
a) Zn + O2 → ZnO
b) Na + Cl2 → NaCl
c) CaO + HCl → CaCl2 + H2O
d) Zn + AgNO3 → Zn(NO3)2 + Ag
e) Fe + Cl2 → FeCl3
7 For each of the following reactions, first write an unbalanced equation
and then amend it to produce a balanced equation. Include state symbols
in your balanced equations.
a) sodium + oxygen → sodium oxide
b) zinc + hydrochloric acid → zinc chloride(solution) + hydrogen
c) magnesium carbonate(solid) + hydrochloric acid → magnesium
chloride(solution) + carbon dioxide + water
d) silver nitrate(solution) + copper chloride(solution) → silver
chloride(solid) + copper nitrate(solution)
e) copper(ii) oxide(solid) + nitric acid → copper(ii) nitrate(solution) + water
f) iron(iii) chloride(solution) + sodium hydroxide(solution) → iron(iii)
hydroxide(solid) + sodium chloride(solution)

Ionic equations
Tip In reactions involving ionic compounds (many acids and most compounds
containing a metal) it is not the whole compound that reacts but rather it
This section may be more fully is one or more of the ions that they contain. It therefore makes sense when
understood once Chapter 7 writing an equation to show only those ions that are actually reacting.
on bonding and structure has This is what an ionic equation does; it indicates those particles that react
been studied. and excludes those that, although present, take no part in the reaction.
Remember the ionic bonds in ionic compounds are formed by the electrical
attraction between the positive and negative ions, but the ions are still
separate from each other. When the compound is melted or dissolved in
water the ions become detached from each other and move around freely
and separately. This gives them the capacity to react independently.
By contrast, covalent substances have bonds that involve the sharing of
electrons. The shared electrons bind the atoms together and the molecules
stay as complete entities even when the substance is melted or dissolved.
In an aqueous solution of sodium chloride, the sodium ions and chloride
ions are moving freely and independently. In a solution of glucose –
which is covalent – the glucose molecules would be intact.

Writing an ionic equation

Aqueous silver nitrate reacts with aqueous sodium chloride to produce
insoluble silver chloride. However, it is more correct to say that silver
ions from the aqueous silver nitrate react with the chloride ions from the
aqueous sodium chloride to produce a precipitate of solid silver chloride.
It does not matter that it is a nitrate of silver or the chloride of sodium –
the reaction takes place as a consequence of silver ions and chloride ions 33

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 Tip being made mobile by the dissolving process. The reaction still occurs
if the metal ion associated with the chloride is, for example, potassium,
This reaction is the basis of a magnesium or copper and if the silver ion is dissolved as a sulfate.
method for identifying a chloride
in aqueous solution by adding A standard equation does not make this point clear. The reaction
aqueous silver nitrate (page 139). between silver nitrate and sodium chloride could be written as:
AgNO3(aq) + NaCl(aq) → AgCl(s) + NaNO3(aq)
Tip But this equation does not show that it is only the silver ion and the
Note that in the reaction chloride ion that react. The ionic equation shown below is more precise.
between silver nitrate and
Ag+(aq) + Cl–(aq) → AgCl(s)
sodium chloride, the product,
silver chloride, is included in It indicates that only aqueous silver ions and aqueous chloride ions are involved
the ionic equation but, in this in the reaction. Nitrate and sodium ions are present but do not change. They
example, sodium chloride is move freely and independently at the start of the reaction and also when the
absent. The difference is that reaction has finished. They are sometimes referred to as spectator ions.
when silver chloride is formed
Ionic equations may seem strange because it is not possible to have
as a solid, the silver ions and
silver or chloride ions in isolation; they have to be associated with other
chloride ions held together in
ions. Nevertheless, an ionic equation is a truer representation of what is
a crystal lattice, whereas when
occurring and they are widely used in chemistry.
sodium chloride is in solution, its
ions are free and independent.
Examples of ionic equations
Reaction between aqueous sodium hydroxide and
hydrochloric acid
Aqueous sodium hydroxide reacts with hydrochloric acid to produce aqueous
sodium chloride and water. This can be represented by the equation:
NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l)
Water is covalent and is, therefore, present as intact covalent molecules.
Sodium hydroxide and sodium chloride are ionic and so is the
hydrochloric acid. Their ions can behave independently.
The sodium ions and chloride ions are not changed by the reaction – they
remain in solution as free, independent ions. It is the hydroxide ions and the
Chapter 3  Compounds, formulae and equations

hydrogen ions that react. They combine to form covalent water molecules.
This is shown by the ionic equation:
H+(aq) + OH – (aq) → H2O(l)
This ionic equation demonstrates the important fact that all hydroxides
in aqueous solution react with a source of hydrogen ions (i.e. an acid) to
produce water.

Reaction between a carbonate and an acid

Aqueous sodium carbonate reacts with hydrochloric acid to produce
sodium chloride, carbon dioxide and water:
Na2CO3(aq) + 2HCl(aq) → 2NaCl(aq) + CO2(g) + H2O(l)
The sodium ions and chloride ions are not involved in the reaction –
they remain unchanged in solution. The carbonate ions and hydrogen
ions react to form the two covalent products, carbon dioxide and water.
This is represented by the ionic equation:
34
CO32–(aq) + 2H+(aq) → CO2(g) + H2O(l)

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 Ionic equations
Ionic equations must be balanced. In the example above, a ‘2’ has to be
placed before the ‘H+’. The equation indicates that all carbonates react with
acids to form carbon dioxide and water. For sulfuric acid, the equation is:
Na2CO3(aq) + H2SO4(aq) → Na2SO4(aq) + CO2(g) + H2O(l)
However the ionic equation is the same as for the reaction between
sodium carbonate and hydrochloric acid:
CO32–(aq) + 2H+(aq) → CO2(g) + H2O(l)
Do not be tempted to write ‘H2+(aq)’ or ‘H22+(aq)’ to represent the
hydrogen ions arising from H2SO4. Once in solution, the ions are detached
and are simply H+. The equation shows that two hydrogen ions are needed
for each carbonate ion. ‘H2+(aq)’ would imply that the two hydrogen atoms
are bonded covalently and have acquired a positive charge; ‘H22+(aq)’
indicates the same, but with a charge of ‘2+’. Neither representation is
correct.

Reaction between zinc and aqueous copper sulfate

Zinc metal reacts with aqueous copper sulfate to form copper metal and
aqueous zinc sulfate, according to the equation:
Zn(s) + CuSO4(aq) → Cu(s) + ZnSO4(aq)
Copper sulfate and zinc sulfate are both ionic, so the ionic equation for
this reaction is:
Zn(s) + Cu2+(aq) → Cu(s) + Zn2+(aq)

Reaction between solid magnesium oxide and hydrochloric

acid
Remember that ionic substances must be in solution to exist as free
ions. The equation for the reaction of solid magnesium oxide with
hydrochloric acid to form magnesium chloride and water is as follows:
MgO(s) + 2HCl(aq) → MgCl2(aq) + H2O(l)
In this case, the ions in the solid magnesium oxide are held in an ionic
lattice and are not free to move. The only ions that are ‘free’ throughout
this reaction are the chloride ions. Therefore, the ionic equation is:
MgO(s) + 2H+(aq) → Mg2+(aq) + H2O(l)
During this reaction the magnesium oxide lattice breaks down, releasing
magnesium ions into the solution. The oxide ions combine with the
hydrogen ions from the acid to form water.

Test yourself
8 Write ionic equations for each of the reactions below. Include state symbols.
a) reacting aqueous silver nitrate and aqueous sodium bromide to produce
a precipitate of silver bromide and a solution of sodium nitrate
b) reacting aqueous barium chloride and aqueous sodium sulfate to produce
a precipitate of barium sulfate and a solution of sodium chloride
c) reacting sulfuric acid and aqueous sodium hydroxide
d) reacting hydrochloric acid and aqueous potassium carbonate
e) reacting magnesium and aqueous zinc chloride
f) reacting solid zinc oxide and sulfuric acid
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 Practice questions
Multiple choice questions 1–10 6 If the formula of nitrous acid is HNO2, which one
1 Which one of the following is the correct formula of the following is the formula of calcium nitrite?
of chromium(iii) hydroxide ? A CaNO2
A Cr3OH B Ca2NO2
B Cr3(OH) C Ca(NO2)2
C CrOH3 D Ca(NO)2
D Cr(OH)3
7 If the formula of iron(iii) arsenate is FeAsO4, the
2 Which one of the following is the correct formula formula of iron(ii) arsenate will be
of cerium(iv) sulfate? A Fe(AsO4)2
(The symbol for cerium is Ce.) B Fe(AsO4)3
A Ce(SO)4 C Fe2(AsO4)3
B Ce(SO4)2 D Fe3(AsO4)2
C Ce(SO4)4
Use the key below to answer Questions 8, 9 and 10.
D Ce4SO4
A B C D
3 When magnesium hydroxide reacts with
1, 2 & 3 correct 1, 2 correct 2, 3 correct 1 only correct
hydrochloric acid magnesium chloride and water
are formed. 8 Gallium is in Group 13 of the periodic table.
Which one of the following gives the correct Which of the following give correct information
balancing numbers in the equation? about gallium compounds?
1 Gallium hydroxide has three times as many
Magnesium Hydrochloric Magnesium Water
hydroxide ions as gallium ions.
hydroxide acid chloride
2 Gallium oxide has 1½ times as many oxide
A 1 1 1 1
ions as gallium ions.
B 1 2 1 1
3 Gallium bromide has three times as many
C 1 2 1 2
bromide ions as gallium ions.
D 1 2 2 2
9 Which of the following ions are present in a
4 Aqueous potassium hydroxide reacts with
mixture of aqueous sodium sulfate and aqueous
aqueous sulfurous acid (H2SO3) to form aqueous
sodium nitrate?
potassium sulfite and water.
1 Na2+(aq)
Chapter 3 Compounds, formulae and equations

Which one of the following gives the correct ionic

equation for this reaction? 2 SO42–(aq)
A H+(aq) + OH–(aq) → H2O(l) 3 NO3–(aq)
B 2H+(aq) + OH–(aq) → H2O(l) 10 The correct ionic equation for the reaction of
C 2H (aq) + O (aq) → H2O(l)
+ 2– solid zinc carbonate with hydrochloric acid is:
ZnCO3(s) + 2H+(aq) → Zn2+(aq) + CO2(g) + H2O(l)
D 2K+(aq) + SO32–(aq) → K2SO3(aq)
Which of the following give a correct explanation
5 Aqueous barium nitrate reacts with aqueous of this equation?
magnesium sulfate to form aqueous magnesium
1 The zinc carbonate is written as its full
nitrate and a precipitate of barium sulfate.
formula, ZnCO3(s), as its ions are not free
Which one of the following gives the correct ionic
to move.
equation for this reaction?
2 The carbon dioxide is written as its full
A Ba+(aq) + SO42–(aq) → Ba2SO4(s) formula as it does not contain ions.
B Ba2+(aq) + SO42–(aq) → BaSO4(s) 3 The chloride ion from the hydrochloric acid is
C Ba+(aq) + SO4–(aq) → BaSO4(s) excluded from the equation because it is not
D Ba2+(aq) + SO4–(aq) → BaSO4(s) present when the reaction has finished.

36

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 Practice questions
11 Identify which of the following substances are ionic a) Write equations, including state symbols,
and give the formulae of the ions formed when the for the sequence of reactions that are
substances are dissolved in an aqueous solution. taking place.
a) NaNO3 b) Write ionic equations for each reaction in
b) NO the sequence. (6)

c) CCl4 16 Write ionic equations for the following reactions.

d) Pb(NO3)2 Include appropriate state symbols.
a) silver nitrate solution + potassium iodide
e) K2SO4
solution → silver iodide precipitate +
f) CH4 potassium nitrate solution
g) H2SO4 b) potassium hydroxide solution + nitric acid →
h) MgCl2 (8) potassium nitrate solution + water
c) zinc metal + hydrochloric acid → zinc
12 Write equations for each of the following chloride solution + hydrogen gas
reactions: d) magnesium metal + copper sulfate solution →
a) hydrogen + copper oxide → copper + water magnesium sulfate solution + copper metal
b) potassium hydroxide + nitric acid → e) lithium carbonate solution + hydrochloric acid
potassium nitrate + water → lithium chloride solution + carbon dioxide
c) calcium hydroxide + hydrochloric acid → + water
calcium chloride + water f) sodium hydroxide solution + copper nitrate
solution → copper hydroxide precipitate +
d) sodium + water → sodium hydroxide + hydrogen
sodium nitrate solution
e) chlorine + potassium iodide → potassium g) sodium hydroxide solution + aluminium
chloride + iodine sulfate solution → aluminium hydroxide
f) magnesium + aluminium sulfate → precipitate + sodium sulfate solution
magnesium sulfate + aluminium (6) h) zinc oxide solid + hydrochloric acid → zinc
13 A surprising use of copper is to remove hydrogen chloride solution + hydrogen (8)
sulfide from beer. During fermentation, hydrogen 17 The chemical industry processes large amounts
sulfide is produced as a natural by-product. of limestone (calcium carbonate). It is heated
However, because of its unpleasant odour, even to produce calcium oxide for use in cement
tiny amounts can spoil the flavour of the beer. production and in neutralising excess acidity in
Low concentrations of copper ions are sufficient to soils (liming). Carbon dioxide is given off when
give a precipitate of copper sulfide, which is then limestone is heated.
removed, leaving the beer free from this impurity. Calcium oxide is also used in a reaction with
Write an ionic equation for this reaction. (2) carbon to form an unusual compound, calcium
14 a) The formula of rubidium chloride is RbCl. carbide, CaC2, with carbon dioxide as a by-
What is the formula of rubidium sulfate? product. Calcium carbide, CaC2, reacts with
b) The formula of manganese sulfate is MnSO4. water to produce the flammable gas ethyne
What is the formula of manganese bromide? (acetylene), C2H2.
c) The formula of chromium chloride is CrCl3. Calcium oxide reacts with water to form calcium
What is the formula of chromium sulfate? hydroxide. Calcium hydroxide reacts with chlorine
d) The formula of silver phosphate is Ag3PO4. to produce an aqueous paste of bleaching
What is the formula of phosphoric acid? (4) powder. This is a mixture of water, calcium
chloride and calcium hypochlorite, Ca(OCl)2.
15 When iron reacts with hydrochloric acid, iron(ii) Calcium hydroxide is also used for liming and, in
chloride and hydrogen are produced. If chlorine one industrial process, in a reaction with sodium
gas is passed into the iron(ii) chloride solution carbonate to produce sodium hydroxide and a
it reacts to form iron(iii) chloride. The iron(iii) precipitate of calcium carbonate.
chloride reacts with potassium iodide to form Write equations for the following reactions:
iron(ii) chloride, potassium chloride and a a) the action of heat on calcium carbonate
precipitate of iodine is obtained. b) the reaction between water and calcium oxide
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 c) the reaction between calcium hydroxide and i) copper ethanoate
sodium carbonate ii) copper arsenite. (5)
d) the reaction between calcium oxide and carbon
19 Scheele’s Green (copper hydrogenarsenate,
e) the reaction between calcium carbide and water CuHAsO3) was developed in the nineteenth
f) the production of bleaching powder. (6) century to improve the variety and quality of
dyes. It was used by wallpaper manufacturers;
Challenge William Morris included it as a dye. They were
18 One of the biggest challenges for firework either unaware of or indifferent to the fact that
manufacturers is creating satisfactory blue colours the formulation is poisonous. Miners at the Devon
for stars and cascades. Copper(ii) chloride can give Great Consuls mine near Tavistock who extracted
this colour when mixed with a reagent such as the arsenic ore from which Scheele’s Green was
potassium chlorate, but it tends to be unstable at made suffered badly from the effects of their work.
high temperature and the colour is then lost. A recipe from the nineteenth century describes a
Copper chloride is manufactured either by the process for making Scheele’s Green:
reaction of chlorine directly with copper metal or ● A mixture of arsenic(iii) oxide is boiled with
by dissolving copper oxide in dilute hydrochloric potassium carbonate and water until no more
acid. The potassium chlorate (KClO3) releases carbon dioxide is produced. In this reaction
oxygen to the firework mixture by decomposing potassium hydrogenarsenate is also formed.
to form potassium chloride. ● A solution of copper sulfate is then added
a) Write an equation to represent: to this mixture and an impure precipitate of
i) the reaction between chlorine and Scheele’s Green is formed.
copper metal Some purification is then required before a usable
ii) the reaction between copper oxide and powder is obtained.
dilute hydrochloric acid a) Deduce the formula of potassium
iii) the decomposition of potassium chlorate. hydrogenarsenate.
A mixture that has been proposed to intensify b) Suggest an equation for the reaction described
the blue colour includes a pigment called Paris in the first bullet point above. (Note: water is
Green. This pigment is a salt containing one part required as a reactant.)
of copper ethanoate and three parts of copper c) Suggest an equation for the reaction in the
arsenite. The ethanoate ion has the formula second bullet point. (5)
CH3CO2–. The formula of the arsenite ion is AsO2–.
b) Write the formula for:
Chapter 3  Compounds, formulae and equations

38

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 Chapter 4
Amount of substance –
moles in solids and gases
Prior knowledge
In this chapter it is assumed you will be able to:
● write the formulae of simple substances
● write balanced equations including state symbols.

You will also need to be confident at:

● rearranging equations
● understanding significant figures
● understanding standard (index) form.

Test yourself on prior knowledge

1 Write equations for the following reactions, including state symbols:
a) heating calcium carbonate to produce calcium oxide
b) copper carbonate and nitric acid to form copper nitrate, carbon
dioxide and water
c) magnesium and aluminium oxide
d) zinc and aqueous silver nitrate
e) the decomposition of iron(iii) oxide to iron(ii) oxide and oxygen.
2 If n = m/M,
a) write m in terms of n and M
b) write M in terms of n and m.
3 Write each of the following numbers to three significant figures.
a) 20.78 e) 0.6577
b) 18.85 f) 0.05232
c) 15.448 g) 0.003987
d) 207.341
4 Write each of the numbers in Question 3(d)–(f) in standard (index) form.
5 Write each of the following numbers in non-standard form.
a) 3.02 × 102 c) 2.25 × 10 -2
b) 4.57 × 10 3
d) 4.11 × 10 -4

Relative atomic mass

Nineteenth-century chemists established the formulae of common
substances and also calculated the relative masses of the atoms from
which they are made. It was by no means an easy task and it took several
decades before agreement was reached. What they discovered was not the
individual masses of the atoms – they knew that atoms were small and
would have assumed that it would never be possible to know these values
– but how the masses of atoms compared with each other. For example,
it was established that a sulfur atom was twice as heavy as an oxygen
atom and that an oxygen atom was 16 times heavier than a hydrogen
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 Key term atom. A nominal value of 1 was assigned to the mass of the lightest atom,
hydrogen, and the masses of other elements were reported relative to
Relative atomic mass is the this standard. Thus, the relative mass of an oxygen atom is approximately
weighted mean mass of an atom 16 and that of a sulfur atom, 32. Every element can be given a number
1
of an element compared with that indicates its atomic mass relative to that of a hydrogen atom. These
12
the mass of an atom of carbon-12, numbers are now known to relate to the sum of the numbers of protons
which is taken as exactly 12. and neutrons present in the nucleus of an atom (Chapter 2).
For many years this was the basis on which the masses of atoms were
compared. The choice of the lightest element as the standard may seem
Tip the most obvious thing to do, but the situation becomes more complex
As explained in Chapter 2 the when isotopes are taken into account. This is one reason why the
expression ‘weighted mean standard element used for comparison today is the isotope of carbon
mass’ takes into account that has mass number 12.
isotopes that are present in The mass of an element compared to carbon-12 is called the relative
different amounts. atomic mass.
Relative atomic masses have no units because they are a comparison
Tip between the element and carbon-12.

It is a common mistake in exams Relative atomic masses are listed in most versions of the Periodic Table
to give relative atomic mass a (page 116). They will be available to you in an examination, so you do
unit such as grams. Remember not have to learn them.
that it is just a number with no
units. When using the Periodic Definitions linked to relative atomic mass
Table, make sure that you do Other definitions follow from the definition for relative atomic mass.
not use the atomic number by The relative isotopic mass for a particular isotope of an element is
mistake. For example, the atomic closely related.
number of oxygen is 8, but its
relative atomic mass is 16. A similar statement can be made for compounds. If the compound
is covalent (Chapter 7), the smallest unit is a molecule, so the term
relative molecular mass is used.
Chapter 4  Amount of substance – moles in solids and gases

Key terms For ionic substances (such as those containing a metal) the smallest
Relative isotopic mass is the mass units are the ions indicated by their formulae and the expression
of an atom of an isotope of the relative formula mass should be used. Relative formula mass can also
1 be used when referring to covalent compounds.
element compared with the
12
mass of an atom of carbon-12,
which is taken as exactly 12. Tip
Relative molecular mass is It is incorrect to call the smallest unit of an ionic compound a molecule.
the weighted mean mass of If you are in doubt as to whether a compound is covalent or ionic, always
a molecule of the compound use the expression relative formula mass or where appropriate use the
1
compared with the mass of formula of the substance.
12
an atom of carbon-12, which is
taken as exactly 12.
Relative formula mass is the
weighted mean mass of a Obtaining relative molecular mass and relative
formula unit of the compound formula mass
1 The relative molecular or formula mass of a compound is obtained by
compared with the mass of
12
an atom of carbon-12, which is adding together the relative atomic masses of its component atoms. In
taken as exactly 12. each of the following examples, the values of the relative atomic masses
have been obtained from the Periodic Table (page 116).
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 Relative atomic mass
Example 1
Glucose has the formula C6H12O6. What is its relative molecular mass?
Answer
The relative molecular mass of glucose is (6 × 12.0) + (12 × 1.0) + (6 × 16.0)
= 180.0.

Example 2
Magnesium carbonate has the formula MgCO3. What is its relative formula mass?
Answer
The relative formula mass of magnesium carbonate is 24.3 + 12.0 + (3 × 16.0)
= 84.3.

Example 3
Copper sulfate crystals have the formula CuSO4 5H2O. What is the relative
●

Tip
formula mass of copper sulfate?
Many students misread the Answer
formula of crystals such as The formula CuSO4 5H2O means that there are five molecules of water for
●

CuSO4 5H2O and wrongly

●
each CuSO4. Therefore its relative formula mass is 63.5 + 32.1 + (4 × 16.0) +
interpret the formula to contain (5 × 18.0) = 249.6.
one Cu, one S, four oxygen,
ten hydrogen and one more
oxygen. The ‘5’ in front of the
Note that ‘relative formula mass’ is used in Examples 2 and 3 instead
H2O shows that the formula unit
of relative molecular mass, because magnesium carbonate and copper
contains five H2O molecules.
sulfate are ionic.
With more complicated formulae, be careful to use the correct number
of atoms of each type. For example, calcium nitrate has the formula
Ca(NO3)2, which means that it contains one calcium, two nitrogens and
six oxygens – the brackets mean that there are two NO3− ions.

Test yourself
1 For each of the following, write the formula and calculate the relative
formula mass:
a) lithium chloride b) potassium bromide
c) magnesium hydroxide d) sulfuric acid
e) sodium sulfate f) barium nitrate
g) iron(ii) chloride h) iron(iii) sulfate
i) sodium carbonate crystals j) iron(ii) sulfate crystals
(Na2CO3 10H2O)
●
(FeSO4 7H2O).
●

2 Calculate the relative molecular mass of each of the following covalent

compounds:
a) ethane, C2H6 b) ethanol, C2H5OH
c) ethanoic acid, CH3COOH d) chloromethane, CH3Cl
e) aminoethane, C2H5NH2 f) nitrogen gas.

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 Key term The mole
One mole (abbreviated mol) is The relative formula masses that you have calculated are related by
the amount of substance that their definition to the mass of carbon-12 and each of these masses will
contains as many elementary contain a fixed number of particles which is known as the mole.
particles as there are atoms in You can have a mole of atoms, molecules or any other unit. When
exactly 12g of carbon-12. Its writing 1 mole of something you should be precise about what it is the
symbol is ‘mol’. mole refers to. So you can refer to 1 mole of oxygen atoms
(meaning O) or 1 mole of oxygen molecules (meaning O2). When
considering an ionic compound such as sodium chloride, you should
write 1 mole of NaCl.

Example 4
The balanced equation for the reaction between magnesium and oxygen is:
2Mg(s) + O2(g) → 2MgO(s)
State what this indicates about the amounts in mol required for the reaction
and the amount in mol of MgO obtained.
Figure 4.1 One mole amounts of copper
(Cu), carbon (C), iron (Fe), aluminium (Al), Answer
mercury (Hg) and sulfur (S).
2Mg(s) + O2(g) → 2MgO(s)
Tip
This means that 2 mol of magnesium atoms reacts with 1 mol of oxygen
Do not make the mistake of molecules to form 2 mol of magnesium oxide.
reading the amount in moles of
O2 as being ‘2 mol’ just because
the formula of oxygen has Example 5
two atoms combined together.
The balanced equation for the reaction between hydrogen and oxygen is:
This would be incorrect. It is
the balancing coefficients in 2H2(g) + O2(g) → 2H2O(l)
the equation that tell you the
Chapter 4  Amount of substance – moles in solids and gases

State what this indicates about the amounts in mol required for the reaction
amount in moles. So in this case
and the amount in mol of water molecules obtained.
it is 1 mol of O2 molecules.
Answer
The equation tells us that 2 mol of hydrogen molecules react with 1 mol of
oxygen molecules to form 2 mol of water molecules.

Test yourself
3 For the following balanced equations, write down the amounts in mol of
each reactant used and the amount in mol of the product obtained.
a) Mg + S → MgS b) S + O2 → SO2
c) Zn + I2 → ZnI2 d) N2 + O2 → 2NO
e) N2 + 3H2 → 2NH3 f) 2Al + 3O2 → Al2O3

The Avogadro Constant, NA

The scientists who painstakingly compiled the relative masses of the
atoms in the 19th century might not have thought it possible to count
how many atoms there were in a mole of substance. However, advances
in understanding and the availability of sophisticated measuring devices
have since made this possible.
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 Relative atomic mass
It turns out that 6.02 × 1023 atoms (602 000 000 000 000 000 000 000
atoms) of carbon are needed to obtain a mass of 12.0 g and this number
is referred to as the Avogadro constant and given the symbol NA. Since
the mole of any substance contains the same number of particles as
carbon-12 it follows that the Avogadro constant is also the number of
particles that are present in 1 mole of any substance. For example 1 mol
of sodium atoms is the mass that contains NA atoms of sodium and this
has a mass of 23.0g.
Knowing the Avogadro constant allows you to determine the number of
particles that are present in a given mass.

Example 6
What is the number of atoms in 0.391 g of potassium?

Answer
1 mole of potassium atoms has a mass of 39.1 g and this mass contains
Avogadro’s number (NA) of atoms i.e 6.02 × 1023.
1
0.391 g is th of the mass of 1 mole of potassium.
100
1
So the number of atoms of potassium is 6.02 × 1023 × = 6.02 × 1021 atoms.
100

Key term Molar mass (M)

The molar mass of a substance The molar mass of a substance is the same as the formula mass
is the mass of one mole of a expressed in grams per mole. So the molar mass of sodium is 23 g mol-1
substance. It has units of g mol-1. and the molar mass of methane, CH4 , is 16.0 g mol-1.

The relationship between amounts in moles and

masses in grams
You cannot measure the amount of substance in moles in the
Tip laboratory so in order to decide what mass you would need for a
To emphasise how the terms are balanced chemical reaction you need to know how the amount of
related and to show how careful substance measured in moles relates to the mass of that substance.
you must be to supply the The mass of substance is related to the amount of substance using
correct units, note the following: the equation:
The relative molecular mass of Mass in grams (m) = the amount of substance in mol (n) × the molar
methane, CH4, is 16.0. mass of the substance (M)
The mass of 1 mol of methane
molecules is 16.0 g. From this, it follows that
m
The molar mass of methane is M= n
16.0 g mol-1.
The relative formula mass of zinc and
m
sulfide is 97.5. n=
The mass of 1 mol of ZnS is 97.5 g.
M
The molar mass of ZnS is These relationships enable you to calculate the masses to use in a
97.5 g mol-1. reaction and to determine the masses of the products that would
be obtained.

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 Tip Example 7
Using the correct unit for a Calculate the amount in moles of 4.52 g of carbon atoms.
quantity can be easily forgotten Answer
but must not be ignored. Try to The molar mass of carbon is 12.0 g mol-1.
get into the habit of thinking
mass in grams (m ) 4.52 g
about the correct unit every amount in moles (n ) = = = 0.377 mol
molar mass (M ) 12.0 g mol −1
time you write a number down.
Units can be helpful in reminding
you of the relationship between Example 8
quantities. The units of molar
mass indicate that it must relate Calculate the amount in moles of 5.00 g of chlorine gas molecules.
to a mass in g divided by an Answer
amount in mol. The molar mass of Cl2 = 71.0 g mol-1.
mass in grams (m ) 5.00 g
amount in moles (n ) = = = 0.0704 mol
molar mass (M ) 71.0 g mol −1

Example 9
Calculate the amount in moles of 8.48 g of CaSO4.
Answer
The molar mass of calcium sulfate, CaSO4 = 40.1 + 32.1 + (4 × 16.0)
= 136.2 g mol-1
Test yourself m 8.48 g
n= = = 0.0623 mol
4 How many atoms are there in M 136.2 g mol −1
2.00 g of magnesium?
5 Determine the amount in moles
in each of the following: Example 10
a) 2.4 g of magnesium Calculate the mass (in grams) of 0.25 mol of CaCO3.
b) 4.8 g of oxygen molecules
Answer
c) 1.68 g of calcium oxide.
Chapter 4  Amount of substance – moles in solids and gases

The molar mass of calcium carbonate, CaCO3 = 40.1 + 12.0 + (3 × 16.0)

6 Calculate the mass (in grams) of
each of the following: = 100.1 g mol-1
a) 0.5 mol of argon atoms mass in grams (m) = amount in moles (n) × molar mass (M)
b) 0.2 mol of KCl. mass of 0.25 mol = 0.25 g mol × 100.1 g mol-1 = 25.025 g
7 Calculate the molar mass of
each of the following and use
the Periodic Table to identify Example 11
the element:
a) 0.1 mol of an element that Calculate the molar mass of an element if 0.10 mol has a mass of 6.54 g.
has a mass of 10.79 g Answer
b) 0.05 mol of an element that mass in grams (m ) 6.54 g
molar mass (M ) = = = 65.4 g mol −1
has a mass of 2.60 g. amount in moles (n ) 0.10 mol
8 Calculate the molar mass
of each of the following
compounds in which: The balanced equation for a reaction gives information about the
a) 0.03 mol has a mass of 1.92 g amounts in moles required. It is possible to determine the masses
b) 0.75 mol has a mass of 43.88 g. required for the reaction and the masses of the products obtained using
the relationship between m, n and M.

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 Relative atomic mass
Example 12
 hat mass of sulfur will react with 1.86 g of iron and what mass of iron(iii)
W
sulfide will be formed? The equation for this reaction is:
2Fe + 3S → Fe2S3
Answer
The molar mass (M) of iron is 55.8 g mol-1 so the amount in mol used is
m/M = 1.86/55.8 = 0.033 mol.
The equation indicates that 2 mol of iron atoms react with 3 mol of sulfur
atoms to make 1 mol of Fe2S3.
Therefore 0.033 mol of iron atoms will react with 0.033 × 3/2 = 0.05 mol of
sulfur atoms.
The molar mass of sulfur is 32.1 g mol-1.
m = n × M so 0.05 mol of sulfur has a mass of 0.05 × 32.1 = 1.605 g.
The molar mass of iron(iii) sulfide is (2 × 55.8 + 3 × 32.1) = 207.9 g mol-1.
So the mass of iron(iii) sulfide formed would be (0.033/2) × 207.9 = 3.465 g.
Since no mass is lost during the reaction, the mass of iron(iii) sulfide
could also have been obtained by adding together the masses of iron
and sulfur used.

Example 13
 alculate the mass of silver formed when 3.27 g of zinc reacts completely
C
with excess silver nitrate solution.
Answer
The equation for this reaction is:
Zn(s) + 2AgNO3(aq) → Zn(NO3)2(aq) + 2Ag(s)
The molar mass of zinc is 65.4 g mol-1 so the amount in mol used is
m/M = 3.27/65.4 = 0.05 mol.
The equation indicates that 1 mol of zinc atoms make 2 mol of silver atoms.
Therefore 0.05 mol of zinc will make 2 × 0.05 = 0.10 mol of silver.
The molar mass of silver is 107.9 g mol-1.
m = n × M so 0.10 mol of silver has a mass of 0.10 × 107.9 = 10.79 g.

Example 14
 alculate how many tonnes of iron would be produced in a blast furnace
C
from 39.9 tonnes of iron ore, Fe2O3.
2Fe2O3 (s) + 3C (s) → 4Fe (s) + 3CO2 (g)
Answer
Tip The molar mass of Fe2O3 is (2 × 55.8) + (3 × 16.0) = 159.6 g mol-1.
If questions involve quantities If 39.9 g had reacted, the amount in mol used, n = m/M = 39.9/159.6
in tonnes (or any units of mass = 0.25 mol.
such as kg, mg or µg), it is easier The equation indicates that 2 mol of Fe2O3 react to produce 4 mol of iron.
to do the equivalent calculation Therefore, 1 mol of Fe2O3 produces 2 mol of Fe.
in grams and then change this Therefore, 0.25 mol of Fe2O3 will produce 0.50 mol of Fe.
into tonnes (or kg, mg or µg). The molar mass of iron is 55.8 g mol-1.
Using tonnes instead of grams is m = n × M so 0.50 mol of iron has a mass of 0.5 × 55.8 = 27.9 g.
common in exam questions. It follows that 39.9 tonnes of iron(iii) oxide produces 27.9 tonnes of iron. 45

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 Test yourself
  9 What mass of aluminium oxide can be obtained by reacting 8.00 g of
aluminium with excess oxygen?
4Al(s) + 3O2(g) → 2Al2O3(s)
10 What mass of zinc chloride is obtained by reacting 3.25 mg of zinc with
excess chlorine?
Zn(s) + Cl2(g) → ZnCl2(s)
11 What mass of calcium oxide would be obtained by heating 2002 tonnes
of limestone (CaCO3)?
CaCO3(s) → CaO(s) + CO2(g)

Empirical formulae
An experiment to find an empirical formula involves measuring the
Tip masses of elements that combine in the compound. From these masses,
it is possible to calculate the amounts in moles of the atoms that react
Determining empirical formulae and this gives their ratio. This then can be converted into the simplest
is often important in establishing whole number ratio for the atoms of the different elements in the
the formulae of organic compound.
compounds. You will find further
examples of the procedure in This can be summarised as:
simplest whole
Chapter 12. mass in grams convert
 into → amount in moles convert
 into →
number ratio

Example 15
Analysis of 20.1 g of iron bromide showed that it contained 3.8 g of iron and
16.3 g of bromine. What is its empirical formula?

Answer
Chapter 4  Amount of substance – moles in solids and gases

The calculation is summarised in the table below.

Fe Br
Mass in grams 3.8 16.3
Amount in moles 3.8/55.8 = 0.068 16.3/79.9 = 0.204
Simplest ratio 0.068/0.068 = 1 0.204/0.068 = 3
Empirical formula FeBr3

Key terms
Water of crystallisation is the
water present in hydrated salts. Water of crystallisation
A hydrated compound contains Anhydrous and hydrated salts
water as part of its structure.
Anhydrous is the term used to All salts exist in the solid state either as pure substances or in the form
describe a hydrated compound of crystals that contain water molecules as part of their structure.
after it has lost its water of The pure substance is anhydrous, which means that it contains no
crystallisation. water. The crystals containing water are said to possess water of
crystallisation and are, therefore, hydrated.

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 Relative atomic mass
The water in hydrated salts is indicated by writing the formula of the
substance followed by a full stop and the number of molecules of water.
For example, iron(ii) sulfate crystals have the formula FeSO4 7H2O. ●

Given the relationship between mass in grams and the amount of

substance in moles (page 43), you should be able to use experimental
data to determine the formula of a hydrated salt, as illustrated in the
worked example below.

Example 16
A sample of copper sulfate crystals has a mass of 6.80 g. The sample is heated
to drive off all the water of crystallisation. The mass is reduced to 4.35 g.
Calculate the formula of the copper sulfate crystals.

Answer
mass of water in the crystals driven off by the heating = 6.80 − 4.35 = 2.45 g
2.45
amount (in moles) of water of crystallisation = = 0.136 mol
18
molar mass of anhydrous copper sulfate = 63.5 + 32.1 + (4 × 16.0) = 159.6g
4.35
amount (in moles) of anhydrous copper sulfate = = 0.02726 mol
159.6
ratio of moles of anhydrous copper sulfate to moles of
water = 0.02726:0.136 or 1:5
Therefore, the formula of hydrated copper sulfate is CuSO4 5H2O.
●

Example 17
A sample of magnesium sulfate crystals contains 9.78% Mg2+, 38.69% SO42−
and 51.53% H2O by mass.
Determine the formula of the crystals.

Answer
9.78
amount (in moles) of magnesium = = 0.4025 mol
24.3
amount (in moles) of sulfate = 38.69 = 0.4026 mol
96.1
51.53
amount (in moles) of water = = 2.863 mol
18
ratio = 0.4025:0.4026:2.863 or 1:1:7
Therefore, the formula of magnesium sulfate crystals is MgSO4 7H2O.
●

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 Activity
Experiment to determine the number of molecules of water of crystallisation
in FeSO4 xH2O
●

Crystalline salts often contain water bound up in the crystal. There is a fixed ratio
between the number of molecules of water and the number of formula units of the salt.
The apparatus is set up as shown below.
Method
crucible
a) Weigh the crucible and record the mass. hydrated
b) Half fill the crucible with hydrated iron (ii) FeSO4•xH2O
sulphate and reweigh.
c) Support the crucible on a pipe clay triangle
on a tripod and heat using a clean blue flame
which should be low at first and gradually
increased.
d) Heat strongly for about five minutes until no
further change is observed.
e) Allow to cool and then reweigh the crucible
together with its contents.
f) Reheat the crucible, then cool and reweigh.
g) Repeat (f) until successive weighings are
identical.
Results Figure 4.2
Mass of crucible = 19.75g
Mass of crucible + hydrated iron(ii) sulphate = 22.53g
Mass of crucible + anhydrous iron(ii) sulphate (first) = 21.46g
Mass of crucible + anhydrous iron(ii) sulphate (second) = 21.27 g
Mass of crucible + anhydrous iron(ii) sulphate (third) = 21.27 g
Chapter 4  Amount of substance – moles in solids and gases

Questions
1 What do you initially see happening when the crystals are heated?
2 How do you know that all the water of crystallisation has been lost?
3 What was the mass of hydrated iron(ii) sulfate at the start of the experiment?
4 What mass of anhydrous iron(ii) sulfate remained at the end?
5 What is the mass of water lost from the hydrated iron(ii) sulfate?
6 What is the mass ratio of anhydrous iron(ii) sulfate : water?
7 What is the mole ratio of anhydrous iron(ii) sulfate : water?
8 What is the formula of anhydrous iron(ii) sulfate?

Test yourself
12 When 8.94 g of hydrated sodium carbonate are heated, 3.32 g of
anhydrous sodium carbonate is formed. Calculate the formula of the
hydrated sodium carbonate.

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 Relative atomic mass
Activity
Finding the formula of red copper oxide
A group of students investigated the formula of red copper oxide by reducing it to
copper using natural gas as shown in Figure 4.3.
red copper oxide excess natural
gas burning
combustion tube

natural
gas

Figure 4.3 Reducing red

copper oxide by heating
in natural gas. strong heat

The experiment was carried out five times, starting with different amounts of
red copper oxide. The results are shown in Table 4.1.
Table 4.1

Experiment number Mass of copper in the oxide/g Mass of red copper oxide/g
1 1.43 1.27
2 2.14 1.90
3 2.86 2.54
4 3.55 3.27
5 4.29 3.81

  1 Look at Figure 4.3. What safety precautions should the students take during the experiments?
  2 What steps should the students take to ensure that all the copper oxide is reduced to copper?
  3 Start a spreadsheet program on a computer and open up a new spreadsheet for your results. Enter the experiment
numbers and the masses of copper oxide and copper in the first three columns of your spreadsheet, as in Table 4.1.
  4 a) Enter a formula in column 4 to work out the mass of oxygen in the red copper oxide used.
b) Enter a formula in column 5 to find the amount of copper in moles in the oxide.
c) Enter a formula in column 6 to find the amount of oxygen in moles in the oxide.
  5 From the spreadsheet, plot a line graph of amount of copper (y-axis) against amount of oxygen (x-axis). Print out
your graph. If you cannot plot graphs directly from the spreadsheet, draw the graph by hand.
  6 Which of the points should be disregarded in drawing the line of best fit?
amount of copper/mol
  7 a) What, from your graph, is the average value of the ratio: ?
amount of oxygen/mol
b) How much copper, in moles, combine with one mole of oxygen in red copper oxide?
c) What is the formula of red copper oxide?
  8 Give reasons why the students could claim that their answer for the formula of the oxide was valid.
  9 Write a word equation, and then a balanced equation, for the reduction of red copper oxide to copper using
methane (CH4) in natural gas. (Hint: The only solid product is copper.)

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 Volumes of gases
Key term If a substance is a solid, mass is used to measure the amount needed for
a reaction. However, if a reactant or product is a gas, it is unlikely that it
Avogadro’s Law states that equal could be weighed; it would be easier to measure its volume. In the 19th
volumes of all gases measured century, the chemist Amedeo Avogadro made the important discovery
at the same temperature and known as Avogadro’s Law.
pressure will contain the same
number of molecules. This means that, for example, if the volumes of both gases are
measured at the same temperature and pressure, 50 cm3 of oxygen will
contain exactly the same number of molecules as 50 cm3 of carbon
dioxide, despite the fact that the carbon dioxide molecule is larger and
weighs more.

Tip Molar volume

The requirement that the If a volume of gas contains a fixed number of molecules, then it is useful
measurements are made under to know what volume contains the Avogadro number of particles. This
the same conditions is important volume is known as the molar volume. There are two useful
because the volume of gas varies benchmarks:
with changes in temperature and
l Under standard conditions of 0 °C and 100 kPa pressure, the molar
pressure.
volume is 22.7 dm3 mol-1. (Standard conditions are abbreviated to STP.)
l Under normal laboratory conditions, the molar volume is taken as
24 000 cm3 mol-1. This value is used in calculations for reactions at
room temperature and pressure, although it should be appreciated
that it does vary according to the exact conditions. (Room
temperature and pressure is abbreviated to RTP.)
Molar volumes can be expressed in dm3:
Tip
l At STP 1 mol of a gas occupies 22.7 dm3.
Remember there are 1000 cm3
in 1 dm3. l At RTP 1 mol of a gas occupies 24.0 dm3.
Chapter 4  Amount of substance – moles in solids and gases

The key relationship between the amount in moles of gas molecules and
the volume of the gas is:
volume of gas (V )
amount of gas in moles (n ) =
molar volume at that temperature and pressure
At RTP, n = V if V is measured in cm3.
24 000
or
V (in cm3) = 24 000 × n

Example 18
Calculate the volume of 8.0 g of methane at RTP.
Answer
Molar mass of methane, CH4 = 12.0 + (4 × 1.0) = 16.0 g mol-1
8.0
Amount in mol of methane molecules (m/M) = = 0.50mol
16.0
Volume of 1 mol of methane = 24.0 dm3 at RTP.
Volume of 0.50 mol of methane = 0.50 × 24.0 = 12.0 dm3

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 Volumes of gases
Example 19
Calculate the mass of 500 cm3 of oxygen at RTP. Give your answer to three
significant figures.
Answer
Volume of 1 mol of oxygen molecules at RTP = 24 000 cm3
500
Amount in mol in 500 cm3 = = 0.0208mol
24 000
Molar mass of oxygen, O2 = 32.0 g mol-1
So mass of 0.0208 mol = 0.0208 × 32.0 = 0.667 g.

Ideal gas equation

The volume of a gas at temperatures or pressures other than STP or RTP
can be calculated using the ideal gas equation.
The difference between gases and solids or liquids is that the particles of
a gas are very much further apart than the particles in a solid or a liquid.
Distance between the particles

Solids Liquids Gases

Because of this the volume of a gas depends on the temperature, the

pressure as well as the number of moles of the gas.
l If the amount in moles, n, of a gas is increased, the volume will increase.
This is summarised by Avogadro’s Law which can be written as V ∝ n
l If the temperature, T, of a gas is increased, the volume will increase.
This is summarised by Charles’ Law which can be written as: V ∝ T
(where T is in kelvin, K)
l If the pressure, P, is increased, the volume will decrease. This is
1
summarised by Boyle’s Law which can be written as: V ∝
P
By combining the three gas laws we obtain:
V ∝n
V ∝T
1 T
V ∝ which when combined gives V ∝ n or PV ∝ nT
P P
Adding a constant of proportionality results in the relationship
PV = nRT which is known as the ideal gas equation. The constant of
proportionality, R, is known as the gas constant.
The value of R can be calculated using standard conditions with the
more accurate standard temperature of 273.16 K, and a pressure of
101.32 kPa and, for 1 mol of gas, a volume of 22.414 dm3.
PV = nRT hence R = PV = 101.31 x 22.414 51
nT 1 x 273.16

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 The units of the gas constant, R¸ are J K-1 mol-1 (joules per kelvin per mole)
Note that in SI units pressure should be given in Pa and volume in m3.
In which case the pressure is 101320 Pa and the volume is 0.022414. PV
would therefore be 101320 x 0.022414 (= 2270.99) but this is the same
as measuring the pressure in kPa and the volume in dm3 101.32 x 22.414
(= 2270.99). As this is the case it is usual in calculations to use volume
in dm3 and pressure in kPa. All the examples in this book will do this.

Tip
Explanation of units of the gas constant R
The SI unit of pressure is Pa (1 Pa = 1 N m-2 (1 newton per square metre)
therefore 1 kPa = 1 x 103 N m-2.
The SI unit of volume is m3 (metres cubed) therefore 1 dm3 = 1 x 10 -3 m.
Tip The SI unit of temperature is K (Kelvin) To convert from oC to K add 273.
The units of R can be worked out using
The value and units of the gas PV
constant will be on the data R= = (N m –2)(m3)/(mol)(K) = N m/(mol)(K) = N m mol–1 K-1
nT
sheet which will be supplied in In SI units 1 newton metre (N m) = 1 joule (J)
all examinations. So the units of R are J mol–1 K–1.

Another way of expressing the relationship between the temperature,

pressure and volume of a gas is as follows:
PV
By combining Charles’ Law and Boyle’s Law we have = constant (for
a given amount in mol of a gas) T

It follows that
P1V1 P2V2
= (P , V and T1 are the initial pressure, volume and
T1 T2 1 1
temperature and P2 V2 and T2 are the final pressure, volume and temperature.
Chapter 4  Amount of substance – moles in solids and gases

Ideal gases follow these gas laws exactly but require very specific factors
to apply. An ideal gas is one that is composed of independent particles
(molecules or atoms) which are widely separated from each other. An
ideal gas can be described by the following:
1 The molecules (or atoms) are in continuous random motion
2 There are no intermolecular forces between the individual molecules
(or atoms)
3 All collisions are perfectly elastic with no exchange of kinetic energy
4 The molecules (or atoms) have no size (i.e. they occupy zero volume)
In reality gases deviate from these ideal conditions but gases do approach
ideal behaviour at very high temperatures and at very low pressures.
Calculations assume that all gases follow the ideal gas equation exactly.

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 Volumes of gases
Example 20
If the volume of a gas collected at 50 oC and 110 kPa is 75 cm3, what would
the volume be at STP?

Answer
For calculations of this type it is best to use the equation
P1V1 P2V2
=
T1 T2
and the only unknown is V2 so the equation can be rearranged
PVT
to give 1 1 2 = V2
P2T1
Pressure is in kPa. Standard pressure is 100 kPa.
Temperatures must be in K, T1 = 50 oC + 273 = 323 K. Standard temperature
is 0 oC = 273 K.
Whatever the units of volume used for V1 will also be the units of the
calculated volume V2.
110 × 75 × 273 = 2252250 = 70 cm3
100 × 323 32300

Example 21
5.6 g of liquid nitrogen was added to an evacuated 5.0 dm3 volumetric flask
and the temperature was allowed to rise to 25 oC. Calculate the pressure
inside the volumetric flask at 25 oC.

Answer
nRT
Use the ideal gas equation, PV = nRT and rearrange to get P =
V
n = 5.6/28 = 0.20 mol
R = 8.314 J mol-1 K-1
T = 25 + 273 = 298 K
V = 5.0 dm3
P = (0.20 × 8.314 × 298)/5 = 99.1 kPa

Example 22
1.68 g of a noble gas occupies a volume of 500 cm3 at RTP. Identify the noble gas.

Answer
Use the ideal gas equation, PV = nRT. Since we are using RTP, the only
unknown is the amount in moles, n.
(100 × 0.5) 50
n= = = 0.02 mol
(8.314 × 298) 2477.6
PV
The ideal gas equation can be rearranged to give n =
RT
We now know that 0.02 mol of the noble gas atoms have a mass = 1.68 g,
therefore the atomic mass of the noble gas is
m
AR = = 1.68/0.02 = 84, therefore the noble gas is krypton.
n
(Krypton has an atomic mass = 83.8 g mol-1) 53

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 Test yourself
13 Under standard conditions the volume of 1 mole of a gas is 22.0 dm3.
Calculate the volume of 1 mole of gas at RTP
14 Calculate the following gas volumes when converted to STP.
a 200 cm3 at 27 oC and 100 kPa
b 5.60 dm3 at 425 K and 200 kPa
15 1.73 g of a halogen gas occupies a volume of 600 cm3 at RTP. Identify the
halogen gas.

Volumes of gas produced in a reaction

To calculate the volume of gas produced in a reaction, use the balanced
equation, as shown in the following examples. The molar volume
appropriate to the conditions of the measurement is always given.

Example 23
Calculate the volume of hydrogen produced when excess dilute sulfuric acid
is added to 5.00 g of zinc. Assume that under the conditions of the reaction
the molar volume is 24 000 cm3. Give your answer to three significant
figures.

Answer
The equation is:

Zn(s) + H2SO4(aq) → ZnSO4(aq) + H2(g)

The equation shows that 1 mol of zinc atoms produces 1 mol of hydrogen
molecules. (It also shows that 1 mol of H2SO4 is used and 1 mol of ZnSO4 is
formed, but this is not relevant here.)
Molar mass of zinc = 65.4 g cm-3
Chapter 4  Amount of substance – moles in solids and gases

5.00
Amount in moles of zinc atoms used, n/M = = 0.076452599mol
65.4
It follows from the equation that 0.0765 mol of hydrogen molecules is
produced.
Molar volume = 24 000 cm3
Volume of hydrogen produced = 0.076452599 × 24 000 = 1834.862385 cm3
which, to three significant figures, is 1830 cm3.

The last example shows the importance of keeping all the digits in your
calculator throughout the calculation. If 0.076452599 had been rounded to
0.0765 mol after the first step and then multiplied by 24 000 in the second
step, the answer obtained would be 1836 cm3 which, when rounded to
three significant figures, would have given an answer of 1840 cm3.

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 Volumes of gases
Example 24
Calculate the volume of hydrogen produced when excess dilute sulfuric acid
is added to 5.00 g of aluminium. Under the conditions of the reaction, the
molar volume is 24 000 cm3.

Answer
The equation for the reaction is:
2Al(s) + 3H2SO4(aq) → Al2(SO4 )3(aq) + 3H2(g)
The equation indicates that 2 mol of aluminium atoms produces 3 mol
of hydrogen molecules or 1 mol of aluminium atoms produces 1.5 mol of
hydrogen molecules.
5.00
Amount in moles of Al atoms used = = 0.185mol
27.0
Amount in moles of H2 molecules produced = 1.5 × 0.185 = 0.278 mol
Volume of H2 produced = 0.278 × 24 000 = 6670 cm3.

Example 25
A gas syringe has a maximum capacity of 100 cm3. Calculate the mass of
copper(ii) carbonate that would have to be heated to produce enough
carbon dioxide to just fill the syringe at RTP.

Answer
The equation for the reaction is:
CuCO3(s) → CuO(s) + CO2(g)
100
Syringe volume of 100 cm3 is equivalent to = 0.00417 mol of gas
24 000
molecules.
0.00417 mol of carbon dioxide is obtained by heating 0.00417 mol of copper
carbonate.
Mass of 1 mol of copper carbonate = 63.5 + 12.0 + (3 × 16) = 123.5g
Mass of 0.00417 mol of copper carbonate = 0.00417 × 123.5 = 0.514995g
which, to three significant figures, is 0.515 g.

The answer to the last example is the theoretical mass that could be
used. In practice, it would be unwise to heat a mass as large as this
because, although the gas when cooled would fit inside the syringe, the
hot gas produced would have a volume greater than 100 cm3.

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 Test yourself
16 What is the amount, in moles, of gas at room temperature and pressure in:
a) 240 000 cm3 chlorine
b) 48 cm3 hydrogen
c) 3 dm3 ammonia?
17 What are the volumes, in cm3, of the following amounts of gas at RTP:
a) 2 mol nitrogen molecules
b) 0.0002 mol neon atoms
c) 0.125 mol carbon dioxide molecules?
18 What is the volume in cm3 of the following gases at RTP:
a) 8.50 g of ammonia (NH3)
b) 1.10 g of carbon dioxide?
19 What is the mass of 250 cm3 of sulfur dioxide (SO2) measured at RTP?
Give your answer to three significant figures.
20 Calculate the volume of hydrogen produced at RTP when 0.802 g of
calcium reacts with water.
Ca(s) + 2H2O(l) → Ca(OH)2(aq) + H2(g)
21 When reacted with excess dilute hydrochloric acid, what mass of
calcium carbonate produces 1 dm3 of carbon dioxide measured at RTP?

Activity
Finding an equation for the reaction of magnesium Here are the results.
with hydrochloric acid
Mass of magnesium added = 0.061 g
A small piece of magnesium was weighed and then
added to excess dilute hydrochloric acid (HCl(aq)) Volume of hydrogen produced = 60 cm3
in the apparatus shown in Figure 4.4. A vigorous 1 Why is it important to use excess hydrochloric acid?
reaction occurred and hydrogen gas (H2) was produced. 2 What modifications could you make to prevent
Eventually all the magnesium reacted and the reaction
Chapter 4  Amount of substance – moles in solids and gases

hydrogen escaping from the flask before the apparatus

stopped. is reconnected after adding the magnesium?
3 How many moles of magnesium reacted? (Ar(Mg) = 24.3)
4 How many moles of hydrogen were produced?
(Assume that the molar volume of hydrogen is
graduated 100 cm3 syringe 24.0 dm3 mol-1.)
5 Copy and complete the following statements:
mol magnesium, Mg, produced
mol hydrogen, H2.
So 1 mol magnesium, Mg, produces
dilute hydrochloric acid mol hydrogen, H2.
6 Use your result from Question 5 to write a balanced
small piece of magnesium
equation, with state symbols, for the reaction of
Figure 4.4 Measuring the volume of hydrogen produced magnesium with hydrochloric acid to form hydrogen.
when magnesium reacts with dilute hydrochloric acid. (Assume that magnesium chloride (MgCl2) is also
produced.)

Reactions between gases

Avogadro’s Law is extremely useful when relating the volume of gas to
56 an equation, as shown in the following examples.

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 Volumes of gases
Example 26
Assuming the measurements are made at the same temperature and
pressure, what volume of oxygen reacts exactly with 100 cm3 of hydrogen?

Answer
The equation for the reaction is: 2H2 ( g ) + O2 ( g ) → 2H2O (l )
The equation shows that 2 mol of hydrogen molecules reacts with 1 mol of
oxygen molecules.
The number of molecules in 100 cm3 of hydrogen is not known. However,
applying Avogadro’s Law it is known that 100 cm3 of oxygen contains the
same number of molecules as there are in the 100 cm3 of hydrogen.
Since the equation indicates that half the number of oxygen molecules as
hydrogen molecules are needed, it must be that 50 cm3 of oxygen reacts with
100 cm3 of hydrogen.

In this last example, if the temperature were such that the H2O was
gaseous, then the volume produced would be 100 cm3. Be careful not to
assume that you can simply add the volumes of the reactants to obtain
the volume of the product. The total mass on the left-hand side of the
Tip equation must equal the total mass on the right-hand side, but this does
Remember not apply to volumes because the densities affect the mass. In this case,
volume = mass/density 100 cm3 of hydrogen reacts with 50 cm3 of oxygen but only 100 cm3 of
steam is produced.

Example 27
Assuming the measurements are made at the same temperature and
pressure, what volume of oxygen reacts exactly with 30 cm3 of methane and
what volume of carbon dioxide is obtained?

Answer
The equation for the reaction is: CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
The equation shows that when1 mol of methane molecules react with 2 mol
of oxygen molecules, 1 mol of carbon dioxide is formed. Using Avogadro’s
Tip
Law, it follows that 30 cm3 of methane requires 60 cm3 of oxygen to produce
As water is a liquid, you cannot 30 cm3 of carbon dioxide.
deduce its volume using
Avogadro’s Law.
Test yourself
22 Assuming that all gas volumes are measured at the same temperature
and pressure, what volume of oxygen is needed to react with 50 cm3
ethane, C2H6, when it burns and what volume of carbon dioxide forms?
23 What volume of oxygen reacts with 200 cm3 of propane, C3H8, and what
volume of carbon dioxide is produced? (Assume that all volumes are
measured at room temperature and pressure.)

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 Practice questions
Multiple choice questions 1–10 A 300 cm3 B 500 cm3
1 Which one of the following contains the greatest C 700 cm3 D 1100 cm3
number of molecules? 7 At 50oC and 200kPa, the volume of a sample of a
A 30g of methane (CH4) gas is V cm3. Which one of the following changes
B 1.5 mol of methane to the temperature and pressure would cause the
C 30g of ethane (C2H6) maximum increase in the volume of the gas?
D 1.5 mol of ethane
Temperature Pressure
2 Which one of the following contains a number of A   50 C
o
  50kPa
particles equal to the Avogadro constant?
B 100oC 100kPa
A molecules in 1.0g of hydrogen gas
C 200oC 150kPa
B atoms in 1.0g of carbon
C chloride ions in 1 mol of calcium chloride D 400 C
o
200kPa
D carbonate ions in 1 mol of calcium carbonate Key
3 Copper nitrate decomposes when heated as
A B C D
shown by the following equation:
1, 2 and 3 1 and 2 2 and 3 1 only
2Cu(NO3)2(s) → 2CuO(s) + 4NO2(g) + O2(g) correct correct correct correct
Which one of the following correctly describes the
Use the key above to answer questions 8, 9 and 10.
full decomposition of 1 mol of copper nitrate?
A A total of 3 mol of gas are formed 8 Which of the following statements about ethane
B The volume of NO2(g) produced is twice that is correct?
of oxygen 1 30g of ethane contains 1 mol of ethane
C The total amount in mol of gas produced is molecules
212 times the amount in mol of the copper 2 Ethane has a molar mass of 30 g mol–1
nitrate used. 3 Ethane has a relative molecular mass of 30 g
D A total of 7 mol of products is obtained. 9 The equation for the combustion of but-1-ene is:
4 Which one of the following is the molecular C4H8(g) + 6O2(g) → 4CO2(g) + 4H2O(g)
Chapter 4  Amount of substance – moles in solids and gases

formula of a hydrocarbon containing 80% by Which of the following would be present in a

mass of carbon? closed container if 10 cm3 of but-1-ene was
A CH4 completely burned in 100 cm3 of oxygen?
B C2H4 (Assume all volumes were measured at a
C C2H6 temperature above 100oC)
D C3H6 1 40 cm3 of carbon dioxide
5 When heated with sodium hydroxide, 2 40 cm3 of water vapour
ammonium sulfate completely reacts to form 3 40 cm3 of oxygen
ammonia gas. 10 When heated copper oxide reacts with gaseous
What is the maximum amount of ammonia that ammonia to form copper;
can be obtained at RTP if 0.2 mol of ammonium
2CuO(s) + 2NH3(g) → 2Cu(s) + N2(g) + 3H2O(g)
sulfate is completely reacted?
(I mol of gas has a volume of 24.0 dm3 at RTP) If the reaction takes place to completion using
A 0.8 mol ammonia and an excess of copper oxide, which of
B 0.4 mol the following will be found?
C 0.2 mol 1 At 400 oC, the volume of the products will
D 0.1 mol be twice the volume of the ammonia that
was used.
6 What volume of oxygen measured at the same 2 If the reaction is cooled to room temperature,
temperature and pressure is needed to burn the volume of the products will be half the
completely 100 cm3 of propane (C3H8)? volume of ammonia that was used.
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 Practice questions
3 The amount in mol of copper obtained will be 20 Zinc nitrate decomposes when heated to form
half the amount in mol of copper oxide that zinc oxide:
was used.
2Zn (NO3 )2 ( s) → 2ZnO ( s) + 4NO2 ( g ) + O2 ( g )
11 a) Calculate the relative formula mass of
sodium carbonate, Na2CO3. (1) a) What are the mole ratios in the equation? (2)
b) Calculate the relative formula mass of b) Calculate the mass of zinc nitrate that
barium chloride crystals, BaCl2 2H2O.
●
(1) would have to be heated to produce 3.6 g
of zinc oxide. (2)
12 Determine the amount in moles present in
each of the following: 21 Calculate how many tonnes of lead could be
a) 8.0 g of sulfur (1) produced in a furnace by reacting 50.0 tonnes of
b) 1.68 g of calcium oxide. (1) lead oxide, PbO, with carbon. Give your answer
to 3 significant figures. (5)
13 Calculate the mass in grams for each of the
following. Give your answers to 2 significant 22 When 10.80 g of hydrated iron(ii) sulfate
figures. were heated, the water of crystallisation
a) 0.040 mol of aluminium chloride (2) was driven off. This left 5.91 g of anhydrous
b) 0.45 mol of aluminium hydroxide (2) iron(ii) sulfate.
a) How many moles of FeSO4 and H2O
14 Calculate the mass of each of the following
are present in 10.80 g of hydrated
volumes measured at RTP:
iron(ii) sulfate? (2)
a) 4 dm3 of carbon dioxide (2)
b) What is the formula of hydrated iron(ii)
b) 500 cm3 of ethane. (2)
sulfate? (2)
15 Calculate the molar mass of an element if
23 Calculate the volume in dm3 at RTP of each of the
3.745 g is equivalent to 0.0500 mol of that
following gases:
element. Identify the element. (2)
a) 1 g of hydrogen (1)
16 0.02 mol of the hydroxide of X has a mass of b) 2 g of methane, CH4 (1)
1.48 g. X is a divalent metal. c) 8.8 g of carbon dioxide (1)
a) Calculate the molar mass of the d) 4.0 g of nitrogen monoxide, NO. (1)
hydroxide of X. (1)
24 Calculate the mass of each of the following
b) What is the formula of the hydroxide of X?(1)
volumes. Assume that the conditions are RTP. i.e.
c) Identify the metal, X. (1)
1 mol of gas has a volume of 24 dm3.
17 How many atoms are there in 5.0 g of silicon? (2) a) 12 dm3 of oxygen (1)
b) 4 dm of carbon dioxide
3
(1)
18 How many molecules are there in 5.0 g of
c) 500 cm3 of ethane, C2H6 (1)
oxygen gas? (2)
d) 100 cm3 of nitrogen (1)
19 a) Write the equation, including state symbols,
25 What is the volume of each of the following
for the reaction of magnesium with aqueous
gases at 25oC and 100kPa?
zinc sulfate to form zinc metal and aqueous
a) 5.60 dm3 of gas at 425oC and 80kPa (1)
magnesium sulfate. (1)
b) 100 cm3 of gas at 103kPa and 120oC (1)
b) What mass of zinc is obtained by reacting
3.0 g of magnesium with excess zinc sulfate 26 100 cm3 of oxygen is collected in a syringe at
in solution? Give your answer to 2 150oC. If the pressure remains unchanged, by how
significant figures. (2) much will the volume contract if it is allowed to
c) Why is it necessary to specify that the cool to a room temperature of 20oC? (2)
aqueous zinc sulfate is in excess? (1)
27 0.363g of a solid element, Y, is vapourised at 400K
and 100kPa. Its volume is found to be 47 cm3.
Calculate the relative atomic mass of the element
and identify Y. (3)

59

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 28 a) Compound X is a volatile liquid and is known 33 Calculate the mass of magnesium that could
to contain 52.17% C; 13.0% H and 34.78% be reacted with excess sulfuric acid at RTP such
O by mass. Calculate the empirical formula of that the hydrogen produced would fill a 250 cm3
compound X. Show your working. (2) measuring cylinder with hydrogen. (3)
b) 0.25g of X is vapourised at 90oC and 101kPa
34 Dinitrogen monoxide can decompose to nitrogen
pressure and is found to have a volume of 162
and oxygen when heated.
cm3. Calculate the molecular formula of X. (3)
2N2O(g) → 2N2(g) + O2(g)
29 In parts (a)–(c), correct any errors that you find. What volumes of oxygen and nitrogen would be
a) Consider the reaction: obtained when 50 cm3 of dinitrogen monoxide
Zn(s) + 2HCl(aq) → ZnCl2(aq) + H2(g) was decomposed? (2)

i) The equation indicates that 1 mol of zinc 35 Carbon monoxide reacts with oxygen to form
reacts with 2 mol of hydrochloric acid to carbon dioxide:
produce 1 mol of zinc chloride and 2 mol 2CO(g) + O2(g) → 2CO2(g)
of hydrogen atoms. What volume of oxygen is required to react with
ii) The equation indicates that 1 mol of zinc 40 cm3 of carbon monoxide and what volume
produces 48 dm3 of hydrogen at room of carbon dioxide would be formed? Assume
temperature and pressure. (2) that all volumes are measured at the same
b) Consider the reaction: temperature and pressure. (2)

CH4 + 2O2 → CO2 + 2H2O 36 When a group (ii) carbonate is heated, 0.74 g
of an oxide is obtained and 172 cm3 of carbon
The equation indicates that, at room dioxide is collected at room temperature and
temperature and pressure, 24 dm3 of methane pressure. Identify the group (ii) carbonate and
reacts with 48 dm3 of oxygen to produce explain how you obtained your answer. (4)
24 dm3 of carbon dioxide and 48 dm3
of water. (1) 37 Ammonia can be manufactured by combining
c) Gaseous nitrogen monoxide (NO) reacts with nitrogen and hydrogen under high pressure
oxygen to form gaseous nitrogen dioxide and with a controlled temperature. Even so,
(NO2), according to the equation: the process is not very efficient. Some of the
ammonia produced is converted in a reaction
Chapter 4 Amount of substance – moles in solids and gases

2NO(g) + O2(g) → 2NO2(g) with sulfuric acid into ammonium sulfate for
The equation indicates that 2 mol of nitrogen use as a fertiliser. A process using 15 000 dm3 of
monoxide react with 1 mol of oxygen. So nitrogen operates such that the reaction is only
48 dm3 of nitrogen monoxide reacts with 22% efficient. The ammonia produced is then all
24 dm3 of oxygen and 72 dm3 of nitrogen converted into ammonium sulfate.
dioxide is obtained. (2) a) What volume of hydrogen would be required
to react completely with the 15 000 dm3
30 Calculate the volume of hydrogen in cm3 at RTP of nitrogen and what volume of ammonia
that is produced by reacting 1.00 g of magnesium would be produced? (3)
with excess hydrochloric acid. (3) b) What mass in tonnes (1000 kg) of ammonium
31 Calculate the volume of carbon dioxide in cm3 at sulfate would be formed if the reaction was
RTP that could be obtained when 3.00 g of carbon only 22% efficient? Give your answer to
is burned in excess oxygen. (2) 3 significant figures. (3)

32 Calculate the volume of hydrogen in cm3 at

RTP that is needed to convert 7.95 g of copper
oxide into copper metal. The equation for the
reaction is:
CuO(s) + H2(g) → Cu(s) + H2O(l) (2)

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 Practice questions
Challenge a) Write a balanced equation for the reaction
between carbon dioxide and sodium
he work of Avogadro was important because it
T
hydroxide solution. Include state symbols.
provided the means of establishing the formulae
b) What volume of carbon dioxide is formed in
of some gases. This question shows you how this
the reaction?
might have been done. You have to establish the
c) What volume of oxygen is used in reacting
formula of a gas, CxHy, from experimental data.
with CxHy?
Compound CxHy burns in oxygen to form carbon
d) The equation for the reaction can be written
dioxide and water, provided that enough oxygen
in terms of x and y.
is supplied.
In an experiment, 40 cm3 of CxHy and 500 cm3 of y
C x H y + ....... O2 → x CO2 + HO
oxygen are mixed together at room temperature 2 2
and pressure. An electrical spark is then applied opy and complete the equation by providing
C
which causes the CxHy to react completely. When the balancing number for the oxygen molecules.
cooled to room temperature and pressure, droplets e) Use the volumes you have established in parts
of water are observed and the volume of gas is (b) and (c) and the equation in part (d) to
420 cm3. This gas consists of the carbon dioxide determine the value of x and then the value of y.
formed and unreacted oxygen. f) Write the formula of CxHy.
The 420 cm3 of gas is shaken with sodium hydroxide g) Use the balanced equation to determine
solution. This absorbs the carbon dioxide by forming the mass of water produced when 40 cm3
sodium carbonate and water. The volume of gas (measured at RTP) of CxHy is burned.
remaining is 260 cm3. h) The density of water is 1 g cm−3.  What volume
of water is obtained in the experiment? (12)

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 Chapter 5
Amount of substance –
moles in solution
Prior knowledge
This chapter extends the ideas met in Chapter 4 and you should make sure
the work covered in that chapter is fully understood before proceeding. You
will therefore need to be familiar with:
● writing equations
● interpreting the information in an equation in terms of the amount in

moles required for a complete reaction

● the relationship between the amount in moles, the mass in grams and

the molar mass of a substance (n = m/M)

● the meanings of the terms solute, solvent and solution.

