Longhorn Secondary Chemistry FORM 4

Longhorn Secondary
Chemistry
Form 4
George Ngaruiya
Joan Kimaru
Paul Mburu
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Published by:

Longhorn Publishers (K) Ltd.,
Funzi Road, Industrial Area,
P.O. Box 18033-00500,
Nairobi, Kenya.
Longhorn Publishers (U) Ltd.,

Plot M220, Ntinda Industrial Area,
Jinja Road,
P.O. Box 24745,
Kampala Uganda.
Longhorn Publishers (T) Ltd.,

Plot 664, Msasani Village,
Old Bagamoyo Road,
P.O. Box 1237,
Dar es Salaam, Tanzania.
© George Ngaruiya • Joan Kimaru • Paul Mburu, 2005
All rights reserved. No part of this publication may be

reproduced, stored in a retrieval system or transmitted
in any form or by any means, electronic, mechanical,
photocopying, recording or otherwise without the prior
written permission of the Copyright owner.
First published 2005

Reprinted 2005, 2007
Corrected 2008
ISBN 9966 49 565 7
Illustrations by Timothy Maleche
ii
CONTENTS
Unit 1: Acids, Bases and Salts.............................................................................................. 1

1.1 Acids, bases and salts................................................................................................... 1
1.2 Strong and weak acids and bases.................................................................................. 2
1.3 Electrical conductivity of weak and strong acids and bases......................................... 5
1.4 Characteristics of amphoteric oxides and hydroxides.................................................. 7
1.5 Effect of solvent in acid-base characters......................................................................11
1.6 Salts..............................................................................................................................15
1.7 Precipitation reactions in salt preparation....................................................................17
1.8 Reactions of cations in aqueous solution with sodium hydroxide and
ammonia solution.........................................................................................................18
1.9 Test for cations..............................................................................................................21
1.10 Reactions of cations in aqueous solution with chloride,
carbonate, sulphite and sulphate ions...........................................................................23
1.11 Complex ions................................................................................................................26
1.12 Solubility......................................................................................................................29
• Solubility curves......................................................................................................30
• Fractional crystallisation of salts...........................................................................35
• Application of solubility curves..............................................................................36
1.13 Water hardness..............................................................................................................37
• Effects of water hardness........................................................................................41
• Methods of removing water hardness.....................................................................42
Revision Exercise 1......................................................................................... 46
Unit 2: Energy changes in physical and chemical processes............................... 47
2.1 Exothermic and endothermic reactions........................................................... 47
2.2 Energy changes in physical processes............................................................. 54
2.3 Energy changes in chemical processes............................................................ 57
2.4 Hess’s Law of constant heat summation.......................................................... 85
2.5 Relationship between heat of solution, hydration
and lattice energy............................................................................................. 93
2.6 Energy contents of common fuels................................................................... 96
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Unit 3: Reaction rates and reversible reactions................................................... 106
3.1 Rates of reactions............................................................................................. 106
3.2 Collision theory and activation energy............................................................ 106
3.3 Methods used to measure rates of reactions ................................................... 109
3.4 Factors affecting rates of reaction.................................................................... 110
3.5 Reversible reactions......................................................................................... 122
3.6 Effects of different factors on the position of equilibrium.............................. 127
3.7 Uses of reversible reactions in industrial processes........................................ 133
Unit 4: Electrochemistry......................................................................................... 140
4.1 Redox reactions............................................................................................... 140
4.2 Displacement reaction as redox reaction......................................................... 148
4.3 Electrochemical cell........................................................................................ 151
4.4 Electrolysis...................................................................................................... 163
4.5 Application of electrolysis............................................................................... 184
Unit 5: Metals........................................................................................................... 191
5.1 Extraction of metals......................................................................................... 191
5.2 General methods of extracting metals............................................................. 191
5.3 Extraction of sodium, aluminium, iron, copper and zinc from
their ores.......................................................................................................... 195
• Sodium........................................................................................................ 195
• Aluminium.................................................................................................. 197
• Iron............................................................................................................. 202
• Zinc............................................................................................................. 205
• Copper........................................................................................................ 207
5.4 Properties of metals......................................................................................... 211
• Physical properties of some metals............................................................ 211
• Chemical properties of some metals........................................................... 213
5.5 Uses of some metals........................................................................................ 223
5.6 Some alloys and their uses............................................................................... 225
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5.7 Pollution effects of the industrial production of metals
on the environment.......................................................................................... 227
Revision exercise 5.......................................................................................... 230
Unit 6: Organic Chemistry II............................................................................... 232
6.1 Alkanols (alcohols).......................................................................................... 232
• General formula and nomenclature of alkanols......................................... 232
• Preparation of alkanols.............................................................................. 235
• Properties of alkanols................................................................................. 237
• Uses of ethanol........................................................................................... 243
6.2 Alkanoic acids (carboxylic acids).................................................................... 244
• General formula and nomenclature of alkanoic acids............................... 244
• Preparation of alkanoic acids.................................................................... 247
• Properties of alkanoic acids....................................................................... 249
• Uses of ethanoic acid................................................................................. 257
6.3 Detergents........................................................................................................ 257
• Soapy detergents......................................................................................... 257
• Soapless detergents..................................................................................... 264
6.4 Polymers and fibres......................................................................................... 269
6.5 Advantages and disadvantages of synthetic and
natural polymers and fibres.............................................................................. 277
Unit 7: Radioactivity..................................................................................... 284

7.1 Stability of isotopes and other nuclides........................................................... 284
7.2 Radioactivity.................................................................................................... 286
7.3 Nuclear fission and fusion............................................................................... 297
7.4 Application of radioactivity and radioisotopes................................................ 300
7.5 Pollution effects of radioactivity..................................................................... 302
Test Papers....................................................................................................... 307
Glossary........................................................................................................... 330
Appendix I....................................................................................................... 337
Appendix II...................................................................................................... 338
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Unit 1: Acids, Bases and Salts II
1.1 Acids, bases and salts
We learnt about acids, bases and salts in Form One.
Acids
An acid is a substance which dissociates in water to give hydrogen ions as the
only positively charged ions. For example;
HCl(aq) H+(aq) + Cl–(aq)

H2SO4(aq) 2H+(aq) + SO42–(aq)

HNO3(aq) H+(aq) + NO–3(aq)
Gases like chlorine, hydrogen chloride, carbon(IV) oxide and other acidic
gases can only have acidic properties when dissolved in water.
Bases
A base is a substance which dissociates in water to give hydroxide ions as the
only negatively charged ions. For example;
NaOH(aq) Na+(aq) + OH–(aq)
KOH(aq) K+(aq) + OH–(aq)
Ca(OH)2(aq) Ca2+(aq) + 2OH–(aq)
As it can be seen above, just like acids avail H+ ions, bases show basic properties
only in aqueous solution by availing OH– ions.
Salts
A salt is an ionic compound formed when a cation derived from a base combines
with an anion derived from an acid during neutralization reactions.
Acid + base salt + water

Examples are:
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)
HNO3(aq) + KOH(aq) KNO3(aq) + H2O(l)
HCl(aq) + NH4OH(aq) NH4Cl(aq) + H2O(l)
As we learnt earlier, there are several methods of salt preparation and

neutralisation is one of them.
1
Self-assessment exercise 1.1
1. (i) Explain why dry blue litmus paper is not affected by dry hydrogen
chloride gas or any other acidic gas.
(ii) Explain why dry red litmus paper is not affected by dry ammonia gas.
2. Which ions give
(i) An acid its characteristics?
(ii) A base its characteristics?
3. During salt formation by neutralisation method, which substance donates
(i) a cation?
(ii) an anion?
4. Define the terms
(i) Salt
(ii) Neutralisation reaction.
1.2 Strong and weak acids and bases

(a) Strong and weak acids
A particular acid is described as strong or weak depending on its ability to give
hydrogen ions when dissolved in water. In other words, it is based on the degree
to which they dissociate into ions in aqueous solution.
The three examples of acids we described above i.e. hydrochloric, nitric(V)
and sulphuric(VI) acids are said to be strong.
A strong acid is one which dissociates completely in water to give all its
hydrogen ions. For example.
HCl(aq) ––––– H+(aq) + Cl–(aq)
HNO3(aq) ––––– H+(aq) + NO–3(aq)
H2SO4(aq) ––––– 2H+(aq) + SO42–(aq)
A weak acid is one which is only slightly or partially dissociated in aqueous

solution. That is, it gives very few hydrogen ions when dissolved in water.
Examples are ethanoic acid and carbonic acid.
CH3COOH(aq) H+(aq) + CH3COO–(aq)
H2CO3(aq) H+(aq) + HCO3–(aq) 2H+(aq) + CO32–(aq)
The reverse half arrows ( ) show that the acid is weak and the process is
reversible.
A weak acid contains more molecules than ions.
2
Self-assessment excercise 1.2
Write dissociation equations for each of the following acids.
(a) Sulphuric(IV) acid — H2SO3, a weak acid.
(b) Nitric(III) acid — HNO2, a weak acid.
(c) Sulphuric(VI) acid, H2SO4, a strong acid.
(b) Strong and weak bases

A particular base is described as strong or weak depending on its ability to yield
hydroxide ions when dissolved in water.
A strong base is one which completely dissociates to give all its hydroxide
ions when dissolved in water.
Examples are, sodium hydroxide and potassium hydroxide.
water Na+(aq) + OH–(aq)
NaOH(s) ––––––
water K+(aq) + OH–(aq)
KOH(s) ––––––
A weak base partially dissociates to give few hydroxide ions when dissolved
in water. An example is ammonium hydroxide.
NH3(g) + H2O(l) NH4OH(aq) NH4+(aq) + OH–(aq)

Write dissociation equations for each of the following strong bases.
(a) Potassium hydroxide
(b) Rubidium hydroxide
(c) Lithium hydroxide
Experiment 1.1
Determining the pH of weak and strong acids and bases
Apparatus and chemicals
• beakers.
• droppers.
• 2M hydrochloric acid.
• 2M ethanoic acid.
• 2M sodium hydroxide.
• 2M ammonia solution.
• universal indicator solution
• pH chart.
Procedure
1. Place about 20 cm3 of dilute hydrochloric acid, ethanoic acid, sodium
hydroxide solution and ammonia solutions in different beakers.
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2. Add 2 - 3 drops of universal indicator solution. Note the colour of the solution.
3. Compare the colours of the solutions with colours given on the universal
indicator standard colour chart to determine the pH values.
4. Record the pH values in your notebook as shown in Table 1.1 below.
Table 1.1 pH values for weak and strong acids and bases
Substance being tested Colour obtained pH Indicate whether

on adding value they are weak or
universal indicator strong base or acid
2M hydrochloric acid
2M ethanoic acid
2M sodium hydroxide
2M ammonia solution
5. Classify the solutions into strong or weak acid and base.

Note: Universal indicator paper can also be used. One just needs to dip the paper
into the solution to be tested and then compare the colour change on the paper
with the standard colour chart.
An example of standard colour chart is shown in Table 1.2
.
Table 1.2 Example of standard colour chart
n
nge
igo
e
roo
en
rpl
blue
llo
violet
k
ey
gre
Colour
pin
ind
pu
ora
d
ma
ye
gr
re
pH 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Increase in hydrogen Increase in hydroxide

ions concentration ions concentration or increase in
or increase in strength strength of base
of acid
Neutral
Strong acids have high concentration of hydrogen ions (H+) and their pH ranges
from 1 –– 3.5. Weak acids have lower concentration of hydrogen ions and their
pH ranges from 3.5 –– 6.5. pH of pure water is the dividing line. Water has a pH
value of 7.0 and it is said to be neutral.
Weak bases have lower concentration of hydroxide ions and their pH ranges
from 7.5 ––10.5. Strong bases have a higher concentration of hydroxide ions and
their pH ranges from 10.5 –-14. From the experiment, the pH of dilute hydrochloric
4
acid shows that it is a strong acid while that of ethanoic acid shows that it is a
weak acid. The pH of dilute sodium hydroxide solution shows that it is a strong
base while that of dilute ammonia solution shows that it is a weak base.
It must be emphasised that the term “strong” applies to acids and bases when
they are completely dissociated in aqueous solutions. It does not indicate the
molarity (concentration) of the acid or base.
Self-assessment excercise 1.4

1. Define the following terms
(i) strong acid
(ii) weak base
2. Ethanoic acid turns blue litmus paper weakly red, hydrochloric acid
turns it strongly red. Explain why this happens.
3. Is the pH value of a strong acid low or high?
1.3 Electrical conductivity of weak and strong acids and bases

Substances that conduct electricity in their aqueous solutions are called electrolytes.
Acids and bases are electrolytes. They contain charged particles called ions. These
ions can conduct electricity when they move in the solution.
Electrical conductivity depends on the strength of the acid or base used as
electrolyte. Strong acids and bases have higher conductivity compared to weak
acids and bases. This is because strong acids and bases dissociate fully releasing all
the ions which conduct electricity. Weak acids and bases do not readily dissociate
into ions and therefore avails only a few ions to conduct electricity.
Experiment 1.2
Determining the electrical conductivity of weak and strong acids and bases
• 250 cm3 beaker
• two 1.5 V dry cells
• 2.5 V bulb
• carbon rods
• connecting wires
• switch
• 2M hydrochloric acid
• 2M ethanoic acid
• 2M sodium hydroxide
• 2M ammonia solution
Procedure
1. Put 50 cm3 of 2M hydrochloric acid in the beaker.
2. Make a complete circuit using carbon electrodes as shown in Fig. 1.1.
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bulb
switch
carbon rod
(anode)
carbon rod
(cathode)
solution to be tested
Fig. 1.1: Investigating the electrical conductivity in acids and bases

3. Switch on the current.
• Does the bulb glow?
• Note the intensity of the light given out?
• What do you observe on the carbon rods? What does this indicate?
4. Repeat the same experiment with 2M ethanoic acid, 2M sodium hydroxide
and 2M ammonia solution. Use 50 cm3 of each solution.
Note: Rinse the beaker and the rods thoroughly with distilled water before
adding the next solution.
5. Note the changes occurring around the carbon rods, in the contents of the
beaker and in the brightness of the bulb.
6. Copy Table 1.3 in your notebook and fill in your observations and conclusions.
Table 1.3: Electrical conductivity in acids and bases
Solution Brightness of the bulb Conclusion
(use bright light or faint
light)
2M hydrochloric acid
2M ethanoic acid
2M sodium hydroxide
2M ammonia solution
When bases, and acids are dissolved in water, they dissociate to form ions which
conduct electricity. The more the dissociation the higher the yield of the ions. The
higher the yield of the ions the greater the electrical conductivity of the aqueous
solutions and hence the brighter the light from the bulb.
Strong acids, like hydrochloric acid, yield many ions when in aqueous form and
therefore they show a high electrical conductivity. They form strong electrolytes.
Weak acids, like ethanoic acid yield few ions when in aqueous form. They form
weak electrolytes.
6
Likewise, strong bases like sodium hydroxide, yield many ions when in aqueous
form and they form strong electrolytes. Weak bases, like aqueous ammonia, yield
few ions and they form weak electrolytes.
All electrolytes decompose during electrolysis forming various substances
around the electrodes.
1. Define the following terms
(i) strong electrolyte
(ii) weak electrolyte
2. Compare the electrical conductivity of aqueous carbonic acid
with that of dilute sodium hydroxide.
1.4 Characteristics of amphoteric oxides and hydroxides

Amphoteric oxides and hydroxides exhibit both acidic and basic properties
They react with both acids and bases to form salts.
Metal oxides and hydroxides react with strong acids like sulphuric, nitric and
hydrochloric acids to form simple salts. For example
Zinc + nitric(V) ––––– zinc + water
hydroxide acid nitrate
Zn(OH)2(s) + 2HNO3(aq) ––––– Zn(NO3)2(aq) + 2H2O(l)
However, there are some metallic oxides and hydroxides which can react with
both acids and bases to form complex salts. They are called amphoteric oxides
and hydroxides. This is because they have both acidic and basic properties.
Some examples of amphoteric oxides are:
• zinc oxide
• lead(II) oxide
• aluminium oxide
Examples of amphoteric hydroxides include:
• zinc hydroxide
• lead(II) hydroxide
• aluminium hydroxide
Experiment 1.3
Reactions of some metal oxides and hydroxides with acids and alkalis
• boiling tubes
• dilute nitric(V) acid
• 2M sodium hydroxide solution.
• zinc oxide
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• lead(II) oxide
• aluminium oxide
• zinc hydroxide
• lead(II) hydroxide
• aluminium hydroxide
Procedure
1. Put a small amount of zinc oxide (a half spatula-endful) in a boiling tube.
2. Add about 5 cm3 dilute nitric acid. Heat the contents of the tube gently. Record
your observations in your notebook.
3. Repeat the same experiment with lead(II) oxide, aluminium oxide, zinc
hydroxide, lead(II) hydroxide and aluminium hydroxide.
4. Repeat 1,2 and 3. Use 2M sodium hydroxide solution instead of acid.
5. Record your observations and conclusions in your notebook as shown in the
tables below.
Table 1.4 (a) Reaction of amphoteric oxides and hydroxides with acids
Amphoteric oxides or hydroxides Observations Conclusions
aluminium oxide
zinc oxide
zinc hydroxide
lead(II) oxide
lead(II) hydroxide
aluminium hydroxide
Table 1.4 (b) Reactions of amphoteric oxides and hydroxides with alkalis
Amphoteric oxides and hydroxides Observations Conclusions
aluminium oxide
zinc oxide
zinc hydroxide
lead(II) hydroxide
aluminium hydroxide
(I) Reactions of zinc oxide and zinc hydroxide with acid and alkali
(a) Zinc + nitric(V) ––––– zinc + water
oxide acid nitrate
ZnO(s) + 2HNO3(aq) ––––– Zn(NO3)2(aq) + H2O(l)
In reaction (a), zinc oxide is showing basic property by forming a simple salt,
i.e. zinc nitrate and water only when reacted with nitric acid.
8
(b) Zinc + sodium + water –––– sodium
oxide hydroxide zincate
ZnO(s) + 2NaOH(aq) + H2O(l) –––– Na2Zn(OH)4(aq)
In reaction (b), zinc oxide is showing acidic property by forming a complex salt
i.e. sodium zincate when reacted with sodium hydroxide.
(c) Zinc + nitric(V) –––– zinc + water
hydroxide acid nitrate
Zn(OH)2(s) + 2HNO3(aq) –––– Zn(NO3)2(aq) + 2H2O(l)
In reaction (c), zinc hydroxide is showing basic property by forming a simple
salt i.e. zinc nitrate and water only when reacted with nitric acid.
(d) Zinc + sodium ––––– sodium
hydroxide hydroxide zincate
Zn(OH)2(s) + 2NaOH(aq) ––––– Na2Zn(OH)4(aq)
In reaction (d), zinc hydroxide is showing acidic property by forming a complex
salt i.e. sodium zincate when reacted with sodium hydroxide.
(II) Reactions of lead(II) oxide and lead(II) hydroxide with acid and alkali
(a) Lead(II) oxide + nitric(V) acid ––––– Lead(II) nitrate + water
PbO(s) + 2HNO3(aq) ––––– Pb(NO3)2(aq) + H2O(l)
• Lead(II) oxide is showing basic property.
(b) Lead(II) oxide + sodium + water –––– sodium

hydroxide plumbate
PbO(s) + 2NaOH(aq) + H2O(l) –––– Na2Pb(OH)4(aq)
• Lead(II) oxide is showing acidic property.
(c) Lead(II) hydroxide + nitric(V) acid ––– Lead(II) nitrate + water

Pb(OH)2(s) + 2HNO3(aq) ––– Pb(NO3)2(aq) + 2H2O(l)
• Lead(II) hydroxide is showing basic property.
(d) Lead(II) hydroxide + sodium hydroxide –––– Sodium plumbate

Pb(OH)2(s) + 2NaOH(aq) –––– Na2Pb(OH)4(aq)
• Lead(II) hydroxide is showing acidic property.
(III) Reactions of aluminium oxide and hydroxide with acid and alkali
(a) Aluminium + nitric acid(V) ––––– aluminium + water
oxide nitrate
Al2O3(s) + 6HNO3(aq) –––––– 2Al(NO3)3(aq) + 3H2O(l)
9
• Aluminum oxide is showing basic property.
(b) Aluminium + sodium + water –––– sodium
oxide hydroxide aluminate
Al2O3(s) + 2NaOH(aq) + 3H2O(l) ––– 2Na Al(OH)4(aq)
• Aluminium oxide is showing acidic property.
(c) Aluminium + nitric(V) acid ––– aluminium + water
hydroxide nitrate
Al(OH)3(s) + 3HNO3(aq) ––– Al(NO3)3(aq) + 3H2O(l)
• Aluminium hydroxide is showing basic property.
(d) Aluminum + sodium hydroxide –––– sodium
hydroxide aluminate
Al(OH)3(s) + NaOH(aq) –––– NaAl(OH)4(aq)
• Aluminum hydroxide is showing acidic property.
Table 1.5: Summary of properties of amphoteric oxides and hydroxides

Metal Metal Simple salt Complex salt
oxide hydroxide from nitric acid from sodium
hydroxide
Zinc oxide Zinc hydroxide Zinc nitrate Sodium zincate
ZnO Zn(OH)2 Zn(NO3)2 Na2Zn(OH)4
Lead(II) Lead(II) Lead(II) Sodium
oxide hydroxide nitrate plumbate
PbO Pb(OH)2 Pb(NO3)2 Na2Pb(OH)4
Aluminium Aluminium Aluminium Sodium
oxide hydroxide nitrate aluminate
Al2O3 Al(OH)3 Al(NO3)3 NaAl(OH)4

1. Name two amphoteric oxides and two amphoteric hydroxides.
2. Why is it not advisable to use sulphuric acid on lead(II) oxide or on
lead(II) hydroxide?
3. Can the same results be obtained when amphoteric oxides and hydroxides
are reacted with 2M potassium hydroxide solution? Explain.
4. Why is it not advisable to wash aluminium appliances with potassium
hydroxide solution?
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1.5 Effect of solvent in acid-base characters
Hydrogen chloride gas dissolves in water to form hydrochloric acid. It also
dissolves in methylbenzene. Ammonia gas dissolves in water. A solution of
ammonia gas in water is called aqueous ammonia or ammonia solution or
ammonium hydroxide solution.
Experiment 1.4
To determine the properties of a solution of hydrogen chloride in water and in
methylbenzene.
• two beakers
• a filter funnel
• wooden splint
• source of hydrogen chloride
• test tubes
• dry methylbenzene
• dry blue litmus papers
• clean magnesium ribbon
• marble chips (calcium carbonate)
• teat pipettes
• aqueous calcium hydroxide
Procedure
1. Prepare aqueous hydrogen chloride (hydrochloric acid) by passing hydrogen
chloride gas into water in a beaker via a filter funnel. As shown in Fig. 1.2.
delivery tube hydrogen chloride
beaker funnel
water or methylbenzene
Fig. 1.2: Preparation of hydrogen chloride solution in water or

methylbenzene
• Why do we take the precaution of using the funnel?

2. Label this solution X.
3. Repeat the same procedure, but use dry methylbenzene instead of water.
• Label this solution Y. Hydrogen chloride gas should be completely dry.
• How do we dry hydrogen chloride?
4. Put about 10 cm3 of solution X in a set of three test tubes.
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5. Repeat step 4 using solution Y.
6. Perform the following tests using these portions of solution X and Y. Copy
Table 1.6 in your notebook and record your observations and conclusions.
Table 1.6: Determining the properties of hydrogen chloride in different

solvents
Test Observations Observations Conclusions
in solution in solution
X Y
Put dry blue litmus paper

into X and Y solutions.
Note the colour change
(if any).
Add a small cleaned piece
of magnesium ribbon into
X and Y solutions. Test
the gas evolved (if any)
with a burning splint.
Add two or three small
pieces of marble chips in
X and Y solutions. Test
the gas evolved (if any)
with aqueous calcium
hydroxide.
Give the reason for the conclusions you have made.