Test yourself on prior knowledge

1 Solid sodium carbonate reacts with dilute hydrochloric acid to form
sodium chloride, carbon dioxide and water.
a) Write an equation for the reaction including state symbols.
b) What does the equation tell you about the amount in moles of the
reactants that would be required for a complete reaction to take place?
c) What does the equation tell you about the amount in moles of
the products that would be formed when a complete reaction had
taken place?
d) What amount in moles of hydrochloric acid would be required to react
completely with 0.32 mol of sodium carbonate?
e) What amount in moles of hydrochloric acid would be required to react
completely with 0.32 g of sodium carbonate? Give your answer to 2
significant figures.
f) What mass of sodium chloride would be formed from the reaction in
(e)? Give your answer to 2 significant figures.
2 If sodium chloride is shaken with water until it dissolves, which is the
solvent and which is the solute?

Concentrations of solutions
Many chemical reactions only occur if the reactants involved are in
aqueous solution. The common acids, for example, usually only react
when dissolved in water. In order to decide on the correct amounts to
use for a chemical reaction it is necessary to know how much of the
reacting substance is present in a given volume of the solution. This is
the concentration of the solution and solutions for quantitative work are

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 Concentrations of solutions
specified by how many grams or moles of the substance there are in a
certain volume of solution. This volume is usually 1 dm3 (1000 cm3).
For example, consider a solution of sodium carbonate containing 2 mol
of Na2CO3 in every 1 dm3 of the solution. The concentration is 2 mol per
dm3, which is written as 2 mol dm –3. It follows that 500 cm3 (0.5 dm3)
of this solution contains 1 mol. Different volumes of solution contain
different numbers of moles.
In general:
amount in moles = concentration of solution × volume of solution
units: (mol) (mol dm –3) (dm3)
equation: n = cV

Example 1
What is the amount in moles of NaOH in 50 cm3 of a solution whose
concentration is 2 mol dm–3?

Answer
The volume given is in cm3 and must be converted to dm3 by dividing by 1000.
Then using n = cV:
50
amount in moles (n) = 2 × = 0.1 mol
1000

Example 2
What volume of a solution of hydrochloric acid of concentration
0.5 mol dm–3 contains 0.15 mol?
Give the answer in cm3.

Answer
Rearrange the equation n = cV:
n
V=
c
0.15
V= = 0.3 dm3
0.5
To convert 0.3 dm3 to cm3, multiply by 1000.
volume of solution = 300 cm3

Example 3
If 0.4 mol of Na2CO3 is dissolved to make 200 cm3 of solution, what is its
concentration in mol dm–3?

Answer
Rearrange the equation n = cV:
n
c=
V
0.4
c= = 2 mol dm–3
0.2
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 Example 4
8.00 g of sodium hydroxide is dissolved to make 100 cm3 of solution.
What is its concentration of the solution in mol dm–3?

Answer
The molar mass of sodium hydroxide is 40.0 g mol–1.
So the amount used in moles is:
m 8.00
= = 0.200 mol
M 40.0
This is dissolved in 100 cm3 (0.1 dm3) so the concentration in mol dm–3 is:
n 0.200
= = 2.00 mol dm–3
V 0.1

Diluting solutions
Tip Hydrochloric acid is often sold as a solution of concentration 10 mol dm–3. If
a solution of concentration 2 mol dm–3 is required, then it has to be diluted
A common mistake is to think five times. For example, 200 cm3 of the concentrated acid requires 800 cm3
that 200 cm3 of concentrated water to make 1000 cm3 of dilute acid of concentration 2 mol dm–3.
acid would require 1000 cm3
of water in order to dilute it The dilution that is required is calculated using the following using
five times. That would create equation A shown below:
1200 cm3 of solution, which is a Equation A
six-fold dilution. concentration of the original solution
dilution =
concentration of the diluted solution
So to make 200 cm3 of a solution of concentration 0.5 mol dm–3 from a
2
Tip stock solution of concentration 2 mol dm–3, the dilution required is = 4,
which is a four-fold dilution. 0.5
Diluting concentrated acids
is an exothermic process. If a Therefore, the stock solution has to be diluted four times. To make
small volume of water is added 200 cm3 of concentration 0.5 mol dm –3 requires 50 cm3 of the stock
solution and 150 cm3 of water.
Chapter 5  Amount of substance – moles in solution

to concentrated acid, the heat

produced may cause the water The volume of the original stock solution can be calculated by using
to boil, which can be dangerous. equation B shown below.
Concentrated acid should always
be added slowly to water; Equation B
water should never be added to volume of original stock total volume of diluted solution required
concentrated acid. =
solution needed dilution (calculated in equation A)

Example 5
How can 500 cm3 of a 0.4 mol dm–3 solution of sulfuric acid be prepared from
a solution of concentration 2 mol dm–3?

Answer
2
Equation A dilution required = =5
0.4
500
Equation B volume of original stock solution = = 100 cm3
5
Therefore, 100 cm3 of the dilute sulfuric acid of concentration 2 mol dm–3
should be further diluted by the addition of 400 cm3 of water.

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 Titrations
Example 6
What is the concentration in mol dm–3 of 375 cm3 aqueous sodium
hydroxide that has been prepared by diluting 75 cm3 of sodium hydroxide of
concentration 0.6 mol dm–3 with 300 cm3 of water?

Answer
In exams, a solution of a substance such as sodium hydroxide will be referred
to as ‘aqueous sodium hydroxide’, which indicates that it has been dissolved
in water.
volume of dilute solution = 375 cm3
75
concentration = × 0.6 = 0.12 mol dm–3
375

Test yourself
1 State the amount in moles in each of the following:
a) 2 dm3 of sodium hydroxide solution of concentration 0.1 mol dm –3
b) 200 cm3 of sulfuric acid of concentration 0.5 mol dm –3.
2 Calculate the volume of 0.5 mol dm –3 aqueous potassium chloride that
contains:
a) 1 mol
b) 0.2 mol.
3 Give the concentration of each of the following solutions in mol dm –3:
a) 100 cm3 of potassium chloride containing 0.1 mol
b) 50 cm3 of sodium nitrate containing 0.01 mol.
4 Calculate the mass of solid that on dissolving would produce:
a) 250 cm3 of aqueous sodium hydroxide of concentration 0.2 mol dm –3
b) 100 cm3 of aqueous sodium carbonate of concentration 0.4 mol dm –3.
5 Describe how each of the following solutions of sulfuric acid could be
prepared from a solution of acid of concentration 1 mol dm –3:
a) 1 dm3 of solution of concentration 0.1 mol dm –3
b) 500 cm3 of solution of concentration 0.2 mol dm –3.
6 What is the concentration obtained by diluting 50 cm3 of 2 mol dm –3
aqueous sodium carbonate with water to make:
a) 500 cm3 of solution
b) 650 cm3 of solution?

Titrations
In general, a titration is a procedure used to determine the
concentration of a solution by reacting it with another solution whose
concentration is known. An example is the titration of an alkali with an
acid, which requires the use of an acid–base indicator, such as methyl
orange, to show when the reaction is complete.
When an acid neutralises an alkali, the pH of the solution changes. We
can follow the pH change using an indicator. The indicator shows how
much acid is needed to react with all of the alkali.
In an experiment, a known volume of one solution is pipetted into a
conical flask. The second solution is put into a burette and added bit by
bit to the first solution until the reaction is complete.
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 safety filler 0
burette
10

20

pipette 30 solution of HCl(aq)

40

50

pipetted volume of
conical flask NaOH(aq) and a few drops
containing NaOH(aq) of methyl orange indicator

Figure 5.1 The apparatus used for a titration.

Tip
Performing an acid–base titration
The following are the steps to take when 25.0 cm3 of an aqueous
The choice of an indicator does solution of sodium hydroxide is titrated against hydrochloric acid using
depend on the nature of the methyl orange as the indicator.
acid and alkali being titrated.
However, usually many different 1 Using a pipette, take exactly 25.0 cm3 of the aqueous sodium hydroxide.
indicators can be used. The best 2 Transfer the solution to a conical flask.
to select is one that gives a clear
colour change that suits your 3 Add a few drops of methyl orange indicator. As aqueous sodium
eyes. This may vary from person hydroxide is alkaline, the methyl orange appears yellow.
to person depending on the 4 Place the hydrochloric acid in a burette and note the initial reading
sensitivity of their eyes. of the burette.
5 Add the hydrochloric acid carefully from the burette until the indicator
turns orange. This shows that the neutral point has been reached.

Tip 6 Note the final reading of the burette and subtract the initial reading
to determine the volume of hydrochloric acid that has been added.
The correct use of pipettes and
burettes and the limits of their 7 Repeat the titration until concordant (consistent) results for the volume
accuracy are covered in Chapter 1. of hydrochloric acid added are obtained. With care, it is possible to
obtain reproducible results that are accurate to within 0.1 cm3.
The point at which the two solutions have reacted completely is called
Chapter 5  Amount of substance – moles in solution

the end point of the titration; the volume of solution added from the
burette is known as the titre.

Tabulating the results of a titration

The results of a titration should be recorded in an orderly way. It is best
to tabulate the data. For each titration, record the initial burette reading
and the final reading, and then calculate the volume used.
Table 5.1 shows how the results of a titration should be recorded.

Table 5.1 Results of a titration.

Tip Titration Rough 1 2 3
3
Do not forget to include the Final burette reading/cm 19.10 18.55 18.85 37.50
initial reading, even if it is zero, Initial burette reading/cm 3
  0.00   0.00   0.00 18.85
and give it to the same level of Volume (titre) used/cm 3
19.10 18.55 18.85 18.65
accuracy as the final reading. Titre volumes used in calculations ✗ ✓ ✗ ✓

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 Titrations
Tip A burette reading is usually accurate to 0.05 cm3 and the results
recorded should indicate this. It is usual, but not essential, to do a
The solutions in the conical ‘rough’ titration first as a guide to the end point of the titration. This is
flask should be mixed together then followed by obtaining more accurate readings taking particular care
carefully to ensure the reaction to add the solution from the burette drop by drop as the end point is
has fully taken place. approached. The ‘rough’ value is not used in working out the titre.
Tip The results in Table 5.1 show that the titres from the first and third
accurate titrations are in close agreement. The titre from the second
In an exam you may be asked
accurate titration is out of line and is not used in calculating the mean
to quote the mean value of the
titre. Therefore, the mean value for the results of this titration is 18.60 cm3.
titration to just 1 decimal place.
Always check that you have (Chapter 1 gives more details on the precision that you should use when
followed the instruction given. recording results.)

Activity
Comparing the acidity of different vinegars burette
Two students were asked to compare the 30
acidity of different white wine vinegars. The
safety pipette filler
acid in vinegar is ethanoic acid, CH3COOH. The 40
students decided to use 25.0 cm3 of each vinegar sodium hydroxide
and then measure how much 1.0 mol dm –3 solution
mark scratched on 50
sodium hydroxide just reacts with each vinegar pipette at 25 cm3 level
using phenolphthalein indicator. Phenolphthalein tap
is colourless in acid and pink/red in alkali.
25.0 cm3 of the first vinegar was measured into
a conical flask using a pipette (Figure 5.2). conical flask

After adding 5 drops of phenolphthalein, the

sodium hydroxide solution was slowly added
from the burette (Figure 5.3) while the contents
of the conical flask were kept well mixed. When white wine vinegar
the first permanent tinge of pink/red appeared Figure 5.3 Adding sodium
in the mixture, the students recorded the Figure 5.2 Measuring 25.0 cm3 of vinegar hydroxide solution from a burette
into a conical flask using a pipette. to 25.0 cm3 of white wine vinegar.
volume of sodium hydroxide added.
This method of adding one solution from a burette to a measured volume of another solution is called a titration.
Titrations enable chemists to determine how much of the two solutions will just react.
The first titration is only a rough titration and the students then carried out three accurate titrations. To do this, they
added 1 cm3 less sodium hydroxide solution than the total amount required in their rough titration. They then added
the sodium hydroxide solution one drop at a time until the first permanent tinge of pink/red appeared in the mixture.
The students’ results are shown in Table 5.2, together with the results for the second white wine vinegar.
Table 5.2 Results of the titration.

Experiment Rough titration Accurate titrations

First wine vinegar
Final burette reading/cm3 20.50 40.15   19.60   39.30
3
Initial burette reading/cm   0.00 20.50    0.00   19.60
Second wine vinegar
Final burette reading/cm3 13.70 26.80   40.65   13.10
3
Initial burette reading/cm   0.00 13.70   26.80    0.00

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 1 Why does the mixture in the conical flask suddenly change from colourless to pink/red during the addition of
sodium hydroxide solution?
2 Why must the contents of the conical flask be well mixed during the titration?
3 Calculate the volumes of sodium hydroxide solution added in the rough and accurate titrations for both wine
vinegars in Table 5.2.
4 Calculate an average value for the accurate titration with the first wine vinegar.
5 What did the students do to increase the reliability of their results?
6 a) What value will you take for the accurate titration with the second wine vinegar?
b) Explain why you have taken this value.
7 Compare the acidity of the two vinegars.
8 State three factors the students must control in their experiments in order to compare the two vinegars fairly.

Calculation of an unknown concentration from a

titration
Suppose the concentration of the pipetted sodium hydroxide used in the
titration is 0.100 mol dm –3 and the mean titre obtained is 18.60 cm3, the
concentration of the hydrochloric acid can be calculated as follows.
Step 1 Calculate the amount (in moles) of NaOH used.
This is possible because the concentration, c, and the volume, V,
are known.
concentration of sodium hydroxide = 0.100 mol dm –3 (i.e.
0.100 mol are present in 1000 cm3 of solution)
25.0 cm3 was taken in the pipette and this sodium hydroxide
contains
25.0
0.100 × = 0.00250 mol
1000
(or n = cV = 0.100 × 0.0250)
Step 2 Refer to the balanced equation to find the amount in moles of
Chapter 5  Amount of substance – moles in solution

HCl needed to react with 0.00250 mol of NaOH.

The equation for the reaction is:
NaOH + HCl → NaCl + H2O
which shows that 1 mol of NaOH reacts with 1 mol of HCl.
So 0.002 50 mol of HCl must react with 0.00250 mol NaOH.
Since 18.60 cm3 of HCl was added from the burette, it follows
that 18.60 cm3 contains the 0.002 50 mol of acid.
Step 3 Calculate the concentration of hydrochloric acid in mol dm –3.
18.60
volume of hydrochloric acid = 18.60 cm3 =  dm3
1000
amount in moles of hydrochloric acid = 0.00250 mol
= 0.0186 dm3
0.00250
concentration of hydrochloric acid = = 0.134 mol dm –3
0.0186

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 Titrations
Example 7
25.0 cm3 of aqueous sodium carbonate is neutralised by 27.20 cm3 of
hydrochloric acid of concentration 0.120 mol dm–3. What is the concentration
in mol dm–3 of the aqueous sodium carbonate?

Answer
The concentration, c, and the volume, V, of the hydrochloric acid are known.
concentration of hydrochloric acid = 0.120 mol dm–3
27.20
27.20 cm3 of acid contains × 0.120 mol = 0.003 264 mol
1000
The equation for the reaction is:
Na2CO3 + 2HCl → 2NaCl + H2O + CO2
2 mol of hydrochloric acid reacts with 1 mol of sodium carbonate, so for
every 1 mol of hydrochloric acid that reacts, 0.5 mol of sodium carbonate
is required. Therefore 0.003 264 mol of hydrochloric acid reacts with
0.5 × 0.003 264 = 0.001 632 mol of sodium carbonate.
This amount must have been present in the 25.0 cm3 of sodium carbonate used.
 25.0 
volume of sodium carbonate solution = 25.0 cm3 =  = 0.025 dm3
1000 
Therefore:
0.001632
concentration of sodium carbonate = = 0.0653 mol dm–3
0.025

It is sometimes possible to deduce other information from a titration, as

illustrated by the following example.

Example 8
5.00 g of an impure sample of potassium carbonate is weighed out and
dissolved to make 1.00 dm3 of solution. 25.0 cm3 of this solution is titrated
against 0.0500 mol dm–3 hydrochloric acid.
28.80 cm3 of the hydrochloric acid is needed to neutralise the aqueous
potassium carbonate.
a) Use the titration results to calculate the concentration in mol dm–3 of the
aqueous potassium carbonate.
b) Deduce the percentage purity of the solid sample of potassium carbonate.
Answer
a) concentration of hydrochloric acid = 0.0500 mol dm–3
28.80 cm3 of hydrochloric acid contains
28.80
× 0.0500 mol = 0.001 44 mol
1000
The equation for the reaction is:
K2CO3 + 2HCl → 2KCl + H2O + CO2
2 mol of hydrochloric acid reacts with 1 mol of potassium carbonate, so
for every 1 mol of hydrochloric acid that reacts, 0.5 mol of potassium
carbonate is required.

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 0.001 44 mol of hydrochloric acid reacts with 0.5 × 0.001 44 = 0.000 720 mol
of potassium carbonate
This amount must have been present in the 25.00 cm3 of potassium
carbonate used.
 25.0 
volume of potassium carbonate = 25.0 cm3 =  = 0.025 dm3
1000 
0.000720
Therefore the concentration of potassium carbonate   =
0.025
= 0.0288 mol dm–3
b) The relative formula mass of potassium carbonate,
K2CO3 = (2 × 39.1) + 12.0 + (3 × 16.0) = 138.2
mass of K2CO3 in the 0.0288 mol dm–3 solution is therefore
0.0288 × 138.2 = 3.98 g
This is the mass of pure potassium carbonate in the original 5.00 g.
3.98
So the percentage purity = = 79.6%
5.00

Test yourself
7 25.0 cm3 of nitric acid was neutralised by 18.0 cm3 of 0.15 mol dm –3
sodium hydroxide solution.
a) Write an equation for the reaction.
b) Calculate the amount in moles of sodium hydroxide present in the
18.0 cm3.
c) Calculate the concentration of the nitric acid in mol dm –3.
8 2.65 g of anhydrous sodium carbonate was dissolved in water and the
solution was made up to 250 cm3. In a titration, 25.0 cm3 of this solution
was pipetted into a flask and the end point was reached after adding
22.5 cm3 of hydrochloric acid.
a) Write an equation for the reaction.
b) Calculate the concentration of the sodium carbonate solution in
Chapter 5  Amount of substance – moles in solution

mol dm –3.
c) Calculate the amount in moles present in 25.0 cm3 of the sodium
carbonate solution
d) Calculate the concentration of the hydrochloric acid in mol dm –3.
9 45.0 cm3 of 0.200 mol dm –3 NaOH just react with 10.0 cm3 of
0.300 mol dm –3 H3PO4 (phosphoric acid).
a) How many moles of NaOH react?
b) How many moles of H3PO4 react?
c) How many moles of NaOH react with 1 mole of H3PO4?
d) Write an equation for the reaction.

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 Practice questions
Practice questions
Multiple choice questions 1–10 6 100 cm3 of 0.100 mol dm–3 potassium hydroxide
1 Which one of the following solutions would have is diluted by adding x cm3 of water. The new
the highest number of hydroxide ions? concentration of the potassium hydroxide is
A 500 cm3 of 0.01 mol dm–3 sodium hydroxide 0.0800 mol dm–3.
B 400 cm3 of 0.01 mol dm–3 calcium hydroxide Which one of the following gives the value
C 300 cm3 of 0.02 mol dm–3 potassium hydroxide of x in cm3?
D 200 cm3 of 0.02 mol dm–3 lithium hydroxide A 20
B 25
2 What volume of 0.40 mol dm–3 nitric acid will C 40
react with 20.0 cm3 of 0.20 mol dm–3 potassium D 80
carbonate?
The equation is: 7 9.0 g of an acid H2X is dissolved to make 1 dm3
K2CO3(aq) + 2HNO3(aq) → 2KNO3(aq) + H2O(l) of solution.
When 25.0 cm3 of this solution is titrated against
+ CO2(g)
0.200 mol dm–3 sodium hydroxide, 25.0 cm3 is
A 5.0 cm3 required to reach the end-point of the titration.
B 10.0 cm3 Which one of the following gives the relative
C 20.0 cm3 molecular mass of H2X?
D 40.0 cm3 A 90
3 A solution is made by dissolving 5.72 g of sodium B 45
carbonate crystals, Na2CO3 10H2O to make
● C 20.5
200 cm3 of solution. (The molar mass of Na2CO3 D 11.25
is 106.0 g mol–1.) Use the key below to answer Questions 8, 9 and 10.
The concentration of this solution to 1 significant
A B C D
figure will be:
A 0.004 mol dm–3 1, 2 & 3 correct 1, 2 correct 2, 3 correct 1 only correct
B 0.008 mol dm–3 8 Sodium carbonate solution is sucked into a
C 0.05 mol dm–3 pipette but is incorrectly filled so that the top
D 0.1 mol dm–3 of the meniscus of the solution is level with
4 25.0 cm3 of 0.100 mol dm–3 sodium hydroxide the mark on the pipette. A titration against
is neutralised by 20.0 cm3 of nitric acid. The hydrochloric acid is then correctly carried out.
equation is: Which of the following would be a consequence
NaOH + HNO3 → NaNO3 + H2O of the error in the use of the pipette?
The concentration of the nitric acid is therefore: 1 The concentration of the sodium carbonate
A 0.080 mol dm–3 used would be less than it should be.
B 0.120 mol dm–3 2 The volume of hydrochloric acid required in
C 0.125 mol dm–3 the titration would be less than it should be.
D 0.150 mol dm–3 3 The concentration of the hydrochloric acid
calculated from the titration would be greater
5 30.0 cm3 of a 0.100 mol dm–3 solution of than it should be.
hydrochloric is diluted by adding 15.0 cm3 of
water. The whole of this diluted solution is then 9 25 cm3 of 0.04 mol dm–3 of sodium sulfate is added
titrated against a 0.100 mol dm–3 solution of to 25 cm3 of 0.04 mol dm–3 barium nitrate. A reaction
sodium hydroxide. occurs and some barium sulfate is precipitated.
Which one of the following will be the volume of Which of the following describes the mixture that
the sodium hydroxide in cm3 required to reach is obtained?
the end point of the titration? 1 The number of sodium ions in the solution
A 15.0 B 22.5 will be the same as the number of nitrate
C 30.0 D 45.0 ions in the solution.
2 0.001 mol of barium sulfate is precipitated.
3 No sulfate ions remain in the solution. 71

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 10 When 10 cm3 of 0.1 mol dm–3 of magnesium 16 A solution of potassium carbonate has a
chloride solution is added to 10 cm3 of concentration of 0.04 mol dm–3. 25.0 cm3 of
0.1 mol dm–3 silver nitrate, silver chloride is this solution is neutralised by 28.10 cm3 of
precipitated. hydrochloric acid.
Which of the following apply to this reaction? a) Write a balanced equation for the reaction
1 The solution obtained after the reaction will between potassium carbonate and
not contain any nitrate ions. hydrochloric acid.
2 The solution obtained after the reaction will b) What amount in moles of potassium
contain 0.001 mol of chloride ions. carbonate is contained in 25.0 cm3 of solution?
3 0.001 mol of silver chloride will be c) What amount in moles of hydrochloric acid is
precipitated. needed to neutralise the number of moles of
potassium carbonate in 25.0 cm3 of solution?
11 State the amount in moles in each of the
d) What is the concentration of the hydrochloric
following:
acid in mol dm–3? (4)
a) 50 cm3 of aqueous sodium carbonate of
concentration 0.05 mol dm–3 17 Describe how each of the following solutions of
b) 25 cm3 of hydrochloric acid of concentration sulfuric acid could be prepared from a solution of
0.1 mol dm–3. (2) acid of concentration 1 mol dm–3:
a) 100 cm3 of solution of concentration 0.15 mol dm–3
12 Calculate the volume of 0.5mol dm–3 aqueous
b) 25 cm3 of solution of concentration
copper sulfate that contains:
0.15 mol dm–3. (6)
a) 0.05 mol
b) 0.36 mol. (2) 18 What is the concentration obtained by diluting
25 cm3 of 0.50 mol dm–3 aqueous sodium
13 Give the concentration of each of the following
carbonate with water to make:
in mol dm–3:
a) 1 dm3 of solution
a) 5 dm3 of hydrochloric acid containing 2 mol
b) 320 cm3 of solution? (4)
b) 25 cm3 of aqueous magnesium sulfate
containing 0.027 mol. (2) 19 A solution of potassium hydroxide contains
5.61 g dm–3. This solution is used to neutralise
14 Calculate the mass of solid that on dissolving
20.0 cm3 of a solution of sulfuric acid of
would produce:
concentration 0.0500 mol dm–3.
a) 50 cm3 of potassium sulfate solution of
a) Write an equation for the reaction.
concentration 0.15 mol dm–3
b) Determine the volume of potassium
b) 75 cm3 of sodium chloride solution of
hydroxide solution that is required to
Chapter 5 Amount of substance – moles in solution

concentration 0.4mol dm–3. (4)

neutralise the sulfuric acid. (5)
15 A solution of potassium hydroxide has a
20 The concentration of calcium hydroxide in lime
concentration of 0.100 mol dm–3. 25.0 cm3 of
water can be determined by titrating a measured
this solution is neutralised by 22.50 cm3 of
volume of lime water with a standard solution of
hydrochloric acid.
hydrochloric acid.
a) Write a balanced equation for the reaction
In an experiment, 25.0 cm3 of limewater was
between potassium hydroxide and
titrated against 0.050 mol dm–3 hydrochloric acid.
hydrochloric acid.
a) Copy and complete the results below.
b) What amount in moles of potassium
In the flask: 25.0 cm3 of lime water
hydroxide is contained in 25.0 cm3 of
In the burette: 0.050 mol dm–3
solution?
The indicator was
c) What amount in moles of hydrochloric acid
will neutralise the potassium hydroxide Titration number 1 (rough) 2 (accurate) 3 (accurate)
present in 25.0 cm3 of solution? Final burette 22.00 42.70 22.15
d) What is the concentration of the reading/cm3
hydrochloric acid in mol dm−3? (4)
Initial burette 0.45 21.90 1.25
reading/cm3
Titre/cm3
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 Practice questions
b) Calculate the average accurate titre. 25 A solution is made by dissolving 5.00 g of sodium
c) Write an equation for the reaction of calcium hydroxide to make 1 dm3 of solution. A solution
hydroxide with hydrochloric acid. of an acid, H2X, is made by dissolving 7.66 g to
d) Calculate the amount in moles of hydrochloric make 1.0 dm3 of solution. 25.0 cm3 of the solution
acid in the average accurate titre. of sodium hydroxide is neutralised by 20.0 cm3 of
e) Calculate the concentration of calcium the solution of the acid H2X.
hydroxide in lime water in mol dm–3 . (7) a) Write an equation for the reaction.
b) Calculate the concentration of the sodium
21 Magnesium oxide neutralises nitric acid. In an
hydroxide in mol dm–3.
experiment, it is found that 1.20 g of magnesium
c) Calculate the amount in moles of sodium
oxide is neutralised by 24.20 cm3 of nitric acid.
hydroxide in 25.0 cm3.
a) Write an equation for the reaction between
d) Calculate the amount in moles of H2X in
magnesium oxide and nitric acid.
20.0 cm3 of solution.
b) What is the amount in moles of 1.20 g of
e) Calculate the concentration of H2X in mol dm–3.
magnesium oxide?
f) Calculate the mass of the anion, X2–.
c) What amount in moles of nitric acid is
g) Suggest an identify for the anion X2–. (8)
contained in 24.20 cm3?
d) What is the concentration of the nitric acid 26 10.00 g of sodium carbonate crystals
in mol dm–3? (4) Na2CO3 xH2O are dissolved to make 1 dm3 of
● 

solution. 25.0 cm3 of this solution is neutralised

22 a) Write an equation for the reaction between
by 17.50 cm3 of hydrochloric acid of
zinc oxide and hydrochloric acid.
concentration 0.100 mol dm–3.
b) What is the amount in moles of 4.07 g of
a) Calculate the amount in moles of hydrochloric
zinc oxide?
acid present in 17.50 cm3.
c) Calculate the volume of 2.00 mol dm–3
b) What is the amount in moles of sodium
hydrochloric acid that would react exactly
carbonate present in 25.0 cm3 of solution?
with 4.07 g of zinc oxide.
c) Calculate the concentration in mol dm–3 of the
d) If 2.00 mol dm–3 sulfuric acid is used instead
sodium carbonate solution.
of 2 mol dm–3 hydrochloric acid, what volume
d) Use your answer to (c) to calculate the molar
of sulfuric acid would be required? (6)
mass of the sodium carbonate crystals.
23 100 cm3 of hydrochloric acid is diluted to form e) Deduce the value of x in Na2CO3 xH2O●  (7)
1 dm3 of solution. When the diluted acid is
27 41.0 g of the acid H3PO3 was dissolved in water
titrated against 0.500 mol dm–3 sodium carbonate
and the solution was made up to 1.0 dm3.
solution, it is found that 27.20 cm3 of the diluted
20.0 cm3 of this solution just reacted with
hydrochloric acid is needed to neutralise 25.0 cm3
25.0 cm3 of 0.080 mol dm–3 sodium hydroxide.
of the sodium carbonate solution.
a) Write the equation for the reaction.
What is the equation for the reaction?
b) Calculate the amount in moles of sodium
(H = 1, O = 16, P = 31) (6)
carbonate in 25.0 cm3 of solution.
Challenge
c) Calculate the concentration of the diluted
hydrochloric acid. 28 Beachy Head, near Eastbourne in East Sussex,
d) What is the concentration of the is a dominating chalk cliff characteristic of the
hydrochloric acid before dilution? (5) scenery of that part of the south coast. The soft
chalk is subject to erosion by the sea. Areas of
24 25 cm3 of 0.050 mol dm–3 sodium hydroxide the cliff edge have to be cordoned off when they
solution, NaOH(aq), just reacts with 27.8 cm3 of become unstable; they will eventually fall into the
0.045 mol dm–3 ethanoic acid, CH3COOH(aq). sea. Constant monitoring of the state of the cliff
a) Calculate how many moles there are in each is essential to ensure public safety.
solution and use this to state how many A soil sample taken from the area consists of
moles of sodium hydroxide react with one large amounts of chalk (calcium carbonate) with
mole of ethanoic acid. some clay and other silicate materials, as well as
b) Write an equation for the reaction. (4) decomposing organic matter. Assuming that the

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 chalk is the only material that reacts with dilute d) Deduce the amount in moles in 100.0
acid, there are several ways of determining the cm3 of the hydrochloric acid after it
percentage of chalk in the soil sample. reacts with the soil sample.
A Collection of carbon dioxide e) Calculate the amount in moles of
A 1.00 g sample of a soil is reacted with hydrochloric acid in the 100.0 cm3 before
excess hydrochloric acid and the carbon it reacts with the soil sample.
dioxide evolved is collected over water. After f) Use your answers to (d) and (e)
cooling to room temperature, 89 cm3 of to deduce the amount in moles of
carbon dioxide is obtained. hydrochloric acid that react with the soil
a) Write a balanced equation for the sample.
reaction between calcium carbonate and g) Write the equation for the reaction
hydrochloric acid. between calcium carbonate and
b) Calculate the amount in moles of carbon hydrochloric acid.
dioxide obtained. h) Use the equation in (g) and your answer
c) Deduce the amount in moles of calcium to (f) to state the amount in moles of
carbonate that react. calcium carbonate in 10.00 g of soil.
d) Calculate the mass of calcium carbonate i) Deduce the mass of calcium carbonate in
that reacts. 10.00 g of soil.
e) Calculate the percentage of chalk in the j) Calculate the percentage of chalk in the
soil sample. soil sample.
B Back titration C Consider the experimental methods in
10.00 g of soil is added to 100.0 cm3 Questions A and B. Suggest reasons for the
of hydrochloric acid of concentration difference in the answers for the percentage
1.00 mol dm–3. Once all the chalk has reacted, of chalk in the soil sample obtained by the
the residue is allowed to settle. Excess acid two methods.
remains in the solution. Using a pipette, D Two other possible methods of determining
25.00 cm3 of this solution is carefully removed the percentage of chalk in a sample of the soil
and titrated against 0.0500 mol dm-3 sodium are as follows:
carbonate solution. 23.10 cm3 is required to • A weighed sample of the soil is heated
neutralise the acid. strongly and the volume of carbon dioxide
a) Write a balanced equation for the evolved is measured.
reaction between sodium carbonate and • A weighed sample of the soil is reacted
hydrochloric acid. with dilute hydrochloric acid until all the
Chapter 5  Amount of substance – moles in solution

b) Calculate the amount in moles of sodium chalk dissolves. The solution is filtered
carbonate in the 23.10 cm3 required by and the mass of the unreacted residue is
the titration. found.
c) Use your answer to (b) to deduce the Consider each of these methods and
amount in moles of hydrochloric acid suggest, with reasons, whether they would
contained in 25.00 cm3 of the solution. be likely to produce an accurate result. (20)

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 Chapter 6
Types of reaction –
precipitation, acid–base
and redox
Prior knowledge
In this chapter it is assumed that you are familiar with:
● formulae
● balancing equations
● mole calculations.

For example, you should be aware that reactions occur because atoms can
lose, gain or share electrons with other atoms. The number of electrons
gained, lost or shared by an atom is known as its valency and the valency
can be used to determine the formula of compounds. Valencies for common
elements and groups are shown in Table 3.1, page 29.

Test yourself on prior knowledge

1 Write the formula of:
a) sodium carbonate
b) calcium hydroxide
c) ammonium sulfate
d) magnesium hydrogencarbonate.
2 Calculate the molar mass of:
a) Ca(OH)2
b) C6H12O6
c) CuSO4 5H2O
●

d) K2Cr2O7.
3 a) Calculate the mass of 0.25 mol of NaOH.
b) Calculate the amount in moles in 25.0 cm3 of 0.2 mol dm –3 solution of
H2SO4.
c) Calculate the volume, at room temperature and pressure, of 0.25 mol
Tip of H2(g).
If you are unfamiliar with simple 4 Divide the following compounds into two groups: ionic and covalent.
ideas of bonding, you should copper(ii) hydroxide  silver nitrate  phosphorus trichloride 
look at Chapter 7 pages 89–92 chromium(iii) oxide  ammonium chloride  sulfur dioxide 
and 94–96. silicon dioxide  carbon disulfide  barium chloride  magnesium oxide

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 Classifying chemical reactions
Classification of chemical reactions helps chemists to understand the
way in which elements or compounds react. There are a limited number
of reaction types:
● precipitation reactions
● redox reactions
● acid–base reactions.

Precipitation reactions
In a precipitation reaction, a cation and an anion in solution combine
to form an insoluble substance that precipitates out as a solid.
Cations are positive ions such as Na+, Mg2+ and Cu2+. They are usually
metallic ions but do include H+ and NH4+.
Anions are negative ions such as Cl–, Br–, CO32–, SO42–, NO3 – and OH –.
If two solutions are mixed, one being an aqueous solution of a
carbonate and the other containing a metal with an insoluble carbonate,
the metal carbonate precipitates instantly. Insoluble copper(ii) carbonate,
Tip for example, can be formed by mixing aqueous sodium carbonate with
Use the state symbols as a guide: aqueous copper(ii) sulfate:
● (aq) indicates an ionic Na2CO3(aq) + CuSO4(aq) → CuCO3(s) + Na2SO4(aq)
substance and the ions are
The best way to summarise this is to use an ionic equation (Chapter 3,
mobile and separate and
pages 33–35). The equation includes state symbols.
therefore can be written as
separate ions CO32–(aq) + Cu2+(aq) → CuCO3(s)
Chapter 6  Types of reaction – precipitation, acid–base and redox

● (g) indicates a gas which is

A second precipitation reaction involves the reaction between a solution
usually covalent
of potassium chloride and solution of silver nitrate.
● (l) indicates a liquid which is
usually covalent KCl(aq) + AgNO3(aq) → AgCl(s) + KNO3(aq)
● (s) indicates a solid in which
This can be simplified to:
the particles are not mobile;
even if the substance is ionic Cl–(aq) + Ag+(aq) → AgCl(s)
the ions should not be written
Precipitation reactions are used as a test for halide ions (Chapter 9,
separately.
page 139).

Test yourself
1 Write an ionic equation for the following reactions:
a) 2NaOH(aq) + FeCl2(aq) → 2NaCl(aq) + Fe(OH)2(s)
b) Na2SO4(aq) + BaCl2(aq) → BaSO4(s) + 2NaCl(aq)
c) PbCl2(aq) + K2S(aq) → PbS(s) + 2KCl(aq)
d) formation of solid zinc hydroxide from solutions of zinc chloride and
sodium hydroxide.

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 Redox reactions
Redox reactions
In a redox reaction, electrons are transferred from one substance to
another. Some everyday examples of redox reactions include combustion
of fuels and the rusting of iron.
Oxidation was originally defined as the gaining of oxygen. For example,
when zinc reacts with oxygen to form zinc oxide, the zinc is oxidised:
Zn(s) + 1 O2(g) → ZnO(s)
2 
Closer inspection shows that the zinc atom becomes a zinc ion and in
doing so loses two electrons:
Zn → Zn2+ + 2e–
Therefore, a species is oxidised if it loses electrons; a species is reduced
if it gains electrons. You may find the mnemonic OILRIG useful:
Oxidation Is Loss Reduction Is Gain

Oxidation number
Chemists use oxidation numbers to keep track of the electrons
transferred or shared during a reaction. It is a convenient way of quickly
identifying whether or not a substance has undergone oxidation or
reduction. If oxidation numbers change during a reaction then oxidation
and reduction has occurred and a redox reaction has taken place.
In order to work out the oxidation number, you must first learn a few
simple rules (Table 6.1).
Table 6.1 Rules for determining oxidation numbers.

Rule Example
All elements in their natural state have Hydrogen, H2; oxidation number = 0
the oxidation number zero
Oxidation numbers of the atoms of any Water, H2O; sum of oxidation
molecule add up to zero numbers = 0
Oxidation numbers of the components of Sulfate, SO42–; sum of oxidation
any ion add up to the charge on that ion numbers = –2

The oxidation numbers of some elements in a molecule or ion never

change; other elements have more than one oxidation number.
When calculating the oxidation numbers of elements in either a
molecule or an ion, you should apply the following order of priority:
1 The oxidation numbers of elements in Groups 1, 2 and 13 are always
Tip
+1, +2 and +3 respectively.
If an element can form
2 The oxidation number of fluorine is always –1.
compounds in which its
oxidation state varies, Roman 3 The oxidation number of hydrogen is usually +1.
numerals are used in the name
4 The oxidation number of oxygen is usually –2.
to differentiate between them.
For example iron chloride can 5 The oxidation number of chlorine is usually –1.
be either FeCl2 or FeCl3. FeCl2 is
Using these rules, it is possible to deduce any oxidation number.
named iron (ii) chloride whilst
However, it is important that they are applied in sequence, as hydrogen,
FeCl3 is named iron (iii) chloride.
oxygen and chlorine can vary.
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 In a metallic hydride such as NaH, H has oxidation number –1 and not
the usual +1 (Na is in group 1 and has priority over the H).
In a peroxide such as H2O2, O has oxidation number –1 and not the
usual –2 (H has priority over O).
The following worked examples show how the oxidation number of
chlorine can also vary.

Example 1 Using the order of priority given above, the oxidation

Deduce the oxidation number of Cl in NaCl. number of Na must be +1.

Answer The oxidation number of Cl must balance this.

The sum of the oxidation numbers in NaCl must add up Therefore, the oxidation number of Cl in NaCl is –1.
to zero.

Example 2 In order of priority, Na comes first and its oxidation

Deduce the oxidation number of Cl in NaClO. number must be +1; O is second and its oxidation
number is –2.
Answer
The sum of the oxidation numbers in NaClO must add For the oxidation numbers to add up to zero, the
up to zero. oxidation number of Cl in NaClO must be +1.

Example 3 There are three oxygen atoms in ClO3– so the total

Deduce the oxidation number of Cl in ClO3–. for oxygen is –6.

Answer For the oxidation numbers to add up to –1 (the charge

The sum of the oxidation numbers in ClO3– must add up of the ion), the oxidation number of Cl in ClO3– must
to the charge on the ion, i.e. they must add up to –1 be +5. This is reflected in the name of ClO3– which is
Chapter 6  Types of reaction – precipitation, acid–base and redox

chlorate(v).
In order of priority, O comes first and its oxidation
number is –2.

oxidation numbers Consider the following reaction:

0 +1 –2 +2 –2 0 Mg(s) + H2O(g) → MgO(s) + H2(g)
Mg(s) + H2O(g) → MgO(s) + H2(g) This reaction occurs when magnesium is heated with steam. It is easy to
see that magnesium is oxidised (it has gained oxygen) and that water is
reduced (it has lost oxygen). The oxidation numbers for this reaction are
Mg loses electrons H gains shown on the left:
an electron ● An increase in oxidation number is due to oxidation. Magnesium
changes from 0 to +2.
Tip ● A decrease in oxidation number is due to reduction. H changes from
In the reaction above the +1 to 0.
oxidation number of Mg Consider the reaction between Mg(s) and Cl2(g):
increases by +2 and H decreases
by –1. oxidation numbers 0 0 +2 –1
Mg(s)  +  Cl2  →  MgCl2

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 Redox reactions
Electron transfer can be shown by half-equations. In this example, the
half-equations are:
Mg → Mg2+ + 2e– (loss of electrons = oxidation) (magnesium readily
loses electrons)
Cl2 + 2e– → 2Cl– (gain of electrons = reduction) (chlorine readily
gains electrons)
● An oxidising agent encourages oxidation. It is a substance that
receives electrons readily.
● A reducing agent encourages reduction. It is a substance that
donates electrons readily.
Group 2 elements form 2+ ions, each atom releasing two electrons.
Therefore, they are reducing agents.
Group 17 elements form 1– ions, each atom receiving one electron.
Therefore, they are oxidising agents.
Electron loss occurs more readily on descending a group of the periodic
table (page 120).
Electron loss occurs less readily across a period of the periodic table.
It follows from this that, in Groups 1 and 2, the elements at the bottom
of the groups most easily lose electrons and are therefore:
● most easily oxidised
● the best reducing agents.
The opposite is true for the ability to gain an electron, so fluorine is the
best oxidising agent.
The trends shown in Table 6.2 occur elsewhere in the periodic table.
Table 6.2 Reducing and oxidising power in Groups 2 and 17.

Group 2 Group 17
Be A barium atom loses its F2 A fluorine atom is most
Mg outer electrons most easily, Cl 2 likely to gain an electron,
therefore it is: therefore it is:
Ca ● most easily oxidised Br2 ● most easily reduced
Sr ● the best reducing agent I2 ● the best oxidising agent
in Group 2 in Group 17
Ba

Test yourself
2 Deduce the oxidation numbers of each element in the following:
a) i) H2O  ii)  NaOH  iii)  KNO3  iv)  NH3   v)  N2O
b) i) SO42–  ii)  CO32–   iii)  NH4+  iv)  MnO4 –  v)  Cr2O72–
3 In the reaction Ca(s) + 2HCl(aq) → CaCl2(aq) + H2(g)
a) what has been oxidised
b) what is the reducing agent?

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 Acid–base reactions
Testing for acids and bases
You will be aware of the pH scale and that:
● acids and acidic solution have pH below 7
● alkalis and alkaline solutions have pH above 7
● neutral solutions have a pH of 7.

Key term Indicators are a convenient method for testing for acids and bases
(Figure 6.1).
An indicator is a substance that
changes colour with a change in pH. pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
strong acid weak acid neutral weak alkali strong alkali
increasing acidity increasing alkalinity

litmus

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
universal
indicator
Figure 6.1 Colours of litmus and universal indicator with solutions at different pH.

Acids and bases

Key term Reactions of acids involve the transfer of a hydrogen ion from one
substance (the acid) to another (the base). Since the hydrogen ion, H+, is
An acid is a proton donor. in fact a proton, acids are described as proton donors.
Acids include:
Chapter 6  Types of reaction – precipitation, acid–base and redox

● hydrochloric acid, HCl

● sulfuric acid, H2SO4
● nitric acid, HNO3
● phosphoric acid, H3PO4
● ethanoic acid, CH3COOH

Key terms Acids such as HCl, H2SO4 and HNO3 are strong acids and, when
dissolved in water, completely dissociate into their ions. Equations for
A strong acid is a proton donor strong acids always contain the ‘→’ arrow symbol.
that completely dissociates into
its ions in water. HCl(aq) → H+(aq) + Cl–(aq)
A weak acid is a proton donor that Organic acids such as CH3COOH are weak acids and when dissolved in
only partially dissociates into its water only partially dissociate into their ions. Equations for weak acids
ions in water. always contain the ‘  ’ arrow symbol.
CH3COOH(aq)  CH3COO–(aq) + H+(aq)
Water plays an important role in acidity. In the absence of water, many
of the substances called acids show none of the typical acid properties.
Hydrochloric acid, for example, is an aqueous solution of the covalent
gas hydrogen chloride. Non-metallic oxides such as CO2 or SO2 can
react with water to form acidic solutions.
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 Acid–base reactions
CO2(g) + H2O(l)  H2CO3(aq)  2H+(aq) + CO32–(aq)
SO2(g) + H2O(l)  H2SO3(aq)  2H+(aq) + SO32–(aq)
Both H2CO3(aq) and H2SO3(aq) are able to donate H+(aq) ions and so
can behave as acids.
A base is a substance that can react with the hydrogen ion released by
Key terms
an acid. Bases can be regarded as proton (hydrogen ion) acceptors.
A base is a proton acceptor. Typical bases are oxides or hydroxides of metals.
An alkali is a soluble base; it can
If a base dissolves in water (most do not), it is referred to as an alkali.
accept protons in solution.
Examples include:
● sodium hydroxide, NaOH
● potassium hydroxide, KOH
● ammonia, NH3.
An alkali releases hydroxide ions (OH –) in aqueous solution. For example:
Tip
NaOH(aq) → Na+(aq) + OH –(aq)
The ‘→’ symbol indicates that
NaOH is a strong base and The inclusion of ammonia in the list of alkalis may seem odd because,
completely dissociates into its as a gas, it does not contain hydroxide ions. However, when ammonia
ions- dissolves in water it reacts to produce the ionic compound ammonium
hydroxide, NH4OH which is a weak base. The reaction is an example of
Bases an equilibrium reaction since, once dissolved, there is a mixture of all
NaOH four components, NH3, H2O, NH4+ and OH –:
Na2O
NH3(g) + H2O(l)  NH4OH(aq)  NH4+(aq) + OH –(aq)
KOH
Alkalis In this example it is easy to see why bases are regarded as proton
CuO
e.g. NaOH, KOH, acceptors. The ammonia molecule, NH3, has received a hydrogen ion to
Ca(OH)2, NH3 become an ammonium ion, NH4+.
NH3
K2O Some metallic oxides react with water to produce hydroxides:
Ca(OH)2
Cu(OH)2 K2O(s) + H2O(l) → 2KOH(aq)
CaO(s) + H2O(l) → Ca(OH)2(aq)
Figure 6.2 Alkalis are a subsection of
bases. They are soluble in water. Most other metal oxides and hydroxides are insoluble in water and are
therefore bases not alkalis.

The role of water in acidity and alkalinity

The properties of acids and alkalis described above apply to their solutions in
water. If water is not present dry hydrogen chloride and dry sulfuric acid have
no effect on dry litmus paper, which means that substances that we call
acids do not behave like acids in the absence of water. When water is added,
they become acidic straight away. Blue litmus paper turns red immediately.
Similar experiments with dry calcium hydroxide show that water must
be present before it will behave like an alkali.
As a general rule, water must be present for substances to act as acids
and alkalis:
● when acids dissolve in water, H+ ions are formed
● when the alkalis dissolve in water, OH – ions are formed.
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 water
HCl(g) H+(aq) + Cl–(aq)
acid
water
NaOH(s) Na+(aq) + OH –(aq)
base
In water, hydrogen ions, H , are attached to water molecules. Because
+

of this, the H+ ions are described as hydrated and are sometimes

represented as H3O+(aq), or more usually as H+(aq).
In water, the hydroxide ions, OH –(aq), are mobile and free to move.
Water is a polar molecule and is attracted to the ions in the lattice.
This attraction, hydration energy, is sufficient to break down the bonds
within the lattice such that the hydrated ions are free to move (see
Chapter 7, page 93).
Key term
A salt is formed when an acid has Salts
one or more of its hydrogen ions Acids react with metals, carbonates, bases or alkalis to form salts.
replaced by either a metal ion or
The formation of salts is illustrated by the following typical reactions
an ammonium ion.
of acids.

Tip Reaction of an acid and a base – neutralisation

MgO is ionic but because it is in Dilute hydrochloric acid reacts with magnesium oxide to produce
the (s) state we do not write the magnesium chloride and water, according to the equation:
ions separately, as when solid 2HCl(aq) + MgO(s) → MgCl2(aq) + H2O(l)
the ions are not mobile.
The ionic equation is:
Chapter 6  Types of reaction – precipitation, acid–base and redox

2H+(aq) + MgO(s) → Mg2+(aq) + H2O(l)

Reaction of an acid and an alkali – neutralisation

Dilute hydrochloric acid reacts with sodium hydroxide to produce
sodium chloride and water, according to the equation:
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)
The ionic equation is:
H+(aq) + OH – (aq) → H2O(l)
Ammonia can react with an acid to produce a salt. Ammonium
sulfate, (NH4)2SO4, is used as a fertiliser. It is manufactured by reacting
ammonia with sulfuric acid:
2NH3(aq) + H2SO4(aq) → (NH4)2SO4(aq)
The ionic equation is:
2NH3(aq) + 2H+ (aq) → 2NH4+(aq)

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 Acid–base reactions
Tip Some organic molecules that contain the –COOH are also acidic. The H
in the –COOH is the acidic hydrogen and such chemicals can donate a
All acid–base reactions can H+(aq).
be represented by the ionic
equation: CH3COOH(aq) + NaOH(aq) → CH3COONa (aq) + H2O(l)
H+(aq) + OH –(aq) → H2O(l) The ionic equation is:
H+(aq) + OH – (aq) → H2O(l)

Reaction of an acid and a carbonate – neutralisation

Dilute hydrochloric acid reacts with sodium carbonate to produce
sodium chloride, water and carbon dioxide, according to the equation:
2HCl(aq) + Na2CO3(aq) → 2NaCl(aq) + H2O(l) + CO2(g)
The ionic equation is:
2H+(aq) + CO32–(aq) → H2O(l) + CO2(g)

Reaction of an acid and a metal

Most metals react with an acid to produce a salt. Metals such as copper
and silver only react with very concentrated acids. Some acids (e.g. nitric
acid) produce complex products, but many acids (e.g. dilute hydrochloric
and sulfuric acids) react with a metal to produce a salt and hydrogen.
Magnesium reacts with sulfuric acid to produce magnesium sulfate and
hydrogen, according to the equation:
Mg(s) + H2SO4(aq) → MgSO4(aq) + H2(g)
The ionic equation is:
Mg(s) + 2H+(aq) → Mg2+(aq) + H2(g)
It can be seen from the equations that this is a redox reaction. The
magnesium atom loses two electrons to become an Mg2+ ion; the two
hydrogen ions from the acid each gain an electron to create a diatomic
molecule of hydrogen gas. The magnesium is oxidised and the hydrogen
ions are reduced.
In terms of oxidation number:
● the magnesium changes from oxidation number 0 to +2
● each hydrogen ion changes from oxidation number +1 to 0
All the reactions between acids and metals are redox reactions. A
further illustration is the reaction of hydrochloric acid and zinc to
produce zinc chloride and hydrogen:
Zn(s) + 2HCl(aq) → ZnCl2(aq) + H2(g)
The ionic equation is:
Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g)
The zinc is oxidised and the hydrogen is reduced.

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 Salts formed from acids with more than one
acidic hydrogen
There are a number of acids that contain more than one acidic
hydrogen; the most common example is sulfuric acid, H2SO4. Sulfuric
acid has two acidic protons and one mole of H2SO4 can react with
two moles of a base such as NaOH(aq), hence the term ‘dibasic acid’
or ‘diprotic acid’. It is possible to form two different salts by reacting
sulfuric acid with sodium hydroxide. If one acid proton is replaced by the
sodium ion we obtain sodium hydrogensulfate, NaHSO4, but if both are
replaced sodium sulfate is produced, Na2SO4.
Phosphoric acid, H3PO4, is a tribasic acid as it has three acidic hydrogens
and it is possible to form three different salts:
Tip 1 sodium dihydrogenphosphate, NaH2PO4, in which one acidic
Sodium hydrogenphosphate hydrogen is replaced by the metal ion
could also be named as 2 sodium hydrogenphosphate, Na2HPO4, in which two acidic
disodium hydrogenphosphate. hydrogens are replaced by the metal ions
Sodium phosphate could also be
named as trisodium phosphate. 3 sodium phosphate, Na3PO4, in which three acidic hydrogens are
replaced by the metal ions.

Tests for ions

Ions in solution can be detected by a range of simple qualitative test-
tube reactions. The sequence of testing should be test for carbonate
Tip first, then test for sulfate and finally test for halide as BaCO3 and Ag2SO4
are both white insoluble compounds.
It is better to use Ba(NO3)2(aq)
as the nitrate ion would not
Tests for carbonate ions
Chapter 6  Types of reaction – precipitation, acid–base and redox

interfere with the subsequent

halide test. All carbonates react with dilute acids to produce a salt, water and
carbon dioxide. The evolution of carbon dioxide can be observed by the
effervescence (bubbles) (Table 6.4).
Table 6.4 Tests for carbonate ions.

Reaction Observations
CaCO3(s) + 2HCl(aq) → CaCl 2(aq) + H2O(l) + CO2(g) Solid reacts and goes into solution
CaCO3(s) + 2H+(aq) → Ca2+(aq) + 2Cl–(aq) + H2O(l) + CO2(g) Bubbles are given off / effervescence
Na2CO3(aq) + 2HCl(aq) → 2NaCl(aq) + H2O(l) + CO2(g) Bubbles are given off / effervescence
CO32–(aq) + 2H+(aq) → H2O(l) + CO2(g)

Tests for sulfate ions

Sulfates can be detected by adding a solution of barium chloride,
BaCl2(aq) or Ba(NO3)2(aq). A white precipitate of BaSO4(s) is produced
(Table 6.5).
Table 6.5 Test for sulfate ions.

Reaction Observations
Na2SO4(aq) + Ba(NO3)2(aq) → 2NaNO3(aq) + BaSO4(s) A white precipitate is formed
SO42–(aq) + Ba2+(aq) → BaSO4(s)

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 Acid–base reactions
Tests for halide ions
Halides can be detected by adding a solution of silver nitrate, AgNO3(aq)
(Table 6.6). Precipitates of the silver halides are formed except with the
fluoride. Ammonia can be added to the precipitates; the chloride
re-dissolves in dilute ammonia, the bromide re-dissolves in concentrated
ammonia and the iodide remains insoluble.
Table 6.6 Tests for halide ions.

Reaction Observations
NaCl(aq) + AgNO3(aq) → NaNO3(aq) + AgCl(s) A white precipitate is formed which re-dissolves in dilute ammonia
Cl–(aq) + Ag+(aq) → AgCl(s)
NaBr(aq) + AgNO3(aq) → NaNO3(aq) + AgBr(s) A cream precipitate is formed which re-dissolves in concentrated ammonia
Br–(aq) + Ag+(aq) → AgBr(s)
NaI(aq) + AgNO3(aq) → NaNO3(aq) + AgI(s) A yellow precipitate is formed which remains insoluble
I –(aq) + Ag+(aq) → AgI(s)

Tests for ammonium ions

Ammonium ions can be detected by warming NH4+(aq) with dilute
sodium hydroxide (Table 6.7). NH3(g) is produced which turns moist red
litmus blue.
Table 6.7 Tests for ammonium ions.

Reaction Observations
NH4Cl(aq) + NaOH(aq) → NaCl(aq) + NH3(g) + H2O(l) NH3(g) will be evolved
NH4+(aq) + OH –(aq) → NH3(g) + H2O(l) NH4+(aq) and and the litmus will
NaOH(aq) turn blue
moist red
litmus
heat

Test yourself
4 Write balanced equations for each of the following reactions:
a) barium hydroxide(s) + nitric acid(aq) → barium nitrate(aq) + water(l)
b) copper(ii) carbonate(s) + sulfuric acid(aq) → copper(ii) sulfate(aq) + water(l) + carbon dioxide(g)
c) lithium(s) + hydrochloric acid → lithium chloride(aq) + hydrogen(g)
5 Write an ionic equation for each of the following reactions:
a) barium hydroxide(s) + nitric acid(aq) → barium nitrate(aq) + water(l)
b) copper(ii) carbonate(s) + sulfuric acid(aq) → copper(ii) sulfate(aq) + water(l) + carbon dioxide(g)
c) lithium(s) + hydrochloric acid → lithium chloride(aq) + hydrogen(g)
6 Deduce the formula of all possible salts that could be formed from:
a) reaction of KOH(aq) with H2S(aq)
b) reaction of Ca(OH)2 with H2CO3(aq)

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 Practice questions
Multiple choice questions 1–10 11 Deduce the oxidation numbers of the element
Answers to Questions 1 to 6 relate to the following underlined in each of the following:
types of reaction: a) Rb2O
A precipitation only b) SnCl2
B redox only c) SnO2
C acid–base only d) S2O32– (4)
D a combination of more than one of the above. 12 What are the oxidation numbers of nitrogen in
Which type of reaction is illustrated by each of the these molecules:
following? N2, NH3, N2H4, HNO3, NH4Cl, HNO2, NH2OH
1 Br2(aq) + 2NaI(aq) → 2NaBr(aq) + I2(aq) and NF3? (8)
2 BaCl2(aq) + H2SO4(aq) → BaSO4(s) + 2HCl(aq) 13 Write equations, including state symbols, for
3 CH3COOH(aq) + NaOH(aq) → each of the following reactions.
CH3COO–Na+(aq) + H2O(l) State what you would see, if anything, during
each reaction.
4 Ba(OH)2(aq) + H2SO4(aq) → BaSO4(s) + 2H2O(l) a) magnesium + sulfuric acid
5 SrO(s) + 2HNO3(aq) → Sr(NO3)2(aq) + H2O(l) b) lithium carbonate solid + nitric acid
c) aluminium oxide solid + hydrochloric acid (3)
6 Cu(s) + 4HNO3(aq) → Cu(NO3)2(aq) + 2NO2(g)
+ 2H2O(l) 14 Chlorine forms a number of different chlorate
Use the key below to answer Questions 7 to 10. ions with oxygen. In each of the ions below
deduce the oxidation number of chlorine and
A B C D name the ions.
1, 2 & 3 1, 2 correct 2, 3 correct 1 only Cl– oxidation number ...............................................
correct correct name ..............................................................................
ClO– oxidation number ...........................................
7 Which of the following underlined elements have name ..............................................................................
Chapter 6 Types of reaction – precipitation, acid–base and redox

oxidation state 6? ClO2– oxidation number ..........................................

1 NaClO3 2 SO42– 3 K2Cr2O7 name ..............................................................................
ClO3– oxidation number ..........................................
8 In which of these conversions is the chlorine
name ..............................................................................
oxidised?
ClO4– oxidation number ..........................................
(The conversions shown below are not balanced
name .............................................................................. (5)
and do not represent equations.)
1 Cl2 → ClO– 15 These are incomplete half-equations for changes
2 ClO– → ClO3– involving reduction. Copy and complete and
3 Cl2 + I2 → ICl balance the half-equations. You need to add the
electrons.
9 In which of the following reactions is the
a) H+(aq) → H2(g)
underlined the reducing agent?
b) Fe3+(aq) → Fe2+(aq)
1 4Au(s) + 8CN–(aq) + 2H2O(l) + O2(g) →
c) Br2(aq) → 2Br–(aq) (3)
4[Au(CN)2] –(aq) + 4OH–(aq)
2 2Cu2+(aq) + 4I– (aq) → 2CuI(s) + I2(aq) 16 These are incomplete half-equations for changes
3 Ag2S(s) + 4CN–(aq) → 2 [Ag(CN)2] –(aq) + involving oxidation. Copy and complete and
S2–(aq) balance the half-equations. You need to add the
electrons.
10 Phosphoric acid, H3PO4, can react with
a) Na(s) → Na+(aq)
magnesium hydroxide, Mg(OH)2, to form a salt
b) Zn(s) → Zn2+(aq)
and water. The salt could have the formula:
c) I–(aq) → I2(aq) (3)
1 Mg(HPO4) 2 Mg3(PO4)2 3 Mg(H2PO4)2

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 Practice questions
17 Pick a reduction from Question 15 and an i) One type of indigestion tablet contains
oxidation from Question 16 and combine them magnesium hydroxide. Write an
to give the full ionic equation for the reactions equation, with state symbols, for the
between: reaction of magnesium hydroxide with
a) bromine with iodide ions hydrochloric acid.
b) iron(iii) ions with iodide ions ii) How does the pH in the stomach
c) hydrogen ions with zinc. (6) change after a person takes the tablets?
iii) Explain why magnesium hydroxide acts
18 Ammonium sulfate was prepared by adding
as a base when it reacts with stomach
ammonia solution to 25 cm3 of 2.0 mol dm–3
acid. (10)
sulfuric acid.
20 a) An aqueous solution of compound A reacts
2NH3(aq) + H2SO4(aq) → (NH4)2SO4(aq)
with an aqueous solution of hydrochloric
a) i) What volume of 2.0 mol dm–3 ammonia acid and a vigorous effervescence in seen.
solution will just neutralise the sulfuric In a second reaction compound B reacts
acid? with aqueous sodium hydroxide and the
ii) How could you test to check that fumes turn moist red litmus blue. Write ionic
enough ammonia had been added to equations for each reaction. Explain your
neutralise all of the acid? reasoning.
b) Explain why hydrogen chloride, HCl, acts as b) An aqueous solution of compound B reacts
an acid and ammonia, NH3, acts as a base in separately with aqueous solutions of sulfuric
the equation below. acid and with silver nitrate to produce a
white precipitate in each reaction. Write ionic
HCl(g) + NH3(g) → NH4+Cl–(s)
equations for each reaction. Explain your
c) Which of the reactants acts as an acid in the reasoning. (10)
following equation?
21 Acids are proton donors and salts are formed
HCO3 (aq) + H2O(l) → CO3 (aq) + H3O (aq)
– 2– + when the H+ in an acid is replaced by either a
metal ion or an ammonium ion. The table below
d) Which of the reactants acts as a base in the
shows the formula of some acids:
following equation?
Acid Carbonic Phosphoric Chloric(i)
HCO3–(aq) + H3O+(aq) → H2CO3(aq) + H2O(l) acid acid acid
(5) Formula of H2CO3 H3PO4 HOCl
acid
19 Acids and bases are commonly used in our homes.
a) Baking powder contains sodium hydrogen- Deduce the formula of all possible salts that
carbonate, NaHCO3, mixed with an acid. could be formed when:
i) When water is added, the baking powder a) potassium hydroxide reacts with carbonic acid
releases carbon dioxide. Why does the b) magnesium hydroxide reacts with carbonic acid
reaction not occur until water is added? c) potassium hydroxide reacts with phosphoric
ii) The acid in baking powder can be acid
written as H2X. This produces two H+ d) magnesium oxide reacts with phosphoric acid
ions per molecule of H2X. Write an e) potassium hydroxide reacts with chloric(i) acid
equation to show the ions produced f) magnesium oxide reacts with chloric(i) acid
from H2X when water is added to it. (11)
iii) Write an equation for the reaction 22 a) Many naturally occurring organic compounds
between sodium hydrogencarbonate are acidic. Most contain the –COOH group in
and H2X when water is added to baking which the H can be replaced to form a salt.
powder. Ethanoic acid has the formula CH3COOH and
b) Indigestion tablets contain bases that it can react with NaOH, a base, to form the
cure indigestion by neutralising excess salt sodium ethanoate, CH3COO–Na+, which
hydrochloric acid in the stomach. can be written more simply as CH3COONa.

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 What is the formula of magnesium b) The gastric juice of the patient was found
ethanoate? to contain the equivalent of a 0.05 mol dm–3
b) Ethanedioic acid (also known as oxalic acid), solution of hydrochloric acid. The patient
HOOC–COOH, can also form salts. What is produces 2 dm3 of gastric juice in a day. This
the formula of: volume of gastric juice is to be treated with
i) potassium ethanedioate (also known as tablets containing aluminium hydroxide. Each
potassium oxalate) tablet contains 520 mg aluminium hydroxide
ii) magnesium ethanedioate (also known per tablet.
as magnesium oxalate)? (3) i) Calculate the mass of aluminium
hydroxide required to neutralise the
23 A sample of limestone (impure calcium
2 dm3 of gastric juice.
carbonate) weighing 0.20 g was reacted with
ii) Deduce the number of tablets that have
50 cm3 of 0.10 mol dm–3 hydrochloric acid.
to be taken. (6)
CaCO3(s) + 2HCl(aq) → CaCl2(aq) + CO2(g) +
H2O(l) Challenge
25 Lactic acid, CH3CH(OH)COOH is a naturally
The hydrochloric acid was in excess, and
occurring acid that reacts with NaOH(aq) to
the excess HCl(aq) reacted with 14 cm3 of
produce the salt sodium lactate, CH3CH(OH)
0.10 mol dm–3 sodium hydroxide.
COO–Na+.
Calculate the percentage by mass of calcium
Citric acid, HOC(COOH)3, is also a naturally
carbonate in the limestone. (7)
occurring acid and forms salts in the same way
24 A patient suffering from a duodenal ulcer as lactic acid.
displays increased acidity in their gastric juices. a) Deduce the formula of sodium citrate.
The acid responsible for the acidity in the gastric Citric acid also reacts with calcium hydroxide.
juice is hydrochloric acid. One of the most b) Construct a balanced equation for the
common medications designed for the relief of reaction between citric acid and calcium
excess stomach acidity is aluminium hydroxide. hydroxide. (5)
a) Write an equation for the reaction between
hydrochloric acid and aluminium hydroxide.
Chapter 6 Types of reaction – precipitation, acid–base and redox

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 Chapter 7
Bonding and structure
Prior knowledge
In this chapter it is assumed that you are familiar with:
● atomic number and mass number
● composition of atoms and ions in terms of protons, neutrons and

electrons
● electronic configuration using the s, p and d notation.

Test yourself on prior knowledge

1 Define atomic number and mass number.
2 Deduce the numbers of protons, neutrons and electrons in each of the
following:
a) 27
13
Al b) 204
81
Tl c) 127
52
Te2– d) 50
23
V3+
3 Sodium and chlorine atoms both have three shells. Draw diagrams of each
to show the distribution of electrons.
4 Write the full electronic configuration of:
a) 75
33
As b) 32
16
S2– c) 52
24
Cr d) 56
26
Fe3+

Introducing bonding and structure

One of the central aims in chemistry is to explain the properties of
different substances in terms of their bonding and structure. The
bonding and structure is determined by the arrangement of electrons in
the outer shells of the atoms involved in the bonding. Atoms bond or
combine in two main ways:
● by losing or gaining electrons (ionic bonding)
● by sharing electrons (covalent bonding).
The noble gases are not reactive and in the early twentieth century it was
suggested that this lack of reactivity was associated with the electron
configuration of the noble gases. This led to the suggestion that when atoms
of elements combine to form compounds, they do so by gaining, losing or
sharing electrons to attain the same number of electrons as a noble gas.
The full electron configurations of the noble gases helium, neon, argon
and krypton are:
●
2
He – 1s2
●
10
Ne – 1s22s22p6
●
18
Ar – 1s22s22p63s23p6
● Kr – 1s22s22p63s23p63d104s24p6 which can also be written as
36
1s22s22p63s23p64s23d104p6.