Hydrogen chloride gas is dried by passing it through concentrated sulphuric acid
or through anhydrous calcium chloride.
When disolved in water, hydrogen chloride gas has the following properties.
• It turns blue litmus red.
• the solution reacts with some metals like magnesium to give a salt and hydrogen
gas which produces a “pop” sound with a burning splint.
Magnesium + hydrochloric –––– magnesium + hydrogen
acid chloride
Mg(s) + 2HCl(aq) –––– MgCl2(aq) + H2(g)
• It reacts with carbonates like calcium carbonate, to give a salt, water and carbon(IV)
oxide (which forms white precipitate with aqueous calcium hydroxide).
Calcium + hydrochloric –––– calcium + water + carbon(IV)
carbonate acid chloride oxide
CaCO3(s) + 2HCl(aq) –––– CaCl2(aq) + H2O(l) + CO2(g)
12
These reactions are possible because when dissolved in water, hydrogen chloride
gas forms hydrochloric acid which dissociates to form hydrogen ions (H+) and
chloride ions (Cl–). i.e.
water
HCl(g) ––––––– H+(aq) + Cl–(aq)
These hydrogen ions give the solution acidic properties. On the other hand, when
hydrogen chloride gas is dissolved in organic solvents like methylbenzene, there
is no effect on dry blue litmus, magnesium or marble chips. This is because dry
hydrogen chloride gas dissolved in methylbenzene, does not dissociate to form
hydrogen ions. It retains the properties of covalent compounds as shown in Fig.
1.3 below.
water methylbenzene
Cl– ion HCl molecule

H+ ion
Fig. 1.3: Effect of solvent in acid character
It can therefore be concluded that the hydrogen ions (H+) give the solution the
acidic properties and these ions can only be produced in the presence of water.
Note: A filter funnel is used when dissolving hydrogen chloride to prevent
“sucking back” of water. This is because the gas is very soluble in water.
Table 1.7: Differences between a solution of hydrogen chloride in water and
in methylbenzene
In water In methylbenzene
1. Turns blue litmus paper red. 1. Does not affect litmus papers.
2. Reacts with carbonates 2. Does not react with carbonates and
and hydrogencarbonates. hydrogencarbonates.
3. Conducts electricity. 3. The solution does not conduct electricity.
4. Produces hydrogen when 4. Does not react with metals to form
reacted with some metals. hydrogen.
Experiment 1.5
To determine the properties of ammonia in water and methylbenzene solution.
• Two beakers
• A filter funnel
• Dry methylbenzene
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• Source of dry ammonia gas
• Dry red litmus paper
Procedure
1. Dissolve ammonia in water using a set-up similar to the one in Fig. 1.2. Label
this solution X.
2. Direct dry ammonia in dry methylbenzene, using the same set-up. Label this
solution Y.
• Which drying agent do we use for drying ammonia?
3. Test solution X and Y with dry red litmus paper.
4. Test for electrical conductivity of solutions X and Y using the set-up as in Fig.
1.1. Record your observations and conclusions in a table similar to Table 1.8
below.
Table 1.8 Properties of ammonia in different solvents
Test Observations Conclusions
solution X solution Y
Effect on dry
red litmus paper
Electrical
conductivity
When dissolving ammonia, a filter funnel is used to prevent “sucking back” of water.
Ammonia is dried using calcium oxide. Ammonia gas dissolved in water turns red
litmus paper blue. The solution is a weak electrolyte. When dissolved in water it
forms ammonium hydroxide, which dissociates partially to form ammonium ions
(NH+4) and hydroxide ions (OH–).
NH3(g) + H2O(l) –––– NH4OH(aq) NH+4(aq) + OH–(aq)
Hydroxide ions give aqueous ammonia the alkaline properties. Since ammonia
does not dissociate fully in aqueous solution, it is a weak electrolyte.
Ammonia gas in dry methylbenzene has no effect on dry red litmus paper. This
is because when dissolved in methylbenzene, it does not dissociate to form ions.
It retains the properties of covalent compounds.
We can therefore conclude that the hydroxide ions (OH–) in the solution gives
the alkaline properties and these ions can only be produced in the presence of
water. Also the two ions which make ammonia solution an electrolyte are only
produced when water is used as the solvent as shown in Fig. 1.4.
• What can be observed when a moist red litmus paper is put in dry ammonia
gas dissolved in methylbenzene?
14
Water Methylbenzene
NH4+ ion NH3 molecule

OH– ion
Fig. 1.4: Effect of solvent in base character

1. (i) What happens when acids are dissolved in water?
(ii) Name one ion formed when acids are in aqueous solution.
2. (i) Explain the difference in the action of marble chips with
dry hydrogen chloride gas dissolved in dry methylbenzene and in
water.
(ii) Explain the difference in pH of solutions of ammonia gas in water
and in dry methylbenzene.
(iii) Explain why dry ammonia gas dissolved in dry methylbenzene is a
non-electrolyte but an electrolyte when dissolved in pure water.
1.6 Salts
Introduction
We defined a salt as an ionic compound formed when cations derived from
bases combine with anions derived from acids. It is formed when the hydrogen
ions in an acid are wholly or partly replaced directly or indirectly by a metal ion
or an ammonium ion.
Example
1. Sodium + hydrochloric –––– sodium + water
hydroxide acid chloride
NaOH(aq) + HCl(aq) ––––– NaCl(aq) + H2O(l)
Here, the hydrogen ion from hydrochloric acid has been replaced by the
sodium ion from sodium hydroxide to form sodium chloride i.e.

NaOH(aq) + HCl(aq) –––– NaCl(aq) + H2O(l)
Na+ moves here

to replace one H+
If ammonium hydroxide was used instead of sodium hydroxide, ammonium

chloride would have been formed i.e.
15
NH4OH(aq) + HCl(aq) –––– NH4Cl(aq) + H2O(l)
NH4+ moves here
2. Potassium + sulphuric(VI) ––– potassium + water

hydroxide acid sulphate
2KOH(aq) + H2SO4(aq) ––– K2SO4(aq) + 2H2O(l)
2KOH(aq) + H2SO4(aq) ––– K2SO4(aq) + 2H2O(l)
2K+ move here
If all hydrogen ions are not replaced, an acid salt is formed, e.g.
3. Sodium + sulphuric(VI) ––––– sodium + water
hydroxide acid hydrogensulphate
NaOH(aq) + H2SO4(aq) –––– NaHSO4(aq) + H2O(l)
NaOH(aq) + H2SO4(aq) –––– NaHSO4(aq) + H2O(l)
Na+ moves here

to replace one H+
Names of salts are derived from the metal or ammonium ion and the acid radical
from which they are formed.
When naming salts, the name starts with the metal or ammonium ion in the
salt followed by the respective acid radical. See Table 1.9 below.
Table 1.9: Name and formulae of salts
Name Formula Parent acid
Sodium chloride NaCl hydrochloric acid, HCl
Ammonium sulphate (NH4)2SO4 Sulphuric(VI) acid, H2SO4
Potassium nitrate KNO3 Nitric(V) acid, HNO3
Sodium NaHCO3 Carbonic acid, H2CO3
hydrogencarbonate
Calcium Ca3(PO4)2 Phosphoric(V) acid,
phosphate H3PO4
Potassium KHSO4 Sulphuric(VI) acid, H2SO4
hydrogensulphate
16
When the salts are in aqueous or molten form, they form electrolytes. This is
because the metal or ammonium ion and the respective acid radical are free to
move. It should be noted that a strong electrolyte is completely dissociated when
in molten or aqueous form.
Write the formulae of the salts and ionic equations for the following
chemical reactions.
1. Ammonium hydroxide and sulphuric(IV) acid.
2. Zinc oxide and nitric(V) acid.
3. Sodium hydroxide and phosphoric(V) acid.
1.7 Precipitation reactions in salt preparation

These are chemical reactions involving two different salt solutions in which
two different metal ions exchange acid radicals forming an insoluble salt and a
soluble one. These reactions are useful in the preparation of insoluble salts. Let
us consider the following reactions in the following experiment. The insoluble
salt is referred to as the precipitate.
Examples
(i) Lead(II) + sodium ––– lead(II) + sodium
nitrate sulphate sulphate nitrate
Pb(NO3)2(aq) + Na2SO4(aq) ––– PbSO4(s) + 2NaNO3(aq)
Ionic equation
Pb2+(aq) + SO42–(aq) –––– PbSO4(s)
white precipitate
(ii) Lead(II) + sodium ––– lead(II) + sodium
nitrate chloride chloride nitrate
Pb(NO3)2(aq) + 2NaCl(aq) ––– PbCl2(s) + 2NaNO3(aq)
Ionic equation
Pb2+(aq) + 2Cl–(aq) –––– PbCl2(s)
white precipitate
Why is it not advisable to wash the white precipitate of lead(II) chloride with
hot water?
(iii) Silver + sodium ––– silver + sodium
nitrate chloride chloride nitrate
AgNO3(aq) + NaCl(aq) ––– AgCl(s) + NaNO3(aq)
Ionic equation
Ag+(aq) + Cl–(aq) –––– AgCl(s)
white precipitate
17
• Silver nitrate solution can also give a white precipitate when reacted with
sodium carbonate
(a) What is the name of the white precipitate formed?
(b) How can you differentiate it from silver chloride?
(c) Write the ionic equation of the reaction between silver nitrate solution
and sodium carbonate solution.
We learnt earlier that when writing ionic equations, we select the ions that are
responsible for the changes we see, in this case, the precipitate. We leave out the
spectator ions.
(a) Copy the following table and put a tick(√) if a precipitate is formed
when two solutions are mixed and a cross(x) if no precipitate is formed.
Solution Sodium Potassium Ammonium
chloride sulphate carbonate
Barium
chloride
Silver
nitrate
Magnesium
sulphate
Lead(II)
nitrate
(b) Where a precipitate is formed write
(i) word equation
(ii) chemical equation
(iii) ionic equation
1.8 Reactions of cations in aqueous solutions with sodium hydroxide

and ammonia solutions
These reactions are used in testing for the presence of some specific cations. Most
of the cations to be tested form precipitates of different colours when reacted
with sodium hydroxide or ammonia solutions. Some precipitates dissolve when
these alkalis are added in excess.
Experiment 1.6
Reactions of cations in aqueous salt solution with sodium hydroxide and ammonia
solutions.
• test tubes
• droppers
18
• labels
• solutions containing ions of:
magnesium
calcium
iron(II)
iron(III)
barium
zinc
aluminium
lead(II)
copper(II)
in separate test tubes
• 2M ammonia solution
• droppers
• test tubes
• 100 cm3 beakers
Procedure
1. Put about 2 cm3 of each solution in separate test tubes. Make sure you label
the test tubes.
2. To each cations in aqueous solution, add 2–3 drops of sodium hydroxide
solution and then add more sodium hydroxide until in excess.
Draw Table 1.10 in your notebook and record your observations.
3. Repeat procedure above but use aqueous ammonia solution instead of sodium
hydroxide solution. Draw Table 1.10 in your notebook and record your
observations.
Table 1.10: Reactions of ammonia solution with some cations
Cation in Observations on addition of aqueous ammonia
solution
Few drops In excess
Mg2+
Ca2+
Fe2+
Fe3+
Ba2+
Zn2+
Al3+
Pb2+
Cu2+
19
Table 1.11: Reactions of sodium hydroxide solution with some cations
Cation in Observations on addition of sodium hydroxide solution

solution
Few drops In excess
Mg2+
Ca2+
Fe2+
Fe3+
Ba2+
Zn2+
Al3+
Pb2+
Cu2+
• Which ions form coloured precipitates?
• Which ions show no observable change?
• What are your conclusions?
Compare your observations with the ones given in Table 1.12 and 1.13 below.
Table 1.12: Reactions of aqueous ammonia with some cations
Cation in Addition of aqueous ammonia

solution
Few drops In excess
Mg2+ White precipitate Insoluble
Ca2+ Faint white precipitate Insoluble
Fe2+ Green precipitate Insoluble
Fe3+ Red-brown precipitate Insoluble
Ba2+ White precipitate Insoluble
Zn2+ White precipitate Soluble (colourless solution)
Al3+ White precipitate Insoluble
Pb2+ White precipitate Insoluble
Cu2+ Blue precipitate Soluble (forms a deep blue solution)
20
Table 1.13: Reactions of aqueous sodium hydroxide with some cations
Cation in Addition of aqueous sodium hydroxide
solution
Few drops In excess
Mg2+ White precipitate Insoluble
Ca2+ White precipitate Precipitate insoluble
Fe2+ Green precipitate Precipitate insoluble
Fe3+ Red-brown precipitate Precipitate insoluble
Ba2+ White precipitate Precipitate insoluble
Zn2+ White precipitate White ppt soluble (colourless solution)
Al3+ White precipitate White ppt soluble (colourless solution)
Pb2+ White precipitate White ppt soluble (colourless solution)
Cu2+ Blue precipitate Blue precipitate insoluble
The cations of the salt solutions react with sodium hydroxide or ammonia solution
to form insoluble metal hydroxides which are observed as precipitates. The alkalis
provide the hydroxide ion (OH–) to the cations.
1.9 Test for cations

The above reactions are very important in identifying cations. Note that on addition
of few drops of aqueous ammonia and sodium hydroxide solution, the results of
the reactions are the same. The most unique and isolated reactions are when the
precipitates dissolve in excess aqueous ammonia or sodium hydroxide solution.
Note the following:
• The white zinc hydroxide precipitate formed dissolves both in excess ammonia
or sodium hydroxide solution to form a colourless solution.
• The white aluminium hydroxide and lead(II) hydroxide precipitates formed is
insoluble in aqueous ammonia but soluble in excess sodium hydroxide solution
forming a colourless solution.
• The copper(II) hydroxide precipitate formed is soluble in excess aqueous
ammonia forming a deep blue solution but insoluble in excess sodium hydroxide
solution.
The following are the ionic equations for the formation of the precipitates in
Table 1.12 and 1.13.
Mg2+(aq) + 2OH–(aq) –––– Mg(OH)2(s)
white precipitate
Ca2+(aq) + 2OH–(aq) –––– Ca(OH)2
white precipitate
21
Fe2+(aq) + 2OH–(aq) –––– Fe(OH)2(s)
green precipitate
Fe3+(aq) + 3OH–(aq) –––– Fe(OH)3
red-brown
precipitate
Ba2+(aq) + 2OH–(aq) –––– Ba(OH)2(s)
white precipitate
Zn2+(aq) + 2OH–(aq) –––– Zn(OH)2(s)

white precipitate
Al3+(aq) + 3OH–(aq) –––– Al(OH)3(s)

white precipitate
Pb2+(aq) + 2OH–(aq) –––– Pb(OH)2(s)

white precipitate
Cu2+(aq) + 2OH–(aq) –––– Cu(OH)2(s)

blue precipitate
Write ionic equations to show what happens when excess alkali is added to the
precipitates that are soluble
Predicting precipitate reactions

We can predict when a precipitate will be formed if we know which salts are soluble
and which are insoluble. These have been summarised in Table 1.14 below.
Table 1.14 Solubility of ionic salts

Anion Cation in the salt
Soluble Insoluble
Nitrates (NO–3) All None

Chlorides (Cl–) All except Ag+, Pb2+
Sulphates (SO42–) All except Ba2+, Ca2+, Pb2+
Carbonates (CO32–) Li+, Na+, K+, NH4+ All others
Hydroxides (OH–) Li+, Na+, K+, NH4+ All others
22
1. (a) Name three cations which when in aqueous solution, react with
sodium hydroxide solution to form coloured precipitate.
(b) Write the ionic equations for the reactions in (a).
2. For each of the following mixtures of solutions, predict whether or
not a precipitate will occur. Use equations to explain your answers.
(i) Sodium nitrate and potassium sulphate.
(ii) Silver nitrate and potassium sulphate.
(iii) Magnesium sulphate and lead nitrate.
(iv) Potassium sulphate and lead nitrate.
1.10 Reactions of cations in aqueous solutions with chloride,

carbonate, sulphite and sulphate ions
These reactions can be used to test for the presence of some specific cations by
forming precipitates.
Experiment 1.7
Reactions of cations in aqueous solution with chloride, carbonate, sulphite and
sulphate ions.
• stirring rods
• droppers
• test tubes
• 100 cm3 beakers
• aqueous solutions containing
magnesium ions
iron(II) ions
iron(III) ions
barium ions
zinc ions
aluminium ions
lead(II) ions
copper(II) ions
in separate test tubes
• aqueous sodium chloride or any other soluble chloride salt.
• aqueous sodium carbonate or any other soluble carbonate salt.
• aqueous sodium sulphate or any other soluble sulphate salt.
• aqueous sodium sulphite or any other soluble sulphite salt.
Procedure
1. To each cations in aqueous solution, add 2–3 drops of sodium chloride
solution.
23
2. Repeat the same experiment with aqueous sodium carbonate, sodium sulphate
and sodium sulphite.
Copy Table 1.15 in your notebook and record your observations.
Table 1.15: Reaction of some cations with some selected salt solutions
Observations on addition of solution of
Cation in Sodium Sodium Sodium Sodium
solution chloride carbonate sulphate sulphite
Mg2+
Ca2+
Fe2+
Fe3+
Ba2+
Zn2+
Al3+
Pb2+
Cu2+
• Which cations form a precipitate with the solutions of sodium salts used
in the experiment?
• Which cations form coloured precipitates?
• What conclusions do you make from the above observations?
Compare your observations with the ones given in Table 1.16 below.
Table 1.16: Results of the reaction of some cations with some selected salt
solutions
Cation Observation on addition of solution of
in
solution Sodium Sodium Sodium Sodium
chloride carbonate sulphate sulphite
Mg2+No precipitate White No precipitate No precipitate or
or any precipitate observed any observable
observable change
change
Ca2+ No precipitate white White White
or any precipitate
precipitate precipitate
observable
change
24
No precipitate No precipitate
Fe2+ or any observable Green or any observable Green
change precipitate change precipitate
No precipitate No precipitate
Fe3+ or any observable red-brown or any observable deep red
change precipitate change solution
No precipitate
Ba2+ white white white
or any observable
precipitate precipitate precipitate
change
Zn2+ No precipitate white No precipitate White
or any observable precipitate or any observable precipitate
change change
Al3+ No precipitate White No precipitate White
or any observable precipitate or any observable precipitate
change change
Pb2+ White White White White

precipitate precipitate precipitate precipitate
Cu2+ No precipitate Green No precipitate Light

or any observable precipitate or any observable green
change change precipitate
Some cations in the various solutions react with sodium chloride or sodium
sulphate solutions to form precipitates while others do not.
All the cations above form precipitates with sodium carbonate solution. Also,
all cations except magnesium and iron(III) form precipitates with sodium sulphite
solution.
Ionic equations representing some of the reactions are as follows.
Pb2+(aq) + 2Cl–(aq) ––––––– PbCl2(s)
white precipitate
Ba2+(aq) + SO42–(aq) –––––– BaSO4(s)
white precipitate
Zn2+(aq) + CO32–(aq) ––––––– ZnCO3(s)
white precipitate
Barium or lead(II) ions in solution form can be used to test the presence of
sulphate ions in a solution. The insoluble white sulphate salts formed should be
differentiated from insoluble white sulphite salts which can be formed with sulphite
ions by adding dilute nitric or hydrochloric acid. Sulphite salts precipitated react
with dilute nitric acid or hydrochloric acid.
25
Lead(II) ions and silver ions can also be used to test the presence of chloride
ions in a solution. But the white precipitate (PbCl2) is soluble in hot water.
Note the following when confirming the presence of some anions.
Chloride (Cl–)– When a chloride is treated with concentrated sulphuric acid, a
colourless gas (hydrogen chloride) is produced which forms dense white fumes
when exposed to concentrated aqueous ammonia solution.
NH3(g) + HCl(g) –––––– NH4Cl(s)
Carbonate (CO32–) When a dilute acid is added to a carbonate, carbon(IV) oxide
is produced which forms a white precipitate with calcium hydroxide solution.
Sulphite (SO32–) When dilute hydrochloric acid is added to a sulphite and the
mixture is heated, colourless sulphur(IV) oxide gas is produced. The sulphur(IV)
oxide has an irritating smell and turns potassium dichromate(VI) from orange to
green. This gas has no effect on lead nitrate solution in the presence of an acid
like nitric acid.
Sulphate (SO42–) When dilute hydrochloric or nitric acid and barium chloride or
barium nitrate solutions are added to a solution of a sulphate, a white precipitate
of barium sulphate is formed. It also forms a white precipitate with lead nitrate
solution in presence of nitric acid.
1. (a) Name three cations which, when in aqueous solution react
with solution of ammonia to form coloured precipitates
(b) Write the ionic equations for the reactions taking place in 1(a).
2. (a) Name three cations which, when in aqueous solution
react with sodium sulphite solution to form coloured precipitates.
(b) Write the ionic equations of the reactions taking place in 2(a).
3. (a) Explain why barium ions in aqueous solution cannot form
a white precipitate when reacted with sodium sulphite in
the presence of hydrochloric acid.
(b) Explain why it is not advisable to wash with hot water the
white precipitate formed by reaction between lead nitrate and sodium
chloride solutions.
1.11 Complex ions

Refer to the results of experiment 1.6 to answer the questions in the following
activity
Activity 1.1
In groups of two students, discuss the following questions and record your findings
in your notebooks.
1. Name the cations that form precipitates that dissolve in excess aqueous ammonia.
26
2. Name the cations that form precipitates that dissolve in excess sodium
hydroxide solution.
3. With the help of the following tables, copy and indicate the observations made
when the cations in (1) and (2) above react with 2–3 drops of alkali solution and
when the alkali is added in excess solution. Then refer to Table 1.12 and 1.13.
Table 1.17: Reaction of some cations with aqueous ammonia
Cation in Observation made on addition of aqueous
solution ammonia
2–3 drops In excess
Table 1.18: Reaction of some cations in aqueous solution with sodium

hydroxide solution
Cation Observation made on addition of sodium
hydroxide solution
Precipitates formed by solutions containing zinc and copper(II) ions (Zn2+ and Cu2+)
dissolve in excess aqueous ammonia. Precipitates formed by solutions containing
aluminium, zinc and lead(II) ions (Al3+, Zn2+ and Pb2+) dissolve in excess sodium
hydroxide solution. The observations made are summarised in Table 1.19 and 1.20 below.
Table 1.19: Results of the experiment
Cation Observation made on addition of aqueous ammonia
Zinc (Zn2+) White precipitate White precipitate dissolves to form colourless
solution
Copper (Cu2+) Blue precipitate White precipitate dissolves to form deep blue
solution
Silver Ag+ White precipitate White precipitate dissolves to form colourless
solution
Table 1.20: Results of the experiment

Cation Observation made on addition of sodium
hydroxide solution
3+
Aluminium (Al ) White precipitate Colourless solution
27
Zinc (Zn2+) White precipitate White precipitate dissolves to form colourless
solution
Lead (Pb2+) White precipitate White precipitate dissolves to form colourless
solution
The ionic equations for the formation of precipitates for the above reactions are
as follows:
Zn2+(aq) + 2OH–(aq) –––– Zn(OH)2(s)
white precipitate
Cu2+(aq) + 2OH–(aq) –––– Cu(OH)2(s)
blue precipitate
Al3+(aq) + 3OH–(aq) –––– Al(OH)3(s)
white precipitate
Pb2+ (aq) + 2OH–(aq) –––– Pb(OH)2(s)
white precipitate
The precipitates formed above dissolves in excess solutions as shown in Table
1.18 and 1.19. This is due to the formation of complex ions. Complex ions consist
of a central metal ion surrounded by neutral molecules e.g. ammonia molecules
(NH3)or other ions e.g. hydroxide ions. These cations form insoluble metal
hydroxides with a few drops of either sodium hydroxide or ammonia solutions.
Zinc hydroxide, lead(II) hydroxide and aluminium hydroxide form soluble
complex salts with excess sodium hydroxide. The solutions are colourless.
Zinc hydroxide and copper(II) hydroxide form soluble complex salts with
excess ammonia solution. The complex salt solution formed by zinc hydroxide
is colourless while that one for copper(II) hydroxide is deep blue.
Study Table 1.21 and 1.22 below which shows the names and the formulae of
the complex ions formed.
Table 1.21: Some complex ions formed with excess sodium hydroxide
solution
Name Formula of Colour in
complex ion solution
Zincate ion [Zn (OH)4]2– Colourless
Plumbate ion [Pb(OH)4]2– Colourless
Aluminate ion [Al(OH)4]– Colourless
28
Table 1.22: Some complex ions formed with aqueous ammonia solution
Name Formula of Colour of
complex ion solution
Tetraamminezinc(II) ion [Zn(NH3)4]2+ Colourless
Tetraamminecopper(II) ion [Cu(NH3)4]2+ Deep blue

1. Zinc ions form a colourless solution with excess ammonia solution
but aluminium ions only form a white precipitate. Explain.
2. Copper(II) ions form a blue precipitate with excess aqueous sodium hydroxide,
but a deep blue solution with excess aqueous ammonia. Explain.
1.12 Solubility
There is a limit as to how much a solute can be dissolved in a solvent at a particular
temperature. When a point is reached where no more solute will dissolve, the
solution is said to be saturated.
A saturated solution is one which will not dissolve any more of a solute at a
particular temperature. If more solute is added to the solution at this point, it
will just settle at the bottom of the solution undissolved. But, when a saturated
solution is heated, some more solute dissolves.
The maximum mass in grams of solute that will dissolve in 100 g of solvent at
a given temperature is known as solubility. The solubility of some solutes is often
found to increase with an increase in temperature.
Solubility = 100 cm3 × mass of solute(g)

Volume of water (cm3)
Unit are: g/100g of water
You can also use the first principle method to calculate solubility of a salt. Study
the following examples to guide you on how to solve problems on solubility.
Worked examples
(i) Calculate the solubility of potassium chlorate if 5 grams of it saturate
10 cm3 of water. (Density of water = 1 g/cm3).
29
First Principle Method Formula Method
10 cm3 of water = 10 grams 100 cm3 × mass(g)

Solubility =
5 g of KClO3 dissolve in 10 g of water Volume (cm3)
x g of KClO3 dissolve in 100 g of water
Cross multiply and solve for x 100 cm3 × 5g
=
x × 10g = 100 × 5 g 10 cm3
100 × 5 g = 50 g
x =
10
= 50 g
Therefore, the solubility of KClO3 is 50 g/100 g water

(ii) Calculate the solubility of potasium nitrate if 5 grams of it saturate
40 cm3 of water at 8˚C.
First Principle Method Formula Method

100 cm3 × mass(g)
40 cm3 of water = 40 grams Solubility =
Volume (cm3)
5 g of KNO3 dissolves 40 g of water
x of KNO3 dissolves 100 g of water 100 cm3 × 5g
Cross multiply and solve for x =
40 cm3
x × 40 g = 100 × 5 g = 12.5 g
100 × 5
x = g
40
= 12.5 g
Therefore, the solubility of KNO3 is 12.5 g/100 g water at 8˚C.

1. The solubility of potassium chloride is 52 g per 100 g of water at
100˚C. How much can dissolve in 50 g of water at 100˚C?
2. How much potassium chlorate can saturate 25 g of water at 20˚C?
The solubility of this salt is 75 g per 100 g of water at 20˚C
Solubility curves
Experiment 1.8
To determine the solubility of potassium chlorate and potassium nitrate
• boiling tubes
• thermometer (–10˚C – 110˚C)
• 10 cm3 measuring cylinder
30
• 250 cm3 beaker
• potassium chlorate
• potassium nitrate
• graph papers
Caution: The potassium chlorate and potassium nitrate are strong oxidising agents.
Procedure
1. Weigh 5 grams of potassium chlorate and put it in a boiling tube.
2. Measure out 10 cm3 of distilled water using the measuring cylinder, and add
it to the boiling tube containing potassium chlorate.
3. Insert a thermometer into the boiling tube and heat the mixture while stirring
until all the solid dissolves. The thermometer bulb is fragile; handle it gently.
4. Allow the solution to cool while stirring gently with the thermometer. Observe
the solution as it cools. As soon as crystallisation begins, note and record the
temperature of the solution.
Note: It is easiest to see crystals by looking at the bottom of the boiling tube
where they will collect as soon as they begin to form. The cooling of the
solution can be speeded up by dipping the boiling tube into a beaker of cold
water for a few seconds and removing it.
Thermometer
Potassium chlorate or
nitrate solution
Cold water
Fig. 1.5: Cooling of the salt solution

5. Add another 10 cm3 of water to the solution and repeat the procedure and
note the temperature at which the crystals start forming.
When the volume of solution cannot fit in the boiling tube, use a 100ml beaker.
6. Continue adding 10 cm3 portions of water until 60 cm3 of water has been
added, noting the temperature at which crystallisation occurs in each case.
Draw Table1.23 in your notebook and record your results
Table 1.23: Solubility of KClO3
Total volume of water
added to 5 g of KClO3 (cm3) 10 20 30 40 50 60
Mass of KClO3 in grams 50
per 100 g of water
Crystallisation temperature ˚C
31
7. Repeat the whole experiment with potassium nitrate and record your data in
a table similar to the one shown in Table 1.23.
8. Convert your grams/10cm3 values to gram/100 cm3 values.
9. From the two tables, draw a graph of solubility of potassium chlorate and
potassium nitrate in grams per 100 grams of water against crystallisation
temperature (on x – axis) using the same axes.
10. Extrapolate the curves to the temperature limits of your graph by using a
dashed line to indicate extrapolation (i.e. from 0˚C to 100˚C).
• State how the solubility of these two salts vary with temperature.
• From your solubility curve, predict:
(a) the solubility of KNO3 at 30˚C
(b) The solubility of KNO3 at 10˚C.
(c) The mass of KNO3 in its saturated solution at 50˚C.
(d) The percentage of KNO3 that will crystallise out when its saturated
solution at 100˚C is cooled to 10˚C
• Do the same four predictions for KClO3.
The amount of solute which dissolves in a solvent e.g. water at a particular
temperature is different for different substances. A graph of solubility against
temperature is called a solubility curve.
The graph below shows the solubility curves of potassium chlorate and potassium
nitrate.
120
Solubility (in g of solute per 100g of water)
110
100
90
80
70
te
ra
nit
60
ium
50
s
tas
40
rate
Po
30 um chlo
Po tassi
20
10
0 10 20 30 40 50 60 70 80 90 100 110
Temperature (˚C)
Fig. 1.6: Solubility curves for potassium nitrate and potassium chlorate
NOTE: The two graphs are drawn on the same axes so that you can compare Note:
32
The two graphs are drawn on the same axes so that you can compare them easily.
It does not mean that they were both dissolved together in the same solution.
• Study the above solubility curves and discuss the following questions.
1. For which salt does the solubility increase most rapidly with increase in
temperature?
2. Given a mixture of equal masses of potassium nitrate and potassium
chlorate, how would you compare their crystallisation?
The graphs above show how the solubility of potassium nitrate and potassium chlorate
vary with temperature rise. The solubility of potassium nitrate rises steeply as the
temperature increases while that of potassium chlorate show moderate increase.
Any point on the solubility line represents a saturated solution at that temperature.
Any part below the solubility line represents unsaturated solutions at that
temperature.
It is possible to predict using the solubility curves, what will happen when the
solution is cooled or heated. The curves are also useful because they can be used
to show temperature when crystals are obtained from saturated solutions. Let us
consider the following example.
1. If 110g of a saturated solution of potassium chlorate at 30˚C containing 10 g
of salt is cooled to 10˚C, determine the amount of salt that crystalises.
2. If a saturated solution of potassium nitrate at the same temperature (30˚C) containing
62 g of salt is cooled to 10˚C, determine the amount of salt that crystallises.
3. Which salt above crystallises the most? Use the graph shown in Fig. 1.7 below.
Solution
120
KNO3
110
100
90
80
70
60 KClO3
50
40
30
20
10
0 10 20 30 40 50 60 70 80 90 100 110
Temperature (˚C)
Fig. 1.7: Solubility curves of potassium nitrate and potassium chlorate
33
1. From the graph above, at 10˚C, the solubility of potassium chlorate is 6g/100g of
water and at 30˚C, it is approximately 10 g/100 g of water. To obtain the amount
of salt that will crystallise, we subtract the solubility at 10˚C from that at 30˚C.
= (10 – 6)g
= 4 g of potassium chlorate will crystallise.
2. At 10˚C the solubility of potassium nitrate is 22g/100g of water as shown in
the graph. At 30˚C, it is 62 g/100 g of water
Amount of salt that crystallised = (62 – 22)g
= 40 g
3. Potassium nitrate crystallises the most with 40 g compared to potassium
chlorate with only 4 g.
Fig. 1.8 below shows the solubility curves of some common substances.
70
te
tra
60
ni
m
siu
50
tas
40 te
Po
hlora Sodium chloride

30 mc
a ssiu
Pot
20
Calcium sulphate
10
0 10 20 30 40 50 60 70 80 90 100
Temperature (˚C)
Fig. 1.8: Solubility curves for some common salts

• In which salt is there a decrease in solubility with increase in temperature?
For most salts, solubility increases as the temperature increases. However,
solubility of sodium chloride remains almost constant with change in temperature.
For calcium sulphate, it increases slowly and at higher temperatures, it also
decreases slowly.
Refer to Fig. 1.8 for the solubility curves.
(a) Which salts has the same solubility at 68˚C?
(b) Which of the salts shown has the greatest solubility at 30˚C?
(c) Which salt has its solubility most affected by temperature changes?
(d) Which salt has its solubility least affected by temperature changes?
34
Apart from using solubility curves to predict what happens when the solution
is cooled or heated, you can also calculate, using given data, the amount of salt
dissolved or deposited. Below are worked examples to explain how this is done.
Example 1
1. At 100˚C, the solubility of a salt X is 80g/100g of water. At 20˚C its solubility
is 42 g/100 g of water. How much salt X will be deposited if initially it was
saturated and the solution filtered at 100˚C in 100 g of water and then cooled
to 20˚C.
At 100˚C 80g of X dissolved
At 20˚C 42g of X dissolved
Therefore, the amount of X deposited = (80 – 42)g
= 38 g
Example 2
1. Salt X and Y are mixed together and dissolved to saturate 100g of water at
100˚C. The solution was then filtered. This solution was then cooled to 30˚C.
The solubility of X at 100˚C is 80g/100g of water and at 30˚C it is 36g/100g
of water.
The solubility of Y at 100˚C is 100g/100g of water and at 30˚C it is 50g/100g
of water. What is the composition of the mixture at 30˚C?
At 30˚C, the mass of X deposited = (80 – 36)
= 44 g
At 30˚C, the mass of Y deposited
= (100 – 50)g
= 50 g
Therefore, the mixture contains
(i) 36 g of X in solution and 44 g of X undissolved.
(ii) 50 g of Y in solution and 50 g of Y undissolved.

1. The solubility of potassium nitrate at 20˚C is 25g/100g of water.
How much potassium nitrate will dissolve in 80g of water at 20˚C?
2. The mass of a solution of salt X is 65 g. This solution has 5g of
salt X dissolved in it. The solubility of this salt is 25g/100g of water
at 20˚C. 60 g of salt X are added to the solution at 20˚C. How much
salt X will remain undissolved?
Fractional crystallisation of salts

Fractional crystallisation is a method of separating mixtures of soluble solids by
dissolving them in suitable hot solvent and then lowering the temperature slowly.
The least soluble component will crystallise out first, leaving the other components
35
in the solution. By controlling the temperature, it is sometimes possible to remove
each component in turn.
Crystallisation is the process of forming crystals from a saturated solution.
However, the term usually means what happens when the solvent from a solution
has evaporated to a point beyond the solubility limit of the solute, making solid
crystals ‘grow’ out of solution.
For example, if a mixture of two salts contain 20g of potassium chlorate and 30 g
of potassium nitrate in 100 g of water at 50˚C, separation of one of the salts can be
done very easily by fractional crystallisation using the information in Table 1.24
Table 1.24: Solubility of potassium chlorate and potassium nitrate
Name of salts Solubility at various temperatures
50˚C 25˚C
Potassium chlorate 18 g 10 g
Potassium nitrate 85 g 32 g
If the mixture is cooled slowly from 50˚C to 25˚C, 8 g of pure potassium chlorate
will crystallise out. Potassium nitrate will still be in solution form as its solubility
is higher. These crystals can be filtered off.
If two substances in a mixture are present in comparable proportions, they can be
separated by fractional crystallisation using information from solubility curves.
Uses of solubility curves
We have seen that solubility curves help us to:
• know the effect of temperature on the solubility of salts.
• know how to separate a mixture of salts in solid or solution form using
differences in solubilities of the salts in the mixture.
• determine the mass of crystals that would be obtained by cooling a given
volume of hot saturated solution from one known temperature to another.
Application of solubility curves

Extraction of sodium carbonate from Lake Magadi
The existence of trona in Lake Magadi is as a result of the process of natural
fractional crystallisation. The lake consist of a deep crystalline bed of trona which
is a mixture of sodium sesquicarbonate, a double salt of sodium carbonate and
sodium hydrogencarbonate, sodium chloride, other sodium salts and clays together
with a small amount of organic matter.
How natural fractional crystallisation of trona occurs
Lake Magadi lies in the Great Rift Valley at an altitude of 605 m above sea level.
Temperatures range from 29˚C to 41˚C giving a high evaporation rate. Rain water
in and around the Rift Valley drains underground and is heated geothermally.
36
The hot water dissolves chemical compounds of sodium which occur in the
underground rock strata. The solution comes to the surface in the form of hot
mildly alkaline springs which can be found all around the edge of the lake.
Lake Magadi’s high temperatures and long sunny days cause the solution to
concentrate by evaporation to saturation point. At this point, the solid crystals of
trona grow out of the solution, eventually giving rise to more trona. The trona
can be up to 30 meters thick.
The first step in extraction of sodium carbonate involves washing or cleaning the
trona. The knowledge of solubility curves is used to predict the solution required
for washing the trona. Clean water is not used because it will dissolve sodium
chloride which is required as a by product. Initially, interstitial liquor, which is
the concentrated solution from the lake is used and then finally it is replaced by
clean water to remove the sodium carbonate.
Sodium chloride in Ngomeni
Most of the sodium chloride needed for human consumption is extracted by the
evaporation of ocean water at Ngomeni. Ocean water is collected into a series
of ponds during high tides. In these ponds, the concentration of sodium chloride
increases from one pond to another as evaporation due to sun’s heat continues. In
the final pond, sodium chloride crystals, crystallises out and are scrapped together,
piled in a heap and washed with concentrated sodium chloride solution.
The process of fractional crystallisation is applied during the washing.
Washing with clean water will dissolve the sodium chloride already obtained.
Instead, it is washed with a salty solution. After it is clean, it is dried and finally
packed for use as table salt. This salt has impurities of magnesium chloride and
calcium chloride which also crystallise from ocean water. These impurities make
the table salt damp because they are hygroscopic, sodium chloride is not.
1. What is fractional crystallisation?
2. (i) Name one local industry which uses this process to get their products.
(ii) Name the products.
(iii) Write a word equation and chemical equation in one of the process
in this industry.
1.13 Water hardness

In some regions, soap will not easily form lather with water. In distilled or rain
water, soap forms lather with great ease.
Water which forms lather with soap easily is said to be soft. The water which
does not easily form lather is said to be hard.
Experiment 1.9
Action of soap on soft and hard water and types of water hardness
37
• distilled water
• tap or river, well, pond, lake, etc. water
• boiled tap or river, well, pond, e.t.c. water
• rain water
• boiled rain water
• sea water
• boiled sea water
• distilled or rain water
• water to which magnesium sulphate has been added
• boiled magnesium sulphate solution
• water to which calcium chloride has been added
• aqueous calcium hydrogencarbonate
• boiled solution previously containing calcium hydrogencarbonate
• distilled water containing calcium carbonate powder
• sodium chloride solution
• aqueous calcium hydroxide
• soap
• 250 cm3 conical flasks
• burette
Note: You have been given water from various sources. Use what is available
within your environment. Calcium hydrogencarbonate solution can be prepared
by passing carbon(IV) oxide into aqueous calcium hydroxide for a long time (until
the precipitate formed dissolves again).
Procedure
1. Dissolve 20g of soap in hot distilled water. Add water to make up a litre of
soap solution.
2. Put 25 cm3 of distilled or rain water in a conical flask. Add about 2cm3 of
soap solution from a burette and shake the mixture.
Does lather form?
3. If lather does not form in conical flask, add the soap solution drop by drop,
shaking it after every addition until a permanent lather, lasting for about 2
minutes without breaking is formed.
Copy Table 1.25 in your notebook and record the volume of soap solution
used in each case.
4. Repeat procedure 2 and 3 with boiled 25 cm3 of distilled or rain water.
38
Table 1.25 Action of soap on soft and hard water
Sample solution/ Volume of soap used Volume of soap
water e.g. before it is boiled (cm3) used after it is boiled
Distilled water
Tap water
Calcium chloride
solution
Magnesium sulphate
solution
Rain water
5. Repeat the same procedure using the other solutions and the suspension of
calcium carbonate. Record the volumes of soap solution used in a table like
the one shown in Table 1.25.
• Which of your sample solutions lather readily and which ones lather
least with soap.
• Which cations are present in solutions that formed lather easily with the
soap solution?
• Which cations are present in solutions that did not form lather easily with
the soap solution?
• Compare the amount of soap used when the sample solution is not boiled
and when boiled.
(i) List the sample solutions that lather readily when they are not
boiled and when boiled.
(ii) List the sample solutions that lather readily when boiled.
(iii) List the sample solutions that do not lather readily even when
boiled.
• What happens when a solution of calcium hydrogencarbonate is boiled?
• What happens when a solution of magnesium sulphate is boiled?
Distilled or rain water produced lather very easily with soap. Tap, well, river, lake
and sea water will vary in the amount of soap used depending on the location
of your school. Sodium chloride solution also produces lather easily. Solutions
containing calcium and magnesium ions did not produce lather easily. In these
solutions which did not lather easily, there was a formation of grey–white
suspension or scum, as it is popularly known.
You must have noted that distilled water containing calcium carbonate powder
produced lather very easily. Calcium carbonate is insoluble in water and therefore
it does not form calcium ions.
39
From the observations above, distilled water or pure water contains no dissolved
solid impurites. It lathers easily with soap. Rain water lathers almost the same
as distilled water. The water that readily forms lather with soap is known as soft
water. Hard water does not readily form lather with soap.
When calcium hydrogencarbonate solution was boiled, it decomposed into
calcium carbonate which precipitated from the solution. The water which was
formed lathered easily.
boiling
Calcium ––––– calcium + water + carbon(IV)
hydrogencarbonate carbonate oxide
boiling
Ca(HCO3)2(aq) –––––– CaCO3(s) + H2O(l) + CO2(g)
When magnesium sulphate solution was heated, the resulting hot solution did not
lather easily. This is because magnesium sulphate does not decompose on heating.
We can conclude that calcium and magnesium ions cause hardness in water.
There are two types of water hardness.
• Temporary hardness
• Permanent hardness
Temporary hardness
Water contains dissolved carbon(IV)oxide. Some of this gas form carbonic acid.
Carbon(IV) oxide + water –––– carbonic acid
CO2(g) + H2O(l) –––– H2CO3(aq)
When this water passes over limestone (calcium carbonate) or dolomite (magnesium
carbonate), calcium hydrogencarbonate and magnesium hydrogencarbonate
respectively are formed.
Calcium + carbonic ––––– calcium
carbonate acid hydrogencarbonate
CaCO3(s) + H2CO3(aq) ––––– Ca(HCO3)2(aq)
Magnesium + carbonic ––––– magnesium
carbonate acid hydrogencarbonate
MgCO3(s) + H2CO3(aq) ––––– Mg(HCO3)2(aq)
Temporary hardness in water is caused by the presence of dissolved calcium
hydrogencarbonate and/or magnesium hydrogencarbonate. It is called temporary
hardness because it can be removed by boiling.
Permanent hardness
Permanent hardness in water is caused by dissolved calcium sulphate and
magnesium sulphate. This occurs when water dissolves small amounts of calcium
and magnesium sulphate from ground rocks as it passes on its way to reservoirs,
lakes, rivers or to the sea. This type of hardness cannot be removed by boiling. It
can however be removed through chemical treatment or distillation.
40
Note: Methods used to remove permanent hardness in water can also be applied
in removing temporary hardness.
Effects of water hardness

As we mentioned earlier; hard water does not lather easily with soap. Instead, a
grey-white suspension or scum is formed in the water.
The main constituent of common soap is a soluble sodium salt known as sodium
octadecanoate. When soap dissolves in water, its octadecanoate ion is produced.
water
Sodium –––– octadecanoate + sodium
octadecanoate ion + ion
The octadecanoate ions combine with calcium or magnesium ions from the hard
water to form an insoluble salt which is scum.
Octadecanoate + calcium –––– calcium
ion ion octadecanoate
(scum)
Octadecanoate + magnesium –––– magnesium
ion ion octadecanoate
(scum)
Table 1.26 Advantages and disadvantages of hard water
Advantages Disadvantages
1. The calcium compound 1. Waste of soap during scum formation.
present in hard water is
good for teeth and bone
formation.
2. Helps to form a lead carbonate 2. Scum leaves dirty marks on clothes
coat in water pipes made of after washing.
lead. This prevents some lead
from dissolving in water giving
rise to lead poisoning.
3. Good for formation of shells of 3. Deposits carbonates of calcium and
animals. Snails obtain calcium magnesium as “fur” on electrical
from hard water. appliances e.g. kettles, boilers thereby
making them inefficient, hence
increasing running costs.
4. Calcium and magnessium 4. The deposits of carbonates of calcium
are necessary for both plant and magnesium can block pipes from
and animal growth. Hard boilers and also reduce efficiency of
water is a source of this. boilers (reduced heat conductivity)
41
1. What is meant by hard water?
2. What is the difference between temporary hard water and permanent hard water?
3. In an experiment, soap solution was added to three separate samples of water.
The following table shows the volumes of soap solution required to form lather
with 1000 cm3 of each sample of water before and after boiling.
Sample A Sample B Sample C
Volume of soap before 15.2 30.0 2.5
water was boiled (cm3)
Volume of soap after 2.8 30.0 2.5
water was boiled (cm3)
(a) Which water sample is likely to be soft? Explain.

(b) Explain the change in the volume of soap solution used in sample A.
Methods of removing water hardness
Temporary hardness
Temporary hardness can be removed by:
(a) Boiling
Boiling decomposes the soluble hydrogencarbonates to insoluble carbonates,
carbon(IV) oxide and water as shown in the equations below.
boiling
Calcium ––––– calcium + water + carbon(IV)
boiling
Ca(HCO3)2(aq) ––––– CaCO3(s) + H2O(l) + CO2(g)
boiling
Magnesium ––––– magnesium + water + carbon(IV)
boiling
Mg(HCO3)2(aq) –––– MgCO3(s) + H2O(l) + CO2(g)
The insoluble carbonates formed remove the calcium and magnesium ions from
the water hence the water becomes soft.
Addition of calcium hydroxide or sodium carbonate
The method of removing temporary hardness by boiling is too expensive to be used
on a large scale. This can be done commercially by adding calculated amounts
of calcium hydroxide or sodium carbonate. This causes precipitation of calcium
and magnesium ions as carbonates.
Calcium + calcium –––– calcium + water
hydrogencarbonate hydroxide carbonate
42
Ca(HCO3)2(aq) + Ca(OH)2(aq) –––– 2CaCO3(s) + 2H2O(l)
Calcium + sodium –––– calcium + sodium
hydrogencarbonate carbonate carbonate hydrogencarbonate
Ca(HCO3)2(aq) + Na2CO3(aq) –––– CaCO3(s) + 2NaHCO3(aq)
Note: Sodium ions from sodium hydrogencarbonate as we have seen in our
experiment, do not cause water hardness.