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 Lighter elements, for example hydrogen and lithium, produce compounds
Tip with two electrons in their outer shells, so they have the same electron
Isoelectronic means ‘the same configuration as helium. Most other elements form compounds in which
number of electrons’. they have eight electrons in their outer shell and are isoelectronic with
a noble gas.
The capacity of an atom to form chemical bonds is the valency of
the element, see Chapter 3, page 29. This depends on the number of
electrons in the outer electron (valence) shell. The periodic table can be
used as a simple guide to predict the valency and, therefore, the number
of chemical bonds formed by an element (Table 7.1).
Table 7.1 The periodic table and valency.

Group 1 Group 2 Group 13 Group 14 Group 15 Group 16 Group 17

Period 3 Na Mg Al Si P S Cl
Valency (number of chemical bonds) 1 2 3 4 3 2 1

There are exceptions, so this table should be used only as a guide.

Ionic bonding
Key term Ionic bonds are usually formed between a metal and a non-metal.

An ionic bond is the electrostatic A metal atom loses one or more electrons from its outer (valence) shell
attraction between oppositely and the electrons are transferred to the non-metal atom or atoms. The
charged ions, the attraction resultant ions each have the electronic structure of a noble gas. (Apart
between positive and negative ions. from helium, this means eight electrons in their outer shells.)
Sodium chloride is an ionic compound formed by the transfer of an
electron from sodium atoms to chlorine atoms.
Sodium is element 11 (11Na). A sodium atom has the electron
configuration 1s22s22p6 3s1, with one electron in its outer third shell. It
loses the single outer-shell electron and forms a positive ion with the
electron configuration 1s22s22p6.
Chlorine is element 17 (17Cl). A chlorine atom has the electron
configuration 1s22s22p63s23p5, with seven electrons in its outer third shell.
It follows that chlorine will gain one electron to achieve the electron
configuration 1s22s22p63s23p6. As it has gained an electron, it is now an
ion with 18 electrons and 17 protons. Therefore, it has a charge of 1–.
The formation of sodium chloride can be shown by a dot-and-cross
Chapter 7  Bonding and structure

diagram. Dot-and-cross diagrams are simplified structures showing the

electrons in rings around the nucleus.
A sodium atom needs to lose one electron from the outer shell and a
chlorine atom needs to gain one electron:
××
××
×
× × ×
Na × × Cl × ×
× ×
××
××

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 Ionic bonding
The resultant sodium and chloride ions each have eight electrons in their
outer shells.
×× −
+ ××
••
• ×
•× × × ×

••

••
Na × Cl × ×
• ×
•• ××
Tip ××

The sodium ion could also be In examinations it is usual to show the outer electrons only:
shown with 8 electrons in the + –
•• ××
outer shell. ××

••

••
Na Cl Na + Cl

××
•

××
×

•
××
•• ××
sodium atom chlorine atom sodium ion chloride ion
(2, 8, 1) (2, 8, 7) (2, 8) (2, 8, 8)

Key term Ions formed from metal atoms are always created by the loss of
electrons and are, therefore, positively charged. They are called cations.
Cations are positively charged Ions formed from non-metal atoms by gaining electrons are negatively
ions and anions are negatively charged. They are called anions.
charged ions.
The oppositely charged ions are attracted to each other and this
constitutes the ionic bond.
×× −
•• + ××
Na+ • ×
Na •× ×
Cl × ×
••

••
× × ×
Cl− • ×
•• ××
××

When sodium and chlorine react together, vast numbers of

atoms react simultaneously. Each positive sodium ion produced
is not attracted to just one chloride ion. It is attracted to other
Figure 7.1 Ion attraction in sodium chloride. surrounding chloride ions; each chloride ion is attracted to other
surrounding sodium ions. In fact, each sodium ion is attracted to six chloride
ions and each chloride ion is attracted to six sodium ions (Figure 7.1).
In this way, the ions of sodium chloride build into a crystal structure.
In sodium chloride, each ion is co-ordinated (bonded ionically) to six
oppositely charged ions:
A giant ionic lattice is formed, which is said to be ‘6 : 6 coordinate’. In
Figure 7.2 Ionic bonding in sodium chloride, the shape of the crystal is cubic.
sodium chloride.

Cl – Na + Cl – Na +

Na + Cl – Na + Cl –

Cl – Na + Cl – Na +

Na + Cl – Na + Cl –

Figure 7.3 Sodium chloride Figure 7.4 The arrangement of ions in one Figure 7.5 The arrangement of the ions in
ionic lattice. layer of a sodium chloride crystal. several layers of a sodium chloride crystal. 91

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 Every ionic compound forms a giant ionic lattice that is held together
by strong electrostatic attractions (ionic bonds) throughout the lattice.
The ions are held in a fixed position within the lattice and are not free
to move.

Tip
Ionic substances, like NaCl, do not exist as single molecules. Ionic
substances form giant structures containing a very large number of
positive and negative ions. The formula of sodium chloride might be
better represented as (Na+Cl–)n, where n is a very large number.

Activity
Atoms, ions and the periodic table
Look carefully at Table 7.2. This shows the electron structures of the atoms and ions
of the elements in Period 3 of the periodic table.
Table 7.2 Electron structures of the atoms and ions of elements in Period 3.

Elements in Period 3 Na Mg Al Si P S Cl Ar
Group 1 2 13 14 15 16 17 18
Electron structure 2,8,1 2,8,2 2,8,3 2,8,4 2,8,5 2,8,6 2,8,7 2,8,8
No. of electrons in outer shell 1 2 3 4 5 6 7 8
+ 2+ 3+ 3- 2- -
Common ion Na Mg Al No ion P S Cl No ion
Electron structure of ion 2,8 2,8 2,8 – 2,8,8 2,8,8 2,8,8 –

1 What pattern can you see in the ions formed by elements in Groups 1, 2 and 13?
2 Predict the ions formed by the following atoms:
a) Li
b) Be
c) K
d) Ca.
3 We can write an equation for the formation of a sodium ion, Na+, when a sodium atom,
Na, loses an electron as:
Na  →  Na+ + e–
(2,8,1) (2,8) electron
Write a similar equation for the formation of a magnesium ion, Mg2+, from a
magnesium atom, Mg.
Chapter 7  Bonding and structure

4 What pattern can you see in the ions formed by elements in Groups 15, 16 and 17?
5 Predict the ions formed by the following atoms:
a) N
b) O
c) F.
6 Why does argon not form an ion?
7 Use your answer to Question 6 to explain why argon is used to fill electric light bulbs.
8 Suggest why silicon does not form Si4+ or Si4– ions.

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 Ionic bonding
Typical properties of ionic compounds
Ionic compounds contain strong ionic bonds throughout the giant
lattice. Typical properties of ionic substances are shown in Table 7.3.
Table 7.3 Properties of ionic substances.

Property Explanation of property

High melting (and boiling) points Ionic bonds are strong and occur throughout the giant lattice. In order to melt an ionic
solid, all the ionic bonds in the lattice have to be broken. This requires a large amount of
energy. Hence the melting (and boiling) point is high.
Poor conductor of electricity When solid, the ions are held in a fixed position within the lattice and cannot move.
when solid There are no mobile charge carriers, hence ionic solids are poor conductors.
Good conductor of electricity When melted or dissolved in water the ions are mobile and free to move, hence molten
when molten or dissolved in water and aqueous ionic compounds are good conductors.
Soluble in water and polar solvents As a rough guide to solubility we can say ‘like dissolves like’. Water has dipoles (charges),
as do ionic solids (see below).

Solutions of ionic solids in water

It is not easy to see why a solid like sodium chloride readily dissolves
in water. The explanation for the solubility of ionic salts, such as
sodium chloride, in water is that the charged ions, both Na+ and Cl–
are strongly attracted to polar water molecules. The water molecules
are attracted to the ions and bind to them. This binding of water
molecules to ions is called hydration, which will be studied in detail in
the second year of the A Level course. In the case of sodium chloride,
the energy released as water molecules bind to the ions is enough
to compensate for the energy needed to overcome the ionic bonding
between the ions.
Some salts, like Ca(OH)2 and BaSO4, are sparingly soluble or insoluble
in water because the energy that would be released when the ions are
hydrated is not sufficient to balance the energy required to separate
the ions.
ionic crystal
lattice

hydrated
– + – cation

+ – + –

– + – +

+ – + – + –

– + – + – +

hydrated
polar water anion
molecule
Figure 7.6 Sodium and chloride ions leaving a crystal lattice and becoming hydrated as
they dissolve in water. The bond between the ions and the polar water molecules is an
electrostatic attraction.

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 Test yourself
1 Draw ‘dot-and-cross’ diagrams for:
a) lithium fluoride
b) magnesium chloride
c) lithium oxide
d) calcium oxide.
2 With the help of a periodic table, predict the charges on ions of the
following elements:
a) caesium
b) strontium
c) gallium
d) selenium
e) astatine.
3 Why do metals form positive ions and non-metals form negative ions?
4 a) Write the electronic configurations for the atom and the ion formed by:
i) magnesium
ii) sulfur
ii) rubidium
iv) bromine.
b) Predict the formula of magnesium bromide and rubidium sulfide.
5 The melting point of sodium fluoride is 993 °C but that of magnesium
oxide is 2852 °C.
a) Write the formulae of these two compounds showing charges on the
ions.
b) Suggest why the melting point of magnesium oxide is so much higher
than that of sodium fluoride.

Covalent bonding
Key term Covalent bonds are usually formed between two non-metal atoms.

A single covalent bond is formed Both non-metal atoms share electrons from their outer (valence) shell.
by the sharing of two electrons Each atom achieves the electron configuration of a noble gas, which,
between two adjacent atoms. apart from helium, is eight electrons in the outer shell.
Each atom provides one electron. Many compounds in everyday life are covalent. Almost all the
The electrostatic attraction compounds in food and most of the compounds in our bodies are
between the shared pair of bonded covalently. Covalent compounds usually exist as simple discrete
electrons and the nuclei of the
Chapter 7  Bonding and structure

molecules, but some form giant structures (page 110).

two bonded atoms constitutes
the covalent bond.
Single covalent bonds
Some non-metallic elements exist as pairs of atoms linked together. The
bonding is covalent and occurs because, by sharing electrons, each atom
achieves the stability of a noble gas configuration. A single covalent
bond is formed from the sharing of two electrons by adjacent atoms.
Each hydrogen atom has one electron in its outer orbit:

H × H

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 Covalent bonding
A hydrogen molecule is a simple diatomic molecule in which the atoms
are held together by a single covalent bond:

H H

The hydrogen molecule can be represented as H–H.

A fluorine molecule is also a diatomic molecule with the atoms held
together by a single covalent bond. Each fluorine atom has seven
electrons in its outer orbit and is, therefore, one electron short of
attaining the octet.
By sharing electrons, each fluorine atom has eight electrons in its outer
shell and the fluorine molecule can be represented as F–F (Figure 7.7).
××

×
×
× ×
F × F × F ×
F ×

××
×
×
Figure 7.7 Covalent bonding in a fluorine molecule.

H H Covalent bonds also occur between atoms of different non-

× × H H metallic elements. For example, methane is a simple covalent
compound. A molecule of methane consists of one carbon atom
C C and four hydrogen atoms. A carbon atom requires four electrons
to be isoelectronic (have the same number of electrons) with a
H H
× × noble gas; each hydrogen atom requires one electron. By sharing
H H
electrons, each atom in a molecule of methane achieves a stable
Figure 7.8 Covalent bonding in methane. electron configuration (Figure 7.8).
Dot-and-cross diagrams showing only the electrons in the outer
shell provide a simple way of representing covalent bonding, as
H H H
×× shown in Figure 7.9.
×
•

•
×
•
×

× × ×
• •
H C H
•
H N •H
•
F F H O
••

× × × ×
×
×× •• ••
•
×

H
Multiple covalent bonds
H H H

F F H O H N H H C H
Double bonds
If two atoms share four electrons, two covalent bonds are formed –
H a double bond. The simplest substance containing a double bond
Figure 7.9 Dot-and-cross diagrams representing is an oxygen molecule. Each oxygen atom has six electrons:
covalent bonds.

O O

By sharing two of its electrons, each oxygen atom has eight electrons in
its outer shell:

O O

The oxygen molecule can be represented as O=O.

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 Carbon–carbon double bonds are often referred to as unsaturated
bonds and are common in organic molecules. Ethene has a double bond,
H2C=CH2. Carbon–oxygen double bonds are also common in organic
H
I
chemistry, for example methanal, H–C=O.
Figure 7.10 shows the single and double covalent bonds in these
compounds.
ethene, C2H4 methanal, HCHO

H H H ××

•
•×
×
• ×
C C C O

••

••
•× • ×
•
××

×
H H H

two shared electrons four shared electrons two shared electrons four shared electrons
form a single form a double form a single form a double
covalent bond covalent bond covalent bond covalent bond

H H H

C C C O

H H H

Figure 7.10 Multiple covalent bonding in ethene and in methanal.

Triple bonds
Nitrogen molecules contain a triple covalent bond, formed by sharing
six electrons. Each nitrogen atom has five electrons in its outer shell and
each, therefore shares three electrons with the other nitrogen atom:

× ×
N × N ×
×

By sharing three of its electrons, each nitrogen atom attains a stable

outer octet:

×
N N ×

The nitrogen molecule can be represented as:

N N
Chapter 7  Bonding and structure

Lone pairs of electrons

In many molecules and ions, there are atoms with pairs of electrons in
their outer shells which are not involved in the bonding between atoms.
Chemists call these ‘lone pairs’ of electrons. Lone pairs of electrons:
● can form a variation on the covalent bond known as a dative
covalent bond
● affect the shapes of molecules (see pages 99–103)
● are important in the chemical reactions of some compounds,
including water and ammonia
● can behave as nucleophiles in organic reactions (see page 235).
96 A lone pair of electrons can also be described as a non-bonding pair of
electrons.

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 Covalent bonding
Dative covalent (coordinate) bonding
Key term When adjacent atoms bond together and share two electrons, it is
A dative covalent bond is a bond usual for each atom to provide one electron. Sometimes, however,
in which two atoms share two one atom supplies both electrons. Two electrons are shared, so the
electrons but one atom provides bond is covalent, but, because both shared electrons come from one
both electrons. The electrostatic of the atoms, the bond is called a dative covalent bond (coordinate
attraction between the shared bond).
pair of electrons and the nuclei A simple example of a dative covalent bond also explains how ammonia
of the two bonded atoms (NH3) forms the ammonium ion, NH4+. This is possible because the
constitutes the covalent bond. nitrogen atom in ammonia has eight electrons in its valence shell, two
of which are not bonded to other atoms. This pair of electrons is called
a lone pair.
If a hydrogen ion (which has no electrons) is provided by an acid, the
lone pair of electrons on the nitrogen atom can form a dative covalent
bond with the hydrogen ion to form an ammonium ion, which has a
charge of 1+, is formed (Figure 7.11).
H H +
•× •×
H •× N •• H+
• N •H
H× •
•× •×
H H

ammonia proton ammonium dative bond

ion

H H +

H N •• H+ H N H

H H
Figure 7.11 Dative covalent bonding in the ammonium ion.

In an ammonium ion, all four bonds from nitrogen to hydrogen are

equivalent. It is not possible to identify which is the dative covalent
bond. It is simply the method of bond formation that is different. The
electrical charge of the cation, NH4+, is spread over the whole ion.
Dative covalent bonding can sometimes occur between molecules –
for example, when ammonia combines with boron trifluoride, BF3. The
boron atom has six electrons in its valence shell and, therefore, requires
two electrons. These are provided by the lone pair of electrons on the
nitrogen atom of the ammonia molecule:

F
H

H N B F

H
F

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 The lone pair of electrons donated by the nitrogen atom is shared with
the boron atom. A dative covalent bond is formed and the nitrogen and
boron atoms:

F
H

H N B F

H
F

Typical properties of covalent compounds

Many covalent compounds are liquids or gases with low melting points.
If solid, they are not dense and tend to be soft and easily broken, unlike
ionic crystals, which are hard and have a specific shape. Candle wax is a
mixture of solid covalent compounds.
Tip
The properties of covalent Most covalent compounds exist as small discrete molecules such as H2,
compounds listed in Table 7.4 P4, H2O and CH4. There are some exceptions such as diamond, graphite,
apply only to simple molecular graphene and silicon. The covalent bonds within the molecules are
compounds and not to strong but the bonds between individual molecules are much weaker
compounds with giant covalent and are easily broken.
structures. General properties of covalent compounds are summarised in the table
below.
Table 7.4 Properties of covalent compounds.

Property Explanation of property

Low melting points and They exist as discrete (separate) molecules and the attraction between neighbouring covalent
low boiling points molecules is weak. When melted or boiled only the weak bonds between the molecules are broken so
only a small amount of energy is required to break them, hence the melting and boiling points are low.
Poor conductor of There are no mobile charge carriers, ions or electrons, to carry the electric charge. Graphite and
electricity graphene are exceptions to this.
Soluble in non-polar As a rough guide to solubility we can say ‘like dissolves like’ Covalent compounds are non-polar and
solvents such as hexane hence tend to be soluble in non-polar solvents.

Test yourself
6 Draw ‘dot-and-cross’ diagrams to show the covalent bonding in:
a) hydrogen sulfide, H2S
b) ethane, C2H6
c) carbon disulfide, CS2
Chapter 7  Bonding and structure

d) nitrogen trifluoride, NF3.

7 Identify the atoms with lone pairs of electrons in the following molecules
and state the number of lone pairs:
a) ammonia
b) water
c) hydrogen fluoride
d) carbon dioxide.
8 Draw dot-and-cross diagrams for:
a) PH3
b) PH4+
c) PH2–.
9 In aqueous solutions acids donate protons, H+, to water to form H3O+.
Draw a dot-and-cross diagram of H3O+.
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 Shapes of simple molecules and ions
Shapes of simple molecules and ions
Simple covalent compounds exist as discrete molecules with atoms held
together by shared pairs of electrons. The shared pair of electrons is
located between the two nuclei and this means that the atoms always
stay in the same position relative to each other. The central atom may
also be bonded to other atoms also held in fixed positions, which means
that the covalent molecule will have a fixed shape.

Electron pair repulsion theory

Key term The shape of a molecule is determined by the numbers of bonded and
lone (non-bonded) electron pairs around the central atom. A simple
The electron pair repulsion model of molecular shape is based on the fact that pairs of electrons
theory states that the electron (both bonded and non-bonded) repel each other to be as far apart in
pairs repel each other and the space as possible. This is known as the electron pair repulsion theory.
overall shape of the molecule
depends on the number and From strongest to weakest, the order of strength of repulsion is:
type of electron pairs around the lone pair–lone pair > lone pair–bonded pair > bonded pair–bonded pair
central atom. Lone pairs (non-
bonded pairs) repel more than The overall shape of a covalent molecule (or ion) is determined by the
bonded pairs of electrons. number and type of electron pairs around the central atom.
The way to determine the shape is to draw a dot-and-cross diagram and
use this to deduce the number (and types) of electron pairs around the
Tip central atom.
Lone pairs repel more because
they are closer to the central Two bonded pairs and no lone pairs
atom than a bonded pair.
Covalent molecules containing two single covalent bonds are not
common. The simplest example is beryllium chloride, BeCl2, which,
unusually for a metallic compound, is covalent. The beryllium atom has
two bonded pairs and no lone pairs. The bonded pairs repel each other
until they are as far apart as possible. The resultant shape is linear; the
bond angle is 180°.
×× ××

× Cl Be Cl ×
× × × ×
Cl Be Cl
×× ××    180°

Linear shape is more common in molecules containing multiple – double

or triple – bonds, such as carbon dioxide, CO2. The central carbon atom
and each oxygen atom in carbon dioxide are connected by two pairs of
bonded electrons, each constituting a double covalent bond. The double-
bonded pairs repel each other until they are as far apart as possible. The
resultant shape is linear and the bond angle is 180°:

O ••×× C O O C O
180°

Three bonded pairs and no lone pairs

Boron forms covalent molecules with the halogens. In boron trichloride,
BCl3, the central boron atom has three bonded pairs and no lone pairs.

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 The bonded pairs repel each other so that they are as far apart as
possible. The resultant shape is trigonal planar; the bond angle is 120°:

Cl Cl
120°
B B
Cl Cl
Cl Cl

Four bonded pairs and no lone pairs

Carbon forms many compounds containing four covalent bonds. The
simplest is methane. The central carbon atom in methane has four
bonded pairs and no lone pairs. The bonded pairs repel each other so
that they are as far apart as possible. The resultant shape is tetrahedral;
the bond angle is 109.5°:
H
H
Tip H C H C
H
H
The bond angle in a tetrahedron H 109.5°
is actually 109° 28’. H

28’ represents 28 minutes – bond in the plane of the page

bond in front of the plane of the page
there are 60 minutes in 1°.
bond behind the plane of the page

Five bonded pairs and no lone pairs

The non-metallic elements in Period 3 can form compounds in which
there are more than eight electrons around the central atom. An
example is phosphorus pentafluoride, PF5. The phosphorus atom has five
bonded pairs and no lone pairs. The bonded pairs repel each other so
that they are as far apart as possible. The resultant shape is trigonal
bipyramidal (base-to-base triangular pyramids); the bond angles are
120° and 90°:

F F
× 90°
F
F F
×

120° P F
×

P
F
Chapter 7  Bonding and structure

× ×

F F F

Six bonded pairs and no lone pairs

Sulfur can also form compounds with more than eight electrons in the
outer shell. Sulfur forms six covalent bonds in compounds such as sulfur
hexafluoride. The sulfur atom has six bonded pairs and no lone pairs.
The bonded pairs repel each other to the point of maximum separation
to give an octahedral shape (base-to-base square pyramids); the bond
angles are all 90°:

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 Shapes of simple molecules and ions
F
F
F F 90°
F F
S S
90°
F F F F

F F

Covalent molecules that contain lone pairs of

electrons
Many covalent compounds contain lone pairs of electrons as well as
bonded pairs. These lone pairs affect the shape of the molecule, because
lone pairs repel more than bonded pairs.
Ammonia
A dot-and-cross diagram of ammonia is shown below:
••

H N H N

×
×

×
H H H
  H

The central nitrogen atom in ammonia has four pairs of electrons

around it and, therefore, you might expect them to be repelled to form
tetrahedral bond angles of 109.5°. However, the four pairs of electrons
are not identical; there are three bonded pairs and one lone pair. The
lone pair repels more than the bonded pairs, which results in the
bonded pairs being forced closer together. The angle between the N–H
bonds contracts from 109.5° to about 107°. The shape of the ammonia
molecule is pyramidal:
•
•

N
H
H
107°
H

Water
A dot-and-cross diagram for water is shown below:
•• ••

O O
× ×
H H H
   H

The central oxygen atom in a water molecule has four pairs of

electrons around it and, therefore, you might expect the molecule to
be tetrahedral with a bond angle of 109.5°. However, the four pairs of
electrons surrounding the oxygen atom consist of two bonded pairs and
two lone pairs. The lone pairs repel more than the bonded pairs, forcing
the bonded pairs closer together. The bond angle contracts from 109.5°
to about 104.5°. The shape of the water molecule is angular or bent.
The shapes of covalent compounds are summarised in Table 7.5.

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 Table 7.5 Shapes of covalent compounds.

Number of electron pairs Number of Number of Shape Bond angle Example

around the central atom bonded pairs lone pairs
2 2 0 Linear 180° CO2
O C O

3 3 0 Trigonal planar 120° BCl3

Cl

B
Cl Cl

4 4 0 Tetrahedral 109.5° CH4

H
C
H H
H

5 5 0 Trigonal bipyramidal 120° and 90° PF5

F
F
F P
F
F

6 6 0 Octahedral 90° SF6

F
F
F S
F
F
F

4 3 1 Pyramidal 107° NH3

••
N
H H
H

4 2 2 Angular (bent) 104.5° H2O

••

O ••

H H

Shapes of ions
Chapter 7  Bonding and structure

Ions such as the ammonium ion, NH4+, and the amide ion, NH2–, contain
covalent bonds and, therefore, have a fixed shape and a defined bond
angle.
When an ammonium ion is formed from ammonia, a proton is gained.
The central nitrogen atom has four bonded pairs of electrons. The shape
is tetrahedral and the bond angle is 109.5°.
When an amide ion is formed from ammonia, a proton is lost. The
central nitrogen atom has two bonded pairs of electrons and two lone
pairs. The shape is angular (bent) and the bond angle is about 104°.

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 Metallic bonding
H N H

×
×

×
H

H + –

H N H H N

×
×

×
×

×
H H

ammonium ion amide ion

Test yourself
10 State the electron pair repulsion theory.
11 Determine the number, and type, of electrons pairs around the central
atom(s) in each of the following. Predict the shape and bond angles of
each. (Hint: it may help to draw dot-and-cross diagrams.)
a) hydrogen sulfide, H2S
b) phosphine, PH3
c) sulfur dichloride, SCl2
d) dichloromethane, CH2Cl2
e) CH3+
f) C2H4
g) COCl2
h) XeF4

Metallic bonding
Key terms Metal atoms pack together in a regular arrangement (Figures 7.12 and 7.13).

Delocalised electrons are bonding second-layer atom

electrons that are not fixed
between two atoms in a bond.
They are mobile and are shared
by several or many atoms.
The metallic bond is the electrostatic
attraction between the delocalised
electrons and the positive ions held
within the lattice. first-layer atom

Figure 7.12 The close packing of atoms Figure 7.13 Atoms in two layers of a metal
positive ion in one layer of a metal.    crystal.
The outer orbital electron clouds overlap and the electrons are free
to move from one atom to another – they are delocalised. The
attraction between these electrons and the positive ions forms the
metallic bond.
delocalised electrons
The electrons move through a giant lattice of positive ions (Figure 7.14). The
Figure 7.14 Metallic bonding results delocalised electrons are sometimes called ‘a sea of mobile electrons’.
from the strong attractions between the
metal ions in the lattice and the mobile
delocalised electrons.
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 Tip The delocalised electrons are able to move anywhere within the lattice,
so the metallic bond is non-directional.
The ‘+’ sign in Figure 7.14
indicates a positive Group 1 metal
ion, not a proton or the nucleus.
Typical properties of metals
General properties of metallic compounds are summarised in Table 7.6.
Table 7.6 Properties of metallic compounds.

Property Explanation of property

High melting points and high High temperatures are needed to melt metals because the metallic bond is strong and exists
boiling points throughout the giant lattice. In order to melt a solid metal, all the bonds in the lattice have to
be broken, which requires a large amount of energy.
Good conductor of electricity Metals are good conductors of electricity because they contain mobile charge carriers that are
free to move, even in the solid. The mobile charge carriers are the delocalised electrons.
Malleable (re-shaped) This is because the metallic bond is non-directional, is independent of shape and exists in all
and ductile (stretched directions.
into wires)

Activity
Choosing metals for different uses
Various properties of six metals are shown in Table 7.7.
Table 7.7 Various properties of six metals.

Metal Density/g cm–3 Tensile strength/ Melting Electrical resistivity/ Thermal conductivity/ Cost per
107 N m –2 point/°C 10 –8 ohm m J s –1 cm –1 K–1 tonne /£
Aluminium   2.7  8   660   2.5 2.4 960
Copper   8.9 33 1083   1.6 3.9 1 200
Iron   7.9 21 1535   8.9 0.8 130
Silver 10.5 25   962   1.5 4.2 250 000
Titanium   4.5 23 1660 43.0 0.2 27 000
Zinc   7.1 14   420   5.5 1.1 750

1 Use the information in Table 7.7 to explain the following statements.

a) Copper is used in most electrical wires and cables, but high-tension cables in the National Grid are made of
aluminium.
b) Bridges are built from steel, which is mainly iron, even though the tensile strength of iron is lower than that of
some other metals.
c) Metal gates and dustbins are made from steel, coated (galvanised) with zinc.
d) Silver is no longer used to make coins in the UK.
e) Aircraft are now constructed from an aluminium/titanium alloy rather than pure aluminium.
Chapter 7  Bonding and structure

f) The base of high-quality saucepans is copper rather than steel (iron).

2 If the atoms in a metal pack closer, the density should be higher, the bonds between atoms should be stronger and
so the melting point should be higher. This suggests there should be a relationship between the density and melting
point of a metal.
a) Use the data in the table to check whether there is a relationship between density and melting point.
b) Is there a relationship between the densities and melting points of the metals? Say ‘yes’ or ‘no’ and explain your
answer.
3 The explanation of both electrical and thermal conductivity in metals uses the concept of delocalised electrons.
This suggests there should be a relationship between the electrical and thermal conductivities of metals.
a) Use the data in the table to check whether there is a relationship. (Hint: Electrical resistivity is the reciprocal of
electrical conductivity.)
b) Is there a relationship? Say ‘yes’ or ‘no’ and explain your answer.

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 Electronegativity and bond polarity
Electronegativity and bond polarity
It is rare for a compound to be 100% ionic. Only simple diatomic
molecules like H2 and O2 in which the covalent bond exists between
two identical atoms are 100% covalent. There is a range of intermediate
types of bond between the extremes of ionic and covalent.
Many bonds are described as essentially:
● covalent with some ionic character
● ionic with some covalent character.

Key term Bond polarity

Electronegativity is the ability of In a covalent molecule, ionic character is introduced when the pair
an atom of an element to attract of electrons making up the covalent bond is not shared evenly
the shared pair of electrons in a between the component atoms. This is a result of the difference in the
covalent bond. electronegativity of the two atoms forming the covalent bond.

electronegativity
increases

Figure 7.15 Trends in electronegativity in the periodic table.

You should appreciate that:

● electronegativity increases across a period
● electronegativity decreases down a group.
Linus Pauling (1901–1994) developed, by comparing one element with
another, a quantitative scale (Figure 7.16).

H
2.1

Li Be B C N O F
1.0 1.5 2.0 2.5 3.0 3.5 4.0

Na Mg Al Si P S Cl
0.9 1.2 1.5 1.8 2.1 2.5 3.0
Tip K Ca Br
0.8 1.0 2.8
You do not need to learn
the numerical values for the Rb Sr I
electronegativity of any element. 0.8 1.0 2.5
It is sufficient to know the trends.
Figure 7.16

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 In a covalent bond, the element with the greater electronegativity attracts
the bonding electrons towards itself. Elements with high electronegativity
such as fluorine and oxygen have a strong attraction for the shared covalent
electrons.
In a molecule of hydrogen, H2, both hydrogen atoms have the same
attraction for the two bonded electrons. Hence, they are shared equally.
H H
2.1 2.1

In a molecule of hydrogen chloride, HCl, the hydrogen atom and the chlorine
atom have a different attraction for the two bonded electrons. Hence, the
electrons are not shared equally. The molecules are not 100% covalent
because the electrons are more concentrated towards the chlorine atom:
H Cl
2.1 3.0

The chlorine atom becomes slightly negatively charged with respect to

the hydrogen; the hydrogen is left with a slight positive charge. A small
degree of charge is indicated on a molecule by using the symbol δ+ or δ–:
δ+ δ–
H Cl

A covalent bond with some charge separation is said to have a dipole.

A dipole indicates that the bond has a small amount of ionic charge; the
bond is best described as essentially covalent, with some ionic character.

Polar bonds and polar molecules

A polar bond is due to the difference in electronegativity of the atoms in
a covalent bond. However, molecules with polar bonds are not necessarily
polar molecules. If a molecule is symmetrical, the dipoles cancel out, even
if the bonds are polar. For example, in a molecule of carbon dioxide, the
electrons in the covalent bonds are pulled towards the oxygen atoms:
δ– δ+ δ–
O C O
3.5 2.5 3.5

However, because the molecule is symmetrical, the dipoles cancel

each other out. The net result is that the C=O bonds are polar, but the
carbon dioxide molecule is not.
Symmetrical shapes include linear, trigonal planar, tetrahedral and
octahedral. If the atoms bonded to the central atom are the same, any
Chapter 7  Bonding and structure

Tip dipoles in the bonds cancel each other out and the molecule is non-
polar – for example, methane, CH4.
If the central atom of a molecule
has one or more lone pair of Non-symmetrical shapes include pyramidal and angular (or bent).
electrons the molecule will Molecules with these shapes are always polar, even when the central
almost always be polar. atom is attached to atoms that are the same. Ammonia molecules are
pyramidal and polar; water molecules are angular and polar.
A compound consisting of two or more different non-metals is
essentially covalent with some ionic character. In general, the molecules
of such compounds are polar. However, if the molecule is symmetrical
this is not the case, because the dipoles cancel each other out.
A compound consisting of a metal and a non-metal is essentially ionic
with some covalent character.
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 Electronegativity and bond polarity
Activity
Interpreting electronegativity values
Electronegativity is defined as the attraction for electrons within a covalent bond.
Figure 7.16 on page 105 shows the electronegativity of some elements according to Pauling’s electronegativity values.
Use the data to answer the questions below.
1 Suggest why the electronegativity values for the noble gases are not included in Figure 7.16.
2 Explain the trend in electronegativity:
a) across a period (Li to F)
b) down a group (F to Br)
3 a) Draw dot-and-cross diagrams for H2S, SO2, PH3and COCl2.
b) Sketch molecules of H2S, SO2, PH3 and COCl2 showing shape, bond angles and any dipoles.
In a molecule of hydrogen chloride, HCl, the H atom and the chlorine atom have a different attraction for the two
bonded electrons and hence they will not be equally shared. Molecules like HCl, cannot be regarded as 100% covalent.

the bonded electrons this results in the Cl being δ+ δ–

H Cl slightly negatively charged,
are pulled towards the Cl 2.3 3.0 H Cl
leaving the H with a slight
positive charge

The dipoles show that the H–Cl bond has some charge and is hence a little bit ionic.
Table 7.8 tries to be quantitative about the effect of differences in electronegativity and uses the differences to
estimate a % ionic character within a covalent bond.
Table 7.8 Using electronegativity to estimate percentage ionic character in a covalent bond.

Difference in 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9
electronegativity
% ionic character 2 4 6 9 12 15 19 22 26 30 34 39 43 47 51 55 59
of the bond

The difference in electronegativity between H and Cl is 0.9, which means that the bond has some ionic character.
A difference in electronegativity of 0.9 suggests an ionic character of about 19%. The H–Cl bond is essentially
covalent (81%) but with ionic (19%) character. This type of bond is described as a polarised bond and H–Cl has a
permanent dipole.
4 a) Estimate the percentage ionic/covalent character of the:
i) O–H bond in H2O
ii) S–H bond in H2S
iii) C–H bond in CH4
iv) C–Cl bond in CH3Cl.
b) Divide the molecules; H2O, H2S, CH4 and CH3Cl into two groups – polar and non-polar.
c) The boiling points of H2O and H2S are 100 oC and –61 oC respectively. H2O and H2S are both covalent molecules
with similar shapes. Suggest an explanation for this large difference in boiling points.

Test yourself
12 Use the electronegativity values in Figure 7.16 on page 105 to help
answer the following:
a) Sketch HBr, CO2, NH3 and NO2 and use δ+ and δ– to show bonds
that have charge separation.
b) Divide HBr, CO2 and NH3 into polar and non-polar molecules.
c) Draw a dot-and-cross diagram of N2H4.
d) Is N2H4 polar or non-polar?

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 Intermolecular forces
Ionic, covalent and metallic bonds are all strong bonds; to break them
Key term
generally requires between 200 kJ mol–1 and 800 kJ mol–1. There is
Intermolecular forces are forces a second set of bonds or types of interaction which form between
of attraction that occur between molecules and are known as intermolecular forces. Compared to ionic,
molecules. covalent and metallic bonds these are weak and only require between
2 kJ mol–1 and 40 kJ mol–1 to overcome them.
Tip
The prefix ‘inter-’ means
Permanent dipole–dipole interactions
between. A football match The covalent C–Cl bond in chloromethane, CH3Cl is has a permanent
between two nations is an dipole and the molecules are also polar because chloromethane, CH3Cl,
international match. is not symmetrical and the bond dipoles do not cancel each other out.
H
δ+ δ– δ+ δ–
H C Cl or H3C Cl

Oppositely charged dipoles attract:

δ+ δ– δ+ δ–
Key terms H3C Cl H3C Cl

Permanent dipole–dipole There is a weak electrostatic attraction between the dipoles of

interactions are the weak neighbouring molecules. This is called a permanent dipole–dipole
electrostatic attractions interaction.
between polar molecules that
are essentially covalent but have
some ionic character.
Hydrogen bonding
Hydrogen bonds are the relatively Hydrogen bonding is a special form of permanent dipole–dipole
strong electrostatic attractions interactions.
between polar molecules that A hydrogen bond is a relatively strong intermolecular attraction
contain hydrogen covalently between molecules that involves a lone pair of electrons from the
bonded to elements with nitrogen, oxygen or fluorine.
high electronegativity such as
fluorine, oxygen and nitrogen. Hydrogen bonds exist between molecules in ammonia, NH3, water,
H2O, and hydrogen fluoride, HF. They are also present in compounds
that contain the –OH group (e.g. alcohols and carboxylic acids) and
compounds that contain the –NH2 group (e.g. amines). Hydrogen
bonding is important in amino acids, peptides and proteins.
Chapter 7  Bonding and structure

Water can be used to illustrate some features of hydrogen bonding.

The hydrogen bond is formed between a lone pair of electrons on
the oxygen atom in one water molecule and a hydrogen atom in an
adjacent water molecule:
δ– hydrogen
••
O bond
δ+ •• δ+
H H
δ+
δ– H
O
••
••

the ‘O–H O’ arrangement is linear

δ+
H

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 Intermolecular forces
The presence of a lone pair of electrons on the electronegative atom is
essential for hydrogen bonding to take place.
Hydrogen bonding in water causes some anomalous properties. The
most important are that:
● the solid (ice) is less dense than the liquid (water)
● water has unexpectedly high melting and boiling points.
Ice floats on water because when water is frozen, the water molecules
hydrogen-bond together to form interlocking hexagonal rings. This
Figure 7.17 Snowflakes have a means that the molecules in any particular hexagon are held further
characteristic six-fold symmetry and can apart, so that ice has a greater volume and thus lower density than
come in an infinite range of shapes.
water.
The structure of ice is complex, as can be seen in the patterns created
by snowflakes (Figure 7.17).
150
Water is a hydride of oxygen. If water followed the trend shown by the
100
boiling points
hydrides of the elements in same group of the periodic table (Figure
Temperature/°C

melting points 7.18), the melting point of water would be approximately –100 °C and
50
the boiling point approximately –80 °C.
0 The unexpectedly high melting point of 0 °C and boiling point of 100 °C
are due to the additional energy required to break the hydrogen bonds
–50
between adjacent water molecules. The intermolecular forces between
–100 the other Group 16 hydrides are smaller and, therefore, less energy is
H2O H2S H2Se H2Te required to break them.
Hydrides of Group 16

Figure 7.18 Melting and boiling points of

the hydrides of Group 16 elements.
Induced dipole–dipole interactions
The weakest of the intermolecular forces are induced dipole–dipole
interactions forces. These act between all molecules, polar or non-
Tip polar. To understand these forces you must appreciate that the
Induced dipole–dipole electrons are not static. Temporary movement of electrons leads to
interactions can also be referred temporary induced dipoles. These temporary instantaneous dipoles can
to as London (dispersion) forces. induce dipoles in neighbouring molecules. The attraction between the
induced dipoles are called induced dipole–dipole interactions.
The strength of these forces depends on the number of electrons in the
Key term molecule. The greater the number of electrons in an atom or molecule,
To define an induced dipole–dipole the greater the number of induced dipole–dipole forces.
interaction there are three Although these forces are weak, their presence explains some physical
key features that have to be properties. For example, the boiling point of butane (C4H10) is higher
considered: than that of propane (C3H8). This is because a molecule of butane
• The movement of electrons has more bonds, and hence more electrons, than a molecule of
generates an instantaneous dipole. propane. Therefore, there are more intermolecular forces between
• The instantaneous dipole induces butane molecules, and it is these intermolecular forces that have to be
other dipoles in neighbouring overcome for boiling to occur.
atoms/molecules.
• Two dipoles generate a weak
temporary force of attraction
between the atoms/molecules.

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 Test yourself
13 Draw labelled diagrams to show hydrogen bonding between molecules of:
a) ammonia, NH3
b) ethanol, CH3CH2OH
c) ethanol and water.
14 In each of the following, list the type of intermolecular forces present.
State the type of dipole interactions present.
a) Cl2
b) HCl
c) CCl4
d) CH3Cl
15 Suggest why:
a) methane, CH4, is insoluble in water
b) methanol, CH3OH, is soluble in water.
16 Explain why chlorine, Cl2, is a gas, bromine, Br2, is a liquid and iodine,
I2, is a solid at room temperature and pressure.

Structure and physical properties

There are many types of solid compound because of the different ways
in which the atoms of elements or the molecules of compounds can
combine. The types of solids can essentially be broken down into four
different sub-sets:
● giant ionic lattice – NaCl – this has been covered in the section on
Tip ionic bonding (see page 90)
There are many other examples ● giant covalent lattices – graphite, graphene, diamond, silicon and
of the four different types of silicon dioxide
solids. ● giant metallic lattices – this has already been covered in the section
on metallic bonding (see page 103)
● simple molecular lattices – iodine and ice.

Giant structures
For details of giant ionic lattices, giant metallic lattices and their
properties, see pages 91 and 103.
Strong covalent bonds between carbon
atoms in each layer − therefore very
high melting point
Graphite
Giant covalent lattices
Chapter 7  Bonding and structure

The group 14 elements carbon and silicon both have giant covalent
lattices which are held together by strong covalent bonds between atoms.
Carbon, in the form of diamond, and silicon have similar structures and
they have high melting points because there are strong covalent bonds
throughout the lattice. Carbon also exists as graphite which has a giant
lattice. The covalent bonds within the graphite lattice are two dimensional
whereas in diamond and in silicon they are three dimensional. Graphite
Each carbon within a layer Weak dipole-dipole like diamond has a very high melting point; in fact graphite is more
forms only 3 covalent bonds
and therefore each carbon
interactions between
the layers
stable than diamond, but unlike diamond graphite is a good conductor of
has a free mobile
(delocalised) electron −
electricity. This can be explained by the structure of graphite.
hence graphite is a good
conductor. Graphite has a hexagonal layer structure:
Carbon can also exist in the form of graphene. Graphene is a pure
110 form of carbon consisting of a very thin, almost transparent sheet, one

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 Structure and physical properties
atom thick layer of carbon atoms. It is remarkably strong for its low
weight (approximately 100 times stronger than steel) and it is a good
conductor of both electricity and heat. Graphene was first isolated in
the laboratory in 2004. In 2010 two scientists from the University of
Key Manchester were awarded the Nobel Prize for their ground-breaking
silicon atoms experimental work with the two-dimensional graphene.
oxygen atom

The strength and the conductivity of graphene means it has may

Figure 7.19 There are strong covalent potential applications such as semiconductors, electronics, smart phones,
bonds throughout the SiO2 lattice. tablets and battery energy.

Simple molecular lattices

Simple molecules do form larger structures. However, the forces
between the molecules are weak and the solids melt easily. An example
is solid iodine, I2, which has a regular structure built up by repeating the
section shown below:

I2

The lattice is made up of I2 molecules held in position by weak

intermolecular forces. The I–I molecule is non-polar and the only forces
Figure 7.20 The iodine solid in the test
that act between the separate I2 molecules are induced dipole–dipole
tube has been gently heated and purple
fumes of iodine gas can be seen in the forces. When warmed the weak induced dipole–dipole forces are readily
inverted round bottom flask surrounding broken and individual molecules of I2 are released such that iodine
the test tube. sublimes rather than melts (Figure 7.20).
Key
oxygen atom
Tip
hydrogen
bonds hydrogen atom Sublimation is when a solid changes directly to a gas on heating. CO2
also sublimes and on heating CO2(s) → CO2(g), which is why CO2(s) is
known as ‘dry ice’.

Ice also forms a giant molecular lattice in which separate water

molecules are held in position by a combination of intermolecular forces
Figure 7.21 The structure of ice. including hydrogen-bonding (Figure 7.21).

Test yourself
17 Explain in terms of bonding and structure:
a) the melting point of H2O is 0 °C but the melting point of H2S is –85 °C
b) CO2 sublimes at –56 °C but SiO2 melts at 1610 °C.
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 Practice questions
Multiple choice questions 1–14 11 Which of the following molecules would you
Answers to Questions 1 to 3 relate to the following expect to be linear?
types of bonding: 1 H2S
A ionic 2 HCN
B covalent 3 CO2
C metallic 12 Which of the following, in the solid state, has a
D essentially covalent but with some ionic crystal structure that contains simple discrete
character (polar) molecules?
Which type of bonding is present in each of the 1 carbon dioxide
following? 2 silicon dioxide
1 hydrogen sulfide, H2S 3 magnesium oxide

2 Indium sulfide, In2S3 13 Which of the following can accept a lone pair of
electrons and form a dative covalent bond?
3 ammonium ion, NH4+ 1 NH3
Answers to Questions 4 to 6 relate to the following 2 AlCl3
types of intermolecular forces: 3 BF3
A permanent dipole–dipole interactions 14 The dot-and-cross diagram below represents
B hydrogen bonding the electronic structure of a sulfur hexafluoride
C induced dipole–dipole interactions only molecule.
D a combination of hydrogen bonding and
induced dipole–dipole interactions F
Which type(s) of intermolecular forces are present in
F F
each of the following?

×
×

S
4 N2
×
×

F F
5 NH3 ×

F
6 Ne

Answers to Questions 7 to 10 relate to the following
Correct statements about sulfur hexafluoride
shapes:
include:
A trigonal planar
1 All S–F bonds are equivalent (the same).
B tetrahedral
2 SF6 is a polar molecule.
C pyramidal
3 SF6 is a planar molecule.
D angular
What is the shape of each of the following? 15 This question is about calcium and calcium oxide.
Chapter 7 Bonding and structure

a) i) Describe the bonding in calcium.

7 hydrogen selenide, H2Se
ii) Explain why calcium is a good conductor
8 phosphorus trichloride, PCl3 of electricity.
b) Draw ‘dot-and-cross’ diagrams for the ions in
9 carbonyl chloride, COCl2
calcium oxide showing all the electrons and
10 amide ion, NH2– the ionic charges.
c) Under what conditions does calcium oxide
Use the key below to answer Questions 11 to 14.
conduct electricity?
A B C D Explain your answer. (8)
1, 2 & 3 1, 2 correct 2, 3 correct 1 only
correct correct

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 Practice questions
16 a) Use sodium chloride, hydrogen chloride and c) In which of the hydrides of Group 16 are the
copper to explain what is meant by covalent, bonds most polar?
ionic and metallic bonding. d) Which of the hydrides of Group 16 has the
b) Compare and explain the conduction of highest boiling point?
electricity by sodium chloride and copper in Explain your answer. (7)
terms of structure and bonding. (14)
21 Thin streams of some liquids are attracted
17 a) Phosphorus forms the chloride PCl3. Draw a towards a charged rod, but there is no such effect
‘dot-and-cross’ diagram for PCl3. with other liquids.
b) Draw and name the shape of the PCl3 a) Suggest why some liquids are attracted while
molecule. others are not.
c) Explain why PCl3 has this shape. b) Which of the liquids, water, hexane,
d) How does PCl3 form a stable compound with bromoethane and tetrachloromethane, are
BCl3? (7) attracted towards a charged rod? Explain
your answer.
18 The table shows the melting points of the
c) Why are the affected liquids always attracted
elements in Period 3 of the periodic table.
towards the charged rod and never repelled
Element Na Mg Al Si P S Cl Ar by it? (8)
Melting 98 649 660 1410 44 113 –101 –189 22 Aluminium chloride is a white covalent solid
point/°C
which sublimes at 180 °C.
a) Explain why the melting point of sodium is a) Draw a dot-and-cross diagram of AlCl3.
much lower than that of magnesium. b) Predict the shape, bond angles and polarity of
b) Phosphorus and sulfur exist as molecules of the bonds.
P4 and S8 respectively. Explain their difference c) Determine whether or not a molecule of AlCl3
in melting points. would be polar or non-polar. Explain your
c) State the type of structure and the nature of the answer.
bonding in each of the following elements: d) Analysis of aluminium chloride suggests
i) aluminium that the formula is in fact Al2Cl6. Draw two
ii) silicon molecules of AlCl3 side by side and suggest:
iii) chlorine. (12) i) how Al2Cl6 could be formed
ii) the type of bonding in Al2Cl6
19 When space travel was being pioneered, one of iii) the bond angles in Al2Cl6
the first rocket fuels was hydrazine, H2NNH2. iv) whether or not a molecule of Al2Cl6
a) Draw a ‘dot-and-cross’ diagram to show the would be polar or non-polar. Explain
electron structure of a hydrazine molecule. your answer.
b) Predict the value of the H–N–H bond angle e) Suggest an explanation for why aluminium
in a hydrazine molecule and explain your chloride sublimes. (13)
reasoning.
c) Suggest a possible equation for the reaction Challenge
that occurs when hydrazine vapour burns in 23 Electron pair repulsion theory can be used to
oxygen. predict the shapes of most molecules and ions.
d) When 1.00 g of hydrazine burns in excess Sometimes, it requires careful consideration of
oxygen,18.3 kJ of thermal energy is released. how the electrons are distributed. An important
Calculate the energy released when 1 mole of point to note is that while atoms of the elements
hydrazine burns in excess oxygen. (8) in the second period of the periodic table never
20 Three of the hydrides of Group 16 elements are have more than eight electrons in their outer orbits,
H2O, H2S and H2Se. those in the third and subsequent periods often do.
a) Explain why all three hydrides have polar Sulfur forms two oxides, SO2 and SO3, and a range of
molecules. anions, including sulfite, SO32–, and sulfate, SO42–. In
b) State and explain the trend in electronegativity addition, it forms thio compounds. In a molecule of
from O to Se down Group 16. a thio compound, an oxygen atom is replaced by a
sulfur atom. An example is thiosulfate, S2O32–.
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 a) In the structures in parts (i) and (ii), the sulfur c) Another feature of sulfur chemistry is that
atom has ten electrons in its outer shell. sulfur atoms can link together. Naturally
What is the likely shape of: occurring sulfur consists of S8 molecules, in
i) SO2 which the sulfur atoms are linked by single
ii) SO32– (the two electrons forming the bonds to create a ring.
‘2–’ charge must be included in the Draw an S8 ring, giving some indication of its
structure; two of the oxygen atoms each likely shape and bond angles.
have one extra electron added)? d) There are various anions containing linked
b) In the sulfate ion, the sulfur atom sulfur atoms. An example is the dithionite
accommodates 12 electrons in its outer orbit. ion, S2O42–. This ion can be thought of as two
What is the shape of: SO2– ions joined by two sulfur atoms to make
i) SO42– the –O2S–SO2–.
ii) S2O32–? Draw the electron structure of the S2O42– ion
(In these two ions, two oxygen atoms each and suggest its shape. (15)
have one extra electron added.)
Chapter 7  Bonding and structure

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 Chapter 8
The periodic table and
periodicity
Prior knowledge
In this chapter it is assumed that you are familiar with:
● atomic number, mass number and isotopes
● structure of the atom
● electronic configuration
● bonding and structure.

For example, you should be aware that the elements in the periodic
table are arranged in order of increasing atomic number and that their
chemical properties are related to the atomic number and the electronic
configuration.

Test yourself on prior knowledge

1 State the atomic number, the mass number and the number of electrons
in each shell of a S atom.
2 Explain why elements 14 and 32 are in the same group of the periodic table.
3 Explain why 37Cl and 35Cl have the same chemical properties.
4 Give the number of electrons in each shell for:
a) P c) Al3+
b) Br –
d) Ni2+

Introducing the periodic table and periodicity

In this chapter some features of the periodic table are considered. The
periodic table is the arrangement of elements:
● by increasing atomic (proton) number
● in periods showing repeating trends in physical and chemical properties
● in groups having similar chemical properties.

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 1 18
Key
1 atomic number 2

H symbol He
relative atomic mass
1.0 2 13 14 15 16 17 4.0
3 4 5 6 7 8 9 10

Li Be B C N O F Ne
6.9 9.0 10.8 12.0 14.0 16.0 19.0 20.2
11 12 13 14 15 16 17 18

Na Mg Al Si P S Cl Ar
23.0 24.3 3 4 5 6 7 8 9 10 11 12 27.0 28.1 31.0 32.1 35.5 39.9
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.1 40.1 45.0 47.9 50.9 52.0 54.9 55.8 58.9 58.7 63.5 65.4 69.7 72.6 74.9 79.0 79.9 83.8
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.5 87.6 88.9 91.2 92.9 95.9 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
57-71
Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 178.5 180.9 183.8 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0

87 88 89–103 104 105 106 107 108 109 110 111 112 114 116

Fr Ra Rf Db Sg Bh Hs Mt Ds Rg Cn Fl Lv

57 58 59 60 61 62 63 64 65 66 67 68 69 70 71

La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
138.9 140.1 140.9 144.2 144.9 150.4 152.0 157.2 158.9 162.5 164.9 167.3 168.9 173.0 175.0

89 90 91 92 93 94 95 96 97 98 99 100 101 102 103

Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.0 238.1

Figure 8.1 The periodic table.

The International Union of Pure and Applied Chemistry, IUPAC, now
recommends that the groups in the periodic table should be numbered
1 to 18.
● Groups 1 and 2 remain the same as before – classified as the s-block.
● The transition elements now become Group 3 to 12 – classified as
the d-block.
● Groups 3 to 7 now become Groups 13 to 17 and the noble gases
become Group 18 – classified as the p-block.
The blocks are shown in Figure 8.2.
Chapter 8  The periodic table and periodicity

s- p-
block block

d-
block

Figure 8.2 Blocks of the periodic table.

Key term The vertical columns are called groups and the horizontal rows are
Periodicity is a repeating pattern, called periods. Trends in the groups (vertical columns) and periods
in either physical or chemical (horizontal rows) reflect the structures of the atoms of the elements
properties, across different periods. within them, and these in turn affect the chemical properties of the
elements. These repeating properties demonstrate periodicity.
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 Introducing the periodic table and periodicity
Similarities within groups are illustrated by considering the properties
and chemical reactions of the elements in Group 2 and Group 17 (the
halogens).
Elements with the same outer-shell electron configuration are placed in
the same group. For example, all elements with a single s electron in the
outer shell are in Group 1; all elements with four outer-shell electrons
(s2p2) are in Group 14 which until recently was called Group 4.
The elements within a group have similar but steadily changing
properties.
Within a period, the elements go from metals on the left-hand side to
non-metals on the right, with the noble gases on the extreme right.

Trends across a period

Table 8.1 illustrates the trends across Period 3.
Table 8.1 Trends across Period 3.

Element Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon

Atomic radius/nm 0.190 0.160 0.130 0.118 0.110 0.102 0.099 0.095
Type of bonding Metallic Metallic Metallic Covalent Covalent Covalent Covalent /
Structure Giant Giant Giant Giant Simple Simple Simple Simple
lattice lattice lattice lattice molecular molecular molecular atomic
Electrical conductivity Good Good Good Poor Poor Poor Poor Poor
Melting point/°C 98 649 660 1410 44* 113 –101 –189
Boiling point/°C 883 1107 2467 2355 281 445 –35 –186
First ionisation energy/kJ mol –1
496 738 578 789 1012 1000 1251 1521
*White phosphorus

Trends down a group

The trends down Groups 2 and 17 are shown in Tables 8.2 and 8.3
respectively.
Table 8.2 Trends down Group 2.

Group 2 Beryllium Magnesium Calcium Strontium Barium

Atomic radius/nm 0.125 0.160 0.174 0.191 0.198
Ionic radius/nm 0.027 0.072 0.100 0.113 0.136
Melting point/°C 1278 649 839 769 725
Boiling point/°C 2970 1107 1484 1384 1640
First ionisation energy/ 900 738 590 550 503
kJ mol–1

Table 8.3 Trends down Group 17 (the halogens).

Group 17 Fluorine Chlorine Bromine Iodine

Atomic radius/nm 0.07 0.10 0.11 0.13
Ionic radius/nm 0.13 0.18 0.20 0.22
Melting point/°C –220 –101 –7 114
Boiling point/°C –188 –35 59 184
First ionisation energy/kJ mol–1 1681 1251 1140 1008

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 Explaining periodic patterns
Atomic radius

Atomic radii decrease

Atomic radii increase

Na 1
–
Figure 8.3 Periodicity of atomic radii in the periodic table.
10–

Across a period, the atomic radius decreases from left to right (Figure 8.3).
11+
From one atom of an element to the next across a period:
shielding ● the charge of the nucleus increases
electrons in
full shells ● the shielding remains the same
Figure 8.4 Shielding effect of inner Across the period the effect of the nuclear charge on the outer electrons
shell electrons reduces the pull of the increases and the atomic radii decreases.
nucleus in the outer shell.
Down a group, the atomic radius increases.
From one atom of an element to the next down a group:
● the charge of the nucleus increases
● the shielding increases
Down the group the effect of the nuclear charge on the outer electrons
decreases and the atomic radii increases.
Chapter 8 The periodic table and periodicity

Li Na K

outer electron outer electron outer electron

shielded by 2 shielded by 10 shielded by 18
inner electrons inner electrons inner electrons

Figure 8.5 Atoms of the Group 1 elements lithium, sodium and potassium.

Test yourself
1 Put the following elements in order of increasing atomic radius. Justify
your answers:
a) Mg, S, Si
b) Mg, K, Al
c) Si, Cl, K
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 Explaining periodic patterns
Bonding and structure
Across a period, bonding changes from metallic to covalent.
Table 8.4 Trend across Period 3.

Na Mg Al Si P S Cl Ar
Bonding metallic covalent /
Structure giant simple molecular simple
atomic

Down a group, bonding changes from covalent to metallic. This is most

evident in Group 14, formerly Group 4.
Table 8.5 Trend down Group 14.

C Si Ge Sn Pb
Bonding non-metallic Si and Ge show properties metallic
Structure giant covalent lattice associated with metals and giant metallic
with non-metals and can be lattice
regarded as being metalloid

Electrical conductivity
Electrical conductivity is related to the type of bonding. In the third
period, sodium, magnesium and aluminium have metallic bonding.
Metallic elements are good conductors because they possess mobile,
outer-shell electrons. These electrons are delocalised, which allows
metals to conduct heat and electricity, even in the solid state.
The remaining elements across Period 3 are poor conductors because
they do not contain any mobile electrons.
Group 13 elements tend to be better conductors than elements in
Groups 1 and 2 because Group 13 atoms have three electrons in their
outer shells, compared with one and two outer-shell electrons for
elements in Groups 1 and 2, respectively.
Graphite is also a good conductor of electricity as it also possesses mobile,
outer-shell electrons. These electrons are delocalised, which allows graphite
to conduct electricity, even in the solid state, see page 110.

Test yourself
2 Put the following elements in order of increasing conductivity: Mg, Na, Al.
Justify your answer.

Melting point and boiling point

Melting points are related to the type of structure.
● Giant metallic and giant covalent lattices have strong bonds
throughout the lattice, all of which have to be broken. This requires a
great deal of energy and hence the melting points are high.
● Simple covalent molecules have weak intermolecular forces, such as
induced dipole–dipole interactions forces, and little energy is needed
to overcome them. Therefore, the melting points are low.
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 Figure 8.6 shows how melting points change across Period 3. Boiling
points follow the same pattern as melting points, but at a higher
1 500
Si
temperature.
Melting points increase from Group 1 to Group 13. These all have giant
Melting point/°C

1 000
metallic lattices with strong bonds between all the atoms. Group 13
Mg Al
elements tend to have higher melting points than elements in Groups
500
Na S 1 and 2 because the metallic bond is stronger in Group 13 atoms
compared to the elements in Groups 1 and 2 respectively. Silicon (and
0 Cl
P Ar carbon) have very high melting points because they have very strong
covalent bonds throughout the lattice.
−500
Atomic number
In a non-metallic group, such as Group 17 (halogens), the only forces
Figure 8.6 Melting points for elements in
Period 3.
that have to be broken for both melting and boiling to occur are the
intermolecular (induced dipole–dipole) forces (page 109), which depend
on the number of electrons. As Group 17 (halogens) is descended, the
number of electrons increases, so the melting and boiling points also
increase.

Test yourself
3 Explain why boiling points increase down Group 17.
4 Put the following elements in order of increasing melting point: Mg, Na, Al.
Explain your answer.
Key term
The first ionisation energy of an
element is the energy required
Ionisation energy
to remove one electron from The ionisation energy of an element was introduced in Chapter 2 as
the ground state of each atom evidence for the existence of electron subshells. It is possible to measure
in a mole of gaseous atoms of the energy required to remove electrons from an atom in order to
that element, to form a mole of create positive ions. This can be done stepwise. If an atom has seven
gaseous ions of charge 1+. electrons, seven successive ionisation energies can be measured, as
each electron is removed to create ions with a charge of up to 7+.

Tip This can be illustrated by an equation:

Ionisation energy always relates M(g) → M+(g) + e –

to the formation of a positive ion.
Chapter 8  The periodic table and periodicity

Trends in first ionisation energies

When removing an electron the attraction between the electron and
the nucleus has to be overcome. There are three factors that influence
the size of the first ionisation energy of an element.
Factor 1 Atomic radius – the further the electron is away from the
nucleus the easier it is to remove an electron. This tends to
decrease the ionisation energy.
Factor 2 Nuclear charge – as the number of protons in the nucleus
increases its attraction for outer most electrons increases.
This tends to increase the ionisation energy.
Factor 3 Shielding effect – electrons in inner shells exert a repelling
effect on the electrons in an outer shell. This reduces the pull
of the nucleus on the outer electrons. This reduces the effect
of the nucleus and tends to decrease the ionisation energy.
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 Explaining periodic patterns
Down a group
Down a group, the ionisation energy decreases.
The first ionisation energies (kJ mol–1) of the elements in Group 1 of the
periodic table are shown in Table 8.6.
Table 8.6 First ionisation energies of the Group 1 elements.

Element Li Na K Rb Cs
First ionisation energy/kJ mol –1
520 496 419 403 376

Factor 1 Atomic radius – increases down the group and the outer
electron is further from the nucleus. This tends to decrease
the ionisation energy as we go down the group.
Factor 2 Nuclear charge – increases down the group. This tends to
increase the ionisation energy as we go down the group.
Factor 3 Shielding effect – increases down the group. This reduces
the effect of the nucleus. This tends to decrease the
ionisation energy as we go down the group.
Factors 1 and 3 outweigh factor 2 as ionisation energy decreases down
a group.
Across a period
Across a period, ionisation energy increases. This is illustrated in Table 8.7.
Table 8.7 First ionisation energies of elements in Period 2.

Element Li Be B C N O F Ne
First ionisation energy / 520 900 801 1086 1402 1314 1681 2081
kJ mol–1
Electron structure 1s22s1 1s22s2 1s22s22p1 1s22s22p2 1s22s22p3 1s22s22p4 1s22s22p5 1s22s22p6
full sub shell ½ full sub-shell full shell

We can also explain this in terms of the three factors.

Factor 1 Atomic radius – decreases across the period so the outer
electrons are closer to the nucleus. This tends to increase
the ionisation energy as we go across the period.
Factor 2 Nuclear charge – increases across the period. This tends to
increase the ionisation energy as we go across the period.
Factor 3 Shielding effect – generally remains the same across a period
and therefore has little effect on the nucleus.
Factors 1 and 2 both indicate that ionisation energy will increase across
the period.
There is a general increase across a period but there are slight decreases
after the second and the fifth element.
● Elements in Group 13 have an electron structure of s2p1 and the s
electrons provide a slightly greater shielding of the p electron, which
is therefore lost a little more readily.
● Elements in Group 15 have a half-filled set of p orbitals but in Group
16 there is a pair of p electrons and the repulsion between this pair
of electrons is sufficient to make the elements in Group 16 ionise
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 Example
Explain why the first ionisation energy of barium is lower than that of calcium.

Answer
Calcium and barium have the same outer electronic structure (s2p2).
Tip
The barium atom has a larger radius than the calcium atom. Therefore, the
Questions that ask for a outer electrons of barium are further away from the nucleus.
comparison of ionisation
energies are common in exams. The outer electrons of barium are more shielded from the nucleus because
Be careful that you consider there are more intermediate layers of electrons.
all the relevant factors. Most The force of attraction of the barium nucleus on the outermost electrons is
questions of this type are worth lower than that in calcium.
3 or 4 marks, so the examiner is
expecting some detail. Therefore, the first ionisation energy of barium is lower than that of calcium.

Test yourself
5 For each of the following pairs, state which element has the higher first
ionisation energy and explain your answer.
a) Mg and Na
b) Mg and Ca
c) Ne and Na
6 Explain why the first ionisation energy of aluminium, 578 kJ mol–1, is less
than that of magnesium, 738 kJ mol–1.
Chapter 8  The periodic table and periodicity

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 Practice questions
Practice questions
Multiple choice questions 1–9
Questions 1 to 4 relate to the elements shown on the outline of the periodic table below as A to D. (Note: the letters
used A to D are not the chemical symbols for the elements concerned.)

A B

1 Which element has the electronic configuration Use the key below to answer Questions 7 to 9.
1s22s22p63s23p2?
A B C D
2 Which element forms a cation with a charge of 1, 2 & 3 1, 2 correct 2, 3 correct 1 only
2+? correct correct
3 Which element is a non-metal with a high 7 Along which of the series do the melting points of
melting point? the elements rise?
4 Which element has smallest atomic radius? 1 Na, Mg, Al
2 Be, B, C
5 Element X is in Period 3 and the first 3 He, Li, Be
seven ionisation energies (kJ mol–1) are listed
below: 8 Along which of the series of three elements do
789 1577 3232 4356 16 091 the first ionisation energies decrease?
19 785 23 787 29 253 1 Na, K, Rb
Element X is: 2 Ca, K, Rb
A Al 3 P, As, Se
B Si
9 The first six ionisation energies of three different
C P
elements are shown in the diagrams.
D S
Energy/kJ mol−1

6 The melting points of four successive elements in

Period 3 are listed below.
922 K 933 K 1683 K 863 K
Successive ionisation

The four elements are:

Energy/kJ mol−1
energies

A Na, Mg, Al, Si

B Mg, Al, Si, P
C Al, Si, P, S
Energy/kJ mol−1

D Si, P, S, Cl

The three different elements from top to bottom

could be:
1 P, Mg, C 2 K, C, Ca 3 Na, Si, Mg

10 The following data gives Group

the atomic radii for elements in
1 2 13 14 15 16 17 18
Periods 2 and 3 of the
Period 2 Li Be B C N O F Ne
periodic table.
Atomic radius/nm 0.157 0.125 0.090 0.077 0.075 0.073 0.071 0.065
Explain the trend:
Period 3 Na Mg Al Si P S Cl Ar
a) across each period
Atomic radius/nm 0.191 0.160 0.130 0.118 0.110 0.102 0.099 0.095
b) down a group (6) 123

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 11 The table shows the formulae of chlorides for the elements in Periods 2 and 3.

Group
1 2 13 14 15 16 17 18
Period 2 LiCl BeCl 2 BCl3 CCl4 NCl3 OCl 2 FCl –
Period 3 NaCl MgCl 2 AlCl3 SiCl4 PCl3 SCl 2 Cl 2 –

a) Why are there no entries for Group 18 in the formulae of the oxides of the elements in
table? Periods 2 and 3.
b) What periodic pattern is shown by the ii) Is there a periodic pattern in the
formulae of these chlorides? formulae of these oxides? (5)
c) i) Draw up a similar table to show the
12 The table below shows the melting points of the elements in Periods 2 and 3 of the periodic table.

Group
1 2 13 14 15 16 17 18
Period 2 Li Be B C N O F Ne
Melting point/°C 181 1278 2300 3655 –210 –218 –220 –248
Period 2 Na Mg Al Si P S Cl Ar
Melting point/°C 98 649 660 1410 44 119 –101 –189

a) What is the general pattern in melting c) What is meant by the term periodicity?
temperatures across periods in the periodic d) State two other physical properties that can
table? be described as periodic in relation to the
b) How is this general trend related to the periodic table. (7)
different types of elements?
13 The following data gives the boiling point for elements in Periods 2 and 13 of the periodic table.