(a) Write the chemical equation for the reaction which takes place when
magnesium hydrogencarbonate is removed from hard water using
(i) calcium hydroxide solution
(ii) sodium carbonate solution.
(b) What can happen if excess calcium hydroxide solution is used in the
removal of temporary water hardness?
Permanent hardness
Permanent hardness can be removed by;
(a) Addition of sodium carbonate
Addition of sodium carbonate causes the precipitation of calcium and magnesium
ions as insoluble carbonates. Thus
Calcium + sodium –––– calcium + sodium
sulphate carbonate carbonate sulphate
CaSO4(aq) + Na2CO3(aq) –––– CaCO3(s) + Na2SO4(aq)
Magnesium + sodium ––– magnesium + sodium
sulphate carbonate carbonate sulphate
MgSO4(aq) + Na2CO3(aq) ––– MgCO3(s) + Na2SO4(aq)
(b) Distillation
This method removes both permanent and temporary hardness because it removes
all the dissolved solids. However, it is expensive to use it to soften large amounts
of water. It can, however be used in the laboratory to make distilled water for
analytical work or for batteries.
(c) Use of ion-exchange method
This method involves use of a resin made of an insoluble complex of a sodium
salt known as sodium permutit. This method is also referred to as the permutit
process. Permutit releases sodium ions which exchange with the calcium and
magnesium ions in the hard water. Calcium and magnesium ions now become
part of the insoluble complex compound.
43
Hard water in
Hard water
Ca2+
Calcium ions (Ca2+) in
hard water
Ion exchange resin

(sodium permutit)
Soft water out
Sodium ions replace

calcium ions to soften
Na+ Na+ water
Fig. 1.9(a): Permutit process

Sodium ions (Na+(aq)) in water do not cause water hardness.
When all the sodium ions on the permutit column have been exchanged with
calcium or magnesium ions i.e. resin contains ions of calcium and magnesium,
it is said to be discharged. The permutit, can be “regenerated” or “recharged”
by passing concentrated sodium chloride solution(brine) through it. Another
ion–exchange process takes place.
Soft water in
Soft water
Na+
Sodium ions (Na+) from
brine
Ion exchange resin

(calcium permutit)
Hard water out
Calcium ions replace

sodium ions to form
Ca2+ Ca2+ hard water
Fig. 1.19(b): Ion-exchange column during regeneration

44
The calcium or magnesium ions are washed away leaving the permutit now full
of sodium ions (sodium permutit) and ready for re-use.
1. State two advantages and disadvantages of hard water.
2. (a) How does permutit process soften hard water?
(b) A simple formula of sodium permutit is Na2X. Write an ionic
equation to show how a solution of sodium permutit softens hard
water containing calcium hydrogencarbonate.
Summary
• Acids in water form hydrogen ions(H+) which give acidic property to the solution.
• A base in water forms hydroxide ions(OH–) which gives basic property to the solution.
• A strong acid is completely dissociated, that is, it yields many hydrogen ions
when dissolved in water. A weak acid is partly dissociated i.e. it yields few
hydrogen ions when dissolved in water.
• A strong base is completely dissociated, that is, it gives many hydroxide ions
when dissolved in water. A weak base is partly dissociated i.e. it gives few
hydroxide ions when dissolved in water.
• The concentration of an acid or base is the mass of acid or base in a given volume
of solution.
• Amphoteric oxides or hydroxides are metallic oxides or hydroxides which have
both acidic and basic properties.
• Formation of soluble complex salts make zinc hydroxide, lead(II) hydroxide and
aluminium hydroxide dissolve when excess sodium hydroxide is added to them.
• Similarly, formation of complex salts make zinc hydroxide and copper(II)
hydroxide dissolve when excess ammonia solution is added to them.
• Complex salts are made of complex ions.
• A simple salt consists of a metal ion or an ammonium radical and a non-metallic
ion or radical derived from an acid.
• Solubility of a substance at a particular temperature is its concentration in grams
per 100 g of solvent at that particular temperature.
• The solubility of a substance between certain temperature limits may be
conveniently represented by a solubility curve.
• Fractional crystallisation uses the principle of different solubility of substances
in solvents at a particular temperature or temperature range.
• Calcium ions and magnesium ions in water cause water hardness.
• Temporary hardness, which can be removed by boiling is caused by the presence
of calcium and magnesium hydrogencarbonates.
• Permanent hardness, which can not be removed by boiling is caused by the
presence of calcium and magnesium sulphates
• Ion-exchange method of removing hardness in water involves sodium ions exchanging
with calcium or magnesium ions. Sodium ions in water do not cause hardness.
45
Projects
(a) Extract salts from ash or soil.
(b) Investigate water hardness and its removal in various types of water at
your school, its surroundings or at your home.
(c) Visit Magadi Soda company or one of the salt works at Malindi. Write
a report after your visit.
(d) Using red and blue litmus papers, examine any solutions or liquid at
your home for acidity, alkalinity or neutrality.
Revision Exercise 1
1. (i) Explain the terms strong and weak as used in acids and bases.
(ii) Name three common strong acids and two weak acids.
2. Explain the difference in the action of magnesium with
(i) hydrogen chloride gas dissolved in methylbenzene.
(ii) hydrogen chloride gas dissolved in distilled water.
3. Explain what is observed when
(a) sodium hydroxide solution is added drop by drop till in excess to
(i) copper(II) sulphate solution.
(ii) Lead(II) nitrate solution.
(iii) Iron(II) sulphate solution.
(b) Ammonia solution is added drop by drop till in excess to
(i) copper(II) chloride solution.
(ii) zinc nitrate solution.
(iii) aluminium sulphate solution.
4. A student from Wamoro High school performed an experiment to find the
solubility of ammonium chloride at different temperatures.
The student found that
4.0g of this salt saturate 10 cm3 of water at 30˚C
5.0 g of this salt saturate 10 cm3 of water at 50˚C
6.0g of this salt saturate 10 cm3 of water at 70˚C
7.0 g of this salt saturate 10 cm3 of water at 90˚C
(i) Convert your grams/10 cm3 to grams/100 cm3
(ii) Assuming 1 cm3 of water = 1 g
Plot a solubility curve for this salt.
(iii) From your solubility curve, determine the solubility of this salt at 60˚C
and the mass of this salt that will crystallise out when its saturated solution
at 80˚C is cooled to 40˚C.
5. (i) Name two salts responsible for permanent hardness of water.
(ii) Explain the precipitation method used to remove water hardness.
(iii) Give two advantages of using hard water for domestic purposes.
46
Unit 2: Energy changes in physical
and chemical processes
Introduction
The ability or capacity of overcoming resistance or doing work is known as
energy. Thus energy is required to work. Without energy, there could be no life
or movement. The food we eat gives our bodies the energy we need to move,
work and keep ourselves warm. This energy is stored in food as chemical energy.
Fossil fuels such as coal and oil also have chemical energy stored in them. This
is why when we burn petrol, kerosene or liquid petroleum gas (LPG) such as
butane, energy is released. This may be used to move vehicles, planes or cook our
food. There are many forms of energy. These include chemical, heat, electrical
and mechanical energy. Some substances have energy as a result of the fact that
their particles are moving. Such energy is known as kinetic energy (K.E). Other
substances have energy by virtue of their position e.g. coiled spring. This type of
energy is known as potential energy (P.E.).
These forms of energy are interconvertible; one form of energy can be
transformed into another. For example, electrical energy can be transformed into
light energy and heat energy by passing electricity through a filament of a bulb.
Energy cannot be created nor destroyed. It can only be transformed to another form.
Energy changes bring about physical or chemical changes in substances. For
example, when other forms of energy are converted to heat energy, there is a
change in temperature. Conversion of chemical energy to other forms of energy
causes a change in chemical composition of substances.
In this unit, we are going to look at how these energy changes take place in
physical and chemical processes.
2.1 Exothermic and endothermic reactions

What are exothermic and endothermic reactions? To be able to understand them,
let us consider the following experiments.
Experiment 2.1
To investigate what happens when potassium nitrate/ammonium nitrate is dissolved
in water.
• beaker
• glass rod
• spoon/spatula
• ammonium nitrate/potassium nitrate
• water
Procedure
1. Put about 25cm3 of water in a beaker.
47
2. Add 3 spatula-endfuls of ammonium nitrate or potassium nitrate as shown in
Fig. 2.1(a)
Spoon
Stirring rod
Beaker
Water
Potassium
nitrate Hand
(a) Measuring KNO3 using a spoon (b) Stirring to dissolve
Fig. 2.1: Finding whether dissolving potassium nitrate is endothermic or

exothermic
3. Stir the mixture with a glass rod.

4. Hold the beaker in the palm of your hand as shown in Fig. 2.1(b)
5. What do you observe?
6. Record your observations in your notebook.
• What do you feel on your palm?
• Is heat energy being taken from your hand or given out to your hand?
• What do you conclude?
Repeat the experiment but stir the solution with a thermometer.
Caution: Make sure the thermometer does not touch the side or bottom of the
beaker to avoid breakage.
• Copy Table 2.1 below in your notebook and record the initial and final
temperatures of the solution.
Table 2.1 Changes in temperature in physical processes
Initial temperature of water ˚C
Final temperature of solution ˚C
• What do you conclude from the above observation?

When potassium nitrate dissolves, heat energy is absorbed from its surroundings.
In this case, its sorroundings include the beaker, glass rod, the thermometer, air
around, and your palm. This explains why your palm feels cold and the temperature
of the solution is lower than the initial temperature of the water. This is an
endothermic reaction. In endothermic reactions, heat energy is absorbed and the
temperature of the surroundings decrease. Loss of energy is a result of interaction
between a system and its surroundings. The beaker and its contents is the system
48
and the surrounding is everything else around. Fig. 2.2 illustrates how these
interactions occur.
An endothermic reaction is a reaction which takes in heat from the
surroundings
Heat gained
Heat colder than Heat

gained surroundings gained
Heat gained
Fig. 2.2: An endothermic reaction, heat is gained from the surroundings to the
system
Experiment 2.2
To investigate what happens when sodium hydroxide pellets are dissolved in water.
• boiling tube
• thermometer
• sodium hydroxide (pellets)
• water
Procedure
1. Half-fill the boiling tube with water.
2. Record its temperature.
3. Add 3-4 sodium hydroxide pellets.
4. Stir carefully using the thermometer while holding the tube. Note the
temperature of the solution. Does the tube feel cold or hot?
Record your results in a table similar to Table 2.2 below.
Caution: Sodium hydroxide pellets or its solution are highly corrosive. They
should not come into contact with your skin.
Table 2.2
Temperature of water ˚C
Temperature of sodium
hydroxide solution ˚C
• Does the reaction absorb or give out heat?

When sodium hydroxide dissolves in water, heat energy is released to the
49
surroundings, that is, to the thermometer, the beaker, the air around and to your
palm. This is the reason why the palm feels warm and the temperature of the solution
is higher than that of the water. This is an exothermic reaction. In exothermic
reactions, heat energy is given out, and the temperature of the surroundings rise.
When considering the loss of energy, there is interaction between the system and
its surroundings as shown in Fig. 2.3 below.
Heat lost
Heat Heat
lost hotter than
lost
surroundings
Heat lost
Fig.2.3: An exothermic reaction, heat is lost to the surroundings
The beaker and its contents is the system and the surrounding is everything else
around it.
An exothermic reaction is a reaction in which heat energy is produced and
released to the surroundings
• You have seen from experiment 2.1 and 2.2 that reactions either give out heat
or absorb heat from the surroundings. Study Fig. 2.4 below. What happens
to the temperature during exothermic and endothermic reactions?
Room temperature
(a) (b) (c)

Fig. 2.4: Temperatures in endothermic and exothermic reactions
Fig. 2.4(a) shows the room temperature or initial temperature of reactants. Fig. 2.4 (b)
and (c) shows changes of temperature during endothermic and exothermic reactions.
In all endothermic reactions, there is a temperature fall as shown in Fig. 2.4(b) and in
all exothermic reactions, there is a temperature rise as shown in Fig. 2.4(c). Therefore,
when a chemical reaction occurs in an open container, most of the energy gained or
lost is in form of heat. This is observed as/or indicated by an increase or decrease
in temperature depending on whether the reaction is exothermic or endothermic
respectively.
Under conditions of constant pressure, chemical changes are accompanied by heat
50
being absorbed or released i.e. there is change in heat content. The correct term
for ‘heat content’ is Enthalpy. The word enthalpy comes from a German word
‘Enthalten’ which means ‘to contain’. Enthalpy or heat content is symbolised
by letter ‘H’.
We do not measure enthalpy directly, rather we are concerned with the heat added
to or lost by the system. This is referred to as Enthalpy change and denoted by the
symbol ∆H (read as “delta H”) The change in enthalpy (∆H) is the heat added
or lost by the system when the processes occur under constant pressure.
∆H represents the difference between the enthalpy of the system at the beginning
of the reaction and the end of the reaction i.e.
∆H = Hfinal – Hinitial
We can also describe enthalpy change (∆H) for the reaction as the difference
between enthalpies (H) of the products and reactants.
∆H = Hproducts – Hreactants
It is important to note that:
• if the system has higher enthalpy at the end of the reaction, then it has
absorbed heat from the surroundings (endothermic reaction)
• if the system has a lower enthalpy at the end of the reaction, then it gave
off heat during the reaction (exothermic reaction).
Therefore
• For endothermic reactions Hproducts > Hreactants and the value of ∆H is
positive (∆H = +ve)
• For exothermic reaction Hproducts < Hreactants and the value of ∆H is
negative (∆H = –ve).
We can use the analogy in Fig. 2.5 to assist us understand endothermic and
exothermic processes.
Heat “enters” (absorbed) Heat “exits” (released

from surroundings to the surroundings).
Endothermic Exothermic
Fig. 2.5: Analogy of absorption and evolution of heat energy in endothermic and
exothermic reactions.
1. Compare exothermic and endothermic reactions in terms of
(i) heat change with the surroundings.
(ii) the sign of ∆H.
2. (a) A student in experiment 2.1 dissolved potassium nitrate in water.
51
The equation for the reaction which occurs is:-
KNO3(s) K+(aq) + NO3–(aq) ∆H = 34.6kJ.
What sign would you assign the ∆H value, positive or negative? Explain.
(b) What does the symbol ∆H signify in a reaction?
Energy level diagrams for exothermic and endothermic reactions

The relative enthalpies of the reactants and the products can also be shown on a
graph called energy level diagram such as the one shown in Fig. 2.6 below.
y
REACTANTS
∆H = – ve
Energy (kJ)
PRODUCTS
x
Reaction path
Fig. 2.6: Energy level diagram for an exothermic reaction
It shows the enthalpy change of a reaction. The x-axis shows the progress of the
reaction from reactants to products and y-axis shows the enthalpy (Heat content).
From the graph above the enthalpy change is given by
∆H = Hproducts – Hreactants.
The enthalpy, H, of the products is less than that of the reactants. The enthalpy
change (∆H) will be a negative value. For example, assuming that the enthalpy
value of the reactants from the above graph is 50 and the products is 10. The
enthalpy change will be.
= 10 – 50
= – 40
The ∆H value is negative and the reaction is exothermic.
It is referred to as an exothermic reaction.
52
Now let us study Fig. 2.7 below.
PRODUCTS
∆H = + ve
Energy (kJ)
REACTANTS
Reaction path
Fig. 2.7: Energy level diagram for an endothermic reaction

From Fig. 2.7, the enthalpy, H, of the products is more than that of the reactants.
Hence the enthalpy change (∆H) will be a positive value (∆H = +ve). For example,
assume that the value of reactants from the graph above is 10 and the product is 50.
The enthalpy change (∆H) will be
= 50 – 10
= 40
Note: A number without a sign is taken to be positive. The ∆H value is positive
and the reaction is said to be endothermic.
Activity
Consider experiments 2.1 and 2.2. Draw energy level diagrams to represent the
results that you obtained. Compare your results with the information given below.
Dissolving of potassium nitrate resulted in a decrease in temperature indicating
that it was an endothermic reaction whereas dissolving sodium hydroxide pellets
resulted in an increase in temperature indicating that it was an exothermic reaction.
We can represent these results in energy level diagrams as follows
KNO3(aq) NaOH(s)
Energy (kJ)
Energy (kJ)
KNO3(s) NaOH(aq)
Reaction path Reaction path

(a) Dissolving potassium nitrate: Endothermic (b) Dissolving sodium hydroxide: Exothermic
Fig. 2.8: Energy level diagrams for dissolving (a) potassium nitrate and (b) sodium
hydroxide
53
Unit of energy
Heat energy is measured in joules (J) or kilojoules (kJ). It takes 4.18 kJ to heat 1
kg of water through a temperature of 1 Kelvin.
2.2 Energy changes in physical processes

Latent heat
Physical processes to be investigated: Melting and evaporation.
Experiment 2.3
To investigate what happens when ice is heated to its melting point then to its
boiling point
Note. In this experiment, the beaker and its contents is the system.
• Beaker
• Thermometer (–10˚C to 110˚C)
• Burner
• Tripod stand
• Wire gauze
• Stop clock/watch
• Ice
Procedure
1. Half fill the beaker with some ice.
2. Insert a thermometer carefully into the ice and record the steady temperature
Arrange the apparatus as in Fig. 2.9(a) below.
clamp
thermometer
thermometer
beaker steam
ice boiling water
heat heat
(a) (b) (c)
Fig. 2.9: Investigating what happens to ice when heated.

3. Heat the ice gently while carefully stirring with the thermometer as shown in
Fig. 2.9(b).
4. What do you observe?
5. Record the temperature of the ice every 30 seconds in your notebook, until
all ice melts.
54
6. Copy Table 2.3 in your notebook for recording your results.
7. When all ice has melted, heat the liquid strongly, while stirring carefully with
the thermometer as shown in Fig. 2.9(c).
8. Record the temperature at 30 seconds intervals in Table 2.3.
Caution: The thermometer should not touch the sides of the beaker to avoid
breakage.
9. Using your results in the table, draw a graph of temperature (y-axis) against
time (x-axis). Answer the following questions using your graph.
• What is the boiling point of water?
• Is it different from your experience? If yes explain the difference.
Table 2.3: Temperature changes in water
Time (seconds) 30 60 90 120 150 180 210 240
Temperature (˚C)
Melting and boiling are physical processes. They involve change of state, i.e. a
solid changes to a liquid during melting and the liquid changes to vapour during
boiling. They are also known as phase changes. These phase changes involve
energy changes. For example, input of heat is necessary to melt ice or boil
water. The heat energy is used to break the intermolecular forces of attraction
(i.e. hydrogen bonds), between water molecules in the liquid and not covalent
bonds. A large amount of energy is needed to break the covalent bonds between
the atoms making up water i.e O–H bond, in order to split water into hydrogen
and oxygen atoms.
Hydrogen bonds
Fig. 2.10: The structure of ice
For example, in the ice, whose structure is shown in Fig. 2.10 above, the energy
supplied makes the molecules to vibrate more vigorously until the hydrogen bonds
are broken and the solid melts. The amount of heat needed to convert a solid
substance into a liquid at its melting point is called latent heat of fusion.
55
When water is in liquid state, the molecules move randomly. These molecules
already have kinetic energy but tend to stick together because of intermolecular
forces of attraction. When heating is continued, the molecules absorb heat
energy. This heat energy is converted to kinetic energy. This increases the kinetic
energy of the molecules. Its temperature rises till boiling point. The molecules
at the surface acquire enough energy and speed to overcome the intermolecular
forces of attraction between them. They then escape from the liquid state into
the air in gaseous state. At boiling point, the temperature of the boiling water
remains constant until all the liquid changes to vapour. The amount of heat
required to change liquid to vapour at the boiling point is called the latent heat
of vaporisation.
When a solid is heated, the particles gain energy and they vibrate more vigorously.
When they overcome the forces of attraction, the solid melts. Melting is also
known as fusion. The amount of heat required to melt one mole of a substance
is called the molar enthalpy of fusion, denoted by (∆Hfus ).
The molar enthalpy of fusion is the amount of energy required to melt one
mole of a solid at its melting point.
On further heating of the molten substance,the intermolecular forces of the liquid
particles break and the liquid changes to vapour. The amount of energy needed to
change a liquid to vapour depends very much on the strength of intermolecular
forces of attraction which are broken, converting the boiling liquid to a vapour.
The amount of heat required to change one mole of liquid to vapour is called the
molar enthalpy of vaporisation, denoted by (∆Hv ).
The molar enthalpy of vaporisation (∆HV ) is the amount of heat required to
change one mole of liquid into vapour at its boiling point.
Change of state requires energy. In experiment 2.3 you drew a graph. Compare
your graph with the one in Fig. 2.11 below.
boiling
point
melting gas
point boiling
temperature (˚C)
liquid
melting
solid
time in minutes
Fig. 2.11: Graph showing change of state
During melting process, the particles of a solid have enough kinetic energy and
they are able to break the force of attraction while solid changes to liquid. During
boiling, the particles acquire enough kinetic energy and speed to overcome the
56
force of attraction between them and hence (most) escape (from the liquid) during
vaporisation to the air.
The molar enthalpy of vaporisation of a substance is higher than the enthalpy
of fusion because the strength of the bonds which are broken when converting
the liquid to vapour are stronger than the ones broken to change a solid to liquid.
Also, the particles must be separated to a considerable distance in forming the
vapour. For example, in case of metals, most of the metallic bonding still exists
in the liquid state.
1. What happens to the particles of a substance during melting?
2. What happens to the particles of a substance during vaporisation?
3. The molar enthalpy of vaporisation of a substance is usually larger than
the molar enthalpy of fusion. Explain.
4. Compare the relative movement of particles in the solid, liquid and a
gaseous state?
5. How does sweating help us to keep cool in hot weather?
2.3 Energy changes in chemical processes

In physical processes e.g. water, the bonds broken during melting and vaporisation
are the intermolecular forces of attraction but not the strong covalent bonds
between hydrogen and oxygen atoms. In chemical processes, these covalent bonds
are broken and new ones are formed. Enthalpy changes in chemical processes
can be determined through experiments.
The value of enthalpy change, ∆H for a reaction depends on the physical
conditions under which the measurement is done. Just as we indicate the state
symbols of the substances involved in a reaction depending on the temperature
of the surrounding, the value of ∆H depends on the pressure under which the
measurements are made. The changes for most reactions are carried out under
conditions known as the standard conditions for the reaction. These conditions
have been chosen as follows:
Standard temperature = 25˚C (298K).
Standard pressure = 1 atmosphere.
Whenever enthalpy (heat) changes are measured under the above stated standard
conditions, they are called standard enthalpies of the reactions. The special
symbol θ is used as a superscript for ∆H.
∆Hθ is the symbol for standard enthalpy. The superscript θ indicates that the
enthalpy change is measured under standard conditions.
57
Examples of standard enthalpies of reactions include:
∆Hθf denotes the standard enthalpy of formation.
∆Hθc denotes the standard enthalpy of combustion.
∆Hnθ denotes the standard enthalpy of neutralisation.
To determine the final quantity of energy released or absorbed during a reaction,
first find the amount of energy used to start the reaction and amount of energy
released at the end of the reaction. Then compare the two amounts of energies
obtained to see whether the energy used to start the reaction is more or less
than the energy obtained. Let us now learn how to determine energy changes in
chemical processes.
Enthalpies of formation
Let us consider the following general reaction where diatomic molecules of X2
react with diatomic molecules of Y2.
X-X + Y-Y ––––––––––– X-Y + X-Y
Breaking bonds, Forming new bonds,

energy is supplied. energy is released
(endothermic) (exothermic)
Would you say the reaction is exothermic or endothermic?
• The bond energies of each type of bond are as given in Table 2.4.
Table 2.4 Bond energies
Bond ‘Amounts’ of energy required to break bond / released
when bond is formed (kJ mol–1)
X-X 435
Y-Y 240
X-Y 430
Solution
To break bond between X – X, the energy required = 435 kJ mol–1
To break bond between Y – Y, the energy required = 240 kJ mol–1
Total energy required = 675 kJ mol–1
As we discussed earlier, in an endothermic reaction ∆H has a positive value. Since
bond breaking is endothermic, the value should be written as +675 kJmol–1
Forming a bond between X – Y, energy released = 430 kJ mol–1
Forming another bond between X – Y, energy released = 430 kJ mol–1
Total energy released = 860 kJ mol–1
58
Since bond formation is an exothermic reaction, the value should be written as
–860 kJ mol–1
As we have seen, we got 185 kJ more than we ‘invested’ when two (X-Y) bonds
in two XY molecules were formed. That is 860 – 675 = 185 kJ.
Note that if we use ∆H notation, we must insert a negative sign in front of
the answer i.e –185 kJ to show that energy was released. Here, the negative sign
indicates that the reaction is exothermic and the equation can be written as
X2 + Y 2
2XY ∆H = –185 kJ
X – X + Y – Y
X – Y+ X – Y ∆H = 185 kJ
185
=
2
∆H = –92.5 kJmol–1
Now, let us consider another general reaction given as follows:
A – A + B–B A–B+A–B
Use the energy values in Table 2.5, to find out whether the reaction above is
exothermic or endothermic.
Remember that to break bonds for reactants, energy must be supplied (endothermic)
and when bonds for products are formed, energy is released (exothermic).
Table 2.5 Bond energies
Bond Energy used to break bond / released
when bond is formed in kJ mol–1
A – A 435
B – B 497
A – B 463
Compare your work with the following solution.
To break the bond between A – A the amount of energy required
= 435 kJ mol–1
To break the bond between B – B the amount of energy
required = 497 kJ mol–1
The total amount of energy required = 932 kJ
Bond breaking is an endothermic process. Therefore, the value should be assigned
a positive sign i.e. +932 kJ mol–1
But the amount released to form the 2 bonds between A– B = 463 × 2
= 926 kJ mol–1
Total amount of energy required = 926 kJ
Bond formation is an exothermic process. The value should be assigned a negative
sign i.e. –926 kJ mol–1
59
Note that we get less energy when bonds are formed. We spent 932 kJ and got 926
kJ. We have ‘lost’ 6kJ of energy. This energy has been absorbed by the system. The
energy absorbed is +932 – 926 = +6kJ mol–1. The equation can be written as follows:
A2 + B2 2AB ∆H = +6 kJ Two moles are formed. Therefore
∆H = ∆H = +3kJ/mol or +3 kJmol–
6 kJ
2 mol
A reaction where less energy is released than supplied is an endothermic reaction.
Note, that the energy released is less by 6 kJ for every 2(A–B) bonds formed.
Remember when a bond is formed, energy is released and energy is required to
break one.
When particles such as atoms combine to form molecules, they do so by forming
covalent bonds while ions combine by forming ionic bonds. Once this has happened,
energy is stored in the chemical bonds linking the atoms or ions. This energy stored
in the bonds of the molecules of a substance is called potential energy. For example,
when hydrogen atoms combine to form hydrogen molecules, energy is released
in form of heat energy. The reaction is exothermic. Due to the energy released,
the hydrogen molecules formed contain less energy and are said to be stable.
H. + H. H:H or H –H
Bond formation is an
exothermic process
To break the covalent bonds, energy must be supplied.
H –– H H. + H.
Breaking bonds is an
endothermic process
Due to energy absorbed when separating the molecules, free atoms possess
more energy than the molecules. Therefore, they are highly unstable. This is
why hydrogen does not exist as separate atoms. The energies required to break
the covalent bonds of hydrogen molecules is exactly equal to that released
when the separate atoms combine to form molecules. Energy is conserved. The
energy required to break covalent bonds between atoms have been determined
experimentally. These energies are called bond dissociation energies. Table 2.6
shows some of these bond dissociation energies.
Table 2.6: Bond dissociation energies of some bonds
Bond Bond energies (kJ mol–1)
C––H 413
C––C 346
N––H 389
H––H 436
Cl––Cl 242
H––Cl 431
60
Br––Br 193
C––Cl 339
H––Br 365
C––Br 280
Notice from Table 2.6 that some bonds are stronger than others.
• Which is the strongest bond from Table 2.6? Explain
• Which is the weakest bond from Table 2.6? Explain.
The covalent bond between the hydrogen atoms is the strongest. This is because
the hydrogen atoms are very small (i.e. the atomic radii are small), therefore, the
nuclei attract the shared pair of electrons strongly. Hence, the bond requires a lot of
energy to break. The atomic radii of chlorine atoms is larger than that of hydrogen
atoms. The attraction of the shared pair of electrons by the nuclei of chlorine atoms
is relatively weak. Therefore, the bond is weak and requires less energy to break.
Now, let us see how bond energies are used to determine the enthalpy of formation
of some compounds.
Enthalpy of formation is the enthalpy change that occurs when one mole
of a substance is formed from its elements under standard conditions.
Enthalpy of formation of hydrogen chloride

Determine the bonds to be broken and the new bonds to be formed. We know
that hydrogen chloride is made of hydrogen and chlorine atoms. We are also aware
that hydrogen and chlorine are both diatomic gases. Their respective atoms are
linked by strong covalent bonds. Therefore, the reaction needs energy to start it
off. This energy is required to break the bonds of the reactants(endothermic). When
products are formed, new bonds are formed between H and Cl atoms. Formation
of bonds is an exothermic reaction. We are expected to find out from the reaction
below whether breaking the bonds require more energy than the energy released
during bond formation. The bond energies are given in Table 2.6.
The reaction taking place is as follows:
H2(g) + Cl2(g) 2HCl(g)
or
H – H(g) + Cl – Cl(g) H – Cl(g) + H – Cl (g)

bonds broken new bonds formed
61
H H Cl Cl
Separate atoms
bonds Energy needed Energy released when new
to break bonds
Energy (kJ mol–1)
to be bonds are made.

broken 436 + 242 = +678 kJ mol–1 431 + 431 = –862 kJ
H — H + Cl — Cl New bonds formed
Molecules of reactants
436 + 242 ∆Hr
H — Cl H — Cl
431 + 431
Molecules of products
Reaction path
Fig 2.12: The reaction of hydrogen and chlorine involves first breaking of bonds
of the reactants. Then formation of new bonds of products
Calculating the ∆H of formation of HCl

We start by looking at how many H – H and Cl – Cl bonds are broken and how many
H–Cl bonds are formed. Then determine how much energy is spent to break these
bonds. The total energy needed to break these bonds, is the energy needed to start
off this reaction. We get this energy by adding up the bond energies as shown below.
One H – H bond 1 × H - H bond dissociation energy

i.e.
1 × 436 = +436 kJ mol -1
One Cl – Cl bond 1 × Cl – Cl bond dissociation energy
i.e.
1 × 242 = + 242 kJ mol -1
Total energy needed = 436 + 242 = +678 kJ
Note: The +ve signs are necessary because breaking bonds is an endothermic
process.
The total energy released during bond formation is obtained as follows:

Two H –Cl bonds 2 × H – Cl bond dissociation energy
i.e. 2 × 431 = –862 kJ mol –1
Total energy released = –862 kJ
Note: The –ve sign must be written in front of the number because bond
formation is an exothermic process.
62
• We got more energy when making new bonds than we spent when breaking bonds.
Heat of reaction, ∆Hr = energy difference
∆H = sum of energy released when – sum of energy needed

new bonds are formed to break bonds in reactants
∴ ∆Hr = 862 – 678

= –184kJ
∴ 184kJ of energy is released when 2 moles of hydrogen chloride are formed
Therefore, the enthalpy of formation for HCl is, –184 kJ = –92 kJ mol–1
2

1. (a) Hydrogen and bromine react to form hydrogen bromide. Write an
equation for the reaction.
(b) When a reaction takes place, chemical bonds are broken and new
chemical bonds are formed.
(i) To break a chemical bond, energy is supplied. This is represented
by positive sign.
(ii) Copy the table below in your notebook and insert the missing sign
and the missing value.
Energy to break H – H = 435kJ
Energy to break Br – Br = 193kJ
Energy to form H – Br = 365kJ
Energy to form H – Br = …..kJ
(c) Calculate the overall enthalpy change for the reaction.
(d) Is the overall reaction exothermic or endothermic? In terms of ∆H
notation, insert the correct value in equation 1 (a) above.
2. Hydrogen burns in air to form steam.
2H2(g) + O2(g) ––––– 2H2O(g)
(a) Which bonds are broken?
(b) Use the bond energies in the following table to calculate ∆H for the reaction.

Bond Bond energy (kJ mol–1)

H – H 436

O = O 489

O – H 464
(c) Re-write the equation and include ∆H.
63
Determining the enthalpy of formation of chloromethane from methane gas
and chlorine gas
Methane is the first member of the hydrocarbons called alkanes. One or more of
the hydrogen atoms of an alkane, in this case methane, can be substituted by a
halogen atom i.e. chlorine in the presence of ultraviolet light to form chloromethane
as shown below. This is an example of a substitution reaction.
u.v light
Methane + chlorine chloromethane + hydrogen chloride
H H
u.v light
H– C – H (g) + Cl–– Cl (g) H – C – Cl (g) + H –– Cl(g)
H H
• Is this an exothermic or endothermic reaction?
This reaction first involves breaking bonds of the reactants then formation of new
bonds of the products as shown in Fig. 2.13
H H
C Cl
H H Cl
Energy (in kJmol–1)
bond breaking bond making releases energy

absorbs energy
H
H–C–H + Cl – Cl
H H
H – C– Cl + H – Cl
H
Reaction progress
Fig. 2.13: Reaction of methane with chlorine
Notice that:
• All the four C – H bonds in methane and one Cl – Cl are broken
(endothermic).
• When the products are formed, the following bonds are formed.
(i) Three (3) C – H
(ii) One (1) C – Cl exothermic
(iii) One (1) H - Cl
64
Let us use the bond energies given in Table 2.6 to calculate ∆H.
Reactants bonds broken
Four C– H = 4 × 413 = + 1652 kJ
One Cl – Cl = 1 × 242 = + 242 kJ
Total energy needed = + 1894 kJ
Products bonds formed
Three C – H = 3 × 413 = – 1239 kJ
One C – Cl = 1 × 346 = – 346 kJ
One H – Cl = 1 × 431 = – 431 kJ
Total energy given out = – 2016 kJ
Enthalpy of formation = sum of energy released – sum of energy needed to

(∆H) when bonds are broken. break bonds.
∴ ∆H = 2016 – 1894
= –122kJ
The reaction is therefore exothermic.
1. Which of the following reactions are exothermic and which are endothermic?
Explain.
(a) 2A2(g) + B2 (g) 2A2B(l) ∆H = x kJ mol-1
(b) 2H2(g) + O2 (g) 2H2O(l) ∆H = –572 kJ mol-1
(c) 2A2B (l) B2 (g) + 2A2 (g) ∆H = +2y kJ mol-1
2. Ethane can be halogenated using bromine to form 1,2-dibromoethane in
presence of sunlight. Use the values given in Table 2.6 to calculate the
enthalpy change, ∆H of the reaction.
Determining enthalpies through experiments

It was mentioned earlier in this unit that when some solids are dissolved in water,
the process could be either endothermic or exothermic. It is possible to determine
the amount of energy taken in from the surroundings or given out to surroundings
through experiments. In the following experiments, we are going to determine:
• Enthalpy of solution
• Enthalpy of combustion
• Enthalpy of displacement
• Enthalpy of neutralisation
Enthalpy of solution
The enthalpy of solution is the heat evolved or absorbed when one mole of a
substance is dissolved in so much water that gives an infinitely dilute solution.
65
This means that further dilution produces no detectable heat change. To be able
to understand this, we are going to consider the processes of dissolving these
substances in water.
(i) ammonium nitrate.
(ii) concentrated sulphuric acid.
(I) Ammonium nitrate
Experiment 2.4
To determine the enthalpy of solution of ammonium nitrate
• balance
• thermometer
• glass rod/ stirring rod
• measuring cylinder
• beaker (plastic)
• ammonium nitrate
• water
Procedure
1. Measure 100cm3 of distilled water and transfer into a plastic beaker.
2. Measure the temperature of the water as shown in Fig. 2.14 (a).
3. Record this temperature in Table 2.7 as initial temperature.
4. Weigh accurately 0.8 g ammonium nitrate.
5. Add all the 0.8 g into the water holding the beaker in the palm of your hand
and stir as shown in Fig. 2.14(b)
• What do you observe?
• What is the temperature of this solution when the solid dissolves completely?
6. Again record this as the final temperature reached as shown in Table 2.7.
7. Find the temperature change and record as shown in the same table.
Note: Do not remove the thermometer from the solution when reading final
temperature.
Thermometer
Thermometer
Beaker
Beaker
Distilled
water Hand
(a) (b)
Fig 2.14: Dissolving ammonium nitrate in water
66
Table 2.7 Results of experiment.
˚C K
Initial temperature of water = T10C
Final temperature of solution = T20C
Change in temperature, ∆T = (T2 – T1) 0C
• From your result in Table 2.7, did the temperature rise or fall?
• What does this indicate about the reaction?
There was a temperature fall. This shows that as ammonium nitrate was dissolving,
heat was absorbed by the system from the surroundings i.e. from the beaker and
its contents, as well as from the palm of your hand. This is the reason why the
hand felt cold. The reaction is therefore endothermic. This is because the energy
needed to break the forces of attraction between ammonium (NH4+) and nitrate
(NO3– ) ions is a lot.
We have mentioned that the heat gained by the dissolving ammonium nitrate salt
comes from the surroundings. In other words, we can correctly say that the heat
lost by the surroundings is equal to the heat gained by the nitrate and ammonium
ions in solution.
Heat gained = Heat lost.
When a salt dissolves in water, the enthalpy change can be calculated using the
following formula.
∆H = m × c × ∆T or mc ∆T
where;
m = mass of solution
c = specific heat capacity of water
∆T = change in temperature
Let us use the following specimen results in Table 2.8 to show how to calculate
the enthalpy change of dissolution of ammonium nitrate.
Table 2.8 Specimen results

˚C K
Initial temperature T1 24.0 297.0 K
Final temperature T2 22.0 295.0 K
Temperature difference ∆T (T2 – T1) 2.0 2.0
Note that the temperature difference on the Kelvin scale is the same as that on
the Celsius scale. The only difference is that Kelvin scale starts at –273˚C while
67
Celsius starts at zero(0) ˚C, therefore 0˚C = +273 and 24˚C = 273 + 24 = 297
Total heat absorbed is given by ∆H = mc∆T; density of water = 1g cm-3
To calculate the mass of water, we use the formula:-
Mass = volume × density.
Remember the density of water is 1g cm-3.
Therefore,
Mass of water = 100 cm3 × 1g cm–3
= 100 g
Let us now substitute the values
= 100 g × 4.18 Jg-1K-1 × 2K
1000 g
= + 0.836 kJ
This is the energy absorbed by 0.8 g NH4NO3.
Suppose we were required to calculate the energy absorbed by 1 mole i.e. the
molar heat of solution:
1 mole of NH4NO3 = 80 g
0.8 g absorbed 0.836 kJ
∴ 80 g would absorb x kJ
Cross multiply and solve for x
x kJ × 0.8 g = 80 g × 0.836 kJ
x = 80 g × 0.836 kJ = +83.8 kJ mol–1
0.8 g
OR
Convert the number of grams dissolved to moles first as follows:
1 mol of NH4NO3 = 80 g
y mol of NH4NO3 = 0.8 g
Cross multiply and solve for y
y × 80 g = 1 mol × 0.8 g
80 g
= 0.01moles
Then proceed as follows:
0.01mole absorbed 0.836 kJ
1mol would absorb x kJ
x = 0.836kJ
0.01 mol
= +83.6kJ mol–1
68
∴ The molar heat of dissolution of ammonium nitrate = +83.6kJ mol–1
We can represent the dissolving process in an energy level diagram as shown in
Fig. 2.15.
NH4NO3(aq)
Energy (kJ mol–1) ∆H = +83.6 kJ 1mol
NH4NO3(s) + H2O(l)
Reaction path
Fig. 2.15: Dissolving of ammonium nitrate is an endothermic process

1. Ammonium nitrate dissolves in water. State how you test whether the
process is an exothermic or endothermic reaction.
2. NH4NO3(s) –––––– NH4+(aq) + NO3–(aq) ∆H = +83.6 kJmol–1

water
Draw an energy level diagram for the reaction.
II. Sodium hydroxide

Experiment 2.5
To find the enthalpy of solution for sodium hydroxide solution
• balance
• thermometer
• glass rod
• plastic beaker (250cm3) or lagged beaker
• sodium hydroxide pellets
• water
Procedure
1. Repeat procedure as in experiment 2.4 using 0.4 g of sodium hydroxide pellets.
2. Draw a table similar to Table 2.7 and fill it.
• Did the temperature rise or fall?
• Is the reaction exothermic or endothermic?
3. Study the specimen results given in experiment 2.4. Use your results to
calculate the molar heat of dissolution of sodium hydroxide.
69
• Given the molar enthalpy of solution, ∆H of sodium hydroxide is
– 42.7kJ mol-1,state briefly the experimental errors that might have
contributed to the difference between this value and your answer.
As mentioned earlier, heat is given out to the surroundings in all the reactions
where the temperature rises. Dissolution of sodium hydroxide is an exothermic
reaction. Note that your calculated molar heat of dissolution might be different
because of experimental errors. These include making mistakes during weighing,
reading the thermometer, measuring volume of water and not getting the correct
final temperature and lagging the beaker. These errors should be avoided as
much as possible. Calculated value is also different because of heat loss to the
environment by convection, conduction and radiation which was not accounted
for. We can represent the enthalpy change in an energy level diagram as shown
in Fig. 2.16 below.
NaOH(s) + water
Energy (kJ)
∆H = –42.7 kJ/mol
NaOH(aq)
Reaction path
Fig. 2.16: Energy level diagram for dissolving sodium hydroxide
III Concentrated sulphuric(VI) acid

Experiment 2.6
To find the molar enthalpy change for the solution of concentrated sulphuric acid
(dilution).
• funnel
• plastic beaker or glass beaker lagged in a newspaper leaf
• teat dropper
• thermometer
• boiling tube
• test tube rack
• measuring cylinder (10 cm3)
• concentrated sulphuric acid
• water
70
Procedure
1. Measure 98 cm3 of water into a beaker.
2. Measure the temperature of the water. Copy Table 2.7 in your notebook and
record this temperature as the initial temperature of the water.
4. Using a teat dropper, measure 2 cm3 of concentrated sulphuric acid.
5. Tilt the beaker and carefully pour the acid along the sides of the beaker as
shown in Fig. 2.17.
Measuring cylinder
Beaker
Concentrated
Sulphuric acid
Water
Fig. 2.17: Preparing a solution of sulphuric(VI) acid

Caution: Never add water to concentrated sulphuric acid. But add the acid
to water. Do you remember why?
6. Stir the mixture carefully with the thermometer so as to mix the solution
uniformly. Make sure your thermometer does not touch the sides of the beaker
to avoid breakage.
7. Note down the temperature recorded by the thermometer in your notebookas
final temperature. Calculate the temperature change and record it in the table.
• Does the temperature rise or fall?
Let us calculate the molar enthalpy change for dissolution of concentrated
sulphuric acid from the following specimen results.
The density of sulphuric(VI) acid = 1.84 g cm-3
The specific heat capacity of water = 4.18 Jg- 1 K-1
The density of solution = 1g cm-3
Temperature change (∆ T) = 5˚C or 5K (Rise in 1˚C = Rise in 1K)
1 mole of H2SO4 = (1 × 2) = (32 ×1) + (16 × 4) = 98 g
(H = 1; S= 32 ; O = 16, density of water = 1 g cm–3)
Total mass of solution = (98 cm3 × 1 g cm–3) + (2 cm3 × 1.84 g cm3) 101.68g ≈ 100g
The enthalpy change in this experiment is given by the formula
Enthalpy change = mass of solution × specific heat × temperature
capacity change
Enthalpy change (∆H) = m c∆T
= 100 g × 4.18 J-1 g-1 K-1 × 5 K = 2090
= 2090 kJ = 2.09 kJ
1000
∴∆H = – 2.09 kJ
71
But, we know that D = M where, D is density, M is mass and V is volume.
V
The density of sulphuric(VI) acid used is 1.84 g/cm–3 and volume is 2 cm3
M = 1.84 g/cm-3 × 2 cm3
= 3.68 g
1mole of H2SO4 = 98 g
3.68 g of sulphuric(VI) acid produce 2.09 kJ
98 g of sulphuric(VI) acid would produce x kJ
x = 2.09 kJ × 98 g
3.68 g
= 55.66 kJmol-1
∴ The molar enthalpy of dissolving conc. H2SO4 = –55.7 kJ mol–1
OR
1 mole of H2SO4 = (1 × 2) + 32 + (16 × 4) = 98 g = 98 g
y mole of H2SO4 = 3.48 g
y = 3.68 = 0.0376 moles

98
This means 0.038 moles produced 2.90 kJ.
1 mole would produce x kJ.
x = 2.09
0.0376
= –55.65 kJ mol-1
∴ The molar enthalpy of dissolving conc. H2SO4 is ≈ –55.7 kJ mol–1
H2SO4(l) + H2O(l)
∆H = –55.7 kJ 1mol–1
Energy (kJ)
H2SO4(aq)
Progress of reaction
Fig. 2.18: Energy level diagram for dissolution of sulphuric acid
72
Enthalpy of combustion
To explain the quantitative determination of enthalpy of combustion, we will look
at combustion of ethanol as described in the following experiment.
Experiment 2.7
To find the molar enthalpy of combustion of ethanol.
Apparatus and chemical
• balance
• thermometer
• metal calorimeter / tin
• spirit lamp / improvised spirit lamp
• draught shield
• water
• ethanol
Procedure
1. The apparatus is set up as shown in Fig. 2.19.
Thermometer
Calorimeter or (beaker)
Water Clamp
Draught
shield
Spirit lamp
Ethanol
Fig 2.19: Apparatus to determine the heat of combustion of ethanol
2. Place about 400 cm3 of water in a beaker.

3. Measure the initial temperature of water. Let this be temperature T1. (Record
it as T1)
4. Copy Table 2.9 and record the temperature.
5. Half-fill the lamp with ethanol and weigh the lamp with its contents, call this
mass M1.
6. Place the lamp under the tin and light the wick.
7. Stir the water carefully with the thermometer, until the temperature rises by
about 12˚C. Put off the flame. Record the temperature in Table 2.9 as T2.
8. Re-weigh the lamp and its contents, call this mass M2 and record its value in
the table.
9. Calculate the molar enthalpy of combustion of ethanol using your data above.
73
Table 2.9 Results obtained for determination of molar heat of combustion
of a fuel e.g. ethanol
Volume of water in the tin can V cm3
Initial temperature of water, T1 (˚C)
Final temperature of water, T2 (˚C)
Initial mass of lamp + its contents, M1 (g)
Final mass of lamp + its contents, M2 (g)
Mass of fuel used x (g)
Specific heat capacity of water 4.18 Jg-1K-1
• Suggest a reason why it is not necessary to burn all the fuel in the lamp.
• The amount of heat evolved when a fuel is burnt is theoretically higher
than the value obtained practically. Mention four errors in this experiment,
which could be responsible for the poor results.
Now, let us use the following sample results to show how we calculate the molar
heat of combustion of ethanol.
Volume of water used,V = 400 cm3
Initial temperature of water, T1 = 28.0˚C
Final temperature of water, T2 = 40.0˚C
Change in temperature, ∆T = (40 – 28) = 12.0˚C
Initial mass of lamp and its contents (M1) = 28.30 g
Final mass of lamp and its contents (M2) = 27.38 g
Mass of ethanol burnt = (M1 – M2) = (28.30 – 27 .38) = 0.92 g
Specific heat capacity of water = 4.18 Jg–1K–1
Calculate the molar heat of combustion of ethanol.
(C = 12.0; H = 1.0 ; O = 16.0)
Notice that it is not necessary to burn all the ethanol. The little we burn transfers
all the heat into the water. We assume none of the heat evolved is lost, for
example, by being carried away by wind, or some being absorbed by the beaker
or thermometer.
Heat evolved = mass of water × specific heat capacity × temperature change
i.e. ∆H = m c∆T
Substituting the values, we get = 400 × 4.18 ×12
1000
∆H = 20.064 kJ
We burnt only 0.92g of ethanol.
1 mole of ethanol, CH3CH2OH = 46 g
x mole of ethanol = 0.92 g
74
x = 0.92 g
46 g
= 0.02 mol.
This means 0.02 moles evolved 20.064 kJ

∴ 1 mol could evolve y kJ
y = 20.064 kJ
0.02 mol
= 1003.2 kJ mol–1
The molar heat of combustion of ethanol = –1003.2 kJ

Or
0.92 g of ethanol evolved 20.064 kJ
46 g of ethanol would evolve y kJ
∴ y = 20.064 kJ × 46 g
0.92 g
= –1003.2 kJ mol–1
Combustion of ethanol is exothermic, the heat of reaction, ∆H = –1003.2 kJ mol–1.
The equation for the combustion reaction is
Ethanol + oxygen –––– carbon(IV) oxide + water + heat
CH3CH2OH (l) + 3O2(g) –––– 2CO2(g) + 3H2O(l) ∆HC = –1003.2 kJ mol-1

Note that if we burn only a little of fuel, we do not call the amount of heat evolved
molar heat of combustion. We must find the mass of one mole, and then calculate
the molar heat of combustion. We can now define the molar enthalpy of combustion.
The molar enthalpy of combustion of a substance, ∆HC, is the enthalpy
change when one mole of a substance is completely burnt in excess oxygen.

1. The theoretical enthalpy change of combustion of ethanol is – 1368 kJ mol–1.
Explain briefly why the value obtained in experiment 2.7 is – 1003.2 kJ mol–1.
2. Draw the energy level diagram for combustion of ethanol.
3. Calculate the molar enthalpy of combustion of methanol, CH3OH from
the following data.
Volume of water = 500 cm3; temperature change = 7.0˚C,
Mass of CH3OH burnt = 0.87 g; density of water 1 g cm–3
Specific heat capacity 4.18 Jg–1 K–1.
75
Enthalpy of displacement
Experiment 2.8
To find the enthalpy change for displacement of copper from copper(II) sulphate
solution by zinc.
• balance
• beaker lagged with newspaper leaf or plastic cap
• thermometer (-100C to 1100C)
• glass rod or stirring rod
• about 0.8 g of zinc powder
• 0.2M copper(II) sulphate solution
Procedure
1. Wrap up the beaker with a newspaper leaf.
2. Measure out 50 cm3 of 0.2M copper(II) sulphate solution and transfer it into
the beaker. See Fig 2.20(a). Measure the temperature of this solution.
Stirring rod
Test tube
Thermometer
Lagged
beakers Zinc powder
0.2 M
CuSO4(aq)
(a) Measuring temperature (b) Adding zinc to

of CuSO4 solution CuSO4 solution
Fig. 2.20: Reaction of zinc with copper(II) sulphate solution.
3. Copy Table 2.10 and record the steady temperature of solution. This is the
initial temperature of the solution.
• What is the colour of the solution?
4. Pour all the 0.8 g of zinc powder provided into the copper(II) sulphate solution.
5. Stir vigorously with the glass rod. See Fig. 2.20(b) (take care not to break the
thermometer). Do this for about 5-7 minutes and record the highest steady
temperature. This is the final temperature of the solution.
• What happens to the colour of the solution?
• What do you observe at the bottom of the beaker?
76
Table 2.10
˚C K
Initial temperature of copper(II) sulphate solution (T1˚C)

Final temperature of copper(II) sulphate solution (T2˚C)
Change in temperature, ∆T (T2-T1)
Initial colour of solution before reaction takes place
Colour of solution after reaction is complete
Temperature rises during the reaction. The reaction is exothermic.
Copper(II) sulphate solution is blue in colour. This is because of the presence of
copper(II) ions, Cu2+, in the solution. When zinc start reacting with Cu2+ ions, the
blue colour fades slowly and finally the solution turns colourless.
A red-brown solid, which is copper, is deposited at the bottom of the beaker.
(Some zinc may be observed because excess zinc is required to ensure all Cu2+
ions in the solution are reduced by zinc atoms).
This is an exothermic reaction. The reaction that takes place is
Copper(II) sulphate (aq) + zinc(s) copper(s) + zinc sulphate(aq)
CuSO4 (aq) + Zn (s) Cu(s ) + ZnSO4 (aq)
Ionic equation
Copper(II) ions (aq) + zinc (s) copper (s) + zinc ions (aq)
2+
Cu (aq) + Zn(s) Cu(s) + Zn2+(aq)
In the above reaction, we notice that zinc displaces copper from copper(II) sulphate
solution. This is how the reaction takes place. As each zinc atom dissolves, it
gives two electrons. These electrons are taken up by each Cu2+ ion in the solution,
discharging them.
Zn(s) Zn2+(aq) + 2e- oxidation
- 2+ -
Cu (aq) + 2e Cu(s) reduction
Overall reaction: Cu2+(aq) + Zn (s) Cu(s) + Zn2+(aq) redox

As a result, copper is deposited at the bottom of the beaker. This is why this type
of reaction is called displacement reaction.