Group
1 2 13 14 15 16 17 18
Period 2 Li Be B C N O F Ne
Boiling point/°C 1342 2970 2550 4554 –196 –183 –188 –246
(sublimes)
Period 3 Na Mg Al Si P S Cl Ar
Chapter 8 The periodic table and periodicity

Boiling point/°C 883 1107 2467 2355 280 445 –35 –186

a) Identify the elements that would be a gas at the oxygen can be separated by fractional
room temperature and pressure. distillation. Which boils first?
b) The atmosphere contains about 80% N2(g) c) Using ideas about structure, bonding and forces:
and 20% O2(g). If the air is cooled to about i) explain the trend across each period
–200 °C it is liquefied. The nitrogen and ii) explain the trend down each of Group 2
and Group 17. (13)

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 Practice questions
14 The graph shows the boiling points of eight elements in Periods 2 and 3. The sequence of the eight elements
follows the order in which they appear in the periodic table.
F

E
D
Boiling point

C
H

A G

Elements in sequence from Periods 2 and 3

a) Identify element F. Justify your answer.

b) Explain the difference in boiling points between C and D.
c) Identify B and explain why its boiling point is so low. (7)
15 The graph shows the first and second ionisation energies of the elements lithium to sodium.
8 000
1st ionisation energy
2nd ionisation energy

6 000
Ionisation energy/kJ mol−1

4 000

2 000

0
Li Be B C N O F Ne Na

a) Write an equation to illustrate the first e) Explain the general trend in first ionisation
ionisation energy of carbon. energies from Li to Ne.
b) Write an equation to illustrate the second f) Explain why the trend in second ionisation
ionisation energy of nitrogen. energies from Be to Na is similar to the trend
c) Explain why the second ionisation energy is in first ionisation energies from Li to Ne.
greater than the first ionisation energy for all g) Why is the second ionisation energy of Li
elements. much greater than the second ionisation
d) Explain why the difference between first and energy of Na. (12)
second ionisation energies is much larger for
Li and for Na than it is for any of the other
elements.

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 Challenge
16 Two elements are adjacent to each other in a row of the periodic table.
Their successive ionisation energies are shown in the graph below.
25 000
Element X
Element Y
20 000
Ionisation energy/kJ mol–1

15 000

10 000

5 000

0
M M+ M2+ M3+ M4+ M5+ M6+ M7+ M8+ M9+
Successive ioniasations

On the x-axis, each point represents the ionisation energy for that ion.
So, for example, the point at M4+ gives the value of the ionisation energy for the ionisation:
M4+(g) → M5+(g) + e–
a) Decide in which groups of the periodic table elements X and Y would be found.
Element Y has an atomic mass of 127. Element X has several isotopes, as shown in the table.

Mass number 120 122 123 124 125 126 128 130
% abundance 0.1 2.5 0.9 4.6 7.0 18.7 31.7 34.5

b) Use this information to calculate the weighted d) Use the periodic table on page 116 to identify
mean atomic mass of element X. elements X and Y.
c) Compare your answers to (a) and (b) and suggest e) Find one other place in the periodic table
what is unusual about elements X and Y. where the same pattern for two adjacent
elements is observed. (8)
Chapter 8  The periodic table and periodicity

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 Chapter 9
Group 2 and the halogens,
qualitative analysis
Prior knowledge
In this chapter it is assumed that you are familiar with:
● the periodic table and periodicity
● electronic configuration
● redox reactions.

The elements in the periodic table are arranged in order of their atomic
number and they are grouped together in terms of their chemically properties.
Metallic groups tend to occur on the left-hand side of the periodic table and
groups on the right-hand side tend to show properties of non-metals.

Test yourself on prior knowledge

1 What is the electron structure for these elements?
a) C b) V c) As
2 Identify the following atoms or ions:
a) X has electron structure 1s22s22p63s23p5
b) Y2– has electron structure 1s22s22p63s23p6
c) Z2+ has electron structure 1s22s22p63s23p64s23d104p6
3 What is the oxidation number of:
a) Cr in K2CrO4
b) O in K2O2
c) H in LiAlH4?

Be Be2+
Group 2
Electron configuration
Atoms of Group 2 elements have two electrons in their outer shell and
Mg Mg2+ readily form 2+ ions (cations) that have the same electron configuration
as a noble gas.
The electron configurations of the elements are shown in Table 9.1.
Table 9.1 Electron configurations of the Group 2 elements.

Group 2 element Full electron configuration Shorthand

configuration
Ca Ca2+ Beryllium, 4Be 1s22s2 [He]2s2
2 2 6 2
Magnesium, 12Mg 1s 2s 2p 3s [Ne]2s2
Calcium, 20 Ca 1s22s22p63s23p64s2 [Ar]2s2
Strontium, 38Sr 1s22s22p63s23p63d104s24p6 5s2 [Kr]2s2
Figure 9.1 Relative sizes of the atoms and
ions of Group 2 elements. Barium, 56Ba 1s22s22p63s23p63d104s24p64d105s25p66s2 [Xe]2s2

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 Test yourself
1 Explain why the ionic radius of a Group 2 ion is smaller than the atomic
radius of the corresponding Group 2 atom.
2 The graph shows the sum of the first and the second ionisation energies
of the Group 2 metals.
Be2+

Sum of first two ionisation

2500
Mg2+

energies/kJ mol–1
2000
Ca2+ Sr2+
Ba2+
1500

1000

500

0
0 10 20 30 40 50 60
Atomic number

Explain the trend shown by the graph.

3 Explain why Group 2 ions in any period are smaller than the Group 1 ion
in the same period.
Tip
Questions are often set about
conductivity. Remember that
Physical properties
electricity is conducted in metals The elements in Group 2 are all metals. Therefore, they are good
by mobile electrons; in ionic conductors of electricity and have high melting and boiling points.
compounds that are molten or in With the exception of beryllium, generally they form colourless ionic
aqueous solution, it is conducted compounds that also have high melting and boiling points. Their
by mobile ions. compounds are good conductors of electricity when molten or in
aqueous solution, but poor conductors when solid.

Chemical properties
Tip Atoms of Group 2 elements react by losing two electrons. They give up
Chapter 9  Group 2 and the halogens, qualitative analysis

their two s electrons to form M2+ ions (where M represents Mg, Ca, Sr
Isoelectronic with a noble gas or Ba) which are isoelectronic with a noble gas.
means that the ions have the
same number of electrons as a M → M2+ + 2e –
noble gas. It follows that Group 2 elements are reducing agents.

Trend in reactivity
Reactivity increases down the group such that Ba is the best reducing
agent. The reactivity can be explained in terms of the ease with which
they lose electrons. This has been covered in Chapter 8 on page 120.

Reaction with oxygen

Group 2 elements undergo redox reactions with O2. Apart from
beryllium the Group 2 metals burn brightly in oxygen to form ionic
oxides, M2+O2–.
● Magnesium burns, emitting a bright white light:
1
Mg(s) + 2 O2(g) → MgO(s)

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 Group 2
● Calcium burns with a brick-red flame:
1
Ca(s) + 2 O2(g) → CaO(s)
● Strontium burns with a crimson flame:

Sr(s) + 1 O2(g) → SrO(s)

2
● Barium burns with a green flame:
Ba(s) + 1 O2(g) → BaO(s)
2
The oxidation number of the Group 2 element increases from 0 to +2,
hence it is oxidised; the oxidation number of oxygen decreases from 0
to –2, hence it is reduced:

oxidation numbers
are shown in red
0 0 +2 –2
+ 1
Mg(s) O (g)
2 2 MgO(s)
loses two gains two
electrons electrons
to form to form
Mg2+ ion O2– ion
MgO (s)

The Group 2 element is a reducing agent.

The oxides of Group 2 elements, apart from BeO, are all white solids
with high melting points that react with water to form solutions of the
corresponding hydroxide. The oxides are all basic oxides and react with
acids to produce salts.
Table 9.2 shows the melting points of the oxides.
Table 9.2 Melting points of the Group 2 oxides.

Group 2 oxide MgO CaO SrO BaO

Melting point/°C 2852 2614 2430 1918

MgO has a very high melting point and is used as a refractory ceramic
to line furnaces.
CaO is known as ‘quicklime’; it reacts rapidly with water to produce
calcium hydroxide and is used to reduce acidity in soil.

Reaction with water

Group 2 elements undergo redox reactions with water to produce the
hydroxide and hydrogen. The rate of reaction increases down the group.
The general equation for Group 2 metals reacting with water is:
M(s) + 2H2O(l) → M(OH)2(aq) + H2(g) where M is Ca, Sr or Ba.
Magnesium reacts very slowly with water and the Mg(OH)2 is formed,
but it is formed as a white precipitate.
Mg(s) + 2H2O(l) → Mg(OH)2(s) + H2(g)
Magnesium reacts more readily on heating with steam to form the
oxide:
Mg(s) + 2H2O(g) → MgO(s) + H2(g)
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 The oxidation number of the Group 2 element increases from 0 to +2;
the oxidation number of hydrogen changes from +1 to 0:

oxidation numbers
are shown in red
0 +1 +2 0
Ca(s) + H2O(I) Ca(OH)2(aq) + H2(g)
loses two each H gains
electrons an electron
to form to form H2
Ca2+ ion

Reaction with chlorine

All Group 2 metals react with chlorine to form white chlorides.
M(s) + Cl2(g) → MCl2(s) where M is Mg, Ca, Sr or Ba.
Tip
The acids you are expected to Reaction with dilute acids
know are limited to acids such All Group 2 metals react with the dilute acids to produce salts and
as HCl, HNO3, H2SO4 and weak hydrogen gas.
acids such as CH3COOH.
M(s) + 2HCl(g) → MCl2(aq) + H2(g)  where M is Mg, Ca, Sr or Ba.

Test yourself
4 Write balanced equations for the reactions of:
a) calcium with oxygen
b) barium with oxygen
c) strontium with chlorine
d) barium with water.
5 Show that calcium acts as a reducing agent when it reacts with:
a) oxygen
Chapter 9  Group 2 and the halogens, qualitative analysis

b) water.

Reactions of Group 2 compounds

Oxides
All Group 2 metal oxides , except beryllium oxide, BeO, are basic oxides
and react with:
● water to form hydroxides
● acids to form salts.
The general equation for the reaction of the oxide with water is:
MO(s) + H2O(l) → M(OH)2(aq) where M is Ca, Sr or Ba.
Magnesium hydroxide is sparingly soluble and forms a white suspension
known as ‘milk of magnesia’ which can be used as an antacid to treat
indigestion.
Calcium oxide reacts vigorously with water to form a solution of calcium
hydroxide which is known as limewater.

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 Group 2
Tip
Limewater can be used to test for CO2(g). If CO2(g) is bubbled into
limewater initially a white precipitate of CaCO3(s) is formed. However,
if more CO2(g) is bubbled into the mixture the white precipitate re-
dissolves to form a solution of Ca(HCO3)2(aq).
CO2(g) + Ca(OH)2(aq) → CaCO3(s) + H2O(l)
CO2(g) + CaCO3(s) + H2O(l) → Ca(HCO3)2(aq)

The reactions of Group 2 oxides with water are not redox reactions. The
oxidation numbers of all the elements remain the same, for example:
+2 –2 +1 –2 +2 –2+1
CaO(s) + H2O(l) Ca(OH)2(aq)
each H gains an electron to form H2

The resulting hydroxide solutions are alkaline and have pH values in the
range 8–12. The actual pH value depends on the concentration of the
solution and the solubility of the Group 2 hydroxide. Solubility of the
hydroxides increases down the group and it follows that for saturated
solutions the alkalinity will also increases down the group.
The general equation for the reaction of the oxide with an acid is:
MO(s) + 2HCl(aq) → MCl2(aq) + H2O(l)  where M is Mg, Ca, Sr or Ba.

Carbonates
The carbonates of Group 2 all have the general formula MCO3. They are
insoluble in water and all Group 2 carbonates decompose on heating to
form oxides and carbon dioxide. The general equation for the reaction is:
heat
MCO3(s) MO(s) + CO2(g)  where M is Mg, Ca, Sr or Ba.
The ease with which the carbonates decompose decreases down the
group. Beryllium carbonate, BeCO3, is so unstable that it does not exist
at room temperature. Barium carbonate, BaCO3, requires strong heating
to bring about the decomposition. The thermal decomposition of Group
2 carbonates is not a redox reaction. The oxidation number of all the
elements remains the same, for example:
+2 +4 –2 +2–2 +4–2
MgCO3(s) MgO(s) + CO2(g)
heat
Calcium carbonate is used as an antacid to treat indigestion.

Sulfates
The sulfates have the general formula MSO4. They are all white solids
whose solubility in water decreases down the group.
Epsom salts consist of hydrated magnesium sulfate, MgSO4.7H2O, which
is a laxative.
Barium sulfate, BaSO4, is insoluble in water and can be used as a test for
a sulfate.
BaCl2(aq) + Na2SO4(aq) → BaSO4(s) + 2NaCl(aq)
white
precipitate

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 Barium sulfate also absorbs X-rays strongly so it is used in ‘barium
meals’ to help diagnose disorders of the stomach and intestines. Soluble
barium compounds are toxic, but barium sulfate is insoluble so it is not
absorbed. X-rays cannot pass through the ‘barium meal’, which therefore
creates a shadow on the X-ray film.

Activity
Limestone and its uses
Calcium carbonate occurs naturally as limestone (Figure 9.2).
Limestone is an important mineral. Some of the rock is quarried
for road building and construction. Pure limestone is used in the
chemical industry.
Heating limestone in a furnace at 1200 K converts it to calcium
oxide (quicklime). The reaction of quicklime with water produces
calcium hydroxide (slaked lime).
1 Name two other minerals that consist largely of calcium carbonate.
2 Suggest a reason for grinding up limestone lumps before heating
them with sodium carbonate and sand to make glass.
3 Write an equation for the decomposition of calcium carbonate Figure 9.2 Limestone cliff at Malham Cove in
on heating in a furnace. Yorkshire. Limestone gives rise to attractive scenery.
4 With the help of equations, show that both calcium oxide and
calcium hydroxide can be used to increase the pH in soils that are too acidic.
5 Lime mortar was used in older buildings. It is a mixture of slaked lime, sand and water. It sets slowly by reacting
with carbon dioxide in the air. Identify the main product of the reaction of slaked lime with carbon dioxide.
6 A suspension of calcium hydroxide in water is used as an industrial alkali. Suggest why a suspension and not just a
solution of the hydroxide is used.
7 What is the laboratory use of a solution of calcium hydroxide?

Lump Grinding Ground

limestone mills limestone
calcium calcium
Chapter 9  Group 2 and the halogens, qualitative analysis

carbonate carbonate
CaCO3 (s) CaCO3(s)

Used in blast furnaces Heated with sodium carbonate

to extract iron. Used as and sand to make glass. Used
aggregate in concrete as a filler. Used in agriculture
to improve soil fertility

Heat with
Limestone clay
Cement
rock

Milk of lime
Add more Hydrated Add more calcium
Quicklime water lime water
hydroxide
calcium oxide calcium
Strong heating suspended
CaO(s) hydroxide
in a furnace in water
Ca(OH)2(s)
Ca(OH)2(s)

Used in the making of steel. Used in agriculture and Used to treat sewage and to
Used to refine beet sugar. horticulture to improve soil soften water. With chlorine it
Used in agriculture to fertility and to make fungicides. bleaches paper and cotton.
improve soil fertility Used to stabilise soil in the Used in the manufacture of
construction industry leather goods
Figure 9.3 Products from limestone and their uses.
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 The halogens (Group 17)
Test yourself
6 Write balanced equations for the reactions of:
a) barium oxide with dilute hydrochloric acid
b) calcium oxide with water
c) lime water (a solution of calcium hydroxide) with carbon dioxide.
7 Write an equation, including state symbols for:
a) the thermal decomposition of magnesium carbonate
b) the reaction of magnesium carbonate with hydrochloric acid
c) the reaction of magnesium carbonate and ethanoic acid,
CH3COOH(aq).
8 Calcium nitrate decomposes as shown in the equation below.
2Ca(NO3)2(s) → 2CaO(s) + 4NO2(g) + O2(g)
Use oxidation numbers to decide whether or not the decomposition of
calcium nitrate is a redox reaction.

The halogens (Group 17)

Fluorine, chlorine, bromine and iodine belong to the family of halogens.
All four are reactive non-metals readily forming halide anions, X–. The
reactivity increases up the group such that fluorine and chlorine are
particularly hazardous.
The name ‘halogen’ means ‘salt-former’ and halides occur naturally
as salts with metals. The halogens are important economically as the
ingredients of plastics, pharmaceuticals, anaesthetics, dyestuffs and
chemicals for water treatment.
All the halogens consist of diatomic molecules, X2, linked by a single
covalent bond. The halogen molecules are non-polar.
The halogens have similar chemical properties because they all have
seven electrons in the outer shell – one less than the next noble gas in
Group 18.
The halogens (Group 17), like all groups in the periodic table, show a
range of trends including atomic radius (increases down the group)
and ionisation energy (decreases down the group). Reactivity, however,
increases up the group which is in contrast to Group 2. When halogens
react they gain an electron whereas Group 2 elements lose electrons.

Electron configuration
Atoms of Group 17 elements have seven electrons in their outer
shell and readily form a 1– ion (anion) that has the same electron
configuration as a noble gas. The electron configurations of the halogens
are shown in Table 9.2.
Table 9.2 Electron configuration of the Group 17 elements.

Halogen Full electron configuration

Fluorine, 9F 1s22s22p5
Chlorine, 17Cl 1s22s22p63s23p5
Bromine, 35Br 1s22s22p63s23p64s24p5
Iodine, 53I 1s22s22p63s23p63d104s24p64d105s25p5
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 Characteristic physical properties
The elements in Group 17 are non-metals and, hence, are poor conductors.
At room temperature fluorine, F2, is a yellow gas, chlorine, Cl2, is a green
gas, bromine, Br2, is a dark red/brown liquid and iodine, I2, is a grey/black
solid which sublimes to form a purple/violet gas.

Figure 9.5 Bromine is a dark red/

Figure 9.4 Chlorine is a toxic green brown liquid – it is very volatile and Figure 9.6 Iodine is a shiny grey/black solid but when
gas. gives off a toxic brown/orange vapour. warmed gently sublimes to give a toxic purple vapour.

Descending the group from fluorine to iodine, there is an increase

in induced dipole-dipole interactions corresponding to the increased
number of electrons in the molecules. This increase in induced dipole-
dipole interactions reduces volatility. Therefore, the boiling points (and
melting points) increase down the group as shown below (Figure 9.7).
200
I2
Chapter 9  Group 2 and the halogens, qualitative analysis

100
Br2
Boiling point/°C

Cl2

–100

F2
–200
0 50 100 150 200 250
Molar mass/g mol–1

Figure 9.7 Boiling points of the halogens plotted against molar mass.

Fluorine is the most electronegative of all elements (see page 105)

and it is a powerful oxidising agent. Its oxidation state is –1 in all its
compounds. Uses of fluorine include the manufacture of a wide range
of compounds consisting of only carbon and fluorine (fluorocarbons).
The most familiar of these is the very slippery, non-stick polymer
poly(tetrafluorethene) or Teflon®.

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 The halogens (Group 17)
Chlorine reacts directly with most elements. In its compounds, chlorine
is usually present in the –1 oxidation state, but it can be oxidised to
positive oxidation states by oxygen and by fluorine. Chlorine is used
in the production of polymers such as polyvinylchloride (PVC). Water
companies use chlorine to kill bacteria in drinking water. It is used to
bleach paper and textiles.
Bromine, like the other halogens, is a reactive element, but it is a less
powerful oxidising agent than chlorine. Bromine is used to make a range
of products including flame retardants and medicines.
Iodine is also an oxidising agent but less powerful than the other
halogens. Iodine is also used in a range of products including medicines,
dyes and catalysts. Iodine is also needed in our diet so that the thyroid
gland can make thyroxine, a hormone which regulates growth and
metabolism. Foods such as sea-weed, yogurt, milk and eggs provide a
source of iodine but in many regions sodium iodide, NaI, is added to
table salt to supplement the iodine in the diet.

Test yourself
  9 Explain the variation in states of the halogens. Predict the state of
astatine, give your reasons.
10 Write the full electronic configuration of:
a) a chlorine atom
b) a bromide ion.
11 Explain why:
a) atomic radii of halogens increase down the group
b) ionic radii of halides are larger than atomic radii of the corresponding
halogen.
12 Draw dot-and-cross diagrams of the following molecules:
a) fluorine
b) hydrogen bromide
c) iodine monochloride, ICl.
13 Explain why Cl2(g) is a non-polar molecule but HCl(g) is a polar
molecule.

Chemical properties
The halogens in Group 17 react by gaining electrons to form halide
anions. The ease with which the electron is gained by a halogen atom
decreases down the group. This is because atomic radius and shielding
increase down the group and this reduces the attraction of the nucleus
for electrons.
Fluorine is the most reactive halogen. It readily gains electrons and is a
powerful oxidising agent. Iodine is the least reactive halogen. In order of
decreasing activity, halide ions are formed thus:
Tip
F2 + 2e – → 2F–
Make sure that you know the
difference between a halogen Cl2 + 2e – → 2Cl–
and a halide. Many students Br2 + 2e – → 2Br–
confuse chlorine with chloride.
I2 + 2e – → 2I –

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 Halogens react with most other elements to form halides.
They react directly with:
metals: 2Na(s) + Cl2(g) → 2NaCl(s)
Fe(s) + Cl2(g) → FeCl2(s)
non-metals: Si(s) + 2Cl2(g) → SiCl4(l)
P4(s) + 10Cl2(g) → 4PCl5(l)
Chlorine, however, does not react directly with carbon, oxygen or nitrogen.

Displacement reactions
A halogen (F2, Cl2 or Br2) displaces a heavier halide (Cl–, Br– or I –) from
one of its salts (Table 9.3).

Table 9.3 Displacement reactions.

Fluoride, F– Chloride, Cl– Bromide, Br– Iodide, I –

Fluorine, F2 ✓ ✓ ✓
Chlorine, Cl 2 ✗ ✓ ✓
Bromine, Br2 ✗ ✗ ✓
Iodine, I2 ✗ ✗ ✗

● Fluorine displaces Cl–, Br– and I – from solution.

● Chlorine displaces Br– and I – from solution.
● Bromine displaces I – from solution.
● Iodine cannot displace any of the above halides.
These displacement reactions illustrate the decrease in oxidising power
down the group. Chlorine oxidises both bromide and iodide ions to form
orange-brown bromine and in aqueous solution iodine which has a
Chapter 9  Group 2 and the halogens, qualitative analysis

brown-black colour, respectively. Addition of an organic solvent produces

a distinctive violet colour with iodine.
The halogens dissolve readily in non-polar solvents such as hexane,
Figure 9.8 Bromine (left) and iodine (right)
have distinctive colours when dissolved
which is immiscible with water and forms two separate layers. When
in the upper organic layer – the colours dissolved in hexane the solutions have the same colour as the halogen
of the halogens are used to identify if a vapour. Iodine in hexane has a very distinctive purple/violet colour
reaction has occurred or not. (Figure 9.8).
The oxidation reactions of chlorine are represented by the equations:
Cl2(g) + 2Br–(aq) → 2Cl–(aq) + Br2(l)
Cl2(g) + 2I –(aq) → 2Cl–(aq) + I2(s)

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 The halogens (Group 17)
Bromine oxidises I – only.
The oxidation of iodide ions by bromine is represented by the equation:
Br2 + 2I – → 2Br– + I2
Iodine does not oxidise either chloride or bromide ions.
Each displacement reaction is a redox reaction. The halogen higher
in the group gains electrons (is reduced) to form the corresponding
halide.

Uses of chlorine
Chlorine is used in water treatment. It reacts reversibly with water and
the resultant mixture kills bacteria.
Cl2(aq) + H2O(l) L HCl(aq) + HClO(aq)
This reaction is a redox reaction, but it is unusual in that chlorine
undergoes both oxidation and reduction:
Oxidation

Oxidation numbers 0 –1 +1
Key term Cl2 + H2O HCl + HClO
Disproportionation occurs
Reduction
when the same element both
increases and decreases its
One chlorine atom in the Cl2 molecule is oxidised. Its oxidation
oxidation numbers so that
number changes from 0 to +1. The other chlorine atom is reduced. Its
the element is simultaneously
oxidation number changes from 0 to –1. This type of reaction is called
oxidised and reduced.
disproportionation.

Benefits and risks of water treatment

Chlorine is added to drinking water to kill micro-organisms such
as bacteria and viruses. This greatly reduces the risk of waterborne
diseases such as cholera and typhoid fever. The chloric(i) acid
molecules are able to pass through the cell walls of bacteria and once
inside the bacterial cells, the HClO molecules break up and kill the
organism by oxidising and chlorinating molecules that make up the
structure of the cells.
Disinfection with chlorine can produce by-products that may be
harmful. Chlorine can also react with organic matter in the water. This
produces traces of chlorinated hydrocarbons such as trichloromethane,
CHCl3. The amount produced is very small but some studies suggest an
increased risk of bladder cancer and possibly colon cancer in people who
drank chlorinated water for 35 years or more.
However, the interpretation of the evidence remains controversial,
and the links between trichloromethanes and cancer are not firmly
established. Whatever these risks, the benefits of chlorination to prevent
waterborne disease are widely accepted to be much greater than the
small health risks from trihalomethanes.

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 Activity
Water treatment in swimming pools 100%
Swimming pools can be sterilised with chlorine compounds that
produce chloric(i) acid when they dissolve in water. Chloric(i) acid

un-ionised HClO
Percentage of
is a weak acid so it does not easily ionise. The concentration of
un-ionised HClO in a solution depends on the pH, as shown in the
graph in Figure 9.9.
Swimming pool managers have to check the pH of the water
carefully. They aim to keep the pH in the range 7.2–7.8.
0%
4 5 6 7 8 9 10 11
1 Write an equation to show the formation of chloric(i) acid when pH
chlorine reacts with water.
2 Swimming pools were once treated with chlorine gas from cylinders Figure 9.9 Concentration of chloric(i) acid, HClO,
varies over a range of pH values at 20 °C.
that contained the liquefied gas under pressure. Nowadays they
are usually treated with chemicals that produce chloric(i) acid when
they are added to water. Suggest reasons for this change.
3 Explain why sodium chlorate(i) produces chloric(i) acid when it is
added to water at pH 7–8.
4 Explain why the pH of water in swimming pools must not be
allowed to increase above 7.8.
5 Suggest why pool water must not become acidic, even though
this would increase the concentration of un-ionised HClO.
6 Nitrogen compounds, including ammonia, urea and proteins,
react with HClO to form chloramines, which are irritating to
skin and eyes. Chloramines formed from ammonia can react Figure 9.10 Chlorine compounds treat the water in
with themselves to form nitrogen and hydrogen chloride, which swimming pools.
gets rid of the problem. However, if there is excess HClO, another reaction produces nitrogen trichloride, which is
responsible for the so-called ‘swimming pool smell’ and is very irritating to the eyes.
Write equations to show:
a) the formation of the chloramine, NH2Cl, from ammonia and chloric(i) acid
b) the removal of chloramines by the reaction of NH2Cl with NHCl2
Chapter 9  Group 2 and the halogens, qualitative analysis

c) the formation of nitrogen trichloride from chloramine, NH2Cl.

7 Explain why swimming pools do not smell of chlorine if properly maintained.

Chlorine also reacts with sodium hydroxide to form bleach, which is

a mixture of sodium chloride and sodium chlorate(i). This is also a
disproportionation reaction of chlorine:
Cl2(g) + 2NaOH(aq) → NaCl(aq) + NaClO(aq) + H2O
0 –1 +1
Cl2(g) + 2NaOH(aq) NaCl(aq) + NaClO(aq) + H2O(l)

The changes in oxidation numbers of chlorine are shown below:

+1
NaClO(aq)
loses 1
electron
oxidised
0
Cl2(g)

reduced
gains 1
electron –1
NaCl(aq)
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 The halogens (Group 17)
Chlorine reacts with NaOH(aq) to form a number of different chlorates
including sodium chlorate(i), NaClO, sodium chlorate(iii), NaClO2, and
sodium chlorate(v), NaClO3. In each of these reactions NaCl and water
are also formed. Each reaction is a disproportionation reaction.

Example
+5 +5
When chlorine reacts with a hot NaClO(aq) The 5 electrons
loses 5 NaClO(aq)
concentrated solution of NaOH(aq), lost must be loses 5
electrons electrons
sodium chlorate(v), NaClO3(aq) is oxidised counter balanced
0 oxidised
by 5 electrons being 0
formed. Construct an equation for this Cl2(g) gained. Cl2(g)
reaction. reduced
We, therefore need reduced
gains 1 gains 5
–1 5 NaCl where
Answer electron electron –1
NaCl(aq) each Cl gains 1
We know that NaCl(aq) will be formed each Cl 5 NaCl(aq)
electron
gains 1electron
along with NaClO3(aq). The oxidation
changes in Cl are –1 in NaCl and +5 in
NaClO3, as shown below:
We now know that the products will contain 1NaClO3(aq), 5NaCl(aq) and H2O(l) such that the balanced equation can
be constructed to give:
3Cl2(g) + 6NaOH(aq) → NaClO3(aq) + 5NaCl(aq) + 3H2O(l)
It is important to remember that oxidation number changes have to be balanced as well as balancing symbols.
Balancing redox equations will play an important part of Module 5 in the A level course.

Tip Testing for halide ions

The addition of dilute nitric acid Silver chloride, silver bromide and silver iodide are insoluble in water.
prevents the formation of a Therefore the presence of chloride, bromide and iodide ions can be
precipitate of silver oxide, which detected by the addition of an aqueous solution of silver nitrate,
would be misleading. AgNO3(aq). The test solution is first acidified with dilute nitric acid and
silver nitrate is then added. Each of the silver halides forms a different
coloured precipitate (Figure 9.11). The identity of the precipitate is
confirmed by its solubility in ammonia.
● Silver chloride is a white precipitate, which quickly turns grey in
sunlight:
Ag+ (aq) + Cl– (aq) → AgCl(s)
● Silver bromide is a cream precipitate, which rapidly darkens in
sunlight:
Ag+ (aq) + Br – (aq) → AgBr(s)
● Silver iodide is a yellow precipitate:
Ag+ (aq) + I –(aq) → AgI(s)
Figure 9.11 Precipitates (from left to right) The colour changes are not very distinctive but a further test with
of silver chloride, silver bromide and silver ammonia helps to distinguish the precipitates. Silver chloride dissolves in
iodide. dilute ammonia, silver bromide dissolves in concentrated ammonia and
silver iodide doesn’t dissolve in ammonia at all (Table 9.4).

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 Table 9.4 Tests for halides.

Halide Effect of adding Effect of adding ammonia

AgNO3(aq)
Chloride White precipitate Precipitate dissolves in dilute NH3 to give a
colourless solution
Bromide Cream precipitate Precipitate dissolves in concentrated NH3 to give a
colourless solution
Iodide Yellow precipitate Precipitate does not dissolves in NH3 (dilute or
concentrated)

Test yourself
14 Describe the colour changes on adding:
a) a solution of chlorine in water to aqueous sodium bromide
b) a solution of bromine in water to aqueous potassium iodide.
15 Write ionic equations for the reactions of aqueous chlorine with:
a) bromide ions
b) iodide ions.
16 Put the chloride, bromide, and iodide ions in order of their strength as
reducing agents, with the strongest reducing agent first. Explain your
answer.
17 Write ionic equations for the reactions of silver nitrate solution with:
a) potassium iodide solution
b) sodium bromide solution.
18 a) Use oxidation numbers to write a balanced equation for the reaction
of iodine with hot aqueous hydroxide ions to form IO3 – and I – ions.
b) Show that this is a disproportionation reaction.

Practice questions 2 Which one represents the ionic radii of Group 17

elements?
Chapter 9 Group 2 and the halogens, qualitative analysis

Multiple choice questions 1–10 3 Which one represents the thermal stability of
Questions 1 to 5 concern the graphs shown below. Group 2 carbonates ?
A B C D represents the oxidising power of the
4 Which one
×
× halogens ?
× ×
× × × × × ×
× × ×
× × × 5 Which one represents the strength of the hydride
bond in the hydrogen halides of Group 17?
2 3 4 5 2 3 4 5 2 3 4 5 2 3 4 5
Period Period Period The answers to Questions 6 to 8 refer to one of the
Period
following compounds.
B C D
×
× A sodium fluoride
× ×
× × × × ×
× × B magnesium chloride
× × C potassium bromide
5 2 3 4 5 2 3 4 5 2 3 4 5
D barium iodide
Period Period Period
6 Which one of the substances when dissolved in
The graphs represent the approximate variations in water would give a yellow precipitate when a few
properties of the elements down Groups 2 and/or 17. drops of aqueous silver nitrate was added to it?
1 Which one represents the oxidation state of all 7 Which one of the substances when dissolved in
Group 2 elements when they form compounds? water would give a white precipitate when dilute
sulfuric acid was added to it?
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 Practice questions
8 Which one of the substances when dissolved e) Solubility of radium sulfate in water
in water reacts with an aqueous solution of f) Effect of heating radium carbonate (17)
bromine?
14 Identify the element that disproportionates in
Use the key below to answer Questions 9 and 10.
each of the following reactions by giving the
A B C D oxidation states of the element before and after
1, 2 & 3 1, 2 correct 2, 3 correct 1 only the reaction.
correct correct a) 2H2O2(aq) → 2H2O(l) + O2(g)
b) Cl2(aq) + 2NaOH(aq) → NaCl(aq) +
9 The highest occupied energy level of the Group NaClO(aq) + H2O(l)
17 element astatine, At, is 6s26p5. Which of the c) Cu2O(s) + H2SO4(aq) → CuSO4(aq) + Cu(s) +
following statements are likely to be correct? H2O(l)
1 Silver astatide, AgAt, will be soluble in d) 3MnO42–(aq) + 4H+(aq) → 2MnO4–(aq) +
concentrated ammonia. MnO2(s) + 2H2O(l) (4)
2 If astatine, At2, is added to a solution of sodium
bromide, the solution turns orange/brown. 15 Two students were asked to design an experiment
3 Astatine, At2, is a solid at room temperature to identify an unknown Group 2 carbonate.
and pressure. Student 1 decided to heat the carbonate to
constant mass and use the results to determine
10 In which of the following reactions would you the identity of the carbonate. Her results are
expect to see an effervescence? shown below.
1 a solution of sulfuric acid is added to a Mass of crucible = 19.58 g
solution of magnesium carbonate Mass of crucible + carbonate = 23.27 g
2 calcium is added to a solution of hydrochloric Mass of crucible + solid after
acid heating for 3 minutes = 22.54 g
3 a solution of potassium chloride is added to a Mass of crucible + solid after
solution of fluorine. heating for 6 minutes = 22.17 g
11 The elements Mg to Ba in Group 2, and their Mass of crucible + solid after
compounds, can be used to show the trends in heating for 9 minutes = 22.17 g
properties down a group of the periodic table. Use the results to identify the Group 2 carbonate.
State and explain the trend down the group in: A second student decided to identify the
a) atomic radius carbonate by reacting it with HCl(aq) and
b) first ionisation energy collected the carbon dioxide by the displacement
c) reactivity of the metals. (8) of water as shown below.

12 a) Explain, with the aid of an equation, the use of

calcium hydroxide in agriculture. CO2(g)
b) Explain, with the aid of an equation, the use
of magnesium hydroxide in some indigestion
tablets as an antacid. (4)
13 Radium is a highly radioactive element. Use your carbonate 250 ml

and excess
knowledge of the chemistry of the elements Mg HCl(aq)
to Ba in Group 2 to predict properties of radium
and its compounds in terms of the following. The student removed the bung and added 1.23 g
Include descriptions of any chemicals changes, of the carbonate to the conical flask followed
equations and suggest the appearance of the by 100 cm3 of 1.0 mol dm–3 HCl(aq) and quickly
products in your predictions. replaced the bung. He collected 166 cm3 of
a) Reaction of radium with oxygen CO2(g).
b) Reaction of radium with water Use the results to deduce the molar mass of
c) Reaction of radium oxide with water the carbonate. Explain why the results are
d) Reaction of radium hydroxide with dilute inconclusive. Identify two possible sources of
hydrochloric acid error in the experiment. (16)

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 16 a) Write an equation for the reaction of chlorine Construct equations for each of the following
with aqueous sodium hydroxide and use oxides of chlorine when it reacts with OH–(aq):
this example to explain what is meant by c) Cl2O reacts with OH–(aq) to form chlorate(i)
disproportionation. ions and water
b) On heating, chlorate(i) ions in solution d) ClO2 reacts with OH–(aq) to form chlorate(iii)
disproportionate to chlorate(v) ions and ions, chlorate(v) ions and water
chloride ions. Write an ionic equation for this e) Cl2O6 reacts with OH–(aq) to form chlorate(v)
reaction. ions, chlorate(vii) ions and water
c) On heating to just above its melting f) Cl2O7 reacts with OH–(aq) to form
temperature, KClO3 reacts to form KClO4 chlorate(vii) ions and water. (10)
and KCl. Write a balanced equation
for the reaction and show that it is a Challenge
disproportionation reaction. (5) 19 Chlorine can be prepared by the reaction
between KMnO4(s) and hydrochloric acid. The
17 State the trend in the power of chloride, bromide
equation for the reaction is:
and iodide ions as reducing agents. Describe how
you could demonstrate the trend by carrying out 2KMnO4(s) + 16HCl(aq) → 2KCl(aq) + 2MnCl2(s)
experiments in the laboratory. Include in your + 5Cl2(g) + 8H2O(l)
description the main observations that illustrate
a) Use oxidation numbers to show that this is a
the differences between the ions and write
redox reaction.
equations for the reactions. (12)
b) Identify what has been:
18 There are four known oxides of chlorine; Cl2O, i) oxidised
ClO2, Cl2O6 and Cl2O7. ii) reduced.
a) Determine the oxidation number of Cl in c) Calculate the volume of Cl2(g) that could
each of the oxides. be made by reacting 3.95 g KMnO4(s) with
b) Draw dot-and-cross diagrams of Cl2O and excess HCl(aq).
predict the shape and bond angle. d) When 3.95 g KMnO4(s) was reacted
Each of the oxides of chlorine is unstable and with excess HCl(aq), less Cl2(g) than the
dangerously explosive. They all react with alkalis, theoretical volume calculated in part
OH–(aq) to produce a mixture of chlorate ions (c) was collected. Suggest why. (11)
and water.
Chapter 9 Group 2 and the halogens, qualitative analysis

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 Chapter 10
Enthalpy changes
Prior knowledge
In this chapter it is assumed that you will be able to:
● balance equations for the combustion of organic compounds
● calculate amounts of substance in moles.

Test yourself on prior knowledge

1 Write equations for the combustion reactions that occur when each of
the following is burned in a plentiful supply of oxygen:
a) ethene (C2H4)
b) ethane (C2H6)
c) ethanol (C2H5OH).
2 Calculate the amounts (in mol) of carbon dioxide molecules and steam
molecules produced when each of the following are burned in a plentiful
supply of oxygen:
a) 1 mol of ethane molecules
b) 6 g of ethane molecules
c) 2.3 g of ethanol molecules.

Energy changes
Tip Why do some chemicals react together and others do not? This is a
fundamental question central to the study of chemistry. All chemical
The symbol Δ is used to indicate reactions involve a change in which energy is given out or energy is
‘change in’: taken in. One way that chemists have tried to address this issue is to
● ΔT = change in temperature analyse the energy changes that occur when reactions take place. It
● ΔV = change in volume is usually true that reactions in which the products have lower energy
● ΔP = change in pressure than the reactants are able to take place, whereas reactions in which
● ΔH = change in enthalpy. the products have higher energy cannot. An important point, however, is
that the rate at which the reaction occurs may be extremely slow. Thus,
a reaction might potentially proceed, but its progress may not be readily
Key term
apparent.
Enthalpy change, ΔH, is the
difference between the enthalpy Enthalpy change
of the reactants and the enthalpy
All chemical reactions involve a change in energy. The exchange
of the products.
of energy between a reaction mixture and its surroundings is the
ΔH = enthalpy of products enthalpy change. It is given the symbol ΔH and its units are joules, J,
– enthalpy of reactants or kilojoules, kJ.

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 Tip Enthalpy is an energy change measured under constant pressure, which
is normally the condition that applies when a laboratory experiment is
The sign given to an energy carried out.
change is always from the point
of view of the reaction. This When an exothermic reaction takes place, energy is transferred from
means if the reaction loses heat the reaction mixture to the surroundings. Chemical energy is released
to the surroundings then the sign by the reactants and the temperature of the surroundings increases.
will be ‘–’ but if it takes heat from For example, hot packs in self-warming drinks (Figure 10.1, Figure 10.2
the surroundings it will be ‘+’. and Figure 10.3) or for treating painful rheumatic conditions involve
exothermic reactions.
In an exothermic reaction, ΔH is negative because the reactants have
lost energy and given it to the surroundings.

Figure 10.1 A self-warming can of coffee – pressing the bulb on the bottom of the can
starts an exothermic reaction in a sealed compartment. The energy released heats the
coffee.
reactants:
CaO(s) + H2O(l)

calcium
Energy

∆H = –1067kJ oxide
product:
Ca(OH)2 (aq)
calcium
hydroxide
solution
Course of reaction
water
Figure 10.2 An enthalpy profile diagram
calcium
for the reaction of calcium oxide with hydroxide
water. solid
reactants at products at
room temperature room temperature
energy given out
and pressure and pressure
Chapter 10  Enthalpy changes

Figure 10.3 The exothermic reaction that takes place in some hot packs.

Reactions can sometimes be endothermic. In these cases ΔH

is positive because the products have a higher energy than
the reactants and heat is taken from the surroundings. A cold
pack to reduce the swelling that occurs from a bruise utilises an
Figure 10.4 Twist a cold pack and it endothermic reaction to draw heat from its surroundings (Figure
gets cold enough to reduce the pain of
a sports injury. When chemicals in the
10.4) and the absorption of carbon dioxide by green leaves during
cold pack react, they take in energy as photosynthesis is another important example of an endothermic
heat and the pack gets cold. This, in turn, reaction.
cools the sprained or bruised area and
helps to reduce painful swelling.
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 Energy changes
Enthalpy profile diagrams and activation energy
Enthalpy changes can be represented by simple enthalpy profile
diagrams as shown in Figure 10.5.
exothermic reaction endothermic reaction

products
EA EA
∆H

Energy
reactants

Energy
reactants

∆H
products

Course of reaction Course of reaction

Figure 10.5 Enthalpy profile diagrams showing the activation energy for both
exothermic and endothermic reactions.

Key term The enthalpy profiles show that, initially, energy is taken from the
The activation energy is the
surroundings. Reactions need an input of energy to get them started
minimum energy needed for a
because the bonds of the reactants have to be broken before the new
reaction to take place.
bonds of the products are formed. The energy required to do this is
called the activation energy, EA, of the reaction

Calculating the enthalpy changes of gaseous

reactions using bond enthalpies
Tip If the enthalpies required to break and to make bonds are known it is
straightforward to calculate the overall enthalpy change that occurs as a
Remember: Bond breaking is result of a reaction. These enthalpies, called bond enthalpies, are values
endothermic (requires energy). that chemists have collected together using the results of a wide range
Bond formation is exothermic of experiments. They are expressed in kJ mol–1.
(returns energy).
Some average bond enthalpies are shown in Table 10.1.
Table 10.1 Average bond enthalpies.
Key term
Bond ΔH/kJ mol–1
A bond enthalpy is the enthalpy
C–C +347
change required to break and
C=C +612
separate 1 mol of bonds in the
molecules of a gas so that the C≡C +838
resulting gaseous (neutral) C–H +413
particles exert no forces upon C=O +805
each other. O=O +498
Expressed as an equation this is:
O–H +464
X–Y(g) → X(g) + Y(g) C–N +286
N≡N +945
N–H +391
H–H +436

Bond enthalpies can be used to calculate the overall enthalpy change

that occurs in a simple reaction involving gaseous covalent molecules.
For these reactions the correct sign to ΔH is given by using:
ΔH = sum of bond enthalpies of reactants – s um of bond enthalpies
of products 145

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 For example, Figure 10.6 shows the bonds that are broken and formed
when 1 mol of methane is burned. The reaction occurring in this case is:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
H O
O O H H
O
H C H + O C O +
O O H H
H
Reactants Products
Figure 10.6 The enthalpy of combustion of methane using bond enthalpies.

The relevant bond enthalpies from Table 10.1 are:

C–H 413 kJ mol–1 O=O 498 kJ mol–1
C=O 805 kJ mol–1 O–H 464 kJ mol–1
Bond enthalpies of reactants:
4 × (C–H) = 4 × 413 = 1652 kJ mol–1
2 × (O=O) = 2 × 498 = 996 kJ mol–1
sum of bond enthalpies of reactants = 1652 + 996 = 2648 kJ mol–1
Bond enthalpies of products:
2 × (C=O) = 2 × 805 = 1610 kJ mol–1
4 × (O–H) = 4 × 464 = 1856 kJ mol–1
sum of bond enthalpies of products = 1610 + 1856 = 3466 kJ mol–1
ΔH = sum of bond enthalpies of reactants – s um of bond enthalpies
of products
= 2648 – 3466 = –818 kJ mol–1
It is important to note that the figures given for bond enthalpies are
average figures for that type of bond and the true figure will be slightly
different depending on the compound used. The strength of a particular
bond is affected by the neighbouring bonds in the molecule.
● Bond enthalpies are those specific to a bond in a real example (e.g.
the C–O bond in CH3OH).
● An average bond enthalpy is the figure obtained by averaging the
bond enthalpies in all compounds containing that particular bond
(e.g. all C–O bonds).
Chapter 10  Enthalpy changes

The difference can be shown by considering a molecule such as water.

As shown in Figure 10.7, the O–H bonds can be broken successively but
the energy required to do this is different for each bond.
O O
(g) + H(g) ∆H = +496 kJ mol–1
H H(g) H

O
(g) H(g) + O(g) ∆H = +432 kJ mol–1
H
Figure 10.7 The different enthalpies required to break successive OH bonds in water.

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 496 + 432

Energy changes
The O–H bond enthalpy in water is quoted as = +464k J mol–1
2
This is the average (mean) bond enthalpy.
The enthalpy change for the combustion of methane is quoted in
data lists as –890 kJ mol–1, which differs from the value –818 kJ mol–1
calculated above. This is largely explained by the use of average bond
enthalpies for the C–H, C=O and O–H bonds in the calculation, rather
than specific bond enthalpies.

Test yourself
1 Draw an enthalpy profile to illustrate the reaction of methane and oxygen
as calculated in example above.
2 a) Explain, with the aid of an equation, what is meant by the bond
enthalpy of HCl(g).
b) Calculate the enthalpy change that occurs when hydrogen reacts with
chlorine to form hydrogen chloride.
E(H–H) = 436 kJ mol–1  E(Cl–Cl) = 243 kJ mol–1  E(H–Cl) = 432 kJ mol–1
3 Calculate the enthalpy change that occurs in the reaction between ethene
and hydrogen to form ethane.
E(H–H) = 436 kJ mol–1  E(C=C) = 612 kJ mol–1
E(C–H) = 413 kJ mol–1  E(C–C) = 347 kJ mol–1
4 a) Use bond enthalpies to calculate the enthalpy change that would
occur if nitrogen could react with hydrogen to make hydrazine.
N2 + 2H2 → N2H4
E(N≡N) = 945 kJ mol–1
E(H–H) = 436 kJ mol–1
E(N–N) = 158 kJ mol–1
Key term E(N–H) = 391 kJ mol–1
b) Use your answer to part (a) and Question 3 to suggest why ethene
The specific heat capacity of a
reacts quite readily hydrogen but nitrogen does not.
substance is the heat required to
increase the temperature of 1.0 g
of the substance by 1 °C (1 K). Measuring enthalpy changes experimentally
It is relatively easy to measure the temperature changes for
some of the reactions that take place in solution and also for
some combustion reactions.
thermometer
Reactions in solution
The enthalpy change, ΔrH, for reactions that take place
in solution can usually be measured directly using the
polystyrene cup
apparatus shown in Figure 10.8 although the result obtained is
approximate because of heat loss to the surroundings.
The energy released or absorbed when the reaction takes
place, q, can be calculated using the equation:
reaction mixture
q = mcΔT
● m is the mass of the reaction mixture
● c is the specific heat capacity of the reaction mixture
Figure 10.8 Apparatus to measure the enthalpy of
● ΔT is the change in temperature.
reaction. 147

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 Tip The solvent used for most reactions is water. The specific heat capacity
of water is 4.18 J g–1 K–1.
Sometimes the (less accurate)
figure of 4.2 J g–1 K–1 is used Using this value for the specific heat capacity, the enthalpy change for
for the specific heat capacity. the reaction mixture, q, has a value in joules (J). It is usual to adjust this
Always use the figure given on value so that ΔH can be quoted for 1 mol of reactant with the units
the exam paper or the data of kJ mol–1. This means dividing q by 1000 to convert to kJ and then
sheet provided. dividing this by the amount, in moles, n, used.
q (mc ∆T )
Δ H = =
1000n 1000n
Tip Using the formula above the value of ΔH is always positive. It is
essential to take the temperature change into consideration:
Since the solvent for these
experiments is normally water, ● If ΔT increases the reaction is exothermic so ΔH is negative.
the assumption that is usually ● If ΔT deceases the reaction is endothermic so ΔH is positive.
made is that the specific heat
capacity of the solutions used Example 1
or formed will be the same as
When 1.50 g of sodium carbonate is added to 40.0 cm3 of 2.00 mol dm–3
water. i.e. 4.18 J g–1 K–1
hydrochloric acid (an excess) the temperature rises from 19.0 °C to 24.6 °C.
Calculate ΔH for the reaction assuming the density of the acid is 1.00 g cm–3
Tip and the specific heat capacity is 4.18 J g-1 K–1.
Ideally the mass ‘m’ would be Answer
taken as the total mass of the Step 1 Calculate the energy change in the reaction by using q = mcΔT.
solution formed although in
practice this may be difficult to The heat that is released is given to the 40.0 cm3 or 40.0 g of
determine exactly. hydrochloric acid. You can ignore the contribution of the 1.50 g of
sodium carbonate. The temperature rise is 24.6 – 19.0 = 5.6 °C.
energy change = 40 × 4.18 × 5.6 = 936.32 J
Step 2 Convert the answer to kJ mol–1 by dividing by 1000.
940.8
energy change = = 0.936 32 kJ
1000
Step 3 Convert the answer to kJ mol–1 by dividing by the amount (in moles)
used.
Since the hydrochloric acid was in excess it is the sodium carbonate
which is the cause of the rise in temperature that has been measured.
molar mass of sodium carbonate is 46.0 + 12.0 + 48.0 = 106.0 g mol-1
1.50
amount of sodium carbonate used is = 0.01415 mol
106.0
0.936 32
Chapter 10  Enthalpy changes

Δ H = = –66.171 0247 kJ mol-1
0.01415
When giving a value of ΔH it is essential that you indicate whether
Tip the reaction is endothermic or exothermic. In this case the reaction
Remember that during is exothermic so a ‘–’ sign must be included.
calculations you should not Δ H = –66.2 kJ mol-1
round numbers. Exam questions
will usually tell you the number The final answer should be given to a sensible number of significant
of significant figures to use for figures. In this case since all the quantities used are given to 3
the final answer. significant figures it is best to do the same for the final answer.

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 Energy changes
Notice in Example 1, it was specified that the hydrochloric acid used
was ‘in excess’. This was necessary because the calculation assumed that
all of the 1.50 g of sodium carbonate had reacted. In the next example,
the two solutions are in the correct reacting quantities so it is not
necessary to specify which solution was in excess.

Example 2
When 50.0 cm3 of 2.00 mol dm–3 hydrochloric acid is mixed with 50.0 cm3 of
2.00 mol dm–3 sodium hydroxide solution, the temperature increases by 13.7 °C.
Calculate the enthalpy change of neutralisation of hydrochloric acid. Assume
that the specific heat capacity, c = 4.18 J g–1 K–1 and that the density of both
the hydrochloric acid and sodium hydroxide solution is 1.00 g cm–3.

Answer
Step 1 Calculate the energy transferred in the reaction by using:
q = mcΔT
m = mass of the two solutions = 50.0 + 50.0 = 100.0 g
q = 100 × 4.18 × 13.7 = 5726.6 J = 5.7266 kJ
Step 2 Convert the answer to kJ mol–1 by dividing by the number of
moles used.
50.0
amount, n in moles of HCl = cV = 2.00 × = 0.100 mol
1000
q 5.7266 5.72266
Δ H = = = = –57.2266 kJ mol–1
n n 0.100
(Remember that because the temperature rises, this is an exothermic
reaction so ΔH is negative.)
Δ H = –57.2 kJ mol–1 to 3 significant figures

Combustion
The enthalpy change of combustion, Δc H–Ө, for a volatile liquid (e.g.
ethanol) can be measured directly using the apparatus shown in Figure
10.9. The result will be approximate because of heat loss.
known mass
of water Example 3
When 0.230 g of ethanol, CH3CH2OH, is burned, it raises the temperature of
200 cm3 of water by 7.80 °C. Calculate the enthalpy change of combustion of
ethanol. Assume that the specific heat capacity, c, is 4.18 J g–1 K–1 and that the
volatile liquid density of water is 1.00 g cm–3.

Answer
Figure 10.9 Apparatus used to determine Step 1 Calculate the energy transferred in the reaction by using:
the enthalpy change of combustion of a
volatile liquid, such as ethanol. q = mcΔT
m = mass of water = 200 g
q = 200 × 4.18 × 7.80 = 6520.8 J = 6.5208 kJ

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 Step 2 Convert the answer to kJ mol–1 by dividing by the amount in mol used:
mass of ethanol 0.230
amount, n in moles of ethanol = M of ethanol =
r 46.0
= 0.005 00 mol
q 6.5208 6.5208
Δ H = = = = –1304.16 kJ mol–1
n n 0.00500
Remember that because the temperature rises, this is an exothermic reaction.
Therefore, ΔH = –1304 kJ mol–1 (–1300 kJ mol–1)

Activity
Measuring the enthalpy change for the reaction of zinc with copper sulfate solution
Two students decided to measure the enthalpy change for the reaction between zinc and copper(ii) sulfate solution.
Zn(s) + CuSO4(aq) → ZnSO4(aq) + Cu(s)
The method they used is shown in Figure 10.10 and their results are shown in Table 10.2. After adding the zinc, it took
a little while for the temperature to reach a peak and then the mixture began to cool.
0–50°C thermometer excess
powdered zinc

50cm3
0.25 mol dm–3
CuSO4(aq)

Measure the temperature At 3.0 minutes add excess Continue stirring and record
every 30 s for 2.5 minutes. powdered zinc and stir. the temperature every 30 s
for a further 6 minutes.
Figure 10.10 Measuring the enthalpy change for the reaction of zinc with copper sulfate solution.

Table 10.2

Time/min Temperature/°C Time/min Temperature/°C Time/min Temperature/°C

0 24.1 3.5 34.2 6.5 33.7
0.5 24.0 4.0 34.8 7.0 33.6
1.0 24.1 4.5 35.0 7.5 33.5
1.5 24.1 5.0 34.6 8.0 33.4
Chapter 10  Enthalpy changes

2.0 24.2 5.5 34.2 8.5 33.2

2.5 24.1 6.0 33.9 9.0 33.1
3.0 –

1 Plot a graph of temperature (vertically) against time (horizontally) using the results in Table 10.2.
2 Extrapolate the graph backwards from 9 minutes to 3 minutes, as shown in Figure 10.11, in order to estimate the
maximum temperature. This assumes that all the zinc reacted at once and there was no loss of heat to the surroundings.
a) What is the estimated maximum temperature at 3 minutes?
b) What is the temperature rise, ΔT, for the reaction?
3 Calculate the energy given out during the reaction using the equation:
energy transferred = mass × specific heat capacity × temperature change

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 Energy changes
Assume that:
● all the heat is transferred to the solution in the polystyrene cup
● the density of the solution is 1 g cm –3

Temperature/°C
● the specific heat capacity of the solution is 4.2 J g –1 K–1.

4 How many moles of each chemical reacted? ∆T

a) CuSO4
b) Zn
5 What is the enthalpy change of the reaction, ΔHreaction, for the amounts of
Zn and CuSO4 in the equation?
(State the value of ΔHreaction in kJ mol–1 with the correct sign.)
0 3 6 9
6 What are the main sources of error in the measurements and procedure for Time/minutes
the experiment?
Figure 10.11 Estimating the maximum
7 Look critically at the procedures in the experiment and suggest temperature reached by the mixture when
improvements to minimise errors and increase the reliability of the result. zinc reacts with copper sulfate solution.

Reliability of thermochemical experiments

The results obtained from the experiments that have just been described
are not at all reliable. The main reasons for this are likely to be:
● the lack of precision of the measuring equipment such as the
thermometer.
● heat loss to the surroundings
● the slowness of the reaction
In the combustion experiment some of the heat will also be given to the
container and probably there will be a deposit of soot resulting from the
incomplete combustion of the fuel. The results obtained will clearly be
inaccurate. This is a general problem with thermochemistry experiments
that can only be partly addressed. It is often possible to improve matters
by using improved insulation – for example if a polystyrene cup is used
it could be surrounded by better insulation and the cup could include a
lid – but nevertheless only more specialist apparatus such as the bomb
calorimeter shown in Figure 10.12 can provide more reliable results.

thermometer

insulating lids

water bomb calorimeter

oxygen under pressure

electrically heated small dish containing

wire to ignite sample sample under test
stirrer
insulating
air jacket

Figure 10.12 Bomb calorimeter.

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 Test yourself
In questions 5, 6, 7 and 8 assume that the specific heat capacity, c, is
4.18 J g–1 K–1 and that the density of water is 1.00 g cm –3.
5 Burning butane, C4H10, from a Camping Gaz® container raised the
temperature of 200 g water from 18 °C to 28 °C. The Gaz container was
weighed before and after and the loss in mass was 0.29 g. Estimate the
molar enthalpy change of combustion of butane.
6 When 2.0 g of ammonium nitrate, NH4NO3, is dissolved in 50 cm3 of water
at 18 °C, the temperature falls to 15 °C.
a) Calculate the energy absorbed when the ammonium nitrate dissolves
in water.
b) Calculate the enthalpy change per mole when ammonium nitrate
dissolves in water
7 When 2.0 g of sodium hydroxide is dissolved in 50 cm3 of water at 18 °C
the temperature rises to 28.8 °C.
Calculate the enthalpy change per mole when sodium hydroxide dissolves
in water. Give your answer to three significant figures.
8 When 0.500 g of magnesium is added to 100 cm3 of 1.00 mol dm –3
hydrochloric acid at 20.0 °C the temperature rises to 37.5 °C.
a) Write the equation for the reaction.
b) Calculate the amounts in moles of the magnesium and hydrochloric
acid used in the experiment.
c) Calculate the enthalpy change of the reaction if 1 mol of magnesium
had been used.
Tip d) Suppose the experiment had been repeated using 100 cm3 of
2.00 mol dm –3 hydrochloric acid. What difference would this make to
The standard conditions for the temperature rise that would have been obtained?
thermochemical measurements e) Suppose the experiment had been repeated using 1.00 g of
differ from those that can be magnesium. What difference would this have made to:
used for reactions involving i) the temperature rise that would have been obtained
gases which refer to a ii) the enthalpy change per mole calculated in part (c)?
temperature of 273K.
(See page 50.)
Although 298K is used as a
Standard enthalpy changes
standard, values are sometimes Enthalpy changes are measured experimentally at various temperatures
quoted at other temperatures in and pressures. But if these enthalpy changes are to be compared it
which case the temperature will is important that they are measured under the same conditions. The
be specifically indicated. conditions that are used for these thermochemical measurements are
known as standard conditions.
Standard conditions for thermochemical measurements are:
Chapter 10  Enthalpy changes

Tip
● a temperature of 298 K (25 °C)
Standard pressure is sometimes
quoted as 101.3 kPa but OCR ● a pressure of 100 kPa
papers will use 100 kPa as
● all substances in their most stable state at 298 K and 100 kPa. This
standard pressure.
would be relevant if, for example, an element could exist in more
than one crystalline form (called an allotrope). The allotrope which
Tip was the most stable at 298 K and 100 kPa would be selected. An
To convert K to °C subtract 273. example is carbon which can exist at 25 °C either as diamond or
graphite; but the more stable form is graphite.

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 The superscripted symbol, –Ө, is used with ΔH, (i.e. ΔH –Ө) to denote that a

Energy changes
Key terms
change has been measured under or converted to standard conditions.
The standard enthalpy change
of formation, ΔfH –Ө, is the There are a number of thermochemical values that have been measured
enthalpy change when 1 mol of and tabulated by chemists and their precise definition needs to be known.
a substance is formed from its
elements, in their natural state,
Equations representing enthalpy change
under standard conditions. It may be clearer to represent the enthalpy changes by means of an equation.
The standard enthalpy change Standard of enthalpy of formation
of combustion, Δc H –Ө, is the An equation relating to the standard enthalpy change of formation of
enthalpy change when 1 mol of a a substance must reflect the standard definition. Therefore, it must:
substance is burned completely,
● show the reactants as elements in their natural state
in an excess of oxygen, under
standard conditions. ● produce 1 mol of the substance, even if this means that there are
The standard enthalpy change fractions in the equation
of neutralisation, Δneut H –Ө, is the
● include state symbols.
enthalpy change when 1 mol of
water is formed in a reaction The equation for the standard enthalpy change of formation of ethane is:
between an acid and a base.
The standard enthalpy change of 2C(s) + 3H2(g) → C2H6(g)
reaction, ΔrH –Ө, is the enthalpy The equation for the standard enthalpy change of formation of ethanol is:
change when the amount in
moles of the substances in the 2C(s) + 3H2(g)+  1 2 O2(g) → CH3CH2OH(l)
equation as written react under Standard enthalpy of combustion
standard conditions. An equation relating to the standard enthalpy change of combustion
of a substance must reflect the standard definition. Therefore, it must:
Tip ● show 1 mol of the substance reacting completely with excess oxygen,
The carbon would be in the form even if this means having fractions in the equation
of graphite. ● include state symbols.
The products of combustion are usually carbon dioxide and water.
The equation for the standard enthalpy change of combustion of ethane is:
C2H6(g)+ 3  1 2 O2(g) → 2CO2(g) + 3H2O(l)
The equation for the standard enthalpy change of combustion of ethanol is:
CH3CH2OH(l)+ 3O2(g) → 2CO2(g) + 3H2O(l)
The equation for the standard enthalpy change of combustion of
ethanamide (CH3CONH2) is more complex. However, the principles
are the same – the equation must have 1 mol of the reactant and be
balanced, even though this involves odd-looking fractions:
CH3CONH2(s)+ 2 3 4 O2(g) → 2CO2(g) + 2 1 2 H2O(l)+  1 2 N2(g)
Standard enthalpy change of neutralisation
An equation relating to the standard enthalpy of neutralisation of a
substance must reflect the standard definition. It must:
● show 1 mol of water being formed from the named base or acid, even
if this means having fractions in the equation
● include state symbols.

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 Tip Usually the products are a salt and water.

Be careful to remember that if The equation for the standard enthalpy change of neutralisation of
an acid is dibasic (diprotic) that dilute hydrochloric acid with aqueous sodium hydroxide is:
2 mol of water are produced if it HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)
is completely neutralised. So the
enthalpy of neutralisation would An ionic equation could also be used to show the standard enthalpy
1 change of neutralisation:
be for a mole of the acid. For
2
example: H+(aq) + OH –(aq) → H2O(l)
1 H SO (aq) + NaOH(aq) →
2 2 4 Strong acids and strong bases are fully ionised so that the enthalpy
1 change of a reaction between them to form 1 mol of water will be the
Na2SO4(aq) + H2O(l)
2
same regardless of which acid or base is chosen.
However, if the experiment is repeated using a weak acid such as
ethanoic acid and a strong base such as sodium hydroxide, the enthalpy
change measured has a lower value. The reaction is the same but
the difference lies in the strength of the acid. At the start of the
neutralisation the dissociation of ethanoic acid:
CH3COOH(aq) → CH3COO –(aq) + H+(aq)
is not complete. As the H+ is neutralised by the base the acid ionises
further until it is completely neutralised but this requires a certain
amount of energy that would otherwise have been released as heat.
The neutralisation reaction of a weak base such as aqueous ammonia and
a strong acid has an even lower value for the enthalpy of neutralisation.
This is because during the neutralisation the ammonia ionises:
NH3(aq) + H2O(aq) → NH4+(aq) + OH –(aq)
and this requires more energy than that required for the dissociation of
ethanoic acid.
The neutralisation of the weak acid–weak base combination of ethanoic
acid and ammonia results in an even lower value for the enthalpy of
neutralisation.
Experiments of this type can give some indication of the relative
strengths of acids and bases, even though the measurements are not
particularly accurate.

Hess’ law
Chapter 10  Enthalpy changes

Enthalpy changes for combustion reactions and for reactions that take
place in solution can be measured experimentally. However, in reality,
Key term this is not the case for many chemical reactions. If the activation energy
is particularly high or the reaction rate is very slow (these are usually
Hess’ law states that, if a reaction related), it is unlikely that a reaction will take place readily. In these
can take place by more than circumstances an enthalpy change cannot be measured directly.
one route, the enthalpy change
for the reaction is the same Enthalpies that cannot be measured directly are calculated by using
irrespective of the route taken, energy cycles based on enthalpies that can be measured. Since energy
provided that the initial and final cannot be created or destroyed it follows that the enthalpy change for a
conditions are the same. reaction is independent of the route taken. This idea was first proposed
by Germain Henri Hess and is known as Hess’ law.
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 Hess’ law
Tip Hess’ law can be illustrated using a simple enthalpy cycle:

Hess’ law may seem an Route 1

obvious variation of the law of
conservation of energy but when ∆H1 = –200 kJ mol–1
A B
Hess stated his law in 1840 the
law of conservation of energy ∆H2 = –120 kJ mol–1 ∆H3 = ? kJ mol–1
was not generally accepted. C
Route 2

The enthalpy change for route 1 is equal to the enthalpy change for
route 2:
Δ H1 = Δ H2 + Δ H3
Therefore, Δ H3 = Δ H1 – Δ H1
= –200 – (–120)
= –200 + 120
= –80 kJ mol–1

Enthalpy change of formation of carbon monoxide

The usefulness of Hess’ law can be illustrated by the combustion of carbon.
Carbon burns to form either CO(g) or CO2(g). It is impossible to measure
the enthalpy change of formation of CO(g) directly because some CO2(g)
would always be formed but it can be calculated using Hess’ law.
The enthalpy changes for the following reactions can be measured
experimentally:
C(s) + O2(g) → CO2(g)   Δc H = –394 kJ mol–1
CO(g) +  1 2 O2(g) → CO2(g)   Δc H = –284 kJ mol–1
This allows us to determine the enthalpy change for:
C(s) +  1 2 O2(g) → CO(g)
using Hess’ law, as shown below.
Step 1 Start with the enthalpy change that has to be calculated. Call it
ΔH1. Write an equation for the reaction. This is the top line of
the cycle:
Δ H1
C(s) +  1 2  O2 CO(g)
Step 2 Construct an enthalpy cycle with two alternative routes:
∆H1
1
C(s) + –O (g) CO(g)
2 2

∆H2 ∆H3

CO2(g)

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 Step 3 Apply Hess’ law to the cycle.
The simplest way to apply Hess’ law is to look at the direction of the
arrows. Route 1 has arrows that point in the clockwise direction; route 2
has an arrow that points anti-clockwise:
Route 1

∆H1
1
C(s) + –O
2 2
(g) CO(g)

∆H2 ∆H3

Route 2 CO2(g)

route 1 = route 2
Δ H1 + Δ H3 = Δ H2
Therefore, Δ H1 = Δ H2 – Δ H3
= –394 – (–284)
= –394 + 284
= –110 kJ mol–1
The enthalpy change of formation of carbon monoxide is –110 kJ mol–1.

Construction of enthalpy cycles

There are two common enthalpy cycles that you may be asked to
construct which require the use of Hess’ law.
Determining an enthalpy change of formation using enthalpies of
combustion
In order to calculate the enthalpy change of formation using enthalpy
changes of combustion, it is best to construct a cycle with the
combustion products at the bottom. The arrows always then point
downwards to the combustion products.
∆H1
elements products

∆H2 ∆H3

combustion products
(usually CO2 and H2O)
Chapter 10  Enthalpy changes

Applying Hess’ law to the cycle:

Δ H1 + Δ H3 = Δ H2
Therefore, Δ H1 = Δ H2 – Δ H3
Determining an enthalpy change of combustion using enthalpy
changes of formation
For this cycle enthalpy changes of formation are used to calculate an
enthalpy change of combustion. The elements are best shown at the
bottom of the triangle; the arrows then point upwards.

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 Hess’ law
∆H1
reactant combustion products
(usually CO2 and H2O)

∆H2 ∆H3

elements

Applying Hess’ law to the cycle:

Δ H1 + Δ H2 = Δ H3
Therefore, Δ H1 = Δ H3 – Δ H2

Example 4
Use the enthalpy changes of combustion data in Table 10.3 to calculate the
standard enthalpy change of formation of methane.
Table 10.3 Enthalpy of combustion data.

Substance Formula ΔHcӨ   /kJ mol–1

Carbon C(s) –394
Hydrogen H2(g) –286
Methane CH4(g) –890

The enthalpy change of combustion of hydrogen will be to form water rather

than steam as the standard conditions specify a temperature of 25 °C.