1. In the overall ionic reaction:
(i) Which is the oxidising agent?
(ii) Which is the reducing agent? Explain.
77
2. Suppose a student placed zinc sulphate solution in a beaker and added
copper powder, what observation would the student make? Explain.
3. Iron filings can be used in experiment 2.8 in place of zinc powder.
(i) Write the chemical equation for the reaction.
(ii) Write an ionic equation for the reaction.
If you placed copper in zinc sulphate solution, there would be no observable
reaction. This is because zinc metal is more reactive than copper, hence copper
cannot displace the zinc ions, in the solution.
Let us now use the specimen results in Table 2.11 from a similar experiment to
calculate the molar enthalpy of displacement of a reaction.

˚C K
Initial temperature of copper(II) sulphate solution T1 22.0 295.0
Final temperature of solution, T2 32.0 305.0

Change in temperature (T2 – T1), ∆T 10.0 10.0
Assume the density of solution is 1g/cm3

Mass of 50 cm3 of copper(II) sulphate solution = 50 cm3 ×1g cm–3
= 50 g
Enthalpy change (∆H) = mc ∆T
Substituting the values, ∆Hdis = 50 × 4.18Jg-1K-1 × 10 K
1000
= 2.09kJ
The concentration of aqueous CuSO4 is 0.2 M. But we measured 50 cm3 only.
We must calculate the moles of copper ions displaced.
1000 cm3 of CuSO4 contains 0.2 moles
∴ 50 cm3 of CuSO4 contains x moles.
x = 0.2 × 50 cm3
1000 cm3
= 0.01moles
This means that when 0.01 moles of Cu2+ ions are displaced from the solution by
zinc atoms, 2.09 kJ of heat energy is evolved.
We now calculate the molar enthalpy of displacement as follows:
∴ 0.01 mole evolves 2.09KJ
78
1 mole = 2.09 × 1
0.01 moles
= 209 kJ mol-1
Therefore, the molar enthalpy of displacement ∆Hdis = –209kJ mol-1
The complete chemical equation is written as:
CuSO4 (aq) + Zn(s) ––––– Cu(s) + ZnSO4 (aq) ∆H = –209 kJ mol-1
• Draw an energy level diagram for this reaction.
We can now define the molar enthalpy of displacement as follows:-
The molar enthalpy of displacement is the enthalpy change which occurs
when one mole of the substance is displaced from its solution.
Enthalpy of neutralisation
Experiment 2.9
To find the enthalpy of neutralisation of hydrochloric acid.
• 250 cm3 beaker wrapped with cotton wool or newspaper leaf
• thermometer (–10 to 110˚C)
• 50 cm3 measuring cylinder
• distilled water
Procedure
1. Using a measuring cylinder, measure 50 cm3 of 2M hydrochloric acid and
transfer into the wrapped beaker as shown in Fig. 2.21.
2. Note the temperature of the acid. Record it in Table 2.12 as T1.
Thermometer
Beaker wrapped with

paper (lagged)
2 M Hydrochloric acid
Fig. 2.21: Neutralisation of hydrochloric acid with sodium hydroxide

3. Rinse the measuring cylinder with distilled water.
4. Using the same measuring cylinder, measure 50.0 cm3 of 2M sodium hydroxide
solution.
5. Take the temperature of sodium hydroxide and record in the Table 2.12 as T2.
79
6. Find the average temperature of the acid, T1 and the alkali, T2 i.e.
T1 + T2 = T3 and record in Table 2.12
2
7. Pour sodium hydroxide solution,(NaOH) carefully into the hydrochloric
acid , (HCl) in the wrapped beaker.
8. Stir the mixture of the two solutions carefully for a while with the thermometer
(do not touch the sides of the beaker with the thermometer to avoid breakage).
9. Record the highest temperature reached, Ts, in Table 2.12.
10. Find temperature change by substracting Ts – T3.
• Is the reaction exothermic or endothermic?
• Write chemical and ionic equations for the reaction.
• Will the sign of ∆H for this reaction be +ve or –ve? Give a reason for your
answer.
Table 2.12: Results of temperatures obtained
˚C K
Temperature of the acid, T1
Temperature of the alkali, T2
Average temperature of the two solutions, (T1 + T2) = T3
2
Highest temperature of solution reached, TS
Temperature change, ( TS –T3 ) = ∆ T
Repeat the experiment using the following pairs:

(i) 2M nitric(V) acid and potassium hydroxide.
(ii) 2M hydrochloric acid and ammonium hydroxide.
(iii) 2M ethanoic acid and sodium hydroxide.
Write chemical and ionic equations for (i) and (ii).
The rise in temperature seen in this neutralisation reaction indicates that it is
an exothermic reaction. ∆H is therefore negative. It is possible to calculate
the enthalpy change, using the known volumes. Now, let us use the following
specimen experimental results to calculate the energy given out by a neutralisation
reaction.
80
˚C K
Temperature of hydrochloric acid, T1 22.5 295.5
Temperature of sodium hydroxide, T2 22.0 295.0
Average temperature of the two solutions, T3 22.25 295.25
Highest temperature reached, TS 35.5 308.5
Temperature change, ∆T (Ts – T3 ) 13.25 13.25
Assume the density of solution is, 1g cm-3

Total volume of hydrochloric acid + alkali = 100 cm3
The mass of solution = 1 g/cm–3 × 100 cm3 = 100 g
Enthalpy of neutralisation is given by = mc ∆T
= 100 g × 4.18Jg–1 × 13.25

1000
∴ The enthalpy of neutralisation = 5.538 ≈ 5.54 kJ
To get the molar enthalpy of neutralisation, we must first find out the number of
moles that reacted.
1000 cm3 of HCl contained 2 moles
∴ 50 cm3 of HCl contained x moles
x = 2 moles × 50 cm3
1000 cm3
= 0.1moles
0.1 moles of HCl give 5.54 kJ

∴ 1 mole of HCl gives 1 × 5.54
0.1
= –55.4 kJ/mol–1
Similarly, 50cm3 of 2M NaOH also contained 0.1moles.
This means 0.1 moles evolved 5.54 kJ
∴ 1mole would evolve y kJ
Cross multiply and solve for y
y = 5.54 kJ
0.1 moles
= –55.4 kJ/mol–1
81
The molar heat of neutralisation (∆Hn) is 55.4 kJ mol-1
The neutralisation reaction is:
Hydrochloric + sodium –––––– sodium + water + heat
acid hydroxide chloride
HCl (aq) + NaOH (aq) –––– NaCl (aq) + H2O (l) ∆ Hn = -55.4 kJ mol–1
Ionic equation:
H+ (aq) + OH-(aq) ––––– H2O (l) ∆Hn = – 55.4 kJ mol–1
Note that when we measure the temperature rise produced when a known volume
of an acid is neutralised by a known volume of an alkali, we can calculate the
enthalpy change for that neutralisation reaction then proceed and calculate the
molar enthalpy change of neutralisation. Experiments have shown that for strong
acids and strong alkali reactions, the value of the energy liberated is about 57 kJ
mol-1. This is because all strong acids and alkalis are completely dissociated in
aqueous solution.
Examples:
HCl (aq) –––– H+(aq) + Cl- (aq)
HNO3 (aq) –––– H+(aq ) + NO3- (aq)
NaOH (aq) –––– Na+(aq) + OH- (aq)
KOH (aq) –––– K+(aq) + OH- (aq)
For neutralisation reactions involving strong acids and strong bases, the enthalpy
change in the reactions is almost a constant value. See the examples below.
HCl (aq) + NaOH (aq) –––– NaCl (aq) + H2O (l) ∆Hnθ = –57.37kJmol-1
HNO3 (aq) +NaOH (aq) –––– NaNO3 (aq) + H2O (l) ∆Hnθ = –57.33kJmol-1
HCl (aq) + KOH (aq) –––– KCl (aq) + H2O (l) ∆Hnθ = –57.33kJmol-1
HCl(aq) + NaOH(aq)
∆H = –57.4 kJ mol–1
Energy in kJ/mol
NaCl(aq) + H2O(l)
Reaction path
Fig. 2.22: Energy level diagram for neutralisation reaction between

hydrochloric acid and sodium hydroxide
82
When a strong acid e.g. hydrochloric acid is neutralised by a weak base e.g.
aqueous ammonia (ammonium hydroxide), slightly less heat energy is produced.
The energy released is about 52.2kJ mol-1.
When both the acid and the alkali are weak, the neutralisation heat liberated is
even lower, for example, when weak ethanoic acid is neutralised by weak aqueous
ammonia (ammonium hydroxide), the energy released is 51.5kJ mol-1.
Ethanoic acid + ammonium –––– ammonium + water

hydroxide ethanoate
CH3COOH(aq) + NH4OH (aq) –––– CH3COONH4(aq) + H2O (l) ∆Hnθ = -51.5kJmol–1
The enthalpy change is so low because some energy, approximately + 5.5kJ, must
be used to ionise ethanoic acid and ammonium hydroxide. Consequently, less
energy is liberated. The energy level diagram is shown in Fig. 2.23.
CH3COO– (aq) + H+(aq) + NH4+ (aq) + OH– (aq)
∆H1 = +5.5 kJ mol–1

CH3OOH(aq) + NH4OH(aq)
Energy in kJ/mol–1
∆H = –57 kJ mol–1
∆Hn = –51.5 kJ mol–1
CH3COO– (aq) + NH4+ (aq) + H2O(l)
Reaction path
Fig. 2.23: Energy level diagram for the reaction of ethanoic acid and ammonium
hydroxide

1. Define the term enthalpy change of neutralisation.
2. Explain why the quantity of heat liberated when one mole of hydrochloric
acid, HCl, is neutralised by one mole of sodium hydroxide, is the
same quantity as when one mole of nitric acid, is used instead of
hydrochloric acid.
83
Note that energy content stored by the reactants in our above example is more than
that of the products. The difference in energy is given out as heat and therefore,
the temperature rises. In an endothermic reaction, the products have more energy
stored than that stored in the reactants.
Energy level diagrams

We have just learnt how to obtain enthalpy change (∆H) through experiments. We
have also seen examples of exothermic and endothermic reactions.
Let us now learn how energy transfers occur in reactions using energy level
diagrams.
As we had learnt earlier, an energy level diagram shows the energy stored in the
reactants compared to the energy stored in the products. Remember that reactants
are the substances we start with and products are the new substances made after
the reaction.
We have also seen that in some cases, energy is needed to get a reaction started.
This energy is used to break bonds so that new bonds can form as products are
formed. For example, we are familiar with cooking fuels such as charcoal (carbon),
kerosene, firewood and gas (butane). Can you imagine anybody placing a sufuria
with water on a cooker without lighting the fuel? Will he/she manage to cook?
What do you think lighting the fuel does? Study the energy level diagram for
burning charcoal in Fig. 2.24 below.
Charcoal
+
Activation energy
Oxygen
-------
REACTANTS
Carbon(IV) oxide
PRODUCT
Reaction path
Fig. 2.24: Energy level diagram for burning charcoal
The energy level diagram shows that we need certain amount of energy to get
the reaction started. This energy is called activation energy. Without activation
energy, reactions cannot proceed. This explains why we need to light the fuel
before we can cook. Lighting provides activation energy needed to initiate the
reaction between carbon and oxygen i.e.
84
C(s) + O2(g) ––––– CO2(g)
which provides heat used during cooking.
We can also draw an energy level diagram of an endothermic reaction, as shown
in Fig. 2.25 below. The diagram shows that dissolution of potassium nitrate is
an endothermic process and that activation energy is needed for the reaction to
begin.
Activation energy
KNO3(aq)
PRODUCTS
KNO3(s) + H2O(l)
------------------
REACTANTS
Reaction path
Fig. 2.25: Energy level diagram showing the activation energy for dissolution
of potassium nitrate
2.4 Hess’s Law of constant heat summation

A German scientist Henri Hess found out that, a set of reactants can be changed
to the same products by more than one step. The total enthalpy change is the same
regardless of the number of steps involved. This principle was later named the
Hess’s Law of constant heat summation which states that:
The enthalpy change of a reaction is the same, regardless of the reaction
happening in one step or many steps provided that initial reactants and
products are the same.
For example, enthalpies (heat) of

formation can be calculated from an
energy level diagram or an energy cycle
(thermochemical cycle) involving the
enthalpy (heat) of combustion of the
compound and that of the constituent
elements. This is necessary for example,
for the determination of the standard
enthalpy of formation of carbon(II)
oxide from burning of carbon in limited
Fig. 2.26: Henri Hess (1802 – 1850) supply of air. It is practically impossible
85
to measure the standard enthalpy change in this reaction since some carbon(IV)
oxide is always formed. However, Hess’s law offers a way out.
Let us use the following example to show how we calculate the standard
enthalpy of formation of carbon(II) oxide from given data, using:
(a) energy level diagram.
(b) energy cycle.
according to Hess’s Law
Example 1
Calculate the standard enthalpy of formation of carbon(II) oxide from carbon and
oxygen using the values in Table 2.14.
Table 2.14
Substance heat of combustion in kJ/mol-1
Carbon (graphite) –393.5
Carbon(II) oxide –283
Solution
There are two routes of forming CO2.
(a) Using the energy level diagram
Route 1.
This has one step i.e. by directly burning carbon in form of graphite in sufficient
air to form carbon(IV) oxide i.e.
Carbon + oxygen ––––– carbon(IV) oxide
C (s) + O2 (g) ––––– CO2 (g)
OR
Route 2.
This has two steps.
Step 1. First burn carbon in form of graphite in insufficient air to form an
intermediate product i.e. carbon(II) oxide, (CO).
(i) Carbon + oxygen ––––– carbon(II) oxide
(insufficient)
2C (gr) + O2(g) ––––– 2CO(g)
Step 2. The CO formed is then oxidised to carbon(IV) oxide, (CO2).
(ii) Carbon(II) oxide + oxygen ––––– carbon(IV) oxide
2CO(g) + O2(g) ––––– 2CO2(g)
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C(s) + O2(g)
REACTANTS
∆H2 = ∆Hfθ CO(g)
( )
(
∆H1 = ∆Hcθ C (gr) )
CO(g) + 1 O2(g)
2
INTERMEDIATE PRODUCT
∆H3 = ∆Hcθ [CO(g)]
CO2 (g)
PRODUCT
Route 1 Route 2
Reaction path
Fig. 2.27: Energy level diagram for the formation of carbon(IV) oxide
According to Hess’s law, since carbon(IV) oxide has been made in two ways, the
standard enthalpy (heat) of combustion of graphite, ∆HCθ (gr) obtained via route
1 is equal to the total energy obtained via route 2 i.e.
∆H1 = ∆ H2 + ∆H3
∆H2 = ∆H1 – ∆H3
OR
∆HCθ (gr) = ∆Hfθ (CO(g)) + HCθ (CO (g))

∆Hfθ CO(g) ( )= HCθ (gr) – HCθ [CO(g)]
Substituting the values

∆Hfθ (CO(g)) = -393.5-(-283.0)
= -393.5 + 283.0
= -110.5 kJ mol-1
The standard enthalpy of formation of carbon (II) oxide, ∆Hfθ (CO(g)) is –110.5
kJ mol-1
(b) Using energy (thermochemical) cycle
An energy (thermochemical) cycle is kind of an energy relation based on Hess’
Law, showing how you can form products directly from reactants (route 1, ∆H1)
or from reactants which first form intermediate product(s) and then from there,
further reaction forms the final product (route 2, ∆Hfθ and ∆H2) as shown in Fig.
2.28. It forms a kind of a triangular cycle.
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∆Hfθ (Route 2)
Reactants
intermediate product(s)
∆H1 ∆H2
(Route 1)
Final product
Fig. 2.28: Thermochemical (energy) cycle
When we use the energy cycle, the following 3 steps must be followed:
(a) First, write a balanced chemical equation for which the enthalpy (heat)
change is required. Include the correct state symbols in the equation
under normal conditions i.e. solid, liquid or gas.
(b) Using the standard enthalpies given in the problem, complete the triangular
energy cycle.
(c) Then apply Hess’s law to solve for the one unknown value. The sum of
energy in the two sides of route 2 is equal to that of route 1.
Note: In this “triangular” relation based on Hess’ Law, you will have the
‘measurements’ of the sides of the enthalpy changes given and will be unknown
as shown in the following energy cycle of preparation of CO2 from graphite.
∆Hfθ (Route 2)
C (s) + 1 O2(g) CO(g)
2
1
(Route 1) + 2 O2(g)
1
+ 2 O2(g)
∆H2 = -283.0kJmol-1
∆H1= -393.5kJmol-1
1 CO (g)
2
2
In our energy triangle, we have only one side unknown i.e. ∆Hfθ in route 2.
According to Hess’s law, ∆H1 = ∆ Hfθ + ∆H2
Making ∆Hf θ the subject of the formula
∆Hfθ = ∆H1θ - ∆H2
Substituting the values in the equation, ∆Hfθ = -393.5 – (–283.0)
= -393.5 + 283.0
= - 110.5 kJ mol-1
So, the standard heat of formation of CO is –110.5kJmol-1
Note: If we do not want to use the halves in the energy cycle, we multiply the
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equation by 2 as well as energy values and proceed with our calculations as
above.
∆Hfθ
2C(s) + O2 (g) –––––– 2CO(g)
+O2 +O2
∆H1 ∆H2
2CO2(g)
∆Hfθ = 2(-393.5) – 2 (-283)

= -787 – (-566)
= -221kJ
This is the energy released by formation of 2 moles of carbon(II) oxide.
∴ The energy released to form one mole
= –221kJ
2 mole
= –110.5kJ mol-1
Example 2
Calculate the standard enthalpy of formation, ∆Hfθ , of methane (CH4) from the
given standard enthalpies of combustion in kJ mol-1.
Carbon (graphite) = –393.5; hydrogen = –285.7; and methane = –890.4.
Solution
(a) Using an energy level diagram.
C(s) + 2H2(g) + O2(g)

∆H2 = ∆Hfθ
CH4(g) + O2(g)
∆H1 = ∆Hcθ of C(gr) + ∆Hc,H2(g)
∆H3 = ∆Hcθ
CO2(g) + 2H2O (l) CO2(g) + 2H2O(l)

Route 1 Route 2
Reaction path
Fig. 2.29: Energy level diagram for formation of methane
89
Route I
∆H1 represents the total standard enthalpies of combustion of carbon ( graphite)
and two moles of hydrogen.
Route 2
∆H2 represents the standard enthalpy of formation, (Hfθ), of methane (this is what
we are required to find).
∆H1 = ∆H2 + ∆H3
∆H2 = ∆H1 – ∆H3
∆H1 = – 393.5 + 2(-285.7) = –964.9
∆H3 = –890.4 kJ mol-1
Note: We multiply the ∆Hcθ of hydrogen by 2 because 2 moles of hydrogen are
used in the reaction.
Substitute the values obtained in the formula as follows:
∆H2 = ∆H1 – ∆H3
∆H2 = –964.9 + 890.4
= –74.5kJ mol-1
The standard enthalpy of formation , ∆Hfθ, of methane is - 74.5 kJ mol-1
(b)Using energy cycle.
∆Hfθ
C(s) + 2H2(g) –––––– CH4 (g)
+O2 +O2 +O2

Route I ∆H1 ∆H2 Route II
CO2(g) + 2H2O(g)
Route 1
∆H1 represents combustion of C (gr) and 2H2(g), ∆H = - 964.9kJ mol-1
Route 2
∆H2 represents combustion of CH4(g), ∆HCθ = - 890.4kJ mol-1
∆H1 = ∆Hfθ + ∆H2
∆Hfθ = ∆H1 – ∆H2
= - 964.9 – (- 890.4)
= - 964.9 + 890.4
= - 74.5kJmol-1
The standard enthalpy of formation of methane is –74.5kJ mol-1
90
Example 3
Calculate the molar enthalpy of combustion of ethanol, C 2H5OH from the
information below:
Equations enthalpy of formation in kJ mol-1
H2 (g) + O2(g) ––––– H2O (l) ∆H1 = –286
C(s) + O2 (g) ––––– CO2 (g) ∆H2 = –394
2C(s) +3H2(g) +O2 (g) ––––– C2H5OH (l) ∆H3 = –277
Solution
1. Write the equation for combustion of ethanol.
2. Ethanol is formed by combining chemically the elements that make it. (3rd
equation above).
3. The products formed by burning ethanol can be formed by burning elements
C and H (1st two equations) Route 1.
4. Using the above information, construct a triangular energy cycle and solve
for the unknown, ∆HC .
C2H5OH(l) + 3O2(g) ∆Hc 2CO2(g) + 3H2O(l)
(of ethanol) of
(∆H1 + ∆H2) on
+O2
sti ts)
∆H3 u
b n
1)
(Route 2) +O2 +O2(g) o m me
te
(C ele
ou
(Formation)
(R
2C(s) + 3H2(g)
Route 2 Route 1
∆H3 + ∆HC = (∆H1 + ∆H2)
∴ ∆HC = (∆H1 + ∆H2) – ∆H3
∆H1 = 2(-394) = -788kJmol-1
∆H2 = 3(-286) = - 858kJmol-1
(∆H1 + ∆H2) = 1646 kJmol–1
∆H3 = -277
∆HC = -1646- (-277)
= -1646 + 277
= -1369 kJ mol–1
The molar enthalpy of combustion of ethanol is – 1369kJ mol-1
Example 4
Calculate the enthalpy change of formation of calcium carbonate from calcium
oxide and carbon(IV) oxide i.e. CaO(s) + CO2 (g). Use the energies of formation
given below:
Ca(s) + O2 (g) –––––––––– CaO(s) ∆H = –635kJmol-1
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C(s) + O2 (g) –––––––––– CO2 (g) ∆H = –394kJmol-1
Ca(s) + C(s) + 3/2 O2 (g) ––––––––– CaCO3(s) ∆H = –1207kJmol-1
Solution
Note that Hess’s law offers a way out to solve a problem like the one above. If
we had two (or more) reactions that could be added together, then we can add
respective enthalpies of the reactions to get what we want. Let us solve the problem
by (a) adding enthalpies and (b) using energy cycle.
Note
1. We change the sign of ∆H every time we reverse an equation. e.g.
CaO(s) –––––––– Ca (s) + 21 O2 (g) ∆H = + 635 kJmol-1
2. If we want to get rid of a fraction in the equation, we would multiply the
equation by 2 as well as the value of ∆ H.
3. Cross the elements that appear on both sides of the equations and add up.
(a) adding up enthalpies
Ca(s) + 2 O2 (g) ∆H = + 635kJ mol-1
1
CaO(s) ––––––––
CO2 (g) ––––––––– C(s) + O2 (g) ∆H = + 394kJ mol-1
Ca(s) + C(s) + 3/2 O2 (g) –––––– CaCO3(s) ∆H = –1207kJ mol-1
CaO(s) + CO2 (g) ––––– CaCO3(s) ∆H = – 178kJ mol-1
(b) using energy cycle
∆Hfθ
CaO(s) + CO2 (g) ––––––– CaCO3(s)
+O2
∆H1 ∆H2
+O2
3
Ca(s) + C(s) + /2 O2(g)
∆H1 = [Ca (s) + O2(g)] + [C(s) + O2(g)]
= (-635) + (-394)
= - 1029kJ mol-1
∆ H2 = Ca (s) + C(s) + 3/2O2(g)
= -1207 kJ mol-1
But ∆H2 = ∆H1 + ∆Hfθ
∆Hf = ∆H2 – ∆H1
= -1207 – (-1029)
= - 1207 + 1029
= - 178kJ mol-1
Therefore, the enthalpy change of formation of calcium carbonate is –178kJ/mol-1
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1. Calculate the standard enthalpy of formation of ethyne, from the following
standard enthalpies of combustion.
Substance ∆HθC kJ mol-1
C2H2 (g) - 1300
C(s) - 394
H2 (g) - 286
2. Calculate the enthalpy change for the reaction.
C (graphite) + 2H2(g) + O2 (g) ––––– CH3COOH (l)
Given the following standard enthalpies of combustion in kJ mol-1.
C (graphite) = –394
H2 (g) = –286
CH3COOH (l) = –876
3. Diamond is used in jewellery. Two students would like to convert graphite to
diamond. Help them to calculate the enthalpy change of formation of solid carbon
(diamond) from solid carbon (graphite) i.e. the value x kJ mol-1 as shown below:
C(s, graphite) ––– C(s, diamond), ∆Hfθ = × kJ mol-1,
from the following information.
C(s, graphite) + O2 (g) ––––– CO2 (g) ∆HCθ = -394kJ mol-1
C (s, diamond) + O2 (g) ––––– CO2 (g) ∆HCθ = -396kJ mol-1
2.5 Relationship between heat of solution, hydration and lattice energy

We have learnt that when some substances dissolve in water, the process is either
endothermic or exothermic. In dissolving, ‘like dissolves like’ i.e. ionic substances
and other polar substances dissolve in water, which is polar, while non-polar
substances e.g. organic substances dissolve in organic solvents.
Now, let us see why some dissolving processes are endothermic, while others
are exothermic.
For a substance to dissolve, there is solute-solvent attractions as shown in
Fig. 2.30 between ionic solid e.g. NaCl and water.
Polar solvent
molecules
Ionic crystal lattice

Fig. 2.30: Polar water molecules dissolving ionic sodium chloride
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Note in Fig 2.30 the positive ends of polar water molecules are attracted to the
negative ions in the crystal, while the negative ends are attracted to the positive
ions. This means that bonds are being formed. During bond formation, energy
is released. This attraction is so great that the ions are detached from the crystal
lattice. This means that the ionic bonds in crystal lattice are broken. Breaking
these bonds absorbs energy i.e. ∆H is positive .The energy used to break the
lattice (crystal structure) is called lattice energy. This is equivalent to the energy
released when forming a crystalline stucture. Once the ions are free, they are
surrounded by water molecules. In Fig. 2.31 the attraction between the ions and
water molecules releases energy known as hydration energy.
Hδ+ Hδ+ O2δ–

2δ–
O Hδ+ Hδ+
Na+
Cl–
O2δ–
Hδ+ Hδ+ Hδ+
δ+
H
O2δ–
(a) Hydrated positive ions (b) Hydrated negative ions
Fig. 2.31: Hydration of positive, Na+ ions and negative, Cl– ions
Movement of hydrated ions in a solution is greatly reduced as they are surrounded
by water molecles. Hydrated ions diffuse much more slowly than expected.
Enthalpy of solution
The enthalpy (heat) of solution is the enthalpy change, which occurs when one
mole of a substance is dissolved in so much water that further dilution produces
no detectable change in temperature.
The energy relationships involved in the dissolving of an ionic solid, is the lattice
energy ∆Hlatt, i.e .the energy required to break up the crystal lattice and the energy
released when the ions are surrounded by water molecules i.e. hydration energy,
∆Hhyd. ∆Hsol = ∆Hhyd + ∆Hlatt. If the hydration energy is greater than the energy
required to separate the particles, the dissolving process is exothermic, ∆H –ve,
if it is smaller, the dissolving process will be endothermic, ∆H +ve. If we have
to supply so much energy to break up the crystal lattice and very little hydration
energy is released when ions are surrounded by water molecules, the substance
will not dissolve.
The energy relationships involved in dissolving an ionic solid is as shown in
Fig. 2.32 (a) below.
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M+(g) + X–(g) M+(g) + X–(g)
Lattice energy Hydration energy

Hydration Lattice energy
energy M+(aq) + X–(aq)
M+X–(s) Enthalpy of solution
M+X–(s)
Enthalpy of
M+(aq) + X–(aq)
solution
(a) Exothermic dissolving (b) Endothermic dissolving
Fig. 2.32: Energy level diagram relating to enthalpy of solution
Let us illustrate this by drawing the energy level diagrams for the dissolving of
anhydrous copper(II) sulphate salt and hydrated copper(II) sulphate salt, as shown
in Fig. 2.32 and sodium chloride in Fig. 2.33.
Dissolving anhydrous copper(II) sulphate, CuSO4, is an exothermic process
i.e. ∆H is negative, while dissolving hydrated copper(II) sulphate, CuSO4.•5H2O,
is an endothermic process i.e. ∆H is positive.
CuSO4(s) + water
∆H = – ve
Energy in kJ
Cu2+ (aq) + SO42– (aq)

∆H = +ve
CuSO4 • 5H2O (s) + water
Reaction path
Fig.2.33: Energy level diagram for the dissolution of hydrated copper(II) sulphate
in water
The energy level diagram represents the following equation.