Answer
Step 1 Write the equation for the required enthalpy change of formation:
C(s) + 2H2(g) → CH4(g)
Step 2 Construct the enthalpy cycle, writing the combustion products at the
bottom. Both arrows point downwards:
∆H1
C(s) + 2H2(g) CH4(g)
reactants products

∆H2 ∆H3

CO2(g) + 2H2O(l)
combustion products

Step 3 Apply Hess’ law.

Using Hess’ law, Δ H1 + Δ H3 = Δ H2
Therefore, Δ H1 = Δ H2 – Δ H3
Δ H2 = Δc H(C) + 2 × (ΔcH(H2))
= –394 + 2(–286)
= –966 kJ mol–1
Δ H3 = Δc H(CH4) = –890 kJ mol–1
Δ H1 = –966 – (–890) = –76 kJ mol–1
Therefore, the standard enthalpy change of formation of methane, ΔfHӨ   (CH4),
is –76 kJ mol–1.

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 Example 5
Use the standard enthalpy change of formation data in Table 10.4 to
calculate the standard enthalpy change of combustion of ethane.
Table 10.4 Enthalpy of formation data.

Substance Formula Δf HӨ   /kJ mol–1

Ethane C2H6(g) –85
Carbon dioxide CO2(g) –394
Water H2O(l) –286

Answer
Step 1 Write the equation for the required enthalpy change of combustion:
C2H6(g) + 3 1 2 O2(g) → 2CO2(g) + 3H2O(l)
Step 2 Construct the enthalpy cycle, writing the combustion products at the
bottom. Both arrows point upwards:
∆H1
1
C2H6(g) + 3–O (g) 2CO2(s) + 3H2O(l)
2 2
reactants products

∆H2 ∆H3

1
2C(s) + 3H2(g) + 3–O (g)
2 2
elements in their standard state

Step 3 Apply Hess’ law.

Using Hess’ law, ΔH1 + ΔH2 = ΔH3
Therefore, ΔH1 = ΔH3 – ΔH2
ΔH2 for formation of C2H6(g) = –85 kJ mol–1
ΔH3 = 2 × ΔfH(CO2) + 3 × ΔfH(H2O)
= 2(–394) + 3(–286)
= –1646kJ mol–1
(Be careful to multiply the enthalpies to correspond with the number of
moles used in the equation for the combustion.)
ΔH1 = –1646 – (–85) = –1561 kJ mol–1
Therefore, the standard enthalpy change of combustion of ethane, ΔcH–Ө,
is –1561 kJ mol–1.
Chapter 10  Enthalpy changes

Hess’ law can also be used to determine an enthalpy change for an

inorganic reaction that cannot be measured in the laboratory. This is
illustrated by the following worked example.

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 Hess’ law
Example 6
Reaction 1: When 2.60 g of calcium carbonate is added to 50.0 cm3 (an
excess) of hydrochloric acid there is a temperature rise of 2.3 °C.
Reaction 2: When 1.50 g of calcium oxide is added to 50.0 cm3 (an excess) of
hydrochloric acid there is a temperature rise of 11.1 °C.
Use this data to determine the enthalpy change of reaction for the
decomposition of calcium carbonate into calcium oxide:
CaCO3(s) → CaO(s) + CO2(s)

Answer
Tip The energy gained in reaction 1:
The mass (m) in reaction 1 can q = mcΔT
be 52.60g which includes the
mass of the calcium carbonate. m is the mass of hydrochloric acid = 50 g
Either 50.0 or 52.60g is q = 50.0 × 4.18 × 2.3 = 480.7 J  or  0.4807 kJ
acceptable. Likewise in reaction 2
the mass can be 50.0g or 51.5g. The molar mass of calcium carbonate is 100.1 g, so the amount in moles of
calcium carbonate used was:
2.60
= 0.0260
100.1
0.4807
ΔH1 = = –18.5 kJ mol–1
0.0260
The energy gained in reaction 2:
q = 50.0 × 4.18 × 11.1 = 2320 J  or  2.320 kJ
The molar mass of calcium oxide is 56.1 g so the amount in moles of calcium
oxide used was:
1.50
= 0.0267 mol
56.1
2.320
ΔH2 = = –86.9 kJ mol–1
0.0267
The following cycle must now be used to determine the enthalpy change for
the decomposition of calcium carbonate to calcium oxide.
∆rH
CaCO3(s) CaO(s) + CO2(g)

+ HCl(aq) + HCl(aq)
∆H1 ∆H2

CaCl2(aq)

ΔH1 = ΔrH + ΔH2

ΔrH = ΔH1 – ΔH2
ΔrH = –18.5 – (–86.9) = +68.4 kJ mol–1
This answer is different from the theoretical value for this reaction as there
would be substantial heat loss in an experiment of this kind.

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 Test yourself
9 a) By writing a balanced equation, show that the standard enthalpy
change of formation of carbon dioxide is the same as the standard
enthalpy change of combustion of carbon (graphite).
b) Write equations for the standard enthalpy change of formation of:
i) aluminium oxide, Al2O3
ii) hydrogen chloride, HCl
iii) propane, C3H8.
10 Use the data in the table to calculate the standard enthalpy change of
formation for ethene.
Substance Formula Δc H —Ө/kJ mol–1
Carbon C(s) –394
Hydrogen H2(g) –286
Ethene C2H4(g) –1411

11 Use the data in the table to calculate the standard enthalpy change of
combustion of butane.
Substance Formula ΔfH—Ө/kJ mol–1
Butane C4H10 (g) –127
Carbon dioxide CO2(g) –394
Water H2O(l) –286

12 Use the standard enthalpy change of combustion data below to

determine the standard enthalpy change for the following reaction.
C2H6(g) → C2H4(g) + H2(g)
Substance Formula Δc H—Ө/kJ mol–1
Ethane C2H6(g) –1561
Ethene C2H4(g) –1411
Hydrogen H2(g) –286

What does this indicate about the likelihood of this reaction occurring
under standard conditions?
Chapter 10  Enthalpy changes

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 Practice questions
Practice questions
0.1 × 4.18 × 35
Multiple choice questions 1–10 A
1000
Use the reaction profile below to answer Questions 1 B 0.1 × 4.18 × 35 × 1000
and 2.
100 × 4.18 × 35 × 0.1
C
1000
z 100 × 4.18 × 35
D
0.1 × 1000
6 50 cm of 1.0 mol dm–3 sodium hydroxide is added
3

to 50 cm3 of 1.0 mol dm–3 hydrochloric acid and

Energy

the temperature rise as a result of the reaction is

products
y measured as T1 °C.
The experiment is then repeated using 100 cm3
reactants of 1.0 mol dm–3 sodium hydroxide and 100 cm3 of
x
1.0 mol dm–3 hydrochloric acid. The temperature
rise is again measured this time as T2 °C.
Reaction pathway (or progress of reaction)
Assuming any heat losses are the same in each
1 The enthalpy change for the forward reaction to experiment, when the values of T1 °C and T2 °C are
convert the reactants into the products is: compared it will be found that
A y B y– x A T1 = T2 B T1 = 2 × T2
C z– x D z–y C T2 = 2 × T1 D T2 = 4 × T1

2 The activation energy for the reverse reaction to 7 The following are enthalpy changes for the
form the reactants from the products is: reactions shown.
A z B y–x
C(s) + O2(g) → CO2(g) ΔrH = –394 kJ mol–1
C z –x D z–y
3 Which one of the following equations correctly 2CO(g) + O2(g) → 2CO2(g) ΔrH = –566 kJ mol–1
represents the enthalpy change of formation of
Which one the following gives the enthalpy of
ethene from graphite, C(s)?
formation of carbon monoxide in kJ mol–1?
A 2C(s) + 4H(g) → C2H4(g)
A +566 – ( 12 × 394) = +369
B 2C(s) + 2H2(g) → C2H4(g)
B +394 – ( 12 × 566) = +111
C C(s) + H2(g) → 12 C2H4(g)
C –394 + ( 12 × 566) = –111
D C(s) + 2H(g) → 12 C2H4(g)
D –566 + ( 12 × 394) = –369
4 The enthalpy change of combustion of diamond
is –396 kJ mol–1 and the enthalpy change of 8 Hydrogen and chlorine react to form hydrogen
combustion of graphite is –394 kJ mol–1. chloride:
Which one of the following is the enthalpy H2(g) + Cl2(g) → 2HCl(g)
change that occurs when 1 mol of graphite is
converted into diamond? The bond enthalpy of H2 is +436 kJ mol–1 and the
A +790 kJ mol–1 B +2 kJ mol–1 bond enthalpy of Cl2 is 243 kJ mol–1.
C –2 kJ mol –1
D –790 kJ mol–1 If the enthalpy change of the reaction is
–185 kJ mol–1, which one of the following is the
5 When 0.1 mol of ethanol are burned the heat bond enthalpy of HCl?
produced raises the temperature of 100 cm3 of A +864 kJ mol–1
water by 35 °C. B +432 kJ mol–1
The specific heat capacity of the water = 4.18 J g–1 K–1 C –432 kJ mol–1
Which one of the following gives the value D –864 kJ mol–1
(ignoring the sign) of the enthalpy of combustion
of ethanol in kJ mol–1?

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 Use the key below to answer Questions 9 and 10. 16 a) Define standard enthalpy change of
A B C D combustion.
b) Write an equation to illustrate the standard
1, 2 & 3 1, 2 correct 2, 3 correct 1 only
correct correct enthalpy change of combustion of propanone,
CH3COCH3(l). (3)
9 Which of the following processes will be 17 Use the data in the table to calculate the
exothermic? standard enthalpy change of formation for
1 CH3(g) + H(g) → CH4(g) propane.
2 2Ca(s) + O2(g) → 2CaO
Substance Formula Δc H—Ө/kJ mol–1
3 H2SO3(aq) + Ca(OH)2(aq) → CaSO3(aq) +
Carbon C(s) –394
2H2O(l)
Hydrogen H2(g) –286
10 Which of the following is always true for an
Propane C3H8(g) –2219
endothermic reaction?
1 The total enthalpy of the products is greater (4)
than the reactants. 18 Use the values for standard enthalpy changes
2 Heat will be absorbed from the surroundings of combustion below to calculate the standard
when the reaction takes place. enthalpy change of reaction for the formation of
3 The activation energy for the conversion of methanol,
the products into the reactants is less than
the activation energy for the conversion of the Δc H—Ө[CH3OH(l)] = –726 kJ mol–1
reactants into the products. Δc H—Ө[Cgraphite] = –394 kJ mol–1
11 Explain, with the aid of enthalpy profile diagrams, Δc H—Ө[H2(g)] = –286 kJ mol–1 (3)
what is meant by an exothermic reaction and an
19 When a spark ignites a mixture of hydrogen gas
endothermic reaction. On each diagram, label
and oxygen gas, water is produced:
both ΔH and Ea. (6)
H2(g) + 12 O2(g) → H2O(l) ΔH = –285.8 kJ mol–1
12 a) Explain, with the aid of an equation, what is H2(g) + 12 O2(g) → H2O(g) ΔH = –241.8 kJ mol–1
meant by bond enthalpy. a) On the same diagram, draw the enthalpy
b) Some bond enthalpies are given in the table. profile for the formation of both water and
Bond Bond enthalpy/kJ mol–1 steam.
H–H 436 b) Use the enthalpy-profile diagram to deduce
the enthalpy change for the conversion of
Br–Br 193
water into steam:
H–Br 366
H2O(l) → H2O(g) (3)
Calculate the enthalpy change for the
following reaction: 20 Butane, C4H10, burns readily on a camp cooker.
H2(g) + Br2(g) → 2HBr(g) (6) The equation for the reaction is:
13 When 2.0 cm3 of concentrated sulfuric acid is C4H10(g) + 612 O2(g)→4CO2(g) + 5H2O(g)
Chapter 10 Enthalpy changes

added to 48.0 cm3 of water, the temperature of

the mixture rises by 6.7 °C. Calculate the amount Use the following average bond enthalpies to
of heat evolved. Assume that the specific heat calculate the enthalpy change of the reaction.
capacity of the mixture is 4.18 J g–1 K–1. E(C–C) 347 kJ mol–1 E(C–H) 413 kJ mol–1
E(O=O) 498 kJ mol –1

14 State the standard condition for: E(C=O) 805 kJ mol–1 E(H–O) 464 kJ mol–1
a) temperature b) pressure. (2) (3)
15 a) Define standard enthalpy change of formation. 21 A student suggested that ethane might react with
b) Write an equation to illustrate the standard bromine in two different ways in bright sunlight.
enthalpy change of formation of propanal, Reaction 1: C2H6(g) + Br2(l) → C2H5Br(l) + HBr(g)
CH3CH2CHO(l). (3) Reaction 2: C2H6(g) + Br2(l) → 2CH3Br(g)

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 Practice questions
a) Use the following average bond enthalpies to a) Calculate the standard enthalpy change for
calculate the enthalpy changes for the two each of the possible reactions using the data
possible reactions. below.
E(C–C) 347 kJ mol–1 E(Br–Br) 193 kJ mol–1
Δf H—Ө [SnO2(s)] = –581 kJ mol–1
E(C–H) 413 kJ mol–1 E(H–Br) 366 kJ mol–1
E(C–Br) 290 kJ mol–1 Δf H—Ө [CO2(g)] = –394 kJ mol–1
b) Use your calculations to explain which of the
Δf H—Ө [CO(g)] = –110 kJ mol–1
reactions is more likely to occur.
c) Suggest two reasons why your calculated b) Use your calculations to explain which of
enthalpy changes may not agree with the the reactions, on the basis of the enthalpy
accurately determined experimental values. changes, would be most economic for
(10) industry. (9)
22 When 25.0 cm3 of nitric acid of concentration 26 A student is given an unknown alcohol that has
1.00 mol dm–3 is mixed with 50 cm3 of a standard enthalpy change of combustion of
0.50 mol dm–3 sodium hydroxide solution, the –726 kJ mol–1.
temperature increases by 4.6 °C. Calculate the
standard enthalpy change of neutralisation
of nitric acid. Assume that the specific heat
capacity, c, of the mixture is 4.18 J g–1 K–1 and that
the density of both the nitric acid and sodium insulation
hydroxide solutions is 1.00 g cm–3. (6)
23 Use the data in the table to calculate the
100 cm3 water
standard enthalpy change of combustion for
ethanol.
Substance Formula ΔfH—Ө/kJ mol–1
Ethanol C2H5OH(g) –277
Carbon dioxide CO2(g) –394
Water H2O(l) –286
(4) Using the apparatus shown in the diagram, the
student obtains the following results:
24 Use the data in the table to calculate the
• mass of water = 100 g
standard enthalpy change for the reduction of
• initial temperature = 18.69 °C
iron(iii) oxide by carbon monoxide to make iron.
• final temperature = 25.66 °C
Substance Formula ΔfH—Ө/kJ mol–1 • mass of spirit burner + alcohol at the start =
Iron(iii) oxide Fe2O3(s) –824 117.416 g
Carbon monoxide CO(g) –110 • mass of spirit burner + alcohol at the end =
117.288 g
Carbon dioxide CO2(g) –394
The specific heat capacity, c, of the apparatus is
(5) 4.18 J g–1 K–1. Calculate the relative molecular mass
25 Tin is manufactured by heating tinstone, SnO2, at of the alcohol and, hence, identify it. (6)
high temperatures with coke (carbon). 27 In an experiment, 50 cm3 of 2.0 mol dm–3
There are two possible reactions for the process. hydrochloric acid is mixed with 100 cm3 of
Reaction 1: SnO2(s) + C(s) → Sn(s) + CO2(g) 2.0 mol dm–3 of sodium hydroxide. Both solutions
were initially at 21 °C but, after mixing, the
Reaction 2: SnO2(s) + 2C(s) → Sn(s) + 2CO(g) temperature rose to 30.0 °C.
The specific heat capacity, c, of the apparatus is
4.18 J g–1 K–1.
a) Calculate ΔrH for the reaction:
NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l)
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 b) If the experiment was repeated using 100 cm3 30 The Apollo 11 lunar module was the first
of 1.0 mol dm–3 of sodium hydroxide, what manned spacecraft to land on the moon, in
would be the temperature rise obtained when July 1969. It was propelled by Aerozine 50, a
it was mixed with the 50 cm3 of 2.0 mol dm–3 50 : 50 mixture, by mass, of hydrazine (N2H4)
hydrochloric acid ? and 1,1-dimethylhydrazine ((CH3)2 NNH2), with
Explain your answer. dinitrogen tetroxide (N2O4) as an oxidising agent.
c) If the experiment was repeated using 50 cm3
of 2.0 mol dm–3 of sodium hydroxide, what
would be the temperature rise obtained when
it was mixed with the 50 cm3 of 2.0 mol dm–3
hydrochloric acid ?
Explain your answer. (12)
28 Reaction 1: When 8.11 g of anhydrous magnesium
sulfate is added to 100.0 cm3 of water the
temperature of the water goes up by 7.5 °C.
Reaction 2: When 8.23 g of magnesium sulfate
crystals (MgSO4 7H2O) are added to 100 cm3
●

of water the temperature of the water falls by

1.0 °C.
Use this data to determine the enthalpy change The products of the reaction between Aerozine
for the reaction: 50 and dinitrogen tetroxide are nitrogen, water
and carbon dioxide.
MgSO4 + 7H2O → MgSO4 7H2O ●
a) Write an equation for the reaction between
Give your answer to 3 significant figures. hydrazine and dinitrogen tetroxide.
b) Write an equation for the reaction between
The specific heat capacity, c, of the apparatus is 1,1-dimethylhydrazine and dinitrogen
4.2 J g–1 K–1. (8) tetroxide.
c) If 2200 kg of Aerozine 50 is required for
Challenge the lunar module to take off, what mass of
29 a) Write equations to illustrate the standard oxidising agent is needed?
enthalpy changes of formation of N2O5(g) and d) Assuming complete oxidation of the fuel, use
H2O(l). the following standard enthalpies of formation
b) Use the following data to calculate the to calculate the enthalpy released at take-off.
standard enthalpy change of formation of ΔfH—Ө (N2H4) = 50.6 kJ mol–1
N2O5(g): ΔfH—Ө ((CH3)2NNH2) = 49.3 kJ mol–1
● N2O5(g) reacts with water to produce ΔfH—Ө (H2O(g)) = –241.8 kJ mol–1
nitric acid. When 1 mol of N2O5(g) reacts ΔfH—Ө (N2O4) = –19.5 kJ mol–1
with water ΔH = –74 kJ mol–1 ΔfH—Ө (CO2) = –393.7 kJ mol–1
● ΔfH—Ө (H2O(l)) = –286 kJ mol–1 e) A swimming pool contains 350 000 dm3 of
● ΔfH—Ө (HNO3(l)) = –174 kJ mol–1 (5) water. Suppose the enthalpy generated at
Chapter 10 Enthalpy changes

take-off was used to heat this water, which

had an initial temperature of 20 °C. What
would be the final temperature reached?
Ignore heat losses to the surroundings and
assume that the specific heat capacity of the
water is 4.2 J g–1 K–1 and that its density is
1 g cm–3. (22)

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 Chapter 11
Rates and equilibria
Prior knowledge
Before starting this chapter you should make sure that you are familiar with:
● reaction profiles
● activation energy, E
a
● enthalpy change, Δ H for a reaction.
r

These are covered in Chapter 10.

Test yourself on prior knowledge

a) Explain what is meant if a reaction is described as endothermic.
b) What is meant by the activation energy of a reaction?
c) Draw a fully labelled diagram to illustrate the reaction profile of an
endothermic reaction.

Rates of reaction
Reactions vary enormously in the rate at which they occur. Some are
so fast that the reaction mixture explodes while others proceed at
such a slow rate that they may take years to complete. In between
these extremes there are some reactions whose rate can reasonably be
measured in the laboratory. Understanding what causes these different
rates and how they might be controlled is important to chemists,
particularly on an industrial scale where the rate at which a product
can be obtained is of economic importance. It may make the difference
between successfully marketing a chemical or deciding that it is not
viable to produce it at all.

Measuring the rate of a reaction

There are a variety of ways in which the rate of reaction can be
measured in the laboratory. Typically, it might be possible to measure a
change in mass, volume or concentration or possibly a change
in acidity as a reaction proceeds (a pH meter could do this) or
maybe a change in colour.
gas syringe
It is particularly helpful if one of the products is a gas as the
rate at which it is produced can be readily measured using a
syringe.
conical flask Take for example the reaction between calcium carbonate and
hydrochloric acid:
hydrochloric acid and CaCO3(s) + 2HCl(aq) → CaCl2(aq) + CO2(g) + H2O(l)
calcium carbonate

Figure 11.1 Collecting and measuring the volume of In an experiment, the volume of carbon dioxide being produced
carbon dioxide produced during the course of the reaction could be measured as the reaction proceeds in a syringe, as
between calcium carbonate and hydrochloric acid. shown in Figure 11.1.
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 100 It would initially be produced quite quickly but, as the reaction proceeded,
it would gradually slow down as the reactants were used up. Eventually,
Volume of carbon dioxide/cm3

80 once one or both of the reactants had been used up the production of
carbon dioxide would cease. A graph of the volume of carbon dioxide
60 produced against time would appear as shown in Figure 11.2.

40 The rate is not constant but can be given a numerical value at a

particular time by drawing a tangent to the curve and measuring its
20 gradient. For example, in Figure 11.2 the rate at which the reaction is
proceeding at 110 s is given by the gradient of the tangent at that point
0 on the curve. In this case its value is 52 cm3/200 s = 0.26 cm3 s–1.
0 100 200 300 400 500
A rate of particular importance is the initial rate of the reaction. This
Time/s
is because the concentrations of the reactants are precisely known at
Figure 11.2 Graph of the volume of carbon
dioxide collected during the course of the the start of the reaction whereas it is likely to be difficult to measure
reaction between calcium carbonate and the concentrations while the reaction is progressing. The initial rate is
hydrochloric acid. obtained by taking the gradient of the concentration/time graph as the
reaction starts (i.e. time = zero).
Tip
Test yourself
The experiment could also be
followed by measuring the loss 1 a) Draw a sketch of a graph of concentration against time for a reaction
in mass of the reactants as the in which the concentration of a reactant was measured as the reaction
carbon dioxide is produced. proceeded.
b) How would you determine the rate just as the reaction started?

Activity
Investigation of the effect of concentration on the rate of a reaction
look down at cross
from above

time = t seconds
sodium thiosulfate cloudy
solution with acid liquid
added to start the
reaction

cross white paper

Chapter 11  Rates and equilibria

cross
invisible
Figure 11.3 Investigating the effect of the concentration of thiosulfate ions on the rate of reaction in acid solution. The hydrogen
ion concentration is the same in each experiment.

Figure 11.3 illustrates an investigation of the effect of concentration on the rate at which thiosulfate ions in solution
react with hydrogen ions to form a precipitate of sulfur.

S2O32–(aq) + 2H+(aq) → S(s) + SO2(aq) + H2O(l)

The observer records the time taken for the sulfur precipitate to obscure the cross on the paper under the flask. The
rate of the reaction is proportional to 1/t.

166

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 Rates of reaction
The results of the investigation are shown in Table 11.1.
Table 11.1 Results of the investigation in Figure 11.3.

Experiment Concentration of Time, t, for the cross to Rate of reaction, 1/t/s –1

thiosulfate ions/mol dm –3 be obscured/s
1 0.15   43 0.023
2 0.12   55 –
3 0.09   66 0.015
4 0.06 105 0.0095
5 0.03 243 0.0041

1 How would you prepare 50 cm3 of a solution of sodium thiosulfate solution with a concentration of 0.12 mol dm –3
from a solution with a concentration of 0.15 mol dm –3?
2 Calculate the value for the rate of reaction when the concentration of thiosulfate ions is 0.12 mol dm –3.
3 Plot a graph to show how the rate of reaction varies with the concentration of thiosulfate ions.
4 What is the relationship between reaction rate and concentration of thiosulfate for this reaction according to the graph?

Factors affecting the rate of a reaction

Experimental observations show that the rate of reaction is influenced
by temperature, concentration, the use of a catalyst and, for gaseous
reactions, pressure.
The collision theory of reactivity helps to explain these observations.
A reaction cannot take place unless a collision occurs between the
reacting particles although not all collisions lead to a successful reaction.
Key term For reaction to occur:
The activation energy is the ● the colliding particles must be correctly orientated
minimum energy required for a
● the energy of a collision between reacting particles must exceed the
reaction to occur.
activation energy, Ea, for that particular reaction.
The need for colliding particles to be correctly orientated is illustrated
by the reaction between iodomethane, CH3I, and hydroxide ions, OH –
(Figure 11.4). In iodomethane, the C–I bond is polar. The carbon has a
δ+ charge; the iodine has a δ– charge. If a negatively charged hydroxide
ion approaches iodomethane towards the Iδ– there is mutual repulsion
and reaction does not occur. If the approach is towards the Cδ+ and the
energy is high enough, the collision leads to a reaction.

Unsuccessful collision Successful collision

as the OH– approaches as the OH– approaches O C
the Id– the Cd+

I H

Figure 11.4 Effect of orientation on reaction outcome.

167

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 The frequency of collisions can be increased by:
● increasing the concentration
● increasing the surface area of a solid
● increasing the temperature
● increasing the pressure in a gaseous reaction.
Increasing the temperature is the most significant factor because this
increases the energy of the collision.

Effect of concentration
Increasing the concentration increases the chance of a collision between
the reacting particles. The more collisions there are, the faster the reaction.
For a gaseous reaction, increasing the pressure has the same effect as
increasing the concentration because a higher pressure compresses a
mixture of gases and increases their concentration. When gases react,
they react faster at high pressure because there is an increased chance
of a collision.

Effect of surface area

If a reactant is a solid, then its surface area will affect the rate at which
it is able to react. Clearly breaking a solid into smaller particles means
that more of its surface is exposed to the reagent it is reacting with and
the reaction will proceed faster.

Effect of temperature, the Boltzmann distribution

Raising the temperature increases the energy of the particles –
Tip they move faster and collide more often. However, this increased
frequency of collisions does not explain fully the effect that raising the
You won’t be asked to explain temperature has on the rate of reaction. When a collision occurs, the
why there is a distribution particles exchange (gain or lose) energy.
of energy but you should be
able to sketch the Boltzmann The Austrian scientist, Ludwig Boltzmann, showed mathematically that the
distribution. energies of molecules at a constant temperature are distributed as shown
in Figure 11.5. This type of graph is called a Boltzmann distribution.
Number of molecules with

Most probable energy

Chapter 11  Rates and equilibria

a given energy

Ea = activation energy of the reaction

Ea
Energy
Figure 11.5 Boltzmann distribution of energies.

This was an important contribution to our understanding of how

reactions occur. Instead of all reacting particles having a fixed energy at
a fixed temperature, Boltzmann showed that that the energies followed
168 the pattern shown by the distribution curve. In particular:

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 Rates of reaction
● The distribution curve goes through the origin, which shows that
there are no particles with zero energy.
● At high energy, the distribution approaches, but never touches, the
horizontal axis. This shows that there is no theoretical maximum energy.
● The area under the curve represents the total number of particles.
The shaded area in Figure 11.5 represents the number of particles with
energy greater than or equal to the activation energy, E ≥ Ea. This
shaded area, therefore, indicates the number of particles with sufficient
energy to react.
A reaction can occur only if the colliding particles have an energy
greater than, or equal to, the activation energy, Ea. Raising the
temperature increases the energy of the particles and, therefore,
changes the number of particles with energy greater than or equal
to the activation energy. This can be shown by comparing a typical
distribution of energies at an initial temperature, T1, with the distribution
of energies when the temperature is raised to T2 (Figure 11.6). The
number of particles remains the same so the area under both curves
is the same. However, at the higher temperature (T2), the distribution
flattens and shifts to the right. This means that there are more particles
with higher energy and a greater proportion of particles have an energy
that exceeds the activation energy.
Lowering the temperature has the opposite effect.
Number of molecules with

Most probable energy

a given energy

T2
T1
Ea Energy

Figure 11.6 Effect of temperature on the Boltzmann distribution (T2 > T1). The blue area
indicates the proportions of particles with energy greater than the activation energy at
temperature T1. The red and blue areas indicate the proportion of particles with energy
greater than the activation energy at temperature T2.

Effect of the use of a catalyst

Catalysts alter the rate of reactions without themselves being used up
by the overall reaction. Although catalysts are sometimes used to slow
reactions down their purpose is usually to increase the rate of a reaction.
They are divided into two types: homogeneous and heterogeneous. Both
work by providing an alternative route, or mechanism, for the reaction that
has a different activation energy. This is illustrated in Figure 11.7 using an
enthalpy profile and in Figure 11.8 with a Boltzmann distribution. On these
diagrams, Ea is the activation energy of the uncatalysed reaction; Ecat is the
activation energy of the catalysed reaction. 169

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 Number of molecules with
Enthalpy change/kJ mol–1 Ea

a given energy
Ecat
Enthalpy of
reactants

∆H

Enthalpy of products Ecat Ea

Progress of reaction Energy

Figure 11.7 Enthalpy-profile diagram showing the Figure 11.8 Boltzmann distribution showing the effect of a catalyst on
activation energy. The blue area indicates the proportions of particles with energy greater than
the activation energy without the catalyst. The red and blue areas indicate the
proportion of particles with energy greater than the activation energy.
effect of a catalyst on activation energy.

When a catalyst is used the enthalpy change and the distribution of

energies remain the same but the activation energy is lowered so that
more particles now have more energy than the new lower activation
energy, Ecat. Hence the reaction goes faster.
Homogeneous catalysts
The most common example is the formation of an ester, R1COOR2,
by reacting an alcohol with a carboxylic acid using sulfuric acid as the
catalyst. Esterification will be covered fully in the A level Book 2.
Another example involves the oxidation of iodide ions using persulfate
ions (peroxosulfate ions).
Iodide ions, I-(aq) are easily oxidised and the persulfate ion, S2O82-(aq) is
a powerful oxidising agent but surprisingly the reaction between them in
water is slow. The equation for the reaction is:
S2O82− + 2I− → 2SO42− + I2
For the reaction to occur the two ions must collide, however, the rate of
collision is slow because both ions are negative and repel each other.
The reaction can be catalysed by adding aqueous solutions of either
Fe2+(aq) ions or Fe3+(aq) ions.
The transition metal ions catalyse the reaction by providing an alternate
two-step mechanism:

Tip catalyst Fe2+(aq) Fe3+(aq)

Chapter 11  Rates and equilibria

Step 1 S2O82– + 2Fe2+ → 2SO42– + 2Fe3+ 2Fe3+ + 2l– → 2Fe2+ + l2

You will not be expected to
know the details of this reaction Step 2 2Fe3+ + 2l– → 2Fe2+ + l2 S2O82– + 2Fe2+ → 2SO42– + 2Fe3+
but it serves as an illustration Fe2+ is reformed and acts as a Fe3+ is reformed and acts as a
of how a homogeneous catalyst catalyst catalyst
might work. Net S2O82– + 2l– → 2SO42– + l2 S2O82– + 2l– → 2SO42– + l2
reaction

The Fe2+ and the Fe3+ ions provide an alternative mechanism that
involves an intermediate step of lower activation energy. The activation
energy is lowered because the initial step in the mechanism now involves
ions of opposite charge. The iron ions from the catalyst take part in the
reaction, but are released at the end of the reaction, so the final amount
170 of the catalyst is the same as when the reagents were mixed.

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 Rates of reaction
Another example of homogeneous catalysis occurs in the loss of ozone
from the upper atmosphere (stratosphere). This is a gas-phase reaction
in which the catalyst is the chlorine radical (Chapter 14, page 237).
Heterogeneous catalysts
A heterogeneous catalyst is in a different phase from the reactants.
The most common type of heterogeneous catalysis involves reactions of
gases in the presence of a solid catalyst.
The mode of action of a heterogeneous catalyst is different from that of
Tip
a homogeneous catalyst. A heterogeneous catalyst works by adsorbing
Make sure you don’t confuse the gases onto its solid surface. This adsorption weakens the bonds
adsorb with absorb. within the reactant molecules, which lowers the activation energy for
the reaction. Bonds are broken and new bonds are formed. The product
molecules are then desorbed from the surface of the solid catalyst.
Transition metals are often used as heterogeneous catalysts. Iron is the
catalyst in the Haber process for the manufacture of ammonia (page 176).
The iron is either finely divided (and therefore has a large surface area) or
in a porous form containing a small amount of metal oxide promoters:

N2(g) + 3H2(g) 
Fe catalyst
 2NH3(g)
The production of poly(ethene) and other polymers from alkenes requires
the use of a Ziegler–Natta catalyst. This is a mixture of titanium(iv)
chloride and an organic compound of aluminium, Al2(CH3)6. The mode of
action of such catalysts is complicated and not altogether understood.
Another important heterogeneous catalyst is the alloy of platinum,
palladium and rhodium used as catalytic converters in vehicles.

Economic importance of catalysts

Catalysts have great importance economically and industry spends
considerable time trying to develop efficient and cost-effective versions. The
reduction in the energy requirements of reactions means that they operate
at lower temperatures and with a consequent saving of energy. This not
only results in lower costs but may also reduce the demand for fossil fuels
whose combustion is a normal source of the energy supply. Burning of fossil
fuels also creates pollution and the consequent reduction in the emission of
carbon dioxide in particular is an important consideration.

Test yourself
Number of molecules with

2 Define the term ‘activation energy’ (Ea).

3 If the temperature is changed, the distribution of
a given energy

molecular energies changes.

a) Copy the distribution curve on the right and
add two new curves:
T1
i) at temperature T2, which is higher than T1
ii) at temperature T3, which is lower than T1.
b) What do the three curves at T1, T2 and T3 have Ea
in common? Energy
c) Explain why increasing the temperature
increases the rate of reaction.

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 4 a) Explain what is meant by the term ‘catalyst’.
b) Use a Boltzmann distribution curve to explain how a catalyst
works.
c) Explain what is meant by a heterogeneous catalyst. Give an
example.
d) Explain what is meant by homogeneous catalyst. Give an
example.
5 Describe how, and explain why, increasing the pressure on a gaseous original experiment

Volume of hydrogen
reaction affects the rate of reaction. C
B
6 The graph illustrates the effect of changing conditions on the reaction
of zinc metal with sulfuric acid. The red line shows the volume of D
hydrogen plotted against time using an excess of zinc and 50 cm3 of A
2.0 mol dm –3 sulfuric acid at 20 °C.
a) Write a balanced equation for the reaction.
0
b) Identify which line of the graph shows the effect of carrying out the Time

same reaction under the same conditions with the following changes:
i) adding a few drops of copper(ii) sulfate solution to act as a catalyst
ii) increasing the temperature to 30 °C
iii) using the same mass of zinc but in larger pieces
iv) using 50 cm3 of 1.0 mol dm –3 sulfuric acid.

Chemical equilibrium
Reversible reactions
There are many everyday examples of reactions or processes that are
reversible, the best known being the changes of the physical states of
Tip water. When the temperature of water falls below 0 °C, it freezes and
ice forms. When the temperature rises above 0 °C, the ice melts and
In a reversible reaction as shown, water forms again. This process can be represented as:
the reaction from left to right is
called the forward reaction; the H2O(s)  H2O(l)
reaction from right to left is the The symbol ‘  ’ indicates that a reaction is reversible.
reverse reaction.
Another reversible reaction is esterification.
O O
esterification
Chapter 11  Rates and equilibria

H3C C + HO CH2 CH3 H3C C + H2O

OH hydrolysis O CH2 CH3

acid catalyst
ethanoic acid ethanol ethyl ethanoate water

In the presence of an acid catalyst, ethanoic acid reacts with ethanol

to produce the ester ethyl ethanoate and water but ethyl ethanoate is
hydrolysed by water, also in the presence of an acid catalyst, to produce
ethanoic acid and ethanol again.

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 le Chatelier’s principle
Tip Dynamic equilibrium
If ethanoic acid and ethanol are refluxed in the presence of an acid
Refluxing allows the reactants catalyst, the forward reaction is initially fast because the concentrations
to mix together at the boiling of both reagents are high.
point of the mixture without
letting any vapour escape. This is However, as they react, the concentration of each reagent decreases,
achieved by placing a condenser which lowers the rate of the forward reaction.
on top of the flask containing The reverse reaction is initially slow because the amount of ethyl
the reactants (see page 229). ethanoate and water present is small. However, the concentrations of ethyl
ethanoate and water build up, increasing the rate of the reverse reaction.
In summary, the forward reaction starts rapidly but slows
down; the reverse reaction starts slowly and speeds up. A
forward point is eventually reached when the rate of the forward
Rate of reaction

equilibrium reached reaction equals the rate of the reverse reaction (Figure 11.9).
When this happens, the system is in dynamic equilibrium.
● The system is in equilibrium because the amount of
reverse each chemical remains constant.
● The equilibrium is dynamic because the reactants and
Time
the products are both constantly interacting.
Figure 11.9 Graph showing how rates of reaction change
until equilibrium is established. Another example of a dynamic equilibrium occurs during
the formation of stalactites and stalagmites (Figure 11.10).

Key term
A dynamic equilibrium is reached when the rate of the forward reaction equals
the rate of the reverse reaction. The concentrations of the reagents and
products remain constant; the reactants and the products react continuously.

Dynamic equilibrium can only be achieved in a closed system (i.e. no

reagent is allowed to escape).

Figure 11.10 Stalactites and stalagmites A visual representation of a dynamic equilibrium is a ‘Mexican wave’,
form in limestone caves because the often seen at major sporting events. The wave moves around the
reaction of calcium carbonate with carbon stadium (dynamic), but as one person stands to wave, another sits down
dioxide and water is reversible. (equilibrium). The number of people waving and the number of people
CaCo3(s) + H2O(l)+CO2 (g) L Ca(HCO3)2(aq)
sitting is constant but the individuals are constantly changing.

le Chatelier’s principle
Key term The French chemist Henri le Chatelier studied dynamic equilibria
and suggested a general qualitative rule that could be used to predict
le Chatelier’s principle states that the movement of the position of the equilibrium. This is known as
if a closed system at equilibrium le Chatelier’s principle.
is subject to a change, the
system will move to minimise The factors that can be readily changed are concentration, pressure and
the effect of that change. temperature and le Chatelier’s principle tells us that:
● If the concentration of a component is increased, the system will
Tip move to decrease the concentration of that component.
By ‘system’ le Chatelier meant the ● If the pressure is increased, the system will move to decrease the
equilibrium mixture containing pressure.
both the reactants and products.
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 ● If the temperature is increased, the system will move to decrease the
Tip
temperature.
Changing the pressure will only
affect reaction mixtures that
contain a gas or gases.
Effect of changing concentration on the
equilibrium position
Tip Le Chatelier’s principle applies to all reactions at equilibrium. However, there
are only a few reactions where the principle can be observed in action. One
The reaction between chromate such mixture is the equilibrium between the yellow chromate ion, CrO42–,
ions and hydrogen ions is not and the orange dichromate ion, Cr2O72– (Figure 11.11). Each ion is coloured,
one you need to learn. so it is possible to observe the movement of the position of equilibrium.
Adding acid to the chromate(vi)/dichromate(vi) mixture
increases the concentration of the hydrogen ions, H+(aq).
The system now moves to minimise the effect, i.e. it tries to
decrease the concentration of acid, H+(aq). This is achieved
CrO42– Cr2O72– by the additional H+(aq) reacting with some of the CrO42–
(aq) ions to form the products, Cr2O72–(aq) and H2O(l). The
2H+ + 2CrO42– Cr2O72– + H2O position of the equilibrium moves to the right, so the mixture
yellow orange becomes more orange.
Figure 11.11 Equilibrium between the chromate ion,
CrO42–, and the dichromate ion, Cr2O72–.
This can be reversed by adding a small amount of base, OH –
(aq). The base reacts with the H+(aq), which decreases the
concentration of the H+(aq) on the left-hand side of the equilibrium.
The system moves to minimise the effect, i.e. it tries to increase the
concentration of the acid, H+(aq). This is achieved by the H2O(l) reacting
with some of the Cr2O72–(aq) ions to form CrO42–(aq) ions and H+(aq)
ions. The equilibrium position moves to the left and the orange solution
becomes yellow.
Both these changes to the equilibrium mixture are, of course, a
consequence of a change in the rate of reaction on either side of the
equilibrium. Adding H+(aq) increases the rate of reaction between CrO42–
(aq) and H+(aq) so that there will be an increase in the formation of Cr2O72–
(aq) and H2O(l). The equilibrium then proceeds to re-establish itself but the
end result will nevertheless be an increase in the Cr2O72–(aq) present.

Effect of changing pressure on the equilibrium

position
The pressure of a mixture of gases depends on the number of gas molecules
present in a given volume. The greater the number of gas molecules, the
Chapter 11  Rates and equilibria

greater is the pressure in an equilibrium mixture. If the pressure is increased

in a system at equilibrium, the equilibrium position alters to resist the
increased pressure by reducing the total number of gas molecules. Using le
Chatelier’s principle this is achieved by the equilibrium position moving to
the side of the reaction mixture that has fewer gaseous molecules.
If the pressure is increased on a system such as
2SO2(g) + O2(g)  2SO3(g), the equilibrium position moves to the right.
This is because there are three molecules of gas (2SO2(g) + 1O2(g))
on the left-hand side of the equilibrium but only two molecules of gas
(2SO3(g)) on the right-hand side. The result of this shift in equilibrium
position is to reduce the total number of molecules in the mixture and
hence the increase in pressure is resisted.
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 le Chatelier’s principle
Tip If the pressure is increased on a system such as 2HI(g)  H2(g) + I2(g),
the position of the equilibrium does not move because there are equal
Increasing the pressure also numbers of gaseous molecules on each side of the equilibrium.
increases the rate of reaction so
that, in all cases, the equilibrium
would be established faster.
Effect of changing temperature on the
equilibrium position
Temperature influences the rate of reaction and also plays an important
role in determining the equilibrium position. The effect of temperature
can only be predicted if the sign of ∆H for value of the reaction is known.
Consider again the equilibrium between sulfur dioxide, oxygen and sulfur
trioxide.
The forward reaction is exothermic:
2SO2(g) + O2(g)  2SO3(g)   ∆ H = –197 kJ mol–1
and the reverse reaction is endothermic.
If the temperature of the reaction mixture is increased, le Chatelier’s
principle predicts that the mixture will respond by attempting to lower the
temperature again. This will be achieved by moving the equilibrium to the
left. It can perhaps be best understood by rewriting the forward reaction to
Tip emphasise that heat is given to the surroundings when the reaction occurs.
The increased temperature would 2SO2(g) + O2(g)  2SO3(g) + heat
also cause the reaction rate to
increase and the equilibrium So if heat is supplied by increasing the temperature, the reaction
would be established faster. responds by trying to remove some of the heat and therefore more
SO2(g) and O2(g) are formed.

Example 1
At 500 °C, hydrogen iodide forms an equilibrium with hydrogen and gaseous
iodine.
2HI(g)  H2(g) + I2(g)   ∆ H = +51 kJ mol–1
Predict the effect on the rate at which the equilibrium is formed and the
position of the equilibrium if
a) the temperature is increased to 700 °C
b) the equilibrium is cooled to room temperature.
Answer
a) Increasing the temperature will increase the rate at which the equilibrium
will be established.
The equilibrium can be written as:
heat + 2HI(g)  H2(g) + I2(g)
So increasing the temperature will also mean more hydrogen and iodine
will form
b) As the temperature is decreased, the equilibrium will be established
more slowly and the equilibrium will initially shift so that more hydrogen
iodide is formed.
However, iodine is a solid at room temperature so once this starts
forming, iodine is being removed from the equilibrium and all the
hydrogen iodide will then decompose into hydrogen and iodine.
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 Effect of using a catalyst on the equilibrium
position
A catalyst is a substance that speeds up the rate of reaction by
providing an alternative route, or mechanism, that has a lower activation
energy. A catalyst does not alter the amount of product.
In a system at equilibrium, a catalyst speeds up the forward and the
reverse reactions equally. Therefore, a catalyst has no effect on the
position of the equilibrium.
However, catalysts play an important part in reversible reactions
because they reduce the time taken to reach equilibrium. In the
presence of a catalyst, the same amount of product is produced more
quickly.

The use of compromise conditions – the Haber process

Large amounts of nitrogenous compounds, particularly fertilisers, are
needed by humans. Atmospheric nitrogen is in plentiful supply but it
cannot be used directly. It has to be converted (fixed) into a usable
compound. The Haber process ‘fixes’ nitrogen, converting it into ammonia:
N2(g) + 3H2(g)  2NH3(g)   Δ H = –93 kJ mol–1
Le Chatelier’s principle allows the optimum conditions for this industrial
process to be determined.
The enthalpy change is –93 kJ mol–1, so the forward reaction is
exothermic. Therefore, if the temperature is increased, the equilibrium
moves to the left and less ammonia is produced. It follows that a low
temperature is optimum for the formation of ammonia.
If the pressure is increased on the system, the equilibrium position
moves to the right to reduce the number of molecules. Therefore, high
pressure is optimum for the formation of ammonia.
The effect of changing temperature and pressure on the yield of
ammonia is shown in Table 11.2.

Table 11.2 Percentage yield of ammonia under different conditions.

Tip
Temperature/K 25 atm 50 atm 100 atm 200 atm
Atm. is an abbreviation
373 92 94 96 98
for atmosphere. 1 atm is
Chapter 11  Rates and equilibria

approximately equal to 101 kPa 573 28 40 53 67

(or 100 kPa). 773  3  6 11 18

The lowest temperature (373 K = 100 °C) gives the highest percentage

yield. However, at low temperature, the reaction rate is slow. A
compromise has to be reached between yield and rate of reaction.
The highest pressure (200 atm) gives the highest percentage yield
and also increases the reaction rate. However, at high pressure the
operating costs increase. A compromise has to be reached between
yield/rate and costs.

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 The equilibrium constant, Kc
Manufacturing conditions
The manufacture of ammonia in a modern plant is highly efficient. The
operating conditions vary but are typically:
● a temperature of around 700 K (427 °C)
● a pressure of around 200 atm.
These conditions are a compromise.
The rate of reaction is also increased by using a catalyst of either finely
divided iron, or porous iron incorporating metal oxide promoters.
Table 11.3 Boiling points of nitrogen, Additionally, if the equilibrium mixture is cooled to about –233 K
hydrogen and ammonia. (–40 °C), the ammonia gas liquefies but both nitrogen and hydrogen
Gas Boiling point remain as gases (see Table 11.3). Therefore, ammonia gas is lost from
the equilibrium mixture. The system moves to minimise the effect of
Nitrogen 77 K (–196 °C)
this loss so more nitrogen and hydrogen react to replace the ammonia
Hydrogen 20 K (–253 °C)
gas that was liquefied and removed from the system, and any unreacted
Ammonia 240 K (–33 °C) nitrogen and hydrogen are recycled and reacted again.
Most manufacturing processes involving gases require compromise
conditions to determine the best operating conditions to achieve
maximum efficiency for the formation of the desired product.

Test yourself
7 a) Explain what is meant by the term ‘reversible reaction’.
b) Explain what is meant by the term ‘dynamic equilibrium’.
c) State four external variables that could be changed to affect an
equilibrium.
8 Use le Chatelier’s principle to deduce what happens to the following
equilibrium when it is subjected to the changes below:
CH3OH(g)  CO(g) + 2H2(g)   ∆H = –129 kJ mol–1
a) the temperature is increased
b) the pressure is decreased
c) a catalyst is added.

The equilibrium constant, Kc

For any reversible reaction that has reached dynamic equilibrium it
is possible to relate the concentrations of the reactants and products
present using an important constant known as the equilibrium
constant. The equilibrium constant varies with temperature but its
value is the same for any other change in condition.
In general terms for the reaction:
aA + bB  cC + dD
the equilibrium constant Kc is given by:
[C]c[D]d
Kc = a b
[A] [B]
In the expression for Kc the square brackets ‘[  ]’ indicate that the
concentrations of the reactants and products are expressed in units
of mol dm –3. The concentrations of the chemicals on the right-hand
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 Tip concentrations of reactants on the left appear on the bottom line. Each
concentration term is raised to the power of the number in front of its
Although the concentration unit formula in the balanced equation.
is usually ‘mol dm –3’ the square
brackets ‘[  ]’ strictly indicate For the equilibrium:
that the concentrations are in 3H2(g) + N2(g)  2NH3(g)
mole units so that they could be
millimoles per dm3 or other units [NH3(g)]2
Kc =
involving moles and volumes. [H2(g)]3[N2(g)]
If there is a solid reactant or product in the equilibrium then it is not
included in the expression for Kc.
For the equilibrium (which forms at high temperatures):
H2O(g) + C(s)  H2(g) + CO(g)
[H2(g)][CO(g)]
Kc =
[H2O(g)]
The value of Kc is important because it gives an indication of the
balance of reactants and products present in the equilibrium mixture.
If Kc has a large value it will mean that there are more of the products
present than the reactants, if Kc is small then it is the reactants that
must be present in larger quantity. The values of Kc do, in fact, vary
enormously from large values down to values that are very small.
For example in the equilibrium:
CH3COOH(l) + C2H5OH(l)  CH3COOC2H5(l) + H2O(l)
[CH3COOC2H5(l)][H2O(l)]
Kc =
[CH3COOH(l)][C2H5OH(l)]
The value of Kc is approximately 4 at room temperature so there is quite
an equal balance between the reactants and products. Kc will not have
any units because the concentrations of each component will cancel out
in the equilibrium expression.
For the equilibrium between sulfur dioxide, oxygen and sulfur trioxide:

2SO2(g) + O2(g)  2SO3(g)

[SO3(g)]2
Kc =
[SO2(g)]2[O2(g)]
Tip
Chapter 11  Rates and equilibria

The equilibrium constant Kc for this reaction has a size of approximately

You will not be expected to 1.0 × 1012 at 230 °C, so in this case the equilibrium mixture has vastly
supply units for equilibrium more of the product, SO3, than the reactants. In this case Kc will have
constants in the AS exam. units of 1/mol dm –3 which should be written as dm+3 mol–1 because the
concentrations do not completely cancel in the equilibrium expression.

The effect on Kc of a change in temperature

The effect of a change in temperature on the value of Kc is best
explained using an example.
The equilibrium:
2SO2(g) + O2(g)  2SO3(g)   ∆ H = –197 kJ mol–1
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 The equilibrium constant, Kc
is exothermic, and has already been explained on page 175, an increase
in temperature causes more SO2 and O2 to be formed within the
equilibrium mixture. It must therefore follow that the value of the
equilibrium constant will decrease as the temperature rises.

Calculating an equilibrium constant

If the equilibrium concentrations of each component of an equilibrium
mixture is known the equilibrium constant can be calculated by
substituting these values into the expression for the equilibrium constant.

Example 2
At 450 °C, hydrogen and gaseous iodine form an equilibrium mixture with
hydrogen iodide.
H2(g) + I2(g)  2HI(g)
When an equilibrium mixture is analysed it is found to contain
0.015 mol dm–3 of HI, 0.0012 mol dm–3 of I2 and 0.0038 mol dm–3 of H2.
Calculate the value of the equilibrium constant to 2 significant figures.

Answer
The equilibrium constant for the formation of HI is:
[HI(g)]2
Kc =
[H2(g)][I2(g)]
Therefore Kc = (0.015)2/(0.0012)(0.0038) = 49

Test yourself
9 a) Write the equilibrium constant for the equilibrium:
2NO2(g)  N2O4(g)
b) At a certain temperature the equilibrium constant for this reaction
has a value of 0.0025.
(i) What does this indicate about the position of the equilibrium?
(ii) If the concentration of NO2 is 1.0 mol dm –3, calculate the
concentration of the N2O4.
10 When the equilibrium 2NOCl(g)  2NO(g) + Cl2(g) is analysed it is
found that the equilibrium concentrations of the gases are
NOCl = 3.42 mol dm –3, NO = 0.32 mol dm –3, Cl2 = 0.16 mol dm –3.
Use these figures to calculate Kc for the equilibrium.

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 Practice questions
Multiple choice questions 1–10 decompose hydrogen peroxide. Assuming all other
conditions of the experiment are kept constant,
1 The equilibrium concentration of the products of which one of the following would result in curve
the reaction 2 being obtained.
H2O(g)+ C(s)  H2(g) + CO(g) ΔH = +180.5 kJ A 80 cm3 of 1.0 mol dm–3 hydrogen peroxide is
decomposed
can be increased both by: B 20 cm3 of 2.0 mol dm–3 hydrogen peroxide is
A raising the temperature and lowering the pressure decomposed
B raising the temperature and increasing the C 20 cm3 of 4.0 mol dm–3 hydrogen peroxide is
pressure decomposed
C lowering the temperature and increasing the D 10 cm3 of 4.0 mol dm–3 hydrogen peroxide is
pressure decomposed
D lowering the temperature and pressure.
5 A student carries out an experiment to measure
2 In which one of the following reactions would the loss in mass of a container containing excess
a decrease in pressure most increase the marble (calcium carbonate) chips when reacted
equilibrium yield of the products? with 50 cm3 of 1.0 mol dm–3 hydrochloric acid. The
A NH4Cl(g)  NH3(g) + HCl(g) results are shown below.
B Fe3O4(s) + 4H2(g)  3Fe(s) + 4H2O(g)
C 2HBr(g)  H2(g) + Br2(g) Time/min 1 2 3 4 5 6 7
D 2NO2(g)  N2O4(g) Loss in 0.45 0.80 1.02 1.09 1.10 1.10 1.10
mass/g
3 Which one of the following gives the correct
expression for the equilibrium constant for the The student repeats the experiment again using
reaction shown by the equation below? excess marble chips and hydrochloric acid and
4CuO(s)  2Cu2O(s) + O2(g) obtains the following results.
[CuO]4 Time/min 1 2 3 4 5 6 7
A
[Cu2O]2[O2]
Loss in 0.36 0.64 0.82 0.95 1.04 1.10 1.10
B [O2] mass/g

[Cu2O]2 [O2] Which one of the following gives the volume and
C concentration of the hydrochloric acid that the
[CuO]4
student used when the experiment was repeated?
[Cu2O]2 A 25 cm3 of 2.0 mol dm–3
D
[CuO]4 B 50 cm3 of 0.5 mol dm–3
C 100 cm3 of 0.5 mol dm–3
4 1 D 100 cm3 of 1.0 mol dm–3
6 Which one of the following would react to give
Total volume of oxygen
Chapter 11 Rates and equilibria

off 0.01 mol of hydrogen most quickly when

added to excess magnesium ribbon?
2 A 25 cm3 of 1.0 mol dm–3 H2SO4
B 25 cm3 of 1.0 mol dm–3 HCl
C 20 cm3 of 2.0 mol dm–3 HCl
D 15 cm3 of 2.0 mol dm–3 H2SO4

0 7 Two equilibria are shown below:

Time first equilibrium: 2SO2(g) + O2(g)  2SO3(g)
Graph 1 above gives the curve obtained when second equilibrium: 2NH3(g)  3H2(g) + N2(g)
40 cm3 of 2.0 mol dm–3 hydrogen peroxide is Each of these equilibria is formed by starting with
decomposed. the reactants on the left-hand side of the equilibria.
Graph 2 is obtained in another experiment to
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 Practice questions
The rate at which each equilibrium is formed will are collected in a syringe in 50 s. In this reaction
be increased by: the sulfuric acid is in excess.
A using decreased pressure in the first Explain whether the reaction would be faster or
equilibrium and increased pressure in the slower if the experiment was repeated using:
second equilibrium a) 4 g of zinc foil and 50 cm3 of 2.0 mol dm–3
B using increased pressure in the first sulfuric acid
equilibrium and decreased pressure in the b) 2 g of zinc foil are reacted with 50 cm3 of
second equilibrium 1.0 mol dm–3 sulfuric acid
C using decreased pressure in both cases c) 4 g of zinc foil are reacted with 100 cm3 of
D using increased pressure in both cases. 1.0 mol dm–3 sulfuric acid. (3)
Use the key below to answer Questions 8, 9 and 10.
12 Heating limestone, CaCO3, in a closed furnace
A B C D produces an equilibrium mixture of calcium
1, 2 & 3 1, 2 correct 2, 3 correct 1 only carbonate with calcium oxide, CaO, and carbon
correct correct dioxide gas. Heating the solid in an open furnace
decomposes the solid completely into the oxide.
8 How do you account for this difference? (2)
13 NO(g) and Cl2(g) form an equilibrium with
graph 1 NOCl(g):
Number of molecules

NO(g) + 1 Cl2(g)  NOCl(g) ΔH = –77.1 kJ mol–1

2

graph 2 Explain the effect on the equilibrium of:

a) decreasing the temperature
b) decreasing the pressure
c) adding a catalyst. (7)
Energy 14 Methane and steam form an equilibrium mixture
with carbon dioxide and hydrogen.
Graph 1 above represents the Boltzmann
distribution at a given temperature. CH4(g) + 2H2O(g)  CO2(g) + 4H2(g)
Graph 2 would be obtained: Δ H = +165 kJ mol–1
1 by raising the temperature
Explain the effect on the rate at which
2 by adding a catalyst
equilibrium forms and the position of the
3 by reducing the number of molecules
equilibrium of:
present.
a) increasing the temperature
9 Equilibrium is reached in a chemical reaction b) decreasing the pressure
when: c) adding a catalyst. (8)
1 the activation energy of the reaction changes
15 Write an expression for the equilibrium constant
until it becomes the same for both reactants
for each of the following:
and products
a) H2(g) + CO2(g)  H2O(g) + CO(g)
2 the products react together at the same rate
b) H2(g) + I2(g)  2HI(g)
as they are formed
c) CH4(g) + 2H2O(g)  CO2(g) + 4H2(g) (4)
3 the concentrations of the reactants and
products are no longer changing. 16 a) The value of Kc for the equilibrium:
10 Which of the following affect the rate at which H2(g) + CO2(g)  H2O(g) + CO(g)
an equilibrium is established?
is 1.0 × 10–5 at 298 K.
1 an increase in pressure
What does this indicate about the balance of
2 the addition of a catalyst
the equilibrium at 298 K? (2)
3 the size of the equilibrium constant
b) What will be the value of the equilibrium
11 When 4 g of zinc foil are reacted with 50 cm3 of constant for:
1.0 mol dm–3 sulfuric acid, 100 cm3 of hydrogen
H2O(g) + CO(g)  H2(g) + CO2(g) (1)
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 17 An experiment is carried out to measure how the 19 Carbon dioxide is dissolved in water under
rate of reaction changes when 6.54 g of zinc chips pressure to make sparkling mineral water. In a
reacts with 25.0 cm3 of 1.00 mol dm–3 hydrochloric bottle of sparkling mineral water, there is an
acid in a conical flask. equilibrium between carbon dioxide dissolved in
the drink, CO2(aq), and carbon dioxide in the gas
Zn(s) + 2HCl(aq) → ZnCl2(aq) + H2(g)
above the drink, CO2(g).
A graph is plotted of the volume of hydrogen a) Write an equation to represent the
obtained every 30 s. This is shown below. equilibrium between carbon dioxide gas and
carbon dioxide in solution.
400
b) Use this example to explain the term ‘dynamic
350 equilibrium’.
Volume of H2(g)/cm3

300 c) Explain why lots of bubbles of gas form when

250 a bottle of sparkling mineral water is opened.
200
d) Less than 1% of the dissolved carbon dioxide
reacts with water to form hydrogencarbonate
150
ions:
100
50
CO2(g) + H2O(l)  HCO3–(aq) + H+(aq)

0 Use this equation to explain why carbon

0 30 60 90 120 150 180 210 240
dioxide is much more soluble in sodium
Time/s
hydroxide solution than in water. (7)
a) i) Calculate the amounts in mol of the
zinc and hydrochloric acid used in this 20 Nitrogen and oxygen form an equilibrium with
experiment. nitrogen(ii) oxide.
ii) Which of the reactants is in excess? 1 N (g) + 12 O2(g)  NO(g) Δ H = +90.3 kJ mol–1
2 2
b) On a copy of the graph, sketch and label
the lines you would expect to get if the a) Explain the effect on the equilibrium of:
experiment was repeated using: i) decreasing the temperature
i) 10.00 g of zinc and 25 cm3 of 1.00 mol dm–3 ii) increasing the pressure.
hydrochloric acid – label this line A b) Suggest why this equilibrium does not readily
ii) 6.54 g of zinc and 20 cm3 of 1.00 mol dm–3 form at room temperature. (7)
hydrochloric acid – label this line B 21 At 600 °C an equilibrium is established
iii) the original reactants but with the 6.54 g between nitrogen(iv) oxide and a mixture
of zinc broken into smaller pieces – label of nitrogen(ii) oxide and oxygen. When the
this line C. temperature is raised to 700 °C it is found that
Explain each of your answers above. (10) there is less nitrogen(iv) oxide in the equilibrium
18 Under what conditions are the following in mixture.
equilibrium? a) Write the equation for the equilibrium
a) water and ice showing the decomposition of nitrogen(iv)
oxide into nitrogen(ii) oxide and oxygen
Chapter 11 Rates and equilibria

b) water and steam

c) copper(ii) sulfate crystals and copper(ii) b) Explain whether the decomposition is
sulfate solution (3) endothermic or exothermic. (3)

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 Practice questions
22 When the indicator methyl orange is dissolved in water, the following dynamic equilibrium is set up:
H
CH3 CH3
–
OS N –
OS N
3
N N + H+ 3
N+
N
CH3 CH3
yellow
red

a) Hydrochloric acid is added to the equilibrium mixture. State, and explain, the colour change that occurs.
b) Then, aqueous potassium hydroxide, KOH(aq), is added dropwise to the solution in (a) until no further
colour change occurs. Deduce the colour changes that occur.
Explain your answer.
c) Aqueous sodium carbonate, Na2CO3(aq), is added to the original equilibrium mixture.
State what you would see. Explain your answer. (11)
23 a) State le Chatelier’s principle. Challenge
b) The gases NO2 and N2O4 form an equilibrium 26 In the UK, ethanol is manufactured by the
mixture. reaction of ethene with steam in the presence
2NO2(g)  N2O4(g) ΔH = –57.2 kJ mol–1 of a catalyst. The reaction is reversible and
exothermic, with an enthalpy change of reaction
NO2 is brown in colour but N2O4 is colourless. of –46 kJ mol–1. The catalyst is phosphoric acid.
An equilibrium mixture of these gases is It is supported on the surface of an inert solid
placed in a syringe. (silica). The proportion of steam in the reaction
Explain what colour change you would expect has to be controlled to prevent the catalyst
to observe if: taking up water so that it is diluted and runs off
i) the pressure on the mixture of gases is the surface of the solid.
increased The process is carried out at 300 °C at 60–70
ii) the syringe is cooled. (10) times atmospheric pressure. The water : ethene
24 When steam is passed over heated carbon the ratio is around 0.6 : 1.
following equilibrium is established: a) Which alternative method of making ethanol
is mainly used in other parts of the world?
C(s) + H2O(g)  CO(g) + H2(g) b) How can ethene for this process be made?
a) If the pressure is increased, explain what c) i) Write an equation for the reaction of
effect this would have on this equilibrium. ethene with steam and show the enthalpy
b) The enthalpy of formations of H2O(g) and change.
CO(g) are –241.8 kJ mol–1 and –110.5 kJ mol–1 ii) What type of reaction is this?
respectively. d) Suggest a reason for supporting the
i) Calculate the enthalpy change for the phosphoric acid on the surface of silica.
forward reaction to make CO(g) and H2(g). e) State three conditions that favour the
ii) Explain what effect increasing the formation of ethene at equilibrium according
temperature would have on the to le Chatelier’s principle.
equilibrium. f) Suggest reasons why the working conditions
iii) What would happen if the temperature are not those suggested by your answer to
was decreased below 100 °C? (10) part (a).
g) About 5% of the ethene is converted to
25 The values of Kc for the equilibrium ethanol each time the reaction mixture passes
N2O4(g)  2NO2(g) are 1.44 mol dm–3 at through the catalyst bed. Suggest how a yield
400 K and 41 mol dm–3 at 500 K. of 95% conversion is achieved. (8)
a) What is the effect of increasing the
temperature on the position of equilibrium?
b) What is the sign of ΔH for the forward
reaction? (3)

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 Chapter 12
Basic concepts in organic
chemistry
Prior knowledge
In this chapter it is assumed that you are familiar with:
● types of bonding
● shapes, bond angles electronegativity and polarity.

For example, when carbon forms bonds it does so by sharing electrons with
other non-metallic elements. You should know that the number, and type,
of electron pairs around the central atom determines the shape and the
bond angles of the molecule.
If the atoms bonded have a difference in electronegativity it will result in a
polar bond and dipoles will be formed. However, if the molecule is symmetrical
the dipoles will cancel and the overall molecule will be non-polar.
Carbon compounds range from the simple, for example methane, CH4, to
the complex, such as DNA. There is a huge range in between.

Test yourself on prior knowledge

1 State the atomic number, the mass number and the electronic
configuration for a C atom.
2 Explain what is meant by the term ‘covalent bond’.
3 How many single covalent bonds can each carbon atom form?
4 Draw a dot-and-cross diagram and state the expected bond angle in CH4.
5 Explain why methane, CH4 , is non-polar.
6 State the shape and the bond angles in each of:
a) CO2
b) NH3
c) H2O
d) C2H6
e) C2H4.

Functional groups
Carbon is found in millions of different compounds including the
molecules of most living systems. Carbohydrates, fats and proteins all
contain carbon and hydrogen and the study of compounds that contain
the C–H bond is referred to as organic chemistry. There are three main
reasons why carbon can form so many different compounds.
● Carbon, unlike most other elements, has the ability to form chains,
branched chains and rings of varying sizes.
● The C–C and the C–H bonds present in most organic compounds
have strong bonds with very low polarity and are therefore not very
reactive.
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 ● When carbon atoms form chains or rings linked by single covalent

Functional groups
bonds no more than two of the bonds of each carbon atom are used.
The remaining two bonds can bond to other atoms such as hydrogen,
oxygen, nitrogen and the halogens.
This gives rise to millions of organic compounds.
Ethane, CH3CH3, and ethanol, CH3CH2OH have very different properties
despite having very similar structures.
alkyl group - often
give the symbol R
functional
H H H H group

H C C H H C C O H

H H H H
ethane ethanol

● Ethane is a gas, ethanol is a liquid.

● Ethane is unreactive, ethanol is readily oxidised.
Clearly the O–H group in ethanol has a big effect on the properties
(Figure 12.1).
these bonds this active group is
are unreactive found in all alcohols

Key term
A functional group is either a
structural feature (e.g. a carbon- these bonds
the number of are reactive
to-carbon double bond, C=C), a carbon and hydrogen atoms
group of atoms (e.g. a hydroxyl does not have much effect
on the chemistry of alcohols
group, O–H) or a single atom
(e.g. Cl). It is the functional group Figure 12.1 The structure of ethanol labelled to show the reactive functional group and
the unreactive hydrocarbon skeleton.
that determines much of the
chemistry of a compound.
The O–H group in ethanol is an example of a functional group which is
responsible for most of the reactions of ethanol and for other alcohols.
If the O–H group is the only functional group present it reacts in more
Key term or less the same way irrespective of the hydrocarbon chain and it is not
uncommon to represent all alcohols by the formula R–OH.
A homologous series is a group of
compounds: This makes the study of organic chemistry easier as all molecules that
contain the same functional group have similar properties and react
• that have the same general formula in a similar way. Molecules with the same functional group form a
• that contain the same functional homologous series.
group
• in which each member of the Initially four homologous series are studied; alkanes, alkenes, alcohols
homologous series differs from and haloalkanes. However, the reactions of these four series produce
the next by CH2. other functional groups which you will have to recognise. These include
aldehydes, ketones, carboxylic acids and amines (Table 12.1).

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 Table 12.1 Functional groups.

Name Functional group General formula* Prefix or suffix First member Second member†
Alkane None – contains CnH2n+2 -ane CH4 Methane C2H6 Ethane
C–C and C–H
single bonds
Alkene CnH2n n ≠ 1 -ene C2H4 Ethene C3H6 Propene
C C

Alcohol R–OH -ol CH3OH Methanol C2H5OH Ethanol

C OH Hydroxy-

Haloalkane R–X Chloro- CH3Cl Chloromethane C2H5Cl Chloroethane

C Cl Bromo- Iodo-

Aldehyde O O -al HCHO Methanal CH3CHO Ethanal

C R C
H
H

Ketone O O -one CH3COCH3 Propanone C2H5COCH3 Butanone

C R C
R

Carboxylic acid O R–COOH -oic acid HCOOH Methanoic CH3COOH Ethanoic

C acid acid
OH

Amine R–NH2 -amine or CH3NH2 Methylamine C2H5NH2 Ethylamine

C NH2 amino …-ane or aminomethane or aminoethane

*R = alkyl group = CnH2n+1. †Add CH2 to first member.

Test yourself
1 Why do all alcohols have similar properties?
2 Identify the functional groups in each of the following compounds and
the homologous series to which they belong:
a) CH3CH2CHO
Chapter 12  Basic concepts in organic chemistry

b) CH3CH2CH2OH
c) CH3CH2Cl
d) CH3CH=CHCH3
e) CH3COCH3
f) CH3COOH

Naming organic compounds

With such a wide variety of compounds it is necessary to have an
organised way of naming them. Nomenclature should follow the
International Union of Pure and Applied Chemistry (IUPAC) rules. The
IUPAC naming rules are based around the systematic names given to
the alkanes and the prefix or suffix given to each functional group. The
prefixes and suffixes for the functional groups are given in Table 12.1.

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 Naming organic compounds
Table 12.2 Formulae and names of the First, you need to learn the names of the alkanes (Table 12.2).
first ten alkanes.
The name of the alkane is derived from the name of the longest
Formula Name continuous carbon chain. The alkyl, R, groups derived from the name of the
CH4 Methane alkanes are then used to name any side chains or branches (Table 12.3).
C 2H6 Ethane Table 12.3 Naming organic compounds.
C 3H 8 Propane
Number of carbon Stem name Number of carbon Name of alkyl,
C4H10 Butane atoms in the longest of longest atoms in a side R side chain or
C5H12 Pentane straight chain straight chain chain or branch branch
C6H14 Hexane  1 Meth-  1 Methyl
C7H16 Heptane  2 Eth-  2 Ethyl
C8H18 Octane  3 Prop-  3 Propyl
C9H20 Nonane  4 But-  4 Butyl
C10H22 Decane  5 Pent-  5 Pentyl
 6 Hex-  6 Hexyl
Tip  7 Hept-  7 Heptyl

The names of the first four  8 Oct-  8 Octyl

alkanes simply have to be learnt.  9 Non-  9 Nonyl
From the fifth alkane onwards 10 Dec- 10 Decyl
all straight-chain alkanes get
their name by using the Greek
numerical prefix followed by -ane.
Example 1
Give the full name of the compound:

CH3

CH3 CH2 CH2 CH CH3

Answer
The longest carbon chain contains five atoms, so the name includes pent-.
This is an alkane, so it ends with -ane.
There is a branch containing one carbon atom, hence the name contains
methyl.
It is possible to number the carbon chain from the left or the right.
Numbering from the left, the methyl group is on the fourth carbon atom:
4-methyl:

CH3
1 2 3 4 5
CH3 CH2 CH2 CH CH3

Numbering from the right, the methyl group is on the second carbon atom:
2-methyl.

CH3
5 4 3 2 1
CH3 CH2 CH2 CH CH3

The convention is to number from the chain end that results in the lowest
number. In this case, numbering is from the right.
The full name of the compound is 2-methylpentane.

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 Example 2 Example 3
Give the full name of the Give the full name of
compound: H CH3 H

OH H3C C C C CH3
6 5 4 3 2 1
CH3 CH2 CH CH2 CH CH3 CH3 H CH3

Br
Answer
Answer It is an alkane so the name ends in –ane.
The longest carbon chain contains
The longest carbon chain contains five atoms, so the name includes pent-.
six atoms, so the name includes
hex-. There are three side chains each with one carbon, so the name contains
trimethyl-.
The alcohol group is on the second
carbon, hence -2-ol. The methyl side chains are on atoms 2, 3 and 4, so the name contains 2,3,4
trimethyl-.
The bromine atom is on the fourth
carbon, hence 4-bromo-. The full name is 2,3,4 trimethylpentane.
This is an alcohol, so the
name ends in -ol. It is also a
bromoalkane, so the name starts Test yourself
with bromo-. 3 Name each of the following:
The full name is a) H CH3 H b) H
H
4-bromohexan-2-ol. H3C C C C CH3 H 3C C C C
H
H H H H H

c) H CH3 H d) H H H

H C C C H HO C C C OH

H CH3 H H H H
4 Draw each of the following molecules:
a) 2-chloropropane
b) 1-chloropropane
c) butan-2-ol
d) 2-methylpentane
Chapter 12  Basic concepts in organic chemistry

e) 3-methylbut-1-ene.

Types of formula
Key terms Different types of formula are used in organic chemistry. You must be
An empirical formula gives the familiar with both empirical formulae and molecular formulae and be
simplest ratio of the elements able to draw structural formulae, displayed formulae and skeletal formulae.
in a compound. These can be
calculated from the amounts of Calculation of empirical formulae
each element.
Analysis of an organic compound may only provide information about
A molecular formula represents
the ratio of the numbers of atoms present. Therefore, all that can be
the actual number of atoms of
established is its empirical formula. This might be the same as the
each element in the molecule.
molecular formula (as is the case with methane), but usually it is not
It does not provide any detail of
possible to be certain.
the arrangement of the atoms.
For example, the molecular The mass in grams of each element in a sample can be determined by
formula of ethanol is C2H6O. experiment. To find the empirical formula, the mass in grams of each
component must be converted into an amount in moles.
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 Naming organic compounds
Suppose a sample of a compound contains 1.5 g of carbon and 0.5 g of
hydrogen.
mass in grams
amount in moles =
molar mass
Therefore, the amount in moles of carbon atoms must be:
1.5 = 0.125
12.0
The amount in moles of hydrogen atoms must be:
0.5 = 0.50
1.0
Therefore, the ratio of number of moles of carbon to number of moles of
hydrogen is 0.125 : 0.5. This compound contains four times as many moles
of hydrogen atoms as it does carbon atoms. Therefore, each molecule
contains four times as many hydrogen atoms as it does carbon atoms.
The empirical formula of the compound is CH4.

Tip Example 3
In elemental analysis, amounts A 2.8 g sample of a hydrocarbon is found to contain 2.4 g of carbon and 0.4 g
will always be given in terms of hydrogen(H). What is its empirical formula?
of atoms. Hydrogen refers to
Answer
hydrogen atoms (H – mass = 1)
and not hydrogen molecules 2.4
amount in moles of carbon atoms = = 0.2
(H2 – mass = 2). 12.0
0.4
amount in moles of hydrogen atoms = = 0.4
1.0
The ratio of carbon atoms : hydrogen atoms is 0.2 : 0.4.
For every 1 carbon atom there are 2 hydrogen atoms.
The empirical formula is CH2.
The empirical formula, CH2, cannot be the molecular formula of the
compound because a carbon atom has to have four bonds.

Tip Example 4
Do not be put off by the use of A sample of a compound is found to contain 48.65% of carbon, 8.11% of
percentages instead of mass in hydrogen and 43.24% of oxygen. What is its empirical formula?
grams.
Answer
It follows that 100 g of the compound will contain 48.65 g of carbon, 8.11 g
of hydrogen and 43.24 g of oxygen.
C H O
Amount of atoms 48.65 8.11 43.24
= 4.05 = 8.11 = 2.70
mol 12.0 1.0 16.0
Tip 4.05 8.11 2.70
Simplest ratio = 1.5 =3 =1
2.70 2.70 2.70
Do not round during a calculation. The simplest ratio gives the empirical formula as C1.5H3O. It is not possible to
The 1.5 carbon atoms cannot be have 1.5 C atoms so the formula is doubled to give the empirical formula as
rounded up to 2. C3H6O2.

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 Calculation of molecular formula
The steps usually involved in the calculation of a molecular formula are
as follows:
● Calculate the empirical formula from the percentage composition by
mass.
● Use the empirical formula unit and the relative molecular mass to
deduce the molecular formula.

Example 5
Compound A has relative molecular mass 62. Its composition by mass
is carbon 38.7%, hydrogen 9.7%, oxygen 51.6%. Calculate the empirical
formula and the molecular formula of compound A.

Answer
C H O
Percentage 38.7 9.7 51.6
38.7 9.7 51.6
Divide by relative atomic mass = 3.23 = 9.7 = 3.23
12.0 1.0 16.0
3.23 9.7 3.23
Divide by the smallest =1 =3 =1
3.23 3.23 3.23
The simplest ratio of C : H : O is 1 : 3 : 1. The empirical formula is CH3O.
empirical formula mass = 12 + 3 + 16 = 31
The number of empirical units needed to make up the molecular mass is
found by dividing the relative molecular mass by the empirical mass:
Therefore, the molecular formula is made up of two empirical units of CH3O.
The molecular formula is C2H6O2.

Test yourself
5 A compound contained only carbon, hydrogen and oxygen. When
Chapter 12  Basic concepts in organic chemistry

analysed it consisted of 38.7% carbon and 9.68% hydrogen. Its relative

molecular mass is 62.0.
a) What percentage of oxygen did it contain?
b) What is the empirical formula?
c) What is the molecular formula?
6 A hydrocarbon consists of 82.8% carbon and its relative molecular mass
Tip
is 58.
Do not round during the a) Calculate its empirical formula.
calculation. b) Calculate its molecular formula.
7 A sample of a hydrocarbon was burnt completely in oxygen. 1.69 g of
carbon dioxide and 0.346 g of water were produced.
a) What is the percentage of carbon in carbon dioxide?
b) What is the mass of carbon in 1.69 g of carbon dioxide?
c) What is the percentage of hydrogen in water?
d) What is the mass of hydrogen in 0.346 g of water?
e) Use your answers to (b) and (d) to calculate the empirical formula of
the hydrocarbon.

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 Naming organic compounds
Representing chemical formulae
A structural formula uses the least amount of detail needed for an
unambiguous structure. There are two possibilities for the structure of a
compound of molecular formula C4H10: butane and methylpropane. The
formula C4H10 is, therefore, ambiguous.
● The structural formula of butane is CH3CH2CH2CH3, which can be
simplified to CH3(CH2)2CH3.
● The structural formula of methylpropane is CH3CH(CH3)CH3, which
can be simplified to (CH3)3CH.
The structural formula, therefore, makes it clearer how the atoms are
bonded.
A displayed formula gives yet more information. It shows the relative
positions of atoms and the number of bonds between them. Displayed
formulae sometimes indicate the bond angles around each carbon atom.
For methane and ethane the full displayed formulae shows the 3D structure:
H H H

C C C
H H H H
H H H
Tip
Displayed formulae are usually simplified:
The 3D structures are displayed
as a 2D projection. The bond H H H
angles appear to be 90° but they
H C H H C C H
are in fact 109° 28′, which is
approximately 109.5°. H H H

The molecular formula of ethanol is C2H6O and the structural formula is

CH3CH2OH. The displayed formula is:
H H

H C C O H

H H

A skeletal formula is used to show a simplified organic structure by

not writing the carbon and the hydrogen atoms in the alkyl chains,
leaving just a skeleton which shows the bonds between each carbon and
the associated functional groups. The skeletal formulae for butane and
2-methylpropane are shown below:

butane methylpropane

No symbols are shown because butane and 2-methylpropane are both

alkanes. The alcohol group (–OH), present in both butan-1-ol and
2-methylpropan-1-ol, is shown as part of the skeletal formula and the
OH is attached to the carbon–carbon bonds that make up the skeleton
as shown below:

OH
OH
butan-1-ol 2-methylpropan-1-ol

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 Some cyclic alkanes and benzene are represented as shown below:
H2 H2
C C
CH2 H2C CH2 H2C CH2 H2C CH2

H2C CH2 H2C CH2 H2C CH2 H2C CH2

C
H2

cyclopropane cyclobutane cyclopentane cyclohexane benzene

C3H6 C4H8 C5H10 C6H12 C6H6

Compounds that contain a benzene ring are aromatic compounds

whilst compounds that contain a hydrocarbon ring which is not benzene
are alicyclic compounds.

Test yourself
8 Calculate the molecular formula of each of the following compounds:
a) contains 80% C and 20% H and has Mr = 60
b) contains 92.3% C and 7.7% H and has Mr = 78
c) contains 2.4 g C, 0.6 g H and 1.6 g O and has Mr = 46
d) contains 62.1% C, 10.3% H and 27.6% O and has Mr = 58
e) contains 0.36 g C, 0.06 g H and 0.48 g O and has Mr = 180.
9 Draw the displayed formula and the structural formula for each of the
following molecules:
but-1-ene, 2-bromopropane, propan-2-ol and propan-1-ol.
10 Draw the skeletal formula of but-1-ene, 2-bromopropane, propan-2-ol
and propan-1-ol.

Isomerism
Structural isomerism
Chapter 12  Basic concepts in organic chemistry

One reason why carbon forms so many compounds is because it is

sometimes possible to join the atoms together in different ways. C4H10 is
the first alkane in which the atoms can be joined to form two different
structures shown below:
H

H H H H H H C H H

H C C C C H H C C C H

H H H H H H H

butane 2-methylpropane

As the number of carbon atoms increase it is possible to find more and

more different ways of joining them together. It has been calculated that
Tip for the molecular formula C14H30 there are 1858 different ways of joining
You must be able to draw and the atoms together, hence there are 1858 different compounds with the
name structural isomers. formula C14H30. These different forms are called isomers. They can occur
with all functional groups.
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 Isomerism
Key term There are three types of structural isomer: chain, positional and
functional group.
Structural isomers are compounds
that have the same molecular
formula but different structural
Chain isomerism
formulae. Chain isomers have differences in chain length. Examples include:
● butane and methylpropane, as shown above
● but-1-ene and methylpropene.
H H H
H CH3

H C C C H C C
H H

H H C C
H

H H
but-1-ene methylpropene

Positional isomerism
Positional isomers differ by the position of their functional group or
groups. Examples include:
● 1-bromobutane and 2-bromobutane
H H H H H H Br H

H C C C C Br H C C C C H

H H H H H H H H
1-bromobutane 2-bromobutane

● butan-1-ol and butan-2-ol.

H H H H H H OH H

H C C C C OH H C C C C H

H H H H H H H H
butan-1-ol butan-2-ol

Functional-group isomerism
Functional-group isomers have different functional groups. An example
is propanal (an aldehyde) and propanone (a ketone):
H H H O H
O

H C C C H C C C H

H
H H H H

propanal (an aldehyde) propanone (a ketone)

Stereoisomerism
Structural isomerism is common within organic chemistry; however,
stereoisomerism is more limited and requires certain key structural
features. Stereoisomerism in alkenes will be dealt with fully in Chapter 13.
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 Test yourself
11 Draw and name isomers of:
a) C5H12 b) C6H14.
12 Draw skeletal formulae and name the structural isomers of:
a) C5H10 that are alkenes
b) C5H10 that are cycloalkanes.
13 Draw skeletal formulae and name the alcohols that are isomers of:
a) C4H9OH b) C5H11OH.

Bonding in organic compounds

Organic compounds are essentially covalent. A covalent bond is a shared
pair of electrons between two atoms. Each atom provides one electron
of the shared pair.
All organic compounds contain carbon. The electron configuration
of carbon is 1s22s22p2. At first sight, it appears that only the two
2p-electrons are available to form covalent bonds. However, when
carbon forms bonds with other atoms, one of the 2s-electrons is
promoted to the third 2p-orbital, as shown in Figure 12.2.

2p 2p
px py pz px py pz
2s 2s
Energy

Energy
1s 1s

carbon 1s2 2s2 2p2 bonded carbon 1s2 2s1 2p3;

four unpaired electrons

Figure 12.2 Electron configuration for unbonded and bonded carbon.

Carbon now has four unpaired electrons available for sharing and,
therefore, can form four covalent bonds which are referred to as
σ-bonds (sigma bonds), where the two shared electrons are between the
centres of the two nuclei.
Alkanes consist of carbon and hydrogen only (e.g. methane, CH4). The
Chapter 12  Basic concepts in organic chemistry

bonds are all σ-bonds. The four electron pairs involved mean that the
bonds around the carbon atom point to the corners of a regular tetrahedron
(pages 100 and 102). The bond angle is 109° 28′, which is about 109.5°.
Carbon has an electronegativity of 2.5 (see pages 105–106); hydrogen
has an electronegativity of 2.1. Therefore, the C–H bond is slightly polar,
with the electrons drawn towards the carbon atom:
H
δ− δ+
C C H
H H
H

This applies to all four bonds. Therefore, in a molecule of methane the

electrons in each C–H bond are drawn towards the central carbon atom:
H

C
H H
194 H

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 Isomerism
Since the CH4 molecule is symmetrical, the dipoles cancel each other
out. Methane is non-polar, as are all alkanes.
Functional groups such as those in haloalkanes and alcohols disturb
the alkane symmetry. This, together with the electronegativities of the
halogen and oxygen, makes the molecules polar. In polar molecules such
as chloromethane and methanol the dipoles can be determined using
Pauling electronegativity values (Table 12.2; see also page 105).

Table 12.2 Pauling electronegativity values of elements commonly found in organic

compounds.

Element C H O Cl Br N
Electronegativity 2.5 2.1 3.5 3.0 2.8 3.0

In chloromethane the differences in electronegativity, and the lack of

symmetry, results in the shared pair of electrons in each σ-bond moving
along the σ-bonds as shown below:
2.1
H the differences H the alkyl group
in electronegativity CH3– releases
2.5 means the electrons δ+ electrons along H3C CI
C in each σ-bond C the σ-bond
H 3.0 move as shown H δ− towards the Cl
2.1
CI CI
H H
2.1

This movement of the shared pair of electrons in a σ-bond (covalent

bond) is known as the inductive effect. Alkyl groups like CH3 –, CH2CH3 –,
CH2CH2CH3 – (methyl, ethyl, propyl) are described as electron releasing
and are said to have a positive inductive effect. By contrast the Cl in
CH3Cl withdraws electrons from the C–Cl bond and has a negative
inductive effect.
In methanol the differences in electronegativity, and the lack of
symmetry, results in the shared pair of electrons in each σ-bond moving
along the σ-bonds as shown below:
2.1
H the differences H the alkyl group,
in electronegativity CH3– releases
2.5 2.1 mean the electrons δ+ electrons along H C OH
δ+
C H in each σ-bond C H the σ-bond
3

H 3.5 H
2.1 O move as shown O towards the
H H δ− OH group
2.1

Non-polar molecules such as alkanes are unreactive compared with

polar molecules such as chloromethane and methanol. The strength and
the polarity of the bonds affect the chemical properties of a molecule.

Important terms
Tip In order to understand the chemistry of compounds containing
For a reaction of any functional functional groups, you need to know the following terms:
group you are expected to know ● Reagents  These are the chemicals involved in a reaction.
the reagents and conditions. You
also need and to be able to write ● Conditions  These normally describe the temperature, pressure,
a balanced equation and, often, solvent and the use of a catalyst.
the mechanism.
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 ● Aliphatic  a compound containing carbon and hydrogen in straight
chains, branched chains or non-aromatic rings.
● Aromatic  a compound containing a benzene ring.

Calculations in organic chemistry

Most chemistry exams contain questions that require a calculation.
Organic chemistry calculations can include the determination of:
● empirical and molecular formulae – which were explained earlier on
pages 188–189
● percentage yield

● atom economy.

Percentage yield
Very few reactions result in the complete conversion of reactants to products.
Many preparations of organic substances are inefficient and yield only a small
amount of product. Sometimes, losses occur as a result of experimental error.
In these cases, the percentage yield of the reaction is recorded:
amount (in moles) of product obtained × 100
% yield =
theoretical amount (in moles) of product
Percentage yield can also be expressed as:

mass of product obtained

% yield = × 100
theoretical mass of product

Example 6
Ethanol, C2H5OH, can be oxidised to form ethanoic acid, CH3COOH. In an
experiment, 2.3 g of ethanol is oxidised to produce 2.4 g of ethanoic acid.
Calculate the percentage yield.

Answer
In this example, the symbol [O] is used to represent the oxidising agent.
Chapter 12  Basic concepts in organic chemistry

C2H5OH + 2[O] → CH3COOH + H2O

The equation shows that 1 mol of ethanol produces 1 mol of ethanoic acid.
Tip
Step 1 Calculate the amount in moles of ethanol used:
For mole calculations, you need
mass of ethanol
to be able to write a balanced amount in moles of ethanol used = n =
molar mass of ethanol
equation, so that you can use
the mole ratios that it provides. = 2.3 = 0.050 mol
46
The mole ratio ethanol : ethanoic acid is 1 : 1, hence the maximum
amount of ethanoic acid that could be made is 0.050 mol.
Tip
Step 2 Calculate the amount in moles of ethanoic acid produced:
It does not matter if you are mass of ethanoic acid
unfamiliar with this reaction; amount in moles of ethanoic acid produced = n =
molar mass of ethanoic acid
simply focus on the method.
= 2.4 = 0.040 mol
60
Step 3 Calculate the percentage yield:
Tip actual yield 0.040
percentage yield = × 100 = × 100 = 80%
n = m/M maximum yield 0.050
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 Calculations in organic chemistry
In Example 6 there is one organic starting material and one product, and
it is assumed that there is enough oxidising agent for the reaction to go
to completion. If there are two reagents, it may first be necessary to
establish whether the reagents are in the exact proportions for reaction
or whether one of them is in excess.

Example 7
In a reaction between methane and chlorine, the percentage yield of
tetrachloromethane, CCl4, is 72%. Calculate the mass of tetrachloromethane
that could be obtained by reacting 10.0 g of methane with excess chlorine.

Answer
The equation of the reaction is:
CH4 + 4Cl2 → CCl4 + 4HCl
Step 1 Calculate the amount in moles of methane present:
10
amount in moles of methane = = 0.625 mol
16
Chlorine is in excess. Therefore, the equation indicates that if the
reaction were 100% efficient, 0.625 mol of tetrachloromethane
would be produced.
Step 2 Calculate the amount in moles of tetrachloromethane produced:
percentage yield = 72%
amount in moles of tetrachloromethane
72
produced = × 0.625 = 0.45 mol
100
Step 3 Calculate the mass of tetrachloromethane produced:
mass of 1 mol of CCl4 = 154 g
mass of 0.45 mol = 0.45 × 154 = 69.3 g

Atom economy
The percentage yield of a reaction is one measure of the efficiency of
the process. However, a reaction with a good yield of product can still
be inefficient and wasteful if there are other products that have to be
discarded.
Consider the substitution reaction of sodium hydroxide and
1-bromobutane. This produces butan-1-ol and sodium bromide. The
equation is:
C4H9Br + NaOH → C4H9OH + NaBr
A percentage yield of butanol of 70% may be a good yield, but the
process might be considered less than satisfactory if there were no
use for the other product, sodium bromide. There is, therefore, another
measure that can be applied to reactions to take account of wastage.
This is called the atom economy.
molecular mass of the desired product
atom economy = × 100
sum of the molecular masses of all products

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 In the butanol, C4H9OH, example given above, the atom economy would
be calculated as follows:
Mr of C4H9OH is (4 × 12.0) + (9 × 1.0) + 16.0 + 1.0 = 74.0
Mr of NaBr is 23.0 + 79.9 = 102.9
74.0 × 100 = 41.8%
atom economy =
74.0 + 102.9
This result indicates that the reaction is not ideal.
A reaction can be inefficient but have a high atom economy. For
example, the yield of the ester, ethyl ethanoate, from the reaction
between ethanol and ethanoic acid is usually only about 40%.
The equation is as follows:
CH3COOH + C2H5OH → CH3COOC2H5 + H2O
However, the atom economy is good:
Mr of ethyl ethanoate = 88.0
Mr of water = 18.0
88.0 × 100 = 83.0%
atom economy =
88.0 + 18.0
Addition reactions of alkenes have a 100% atom economy because
there is only one product, for example:
H H H H However, the percentage yield may be less than 100%.
Using industrial procedures with a high atom economy
C C + X Y H C C H
would produce less waste. Atom economy is a relatively
H H new concept, but its importance is likely to grow as
X Y
society becomes more concerned about the need to
conserve resources and avoid unwanted by-products.

Tip Test yourself

It is important to recognise 14 Propan-1-ol was prepared by the reaction shown below:
and understand the command H H H H H H
words in a question. In Question
14 the command words are H C C C Br + H2O H C C C OH + HBr
‘calculate’ and ‘deduce’. As you
H H H H H H
Chapter 12  Basic concepts in organic chemistry

might expect ‘calculate’ will

2.46 g of 1-bromopropane was used 0.96 g of propan-1-ol was produced
involve using your calculator but
a) Calculate the amount in moles of 1-bromopropane used.
‘deduce’ can be done without
b) Deduce the amount in moles of propan-1-ol that could be produced.
the use of a calculator. In this
c) Calculate the amount in moles of propan-1-ol actually produced.
case the amount in moles of
d) Calculate the percentage yield.
propan-1-ol can be deduced
e) Calculate the atom economy.
by using the mole ratio in the
Propan-1-ol can also be produced by the reaction between propene and
balanced equation.
steam shown below:
H H H H H H

H C C C + H2O H C C C OH

H H H H H
16.8 g of propene was used 18.0 g of propan-1-ol was produced
f) Calculate the percentage yield and the atom economy of this reaction.
15 2.3 g of ethanol, C2H5OH reacts with ethanoic acid to produce 2.2 g of
ethyl ethanoate as shown below.
C2H5OH + CH3COOH → CH3COOC2H5 + H2O
198 Calculate the percentage yield and the atom economy.

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 Practice questions
Practice questions
Multiple choice questions 1–10 7 There are nine isomers with molecular formula
1 Which one of the following is a ketone? C7H16. How many of the isomers have ‘butane’ in
their systematic name?
A C6H5CH2CHO
A 1
B C6H5COCH3 B 2
C CH3CH2COOH C 3
D CH3CH2OCH2CH3 D 4
2 Which one of the following is the molecular 8 Which one of the following is the number of
formula of compound X, shown below? possible structural isomers of C4H8?
A 3
B 4
C 5
compound X D 6
A C9H18 Use the key below to answer Questions 9 and 10.
B C9H20 A B C D
C C8H16 1, 2 & 3 1, 2 correct 2, 3 correct 1 only
D C8H18 correct correct

3 Which one of the following is the number of 9 Chemicals within the same homologous series:
possible isomers of C6H14? 1 have the same the same functional group
A 3 2 have the same general formula
B 4 3 differ from the next in the series by CH2.
C 5
10 Which of the following hydrocarbons contains
D 6
85.7% carbon by mass?
4 Which one of the following is the name of
1 C3H6
compound X, shown below?
2 C5H10
3 C7H14
11 Identify the functional group in each of the
compound X
following molecules:
A 5-ethyl-3-methylhex-3-ene a) dodecane
B 2-ethyl-4-methylhex-3-ene b) pentene
C 3,5-dimethylhept-3-ene c) propane
D 3,5-dimethylhept-4-ene d) propan-2-ol
5 Which one of the following compounds contains e) 2-bromobutane
a double bond? f) cyclobutane. (6)
A C5H11Br
12 For each of the following, give the formula of the
B C4H9Br next member in the homologous series:
C C3H5Br a) C2H5OH
D C2H5Br b) C3H6
c) CH3I
6 Ethanol, C2H5OH, can be prepared by reacting
d) C7H16. (4)
ethene, C2H4, with steam. Under certain condition
28.0 g of ethene reacted with steam and 28.0 g 13 Draw the displayed formula and the structural
of ethanol was obtained. The approximate formula for the following molecules:
percentage yield for this reaction was: a) 2-chloropropane
A 100% b) 1-chloropropane
B 80% c) butan-2-ol
C 60% d) 2-methylpentane
D 40% e) 3-methylbut-1-ene. (5)
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 14 Name the following organic compounds: 18 Daw the skeletal formula of:
a) butane
a) H CH3 H
b) but-2-ene
H3C C C C CH3 c) 2-bromopropane
d) propan-2-ol
H H H e) propan-1-ol. (5)
b) H 19 Draw and name the structural isomers
H
of C4H8. (5)
H3C C C C
H
20 3.28 g of cyclohexene, C6H10, is prepared from
H H 10.00 g of cyclohexanol, C6H11OH:
c) H CH3 H C6H11OH → C6H10 + H2O
a) Calculate the percentage yield.
H C C C H b) Calculate the atom economy. (4)

H CH3 H 21 Compounds A–F are hydrocarbons.

d) H H H

HO C C C OH A B C D E F

a) The general formula of an alkane is CnH2n+2.

H H H (4) i) Which of the compounds A–F has a
15 a) Calculate the empirical formula for the formula that does not fit this general
compounds described below. formula?
i) Compound A contains the following ii) A, B and C are successive members of
by mass: carbon 37.5%; hydrogen the alkane series. What is the molecular
12.5%; oxygen 50.0%. (2) formula of the next member of the
ii) Compound B contains the following series?
by mass: carbon 29.3%; hydrogen iii) What is the empirical formula of
5.7%; bromine 65.0%. (2) compound B? (3)
iii) Compound C contains the following b) i) Three of compounds A–F are structural
by mass: carbon 53.3%; hydrogen isomers of each other. Identify these
11.1%; oxygen 35.6%. (2) by letter.
b) Compound B has two isomers. Draw and ii) Explain what is meant by the term
Chapter 12 Basic concepts in organic chemistry

name both isomers. (2) ‘structural isomer’. (1)

c) The relative molecular mass of compound c) Calculate the percentage by mass of
C is 90. Deduce the molecular formula of carbon in compound F. (2)
compound C. Draw and name any isomers. (8)
22 The compound 2-chloro-2-methylpropane is
16 Bromobutane can be prepared by the following prepared by shaking 2-methylpropan-2-ol and
reaction: concentrated hydrochloric acid together.
C4H9OH + NaBr + H2SO4 → C4H9Br + NaHSO4 + H2O a) Write a balanced equation for the
Calculate the atom economy for this reaction. (2) reaction between 2-methylpropan-2-ol
and concentrated hydrochloric acid.
17 Name the following compounds:
Water is also produced. (2)
a) CH3CH2CH2CH3 b) In the reaction, 4.0 g of
b) CH3CHBrCH3 2-chloro-2-methylpropane is produced.
c) CH3CHCHCH3 This is equivalent to a 40% yield. Calculate
the mass of 2-methylpropan-2-ol
d) (CH3)4C
that is used. (4)
e) CH3CH2CH(CH3)CH2CH3. (5)

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 Practice questions
23 Compound X is a hydrocarbon with molar H CH2Br Br CH3
mass 68 g mol–1. It contains 88.24% carbon, C C C C
deduce its molecular formula. (Hint: this looks
Br Br Br Br
easy, but be careful.) Compound X is a cyclic
Isomer 1 Isomer 2
alkene. Draw and name all possible isomers of
compound X. (10) i) Draw two other structural isomers of
C3H3Br3 that are bromoalkenes. (2)
Challenge ii) Draw two other structural isomers of
24 Compound X is a bromoalkene. It has the C3H3Br3 that are not bromoalkenes. (2)
following percentage composition by mass: iii) Name isomer 1. (1)
carbon 12.9%; hydrogen 1.1%; bromine 86.0%.
a) i) Calculate the empirical formula of c) 2.787 g of compound X reacts with
compound X. Show your working. (2) hydrogen, H2, to produce 0.843 g of
ii) The relative molecular mass of 1,1,2-tribromopropane.
compound X is 278.7. Show that the i) Calculate the percentage yield of
molecular formula is C3H3Br3. (1) 1,1,2-tribromopropane. (2)
ii) Identify compound X by name and by
b) Compound X is one of six possible structural formula. (2)
isomers of C3H3Br3 that are bromoalkenes. Two iii) What is the atom economy of this
of these isomers are shown below as isomer 1 reaction? (1)
and isomer 2.

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 Chapter 13
Hydrocarbons
Prior knowledge
In this chapter it is assumed that you are familiar with:
● the structure and names of the first five straight-chain alkanes
● the combustion products of hydrocarbons
● balancing equations
● empirical and molecular formula calculations
● the existence of fossil fuels
● fractional distillation and cracking.

Test yourself on prior knowledge

1 Draw and name the first five straight-chain alkanes.
2 Write equations for the complete combustion of:
a) C3H8
b) C8H18
c) C24H50.
3 Explain what is meant by a fossil fuel.
4 Explain how the different fractions of crude oil are separated.
5 Suggest why the combustion of fossil fuels might be bad for the
environment.
6 Write an equation to illustrate the cracking of C10H22 into C8H18.

Hydrocarbons as fuel
The Earth has large, though depleting, reserves of hydrocarbons. These
compounds are particularly important as fuels. Hydrocarbons are
compounds that contain only hydrogen and carbon. The carbon atoms
in hydrocarbons can be linked by single, double or triple bonds and can
be in a chain or a ring.
A fuel is a source of energy. A useful fuel should:
● have a high energy output
● be either abundant or manufactured easily
● be easy to transport and store
● be easy to ignite
● cause minimum environmental damage.
Alkanes are called saturated hydrocarbons.

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 Alkanes
Alkanes
Physical properties
Key terms Melting point and boiling point
The variation in boiling point depends on the degree of intermolecular
A saturated compound is a bonding (page 108). Alkanes are covalent compounds with C–H bonds
molecule in which all the atoms that have a very low polarity and the only intermolecular bonding is
are linked together by single (σ) a consequence of induced dipole–dipole interactions. The strength
bonds only. of the induced dipole–dipole interactions depends on two key
A hydrocarbon is a compound that factors: the number of electrons in the molecules and the shape of
contains hydrogen and carbon the molecules. There are two important trends in the variation of
only. boiling point:
Aliphatic compounds contain
carbon and hydrogen joined ● As the relative molecular mass of the alkanes gets larger, so does the
together in straight chains, boiling point. This is due to the increasing chain length and therefore
branched chains or non– an increase in the number of electrons present. Hence there will
aromatic rings. be more induced dipole–dipole interactions. The boiling points of
the first six alkanes are shown in Table 13.1 and the trend is shown
graphically in Figure 13.1.

Table 13.1 Boiling points of the alkanes.

Alkane Molecular formula Boiling point/K Boiling point/°C State at r.t.p.

Methane CH4 109 –164 Gas
Ethane C 2H 6 185 –88 Gas
Propane C3H8 231 –42 Gas
Butane C4H10 273 0 Gas
Pentane C5H12 309 36 Liquid
Hexane C6H14 342 69 Liquid

400

350
342
300 309

250 273
Boiling point/K

231
200
185
150

100 109

50

0
1 2 3 4 5 6
Number of carbon atoms in the straight chain
Figure 13.1 Trend in boiling point of the first six alkanes.

● For isomers with the same relative molecular mass, the boiling point
decreases as the degree of branching increases. This is illustrated
in Table 13.2 for the three isomers of C5H12, which all have relative
molecular mass 72. 203

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 Table 13.2 Relationship between boiling point and degree of branching.

Name Structure Boiling Boiling State at r.t.p.

point/K point/°C
Pentane 309 36 Liquid
Methylbutane 301 28 Liquid/gas

Dimethylpropane 283 10 Gas

As shown in Figure 13.2, molecules of straight-chain alkanes, such as

pentane, pack together more closely than molecules of branched-chain
alkanes, such as methylbutane and dimethylpropane. This increased amount
of surface contact creates more intermolecular forces (induced dipole–dipole
interactions). More energy is needed to overcome these intermolecular
forces, so the boiling point of pentane is the highest of the three isomers.

pentane methylbutane dimethylpropane

Figure 13.2 Effect of branched chains on packing.

Branched-chain alkanes, such as methylbutane and dimethylpropane,

cannot pack together as tightly. This reduces the intermolecular forces
and, hence lowers the boiling point and melting point.

Solubility
Alkanes have very low polarity, which means that they do not mix with
polar molecules. Therefore, alkanes are insoluble in polar solvents, such as
water. Liquid alkanes are less dense than water and when mixed together
the alkanes will form an immiscible upper layer.
Alkanes dissolve readily in each other because the molecules link
through induced dipole–dipole interactions. Crude oil is a mixture, or
solution, of over 100 different alkanes.

Chemical properties
Chapter 13  Hydrocarbons

Alkanes are unreactive because:

● the C–H bonds have very low polarity
● the single bonds linking together the carbon and hydrogen atoms are
relatively strong.
However, they do undergo two important reactions – combustion and
reactions with halogens.

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 Alkanes
Combustion of alkanes
Combustion of alkanes in excess oxygen produces carbon dioxide and
water:
CH4 + 2O2 → CO2 + 2H2O
1
C2H6 + 3 2 O2 → 2CO2 + 3H2O
C11H24 + 17O2 → 11CO2 + 12H2O
Combustion of alkanes in a limited supply of oxygen produces carbon
monoxide (or carbon) and water:
1
CH4 + 1 2 O2 → CO + 2H2O CH4 + O2 → C + 2H2O
1 1
C2H6 + 2 2 O2 → 2CO + 3H2O C2H6 + 1 2 O2 → 2C + 3H2O
1
C11H24 + 11 2 O2 → 11CO + 12H2O C11H24 + 6O2 → 11C + 12H2O
Carbon monoxide is poisonous and restricts the effectiveness of the
blood to transport oxygen in the body. If the supply of oxygen is even
more limited carbon (soot) and water are the major products. Therefore,
Figure 13.3 Serious faults with the engine
when alkanes are burnt there must be good ventilation, and car
of this lorry means that it is emitting
dangerous and illegal levels of carbon engines must be effectively tuned to ensure that the volume of carbon
(soot) and toxic carbon monoxide from its monoxide in the exhaust is within prescribed limits. Clearly the engine
exhaust system. of the lorry in Figure 13.3 needs to be re-tuned.

Radical substitution
Key terms A radical is a particle with an unpaired electron. The unpaired electron
in a radical can be shown as a dot, e.g. Cl·, ·CH3. Radicals are highly
A radical is a particle that has at reactive and can attack non-polar compounds such as alkanes in a
least one unpaired electron. substitution reaction.
A substitution reaction is one
in which an atom (or group) is The mechanism of such reactions (i.e. the steps involved) is important
replaced by another atom (or and illustrates some general features of radical chemistry.
group). Substitution by chlorine or bromine to form halogenoalkanes
The reaction between methane and chlorine is used as an example.
Tip
Reagent: chlorine
In an alkyl radical such as a
methyl radical. the ‘dot’ should
Conditions: ultraviolet radiation
be on the carbon.
unpaired
single
Equation: CH4 + Cl2 → CH3Cl + HCl
H
electron •×
• C •× H Mechanism: radical substitution
ו
H
There are three distinct steps that make up this mechanism:
● initiation – starts the reaction by forming a radical
● propagation – maintains the reaction by forming one of the products
and a new radical
● termination – ends the reaction by removing the radicals and forming
molecules.

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 Key term In the initiation step, radicals are generated. The ultraviolet radiation
provides sufficient energy to break the Cl–Cl bond homolytically to
Homolysis or homolytic fission produce radicals. Homolysis or homolytic fission occurs when a
occurs when a covalent bond is covalent bond breaks and the atoms joined by the bond separate, each
broken so that the atoms joined atom taking one of the shared pair of electrons:
by the covalent bond each take
one of the shared electrons. Cl–Cl → Cl· + Cl·
→ 2Cl·
Cl–Cl UV
Tip Propagation involves more than one step, each of which maintains the
The first propagation step radical concentration. Usually a Cl· or a Br· radical causes the release
always produces a hydrogen of an alkyl radical, or vice versa. The propagation steps are difficult to
halide (HBr or HCl) and an alkyl control and can lead to a complex mixture of products.
radical; the second propagation For mono-substitution there are two essential propagation steps:
step always produces the
organic product and re-generates Propagation step 1: CH4 + Cl· → HCl + ·CH3
the halogen radical. Propagation step 2: ·CH3 + Cl2 → CH3Cl + Cl·
An important feature of the propagation steps is that the second
reaction generates another Cl·. This means that, in principle, the reaction
might never stop and many molecules of methane might be destroyed
from a single initiation but the chain can be stopped by a termination
reaction.
Termination involves any two radicals reacting together to form a
covalent bond:
Possible termination steps: CH3· + CH3· → C2H6
CH3· + Cl· → CH3Cl
Cl· + Cl· → Cl2
Radicals are extremely reactive. They react with almost any molecule,
atom or radical with which they collide. When CH4(g) and Cl2(g) react
a mixture is formed and will include CH2Cl2, CHCl3 and CCl4 as well as
CH3Cl. Radical substitution reactions almost always result in a mixture
of products which are difficult to separate. The sequence below shows
how CH2Cl2 might be formed.
A chlorine radical could collide with the product molecule, CH3Cl, in
which case the following sequence would occur:
CH3Cl + Cl· → HCl + ·CH2Cl
·CH2Cl + Cl2 → CH2Cl2 + Cl·
Chapter 13  Hydrocarbons

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 Alkenes
Test yourself
1 a) Draw a dot-and-cross diagram to represent a molecule of:
i) ethane
ii) propane.
b) Give the bond angles in:
i) ethane
ii) propane.
2 a) What is meant by electronegativity?
b) Explain why alkanes are unreactive.
3 Draw and name the isomers of C6H14. State which isomer has the highest
boiling point and suggest which two isomers are likely to have low boiling
points. Explain your answers.
4 Why is a series of organic compounds, such as the alkanes, comparable
with a group of elements in the periodic table?
5 a) Write an equation for the complete combustion of propane in Calor gas.
b) What are the products when propane burns in a poor supply of oxygen?
6 Why is it dangerous to allow a car engine to run in a garage with the door
closed?
7 Write equations for all four possible substitution reactions when chlorine
reacts with methane and name the products.
8 a) Explain why a mixture of bromine in hexane remains orange in the
dark but fades and becomes colourless in sunlight.
b) Write an equation for the reaction in part (a).
c) Why can acid fumes be detected above the solution once the colour
has faded?
9 a) Write an equation for the reaction between hexane and bromine in
the presence of UV light.
b) Describe the mechanism for the reaction between hexane and
bromine in the presence of UV light.
c) Explain why the product from the reaction between hexane and
bromine contains many different organic compounds.

Alkenes
Key term Alkenes are unsaturated hydrocarbons and contain carbon–carbon
double bonds.
Unsaturated molecules contain one
or more double (or triple) bonds. Alkenes are unsaturated molecules that contain at least one C=C
double bond. They are invaluable to chemists because they can be used
to make a wide range of useful products such as alcohols and polymers.
Tip Alkenes can be produced from the cracking of heavier fractions of crude
oil. They also occur naturally in plant and animal tissue such as oil, fat
You will recall that cracking and pigments.
breaks long chain alkanes into
a shorter chain alkane and an
alkene; C10H22 → C8H18 + C2H4
Physical properties
Boiling point
As with alkanes, the boiling points of the alkenes increase with
increasing chain length. However, the boiling point of an alkene is lower
than that of the corresponding alkane (Table 13.4).

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 Table 13.4 Comparison of the boiling points of alkanes and alkenes.

Alkane Boiling point/K Alkene Boiling point/K

Ethane 185 Ethene 169
Propane 231 Propene 226
Butane 273 But-1-ene 267
Pentane 309 Pent-1-ene 303

The alkenes have lower boiling points because their molecules cannot
pack together as efficiently as those of alkanes. Hence there are fewer
intermolecular forces (induced dipole–dipole) to overcome.

Solubility
Alkenes, like alkanes, are insoluble in water.

Bonding in alkenes
An alkene molecule contains a C=C double bond. The double bond
consists of a σ-bond and a π-bond.
● A σ-bond is a single covalent bond made up of two shared electrons
with the electron density concentrated between the two nuclei.
● A π-bond is formed by the ‘sideways’ overlap of two p-orbitals on
adjacent carbon atoms, each providing one electron.
H H H H
C C C C
H H H H
p-orbitals above and
p-orbital
below the plane of
the molecule

π-bond
H H
C C
H H
σ-bond

On average the energy required to break a C–C single bond is

347 kJ mol–1 whereas the energy needed to break a C=C bond is
612 kJ mol–1. This indicates that the π-bond is considerably weaker than
the σ-bond.
The C–H bond angle at each side of the C=C double bond is
approximately 120° (usually in the region 116–124°), which results in a
Chapter 13  Hydrocarbons

trigonal planar arrangement of bonds round each carbon atom:

H H

C C 120°

H H

In other alkenes, for example propene and but-1-ene, the equivalent

bond angles on either side of the C=C double bond are approximately
120°, but the bond angles in the alkyl groups are 109.5°, as expected:

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 Alkenes
H H H

109.5° 120° H
109.5° C C 120° H C
H H C C C
C
H H
H H
H H H
propene but-1-ene

Stereoisomerism in alkenes
Key term The C=C double bond in alkenes prevents freedom of rotation, which
under certain circumstances can lead to the existence of stereoisomers,
Stereoisomers have the same known as E/Z isomers.
molecular and structural
formulae but a different three- The two key features of E/Z isomerism are:
dimensional spatial arrangement. ● the presence of a C=C double bond
● each carbon atom in the C=C double bond is bonded to two different
atoms or groups.
Substituents on the molecules shown below cannot twist around the
double bond and move from one side to the other without breaking the
p bond. This means that the molecules are in fact, different.
H Cl Cl Cl
C C and C C

Cl H H H

But-1-ene and but-2-ene both have a CC double bond that prevents
free rotation. However, one carbon atom in the CC double bond in
but-1-ene is bonded to two hydrogen atoms, so but-1-ene does not
exhibit E/Z isomerism. In but-2-ene, both carbon atoms in the double
bond are bonded to different atoms/groups:
H H H H
Tip
C C C C
The prefixes ‘Z’ and ‘E’ come
H CH2 CH3 H3C CH3
from the German words
but-1-ene but-2-ene
‘zusammen’, meaning together
(i.e. on the same side of the
molecule), and ‘entgegen’,
meaning opposite.

But-2-ene possesses both essential key features, and hence has a Z- and
an E- isomer:
H H H CH3

C C C C

H3C CH3 H3C H

Z-but-2-ene E-but-2-ene

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 The skeletal formula of the two stereoisomers of but-2-ene clearly
shows the difference in shape.

Z E

Although the difference in geometry changes the shape of the molecule,

it has little or no effect on the general chemistry of the two isomers.
However, Z-but-2-ene has a slightly higher boiling point than E-but-2-ene.

Rules for assigning E/Z isomerism

Not all alkenes exist as E/Z isomers. It is essential that each C atom
in the C=C double bond is bonded to two different atoms or groups.
Each C atom in the C=C double bond must be asymmetric. Each of the
alkenes below meets this criterion.
H3C CH3 H CH2CH3 H3C H H Cl

C C C C C C C C

H H H3C H Cl OH F Br

Each C in the double bond is bonded to two different atoms or groups.

So it is possible to form at least one stereoisomer.

Cahn, Ingold and Prelog (CIP) rules

There are a set of rules known as the Cahn, Ingold and Prelog (CIP) rules
that enable you to decide whether you should name each isomer as an
E-isomer or a Z-isomer.
According to these rules, the atomic number of each atom bonded
to the C in the C=C double bond determines whether or not it is an
E-isomer or a Z-isomer.
1 If the two attached atoms with the highest atomic numbers are on
the diagonally opposite sides of the double bonds it is an E-isomer.
2 If the two attached atoms with the highest atomic numbers are
not diagonally opposite each other across the double bonds it is a
Z-isomer.
3 If two attached atoms have the same atomic number, then the
adjacent atoms with the highest atomic number are taken into
account. With alkyl groups it therefore follows that
CH3CH2CH2 > CH3CH2> CH3.
Chapter 13  Hydrocarbons

In a compound such as CH3(Cl)C=CHOH, the C on the left-hand side

of the C=C double bond is bonded to a Cl (atomic number 17) and a C
(atomic number 6) whilst the C on the right-hand side is bonded to a H
(atomic number 1) and a O (atomic number 8). So we can apply rules
1 and 2:

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 Alkenes
atomic atomic
number 17 number 1
Cl H
C C
H3C OH
atomic atomic
number 6 number 8

The two with the highest atomic numbers are on diagonally opposite
sides of the C=C double bond so this is an E-isomer.
atomic atomic
number 17 number 8
Cl OH
C C
H3C H
atomic atomic
number 6 number 1

The two with the highest atomic numbers are on the same side of the
C=C double bond so this is a Z-isomer.
In the compounds below, the C atom on the right of the C=C bond is
bonded to two carbon atoms, each with atomic number 6. We therefore
need to apply rule 3.
It is still possible to have E/Z isomers by considering the adjacent atoms:
CH3CH2 has priority over CH3 so it follows that the isomer on the left is
the Z-stereoisomer and the isomer on the right is the E-isomer.
atomic atomic atomic atomic
number 17 number 6 number 17 number 6
Cl CH3 Cl CH2CH3
C C C C
Br CH2CH3 Br CH3
atomic atomic atomic atomic
number 35 number 6 number 35 number 6
Z E

The molecules shown on page 210 can each be assigned as either E or Z,

as shown below.
H3C CH3 H CH2CH3 H3C H H Cl

C C C C C C C C

H H H3C H Cl OH F Br
Z E Z Z

Cis–trans isomerism
Cis–trans isomerism is a special case of E/Z isomerism in which the
substituent groups attached to each carbon atom of the C=C group are
the same.
H3C Cl H3C OH

C C C C
are E/Z isomers but not cis–trans isomers
H OH H Cl

Z isomer E isomer
 

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 H3C OH H3C CH3
C C C C
HO CH3 HO OH
are E/Z isomers and also cis–trans isomers.
Z isomer E isomer
also also
trans isomer cis isomer  
Test yourself
10 a) D
 raw and name the structural isomers of alkenes that have the
formula:
i) C4H8
ii) C5H10
iii) C6H12.
b) Explain what is meant by the term structural isomer.
11 a) Explain what is meant by the term stereoisomer.
b) Use your answers to Question 10 above and decide which, if any,
can form E/Z isomers.
c) Draw and name each E/Z isomer.
d) 2-methylhept-3-ene exists as E/Z isomers.
Draw and label the skeletal form of each isomer.

Chemical properties
The C=C double bond is unsaturated, which means that the main
Key term
reactions of alkenes are addition reactions.
An addition reaction is a reaction
The reactivity of alkenes can be explained in terms of the relatively low
in which two molecules combine
bond enthalpy of the π-bond. In this type of reaction, the π-bond breaks
together to form a single
and an atom, or group, adds to each of the two carbon atoms. The
product.
general reaction can be summarised as:

Tip CH2CH2 + X–Y → CH2XCH2Y

H H
For most organic reactions, H H
you need to know the balanced
C C + X Y H C C H
equation, the reagents, the
conditions and what, if anything H H Y
X
is observed.
Reactions of ethene
Hydrogenation
Ethene reacts with hydrogen to form ethane, according to the following
equation:
Chapter 13  Hydrocarbons

CH2CH2 + H2 → CH3CH3
Reagent: hydrogen
Conditions: nickel catalyst at 150 °C
Observations: no visible change
Hydrogenation of polyunsaturated compounds derived from plant oils is
used in the production of margarine.

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 Alkenes
Bromination
Ethene reacts with bromine (Br2(aq)) to produce 1,2-dibromoethane,
according to the equation:
CH2CH2 + Br2 → CH2BrCH2Br
Tip
Reagent: bromine
Remember that the bromine is
decolorised. In an exam, you Conditions: mix at room temperature
will be penalised if you write that Observations: decolorisation of bromine
it ‘goes clear’ or is ‘discoloured’.
This reaction is used to test for the presence of a CC double bond.
Reaction of ethene with hydrogen bromide
Ethene reacts with hydrogen bromide to produce bromoethane,
according to the following equation:
CH2CH2 + HBr → CH3CH2Br
Reagent: hydrogen bromide
Conditions: mix gases at room temperature
Observations: no visible change
Hydration of ethene
A hydration reaction involves the addition of water and results in a new
organic compound. Ethene is hydrated according to the following equation:
CH2CH2 + H2O → CH3CH2OH
Reagent: water (steam)
Conditions: an acid catalyst, such as phosphoric(v) acid, H3PO4, at
300 °C and high pressure (6 MPa)
Observations: no visible change
All alkenes undergo similar reactions under similar conditions. However,
unsymmetrical alkenes, such as propene, produce two isomers when
Tip reacted with hydrogen chloride or water:
It is easy to confuse hydration H H H H
H H
with hydrolysis, which also
C C + HCl H3C C C H or H3C C C H
involves reacting with water.
H3C H
Hydration – water reacts H Cl Cl H
1-chloropropane 2-chloropropane
with an organic molecule to
produce a single product. H H H H
H H
Hydrolysis – water reacts
C C + H 2O H3C C C H or H3C C C H
with an organic molecule
and two new compounds are H3C H
H OH OH H
produced. propan-1-ol propan-2-ol

Mechanism of electrophilic addition

Key term The mechanism of an electrophilic addition reaction involves an
electrophile.
An electrophile is an electron-pair
acceptor that forms a covalent The movement of electron pairs is tracked by the use of curly arrows.
bond. The curly arrow always points from an area that is electron-rich to an
area that is electron-deficient.
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 a curly arrow shows the movement of an electron pair

The reaction is initiated by the presence of a dipole (charge separation

along a bond) on the molecule that reacts with the alkene. This dipole
could be:
● induced by the presence of the alkene, as is the case with bromine
● permanent, as in hydrogen bromide.
When describing mechanisms, it is essential that you show:
● relevant dipoles
● lone pairs
● curly arrows.

Tip The key features of this mechanism are as follows:

As the Br2 molecule approaches ● When the Br–Br molecule approaches the ethene, a temporary
the alkene, the high electron induced dipole is formed, resulting in polarisation of the Br–Br bond:
density in the CC double bond H H H H
H H
induces a temporary dipole in
the Br–Br bond. C C H C C H H C C H
+
H H
Br
Br δ+ − Br Br
Br
intermediate carbocation
Br δ−

● The initial curly arrow starts at the π-bond (within the CC double
bond) and points to the Brδ+.
● The second curly arrow shows the movement of the bonded pair of
electrons in the Br–Br bond towards the Brδ–, resulting in heterolytic
fission of the Br–Br bond.
● An intermediate carbonium ion (also called a carbocation) is formed
together with a Br– ion, which contains the pair of electrons from the
Br–Br bond.
● The third curly arrow from the lone pair of electrons on the Br–
to the positively charged carbonium ion shows the formation of
1,2-dibromoethane.
When bromine reacts with an alkene, the Br–Br bond undergoes
heterolytic fission; when it reacts with an alkane it undergoes
homolytic fission. Compare the two ways in which the Br–Br bond is
Chapter 13  Hydrocarbons

broken:

Br Br Br+ + Br– Br Br Br• + Br•

Tip heterolytic fission homolytic fission

A single-headed arrow shows the Hydrogen bromide (and hydrogen chloride) are polar molecules and have
movement of a single electron. a permanent dipole. The hydrogen atom has a δ+ charge and acts as
the electrophile.

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 Alkenes
H H H H H H
C C step 1 step 2
H H H C C H H C C H
+
H
H – H Br
Br
Br

In the first step of the reaction between hydrogen bromide and ethene,
an HBr molecule approaches an ethene molecule. The δ+ hydrogen
end of the H–Br is attracted to the electron-dense double bond. As the
H–Br molecule gets even closer, heterolytic fission of the π-bond occurs.
The electrons in the π-bond form a covalent bond to the hydrogen
atom and, at the same time, heterolytic fission of the H–Br bond also
occurs. Electrons in the H–Br bond are taken over by the bromine atom
producing a Br– ion. The other product of step 1 is the highly reactive
carbocation, or carbonium ion, CH3CH2+. This reacts immediately with
the Br– ion in the second step of the reaction to form CH3CH2Br.

The reaction of asymmetric alkenes with HBr and

with H2O
Alkenes such as propene react with both HBr and with H2O in exactly
the same way as ethene reacts with both HBr and H2O, but with
propene in each reaction two possible products are formed.
H3C H

C C

H H
propene

HBr H2O

H H H H H H H H

H3C C C H and H3C C C H H3C C C H and H3C C C H

H Br Br H H OH OH H
1-bromopropane 2-bromopropane propan-1-ol propan-2-ol

One would expect that the yield of each would be approximately

50%, but this is not the case. In the reaction with HBr about 90%
of 2-bromopropane is formed and only approximately 10% of
1-bromopropane. The reaction with H2O is similar and the major
product is always propan-2-ol and not propan-1-ol.
This was first notice in the late nineteenth century by the Russian
Key term chemist Vladimir Vasilevich Markownikoff (sometimes spelt
Markownikoff’s rule stated that Markovnikov), who studied thousands of alkene reactions and noted
the addent other than hydrogen that whenever a compound with general formula HX reacted with an
goes to the least hydrogenated alkene the H atom in HX, always became attached to the carbon atom
carbon atom. which had the larger number of H atoms. This rule became known as
Markownikoff’s rule.
This can be explained by considering the mechanism carefully. There are
two alternatives, as follows:

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 alternative 1
H H H H H H H H
step 1 step 2
H C C C H H C C C H H C C C H
+
H H H H H Br

H δ+ −
Br
Br δ−

alternative 2
H H H H H H H H
step 1 step 2
H C C C H H C C C H H C C C H
+
H H H H Br H
H δ+
−
Br
Br δ−

Step 1 involves the formation of a carbonium ion (also called a

carbocation). This is the slow step in the mechanism.
Step 2 involves the reaction between the bromide ion, Br– and the
carbonium ion. This is the fast step in the mechanism.
Markownikoff’s rule predicts that 2-bromopropane will be the major
product indicating that the preferred mechanism is ‘Alternative 2’
in which a secondary carbonium ion is formed. Carbonium ions are
unstable and can be stabilised by the inductive effect of adjacent alkyl
groups (see page 186). The alkyl groups release electrons along the
σ-bonds as shown below.
H H H H H H
Tip
The classification of primary, H C C C H H C C C H
+
secondary and tertiary is +
explained fully on page 226 H H H H
primary secondary
carbonium ion carbonium ion

The primary carbonium ion is stabilised by one inductive effect whereas

the secondary carbonium ion is stabilised by two inductive effects. As
you might expect, a tertiary carbonium ion is even more stable and
more readily formed.
H

H C H
Chapter 13  Hydrocarbons

H H

H C C C H
+

H H
tertiary
carbonium ion

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 Addition polymerisation of alkenes
Test yourself
12 a) Draw the displayed formula of:
i) ethene
ii) propene.
b) Give the bond angles in:
i) ethene
ii) propene.
c) Draw the skeletal formula of propene.
13 Write the names and draw the structures of the possible products when:
a) HCl reacts with E-but-2-ene
b) H2O reacts with but-1-ene.
14 a) Write a balanced equation for the:
i) complete combustion of propene
ii) reaction between but-1-ene and hydrogen
iii) hydration of but-2-ene
iv) reaction between but-1,3-diene with bromine. State what you
would observe and name the organic product.
b) Explain why the hydration of but-2-ene only gives one organic
product but the hydration of but-1-ene gives two organic products.
15 Describe the mechanism for the reaction between but-2-ene and HBr.
Show relevant curly arrows, dipoles and lone pairs of electrons.
16 Explain why the major product is 2-bromo-2-methylpropane when
2-methylpropene reacts with HBr.

Addition polymerisation of alkenes

Alkenes can undergo addition reactions in which one alkene molecule
joins to another until a long molecular chain is built up. The individual
alkene molecule is referred to as a monomer; the long-chain molecule
is called a polymer.
Polymerisation can be initiated (started) in a number of ways. Often,
the initiator is incorporated at the start of the long molecular chain.
However, if the initiator is disregarded, the empirical formulae of the
monomer and the polymer are the same.

Poly(ethene)
The simplest monomer is ethene, which can be polymerised to produce
poly(ethene). In the formula for poly(ethene), a large number of
monomers, n, join together – this number may be as high as 10 000,
such that a long-chain polymer is formed.
H H H
H
n C C C C

H H H H n
ethene poly(ethene)

carbon

hydrogen

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 Poly(ethene), or polythene as it is commonly called, was developed in
the 1930s. Today, it is widely used in everyday applications. It is tough,
durable and unreactive. Poly(ethene) is non-polar and the molecules
contain only strong covalent bonds. It is an excellent insulator and,
because it is unaffected by the weather, is used for insulating electricity
cables.
Changing the monomer gives polymers with different properties for
different applications (Table 13.5).
The properties of a polymer can also be altered by the addition of a
plasticiser. This is usually a liquid with a high boiling point (e.g. an
ester see page 223). The plasticiser molecules are located between the
polymer molecules, which reduces the intermolecular forces and makes
the polymer more flexible (less rigid).

Table 13.5 The monomer, polymer structure and uses of some important polymers.

Monomer Repeat unit of polymer Properties Uses

Propene Poly(propene) Tough Food boxes
H H H H Very resistant to water, acids Ropes
C C
and alkalis Carpets
C C Easily moulded Toys
H CH3 Easily coloured
H CH3 n

Chloroethane Poly(chloroethane) Tough Clingfilm

(vinylchloride) (polyvinyl chloride/PVC) Rigid Guttering
H H H H Flexible (when plasticiser Window frames
C C
added) Raincoats
C C Very resistant to water, acids Shower curtains
H Cl and alkalis Insulation for cables
H Cl n

Tetrafluoroethene Poly(tetrafluoroethene)/PTFE Tough Coating for non-stick pans/

F F Also known as Teflon® Very resistant to water, acids skis
C C F F
and alkalis Gaskets
F F Low friction solid/slippery Plumbing tape
C C Low friction surfaces for
F F
n
bridges to move as metals
expand and contract
Phenylethene Poly(phenylethene) or polystyrene Excellent insulator Styrofoam® cups
(also known as styrene) H H
Resistant to water, acids and Fast food containers
H H alkalis. Refrigerator insulation
C C Packaging
C C
H
H
Chapter 13  Hydrocarbons

Ethenol (also known as Poly(ethenol) or polyvinyl alcohol Water soluble Hospital laundry bags which
vinyl alcohol) H H can be handled without
H H touching the infected
C C
C C contents
H OH H OH

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 Addition polymerisation of alkenes
Figure 13.4 Clingfilm is just a thin film of Figure 13.5 This little boy is wearing a
PVC (polyvinylchloride). Its correct name PVC waterproof jacket.
is poly(chloroethene).
 

Identification of the monomer from which a

polymer is produced
It is possible to deduce the repeat unit of an addition polymer and,
therefore, to identify the monomer from which the polymer is produced.
For example:

CH3 H CH3 H CH3 H CH3 H

C C C C C C C C

H H H H H H H H
repeat
unit

Therefore, the monomer is propene:

CH3 H

C C

H H
propene

The equation for the polymerisation can be written as

CH3 H
H3C H

n C C C C

H H
H H
n

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 Test yourself
17 There are four alkenes that are isomers of C4H8.
a) Draw and name the four alkenes.
b) Draw the repeat units of each of the polymers that could be formed
from each alkenes in (a).
c) Name each of the polymers formed.
18 Poly(styrene) is made from the following monomer.
H H
C C
H

a) What is the common name for the monomer?

b) The systematic name of the monomer is phenylethene. Write a
systematic name for the polymer.
c) Draw a section of the polymer composed of three monomer units.
19 A section of an addition polymer is shown below. Identify the monomer
from which it was made.

Waste polymers and alternatives

The widespread use of these polymers has created a major disposal
problem. The bonds in addition polymers are strong, covalent and non-
polar, making most of the polymers resistant to chemical attack. In
addition, since they are not broken down by bacteria, they are referred
to as being non-biodegradable.
Plastic waste has in the past been buried in landfill sites, where it
remains unchanged for decades. Some local authorities now collect
waste plastic separately from other refuse.
Plastic waste is much more difficult to recycle than waste metals. There
are many different types of plastic which have to be first separated and
sorted before they can be recycled.
An alternative to dumping is incineration. Polymers are made from
hydrocarbons and are, therefore, potentially good fuels. When burned,
they release useful energy which could be used to generate electricity.
In the UK, only about 10% of plastic is incinerated, but in countries such
as Japan and Denmark up to 70% is burned. Some plastics, such as PVC,
produce poisonous gases (e.g. HCl), so the incinerators have to be fitted
Chapter 13  Hydrocarbons

with gas-scrubbers to prevent these toxins from being released into the
environment.
Another possibility is recycling the polymers and using them as
feedstock for the production of new polymers. Different types of
polymer have to be separated from each other because mixtures yield
inferior plastic products.

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 Addition polymerisation of alkenes
Oil-derived polymers also deplete finite resources and considerable
effort has been put into developing biodegradable polymers that have
useful properties. The aim is to create a polymer that:
● contains an active functional group that can be attacked by bacteria,
● is sustainable and doesn’t use finite resources.
Other biodegradable compounds are based on condensation polymers,
which are studied in the second year of the A Level course.

Activity
A brighter future for plastics
Biodegradable plastics are now being synthesised and produced commercially as replacements for non-biodegradable
plastics. One of the most important of these new biodegradable plastics is polylactic acid (PLA), which is produced
from starch.
Starch is a natural polymer produced during photosynthesis. Cereal plants, such as maize and wheat, and tubers,
such as potatoes, contain starch in large proportions. Starch can be processed directly into a bioplastic, but because
this is soluble in water, articles made from starch swell and deform when exposed to moisture. The problem can be
overcome by modifying the starch into a different polymer.
First, the starch is harvested from maize, wheat or potatoes. Micro-organisms then transform it into the monomer
lactic acid. Finally, the lactic acid is chemically treated so that the molecules of lactic acid link into long chains or
polymers, which bond together forming PLA.
Polylactic acid can be formed into containers and packaging for food and consumer goods as diverse as plant pots and
disposable nappies. The biodegradable and compostable nature of PLA means that it will break down into harmless
natural products under normal outdoor conditions. This gives it big political and environmental advantages over
conventional plastic packaging, which uses an estimated 500 000 barrels of oil every day throughout the world. Its
biodegradable qualities could also take the pressure off the world’s mounting landfills, in which plastics take up an
estimated 25% by volume. However, as PLA is significantly more expensive than conventional oil-based plastics, it has
failed to gain widespread use, although it is becoming a more viable alternative as the price of crude oil continues to rise.
1 What do you understand by the following terms used in the introduction?
a) Bioplastic
b) Compostable
2 What limits the use of starch itself as a plastic?
3 The structural formula of lactic acid is:
H
H O O
H C C C
H H O H

a) Write down the molecular formula of lactic acid.

b) Give the names of the functional groups in lactic acid.
4 Starch reacts with water when micro-organisms transform it into lactic acid. Assuming that the formula of starch
can be written as (C6H10O5)n, write an equation for the conversion of starch to lactic acid.
5 The –OH group and the –COOH group can react as shown below:
R−O−C−R1
R–OH + HOOC–R1 → + H2O
O
Use this to explain how lactic acid molecules can link up to form long chains or polymers.
6 State three advantages of PLA over oil-based plastics.
7 a) What is the major disadvantage of PLA compared with oil-based plastics?
b) Why is this disadvantage becoming less important?