CuSO4(s) + water ––––– Cu2+(aq) + SO42- (aq) ∆H = -ve
CuSO4. 5H2O(s) + water ––––– Cu2+(aq) + SO42- (aq) ∆H = +ve
Let us also consider the energy level diagram for dissolution of sodium chloride
as shown below.
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Na+(g) + Cl–(g) + H2O(l)
∆Hlatt = +776 kJ mol–1
Energy in kJ
∆Hhyd = –771 kJ mol–1
Na+ (aq) + Cl– (aq)

∆Hsoln
NaCl(s) + H2O(l)
Reaction path
Fig. 2.34: Energy level diagram for dissolving sodium chloride in water
When sodium chloride is formed from its gaseous ions, (sodium ions and chloride
ions), the reaction is exothermic i.e. ∆H has a negative value. But in Fig. 2.34 the
lattice energy has a positive sign because energy is supplied to break the crystal
lattice.The lattice energy, (∆Hlatt) hydration energy, ∆Hhyd and the overall enthalpy
change of solution ∆Hsoln ,are related as shown in the following equation.
∆Hsoln = – ∆Hlatt + ∆Hhyd
We can therefore use the above formula to calculate the unknown when two of the
values are given. For example, use the values in Fig 2.34 and the equation above
to calculate the enthalpy change of sodium chloride solution. Is the dissolving
process of sodium chloride in water endothermic or exothermic? Explain.
1. Explain briefly how water dissolves sodium chloride.
2. What do you understand by the following terms.
(i) heat of solution
(ii) hydration energy
(iii) lattice energy
2.6 Energy contents of common fuels

The main source of energy is the sun. It can be generalized that, the energy in
most substances is obtained from sunlight. When the heat and light energy from
the sun fall on the earth, it can be converted to other forms of energy for our daily
use. We also get energy through chemical reactions.
Whenever chemical reactions take place, we get a transfer of energy. The
energy ends up usually as heat or sometimes light and sound energy. For example,
fireworks produce heat, light and sound energy.
Fuels
A substance that undergoes combustion readily and gives out heat energy is known
as a fuel. A fuel can be in form of a solid, a liquid or a gas.
96
(a) Solid fuel
• Charcoal
• Wood
• Coal
• Glucose (the fuel for human life)
(b) Liquid fuel
• petrol
• kerosene
• diesel
• fuel oil
• ethanol
• methylated spirit (ethanol mixed with methanol in spirit lamps and stoves).
(c) Gas fuel
• natural gas e.g. methane
• liquid petroleum gas (LPG) e.g propane, butane
When we burn a fuel, the reaction is called combustion. Combustion of a substance
requires oxygen. In actual fact, it is oxidation. During the process of combustion,
energy is released. For example,
C2H5OH (l) + 3O2(g) –––––– 2CO2(g) + 3H2O(g) ∆H = -1369 kJ mol-1
Combustion in which a flame is produced is described as burning.
To make a fire, we need 3 things.
• Fuel
• Heat
• Oxygen
Hea
l
Fue
Oxygen
Fig. 2.35: Fire triangle
Note that if we remove one of the above, the fire goes out.
• When you turn off the Bunsen burner which one of the above do you remove?
97
Incomplete combustion
Inside a car engine, there is very little amount of oxygen. Therefore, when petrol
(a hydrocarbon), burns, some carbon(II) oxide, a poisonous gas is produced.
Sometimes, fuels burn with a smoky flame. e.g. in diesel engines, kerosene lamps
and gas. This shows that incomplete combustion takes place and carbon itself is
given off as soot.
Fuels contain stored chemical energy. When they burn in air, they release the
stored chemical energy as heat. As mentioned earlier, the unit for measuring energy
is the joule (J). This, as we have seen, can be converted to kilojoules (kJ). We can
calculate the amount of energy produced after burning a given mass of fuel.
Example 1
The amount of energy produced per gram of fuel is given in the units of kJ. This
is termed as the energy content of that particular fuel. For example, 1 mole of
ethanol releases –1369 kJ of heat energy i.e this is the energy produced when 46
g of ethanol is burnt.
If we divide the amount of energy by 46g, we get the amount of energy given
by a unit mass of ethanol.
-1369 kJ = –29.7kJ g-1
46g
The energy content of ethanol, is therefore –29.7 kJg–1. In a similar way, we can
calculate the energy released by a unit volume if the fuel is a liquid which is also
called its heating value. Table 2.15 shows heating values for some fuels.
Table 2.15 Energy content (heating value) of common fuels
Fuels Heating value kJ g-1
Solid fuel
charcoal 33
carbon (gr) 33
coal 29
Liquid fuel
ethanol 30
kerosene 48
Gaseous fuel
methane 56
propane 50
butane 46
Choice of fuel
As we have seen in Table 2.15 it is important to know how much energy is produced
when a fuel burns. This can help us to decide the best fuel to use for a particular
98
purpose. The heating value is not the only factor considered when choosing an
appropriate fuel for a particular purpose. Other factors include the following:
1. Availability: Geographical convenience and production levels.
2. Cost: extraction, transportation, market price.
3. Storage: health and safety issues e.g. if we compare coal and natural gas,
CH4 and butane, C4H10.. Coal is very safe while natural gas is more dangerous
because it can catch fire and explode easily.
4. Pollution of environment and toxicity.
5. Ease of use.
Precautions necessary when using fuels
Use of wood as a fuel should be discouraged because of degradation of our forests
leading to desertification. Some fuels such as liquid petroleum gas ( LPG) should
be handled with a lot of care, especially when we use the fuel for cooking. Leakage
of the gas can lead to fire accidents. Ensure the cooker knobs are turned off and that
the cylinder is not leaking. Other fuels pollute the environment as discussed below.
2.7 Pollution of the environment by common fuels
Pollution is one of the emerging issues that should be of concern to all of us. We
all need pollution free environment.
We have learnt previously that there are various forms of air pollutants. These
include solid as well as gaseous particles.
Charcoal (carbon)
When carbon burns in insufficient air, carbon(II) oxide, which is a very poisonous
gas, is produced. Carbon(II) oxide reacts with haemoglobin and stops it from
carrying oxygen to the brain and other parts of the body. Our bodies can cope
with small amounts of carbon(II) oxide but large amounts can kill.
When carbon is burnt in plenty of air, carbon(IV) oxide is formed. A lot of
carbon(IV) oxide in the air is known to cause global warming. When it dissolves
in rain water, it causes acid rain. Acid rain has burning effects hence is harmful
to both plants and animals. Acid rains also corrode corrugated iron sheets.
Fossil fuels
Crude oil is formed from organic material of the remains of plant and animal
organisms that lived millions of years ago. They decay without oxygen under the
action of heat and pressure to form crude oil over millions of years.
Crude oil is a fossil fuel because it is formed from once living organisms and
the sun which as mentioned earlier, is the original source of energy. Crude oil is
non- renewable form of energy which will run out soon.
The burning of oil and other fossil fuels contribute to environmental pollution.
When fossil fuels are burnt, they produce carbon(IV) oxide.
This gas contributes to the ‘Greenhouse effect’, thus results to global warming.
This happens because carbon(IV) oxide re-radiates sunlight energy from the earth’s
99
surface. The effects are predicted to be, for example, raising sea levels as polar
ice would melt causing flooding in low lying land regions. It also leads to more
frequent unpredictable weather patterns in some regions of the world.
• Fossil fuel contains the element sulphur or compounds of sulphur. When the
fuel is burnt especially in car engines, the sulphur is oxidised to sulphur(IV)
oxide. The gas enters the environment via car exhaust pipes. This is an acidic
gas and dissolves in rain water and comes down as acid rain, polluting the
environment by lowering the pH of the soil and water in ponds, rivers,
lakes and seas. This damages plant and animal life. Acid rain also damages
buildings and metal structures. Limestone (calcium carbonate) buildings are
mostly badly affected.
• Other pollutants that are also added to the environment via exhausts of
vehicles are
– Nitrogen oxides (e.g. NO2), which is acidic and contribute further to acid
rain.
– Carbon(II) oxide, which is toxic.
– Unburned hydrocarbons, CxHy, that can be carcinogenic.
However, the catalytic converters which are fitted to car exhaust systems
have significally reduced these unwanted emissions i.e. CO, NO2 and CxHy
(hydrocarbons) by converting them to less harmful substances through oxidation
or reduction processes. For example
• CO is oxidised to CO2
• CxHy(hydrocarbon) are, oxidised to CO2 and H2O
• NO, NO2, gases are reduced to N2.
Catalyst supported by
ceramic or wire-mesh
CO
CxHy
NOx
H2O
CO2
CxHy = hydrocarbons N2
NOx = oxides of nitrogen
Fig. 2.36: Catalytic converter
The catalytic converters contain a catalyst, which is an alloy of platinum and

rhodium. It catalyses the reactions mentioned above thereby helping to reduce
pollution.
There are other indirect pollution problems, which are associated with burning
fossil fuels. For example, gasoline (petrol), which is rich in straight chain alkanes
such as heptane, ignite easily and irregularly explode in the engine cylinders.
100
This causes “knocking” in the engine. However, there are two ways of improving
engine performance when using gasoline:
• Using gasoline rich in branched-chain alkanes. This makes the gasoline to
burn smoothly.
• Adding anti-knock lead compound, called tetra-ethyl lead(IV), Pb(CH3CH2)4.
To prevent lead accumulating in the engine, 1,2-dibromoethane is also added
to the gasoline. However, this produces lead bromide into the environment.
This lead compound can be inhaled thereby causing damage to the brain and
nervous system. This is the reason why many countries, including Kenya,
are now phasing out the use of leaded petrol and replacing it with unleaded
petrol. Unleaded fuel does not add lead to our environment.

1. What is a fuel?
2. Give examples of fuels found in the following states:-
(i) solid
(ii) liquid
(iii) gas
3. What factors should be considered when choosing a fuel?
4. How do fossil fuels pollute the environment?
5. How do catalytic converters reduce pollution from a car exhaust pipe?
Project
Comparison of heating values of petrol products.
Summary
• Chemical energy is stored in bonds.
• The potential energy stored in molecule bonds is known as ‘heat content’ or
enthalpy, denoted by H.
• Enthalpy (heat) change is symbolised by ∆H.
• Exothermic reactions give out heat. Temperature rises. Using ∆H notation, a
reaction is given a –ve value.
• Endothermic reactions take in heat. Temperature falls. Using ∆H notation, a
reaction is given a +ve value.
• Chemical bonds must be broken first, during a reaction.
• Breaking bonds is an endothermic process, and energy is absorbed.
• Making bonds is an exothermic process and energy is released.
• The energy barrier required to get a reaction started is called activation energy.
It is needed because bonds must first be broken before new bonds can be
formed.
• The standard conditions for enthalpy change are a temperature of 25˚C
(298K) and 1 atmosphere pressure. The standard conditions are indicated by
a superscript symbol, θ.
101
• The standard enthalpy change of formation, ∆Hfθ, is heat released or absorbed when
1 mole of a substance is formed from its elements under standard conditions.
• The standard enthalpy change of combustion of a substance, ∆Hcθ is the
enthalpy change which occurs when 1 mole of the substance is completely
burnt in oxygen.
• The heat change during combustion of a certain amount of fuel e.g. ethanol
can be gained by water and is = mass of water × specific heat capacity ×
temperature change.i.e. ∆H = mc∆T.
• According to Hess’s law, the enthalpy change of a reaction is the same,
regardless of the reaction taking place in one step or many steps.
• Three things are needed to keep fire burning. These are fuel, heat and oxygen.
If one is removed, the fire goes off.
• The reaction of a fuel with oxygen is called combustion. Respiration is a slow
combustion process.
• When a hydrocarbon burns in a plentiful supply of air, it forms carbon(IV)
oxide and water. But, in a limited supply of air, poisonous carbon(II) oxide is
formed.
Revision Exercise 2
1. Petrol burns in a car engine.
(a) Name the poisonous gas produced.
(b) State briefly how this toxic gas is formed and explain how it poisons.
2. A student from Lake Secondary School wanted to determine the enthalpy
change of combustion when a hydrocarbon with formula C6H14 was burnt.
The following are the results of the experiment done.
Mass of water = 100 g
Initial temperature = 17.0˚C
Final temperature = 57.0˚C
Mass of the hydrocarbon burned = 0.43 g
Specific heat capacity = 4.18 kJ kg–1 K–1
(a) (i) Name the hydrocarbon used.
(ii) Write a balanced equation for combustion of the hydrocarbon.
(b) (i) Calculate the heat given out in kJ when 0.43 g of the carbon burn in air.
(ii) What is the mass of 1 mole of the hydrocarbon?
(c) Calculate the number of moles of the compound that were burnt.
(d) Calculate the amount of heat in kJ that would be given out if one mole
of the hydrocarbon were burnt.
(e) The theoretical value of the heat released when one mole of the
hydrocarbon is burnt is 4194.7 kJ mol–1. Give three reasons why the
value obtained from this experiment is less than the theoretical value.
102
3. (a) Explain the meaning of the following symbols.
(i) ∆Hfθ
(ii) ∆Hcθ
(b) (i) State Hess’s law
(ii) Write an equation for complete combustion of ethyne.
(iii) Draw an energy cycle linking the ethyne with its enthalpy change
of combustion and enthalpy change of combustion of its elements
in their standard state.
(iv) Using ∆H1, ∆H2, ∆H3 and ∆H5 show how you can calculate the
standard enthalpy of formation of ethyne.
4. (a) Explain what is meant by the terms
(i) ionisation energy.
(ii) atomisation energy.
(iii) electron affinity.
(iv) lattice energy.
(b) Study the following figure and match letters A, B,C,D, E with parts (i)
(ii) (iii) and (iv) named in 4 (a) above.
Na+(g) + Cl(g)
C ∆H3 = +121 kJ D ∆H = –364 kJ
4
Na+(s) + e– + 12 Cl2(g) Na+(g) + Cl–(g)

∆H2 = +500 kJ
B
Na(g) +1 Cl2(g)
2
∆H1 = +108 kJ
A
Na(s) + 1 Cl2(g)
2
∆Hf (Na , Cl–) = –411 kJ
+ E
Na+, Cl(s)
Reaction path
5. Dissolving concentrated sulphuric(IV) acid is an exothermic process as shown

in the following equation.
H2SO4(l) + aq ––––– H2SO4(aq) ∆H = – 7l kJmol–1
Draw an energy level diagram for dissolution of concentrated sulphuric acid.
6. Calculate the overall energy released during hydrogenation of ethyne to ethene.
Use the bond energy given below.
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Ethyne + hydrogen ––––– ethene
H H
H –– C C –– H(g) + H–– H(g) ––––– C C
H H
Bond Energy (kJmol–1)

H –– H 435
C –– H 413
C C 835
C C 611
7. (a) What is meant by the following terms?
(i) enthalpy (heat) of reaction.
(ii) enthalpy of combustion.
(iii) enthalpy of formation.
(b) Use the data given below to calculate the enthalpy of formation of propane.
C(gr) + O2(g) –––––– CO2(g) ∆Hc = –393.5 kJmol–1
H2(g) + 1/2O2(g) –––– H2O(l) ∆Hc = –285.9 kjmol–1
C3H8(g) + 5O2(g) –––– 3CO2(g) + 4H2O(l) ∆Hc = –2220.0 kJmol–1
8. When we dissolve a salt, the process may be endothermic or exothermic.
What do you understand by the following terms associated with dissolving?
(i) lattice energy.
(ii) hydration energy.
(iii) heat of solution.
9. Calculate the enthalpy of formation of propan-1-ol, from the following
enthalpies of combustion in kJ/mol C3H7OH,–2010; C(s),–394; H2(g) –286.
10. Nitrogen trichloride, NCl3, is unstable yellow oil that explodes at 95˚C with
the release of N2 and Cl2, and 230 kJ mol–1 of heat.
(a) Write a balanced equation for the reaction including ∆H.
(b) Calculate the amount of heat released by decomposition of 10.0 g of NCl3
at 95˚C.
11. Calculate the standard enthalpy change for the reaction
O2(g) + 4NO2(g) + 2H2O(l) –––– 4HNO3(aq)
from the following standard enthalpies of formation.
kJ/mol–1
Water –286
104
Nitrogen(IV) oxide –33
Nitric(V) acid –173
12. In an experiment, when 50 cm3 2M hydrochloric acid was neutralised with
50 cm3 2M sodium hydroxide, a temperature rise of 13.6˚C was obtained.
(a) Calculate the molar enthalpy of neutralisation.
(b) If similar experiment was repeated with 2M ethanoic acids instead of
hydrochloric acid would the energy released be less or more? Explain
your answer.
(c) Suppose the same experiment was repeated with 2M ethanoic and 2M
aqueous ammonia, how would the value obtained in this case compare
with that in (a) and (b)? Explain.
13. A student reacted diatomic substances as shown in the following equation
A2(g) + B2(g) ––––– 2AB(g)
(a) (i) Which bonds are broken?
(ii) Which bonds are formed?
(iii) Will the reaction in (a) be endothermic or exothermic? Explain.
(b) Draw an energy level diagram for the reaction.
Use the bond energies given below
A – A 414 kJ/mol
A – B 431 kJ/mol
B – B 272 kJ/mol
105
Unit 3: Reaction rates and
reversible reactions
3.1 Rates of reaction
Rate of reaction is a measure of how fast or slow a reaction takes place. To be
able to know how fast a reaction is, we measure the rate at which a reactant is
consumed or a product is formed at a given time.
Change in amount of substance
Reaction rate =
Time taken
Therefore we can define the rate of reaction as the rate of change of an amount
or concentration of a particular reactant or product per unit time.
Different reactions have different reaction rates. Some are very fast, some fast
and others slow or very slow. For example, burning of magnesium is very fast,
burning of charcoal is slow and the rusting of iron is so slow that you hardly see
any change when you look at it!
To understand better the definition of reaction rate, let us consider the theories
that explain why a reaction is either fast or slow.
3.2 Collision theory and activation energy

All substances are made up of particles (Kinetic Theory). Chemical reactions are
possible due to collisions of these particles. For a chemical reaction to take place,
the particles must collide. This is what is referred to as the collision theory.
The following points are true about collision theory.
• Reactions take place due to collisions of reacting particles. These particles
include atoms, ions or molecules.
• Not all collisions between particles may be fruitful. By “fruitful”, we mean that
a collision produces products. The collisions which produce a chemical reaction
are called fruitful collisions. The rate at which particles collide is called
collision frequency. The greater the fruitful collision frequency, the faster
the reaction.
• Colliding particles need minimum amount of energy before they can bring
about a chemical reaction. The minimum energy required for this is called
activation energy.
The rate of reaction is actually the number of atoms, ions or molecules that react
per unit time to form products. Increasing the rate of reaction means increasing
the number of fruitful collisions between particles.
Reactions involving solids take place at the surface of the solid because it is only
here that collisions with particles of other reactants can take place.
In a solid lump, most particles are locked up inside. In order to react, these
particles must have fruitful collisions with the reacting reagent.
106
If the reacting reagent is a liquid or a gas, their particles collide with the particles
of the solid as shown in Fig. 3.1 below.
Gas or liquid particles
Solid particles
Fig. 3.1 Collision between particles i.e. solid and gases/liquids

In gases or liquids, the particles are constantly in random motion. During the reaction,
the particles collide. And if they collide hard enough, a reaction takes place effectively.
Lid
Different gas
Different liquid particles
particles
They collide
They collide during reaction
during reaction
(a) (b)
Fig. 3.2 Collision between particles of liquid or gas
Note: There will be no reaction between solid sodium chloride and solid lead(II)
nitrate when they are mixed together. Explain why.
Reactions do not take place between solid particles. This is because the average
distance of particles from one another is too great. They cannot meet to collide
effectively or fruitfully. However, water solution acts as a medium in which the
reaction takes place. When substances are dissolved in water, their particles have
an opportunity to move freely; a chance they do not have in solid form. Under
these circumstances, the particles of the reactants meet, collide and probably react.
1. Define rate of reaction.
2. Explain why solid lead nitrate cannot react with solid potassium
iodide but when both of them are in solution form, they react.
3. Explain why particles sometimes collide and products are not formed.
Activation energy
We already know that chemical reactions involve breaking of chemical bonds
in the reactants and formation of the bonds in products. These processes require
energy. The reacting particles may have some kinetic energy which might not be
107
enough for the particles to have fruitful collisions. The colliding particles must
have sufficient energy for bond breaking to occur before a reaction starts. That
minimum energy that the colliding particles must have in order to react is referred
to as the activation energy.
An example of a reaction where activation energy is involved is the burning of
hydrogen. Unless the gas is ignited in oxygen, the two gases cannot combine to
form water. Ignition provides the initial energy required for the elements to react.
This explains why a mixture of hydrogen and oxygen does not ignite at room
temperature.
Before hydrogen and oxygen can react, they have to be in form of atoms.
2H – H + O – O ––– 4H + 2O ––– 2H2O
Intermediate state Products
Bond of reactants
These bonds must be broken first
To break the bonds, energy is required. This initial energy supplied from some
external source is the activation energy of the reactants. In other words, activation
energy is the minimum amount of energy required to enable chemical bonds to
break and new ones formed in the rearrangement of atoms, ions and electrons as
the reaction proceeds. This has been illustrated in the Fig. 3.3 below.
Oxygen Intermediate state
molecule
Hydrogen
Increasing energy
Activation
molecule Oxygen atom
energy
Water molecule
Hydrogen atom
2H2(g) + O2(g)
2H2O(l)
Reaction progress
Fig. 3.3: Activation energy for formation of water
Thus a mixture of hydrogen and oxygen gases at room temperature remains inert
until the necessary activation energy is introduced by means of a flame or an
electric spark. It may also be supplied in certain reactions by the application of
heat directly to the reactants or sunlight.
The smaller the activation energy required for a reaction, the faster the rate of
reaction. Reactions can only start when the reactants energy is equal to the
activation energy required to start the reaction.
Collision theory and activation energy explain why even exothermic reactions
do not occur at room temperature. If enough activation energy is not provided,
108
particles will bounce off each other without reacting because bonds in them have
not been broken. Collisions must be energetic enough to surmount the activation
energy barrier. We can compare this energy barrier with cross bar in a high jump
or pole vault. One must have enough energy to go over the cross bar.
An exothermic reaction is self-sustaining when it has started. This is because
energy evolved makes more reactants to have enough activation energy. During this
type of reaction, more energy is produced from the formation of new bonds than the
energy needed to break existing bonds and therefore, there is a surplus of energy.
For an endothermic reaction, energy in form of heat, light, etc., has to be
supplied continuously to sustain the reaction. This is because some energy is
absorbed, making it difficult for more reactants to have activation energy.
During this reaction, more energy is required to break existing bonds than
is liberated when new bonds are formed. This deficiency in energy has to be
made up from an external source. Figures 3.4 and 3.5 below are reaction paths
for exothermic and endothermic reactions respectively.
Activation Activation
PRODUCTS
energy ∆E energy
∆E
Energy
REACTANTS
REACTANTS
PRODUCTS
Reaction progress
Reaction progress
Fig. 3.4: Reaction path of an Fig. 3.5: Reaction path of an
exothermic reaction endothermic reaction
1. Explain the term activation energy.
2. Explain why
(i) one has to strike a match stick for it to ignite.
(ii) when the match stick starts burning, the process is self-sustaining.
3. State why high activation energy would slow the rate of a reaction.
3.3 Methods used to measure rates of reactions