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 Practice questions
Multiple choice questions 1–10 Identify the number of errors in the student’s
1 Put the following alkanes in order of increasing response.
boiling points. Start with the lowest boiling A 0
point first. B 1
C 2
D 3
5 2,2-dimethylbutane reacts with bromine, in the
1 2 3 4 presence of UV light, to form a mono-substituted
compound with molecular formula C6H13Br.
A 1, 2, 3, 4
Which one of the following is the number of
B 4, 3, 2, 1
possible isomers that could have been formed?
C 4, 3, 1, 2
A 4 isomers
D 2, 1, 3, 4
B 3 isomers
2 The complete combustion of methane is shown C 2 isomers
below: D 1 isomer
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) 6 When pent-1,4-diene, CH2CHCH2CHCH2,
At room temperature and pressure, which one of is reacted completely with steam at high
the following is the minimum volume of oxygen temperature and high pressure in the presence of
required to burn 16 g of methane? a suitable acid catalyst, the number of different
A 2 dm3 alcohols that could be formed is:
B 64 dm3 A 1
C 24 dm3 B 2
D 48 dm3 C 3
D 4
3 When fossil fuels such as petrol are burnt, carbon
dioxide and water are produced. Assume that a 7 Polymer A, shown below,
petrol contains only octane, C8H18:
OH OH OH OH
C8H18(g) + 12 1
2
O2(g) → 8CO2(g) + 9H2O(l)
Calculate the volume of carbon dioxide produced
when 1 litre (1 dm3) of petrol is burnt. polymer A
(Assume the mass of 1 litre of C8H18 is 684 g and could be made from:
all volumes are measured room temperature A CH3CH2OH.
and pressure where 1 mol of gas has a volume of
B CH3CH2CH2OH
24 000 cm3.)
A 8000 cm3 C CH3CHCHOH
B 48 000 cm3 D CH2CHCH2OH
C 576 000 cm3
Use the key below to answer Questions 8 to 10.
D 1152 000 cm3
Chapter 13 Hydrocarbons

A B C D
4 Students were asked to describe the electrophilic
1, 2 & 3 1, 2 2, 3 1 only
addition mechanism when ethene reacts with correct correct correct correct
bromine using curly arrows and showing all
relevant dipoles. One student’s response is shown 8 Ethane reacts with Cl2 in the presence of UV light.
below. The initiation step in the mechanism is Cl2 → 2Cl . ·
Which of the following correctly represent a possible
H H H H H H
propagation or termination step in the mechanism?
C C
·
H C C H H C C H
+ 1 2CH3CH2 → CH3CH2CH2CH3
H H
Br
Br Br Br
· ·
2 CH3CH2 + Cl → CH3CH2Cl
Br –
·
3 Cl + CH3CH3 → CH3CH2Cl + H ·
222 Br δ–

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 Practice questions
9 Which of the following statements about the 14 a) Name the following alkenes:
reactions of 2-methylpropene are correct? H H H CH3 H3C CH3
1 It reacts with hydrogen to form a saturated
hydrocarbon with empirical formula C2H5. C C C C C C
2 When it reacts with steam in the presence of H A CH3 H B CH3 H C CH3
an acid catalyst one of the products obtained
is a tertiary alcohol.
3 It has a higher boiling point than but-1-ene. H3C CH3 H Br F F

10 Which of the following statements is correct? C C C C C C

1 When HBr reacts with but-1-ene the major H3C CH3 H CH3 F CH3
D E F
product is 2-bromobutane.
2 But-1,2-diene, CH2CHCHCH2 reacts
with steam to form
HOCH2CH(OH)CH(OH)CH2OH.
3 Cyclobutane, C4H8, reacts with H2(g) in the G H I
presence of a Ni catalyst.
b) What is the empirical formula of compounds
11 Name each of the following: A–C?
a) c) What is the molecular formula of
compound D?
H CH3 H H
H d) What is the molecular formula of
H3C C C C CH3 H3C C C C compound I?
H
e) What is the empirical formula of all alkenes
H H H H H with one double bond? (13)
W X
15 a) Explain why the disposal of polymers made
H CH3 H H H H
from alkenes is problematic.
H C C C H HO C C C OH
b) Explain why polymers made from alkenes are
good insulators. (2)
H CH3 H H H H 16 Explain how waste polymers are likely to be
Y Z
treated in the future in order to reduce damage
b) Name the following: to the environment. (4)
CH3CHBrCH3, CH3CHCHCH3, (CH3)4C and 17 a) What is meant by electronegativity?
H3CCH2CH(CH3)CH2CH3. (2) b) Explain why alkanes are unreactive. (2)
12 Explain each of the following terms: 18 Explain what is meant by the term ‘electrophile’.
a) radical Write a balanced equation and the
b) homolytic fission mechanism for the reaction between
c) initiation bromine and cyclohexene, C6 H10. Use
d) propagation curly arrows to show the movement of
e) termination electrons. Show any relevant dipoles and
f) substitution. (6) lone pairs of electrons. (6)
13 a) Write the balanced equation and the
mechanism for the reaction between:
i) propane and bromine
i) cyclobutane and chlorine.
b) Explain why more than one organic product is
formed in each reaction. (11)

223

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 19 The diagram below shows three important 22 The unsaturated compound cyclohex-1,4-diene, C6H8,
reactions of ethene. reacts with an excess of HBr to produce a saturated
compound with molecular formula C6H10Br2.
H2/Ni
CH3CH3 CH2=CH2 CH3CH2OH Draw and name all possible isomers of
Reaction 1 ethene Reaction 2 C6H10Br2. (6)

Reaction 3 23 The action of the bacterium Clostridium

acetobutylicum on biomass, such as sugar beet,
poly(ethene) wheat or straw, is used to produce compound X,
a) i) What conditions of temperature and which is a fuel. The fuel, X, can produce almost as
pressure are used in Reaction 1? much power as petrol, although it cannot be used in
ii) Reaction 1 is used to convert a pure form because it exists as a gel below 25.5 °C.
unsaturated alkenes to saturated alkanes. a) A sample of X contained the following
What is meant by the terms unsaturated elements by mass: carbon 64.9%, hydrogen
and saturated in this context? 13.5%, oxygen 21.6%. Calculate the empirical
iii) Why are saturated and unsaturated formula of X.
chemicals important to dieticians and b) When X is vaporised, it is found that 0.2 g of
nutritionists? X has a volume of 65 cm3 measured at room
b) i) What chemicals are used to produce temperature and pressure. Calculate the
CH3CH2OH in Reaction 2? molecular formula of X.
ii) A common name for CH3CH2OH is c) Compound X reacts with concentrated
alcohol. What is its systematic name? sulfuric acid and a hydrocarbon, Y, is formed
iii) What is the major use of CH3CH2OH that contains the same number of carbon
from Reaction 2? atoms as X. When bubbled into aqueous
c) Draw a section of the poly(ethene) structure bromine, the bromine is decolorised.
that consists of three monomer units. Compound Y could be one of four isomers.
d) State four properties of poly(ethene) that i) Draw the displayed formulae of these isomers.
make it particularly suitable for making plastic ii) Choose one of the isomers and write a
bags. (12) balanced equation for its reaction with
bromine.
20 Calculate the formulae of alkanes A, B, and C. d) Compound Y reacts with hydrogen to give an
a) When 100 cm3 of alkane A is burned in unbranched hydrocarbon, Z.
excess oxygen, 300 cm3 carbon dioxide gas i) Give the conditions for the reaction of
and 400 cm3 water (steam) are produced. compound Y with hydrogen.
Calculate the formula of alkane A. ii) Name hydrocarbon Z.
b) When burned, 0.1 mol of alkane B produces e) When compound Y reacts with steam, two
10.8 g of water. Calculate the formula of alkane B. products are obtained, one of which is X.
c) When 60 cm3 of alkane C reacts with 700 cm3 i) Give the structural formulae of the two
of oxygen (an excess) and is cooled to room products.
temperature, a gaseous mixture with a volume ii) The functional group of X is at the
of 460 cm3 is produced. When this gaseous end of its carbon chain. Name
mixture is passed through limewater, the compound X. (14)
Chapter 13 Hydrocarbons

volume is reduced to 40 cm3.

i) Deduce the volume of carbon dioxide gas Challenge
in the mixture. 24 Pent-1,4-diene, CH2CHCH2CHCH2 reacts at high
ii) Deduce the volume of oxygen gas used temperature and pressure with steam in the
in the reaction. presence of suitable acid catalyst. A mixture of
iii) Calculate the formula of alkane C. Write alcohols is formed, each alcohol having molecular
a balanced equation for the reaction.(12) formula C5H12O2.
21 Alkenes can undergo polymerisation. Write a) Draw and name all possible diols that could
an equation to show the polymerisation of be formed.
cyclohexene. Draw two repeat units of the b) Suggest which is the major product. Justify
polymer. (3) your answer. (10)
224

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 Chapter 14
Alcohols and haloalkanes
Prior knowledge
In this chapter it is assumed that you are familiar with:
● electronegativity and dipoles
● intermolecular bonds such as hydrogen bonds and induced dipole–dipole

interactions
In organic chemistry the bonds that hold the carbon-based molecules
together are covalent bonds. These bonds are strong bonds and are usually
only broken when a chemical reaction occurs. If two different atoms
with different electronegativity are covalently bonded the bond becomes
polarised and dipoles are formed. As well as the bonds within a molecule
there are also bonds that form between molecules. These are called
intermolecular forces and are relatively weak and can be broken by physical
processes such as melting or boiling.

Test yourself on prior knowledge

1 Define electronegativity.
2 The electronegativity of H = 2.1 and of Cl = 3.0. Explain, with the aid of a
diagram, the bonding in a hydrogen chloride, HCl, molecule.
3 Explain, with the aid of a diagram, the intermolecular forces in water.
4 Draw two molecules of ammonia, NH3, and show how hydrogen bonds
are formed between the two ammonia molecules.
5 a) Write equations for the manufacture of ethanol by:
i) fermentation
ii) hydration.
b) Calculate the atom economy for each manufacturing process.
c) Suggest which manufacturing process is more sustainable. Explain
your answer.

This chapter covers the reactions of two more homologous series:

alcohols and haloalkanes.

Alcohols
A molecule of an alcohol contains the hydroxy group, –OH. The names
CH3
of all alcohols end with -ol. Molecules of many naturally occurring
Figure 14.1 Menthol CH compounds, such as carbohydrates, pheromones, vitamins and steroids,
is a naturally CH2 contain an –OH group.
H2C
occurring alcohol
that is extracted H2C CH
from mint oils. It has
CH OH
Classification of alcohols
local anaesthetic and
All alcohols contain a carbon atom bonded to a hydroxy group, C–OH.
anti-irritant properties
and is used to relieve
CH They are classified as primary, secondary or tertiary alcohols:
minor throat irritation. H3C CH3
225

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 Table 14.1 Alcohol classification.

Primary alcohol Secondary alcohol Tertiary alcohol

H CH3 CH3

H3C C OH H3C C OH H3C C OH

H H CH3
Tip The carbon atom bonded The carbon atom bonded The carbon atom bonded
R, R′ and R′′ are used to to the –OH group is to the –OH group is to the –OH group is
bonded to only one other bonded to two carbon bonded to three carbon
represent groups other than –H.
carbon atom atoms atoms

Test yourself
1 Draw, name and classify as primary, secondary or tertiary the alcohols
with molecular formula C4H9OH.
2 Draw, name and classify as primary, secondary or tertiary the alcohols
with molecular formula C5H11OH.
3 Classify each of the following as either primary, secondary or tertiary.
Give the systematic name of each alcohol.
OH
OH OH
a) b) c)

d) e)

OH
OH

Physical properties of alcohols

The simplest alcohols are liquids at room temperature and are miscible
with water. Alcohols have relatively high boiling and melting points. This
can be explained in terms of hydrogen bonding (page 108). A hydrogen
bond forms between the lone pair of electrons on the oxygen in the –
OH group in one alcohol molecule and the hydrogen in the –OH group
in an adjacent alcohol molecule:
Chapter 14  Alcohols and haloalkanes

H3C
•• δ–
O
••

Hδ+

δ+ •• δ–
H O
••

CH3

Boiling point and melting point

When alcohols are boiled (or melted), energy is required to break the
intermolecular forces. All substances, including alcohols, have induced
dipole–dipole interactions that help bind the molecules together.
226

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 Alcohols
Tip In addition, alcohol molecules have hydrogen bonds. Hydrogen bonds are
the strongest of the intermolecular forces, so more energy is required
Volatile compounds easily to break them than to overcome induced dipole–dipole interactions.
change from liquid to gas. Hydrogen bonding decreases the volatility and, therefore, results in an
Compounds with low volatility increase in boiling point.
have high boiling points.
Miscibility with water
Methanol and ethanol are freely miscible (mix together to make a
single layer) with water. When mixed, some of the hydrogen bonds in
the individual liquids are broken, but they are then replaced by new
hydrogen bonds between the alcohol and water:
H3C
δ–
O

••
••
Hδ+

δ+
H
δ– δ+ •• δ–
O H O

••
••
••
CH3
H

As the relative molecular mass of the alcohol increases, the miscibility

with water decreases.

Reactions of alcohols
Alcohols are more reactive than alkanes because the C–O and O–H
bonds are both polar bonds.
δ+ δ− δ− δ+
C O O H

Combustion
Tip Alcohols burn to produce carbon dioxide and water. The reactions are
When balancing the equation, exothermic, releasing large amounts of energy:
don’t forget to include the CH3OH + 1 1 2 O2 → CO2 + 2H2O
oxygen in the alcohol.
C2H5OH + 3O2 → 2CO2 + 3H2O

Oxidation
Tip Primary and secondary alcohols can be oxidised to produce either an
aldehyde, a ketone or a carboxylic acid. Tertiary alcohols do not readily
The structures of aldehydes, undergo oxidation.
ketones and carboxylic acids
are explained fully on pages 228
and 229. primary
aldehyde
carboxylic
alcohol acid

secondary
ketone
alcohol

tertiary resistant to
alcohol oxidation

227

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 Oxidation of an alcohol can only occur if the C bonded to the O–H is
also bonded to at least one H atom.
H CH3 CH3

H 3C C O H H3C C O H H3C C O H

H H CH3
primary alcohol can be secondary alcohol can be tertiary alcohol cannot be
oxidised because there oxidised because there oxidised because there is
are two H attached to the is one H attached to the no H attached to the
C bonded to the OH C bonded to the OH C bonded to the OH

The most common oxidising agent is an acidified solution of

potassium dichromate, K2Cr2O7. The acidified dichromate(vi),
H+/Cr2O72–, is a bright orange solution which turns dark green
when an alcohol is oxidised.
Balanced equations for the oxidation of alcohols can be
written using [O] to represent the oxidising agent. The
equations for the oxidation of a primary alcohol to an
aldehyde or a secondary alcohol to a ketone are similar in
that water is always formed:
● primary alcohol + [O] → aldehyde + water
● secondary alcohol + [O] → ketone + water
Figure 14.2 Result of warming two alcohols, one primary Aldehydes and ketones both contain the carbonyl, CO,
and the other tertiary with an acidic solution of potassium
dichromate(vi). The orange dichromate(vi) is reduced to
group: O
green chromium(ii) ions when there is a reaction. Tertiary
alcohols do not react with potassium dichromate(vi). C

● aldehydes – the carbonyl group is on the end of the carbon chain

● ketones – the carbonyl group is not on the end of the carbon chain.
H H O H O H

H C C C H C C C H

H H H H H
propanal propanone
(an aldehyde) (a ketone)

Oxidation of a primary alcohol to an aldehyde

Chapter 14  Alcohols and haloalkanes

Methanol is oxidised to methanal:

CH3OH + [O] → HCHO + H2O
methanol methanal
Ethanol is oxidised to ethanal:
CH3CH2OH + [O] → CH3CHO + H2O
ethanol ethanal
Oxidation of a secondary alcohol to a ketone
Propan-2-ol is oxidised to propanone:
CH3CH(OH)CH3 + [O] → CH3COCH3 + H2O
propan-2-ol propanone

228

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 Alcohols
Tip Pentan-2-ol is oxidised to pentan-2-one:

When balancing oxidation CH3CH2CH2CH(OH)CH3 + [O] → CH3CH2CH2COCH3 + H2O

reactions, count the [O] which pentan-2-ol pentan-2-one
has to be balanced alongside any
other oxygens in the equation. Further oxidation of a primary alcohol to a carboxylic acid
After an aldehyde has been formed by the oxidation of a primary alcohol,
a further oxidation step can take place. The product is a carboxylic acid
which contains the COOH functional group. Balanced equations for the
oxidation of a primary alcohol to a carboxylic acid can be represented as:
primary alcohol + 2[O] → carboxylic acid + water
Methanol can be oxidised to methanoic acid:
Tip CH3OH + 2[O] → HCOOH + H2O
In an oxidation reaction water methanol methanoic acid
will always be formed along
with an aldehyde or a ketone or Ethanol can be oxidised to ethanoic acid:
a carboxylic acid. Hydrogen, H2, CH3CH2OH + 2[O] → CH3COOH + H2O
will never be formed.
ethanol ethanoic acid
Apparatus used in the oxidation of alcohols
Organic compounds are volatile and reactions are often carried out under
reflux or by distillation. A primary alcohol can be oxidised to form either an
aldehyde or a carboxylic acid and the product depends on the apparatus used.

reflux
condenser

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

Figure 14.4 Reflux ensures

that any volatile aldehyde
propanal condenses and flows back
into the flask, where excess
Figure 14.3 Distillation allows the aldehyde to distil off as it is formed oxidising agent ensures
which prevents formation of the carboxylic acid by further oxidising complete oxidation to form
the aldehyde. the carboxylic acid.
If ethanol is oxidised, either ethanal or ethanoic acid can be produced.
The boiling point of:
● ethanol, CH3CH2OH, is 78 °C
● ethanal, CH3CHO, is 21 °C
● ethanoic acid, CH3COOH, is 118 °C.
The product depends on the apparatus used. 229

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 Oxidation of ethanol to ethanal
The distillation process involves evaporation followed by condensation,
which allows the most volatile component to be separated. When
ethanol is heated with a mixture of potassium dichromate(vi) and
sulfuric acid in a distillation apparatus (Figure 14.3), the volatile
component evaporates first. Ethanal has the lowest boiling point
and, therefore, vaporises most readily. The condenser has cold water
circulating in the outer sleeve, so when the ethanal reaches the
condenser, it condenses and is separated from the reaction mixture and
can be collected.
Oxidation of ethanol to ethanoic acid
Reflux involves a process of continuous evaporation and condensation,
which prevents volatile components from escaping.
As with the distillation, when the reaction mixture is heated the most
volatile component vaporises first. Ethanal has the lowest boiling point and is
vaporised most readily. The vertical reflux condenser has cold water circulating
in the outer sleeve. When the ethanal reaches the condenser, it condenses
and falls back into the oxidising mixture. Therefore, it is not separated from
the reaction mixture. The ethanal is oxidised further to form ethanoic acid.

Elimination or dehydration
When reacted with hot, concentrated sulfuric acid or hot pumice/Al2O3,
an alcohol is dehydrated to form an alkene.
H H
H H
H C C H C C + H2O
H H
H OH
loss of H2O

H H
H H
H3C C C H C C + H2O
H3C H
H OH
loss of H2O
Chapter 14  Alcohols and haloalkanes

Figure 14.5 Elimination reaction: ethanol loses water to become ethene, and
propan-1-ol is dehydrated to form propene.

For alcohols such as butan-2-ol, water can be lost in two ways:

H H H H

H3C C C CH3 H3C C C CH3 + H2O

but-2-ene
H OH
loss of water
H H H H

H3C C C CH2 H3C C C CH2 + H2O

H H OH H
loss of water but-1-ene
230 Figure 14.6 Losing water from butan-2-ol produces but-2-ene or but-1-ene.

9781471827068_OCR_A_Level_Chemistry.indb 230 30/03/15 2:48 PM

 Alcohols
Tip Both the E- and Z-versions of but-2-ene can be formed.

The elimination reaction of The CC bond is formed by an elimination reaction. In this case,
butan-2-ol is often used in the water is eliminated and the reaction could also be described as a
examinations because it is dehydration reaction.
possible to form three different
isomers: but-1-ene, E-but-2-ene Substitution with halide ions
and Z-but-2-ene. Primary, secondary and tertiary alcohols all react with a halide ion (Br–)
in the presence of an acid (H+). The haloalkane is produced by reacting
the alcohol with NaBr/H2SO4.
NaBr/H2SO4
H3C OH + Br– + H+ H 3C Br + H 2O

H H
NaBr/H2SO4
H3C C OH + Br– + H+ H3C C Br + H O
2

CH3 CH3

CH3 CH3
NaBr/H2SO4
H3C C OH + Br– + H+ H3C C Br + H2O

CH3 CH3

Test yourself
4 Explain, with the aid of equations, why the hydration of propene produces
a mixture of alcohols but the hydration of but-2-ene produces a single
alcohol.
5 Write equations for the reaction of pentan-1-ol when:
a) burnt with excess O2(g)
b) refluxed with acidified potassium dichromate
c) heated with concentrated sulfuric acid
d) distilled with acidified potassium dichromate
e) reacts with NaBr in the presence of concentrated sulfuric acid.

Ester formation
All alcohols, primary, secondary and tertiary, can react with carboxylic
acids to form esters. This is covered fully in Module 6, Carboxylic acids
and derivatives of the A level book. The equation for the formation of an
ester is given below.
O conc H2SO4 O
loss of water
R C R C
catalyst
O H H O R O R H O H

carboxylic ester
alcohol water
acid

231

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 Haloalkanes
A haloalkane is a compound in which one or more hydrogen atoms of
an alkane is replaced by a halogen atom. If one hydrogen is replaced,
the general formula is CnH2n+1X (where X = F, Cl, Br or I).
Like alcohols, haloalkanes are subdivided into primary, secondary
and tertiary (Table 14.2). The rules for classification are the same. If
the carbon atom that is bonded to the halogen (X) is bonded to one
carbon atom only, then the compound is a primary haloalkane. If the
carbon atom in the C–X bond is bonded to two other carbon atoms,
the compound is a secondary haloalkane; if it is bonded to three other
carbon atoms, the compound is a tertiary haloalkane.

Table 14.2 Classification of haloalkanes.

Primary haloalkane Secondary haloalkane Tertiary haloalkane

H CH3 CH3

H3C C Cl H3C C Cl H3C C Cl

H H CH3

There are four structural isomers of C4H9Cl: two are primary, one
secondary and one tertiary.

H H H H H H H H

H C C C C H H C C C C H

primary secondary
H H H Cl H H Cl H

H H

H C H H C H

H H H H

H C C C H H C C C H
primary tertiary
H H Cl H Cl H

Figure 14.7 Structures of the isomers of C4H9Cl.

Chapter 14  Alcohols and haloalkanes

Primary, secondary and tertiary haloalkanes behave similarly. They

react with the same reagents, but the rate at which they react differs.
The rate of reaction depends on the strength of the C–X bond.
Tertiary haloalkanes react faster than secondary haloalkanes; primary
haloalkanes react most slowly. This indicates that the C–X bond in
a tertiary haloalkane is the weakest and the C–X bond in a primary
Key term haloalkane is the strongest.

Hydrolysis is a reaction that

involves water and results in the
Substitution reactions of haloalkanes
organic compound being split
and two new products being
Hydrolysis
formed. The substitution reactions of haloalkanes with water are examples of
hydrolysis.
232

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 Haloalkanes
The word ‘hydrolysis’ comes from: ‘hydro’, which is related to water, and
‘lysis’, which means splitting. So the term hydrolysis is used to describe
any reaction in which water causes another molecule to split apart.
Hydrolysis reactions are often catalysed by acids or alkalis. They are also
often substitution reactions in which the chemical attack is by water
molecules (or hydroxide ions).
Hydrolysis of haloalkanes using water is very slow and results in the
replacement of the halogen with –OH groups to form alcohols.
CH3CH2I(l) + H2O(l) → CH3CH2OH(l) + H+(aq) + I –(aq)
The hydrolysis reaction is much quicker in the presence of an alkali
catalyst, :OH –. When a primary haloalkane is heated under reflux with
an aqueous solution of an alkali (e.g. sodium hydroxide or potassium
hydroxide), the haloalkane is hydrolysed to a primary alcohol.
Reagent: sodium (or potassium) hydroxide (an alkali is required)
Conditions: the solvent must be water and the reaction mixture
must be heated under reflux
Key term
Equation: CH3CH2Br + NaOH → CH3CH2OH + NaBr
A nucleophile is an ion or molecule
that is an electron-pair donor
and can form a new covalent
Nucleophilic substitution of primary halogenoalkanes
bond. The carbon–halogen bond is polar, Cδ+–Halδ–. The charge separation
leaves the carbon atom open to attack by a nucleophile.
Common nucleophiles include OH –, �NH3, – CN and H2O.
Key term The reaction is a substitution reaction. The general equation for the
A substitution reaction is a reaction is:
reaction in which an atom or a R—X + :Nu– → R—Nu + :X–
group of atoms is replaced by
another atom or group of atoms. Nucleophilic substitution of a primary haloalkane is described by the
following general mechanism:
H CH3
CH3 –
δ+ δ− –
H3C C Cl HO C H + Cl
••

HO C Cl
H H H H
OH– intermediate in which the
••

nucleophile nucleophile starts to bond

to the C as the Cl starts to
break away from the C

The nucleophile approaches the Cδ+ in the Cδ+ —Xδ– from the opposite
side to the halogen. This is sometimes referred to as ‘backside attack’.
An intermediate is formed that involves both the haloalkane and the
nucleophile. The carbon–halogen bond is partially broken and the
carbon–nucleophile bond is partially formed. The carbon–halogen bond
then breaks to form the product and a halide ion.
The mechanism for the nucleophilic substitution of a primary amine can
be simplified to:
H H
δ+ δ−
–
H3C C Cl H3C C OH + Cl
••

H H
OH– 233
••

nucleophile

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 Trend in rates of hydrolysis of primary haloalkanes
The rate of hydrolysis is different for different haloalkanes. The rate of
reaction can be compared by carrying out the reaction in the presence
of silver ions. The halogen atoms in haloalkanes are covalently bonded
to carbon and give no precipitate of a silver halide. Hydrolysis releases
halide ions, which immediately precipitate as the silver halide.
The rate of reaction can be monitored in one of two ways:
Method 1
The haloalkane is mixed with water and a small amount of aqueous
silver nitrate solution containing some ethanol in a water bath at 60 °C.
The water can act as a nucleophile (using a lone pair of electrons on
its oxygen atom), but the reaction is slow. As the hydrolysis reaction
occurs, the halide ion is displaced and reacts with the Ag+ ions to give
a precipitate. By monitoring the rate at which the precipitate appears,
it is possible to deduce the rate of hydrolysis. The ethanol is added to
aid better mixing of the reagents since, although haloalkanes and water
are immiscible (i.e. they form separate layers when mixed), they both
dissolve in ethanol. The ethanol may also be involved as a nucleophile. If
a comparison has to be made between haloalkanes, the conditions have
to be carefully controlled.
Method 2
The haloalkane is reacted with excess sodium hydroxide for a fixed
period of time. The excess sodium hydroxide is then neutralised by
the addition of nitric acid, HNO3. Aqueous silver nitrate, AgNO3, is
added and the density of the precipitate is monitored (Figure 14.9). The
neutralisation by nitric acid is essential to avoid a precipitate of silver
oxide being formed. The experiment is repeated for other fixed periods
of time.
acidify with add a few drops of
dilute nitric acid silver nitrate solution

NaOH(aq) AgCl(s): white

plus a drop AgBr(s): cream
of the hot AgI(s): yellow
halogenoalkane
Chapter 14 Alcohols and haloalkanes

water
heat

hydrolysis acidification precipitation

Figure 14.9 Hydrolysis of halogenoalkanes makes it possible to distinguish between
chloro-, bromo- and iodo-compounds. Heating the compound with an alkali releases
halide ions. Acidifying with nitric acid and then adding silver nitrate produces a
precipitate of the silver halide.

Reactivity of haloalkanes
When 1-chlorobutane, 1-bromobutane and 1-iodobutane are reacted
under identical conditions, 1-iodobutane reacts the fastest and
1-chlorobutane reacts the slowest. This may seem surprising, since the
dipole is greatest for C–Cl and least for C–I such that the nucleophile
has the strongest attraction to the carbon atom in a chloroalkane.
234

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 Haloalkanes
Table 14.3 Bond enthalpies of carbon– However, the other factor that determines the rate of the reaction is the
halogen bonds. strength of the carbon–halogen bond. Bond strengths (enthalpies) are
Bond Bond enthalpy/kJ mol–1 listed in Table 14.3.
C–F 467 The C–I bond is the weakest and the least energy is required to break it.
C–Cl 340 The C–F bond is so strong that it rarely undergoes hydrolysis.
C–Br 280 The strength of the carbon–halogen bond is the dominant factor
C–I 240 in determining rates of reaction of haloalkanes. For example, when
1-chlorobutane, 2-chlorobutane and 2-chloro-2-methylpropane are
reacted under identical conditions, 2-chloro-2-methylpropane reacts most
Tip quickly and 1-chlorobutane reacts most slowly. This can be explained by
comparing the relevant carbon–chlorine bond enthalpies (Table 14.4).
The comparison of primary,
secondary and tertiary is not in The C–Cl bond in the tertiary chloroalkane is the weakest and, therefore,
the specification and you will requires the least amount of energy to break it. The C–Cl bond in the
not be tested on it. primary chloroalkane is the strongest, so the primary chloroalkane is the
most difficult to hydrolyse.

Table 14.4 Carbon–chlorine bond enthalpies in primary, secondary and tertiary

chloroalkanes.

Bond Bond enthalpy/kJ mol–1

C–Cl (primary) in 1-chlorobutane 340
C–Cl (secondary) in 2-chlorobutane 331
C–Cl (tertiary) in 2-chloro-2-methylpropane 289

Environmental concerns from use of organohalogen

compounds
Haloalkanes are used in the preparation of a wide range of products,
including pharmaceuticals (such as ibuprofen) and polymers (such as
PVC and PTFE). Haloalkanes are also used in industry as solvents and
lubricants.
Table 14.5 shows three complex halogenated compounds and their uses,
other than in the manufacture of the plastics PVC and PTFE.

Table 14.5 Complex halogenated compounds and their uses.

Compound Structure Use

Halothane Cl F Anaesthetic

H C C F

Br F

Thyroxine I I Thyroid hormone

COOH
HO O CH2 CH
NH2
I I

Dichlorodiphenyltrichloromethane H Insecticide used only as a last

resort because it is harmful to
Cl C Cl wildlife
CCl3

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 CFCs
Haloalkanes were used to produce chlorofluorocarbons (CFCs), such as
dichlorodifluoromethane, CF2Cl2, and trichlorofluoromethane, CFCl3.
Their role in the destruction of the ozone layer is discussed below.
The use of CFCs has been phased out. However, it is worth appreciating
why they were originally chosen for use in air conditioning, refrigeration
units and aerosols.
Figure 14.10 CFCs were commonly used These applications require a liquid of suitable volatility that can be
as the propellant in aerosols. readily evaporated and re-condensed. In addition, the liquid must be
unreactive, non-flammable and non-toxic. CFCs fit these criteria and
they were, therefore, considered to be safe and environmentally friendly.
However, it is these properties that make them so persistent in the
atmosphere. At the time of their introduction, the dangerous effect they
would have in the stratosphere was not understood. The manufacture
of CFCs was banned by the Montreal Protocol in 1987 and chemists
worked to find alternatives.
Much effort was put into the development of hydrochlorofluorocarbons,
HCFCs, which introduced hydrogen, making HCFCs less stable and
more likely to break down before reaching the ozone layer. However,
Figure 14.11 CFCs were commonly used
as a refrigerant and still present a problem when HCFCs do break down chlorine radicals are still produced. Current
in the disposal of old fridges. thinking is to use hydrocarbons, but chemists are also developing
hydrofluorocarbons, HFCs, which contain a C–H bond and therefore
degrade in the atmosphere but contain no chlorine so they do not
directly affect stratospheric ozone. The exact nature of the products
of HFC degradation is not fully understood and they may have other
harmful environmental effects.

The ozone layer

Oxygen normally exists as an O2 molecule, but oxygen atoms can also
combine to form ozone, O3. The structure of ozone can be represented
as follows:
double
covalent dative
bond covalent
•• bond
••
••
••
Chapter 14  Alcohols and haloalkanes

O O
••
••
••

O
••

••

O O
O

Ozone is a reactive gas that does not occur normally in the atmosphere
close to the Earth’s surface. However, some 25 km higher up, in the
stratosphere, there is a layer of ozone approximately 15 km deep. This
may sound substantial, but it would have a depth of no more than
3 mm if it existed at lower altitudes, where the atmospheric pressure
is much greater. The ozone layer is important because it absorbs much
of the harmful ultraviolet radiation emitted by the Sun. If this were to
reach the surface of the Earth, it would cause an increase in sunburn
and skin cancers in humans.
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 Haloalkanes
In the stratosphere, ozone is in equilibrium with oxygen:
O3  O2 + O
ozone oxygen molecule oxygen radical
At high altitude the oxygen radical, O, is formed from oxygen molecules:
uv
O2 O+O
An oxygen radical then reacts with an oxygen molecule to produce a
molecule of ozone:
O2 + O → O3

Causes of the hole in the ozone layer

It was a shock when it was discovered, during a polar spring season,
that the ozone layer above the Antarctic had thinned to the point
where a hole had developed. This discovery showed how important the
Tip management of the atmosphere is.

You should appreciate the Chlorine radicals

similarity between this The main cause of the hole in the ozone layer is almost certainly
mechanism and the reactions of chlorine radicals, created by the homolytic fission of a covalent bond.
alkanes with free radicals. One source of chlorine-containing chemicals in the atmosphere is CFCs.
Chlorine radicals attack the ozone layer, as shown below.
Mechanism of action of chlorine radicals
First, there is an initiation step resulting in the formation of a chlorine
radical, Cl·. This is most likely to be the result of the breaking of a C–Cl
bond in a CFC such as C2F2Cl2.
Initiation: C2F2Cl2 → C·2F2Cl + Cl·
The chlorine radical is then involved in the propagation steps:
Propagation: Cl· + O3 → ·ClO + O2
Propagation: ·ClO + O → Cl· + O2
The net reaction of the two propagation steps can be written as
O3 + O → 2O2 and the chlorine radical, Cl·, used in the first propagation
step but regenerated in the second, can be regarded as a catalyst. It
has been estimated that approximately 1000 ozone molecules could be
destroyed as the result of the production of a single chlorine radical.
The sequence is terminated only if the chlorine radical combines with
another radical to remove it from the propagation sequence.
Nitrogen(ii) oxide (NO)
Compounds that contain a C–Cl bond are not alone in supplying radicals
that initiate reactions responsible for the destruction of the ozone layer.
Of growing concern is the role of nitrogen monoxide. Thunderstorms are
a major source of this gas, as lightning causes nitrogen and oxygen to
combine:
N2(g) + Os(g) → 2NO(g)

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 Nitrogen monoxide is also produced by the high-temperature
combustion of nitrogen and oxygen that occurs to a small extent in
internal combustion engines. More significantly, it is present in the
exhaust gases of aircraft.
Complex reactions in the atmosphere may result in most of this gas
being removed. For example, some may be oxidised and combine
with moisture to create nitric acid, which is a contributor to acid
rain. However, a small amount of nitrogen monoxide migrates to the
stratosphere, where it attacks the ozone layer in a series of reactions
analogous to those of the chlorine radical. There is no initiation step,
because nitrogen monoxide already possesses an ‘unpaired’ single
electron.
nitrogen double
monoxide covalent
radical bond

•• ••

••
single
O N • unpaired

••

••
electron

O N•

The propagation steps are as follows:

·NO + O3 → ·NO2 + O2
·NO2 + O → ·NO + O2
The net reaction of the two propagation steps can again be written as
O3 + O → 2O2 and the nitrogen monoxide radical, NO, which used in
the first propagation step but regenerated in the second can be regarded
as a catalyst.

Activity
Alternatives to CFCs

Table 14.6 Alternatives to CFCs.

Formula Type of compound Boiling point/°C Flammable Ozone depleting Global warming
potential potential over 100 years
Chapter 14  Alcohols and haloalkanes

CCl3F CFC-11 24 No 1.0 4600

CCl 2F2 CFC-12 –30 No 1.0 7300
CHClF2 HCFC-22 –41 No 0.05 1700
CF3CCl 2H HCFC-123 +29 No 0.02 100
CH2F2 HFC-32 –51.6 No 0 650
CF3CH2F HFC-134a –26.6 No 0 1300
CH4 Alkane – Yes 0 23
C 3H 8 R-290 –42 Yes 0
CO2 R-744 Liquid under pressure No 0 1
NH3 R-717 –33 Yes 0 0

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 Haloalkanes
  1 What is the chemical name for HFC-134a?
  2 Draw ‘dot-and-cross’ diagrams for these two compounds:
a) CFC-12
b) ammonia.
  3 Suggest reasons why CFC-12 and ammonia have similar boiling points.
  4 Suggest reasons why ammonia is much more chemically reactive
than CFC-12.
  5 What properties made CFC-12 suitable as a replacement for
ammonia as a refrigerant?
  6 Refrigerators and air-conditioning units keep the working fluid in a
sealed system. Even so, the refrigerants continue to cause environmental problems. Suggest reasons why.
  7 Suggest reasons why ammonia is now being reintroduced as a
refrigerant.
  8 The HCFCs and HFCs have been introduced as replacements for
CFCs. They are now being phased out. Suggest why.
  9 Carbon dioxide from burning fuels is an environmental problem,
yet when it is used as a blowing agent or propellant, it is classified as having minimal global warming potential.
How do you account for this?
10 Suggest disadvantages of using propane as an aerosol propellant
for spray paints.

Test yourself
  6 Draw, name and classify the four structural isomers of C4H9Cl.
  7 Which of the following are non-polar: CH3Br, CH2Br2, CHBr3 and CBr4.
Explain your answer.
  8 Describe a chemical test for a haloalkane.
  9 The manufacture of PVC is a three-stage process:
• ethene reacts with chlorine
• 1,2-dichloroethane is heated strongly to chloroethene and hydrogen
chloride
• chloroethene is polymerised.
a) Write equations for the manufacture of PVC.
b) Explain the problems of disposal of PVC.
10 Iodopropane is hydrolysed by aqueous sodium hydroxide.
a) Write an equation for the reaction.
b) Write the mechanism for the reaction. Show curly arrows, relevant
dipoles and lone pairs of electrons.

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 Practice questions
Multiple choice questions 1–10 6 Which of the following is a propagation step
1 Haloalkanes such as CH3CH2Cl, CH3CH2Br and when chlorine radicals react with ozone?
CH3CH2I can be hydrolysed but the rate of ·
A Cl + O3 → ClO2 + O
hydrolysis varies. ·
B Cl + O2 → ClO + O
Which of the following statements is true? ·
C ClO + O → Cl + O2·
A CH3CH2I would be the fastest because the ·
D ClO2 + O → Cl + O3·
C–halogen bond has the biggest dipole. Use the key below to answer Questions 7 to 10.
B CH3CH2Cl would be the fastest because the
A B C D
C–halogen bond has the biggest dipole.
C CH3CH2I would be the fastest because it has 1, 2 & 3 1, 2 2, 3 1 only
correct correct correct correct
the weakest C–halogen bond.
D CH3CH2Cl would be the fastest because it has 7 Which of the following when fully oxidised will
the weakest C–halogen bond. form a molecule containing three atoms of
2 Which one of the following is not readily oxygen?
oxidised? 1 2-methylbutan-2,3-diol
A pentan-2-ol 2 2-methylbutan-1,2-diol
B pentan-3-ol 3 3-methylbutan-1,2-diol
C 2-methylbutan-2-ol 8 Which of the following can be dehydrated to give
D 3-methylbutan-2-ol 2-methylpropene as one of the products of the
3 When pentan-2-ol is dehydrated, which one of reaction?
the following is the number of isomers formed? 1 2-methylpropan-1-ol
A 1 B 2 2 2-methylpropan-2-ol
C 3 D 4 3 2,2 dimethylpropan-1-ol

4 The correct systematic name of this compound is: 9 Which of the following statements is correct?
1 If AgNO3(aq) is added to CH3CH2Br a cream
H Cl Cl H precipitate is formed that dissolves in dilute
H C C C C H aqueous ammonia.
2 When AgNO3(aq) is added to CH3CH2Br the
H H H nitrate ion, NO3–(aq) behaves as a nucleophile.
H C H 3 If AgNO3(aq) is added to CH3CH2Br a cream
H C H precipitate is formed only after hydrolysis has
occurred.
H
10 Butane-1,3-diol could be oxidised to form:
A 2,3-dichloro-2-ethylbutane
Chapter 14 Alcohols and haloalkanes

1 an aldehyde
B 2,3-dichloro-3-ethylbutane 2 a ketone
C 3,4-dichloro-2-methylpentane 3 a carboxylic acid.
D 2,3-dichloro-3-methylpentane.
5 A compound with the formula CnH2n+2O
when fully oxidised forms a compound
CnH2n+1O.
CnH2n+ 2O is likely to be
A a primary alcohol
B a secondary alcohol
C an aldehyde
D a ketone

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 Practice questions
11 a) Name the alcohols A–F:
H H CH3 H H CH3 H H CH3

H C C C CH3 H C C C CH3 H C C C OH

H H OH H OH H H H H
A B C

OH
OH H CH2OH

C C

H 3C H
D E F

b) Answer the following questions about compounds A–F in part (a).

i) What is the molecular formula of compound D?
ii) Identify any secondary alcohols.
iii) What do compounds E and F have in common? (9)
12 a) Name the haloalkanes A–F:
H H CH3 H H CH3 H H CH3

H C C C CH3 H C C C CH3 H C C C Cl

H H Cl H Cl H H H H
A B C
Cl F
Br
H CH2Br
Cl C C H C C

Cl F H Br

D E F

b) Classify compounds A, B and C as either primary, secondary or tertiary.

c) Write a balanced equation for the reaction of compound D with OH–.
d) When compound E is exposed to ultraviolet light it forms radicals.
Explain what is meant by the term ‘radical’. Identify the radicals that are most likely to be formed. (14)
13 The structure of chlordane is shown below. What are the molecular and
empirical formulae of chlordane? (1)
Cl Cl

Cl Cl
Cl

Cl Cl
Cl

14 Haloalkanes undergo nucleophilic substitution reactions.

a) Define a nucleophile.
b) Explain fully the mechanism when 1-bromopropane reacts
with potassium hydroxide, KOH, to produce propan-1-ol. (8)

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 15 A few drops of a halogenoalkane were added 21 Haloalkanes, such as 1-bromobutane, are
to 2 cm3 of ethanol in a test tube, and 5 cm3 of hydrolysed by reaction with NaOH(aq).
aqueous silver nitrate were then added. Finally, AgNO3(aq) is added to confirm the presence of
the test tube was placed in a water bath for a the bromide.
few minutes. A cream precipitate formed. This a) Write an equation, include state symbols, for
precipitate was soluble in concentrated ammonia. the precipitation of silver bromide.
a) Why was ethanol used in this experiment? b) Write an equation for the hydrolysis of
b) Why was the test tube containing the mixture 1-bromobutane.
warmed in a hot water bath? c) Describe, with the aid of curly arrows,
c) What was the formula of the precipitate? the mechanism for the hydrolysis
Explain your answer. of 1-bromobutane. Show relevant dipoles and
d) What can you conclude about the lone pairs of electrons.
halogenoalkane? (4) d) Why is hydrolysis necessary before testing
with AgNO3(aq)?
16 Explain what is meant by the terms ‘reflux’ and
e) Why must nitric acid, HNO3(aq), be added
‘distillation’. (2)
before the AgNO3(aq)?
17 Write a balanced equation for each of the f) Explain why hydrochloric acid could not be
following reactions: used in place of the nitric acid. (10)
a) the complete combustion of propan-1-ol
22 The boiling points of ethane, ethanol and ethane-
b) the dehydration of pentan-3-ol
1,2-diol are shown below.
c) the oxidation of butan-2-ol (use [O] to
represent the oxidising agent). (4) Compound Boiling point/°C
Ethane –89
18 Explain, with the aid of equations, why the
dehydration of pentan-3-ol gives two alkenes, Ethanol 78
whereas the dehydration of pentan-2-ol gives a Ethane-1,2-diol 198
mixture of three alkenes. (4)
a) Explain the variation in boiling points.
19 Identify the organic products formed when b) Which would you expect to be most soluble
2-methylcyclohexanol undergoes dehydration. (3) in water? Explain your answer.
c) Ethane-1,2-diol can be used as an anti-freeze
HO to prevent the freezing of water. State three
reasons why ethane-1,2-diol is suitable to use
as an anti-freeze.
H3C
d) Write a balanced equation for the complete
20 Classify the following conversions as: addition, combustion of ethane-1,2-diol.
elimination, substitution, oxidation, reduction, e) Using [O] to represent the oxidising agent,
hydrolysis or polymerisation reactions. (Note write a balanced equation for the complete
that a reaction may belong to more than one oxidation of ethane-1,2-diol.
Chapter 14 Alcohols and haloalkanes

category.) f) When propane-1,2,3-triol is oxidised a

a) butan-2-ol to but-2-ene mixture of organic products is formed.
b) butane to 1-bromobutane Identify as many of the oxidation products
c) but-1-ene to 1,2-dichlorobutane as possible. (14)
d) butanal to butanoic acid
e) 1-bromobutane to butan-1-ol
f) buta-1,3-diene to synthetic rubber (6)

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 Practice questions
23 Haloalkanes react by nucleophilic substitution but f) The isomers N and P react in a similar way.
under certain conditions an elimination reaction Each produces an alkane when the following
can occur. The mechanism for the elimination reactions are carried out:
reaction is shown below, but the curly arrows i) Compounds N and P are hydrolysed to
have been omitted. produce C4H10O.
ii) C4H10O is then dehydrated to C4H8.
Br− iii) C4H8 is reacted with hydrogen using a
H Br H H H
nickel catalyst.
H C C C H H C C C H + H2O
The alkane formed from compound N has a
H H H H H lower boiling point than that formed from
−O compound P. Identify N and P. Explain your
H
answers.
g) Consider reactions (i)–(iii) in part (f) above.
Copy the mechanism above and add curly arrows Place them in order of decreasing atom
to show the movement of the electron pairs. (3) economy. Calculations are not necessary, but
you must justify your answer.
Challenge h) The mass spectrum of isomer P is shown
24 There are four isomers, L, M, N and P, of molecular below.
formula C4H9X, where X is a halogen.
100
a) Draw skeletal formulae for the four isomers.

Relative abundance
b) Following hydrolysis, each isomer reacts with 80

aqueous silver nitrate to produce a cream 60

precipitate that dissolves in concentrated 40
ammonia. Identify X. Explain your answer. 20
c) Write an ionic equation for the reaction with 0
silver nitrate. 25 50 75 100 125
m/z
d) Isomer L can be hydrolysed to produce a
compound, C4H10O, that does not react i) Calculate the relative molecular mass of
when warmed with a mixture of potassium the isomers.
dichromate(vi) and sulfuric acid. Identify ii) There are two peaks of equal height at
isomer L. Explain your answer. m/z 136 and 138. Suggest why these two
e) Isomer M can also be hydrolysed. The peaks occur.
compound obtained from this reaction iii) The mass spectrum also has a prominent
does react with a mixture of potassium line at m/z 57. Suggest the source of
dichromate(vi) and sulfuric acid. The organic this peak.
product obtained from the reaction with iv) There is also a peak at m/z 29. Explain
acidified dichromate under reflux is neutral. how this peak would enable isomer P to
Identify isomer M. Explain your answer and be distinguished from isomer L. (27)
write equations for the reactions described.

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 Chapter 15
Organic synthesis and
analytical techniques
(infrared spectroscopy, IR,
and mass spectrometry, MS)
Prior knowledge
In this chapter it is assumed that you are familiar with:
● the terms reagents, products and conditions
● empirical and molecular formula calculations
● percentage yield calculations
● mass spectrometry.

Test yourself on prior knowledge

1 Give the empirical formula of the following organic molecules:
a) C4H10
b) C6H6
c) C6H12O6
d) CH3COOCH2CH3.
2 Compound A is an alcohol and has the following composition by mass:
C, 48.6%; H, 8.1%; O, 43.3%.
a) Calculate the empirical formula.
b) The molar mass, M, of compound A is 74. Deduce molecular formula.
c) Draw and name all possible isomers of compound A.
3 In the reaction below 4.6 g ethanol was reacted with an excess of
ethanoic acid. 4.4 g of the ester ethyl ethanoate was produced.
O O
heat + H2O
H3C C + H3C CH2 OH H3C C
conc. H2SO4
OH catalyst O CH2 CH3

a) Why was an excess of ethanoic acid used?

b) Calculate the percentage yield.
c) Suggest why the percentage yield was so low.

Practical skills
Chemists have developed a range of practical techniques for the
synthesis of solid and liquid organic compounds. These methods allow
for the fact that reactions involving molecules with covalent bonds are
often slow and that it is difficult to avoid side reactions which produce
by-products. There are several stages in the preparation of an organic
244 compound. These are summarised in Figure 15.1.

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 Practical skills
Stage 1
PLANNING
Devise a series of reactions that will enable you to make
the ‘target molecule’ from a readily available reagent.
Carry out a risk assessment and identify
any potential hazards

Stage 2
CARRY OUT THE REACTION
Decide on the apparatus you will need for each step.
Decide on suitable quantities for the chosen apparatus.
Stage 3
SEPARATION OF PRODUCT
Solids are normally separated by filtration. Liquids are
normally separated by either removal of impurities by
solvent extraction or by simple distillation.

Stage 4
PURIFICATION OF PRODUCT
The product is usually contaminated with a mixture of
unreacted reagents and by-products.
Solid products are normally purified by recrystallisation.
Liquids are normally purified by fractional distillation.

Stage 5
MEASURING % yield
Compare the actual yield with the theoretical
yield.

Stage 6
IDENTIFICATION OF PRODUCT
Functional groups can be identified by simple chemical tests known
as ‘wet tests’.
Individual compounds can be identified by melting or boiling
points.
Precise identification involves using a combination
of modern methods of analysis including: MS, IR and NMR.

Figure 15.1 Preparation and identification of an organic compound.

Tip Stage 1: Planning

IR - infrared spectroscopy In very many experiments it is not possible to convert a reagent into
MS - mass spectrometry the desired product in a single reaction and often an intermediate step
NMR - nuclear magnetic is required. This is dealt with in the section ‘Synthetic routes’, which
resonance spectroscopy follows (page 249).

Stage 2: Carry out the reaction

When carrying out the reaction, one of the commonest techniques is to
heat the reaction mixture in a flask fitted with a reflux condenser (see
Chapter 14, page 229).

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 Stage 3: Separation of products
When separating a solid product from the reaction mixture, solids are
removed by filtration using a Buchner or Hirsch funnel with suction
from a water pump (Figure 15.2).
filter paper

Buchner funnel
(porcelain)

small holes in base of funnel

to vacuum pump
Chapter 15 Organic synthesis and analytical techniques (infrared spectroscopy, IR, and mass spectrometry, MS)

Buchner flask

Figure 15.2 Separation of solid product by vacuum filtration.

Liquids can often be separated by simple distillation, as shown in Figure 15.3.

to sink

tripod and
gauze

from tap

microburner

Figure 15.3 Distillation. Volatile products are quickly separated from the reagents. Their
boiling point can be measured as they distil over.

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 Practical skills
Another method of separating liquids is using a separating funnel.
(Figure 15.4). When separating a liquid product from the reaction
mixture, the organic liquid is usually immiscible with water and will form
a separate layer. If the organic liquid is less dense than water, the lower
upper organic layer
aqueous layer can be run off and discarded. The organic layer can then
be dried by shaking with an anhydrous salt such as MgSO4 or CaCl2.
lower aqueous layer

Stage 4: Purification of products

The ‘crude’ product is usually contaminated with unreacted reagents or
with by-products. The method of purifying this ‘crude’ product depends
on whether it is a solid or a liquid.

Figure 15.4 Separating funnel for

immiscible liquids.
Purifying solids by recrystallisation
Solids are normally purified by recrystallisation. Recrystallisation is based
on using a solvent which dissolves the product readily when hot, but
only sparingly when cold. The choice of solvent is usually made by trial
and error.
Recrystallisation can be broken down into several steps:
1 Dissolve the impure solid in the minimum volume of hot solvent.
2 If the hot solution is not clear, filter the hot mixture through a
heated funnel to remove insoluble impurities leaving the product
dissolved in the hot solution.
3 Cool the filtrate so that the product recrystallises, leaving the
soluble impurities in solution.
4 Filter the cold solution to recover the purified product.
5 Wash the purified solid with small amounts of pure cold solvent to
wash away any solution containing impurities.
6 Allow the solvent to evaporate from the purified solid in the air.

Purifying organic liquids

Chemists often purify organic liquids which are insoluble in water
by shaking with aqueous reagents in a separating funnel to extract
impurities. This is followed by washing with distilled water, drying with
an anhydrous salt and finally fractional distillation. Fractional distillation
separates mixtures of liquids with different boiling points.

Stage 5: Measuring percentage yield

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

actual yield of product

percentage yield = × 100
theoretical yield of product

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 Example 1
a) What is the theoretical yield of ethanal if 13.14 g of ethanol is heated,
under distillation, with excess acidified potassium dichromate?
b) What is the percentage yield if the actual yield of ethanal is 9.43 g?
Answer
Start by writing an equation for the reaction.
You need to know the mole ratio of reagent : product.
CH3CH2OH + [O] → CH3CHO + H2O
mole ratio 1 mol :  1 mol
molar mass 46 g mol–1 44 g mol–1
Chapter 15  Organic synthesis and analytical techniques (infrared spectroscopy, IR, and mass spectrometry, MS)

a) From the equation 1 mol of ethanol will produce 1 mol of ethanal, so:
46 g of ethanol will produce 44 g ethanal
44
hence 13.14 g of ethanol will produce × 13.14 g = 12.57 g ethanal
46
The theoretical yield is 12.57 g ethanal.
actual yield of product
b) percentage yield = × 100
theoretical yield of product

9.43
= × 100% = 75%
12.57

Stage 6: Identifying products and checking

their purity
Pure solids have sharp melting points – databases now include the melting
points of all known compounds, which makes it possible to check the
identity and purity of a product by checking its melting point. If the solid is
impure the melting point will be lower than expected; the solid will not have
a sharp melting point but will soften and melt over a range of temperature.
Boiling points can be used to check the purity and identity of liquids. If
a liquid is pure, it should all distil over a narrow range, at the expected
boiling point. The boiling point can be measured as the liquid distils over
during fractional distillation. Impurities increase the boiling point and the
range over which it boils.

Qualitative tests for functional groups

Functional groups can be identified by simple qualitative tests. These
‘wet tests’ are summarised in Table 15.1.
Table 15.1 Chemical tests to identify functional groups.
Test Observation Conclusions
pH of solution (add litmus) Red Carboxylic acid
Br2 Decolorises Alkene
Na2CO3 Gas (CO2) given off, bubbles, fizzes Carboxylic acid
AgNO3(aq) in water bath White precipitate Chloroalkane
at about 60 °C Cream precipitate Bromoalkane
Yellow precipitate Iodoalkane
Heat with H+/Cr2O72– Orange to green Primary alcohol
Secondary alcohol
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 Synthetic routes
Test yourself
1 a) Explain what is meant by:
i) reflux
ii) distillation.
b) Ethanal can be prepared by oxidising ethanol. Would you use reflux or
distillation? Explain your answer.
c) Ethanoic acid can be prepared by oxidising ethanol. Would you use
reflux or distillation? Explain your answer.
2 State the practical techniques you would use to obtain a pure sample
each of the following:
a) butanal from a mixture of butanal and butan-1-ol (both are liquids)
b) octane from a mixture of octane and water (both are liquids)
c) benzoic acid and phenyl ethanone (both are solids).
Explain your reasoning for each.
3 Explain what happens to the melting point of pure ice if the ice is
contaminated with salt (NaCl).
4 A sample of benzoic acid was contaminated with mixture of potassium
dichromate and carbon. Use the information in the table to explain how
you could obtain a pure sample of benzoic acid. Describe a chemical test
that you could use to confirm that the product was a carboxylic acid.

Chemical Appearance Solubility in Solubility in

cold water hot water
Benzoic acid White crystalline solid Insoluble Soluble
Potassium Orange crystalline solid Soluble Soluble
dichromate
Carbon Black solid Insoluble Insoluble

5 Propan-1-ol was heated under distillation with a acidified potassium

dichromate. The percentage yield of propanol was 75%.
a) Suggest why the percentage yield was significantly below the
theoretical yield.
b) Suggest the identity of any likely organic impurities.
c) State a simple chemical test that would confirm the presence of the
organic impurities.

Synthetic routes
Functional groups provide the key to organic molecules. Knowledge of
the properties and reactions of a limited number of functional groups
enables the preparation of a wide variety of organic compounds.
Chemists often think of an organic molecule as a relatively unreactive
hydrocarbon skeleton with one or more functional groups in place of
one or more hydrogen atoms. The functional group in a molecule is
responsible for most of its reactions. In contrast, the carbon–carbon
bonds and carbon–hydrogen bonds are relatively unreactive, partly
because they are both strong and have very little polarity.
Your knowledge of functional groups should now cover the reactions of
alkanes, alkenes, alcohols and haloalkanes. Table 15.2 summarises the
reactions of these groups.

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 Table 15.2 Reactions of functional groups

Functional group Type of reactions Reagents that react

Name Group
Alkane C nH2n+2 Radical substitution Cl2, Br2
Alkene Electrophilic addition H2, HBr, Br2 H2O(g)
C C

Alcohol R–OH Oxidation H+/Cr2O72–

Esterification* RCOOH (carboxylic acids)
Elimination H2SO4
Halogenation NaBr/H2SO4
Haloalkane R–Cl Nucleophilic substitution Common nucleophiles
Hydrolysis include: �OH –, �NH3*, �CN –*
Chapter 15  Organic synthesis and analytical techniques (infrared spectroscopy, IR, and mass spectrometry, MS)

*Only likely to be tested after the second year of the A Level course.

Organic chemists synthesise new molecules using their knowledge of

functional groups, reaction mechanisms and molecular shapes – as well
as the factors which control the rate and extent of chemical change.
They often start by examining the ‘target molecule’. Then, they work
backwards through a series of steps to find suitable starting chemicals
that are available and cheap enough. In recent years, chemists have
developed computer programs to help with the process of working back
from the target molecule to a range of possible starting molecules. Table
15.3 outlines some reactions of functional groups.

target
starting functional reagent used functional
group group

Table 15.3 Target functional groups.

Functional group Reagent Target functional group

Alkane Halogen Haloalkane
Alkene Hydrogen halides Haloalkanes
Halogens Di-haloalkanes
Steam Alcohol
Hydrogen Alkanes
Alcohols Carboxylic acids* Esters
H /Cr2O7
+ 2–
Aldehyde, ketone or carboxylic acid
Hot concentrated H2SO4 Alkene
NaBr in presence of H2SO4 Haloalkane

Haloalkane NaOH(aq) Alcohol

NH3(ethanol)* Amine
Cyanide, C≡N*
−
Nitrile
*Only likely to be tested after the second year of the A Level course.

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 Synthetic routes
A simple example is shown below.

Example 2
Explain how you could prepare propanoic acid starting from chloropropane.

Answer
In any two-stage synthesis:
● start
with the target molecule and identify the functional groups that can
be used to make the target functional group
● secondlylook at the starting molecule and identify the functional groups
that can be made from the starting functional group.
In this case:
1-chloropropane → ? → propanoic acid
Target molecule – Using your knowledge so far, the carboxylic acid
functional group can be made from a primary alcohol or an aldehyde.
Starting molecule – The haloalkane acid functional group can be used to
form a primary alcohol.
Clearly the connecting intermediate molecule is a primary alcohol such that
the two-step synthesis is:
1-chloropropane → propan-1-ol → propanoic acid
Step 1 1-chloropropane → propan-1-ol
● Reagents: NaOH(aq)
● Conditions: warm
● Equations: CH3CH2CH2Cl + NaOH→ CH3CH2CH2OH + NaCl
● Type of reaction: nucleophilic substitution
Step 2 propan-1-ol → propanoic acid
● Reagents: acidified dichromate, H+/Cr2O72–
● Conditions: heat (under reflux) with excess H+/Cr2O72–
● Equations: CH3CH2CH2OH + 2[O] → CH3CH2COOH + H2O
● Type of reaction: oxidation

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 Example 3
Explain how you could prepare butanone starting from but-2-ene.

Answer
In this case, the ‘target molecule’ is butanone and the ‘starting molecule’ is an alkene, but-2-ene.
Step 1 Start with the target molecule and identify the compounds that could readily be converted directly into the
target – concentrate on the functional group.
Butanone is a ketone which can be made from the oxidation of a secondary alcohol, butan-2-ol.
Step 2 Look at your starting molecule, but-2-ene. What reactions of alkenes do you know?
alkane di-haloalkane
Chapter 15  Organic synthesis and analytical techniques (infrared spectroscopy, IR, and mass spectrometry, MS)

alkene

haloalkane alcohol

You should now see a possible two-stage synthetic route from your starting molecule to the target molecule. In
this case, the route can go via the alcohol.
O

H3C CH CH CH3 H3C CH2 CH(OH) CH3 H3C CH2 C CH3

starting molecule intermediate molecule target molecule

You will need to know the reagents and conditions for each step:
O
+ 2−
steam H /Cr2O7
H3C CH CH CH3 acid catalyst H3C CH2 CH(OH) CH3 H3C CH2 C CH3
heat under
starting molecule high temp./pressure intermediate molecule reflux target molecule

You may have to write equations for each step:

Step 1 CH3CHCHCH3 + H2O → CH3CH2CH(OH)CH3
Step 2 CH3CH2CH(OH)CH3 + [O] → CH3CH2CHOCH3 + H2O
Chemists normally seek a synthetic route that has the least number of stages and which, therefore, produces a
higher yield of the product. It is rare for any one reaction to be 100% efficient; normally the percentage yield is
significantly below the theoretical yield.

Test yourself
6 Compound A decolorises bromine and when heated with acidified
dichromate the dichromate turns from orange to green. Which of the
three compounds below is compound A most likely to be?
CH3CH2CH2OH CH3CHCHCOOH CH3CHCHCH2OH
Explain your answer.
7 Devise a two-stage synthesis for converting:
a) methane to methanol
b) propene into propanone.
State the reagents and conditions needed for each conversion.

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 Analytical techniques
Analytical techniques
Infrared spectroscopy
Substances used to be identified by means of distinctive chemical tests.
In simple cases, such tests are still useful. However, more powerful
and flexible methods have been developed that use instruments to
detect molecules by their structural characteristics. One such method
is infrared spectroscopy. Infrared radiation causes covalent bonds to
vibrate; particular bonds respond at different frequencies (energies).
Infrared radiation is part of the electromagnetic spectrum, which
extends from low-energy waves, such as radio waves, through to high-
energy waves, such as X-rays and gamma rays. Infrared is the region of
the spectrum that has energy just below that of red light.

Absorptions
Covalent bonds respond to infrared radiation in a number of ways. The
frequencies at which the bonds vibrate are called the absorptions of
that bond. Some absorptions occur over a small range of frequencies
(such as those of the CO bond); others have a wider spread (such as
those of an O–H bond). The absorptions are affected by neighbouring
bonds. For example, the O–H bond of an alcohol responds differently
Figure 15.5 Scientists using an infrared
from the O–H bond in a carboxylic acid group, –COOH. The
spectrometer. The instrument covers
a range of infrared wavelengths, and a complicated patterns that are produced can make the interpretation of
detector records how strongly the sample these spectra difficult.
absorbs at each wavelength. Wherever
the sample absorbs, there is a dip in the
There is no need to consider here how an infrared spectrometer works,
intensity of the radiation transmitted, but Table 15.4 below gives some key absorptions. Absorptions are
which shows up as a dip in the plot of the identified by wavenumber (cm –1).
spectrum.

Table 15.4 Key infrared absorptions.

Wavenumber range/cm –1 Bond Functional groups

750–1100 C–C* Alkanes, alkyl chains
500–800 C–X* Haloalkanes (X = Cl, Br or I)
1000–1350 C–F* Fluoroalkanes
1000–1300 C–O* Alcohol, ester, carboxylic acid
1620–1680 CC Alkenes
Tip
1630–1820 CO Aldehyde, ketone, carboxylic acid, ester
The fingerprint region is the
2850–3100 C–H Any organic compound with a C–H bond
part of the spectrum from about
2500–3300 (very broad) O–H Carboxylic acid
500 to 1500 cm –1, which usually
contains a very complicated 3200–3600 O–H Alcohol
series of absorptions. *These absorptions are difficult to identify as they appears in the ‘fingerprint region’ where
there are usually very many peaks.

Data sheets are supplied when required in exams, so there is no need

to learn the wavenumbers in Table 15.4. The absorptions can be roughly
divided into three distinct sections, as shown in Figure 15.6.

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 Wavenumber range

4000 2500 1900 1500 500 cm−1

fingerprint region
C H contains many peaks
C O
O H often unique to a
C C particular compound
N H
e.g. C O

Figure 15.6 Wavenumber ranges.

Infrared spectrum of an alcohol

The identifying absorptions are indicated on the spectrum in Figure 15.7.
Notice the characteristic broad absorption due to the O–H bond in the
region 3200–3600 cm –1.
Chapter 15  Organic synthesis and analytical techniques (infrared spectroscopy, IR, and mass spectrometry, MS)

100
Transmittance/%

50

0
4000 3000 2000 1500 1000 500
Wavenumber/cm−1
fingerprint region
C–H in region 500–1500 cm−1
O–H in region 3200–3600 cm−1 2850–3100 cm−1 somewhere in there is the
easy to spot as a broad peak almost all organic C–O bond, but there are so
compounds have many peaks it is almost
C–H bonds; peaks impossible to see
are sharp/spiky which is C–O

Figure 15.7 Infrared spectrum of an alcohol.

Infrared spectrum of a carbonyl compound

The infrared spectrum of a carbonyl compound (Figure 15.8) has an
absorption due to the CO bond in the region 1630–1820 cm –1.
100
Transmittance/%

50

0
4000 3000 2000 1500 1000 500
Wavenumber/cm−1

C–H in region 2850–3100 cm−1 C=O in region

almost all organic 1630–1820 cm−1 fingerprint region
compounds have easy to spot as a 500–1500 cm−1
C–H bonds; peaks strong peak and lots of peaks – difficult
are sharp/spiky nothing else in the region to assign any particular one
254 Figure 15.8 Spectrum of a carbonyl compound.

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 Analytical techniques
Infrared spectrum of a carboxylic acid
The infrared spectrum of a carboxylic acid has absorptions due to:
● the CO bond (in the region 1630–1820 cm –1)
● the O–H bond, which is a very broad absorption (in the region
2500–3300 cm –1).
These can be seen in Figure 15.9.
100

Transmittance/%
50

O–H in region
2500–3300 cm−1
easy to spot as 0
a very broad 4000 3000 2000 1500 1000 500
peak Wavenumber/cm−1

fingerprint region
C–H in region C=O in region 500–1500 cm−1
2850–3100 cm−1 1630–1820 cm−1 somewhere in there
almost all organic easy to spot as a is the C–O bond,
compounds have strong peak and but there are so
C–H bonds; peaks nothing else many peaks it is
are sharp/spiky in the region almost impossible
to see which is C–O
Figure 15.9 Spectrum of a carboxylic acid.

The infrared spectra for alcohols, carbonyls and carboxylic acids make it
easy to identify compounds that contain the O–H and CO functional
groups and they also illustrate the use of infrared spectroscopy.
Modern breathalysers employ this technique quantitatively to measure
the amount of ethanol in exhaled breath. The detection of alcohol is
explored more fully in the activity ‘Detecting alcohol’ on page 256,
which is best used as a class-based discussion exercise.
Infrared spectrum of an alkene
The infrared spectrum of an alkene has absorptions due to the CC
bond (in the region 1620–1680 cm –1). These can be seen in Figure 15.10.
100
Transmittance/%

50

0
4000 3000 2000 1500 1000 500
Wavenumber/cm−1

C–H in region C=C in region fingerprint region

2850–3100 cm−1 1620–1680 cm−1 500–1500 cm−1
Figure 15.10 Spectrum of an alkene.
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 Activity The infrared spectrum of ethanol has strong peaks
Detecting alcohol corresponding to the O–H and C–H bond vibrations (see
Infrared spectroscopy is one of the methods used Figure 15.7). The absorption at 2950 cm–1 corresponds
to analyse breath samples from drivers suspected to the C–H bond vibration and is used for analysis.
of drinking. Alcohol from drinks is absorbed into the The test instrument passes infrared radiation at
bloodstream through the walls of the stomach and 2950 cm–1 through a standard cell containing a sample
intestines. The alcohol circulates with the blood through of the driver’s breath. The strength of the absorption
all parts of the body, including the lungs. It is slowly is a measure of the alcohol concentration. A built-in
removed by the liver at a rate of about one unit an hour. computer processes the signal from the instrument, and
the machine prints out the result.
Alcohol moves from the blood into the breath in the
lungs. Analysis of the blood and breath of a range of 1 A unit of alcohol in the UK is 10 cm3 ethanol.
people after drinking has established that, on average, Estimate the number of units of alcohol in:
the ratio of the concentration of the alcohol in the blood a) half a pint (284 cm3) of lager that contains 5% by
Chapter 15  Organic synthesis and analytical techniques (infrared spectroscopy, IR, and mass spectrometry, MS)

to the breath is around 2300 : 1. This makes it possible to volume of alcohol

estimate someone’s blood alcohol level by measuring the b) a small glass (125 cm3) of wine that contains 14%
concentration of alcohol in their breath. The current legal by volume of alcohol.
limits for drivers in the United Kingdom excluding Scotland 2 Show that the values of 80 mg of alcohol per 100 cm3
correspond to 35 mg of alcohol per 100 cm3 breath or of blood and 35 mg of alcohol per 100 cm3 breath
80 mg of alcohol per 100 cm3 of blood. In Scotland the correspond to a concentration ratio of 2300 : 1.
limit is 50 mg of alcohol per 100 cm3 of blood. 3 Suggest reasons why:
a) prosecution does not follow a breath test unless
The police use test instruments that contain fuel cells
the breath alcohol concentration is at least 40 mg
for their roadside tests. In these devices, any alcohol in
per 100 cm3
a driver’s breath acts as fuel to produce an electrical
b) drivers are given the option of having a blood
voltage from the cell. The voltage is automatically
or urine test if the value is between 40 and
converted by the instrument to a measure of
50 mg per 100 cm3 but not if it is higher than
the concentration of alcohol in the blood. These
this range.
instruments are not used as evidence in court, but they
4 Suggest reasons why the C–H peak in the infrared
allow the police to decide whether to take a driver to
spectrum and not the O–H peak is used to analyse
the police station for a further test. For many years,
alcohol in breath.
the accurate breath tests at police stations relied solely
5 Suggest a procedure for checking the accuracy of a
on infrared instruments. The newer machines combine
breath test machine in a police station.
infrared and fuel cell technologies.

Tip Absorption of infrared radiation by

Modern breathalysers (like the
atmospheric gases
one described in the activity The Earth is warmed mostly by energy transmitted from the Sun. This
above) are used to measure the energy consists largely of visible light, but there is also some ultraviolet and
ethanol in breath. In addition, infrared radiation. Most ultraviolet radiation is removed in the upper parts
infrared spectroscopy is used to of the atmosphere (the stratosphere) by the ozone layer. Of the remaining
monitor gases such as carbon radiation, some is reflected and some is absorbed by the atmosphere.
monoxide and oxides of nitrogen Carbon dioxide and water molecules remove part of the incoming infrared
that cause air pollution. radiation. Once at the Earth’s surface, chemical reactions absorb and
transmit this energy. Over time, the surface temperature of the Earth

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 Analytical techniques
has remained approximately constant because an equilibrium has been
established between arriving and departing energy. The departing energy –
which is almost wholly infrared radiation – does not pass unhindered into
outer space. If it did, the Earth would be a very cold place. Many gases in
the atmosphere absorb some of this energy and reflect it back to Earth.
Carbon dioxide and water molecules are not the only molecules to behave
in this way. Gases that have bonds that vibrate in a way that alters the
electrical balance of the molecule also absorb infrared radiation. In fact
the only molecules that do not absorb infrared radiation are diatomic
molecules made up of the same atoms (e.g. O2, N2).

Greenhouse gases
Tip Gases that do absorb infrared are collectively known as greenhouse
gases. There is a wide range of greenhouse gases, since most molecules
Remember that charge contain polar bonds.
separation due to the differing
electronegativities of atoms is Contribution of a gas to the greenhouse effect
an important feature of most The overall contribution of a gas to the greenhouse effect depends on:
covalent bonds. ● its ability to absorb infrared radiation
● its atmospheric concentration
● its residence time (how long it stays in the atmosphere).
These factors can be treated quantitatively. The relative greenhouse
effect of four gases is shown in Table 15.5 below.

Table 15.5 Contribution of gases to the greenhouse effect.

Gas Formula Approximate relative Approximate atmospheric

greenhouse effect concentration (%)
Carbon dioxide CO2 1 0.035
Methane CH4 25 0.00017
Dinitrogen oxide N2O 250 0.000 03
CFC-12 CCl2F2 25 000 ~ 4 × 10 –8

Table 15.5 shows that there are large differences in the contributions
to the greenhouse effect made by individual molecules. However, this
must be set against the amount of each gas present in the atmosphere.
Carbon dioxide has the highest concentration, whereas that of CFC-12 is
low and, as CFCs are phased out, will become lower. A major source of
atmospheric methane is the reduction of carbon-containing compounds
under anaerobic conditions. It may cause amusement that this occurs in
the digestive tract of cows, but it is also a hazard of the decomposition
of rubbish in compacted landfill sites. Dinitrogen monoxide is released as
a result of the reduction of nitrates on agricultural land.
Each of the bonds in the greenhouse-gas molecules (CO in carbon dioxide,
C–H in methane, O–H in water and so on) absorbs infrared radiation of a
particular wavelength and vibrates with increased energy. This energy is then
randomly dispersed, with much of it returning to the Earth’s surface.
Effect of greenhouse gases
As the concentration of greenhouse gases rises, the average temperature
at the Earth’s surface will increase. It is this increase that is usually
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 it the ‘enhanced greenhouse effect’ because it is the extra heating that
is the cause for concern.
The role of carbon dioxide as a contributor to global warming is the
focus of much attention. This is not because it is the most effective
greenhouse gas or that it is a major contributor, but because it is
produced in huge quantities by burning fuels such as wood, coal and
oil products. (In fact, water vapour is the biggest contributor to the
greenhouse effect.) Many attempts have been made to predict the
result of continued emissions of carbon dioxide into the atmosphere at
the current rate. There is no universal agreement, but there is serious
concern that it could result in the melting of the polar ice-caps, causing
extensive flooding of low-lying land, and that changing temperature
patterns could lead to severe droughts in some parts of the world.
Chapter 15  Organic synthesis and analytical techniques (infrared spectroscopy, IR, and mass spectrometry, MS)

Test yourself
8 The three spectra below are the infrared spectra of propan-1-ol,
propanone and propanoic acid.
A 100
Transmittance/%

50

0
4000 3000 2000 1500 1000 500
Wave number/cm−1

B 100
Transmittance/%

50

0
4000 3000 2000 1500 1000 500
Wave number/cm−1

C 100
Transmittance/%

50

0
4000 3000 2000 1500 1000 500
Wave number/cm−1

Identify which is which. Justify your answer.

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 Analytical techniques
Mass spectrometry
The use of the mass spectrometer was discussed in Chapter 2.
The mass spectrometer can be used to analyse both elements and
molecules.
The mass spectrum of an element shows a peak for each isotope of
that element. The mass corresponding to each peak, together with their
relative abundance, can be used to calculate the relative atomic mass of
that element.
The mass spectrum of a molecule shows multiple peaks. The peak with
the largest m/z value, the molecular ion (or the parent ion), shows the
relative molecular mass of the molecule. The rest of the peaks show
fragment ions formed when the molecule breaks up. Molecules break
up more readily at weak bonds or at bonds that give rise to fragments
that are more stable. It turns out that ions with a positive charge on
a tertiary carbon atom are more stable than ions with a charge on a
primary carbon atom.
Some important fragmentation ions are listed in Table 15.6.

Table 15.6 Common fragment ions.

m/z value Ion responsible

15 [CH3]+(g)
29 [CH3CH2]+(g)
43 [CH3CH2CH2]+(g)
Alkyl chains extend by CH2 so it is possible that you will get peaks at 57, 71 etc.
31 [CH2OH]+(g) (primary alcohol)

Figure 15.11 shows the mass spectrum of ethanol. There is a molecular

ion peak (M peak) at m/z = 46 but the spectrum also shows a small
peak at m/z = 47, which is known as the M+1 peak and is due to
the presence of the carbon-13 isotope that is found in all organic
compounds.
100

80
Relative intensity

60

40
M peak
20

0
0 10 20 30 40 50
Mass-to-charge ratio m/z M+1 peak

Figure 15.11 Mass spectrum of ethanol.

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 Activity
Mass spectrometry in space research
In December 1978, space probes landed on Venus for the first time. Weight
limitations meant that the low-resolution mass spectrometers on board
could give measurements of relative masses to only 1 decimal place. A
molecule of relative molecular mass 64.0 was identified, but the analysis
could not show whether it was SO2 or S2.
Since then, mass spectrometers with higher resolutions have been
developed. One reason for this is that space scientists are keen to explore
whether or not there is, or ever has been, life on Mars. Scientists want to
explore the north pole of the planet because evidence from surveys by
orbiting spacecraft suggests that the pole is rich in ice just below the surface.
Chapter 15  Organic synthesis and analytical techniques (infrared spectroscopy, IR, and mass spectrometry, MS)

Beagle was a British-led effort to land a spacecraft on Mars in 2003 to look

for signs of life. Like half of all missions to Mars, the project failed. In this
case, it failed because the spacecraft crashed on landing. However, the mass
spectrometers developed for the mission have been developed further and
have been used in later projects, such as the Phoenix lander, which landed on
Mars in May 2008.
Figure 15.12 Artist’s impression of
Instruments on spacecraft sent to Mars include a combination of high- the Phoenix lander on Mars just as
temperature ovens and a mass spectrometer. These are designed to study it is beginning to dig a trench and
ice and soil samples. After the spacecraft lands, a robotic arm digs a trench. gather samples for analysis by mass
It then scoops up samples and drops them into a hopper that feeds them spectrometry.
into ovens no bigger than a ballpoint pen. As the oven temperatures increase up to 1000 °C, any gases can be mixed
with oxygen and then carried into the mass spectrometer by a stream of gas. The mass spectrometer can detect and
measure the amount of carbon dioxide formed by organic material burning or from decomposing minerals or released
from gases trapped in rocks.
Data from the mass spectrometer also allow scientists to determine ratios of various isotopes of hydrogen, oxygen,
carbon and nitrogen. The ability to measure the ratios of carbon isotopes is key to the search for life, because
photosynthesis is known to bring about a slight separation of these isotopes. During photosynthesis on Earth, plants
show a slight preference for carbon-12 rather than carbon-13. This means that the proportion of the carbon-13 isotope
is slightly lower than average in the chemicals in plants.
1 Why could the mass spectrometers used in 1978 not show whether the molecule found on Venus was SO2 or S2?
(Ar: S = 32, O = 16)
2 High-resolution mass spectrometers can measure relative masses to 3, 4 or even 5 decimal places (Ar: S = 31.972,
O = 15.995). Explain how a high-resolution mass spectrometer could determine whether a molecule is SO2 or S2.
3 What assumptions about the possibilities for life on Mars are built into the design of the methods of analysis for
missions to Mars?
4 Suggest reasons for landing spacecraft to sample and test the soil at the north pole of Mars.
5 Suggest why it is necessary to dig below the surface to look for signs of life on Mars.

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 Analytical techniques
Test yourself
  9 Use this mass spectrum for lithium to calculate the relative atomic mass
of lithium.
100
90

Relative abundance/%
80
70
60
50
40
30
20
10

6 7
Mass-to-charge ratio m/z

10 The graph shows the mass spectrum of ethanol. Match the numbered
peaks with the formulae of these positive ions formed: [C2H5]+,
[CH2OH]+, [C2H5O]+, [C2H5OH]+ and [C2H3]+.

100 3
Relative abundance/%

80

60

40 4

1 2
20 5

0
0 10 20 30 40 50
Mass-to-charge ratio (m/z)

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 Practice questions
Multiple choice questions 1–10 5 The infrared spectrum and the mass spectrum of
1 12.0 dm ethene reacts with steam to produce
3 compound B are shown below.
18.4 g ethanol. The percentage yield is infrared spectrum
A 65.2 100
B 80.0
C 95.2

Transmittance/%
D 100.
2 Propan-1-ol, propanal and propanoic acid can 50
best be separated by
A filtration
Chapter 15 Organic synthesis and analytical techniques (infrared spectroscopy, IR, and mass spectrometry, MS)

B separating funnel
C distillation 0
D reflux. 4000 3000 2000 1500 1000 500
Wave number/cm−1
3 Haloalkanes, such as C2H5Cl, can be detected by
mass spectrum
reacting it with
100
A NaOH
B AgNO3(aq) Relative intensity
80
C AgNO3(aq), ethanol at about 60 °C
60
D H+/Cr2O72–.
40

20

0
0 10 20 30 40 50 60
Mass-to-charge ratio m/z

Compound B could be
A ethanoic acid
B propan-1-ol
C propan-2-ol
D methyl methanoate.
4 The infrared spectrum of compound A is shown
below.
100
Transmittance/%

50

0
4000 3000 2000 1500 1000 500
Wave number/cm−1

Compound A was made by reacting ethanol with:

A propanoic acid in the presence of sulfuric acid
B acidified potassium dichromate(vi) under reflux
C acidified potassium dichromate(vi) under distillation
262 D concentrated sulfuric acid at about 170 °C.

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 Practice questions
6 The mass spectrum of 1-chlorobutane shows a 10 Compound X is shown below.
peak at m/z OH
A 92
B 92.5 H2C C C CH3
H
C 93
CH3
D 93.5.
Compound X will:
7 Ethene can be converted into compound Y via a
1 decolorise bromine.
two-stage synthesis
reaction 1 reaction 2
2 react with H+/Cr2O72– and the colour will
ethene compound X change from orange to green
compound Y 3 react with H+/Cr2O72– and the colour will
Compound Y can be oxidised to form a compound change from green to orange
HOOC–COOH 11 Describe a simple chemical test that could
Compounds X and Y could be: distinguish between:
a) cyclohexane and cyclohexene
X Y b) 1-chloropropane and propan-1-ol
A ethanol ethanal c) chlorobutane and iodobutane
B bromoethane ethanol d) ethanol and ethanoic acid.
C dibromoethane dihydroxyethane For each part, state the reagent(s), observations
D ethanol dihydroxyethane and write an equation. (16)

8 HOCH2CHCHCH2CHO contains three different 12 Compound A contains by mass: 62.1% C; 10.3% H

functional groups. They are: and 27.6% O. The mass spectrum and the infrared
A alcohol, ketone, alkene spectrum of compound A are shown below.
B alcohol, ketone, carboxylic acid infrared spectrum
C alcohol, alkene, ketone
100
D alcohol, alkene, aldehyde.
80
Use the key below to answer Questions 9 and 10.
Relative intensity

A B C D 60

1, 2 & 3 1, 2 2, 3 1 only
40
correct correct correct correct
20
9 The compound with the infrared spectrum shown
below could be: 0
0 10 20 30 40 50 60
100 Mass-to-charge ratio m/z

mass spectrum
Transmittance/%

100

50
Transmittance/%

50

0
4000 3000 2000 1500 1000 500
Wave number/cm−1
0
1 an aldehyde 4000 3000 2000 1500 1000 500
2 a ketone Wave number/cm−1
3 an alcohol
a) Calculate the molecular formula of
compound A. Show all your working.
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 b) Determine the functional group, draw and infrared spectrum
name possible isomers of compound A. Show 100
all your working.
c) Use the fragmentation pattern in the mass

Transmittance/%
spectrum to suggest an identity for compound
A. Explain your reasoning. (11) 50

13 The mass spectrum of 2-chloropropane is shown

below.
100
0
4000 3000 2000 1500 1000 500
80
Wave number/cm−1
Relative intensity

60 Use all of the information to identify compound

Chapter 15 Organic synthesis and analytical techniques (infrared spectroscopy, IR, and mass spectrometry, MS)

W. Show all of your working. (6)

40

20
Challenge
16 Ethene can be converted into compound X via a
0 three-stage synthesis.
0 10 20 30 40 50 60 70 80
Mass-to-charge ratio m/z a) In stage 1 ethene is converted into
1,2-dichloroethane.
The relative molecular mass of 2-chloropropane
Write an equation for the reaction and
is 78.5. Explain why the molecular ion peak in the
calculate the relative molecular mass of
mass spectrum is not at m/z = 78.5. (5)
1,2-dichloroethane.
14 Suggest a two-stage synthesis for each of the
b) The mass spectrum of 1,2-dichloroethane is
following conversions:
shown below.
a) 1-bromopropane → propanoic acid
b) cyclohexene → cyclohexanone 100

O 80
Relative intensity

60

40
c) CH3CH2CH2OH → CH3CHBrCH3.
20
For each stage give the reagents, conditions, if
0
any, and write an equation. (18) 10 20 30 40 50 60 70 80 90 100
m/z
15 Compound W decolorises bromine and also reacts
with acidified potassium dichromate to produce i) Identify the ions responsible for the
an acidic compound. The mass spectrum and the peaks at m/z = 98, 100 and 102.
infrared spectrum of compound W are shown below. ii) Estimate the relative heights of each of
these peaks. Show your working.
mass spectrum
100
c) 1,2-dichloroethene is then converted
compound X via an intermediate, compound Y.
80 ClCH2CH2Cl → compound Y → compound X
Relative intensity

The empirical formula of compound Y is CH3O.

60 Compound Y is then oxidised under reflux to
form compound X.
40
The infrared and mass spectra of compound
20 X are shown below.

0
0 10 20 30 40 50 60
264 Mass-to-charge ratio m/z

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 Practice questions
infrared spectrum mass spectrum
100
100

80
Transmittance/%

Relative intensity
60
50

40

20 90

0
4000 3000 2000 1500 1000 500 0
0 25 50 75 100
Wave number/cm−1
Mass-to-charge ratio m/z

Identify compounds X and Y and draw

their displayed formula. Show all of your
working. (19)

17 Ethyl ethanoate can be prepared by the reaction between ethanol and ethanoic acid. There are two possible
alternative ways of producing the ester:
alternative 1 O O
loss of water
C2 H5 O H H O C CH3 C2H5 O C CH3 + H2O

alternative 1 O O
loss of water
C2 H5 O H H O C CH3 C2H5 O C CH3 + H2O

The reaction was studied by using ethanol in which the oxygen was labelled with the isotope 18O:
18
C2H5 O H

The mass spectrum of the ester, CH3 COOC2H5, is shown below.
100

80
Relative intensity

60

40

20

0
0 10 20 30 40 50 60 70 80 90
m/z

Decide which alternative pathway is correct. Justify your answer. (4)

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 Chapter 16
Maths in chemistry
Prior knowledge
In this chapter it is assumed that you are familiar with routine mathematics.
Calculations will always be part of your chemistry. There are two key
requirements for solving numerical calculations:
● You need to understand the chemistry.
● You need to be able to process the mathematics.

Calculations in chemistry are straightforward and logical – you will be given

some numerical data and asked to use it to calculate some other numerical
value. The connection between the data you are given and the values you
have to calculate is the chemical relationship. You will need to know your
chemistry to recognise what the chemical relationship is.

Rearranging equations and units

A solution of sodium chloride is formed by adding solid sodium chloride
(the solute) to water (the solvent) to form a solution.
The concentration of a sodium chloride solution will depend on two
variables:
● the amount of sodium chloride dissolved
● the volume of the solution formed.
If either of these is changed then the concentration will change.
If the mass of sodium chloride is doubled, the concentration will double.
If the volume of the solution is doubled, the concentration will halve.
The related variables can be linked together by an equation which is
their chemical relationship:
The equation can also be written as:
concentration = mass of solute dissolved ÷ volume of solution
and as:
mass of solute dissolved
concentration =
volume of solution
If you know two quantities it is possible to calculate the third.
Tip
If 10 g of NaCl(s) is dissolved to produce 500 cm3 of solution, calculate
If you weigh yourself and the concentration.
you weigh 150 you need to
know whether it is 150 lb or concentration = mass = 10 = 0.020
volume 500
150 kg. Without the units it is The numerical value is correct but it has little value unless it also has units.
meaningless.
The units can be worked out from the equation:

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 Rearranging equations and units
which means that the units of concentration are:
g
concentration =
cm3
The units of concentration are grams divided by cm3 or grams per cm3,
which can be written as g/cm3. This is more correctly written as g cm –3.
Concentration (conc.) can be calculated if we know the mass (of the
solute) and the volume (of the solution):
You might want to use the above equation to calculate mass. For
instance you might be asked what mass of sodium chloride would you
need to make a 400 cm3 of a solution with a concentration of 0.05 g cm–3.
In the equation above mass is divided by volume, so to get mass by
itself the right-hand side has to be multiplied by volume BUT whatever
you do to one side of an equation you must also do to the other side.
which gives conc. × volume = mass
0.05 × 400 = 20 g
It is always worth checking that the units balance: g cm –3 × cm3 = g
We can also use this relationship to find the volume if both
concentration and mass are known:
We need to move volume across to the left-hand side and transfer
concentration (conc.) to the right-hand side. This can be done in two
ways:
● in two separate steps
Step 1 – multiply each side by volume
mass × volume
conc. × volume = which gives
volume
conc. × volume = mass
Step 2 – divide each side by conc.
conc. × volume mass mass
= which gives volume =
conc. conc. conc.
● by cross-multiplying

mass mass
conc. = which gives volume =
volume conc.
A triangle can be used for rearranging equations.

m as s

conc. x volume

Cover up the quantity you want to find and what is left gives you the
equation you have to use.
To find the relationship for mass place your finger over ‘mass’ and the
triangle shows that:
mass = conc. × volume
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 Test yourself
1 Draw a triangle to show the equation:
amount in moles = conc. × volume
Rearrange to give the equation for:
a) concentration
b) volume.
2 Draw a triangle to show the equation:
mass = density × volume
Rearrange to give the equation for:
a) density
b) volume.
3 The relationship between voltage (V), resistance (R) and current (I) is
voltage = resistance × current  or  V = R × I
(This equation could be written as V = RI – you do not need to include the
multiplication sign.)
Rearrange to give the equation for:
a) R
b) I.

Cross-multiplying
When you are sure that you can rearrange a simple equation you should
be able to use cross-multiplying:
a b
=     c and d can be cross-multiplied to give   ad = bc
c d
To obtain an equation for d use ad = bc and divide each side by a to get
d = bc/a. You should also be able to obtain equations for each of the
variables.
a = bc b = ad c = ad d = bc
d c b a

Test yourself
4 The relationship between pressure, volume and temperature of a gas are
related to the gas constant R by:
P nR
=
T V
Cross-multiply the equation and then rearrange as necessary to give the
equation for:
Chapter 16  Maths in chemistry

a) P
b) V
c) T
d) R
e) n
5 Energy, E, can be related to mass, m, and speed of light, c, by the equation
E = mc2.
Rearrange to give an equation for:
a) m
b) c2
c) c.

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 Ratio calculations
6 Kinetic energy, E, is related to mass, m, and velocity, v, by the equation
1
E = 2 mv2.
a) Rearrange this to give the equation for:
i) m
i) v2
ii) v
b) Calculate the energy of an object with mass 2.0 kg and a velocity of
6.0 m s–1.
c) If an object of mass 0.50 kg has an energy of 6.25 kg m2 s–2, calculate
its velocity.
7 Rearrange the equation:
abc de
=
f gh
to give an equation for:
a) h
b) f
c) b.

Ratio calculations
Many of the calculations in chemistry relate to the equation for a
reaction and to the mole ratio given by the equation.
You will have met ratios in your mathematics. The principles are exactly
the same for chemistry as they are for mathematics.

Example 1
Malcolm buys two tickets for a concert for £28 pounds.
How much does his friend Mavis pay for 5 tickets?

Answer
You can work out the answer by first working out the cost of one ticket. This
is sometimes referred to as the unitary method.
2 tickets cost £28
1 ticket therefore cost £28/2 = £14 (unit cost = £14)
So 5 tickets will cost 5 × £14 = £70

Example 2
If 5.0 g of CaCO3(s) is heated strongly 1.2 dm3 of CO2(g) is produced.
Calculate how much CO2(g) could be produced from 8.0 g of CaCO3(s).

Answer
5.0 g CaCO3(s) produce 1.2 dm3 of CO2(g)
1.2
1.0 g CaCO3(s) produce = 0.24 dm3 of CO2(g) (unit mass of CaCO3(s) )
5
So 8.0 g CaCO3(s) produce 8.0 × 0.24 = 1.92 dm3 of CO2(g)

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 Tip Test yourself
Temperature and pressure have   8 2.43 g of Mg(s) reacts with exactly 1.20 dm3 of oxygen.
to be the same as any change in Calculate how the volume of oxygen required to react exactly with
either pressure or temperature 121.5 g Mg(s) (at the same temperature and pressure).
would result in a change in   9 If 4.00 g NaOH(s) is dissolved in 100 cm3 water a solution with a
volume of the gas concentration of 1.00 mol dm –3 is formed.
Calculate the concentration if 5.00 g NaOH(s) is dissolved in 100 cm3
water.
10 A mining company obtained 40 tonnes of CaCO3(s) from 50 tonnes
of limestone. What mass of limestone must be mined to obtain
100 tonnes of CaCO3(s)?

Using numbers in standard (index) form

Key term Numbers can be written in different formats. A common way to write
numbers is to use the decimal notation, for example 123 456.78 and
Standard notation means writing 0.000 3456. When working with very large numbers (123 456.78) or very
the number in the form A × 10 n small numbers (0.000 3456) it is convenient to write these number in
where: standard notation.
• A is a number between 1 and 10 For example:
• n is an integer.
This is also called standard form. 3124 can be written as 3.124 × 103
312.4 can be written as 3.124 × 102
31.24 can be written as 3.124 × 101
Tip 3.124 can be written as 3.124 × 100
It is always useful to estimate (since 100 = 1, the factor 10 0 is normally omitted)
the answer to a calculation 0.3124 can be written as 3.124 × 10 –1
before doing the calculation on
a calculator. It makes it easy to 0.03124 can be written as 3.124 × 10 –2
spot whether or not you have 0.003 124 can be written as 3.124 × 10 –3
input the data into the calculator
correctly. One advantage of using numbers in standard form is that estimating the
answer to a calculation is easier.
2473 × 79
For example, the calculation
651
is almost impossible to do in your head, but if you change the numbers
into standard form it is easier to estimate the answer.
Chapter 16  Maths in chemistry

( )
2.473 × 103 × (7.9 × 101) (2.473 × 7.9) × (103 × 101)
(6.51 × 102) which is (6.51 × 102)
(2.5 × 8) × 10 4
20 × 102
which approximately gives = = 3 × 102
6.5 × 102 6.5
= 300
The calculator value is 300.1029186 so 300 is a very good approximation
and reassures you that you haven’t made any slips whilst using your
calculator. (But note that you wouldn’t normally quote an answer to 10
significant figures when data you have been given is much less accurate
than that. See the section on significant figures on page 271.)
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 Significant figures
When multiplying powers of 10 you add the powers, and when dividing
powers of 10 you subtract the powers. For example:
103 × 105 = 108
107
107 ÷ 104 = 4 = 103
10
10 × 10 = 103
5 –2

104
= 107
10-3

Test yourself
11 Convert the following numbers into standard (index) form.
a) 734.8
b) 69 845.6
c) 0.003 45
d) 333¼
e) 0.6745
f) 276 545
12 Estimate the value of each of the following calculations (DO NOT use
your calculator before you have estimated the answers).
(6.5 × 10 8 )
a) (4.2 × 102) (3.9 × 10 –4 )

349 × 6578
b)
174.8
2576 × 698
c)
219 × 4.98

Significant figures
In simple cases the number of significant figures is simply the number of
digits in the answer. For example, 31.21 has 4 significant figures, while
31.2 has 3 significant figures and 31 has just 2.
In other cases numbers may need rounding up or down before quoting
the answer to a particular number of significant figures. The number
17.87 has 4 significant figures but to 3 significant figures this is 17.9 (as
17.87 is nearer to 17.9 than 17.8). To 2 significant figures it would be 18
(17.87 is nearer to 18 than 17).
A number ending in a ‘5’ is rather arbitrarily raised to the number above.
So 17.5 must be written as 18 when quoted to 2 significant figures or
25.15 to 3 significant is 25.2.
When a number has 0s after the decimal point these are not considered
as ‘significant’. So 0.004 has only one significant figure because the
0s don’t count. 0.0526 has 3 significant figures, which to 2 significant
figures is 0.053.
A number like 1800 is ambiguous with regards to significant figures.
This presents a problem if the intention is to quote 1800 to 2 significant
figures. The way round it is to write the number in standard (index)
form, i.e. 1.8 × 102. Written like this it would be taken to mean that
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 2 significant figures is intended. If 4 significant figures were intended
then it should be written as 1.800 × 102.
Often your calculator will display an answer containing more digits
than you were given in the data. Suppose you were asked to calculate
the concentration of a NaOH(aq) in which 16.8 cm3 of the NaOH(aq)
Tip was neutralised by 25.0 cm3 of 0.500 mol dm –3 HCl(aq). If you did this
If the number after the calculation correctly your calculator would show the concentration to be
significant number of figures 0.74404761904 mol dm –3. The concentration of the solution isn’t known
is 4 or below the number is to this degree of precision. The accuracy will be limited to the precision
rounded down. of the data or in an experiment the accuracy of the apparatus. In the
If the number after the significant example above the data is given to 3 significant figures and the answer
number of figures is 5 or above should also be limited to 3 significant figures. The figures after the third
the number is rounded up. are dropped and the number is rounded. When rounded to 3 significant
figures, 0.74404761904 is 0.744.
In numbers like 0.74404761904, discount the 0 at the start of the
number such that ‘7’ is the first significant figure.
The list below shows a few simple examples of rounding to a stated
number of significant figures.
4567.46 to 5 significant figures is 4567.5
4567.46 to 4 significant figures is 4567
0.000 3462 to 3 significant figures is 0.000 346
0.000 3462 to 2 significant figures is 0.000 35
Remember in the last two examples we do not count the 0s before the
number starts. If in doubt put the number into standard form and the
0s will disappear: 0.000 3462 in standard form is 3.462 × 10 –3, which
clearly now has 4 significant figures.

Tip When carrying out a calculation always quote your answer to the
same number of significant figures given in the data. If the number of
When adding or subtracting, significant figures in the data varies, the least accurate should be used.
the number of decimal places is
maintained.
Example 3
Two students measured a temperature rise and recorded their results as
shown in the table below.
Student 1 Student 2
Chapter 16  Maths in chemistry

o
Initial temperature / C 21.0 21.5
o
Final temperature / C 29.5 29.0
o
Rise in temperature / C 8.5 7.50
The initial and final temperatures are recorded to 3 significant figures and
at first glance it looks like student 2 has recorded their results correctly.
Tip However, this is incorrect because the accuracy of the thermometer limits
When carrying out calculations the answer to 1 decimal place. The final reading cannot be more accurate
it is essential that you do not than individual readings.
round until the end of the When adding or subtracting numbers the number of figures after the decimal
calculation. If necessary you point indicate the accuracy and may limit the number of significant figures
must use the ‘memory’ function in the answer. Student 2’s value of 7.50 would not be accepted in an exam. The
on your calculator. correct value for student 2 should have been 7.5 (to 1 dp) and not 7.50 (to 3 sf).
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 Drawing graphs
Test yourself
13 Write the following numbers to 3 significant figures.
a) 734.8
b) 69 845.6
c) 0.000 3456
d) 0.6745
e) 276 545
1
f) 274 .
14 Density = mass/volume. Calculate the density of a solution when:
a) 23.1 g of solute was dissolved in 57 cm3 of solution. Quote your
answer to an appropriate number of significant figures.
b) 12.17 g of solute was dissolved in 30.0 cm3 of solution. Quote your
answer to an appropriate number of significant figures.
c) 123 g of solute was dissolved in 1026.45 cm3 of solution. Quote your
answer to an appropriate number of significant figures.

Drawing graphs
The sketch below shows a simple relationship between two variables.
y

∆y
gradient, m = ×
∆x ×
×
× ∆y
× ∆x
×

Tip intercept "c"

The symbol Δ is used to x

represent ‘change in …’ such Figure 16.1 Straight-line graph y = mx + c.
that :
ΔT is change in temperature The relationship between x and y is y = mx + c (where m is the gradient
ΔP is change in pressure and c is the intercept).
ΔV is change in volume.
Δx is the change in x and Δy is the change in y.
There are a number of points to note when drawing graphs.
1 Choose a scale that will allow the graph to cover as much of the
graph paper as possible. It is helpful to start both axes at zero. If all
the points on one axis are between 90 and 100, to start at zero on
that axis would cramp your graph into a small section of the paper
(see Figure16.2a). It is much better to truncate the axis so that the
graph fills as much of the paper as possible (see Figure 16.2b).

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 a b
Tip × ×
The choice of scale for the axes × ×
× ×
depends on whether or not the
× ×
origin is a valid point. In a rates
× ×
graph the origin (0, 0) is a valid
× ×
point and should always be
included.
0 100 90 95 100
this is a poor use of by truncating the x-axis
the graph paper this is a much better use
of the graph paper

Figure 16.2 Choosing the graph scale.

2 Label the axes with the dimensions and the units, for example:
Volume/cm3
Concentration/mol dm –3
3 After plotting all the points on a graph, often due to experimental
error you may not get a perfect straight line or a curve that goes
through all of the points. You have to draw a line of best fit for the
points (Figure 16.3).
a b
×
×
×
×
×
×
×
×
× ×
× ×
Figure 16.3 a) All the points are close to the straight line with some slightly above
balanced by some slightly below. b) It isn’t possible to draw a straight line that is close
to all the points but a curve can be drawn that is close to all the points with some points
above and some below the curve.

4 Drawing tangents to a curve.

Conc./mol dm–3

the tangent just touches the

curve but doesn’t cross the
curve at x seconds
Chapter 16  Maths in chemistry

x Time / s

Figure 16.4 Drawing the tangent to a curve.

By calculating the gradient of the tangent it is possible to work out

how the concentration changes with respect to time after x seconds.
This enables you to calculate the rate of reaction after x seconds.
The units of rate are the units of y/x which are mol dm –3/s; this is
written as mol dm –3 s–1.
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 Chapter 17
Preparing for the exam
Revising for the exam
Revising for exams is one of those boring tasks that no one enjoys
and there is no one way of approaching it that will suit everyone.
Nevertheless, an organised programme that covers all the work by
the date of the exam is essential. At the end of this chapter there is a
suggested timetable for revising Module 2 but it is really better if you
generate your own scheme based on what you feel needs your greatest
attention and the timescale available. When organising your time, make
sure that you plan carefully, allowing enough time to cover each of
the modules. It sounds easy, but it is a difficult thing to do. The most
important point is that any plan at least enables you to see what you
should be doing and when you should be doing it. Don’t try to be too
ambitious – little and often is by far the best way. It would of course be
sensible to put together a longer rolling programme to cover all your AS
subjects. Do not leave it too late. Start sooner rather than later.
For many students there are likely to be topics in chemistry that need
practice over an extended period of time and it is no good leaving these
to the last minute. For example, calculations are a stumbling block that
can only be solved by tackling sufficient examples until the routines
and procedures become second nature. Some students may find they
need practice with the structures and naming of organic molecules, or
perhaps with the steps in the mechanisms of reactions. Everyone will
have their own list, but topics that depend on understanding should
not be left until just before the exam. They are all tasks for the April
holidays and not the summer term. However, there are also many topics
in chemistry that simply require careful learning and these can be tackled
nearer to the time that the exam takes place. Examples are definitions,
atomic structures, the reactions of organic compounds, Group 2 and the
halogens.
There is also considerable evidence to show that revising for 2–3 hours
at a time is counter-productive and that it is much better to work in
short, sharp bursts of between 30 minutes and an hour. Whatever
your style, you must be organised. Sitting down the night before the
examination with a file full of notes and a textbook does not constitute
a revision plan – it is just desperation – and you must not expect a
great deal from it.
Whatever your personal style, there are a number of things you must do
and a number of other things you could do.
Things you must do
● Leave yourself enough time to cover all the material.

● Make sure that you actually have all the material to hand (use this
book or your notes as a basis) and the specification.

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 ● Identify weaknesses early in your preparation so that you have time
to do something about them.
● Familiarise yourself with the terminology used in examination
questions (see the section below).
● Practise examination questions on the topic.
Things you could do to help you learn
● Copy selected portions of your notes.

● Write a summary of your notes, which includes all the key points.
● Write key points on postcards (carry them round with you for quick
revision during a coffee break!).
● Discuss a topic with a friend also studying the same course.
● Try to explain a topic to someone not on the course.

Some general advice

There are various bits of advice that may be of help. Firstly, it is no good
just staring at a page of chemistry in the hope that by some magic its
contents will enter your head. It is all too easy to waste time turning
the pages of a textbook and achieving nothing. It is very possible to read
a page of text while your mind wanders to something else. You really
should force yourself to become engaged in the revision process. For
example, arm yourself with the specification, find a topic and on a blank
sheet of paper scribble down all the main points you can think of that
are relevant. Maybe you won’t think of much, but if you then refer to
your notes or a textbook your attention will be much more directed to
what is written there.
Secondly, do practise some questions against the clock. In the exam you
have to respond quickly to the topic being tested and you only have a
limited time to think. Many students can provide an answer when given
a generous amount of time to collect their thoughts but this won’t be
possible in an exam. Once you feel you have revised sufficiently try
doing some questions as fast as possible. Then check the answers to see
what mistakes you have made. Under pressure perhaps you have missed
a crucial point in a definition or maybe you are prone to making errors
when using your calculator. It is helpful to be aware of where you tend
to go wrong so that you are particularly careful on the day of the exam.
Chapter 17  Preparing for the exam

Thirdly, do make sure you are familiar with the data sheet that will be
provided in the exam. It is surprising how many students seem unaware
that this contains a lot of useful information to help them when
answering a question.
Chemistry students often accumulate a large quantity of notes so it is
useful to keep these in a well-ordered and logical manner. You should
review your notes regularly, maybe rewriting those taken during lessons
so that they are clear and concise, with key points highlighted. You
should check what you have written using textbooks and fill in any gaps.
Make sure that you go back and ask your teacher if you are unsure about
anything, especially if you find conflicting information in your class notes
and textbook. It is a good idea to file everything in specification order
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 The examination
using a consistent series of headings. Before starting your revision you
may also find it helpful to mark your notes to show which topics you
feel you can approach with confidence, which ones require some more
work and which require more intensive revision. This will allow you to
construct a revision plan that focuses on the right areas.

The examination
Terms used in examination questions
You will be asked precise questions in the examinations, so you can save
a lot of valuable time, as well as ensuring you score as many marks as
possible, by knowing what is expected. Examiners spend a lot of time
making sure the questions set specify exactly what they want in the
answer. Terms most commonly used are explained below.
● Define … is intended literally. Only a clear, accurate statement is
required.
Define the standard enthalpy change of formation. This simply requires
a statement quoting the definition which is on page 153.
● Explain … usually requires reference to some aspect of theory but
may expect an answer to involve reasoning. The number of marks
given for the question will indicate the amount of detail expected.
Explain the trend in boiling points of the halogens This would require
a statement of the trend and an explanation of intermolecular forces
in the context of the halogens and how they arise.
● State ... implies a concise answer usually with no explanation
required.
State one reason why chlorine is added to drinking water. This would
require a statement that it makes it safe to drink by killing the
bacteria.
● Describe ... requires candidates to provide the key points of a topic.
Diagrams may be required although usually if these are expected it
will be indicated in the question. It can be used with reference either
to trends or patterns or to experiments. The number of marks given
for the question will indicate the amount of description required.
Describe and explain are sometimes linked together in a question.
Describe what you would see when excess dilute hydrochloric acid
is added to calcium carbonate. Explain your observations. This
requires the observation that bubbling would be seen and the
calcium carbonate would dissolve to form a colourless solution. The
explanation is that carbon dioxide is given off and calcium chloride
solution is formed.
● Deduce/Predict ... implies that candidates are not expected to
know the answer but that it can be worked out from other pieces
of information provided in the question or by using the answers to
previous parts of the question. Predict also implies a concise answer
with little or no supporting statement required.
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 CaO reacts with H3PO4 , deduce/predict the formula of calcium
phosphate. This requires using the formula of H3PO4 to deduce the
valency of the phosphate ion and then to use that to work out the
formula of calcium phosphate to be Ca3(PO4)2.
● Suggest ... can be used in two different ways. It may mean that
there is more than one acceptable answer to the question or
alternatively that candidates should be able to use their knowledge
and imagination to provide a likely answer.
Suggest why SiO2 has a very high melting point and SiCl4 has a very
low melting point. Neither of these chemicals is directly mentioned
on the specification so you are expected to use your knowledge that
substances with high melting points have a giant lattices and that
bonds between non-metals are covalent.
● Calculate ... is used when a numerical answer is required. Working
should always be shown if the answer involves more than one step.
Calculate the amount, in mol, of HCl used … would require using
the data given in the question and processing it using the correct
mathematics.
● Sketch/draw ... when applied to diagrams, implies that a simple,
freehand drawing is acceptable. Nevertheless, care should be taken
over proportions and important details should be clearly labelled. If a
graph is expected essential points might be implied. For example the
position with respect to a line already drawn or the passing of a line
through the origin.
Sketch, with suitable labels, an enthalpy profile diagram for an
exothermic reaction. This requires a simple sketch with the axes
labelled and which clearly shows ΔH and the activation energy.
● Compare … means that candidates should include both the
similarities and differences between substances or concepts.
Compare the relative reactivities of magnesium and barium in their
reaction with water … would require noting that although the reaction
is similar, barium reacts more readily and forms a hydroxide while
magnesium reacts very slowly. The amount of detail expected would
be implied by the marks given for the question.
Chapter 17  Preparing for the exam

On the day of the exam

When you finally open the test paper, it can be quite a stressful
moment and you need to be certain of your strategy.
Time will be very tight; you must be calm and you must have a
practised approach that includes:
● do not begin writing as soon as you open the paper
● briefly scan all the questions before you begin to answer any
● identify those questions about which you feel most confident
● read the question carefully – if you are asked to explain, then explain,
do not just describe
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 The examination
● take notice of the mark allocation and do not supply the examiner
with all your knowledge of any topic if there is only 1 mark
allocated – similarly, you have to come up with four ideas if 4 marks
are allocated
● try to stick to the point in your answer – it is easy to stray into
related areas that will not score marks and will use up valuable time
● do not get stuck on a particular question which you are finding
difficult – it is better to move on to make sure that you complete
the paper
● try to answer all the questions.
Multiple choice questions
Clearly these are questions with just one correct answer from those
suggested. You may find you are under pressure for time so don’t
spend too long on any question trying to deduce the correct answer.
It is better to press on and return to questions that you are not sure
about once you have worked through the whole paper. Don’t leave any
question unanswered but if you are forced to guess at least make sure
that you have rejected any responses that are clearly incorrect.
Structured questions
These are questions that may require a single-word answer, a short
sentence or a response amounting to several sentences. The setter
for the paper will have thought carefully about the amount of space
required for the answer and the marks allocated, so the space provided
usually gives a good indication of the amount of detail required.
Remember though that this space is always generous so if you find
yourself filling it completely you are probably writing too much.
Free-response questions
These questions enable you to demonstrate the depth and breadth of
your knowledge as well as your ability to communicate chemical ideas
in a concise way. The questions may include marks for the quality of
written communication. You are expected to use appropriate scientific
terminology and to write in continuous prose, paying particular
attention to spelling, punctuation and grammar.

Module 1
The first module of the specification covers the development of practical
skills leading to the award of a ‘Practical Endorsement’ at A Level. It is
not part of the assessment at AS chemistry but a minimum of 15% of
the marks available in the exams will be for the assessment of practical
skills. Practical work is an essential part of A Level and can only be fully
appreciated as a result of extensive laboratory experience. This book
provides advice to support this work. For example, explanations of the
use of pipettes and burettes and the procedures used in a titration are
covered as well as the principles of procedures such as refluxing and
distillation. The ‘Activities’ are mostly based on practical work and the
interpretation and evaluation of the results. Chapter 1 is also specifically
devoted to providing a consideration of the reliability of different types
of apparatus.

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 Sample revision plan
The plan that follows suggests a possible way you might approach your
revision of Module 2. The main work is carried out 3 weeks (or more)
before the exam. It does pre-suppose that you are already broadly familiar
with the topics. In the second and third weeks it focuses on doing past
questions and it is assumed that during these two weeks you will also be
revising the other two modules (and of course the other subjects that you
are studying). It is by no means the only way of going about things, but it
does emphasise the need for a clear plan of what you are going to do.

Day Week 1 Week 2 Week 3

Each revision session should be approximately 30 minutes
Mon 30 min Atomic structure Re-read all your summary notes at least You should now have revised all of Module
and isotopes, formulae and twice. Check that you can write formulae 2 and have attempted questions relating to
equations correctly. Write a few equations showing each topic. Make a list of your weaknesses
the reactions of acids. and ask your teacher for help. Re-read all
your summary notes at least twice. Ask
someone to test you.
Tue 20 min Acids, oxidation Using past papers or other question
numbers and redox sources, try a couple of questions on the
reactions determination of empirical formulae and
10 min Moles – masses from equations.
determination of empirical Mark it and list anything you do not
formulae and calculating understand.
masses from equations Allow about 30 minutes
Wed 10 min Electron structure – Using past papers or other question Re-read all your summary notes at least
orbitals sources, try structured questions on twice
10 min Moles – gas volumes electron structure and volumes of gases Concentrate on the weaknesses you
10 min Atom economy and from equations. identified on Monday (by now you should
percentage yields Mark it and list anything you do not understand. have talked to your teacher about them).
Allow about 30 minutes Ask someone to test you.
Thu 15 min Bonding and Using past papers or other question
structure sources, try a structured question on
10 min Bond polarity and bonding and structure.
Intermolecular forces Mark it and list anything you do not
5 min Moles – masses and understand.
volumes from equations Allow about 30 minutes
Fri 10 min Shapes of molecules Using past papers or other question Collect together about five structured
10 min Bonding and sources, try a structured questions on questions and one extended answer
structure shapes of molecules. question covering all six topics and try
10 min Electron structure, Mark it and list anything you do not them under exam conditions.
Chapter 17  Preparing for the exam

acids and redox reactions understand. Allow 60 minutes

Allow about 30 minutes Mark them and list anything you do not
understand.
Sat 15 min Moles – solution Using past papers or other question
volumes and concentrations sources, try a structured question involving
10 min Checking definitions solution volumes and concentrations and
5 min Bond polarity one on any other section of Module 2.
5 min Electron structure, Mark it and list anything you do not
acids and redox reactions, understand.
moles and equations Allow about 30 minutes
Sun 10 min Moles – calculations Using past papers or other question When other modules have been revised,
from equations sources, try tackling a range of multiple try a complete past exam paper under
20 min Electron structure choice questions. exam conditions.
and shapes of molecules, Mark it and list anything you do not Check your answers against the mark
bond polarity, types of understand. schemes.
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 Glossary

acid – a proton donor.

activation energy – the minimum energy needed for a reaction to take place.
addition – a reaction in which two molecules combine together to form a single product.
alkali – a soluble base; it can accept protons in solution.
anion – a negatively charged ion.
atomic number – the number of protons in an atom of an element.

base – a proton acceptor.

bond enthalpy – the enthalpy change required to break and separate 1 mol of bonds in the molecules of a gas so that
the resulting gaseous (neutral) particles exert no forces upon each other. Expressed as an equation this is: X–Y(g) →
X(g) + Y(g)

cation – a positively charged ion.

covalent bond – a bond formed by the sharing of two electrons between two adjacent atoms. Each atom provides one
electron. The electrostatic attraction between the shared pair of electrons and the nuclei of the two bonded atoms
constitutes the covalent bond.

dative covalent bond – a bond in which two atoms share two electrons but one atom provides both electrons. The
electrostatic attraction between the shared pair of electrons and the nuclei of the two bonded atoms constitutes the
dative covalent bond.
delocalised electrons – bonding electrons that are not fixed between two atoms in a bond. They are mobile and are
shared by several or many atoms.
disproportionation – when the same element both increases and decreases its oxidation numbers so that the element
is simultaneously oxidised and reduced.
dynamic equilibrium – equilibrium reached when the rate of the forward reaction equals the rate of the reverse
reaction. The concentrations of the reagents and products remain constant; the reactants and the products react
continuously.

electron pair repulsion theory – states that the electron pairs around a bonded atom repel each other and the overall
shape of the molecule depends on the number and type of electron pairs around the central atom. Lone pairs (non-
bonded pairs) repel more than bonded pairs of electrons.
electronegativity – the ability of an atom of an element to attract the shared pair of electrons in a covalent bond.
electrophile – an electron-pair acceptor that forms a covalent bond.
empirical formula – gives the simplest ratio of the elements in a compound. These can be calculated from the
amounts of each element.
enthalpy change, ΔH – the difference between the enthalpy of the reactants and the enthalpy of the products.
ΔH = enthalpy of products − enthalpy of reactants

first ionisation energy – the energy required to remove one electron from the ground state of each atom in a mole of
gaseous atoms of that element, to form a mole of gaseous ions of charge 1+.
functional group – either a structural feature (e.g. a carbon-to-carbon double bond, CC), a group of atoms (e.g. a
hydroxyl group, O–H) or a single atom (e.g. Cl). It is the functional group that determines much of the chemistry of a
compound.

ground state – state of an atom that shows how it naturally exists with its electrons in their lowest energy position.

Hess’ law – states that, if a reaction can take place by more than one route, the enthalpy change for the reaction is the
same irrespective of the route taken, provided that the initial and final conditions are the same.
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 homologous series – a group of organic compounds that have the same general formula; contain the same functional
group; and in which each member of the homologous series differs from the next by CH2.
homolysis or homolytic fission – occurs when a covalent bond is broken so that the atoms joined by the covalent
bond each take one of the shared electrons.
hydrocarbon – a compound that contains hydrogen and carbon only.
hydrogen bonds – the relatively strong electrostatic attractions between polar molecules that contain hydrogen
covalently bonded to elements with high electronegativity such as fluorine, oxygen and nitrogen.
hydrolysis – a reaction that involves water and results in the organic compound being split and two new products
being formed.

indicator – a substance that changes colour with a change in pH.

induced dipole–dipole interaction – attractive force between atoms/molecules as a result of electrostatic attraction
between neighbouring dipoles: 1) the movement of electrons generates an instantaneous dipole; 2) the instantaneous
dipole induces other dipoles in neighbouring atoms/molecules; 3) two dipoles generate a weak temporary force of
attraction between the atoms/molecules.
intermolecular forces – forces of attraction that occur between molecules.
ion – an electrically charged particle formed by the loss or gain of one or more electrons from an atom or a group of atoms.
ionic bond – the electrostatic attraction between oppositely charged ions, the attraction between positive and
negative ions.
isotopes – atoms of the same element that have different masses are isotopes of that element. The isotopes of an
element all have the same number of protons (and electrons), but different numbers of neutrons.

le Chatelier’s principle – states that if a closed system at equilibrium is subject to a change, the system will move to
minimise the effect of that change.

mass number – the number of protons + neutrons in the nucleus of an atom.

metallic bond – the electrostatic attraction between the delocalised electrons and the positive ions held within the lattice.
molecular formula – represents the actual number of atoms of each element in the molecule. It does not provide any
detail of the arrangement of the atoms. For example, the molecular formula of ethanol is C2H6O.
molecular ion peak – the peak on the mass spectrum corresponding to the molar mass of the compound. (It is
sometimes referred to as the parent ion peak.)

nth ionisation energy – the energy required to remove 1 electron from each (n – 1)+ ion in 1 mole of gaseous (n – 1)+
ions to form 1 mole of gaseous n+ ions.
nucleophile – an ion or molecule that is an electron-pair donor and can form a new covalent bond.

orbital – a region around the nucleus of an atom that can hold up to a maximum of two electrons.

percentage error – the maximum error × 100 .

actual value
periodicity – a repeating pattern, in either physical or chemical properties, across different periods.
permanent dipole–dipole interactions – the weak electrostatic attractions between polar molecules that are
essentially covalent but have some ionic character.

radical – a particle that has at least one unpaired electron.

salt – formed when an acid has one or more of its hydrogen ions replaced by either a metal ion or an ammonium ion.
saturated – a saturated compound is a molecule in which all carbon – carbon bonds are linked together by C–C single
(σ) bonds only.
second ionisation energy – the energy required to remove 1 electron from each 1+ ion in 1 mole of gaseous 1+ ions
to form 1 mole of gaseous 2+ ions.
Glossary

specific heat capacity – for a substance, the specific heat capacity is the energy required to increase the temperature
of 1.0 g of the substance by 1 °C (1 K).
standard enthalpy change of combustion (Δc HӨ    ) – the enthalpy change when 1 mol of a substance is burned
completely, in an excess of oxygen, under standard conditions.
standard enthalpy change of formation (ΔfHӨ    ) – the enthalpy change when 1 mol of a substance is formed from its
elements, in their standard states, under standard conditions.
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 standard enthalpy change of neutralisation (Δneut H –Ө) – the enthalpy change when 1 mol of water is formed in a

Glossary
reaction between an acid and a base.
standard enthalpy change of reaction (ΔrH –Ө) – the enthalpy change when the amount in moles of the substances in
the equation as written react under standard conditions.
standard notation – writing a number in the form A × 10 n where A is a number between 1 and 10 and n is an integer.
This is also called standard form.
standard solution – a solution with a precisely known concentration.
stereoisomers – compounds with the same molecular and structural formulae but a different three-dimensional spatial
arrangement.
strong acid – a proton donor that completely dissociates into its ions.
structural isomers – compounds that have the same molecular formula but different structural formulae.
substitution – a reaction in which an atom or a group of atoms is replaced by another atom or group of atoms.

unsaturated – molecules that contain one or more CC double (or triple) bond.

weak acid – a proton donor that only partially dissociates into its ions.

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 Index

ammonium ions, tests for 85 boron, mass spectrum 14

A anhydrous compounds 46 box diagrams 22–3
absorptions of covalent bonds 253 anions 91 Boyle’s Law 51
accuracy of experimental results 6 apparatus branching of alkanes, relationship to
thermochemical experiments 151 measurement of mass 4–5 boiling point 204
acid–base titrations 66, 67 measurement of temperature 5 bromine 134, 135
acidity, role of water 81–2 precision of 1 reaction with ethene 213, 214
acids 30, 80–1 volumetric 1–4 see also halogens
dilution of 64 aromatic compounds 192, 196 burettes 3, 6
neutralisation reactions 82–3, 153–4 atmospheric gases, absorption of infrared
reaction with Group 2 elements 130
reaction with Group 2 oxides 130
radiation 256–8 C
atom economy 197–8
reaction with metals 56, 83 Cahn, Ingold and Prelog (CIP) rules
atomic number (proton number) 11
testing for 80 210–11
atomic radius, periodicity 118
see also hydrochloric acid calcium see Group 2 elements
atoms 10–11
activation energy 145, 167 calcium carbonate 37, 131, 132, 159
Avogadro constant (NA) 42–3
effect of catalysts 168–9 reaction with hydrochloric
Avogadro’s law 50, 56–7
addition reactions of alkenes 212–15 acid 165–6
calcium oxide, industrial uses 37
polymerisation 217–18
alcohol breath tests 256
B calculations
alcohols 186 back titration 74 ratios 269–270
chemical properties 227–31, 250 balances 4–5 rearranging equations 266–8
classification of 225–6 barium see Group 2 elements significant figures 7, 271–3
infrared spectroscopy 254 barium sulfate 131–2 standard (index) notation 270–1
physical properties 226–7 bases 81 carbon
production from haloalkanes 232–3 neutralisation reactions 82–3, 153–4 electron configuration 194
test for 248 testing for 80 forms of 60, 110
see also ethanol; methanol benzene 193 see also organic chemistry
aldehydes 186, 228 biodegradable plastics 221 carbonates
test for 248 boiling points of Group 2 elements 131
alicyclic compounds 192 alcohols 226–7 reaction with an acid 34–5, 83
aliphatic compounds 196 alkanes 203, 204 tests for 84
alkalinity, role of water 81–2 alkenes 208–9 carbon dioxide
alkalis 81 checking purity of liquids 248 greenhouse effect 257–8
alkanes 186, 187 covalent compounds 98 tests for 131
bonding 194–5 Group 2 elements 128 carbonium ions 216
chemical properties 205–6, 250 halogens 134 carbonyl compounds, infrared
cyclic 192 and intermolecular forces 109 spectroscopy 254
physical properties 203–4 metals 104 carboxylic acids 186, 229
alkenes 186, 207 periodicity 117, 119–20 infrared spectroscopy 255
addition polymerisation 217–18 water 109 test for 248
bonding 208–9 Boltzmann distribution 168–9 catalysts 169–72
chemical properties 212–16, 250 bomb calorimeter 151 economic importance 171
formation from alcohols 230–1 bond enthalpies 145–7 effect on equilibrium position 175
infrared spectroscopy 255 carbon–halogen bonds 235 heterogeneous 171
physical properties 207–8 bonding 89–90 homogeneous 170–1
stereoisomerism 209–12 covalent 94–8 cations 91
test for 248 hydrogen bonds 108–9 chain isomerism 193
allotropes 152–3 ionic 90–2 Charles’ Law 51
amines 186 metallic 103–4 chloride ions, reaction with silver nitrate
ammonia in organic compounds 194–5, 208–9 33–4
Haber process 171, 176–7 periodicity 119 chlorine 134, 135
molecular shape 101 bond polarity 105–6 reaction with Group 2 elements 130

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 Index
uses of 137–9 equilibrium constant (Kc) 177–9 see also alcohols
see also halogens le Chatelier’s principle 173–5 ethene
chlorine radicals, effect on ozone addition reactions 212–16
layer 237 E see also alkenes
chlorofluorocarbons (CFCs) 236, 237 examinations
einsteinium 27
alternatives to 238 preparation for 276–7, 280
electrical conductivity
greenhouse effect 257 strategies 278–9
covalent compounds 98
chloromethane, bonding 195 terms used in questions 277–8
Group 2 elements 128
cis-trans isomerism 211–2 types of questions 279
ionic compounds 93
collision theory of reactivity 167–8 exothermic reactions 144
metals 104
combustion experiments
periodicity 117, 119
of alcohols 227 improvement of 8–9
electron configurations 22–4
of alkanes 205 sources of error 8
carbon 194
enthalpy change 149–50 E/Z isomerism 209–10
Group 2 elements 127
standard enthalpy change of 153, Cahn, Ingold and Prelog (CIP) rules
halogens 133
156–8 210–11
noble gases 89
compounds, mass spectra 16–17 cis-trans isomerism 211–12
electronegativity 105–7
concentrations of solutions 62–4
elements in organic compounds 195
calculations involving 267–8
effect on the rate of a reaction 166–7,
electron pair repulsion theory 99, 113 F
electrons 10–11 filtration 246
168
delocalised 103–4 fingerprint region, infrared spectroscopy
le Chatelier’s principle 174
energy levels 21 253–5
conditions of a reaction 195
lone pairs 96, 97, 99–102 fireworks, sources of colour 38
copper sulphate 41, 47
orbitals 21–4, 27 first ionisation energy, periodicity 120–2
reaction with zinc 35, 150–1
electron shells 18–19 fluorine 134
covalent bonding 94
and ionisation energies 19–20 see also halogens
absorptions 253
electrophiles 213 formation, standard enthalpy change of
dative covalent (coordinate)
electrophilic addition, mechanism of 153, 156–8
bonds 97–8
213–15 fractional distillation 247
multiple covalent bonds 95–6
elimination reactions, alcohols 230–1 functional groups 185–6
in organic compounds 194–5
empirical formulae 46–9 qualitative tests for 248
single covalent bonds 94–5
organic compounds 188–9 reactions of 250
covalent compounds
endothermic reactions 144
molecular shapes 99–102
typical properties 98
energy level diagrams 22–3
energy levels, electrons 21
G
cross-multiplying 269 gas constant (R) 51–3
enthalpy change 143–4
cyclic alkanes 192 gases
bond enthalpies 145–7
experimental measurement 147–51 collection and volume measurement
D Hess’ law 154–6 165
data recording 6 under standard conditions 152–3 ideal gas equation 51–3
dative covalent (coordinate) enthalpy cycles 155–9 le Chatelier’s principle 174–5
bonds 97–8 enthalpy profile diagrams 145 molar volume 50–1
d-block elements 24, 116 equations 31–2 reactions between 56–7
dehydration reactions, alcohols 230–1 ionic 33–5 volumes produced in a
delocalised electrons 103–4 state symbols 32–3 reaction 54–5
dibasic acids 84 equilibrium, dynamic 173–6 giant covalent lattices 110–11
dilution of solutions 64–5 equilibrium constant (Kc) 177–8 giant ionic lattices 91, 110
dinitrogen oxide (N2O), greenhouse effect calculation of 179 giant metallic lattices 103, 110
257 effect of temperature change 178–9 global warming 257–9
dipoles 106, 107 equilibrium reactions 81 graphene 110, 111
displacement reactions, halogens 136–7 errors 8 graphite 110
displayed formulae, organic compounds maximum error 1–3, 4 graphs 274–5
191 percentage error 2, 4–5 greenhouse gases/greenhouse effect
disproportionation 137 esterification 231 257–8
distillation 229, 230, 246 catalysts 170 ground states 18–19, 23–4
fractional 247 reversibility 172–3 Group 2 compounds, reactions of 130–2
dot-and-cross diagrams 90–1, 95–6 ethane 185 Group 2 elements
double bonds 95–6 see also alkanes chemical properties 128–30
in alkenes 208 ethanol 185 electron configuration 127
dynamic equilibrium 173 mass spectrometry 17, 259 physical properties 128
effect of catalysts 176 oxidation of 228, 229–30 Group 17 elements see halogens
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 H iodine 111, 134, 135
see also halogens
see also alkanes
methanol
Haber process 171, 176–7 ionic bonding 90–2 bonding 195
halide ions, tests for 85, 139–40 ionic compounds, typical properties 93 see also alcohols
haloalkanes (halogenoalkanes) 186, ionic equations 33–5 molar mass 43
205–6 ionisation energies 19–20 molar volume 50–1
chemical properties 250 periodicity 120–2 molecular formulae, organic compounds
classification and isomerism 232 ions 11–12 188
environmental concerns 236–8 shapes of 102–3 molecular ion peak (parent ion peak) 16
production from alcohols 231 tests for 84–5 moles 42
reactivity of 234–5 isomerism 192–3 relationship to masses in grams 43–5
substitution reactions 232–3 haloalkanes 232 monomers 217
test for 248 isotopes 12–13 identification of 219
uses of 235
halogens 133
chemical properties 135–7
K N
physical properties 134–5 ketones 186, 228–9 neon
uses of chlorine 137–9 mass spectrum 15
Hess’ law 154–6 L see also noble gases
heterogeneous catalysts 171 neutralisation reactions 82–3
Large Hadron Collider 10
heterolytic fission 214–5 standard enthalpy change of
le Chatelier’s principle 173–5
homogeneous catalysts 170–1 neutralisation 153–4
limestone (calcium carbonate) 132
homologous series 185 neutrons 10–11
limewater 131
homolysis (homolytic fission) 206, 214 nitrogen (II) oxide (NO), effect on ozone
lone pairs of electrons 96, 97
hydrated compounds 46–8 layer 237–8
and shapes of molecules 99–102
hydration 213 noble gases 89
neon 15
hydrocarbons
alkanes 203–6
M nucleophilic substitution, primary
alkenes 207–16 magnesium haloalkanes 233
fuels 202 reaction with an acid 56, 83
hydrochloric acid reaction with oxygen 31, 42
see also Group 2 elements
O
reaction with aqueous sodium orbitals 21–4, 27
hydroxide 34, 66, 68, 149, 154 magnesium oxide, reaction with
organic chemistry
reaction with magnesium 56 hydrochloric acid 35, 82
analytical techniques 253–60
reaction with sodium carbonate 34–5, magnesium sulphate 47, 131
bonding 194–5
83 Markownikoff’s rule 215–16
calculations 190, 196–8
reaction with solid magnesium oxide mass, measurement of 4–5
formula types 188–92
35, 82 mass number (nucleon number) 11
functional groups 185–6
reaction with zinc 83 mass spectra
important terms 195–6
hydrogen bonds 108–9 of compounds 16–17
isomerism 192–3
hydrogen bromide of elements 13–15
nomenclature 186–8
reaction with asymmetric alkenes mass spectrometry 13, 259–61
see also alcohols; alkanes; alkenes;
215–16 accuracy of 17
haloalkanes
reaction with ethene 213, 214–15 maths see calculations; graphs
organic synthesis 244–8
hydrolysis 213 maximum error 1–3, 4
synthetic routes 249–52
haloalkanes 232–4 measuring cylinders 1–2, 6
oxidation
melting points
of alcohols 227–30
checking purity of liquids 248
I covalent compounds 98
see also redox reactions
ice oxidation numbers 77–8
Group 2 elements 128
properties of 109, 111 oxides, Group 2 elements 128, 129–31
ionic compounds 93
structure of 111 oxidising agents 79
metals 104
ideal gas equation 51–3 oxygen, reaction with Group 2 elements
periodicity 117, 119–20
induced dipole–dipole 127–8
water 109
interactions 109 ozone layer 236–7
meniscus, volumetric equipment 2
infrared radiation, absorption by hole in 237–8
menthol 225
atmospheric gases 256–8 metallic bonding 103–4
infrared spectroscopy 253–5 metals, typical properties 104 P
Index

alcohol breath tests 256 methane p-block elements 116

intermolecular forces 108–9 bonding 194–5 percentage error 2, 4–5
iodide ions, catalytic oxidation 170 greenhouse effect 257 percentage yield 197–8, 247–8

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 Index
periodicity 116–22 relative formula mass 40–1 sulfates
periodic table 115–16 relative isotopic mass 40 of Group 2 elements 131–2
Group 2 elements 127–33 relative molecular mass 40–1 tests for 84
groups and periods 116–17 reversible reactions 172 surface area, effect on the rate of a
halogens (Group 17) 133–40 dynamic equilibrium 173–6 reaction 168
and ion formation 92 revision 275–7
trends 117 sample revision plan 280 T
valency prediction 90 temperature
permanent dipole–dipole S effect on equilibrium constant 178–9
interactions 108 effect on the rate of a reaction 168–9
salts 82–4
pi (π) bonds 208 le Chatelier’s principle 175
saturated compounds 202
pipettes 2 measurement of 5
s-block elements 116
plasticisers 218 tertiary alcohols 226
secondary alcohols 226
polar bonds 106 thermometers 5
separating funnels 247
polar molecules 106 titrations 65–7
separation of reaction products 246–7
poly(ethene) (polythene) 217–18 back titration 74
shapes of covalent molecules 99–102
polylactic acid (PLA) 221 calculation of an unknown
shapes of ions 102–3
polymerisation 217–9 concentration 68–70
sigma (σ) bonds 208
polymers tribasic acids 84
significant figures 7, 271–2
biodegradable plastics 221 triple bonds 96
silicon dioxide (quartz) 111
identification of monomers from which
silver nitrate, reaction with halide ions
they are made 219
properties and uses of 218
33–4, 85, 139–40 U
skeletal formulae, organic compounds units 266–7
waste and recycling 220–1
191–2 unsaturated bonds 96
p-orbitals 22
sodium chloride 33–4, 90–2, 93 unsaturated molecules 207
positional isomerism 193
sodium hydroxide
potassium dichromate, reaction with
alcohols 228
reaction with haloalkanes 197, 234 V
reaction with chlorine 138
precipitation reactions 76 valency 29–30, 90
reaction with hydrochloric acid 34,
pressure, le Chatelier’s principle 174–5 vinegars, comparison of acidity 67
66, 68, 149, 154
primary alcohols 226 volatile compounds 227
solubility
principal quantum numbers 21 volume measurement 1–4
covalent compounds 98
propane volumetric flasks 3–4
ionic compounds 93
mass spectrum 16–17
solutions
see also alkanes
calculations involving 266–8 W
protons 10–11 water
concentrations of 62–4
purification of reaction products 247 hydrogen bonding 108–9
dilution of 64–5
checking for purity 248 miscibility with alcohols 227
of ionic solids 93
s-orbitals 22 molecular shape 101
R space research, mass spectrometry 260 properties of 109
radical substitution, alkanes 205–6 specific heat capacity 147 reaction with alkenes 213, 215–16
rate of a reaction 165 spectator ions 34 reaction with Group 2 elements
hydrolysis of primary haloalkanes 234 standard (index) notation 271–2 129–30
influencing factors 166–71 standard enthalpy changes 152–3 reaction with Group 2 oxides 130
measurement of 165–6 standard solutions 4 role in acidity and alkalinity 81–2
ratio calculations 269 state symbols 32–3 specific heat capacity 147
reaction rates see rate of a reaction stereoisomerism 193, 210–11 water of crystallisation 46–7
reactivity, Group 2 elements 128 straight-line graphs 273–4 experimental determination 48
reagents 195 strong acids 80 water treatment, use of chlorine
rearranging equations 266–8 strontium see Group 2 elements 137–8
recrystallisation 247 structural formulae, organic compounds wavenumbers 253–4
recycling polymers 220–1 191 weak acids 80
red copper oxide, experimental structural isomerism 192–3
determination of formula 49 structure, periodicity 119 Z
redox reactions 77–9 sublimation 111 Ziegler–Natta catalyst 171
displacement reactions 136–7 substitution reactions zinc
reducing agents 79 alcohols 231 reaction with aqueous copper sulfate
reflux condensers 229, 230 alkanes 205–6 35, 150–1
relative atomic mass 14–15, 39–40 haloalkanes 232–4 reaction with hydrochloric acid 83

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 Free online resources
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1 Practical skills 3 Compounds, formulae

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2 Atoms and electrons 4 Amount of substance –

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 5 Amount of substance – 12 Basic concepts in

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precipitation, acid–base
and redox

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8 The periodic table and 15 Organic synthesis

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10 Enthalpy changes 17 Preparing for the

exam

11 Rates and equilibria

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9781471827068_OCR_A_Level_Chemistry.indb 290

290
The Periodic Table

The Periodic Table

1 18
Key
1 atomic number 2

H symbol He
relative atomic mass
1.0 2 13 14 15 16 17 4.0
3 4 5 6 7 8 9 10

Li Be B C N O F Ne
6.9 9.0 10.8 12.0 14.0 16.0 19.0 20.2
11 12 13 14 15 16 17 18

Na Mg Al Si P S Cl Ar
23.0 24.3 3 4 5 6 7 8 9 10 11 12 27.0 28.1 31.0 32.1 35.5 39.9
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.1 40.1 45.0 47.9 50.9 52.0 54.9 55.8 58.9 58.7 63.5 65.4 69.7 72.6 74.9 79.0 79.9 83.8
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.5 87.6 88.9 91.2 92.9 95.9 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
57-71
Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 178.5 180.9 183.8 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0

87 88 89–103 104 105 106 107 108 109 110 111 112 114 116

Fr Ra Rf Db Sg Bh Hs Mt Ds Rg Cn Fl Lv

57 58 59 60 61 62 63 64 65 66 67 68 69 70 71

La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
138.9 140.1 140.9 144.2 144.9 150.4 152.0 157.2 158.9 162.5 164.9 167.3 168.9 173.0 175.0

89 90 91 92 93 94 95 96 97 98 99 100 101 102 103

Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.0 238.1
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