The method chosen in the laboratory to measure the rate of a reaction must make
use of a change that is taking place in a reasonable amount of time. The interval
chosen should not be too long or too short depending on the rate of change. i.e
should not be too slow or too fast. It should give an observable change during the
reaction. The change should be measurable either in terms of
(i) volume, in case a gas is produced.
(ii) change in mass of reactants or products.
109
(iii) time taken for a given mass to react and disappear.
(iv) time taken for a certain amount of precipitate to form.
3.4 Factors affecting rates of reactions

There are several factors which determine the rate of a chemical reaction. These
are
1. Concentration of reactants (for aqueous reactants)
2. Pressure (for gaseous reactants)
3. Temperature of reactants
4. Surface area (if the reactants are solids)
5. Light (type and intensity)
6. Catalysts
Any of these factors or a combination of them may affect the rate of a chemical
reaction. The effect on rate of reaction by any one factor can be determined in the
laboratory if the other factors are maintained constant. Let us now look at how
each of the factors affect the rate of chemical reactions.
Concentration
Experiment 3.1
To investigate the effect of concentration on the rate of reaction.
• 250 cm3 conical flasks/100 cm3 beaker
• Filter papers or white papers
• stirring rods
• stopwatch/ clock
• sodium thiosulphate
• black ink
Procedure
1. Place four conical flasks on a bench.
2. Put 200 cm3 of distilled water into each of the 250 cm3 conical flasks. Label
the flasks as A, B, C and D.
3. Put 0.5 g, 1.0 g, 1.5 g and 2.0 g of sodium thiosulphate in flask A, B, C and D
in that order. Stir to dissolve.
4. Place flask A on a piece of filter paper or any white paper with a black ink
cross (X) on it. Add 5 cm3 of 2M hydrochloric acid to beaker A. Start the stop
watch and swirl the content with the beaker placed on the paper. Using the
stopwatch, note and record the time it takes for the cross to be obscurred (when
you cannot see it anymore). See Fig. 3.6.
5. Repeat the same procedure with beaker B, C and D. Record the time taken in
each case for the cross to disappear from your sight in a table similar to Table 3.1.
110
eye eye
Start Mid-way End
Fig. 3.6: Set-up for determining rate of reaction
6. Plot a graph of concentration of sodium thiosulphate used against time(s) taken

for the cross to disappear.
Table 3.1: Effect of concentrations on rate of reaction
Amount of sodium Concentration Time taken (s) for the

thiosulphate used (g) mol dm–3 cross to disappear
0.5 0.0185
1.0 0.0370
1.5 0.0555
2.0 0.0740
Note: To ensure that consistent results are obtained:

• same cross should be used in each experiment.
• identical flasks should be used in all experiments.
• cross should be viewed from the same position.
• use clean flasks.
• the same person should observe.
• same amount of swirling or stirring should be done for each amount of
sodium thiosulphate.
• What is the name of the yellow precipitate?

• What does using more sodium thiosulphate mean?
• Write the chemical equation of the reaction.
• What do you conclude from the graph?
A typical graph as shown in Fig. 3.7 is obtained.
111
thiosulphate used in mol dm–3
Concentration of sodium
Time taken (s)
Fig. 3.7: Graph of concentration of sodium thiosulphate used against time for
the cross to disappear
When sodium thiosulphate and dilute hydrochloric acid are mixed, a yellow
precipitate of sulphur is formed.
Na2S2O3(aq) + 2HCl(aq) –––– 2NaCl(aq) + H2O(l) + SO2(g) + S(s)
yellow precipitate
The more sodium thiosulphate is dissolved in a given amount of water, the higher
the concentration of this solute in the solution. From the graph, the higher the
concentration of sodium thiosulphate solution, the less the time taken for the black
ink cross to disappear. That is, the higher the concentration, the higher the rate of
reaction. If a graph of mass of sodium thiosulphate used against the reciprocal of
time i.e. 1 is drawn, a straight line graph as shown in Fig. 3.8 below is obtained.
t
thiosulphate used
Mass of sodium
1 (s–1)
t
Fig. 3.8: Graph of mass of sodium thiosulpate used against t (s–1)
1
112
From the collission theory, increasing the concentration of reactants increases the
frequency of collision between reacting particles. The greater the number of collisions,
the higher the rate of reaction. From the graph, an increase in mass will imply an
increase in concentration of particles since in this case the solid dissolves. Hence
rate of reaction is increased. The frequency of collisions between reacting particles
therefore will determine the rate of reaction.
Self assessement exercise 3.3
1. State three factors that affect the rates of reaction.
2. How does concentration of reactants affect the rate of a reaction?
3. How does concentrations in Fig. 3.7 change with time?
Temperature
Experiment 3.2
To investigate the effect of temperature on the rate of reaction
• 250 cm3 conical flask
• stop watch or clock
• magnesium ribbon
• Emery paper or a file
• a rubber bung with one hole
• delivery tubes
• graduated syringe
• thermometer (0 – 100˚C)
• 0.5 M hydrochloric acid.
Procedure
1. Clean about 8 cm of magnesium ribbon with an emery paper or a sandpaper
and coil it.
2. Place 40–50 cm3 of 0.5 M hydrochloric acid into a conical flask.
3. Arrange the apparatus as in Fig. 3.8 below.
Syringe
Plunger
Bung Hydrogen gas
0.5M
hydrochloric acid
Magnessiun ribbon
Fig. 3.8: Apparatus to investigate effect of temperature on reaction rate

4. Before the reaction begins, place the bung tightly in the neck of the flask and
113
measure the volume of air displaced on the graduated syringe. Remove the
bung, place the plunger at zero on the scale.
5. Measure and record the temperature of the acid.
6. Place the magnesium coil in the flask and insert the bung as fast as possible.
• Start the stop watch or clock, at the same time.
• Record the volume of hydrogen liberated after every 30 seconds until the
reaction is over.
How will you know when the reaction is over?
7. Draw and fill Table 3.2 in your notebook.
Table 3.2: Effect of temperature on reaction rate
Time taken(s) 30 60 90 120 150 180 210
Volume of hydrogen
(cm3) produced
8. Repeat the experiment using same volume and molarity of acid heated to 30,
40, 50 and 60˚C. For every experiment, copy Table 3.2 in your notebook and
fill it.
9. Plot a graph of volume of hydrogen produced against time in each experiment
on the same axes. Compare your curves with Fig. 3.9.
C
50˚
˚C
e
ur
hydrogen produced
˚C
40
t
era
30
Volume (cm3) of
p
tem
om
Ro
Time (s)
Fig. 3.9: A graph of volume of hydrogen produced against time
• What do you conclude about the relationship between volume of
hydrogen collected per second and the temperature of the acid?
• How does the volume of hydrogen change with time?
• What is your conclusion on effect of temperature on rate of reaction?
Note: the reaction is over when there is no more effervescence.
When the temperature of the acid is increased, a higher volume of hydrogen is
produced per second. The volume of hydrogen produced per unit time is a measure
114
of the rate of reaction in this experiment. Therefore, the rate of reaction increases
because the velocity of all the reacting particles increase as the temperature increases.
Increase in velocity increases the frequency of collisions of reacting particles. This
is because of the increase in kinetic energy of the colliding particles. Increase of
kinetic energy provides the particles with the necessary activation energy required
for the reaction to occur. The reaction therefore proceeds at a faster rate.

1. Explain how an increase in temperature increases the rate of a reaction.
2. Sketch a graph, on the same axes, of the reaction of metal with an acid
at 30˚C and 60˚C.
Surface area
The surface area affects rates of reactions where reactants are solids.
Experiment 3.3
To investigate the effect of surface area of solid reactants on the rate of reaction.
• digital balance or any other suitable balance
• conical flask
• cotton wool
• stop watch or clock
• marble (CaCO3)
(i) 2.5 g fine powder
(ii) 2.5 g small chips
(iii) 2.5 g large chips
• 2 M hydrochloric acid
Procedure
1. Measure 40 cm3 of 2M hydrochloric acid and transfer into a conical flask.
2. Weigh 2.5 grams of fine marble powder (CaCO3) on a watch glass.
3. Put the marble into the flask containing hydrochloric acid and immediately
place the flask and its contents on the balance as shown in Fig. 3.10 below.
Let the initial balance reading be X.
Cotton wool plug
Conical Gas
flask 2M hydrochloric acid
Marble chips
Balance
Fig. 3.10: Determining loss of mass of calcium carbonate
115
• What is the use of the cotton wool?
6. Draw three tables a, b and c like Table 3.3 in your notebook and record the
balance reading (y) after every minute until there is no change in mass.
Table 3.3 Effect of surface area on reaction rate

(a) Marble powder
Time(min) 1 2 3 4 5 6
Mass y g
Loss of mass of
CaCO3 (x–y)g
Calculate the loss in mass and complete your table.
7. Repeat the experiment with 2.5 g of small marble chips complete table (b) and
lastly 2.5 g of large marble chips and complete table (c).
8. Plot a graph of loss in mass against time in each experiment on the same axes.
• Write the chemical equation for the reaction taking place in the flask.
• Why does the reaction stop?
• What do you conclude from the graph?
Calcium carbonate reacts with dilute hydrochloric acid to form calcium chloride,
water and carbon(IV) oxide.
CaCO3(s) + 2HCl(aq) ––– CaCl2(aq) + H2O(l) + CO2(g)
The carbon(IV) oxide escapes through the cotton wool to the atmosphere. The
cotton wool stops the acid spray from escaping during the chemical reaction. The
hydrochloric acid used in this experiment is in excess. Therefore, the reaction
stops only when all the calcium carbonate has reacted.
chips
ed marble
Powder
Loss in mass (g) or mass of
s
le chip
e marb
Larg
CO(g) evolved
ps
le chi
marb
all
Sm
Time (minutes)
Fig. 3.11: Curves of loss of mass of calcium carbonate against time
116
If you were to compare the three graphs the loss in mass is fastest for powdered
marble, slower for small marble chips and slowest for large marble chips. This
means that the rate of reaction is fastest for marble powder, followed by small
marble chips and slowest for large marble chips. The time taken to produce the
same volume of carbon(IV) oxide which is assumed to correspond to loss in mass,
is shorter for powdered marble. The more finely divided the solid, the greater the
surface area as shown in Fig. 3.12 below.
Fig. 3.12: Cutting to smaller pieces increases the total surface area of a substance
Large surface area increases the chances of successful collissions between particles
and hence greater frequency of these collisions. Increased collisions leads to
1
an increase in the rate of reaction. The rate of chemical reaction h t can also be
represented by the graph below.
Surface area of solid
1 (min–1)
t
Fig. 3.13: Graph of surface area of solid reactants against reciprocal of time ( 1 )
t
This experiment, therefore, shows that the rate of reaction increases when surface
area is increased.
Self assessement exercise 3.5
In an experiment, a student from Musaada Secondary School, measured the amount of
hydrogen produced when excess 1.0M hydrochloric acid was reacted with 0.3 g of
zinc granules and obtained the following results at room temperature and pressure.
Time (minutes) Volume of hydrogen (cm3)
0.0 0
0.5 20
1.0 32
2.0 52
5.0 86
7.5 103
117
10.0 112
12.0 118
14.0 120
16.0 120
(i) Draw a graph of volume of hydrogen produced against time.

(ii) Determine the time at which half of the original mass of zinc granules
will have reacted.
(iii) Sketch the approximate curves on the same axes that would represent the
reaction of excess 1 M hydrochloric acid and 0.3 g of zinc powder and
0.3 g of zinc foil.
Catalyst
Experiment 3.4
To investigate the effect of manganese(IV) oxide on rate of decomposition of
hydrogen peroxide.
• boiling tubes
• wooden splint
• 20 volume hydrogen peroxide
• manganese(IV) oxide
• filter funnel
• filter papers
• conical flask
• weighing balance
Procedure
1. Dilute 20 cm3 of 20 volume hydrogen peroxide with 80 cm3 of distilled
water.
2. Put some 20 cm3 of this diluted hydrogen peroxide in a boiling tube. Test
whether oxygen is produced from this solution using a glowing splint.
• Record your observation.
3. Put another 20 cm3 of the diluted hydrogen peroxide in another boiling tube.
Add about 0.5 g of manganese(IV) oxide in this solution. What do you ob-
serve?
• Test the gas evolved with a glowing splint and record your observation.
4. Filter the residue in (3) above using a filter paper of known mass. Wash the
black residue (manganese(IV) oxide) on the filter paper by pouring distilled
water on it several times. Dry the filter paper. Weigh it after it has dried.
• What is the mass of the black solid?
• Did you recover all the original manganese(IV) oxide?
118
• What is your conclusion from this experiment?
• Write the chemical equation for this reaction.
Before manganese(IV) oxide is placed into hydrogen peroxide, the solution gives
off oxygen only slowly, but not enough to re-light a glowing splint.
When manganese(IV) oxide is added, the reaction becomes vigorous and oxygen is
obtained much more quickly. The oxygen is now enough to re-light a glowing splint.
The mass of manganese(IV) oxide before and after the experiment is approximately
the same. Manganese(IV) oxide acts as a catalyst in this reaction. It increases the rate of
a chemical reaction but remains chemically unchanged at the end of the reaction.
MnO2(s)
2H2O2(aq) –––––– 2H2O(l) + O2(g)
• Name another catalyst that can be used in the decomposition of hydrogen
peroxide?
For a reaction to take place, reactants must have activation energy. A catalyst lowers
the activation energy needed by the reactants to react. Hence, more particles can
get over the new activation energy barrier faster resulting in more fruitful colli-
sions as explained earlier by collission theory. This increases the rate of reaction.
Fig. 3.14 below is an analogy of how catalysts act to speed up rates of chemical
reactions.
ducts
Pro
ts
ctan
Rea
Fig. 3.14: Catalyst route is shorter than the route without a catalyst
In the analogy, the catalyst route is easier (requires less energy) than the route
without a catalyst. The vehicle following this route will therefore reach its
destination faster and will require less energy because it will not climb the hill.
The same applies to a reaction where a catalyst is involved. The catalyst lowers
the activation energy required for the reaction to start. The reaction therefore takes
place at a faster rate. Study Fig. 3.15.
119
1
Energy
E1 2 E2
REACTANTS
PRODUCTS
Reaction path
Fig. 3.15: Catalyst lowers the activation energy of the reaction
Curve 1 represents the reaction without a catalyst. It requires activation energy E1.
Curve 2 represents the reaction with a catalyst. It requires activation energy E2.
According to the above graph, E1 is greater than E2. Therefore, a reaction with a
catalyst requires less activation energy.
A catalyst does not cause the reaction. It only speeds up the rate of a chemi-
cal reaction that would have otherwise taken place at a much slower rate in its
absence.

1. (i) Define the term catalyst.
(ii) Give an example of a chemical reaction where a catalyst is used.
Name the catalyst.
2. How does the catalyst in 1(ii) above increase the rate of reaction?
Light
Light is a form of energy. It can be used to initiate (start) certain chemical reactions.
It acts as an external source of energy for the reaction. Just like an increase in
temperature, increase in intensity of light increases the fruitful collisions resulting
in increase in rate of reaction. Some examples of reactions where light is involved
include:
(a) Photosynthesis
This process takes place only in the presence of light. During this process, plants
convert carbon(IV) oxide and water to glucose and oxygen.
Carbon(IV) + water sunlight glucose + oxygen + energy
oxide
sunlight
6CO2(g) + 6H2O(l) C6H12O6(aq) + 6O2(g) + E
(b) Photography
A photographic film, which is coated with silver bromide deposits metallic silver
on exposure to light.
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light
Silver –––– silver + bromine
bromide
light
2AgBr(s) –––– 2Ag(s) + Br2(l)
When the film is developed, the silver deposits give a picture of the object whose
photograph was taken. In total darkness, no reaction can take place and therefore,
no images can be taken.
The higher the intensity of light, the higher the rate of decomposition of silver
bromide.
(c) Reaction of halogens
(i) Chlorine with hydrogen
In diffused light, chlorine reacts slowly with hydrogen to form hydrogen
chloride. In bright sunlight, the reaction is vigorous and can be explosive.
light
Chlorine + hydrogen ––––– hydrogen chloride
light
Cl2(g) + H2(g) ––––– 2HCl(g)
(ii) Chlorine with methane
A mixture of methane and chlorine explodes when placed in bright
sunlight.
light
Methane + chlorine ––––– carbon + hydrogen chloride
light
CH4(g) + 2Cl2(g) ––––– C(s) + 4HCl(g)
In diffused light, chlorine reacts with methane to form a mixture of substitution
products e.g. chloromethane and hydrogen chloride.
CH4(g) + Cl2(g) ––––– CH3Cl(s) + HCl(g)
Self-assessement exercise 3.7

1. (i) Name the substitution products when chlorine reacts with
methane in diffused light.
(ii) Write the chemical equations which lead to the formation of
substitution products.
2. Why should silver nitrate and concentrated nitric acid not be
placed in a place where they can get direct sunlight?
3. How does light affect rate of reaction? Give an example of a light catalysed
reaction and the equation.
Pressure
Look at the syringes below. If the end is sealed, how can you increase the pressure
of the gases inside the syringe?
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Before pushing plunger
Plunger
(a)
After pushing plunger
Syringe seal
(b)
Fig. 3.16: Syringes showing how pressure can be increased (a) low pressure,
(b) high pressure
To increase pressure, you push the plunger downwards as shown. By pressing the
plunger in, you will have the same number of gas particles in a smaller volume.
This reduces the space in which collisions takes place thereby increasing the
chances of fruitful collisions in a given time. As a result, the rate of reaction is
increased.
In reactions involving gases, increasing the pressure, increases the rate of

reaction.

How does increase in pressure affect the rate of reaction for gaseous
reactants? Explain using collision theory.
3.5 Reversible reactions

What is a reversible reaction?
A reversible reaction is a chemical reaction in which the products can be con-
verted back to reactants under suitable conditions. Let us now carry out some
experiments to investigate some reversible reactions.
Reversible reaction in copper(II) sulphate crystals
Experiment 3.5
To investigate what happens when hydrated copper(II) sulphate is heated.
• test tube
• dropper
• source of heat
• distilled water
• hydrated copper(II) sulphate
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Procedure
1. Put two spatula endful of hydrated copper(II) sulphate into a test tube.
• What is the colour of this solid?
2. Heat the test tube gently as shown in Fig. 3.17 below. Stop heating the contents
when the crystals have changed colour. Record this colour in your notebook.
Steam
Condensed vapour
Hydrated copper(II) sulphate

(blue)
Heat
Fig. 3.17: Heating hydrated copper(II) sulphate

3. Let the test tube to cool down and note the colour of the copper(II) sulphate in
the tube.
4. Now, add a few drops of water from a dropper.
thermometer
drops of water
anhydrous
copper(II) sulphate
Fig. 3.18: Adding water to anhydrous copper(II) sulphate
• What is the colour of the solid now?

• What is your conclusion from this experiment?
When blue hydrated copper(II) sulphate solid is heated, it loses its water of
crystallisation. A white anhydrous copper(II) sulphate powder is formed. The
colour persists even on cooling the tube.
Hydrated copper(II) sulphate –––– anhydrous copper(II) sulphate + water
(blue crystals) (white powder)
CuSO4.5H2O(s) ––––– CuSO4(s) + 5H2O(l)
When water is added to anhydrous copper(II) sulphate powder, it turns to blue
hydrated copper(II) sulphate. This is because the water of crystallisation is
regained. This reaction is exothermic and therefore produces a lot of heat.
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The thermometer indicates a sudden rise in temperature when drops of water are
added
Anhydrous copper(II) sulphate + water hydrated copper(II) sulphate
(white powder) (blue crystals)
CuSO4(s) + 5H2O(l) CuSO4.5H2O(s) + heat
Note that the backward reaction shown above can be used to test for water.
This is an example of a reversible reaction. The reactions can go in either directions:
backwards or forwards. Reversible reactions are shown by the arrows pointing in
both directions:
Hydrated copper(II) sulphate anhydrous copper(II) sulphate + water
(blue crystals) (white powder)
CuSO4.5H2O(l) CuSO4(s) + 5H2O(l)

1. What is a reversible reaction?
2. Give an example of a reaction involving change of colour of solid
reaction and solid product.
We can also use indicators to show reversible reactions. Reactions are not reversible
because indicators change colour. Indicators show one colour in acidic solutions
and another in alkaline solutions.
Add alkali
RED Add acid BLUE
Acid with Alkali with

litmus solution litmus solution
Fig. 3.19: Indicators show different colours in alkaline and acidic solutions
This can be further explained using the following experiment.
Experiment 3.6
To investigate chemical equilibrium in chromate(VI) ion/dichromate(VI) ion.
• 100 cm3 glass beaker
• filter paper or a white paper
• droppers
• potassium chromate(VI) solution
Procedure
1. Put 20 cm3 potassium chromate(VI) solution in a glass beaker. Place the
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container on a filter paper or any other white paper.
• What is the colour of the solution?
2. Add 2M hydrochloric acid solution drop by drop until there is a permanent
colour change. Keep this solution for procedure 3.
• What is the new colour of the solution?
3. To the same solution in procedure 2, add 2M sodium hydroxide solution drop
by drop until there is no more change in colour.
• What is the new colour of the solution?
• What is your explanation and conclusion in this experiment?
Potassium chromate(VI) solution in water is yellow in colour. When a few drops
of dilute hydrochloric acid are added to the solution, it turns orange due to forma-
tion of dichromate(VI) ions (Cr2O72–)(aq). This is because as the acid is added,
the concentration of hydrogen ions (H+) increases. An equilibrium is established
with more Cr2O72– in solution than CrO4– , hence orange colour is dormant.
However, on adding a few drops of 2M sodium hydroxide, the colour of the solu-
tion reverts to the original yellow colour.
Equilibrium shifts, on adding acid
2CrO42–(aq) + 2H+(aq) Cr2O72–(aq) + H2O(l)
chromate dichromate
(VI) ion (VI) ion
(yellow) (orange)
Equilibrium shifts, on adding a base
When 2M sodium hydroxide is added, the OH– ions react with hydrogen ions H+
to form water. This reduces the concentration of hydrogen ions H+ in the solution.
The equilibrium shifts to the left. H+ ions are formed to replace the hydrogen ions
used to form water. The backward reaction is favoured and more chromate(VI)
ions are formed turning the solution yellow.
Cr2O72–(aq) + 2OH–(aq) 2CrO42–(aq) + H2O(l)
(orange) (yellow)
H2O HCl NaOH
Excess Excess Excess

Yellow Yellow
2– 2–
2–
CrO4 Orange Cr2O7 CrO4
Fig. 3.20: Chemical equilibrium in chromate(VI)/dichromate(VI) mixture

Altering the concentration of any one of the components of the equilibrium mixture
disturbs the equilibrium by affecting the rate of forward or reverse reaction. Hence,
the reaction proceeds predominantly in that direction until a new equilibrium
is established.
125
Note that the arrows showing reversible reaction at equilibrium are represented
as . They are slightly different from the ones shown earlier
for reversible reactions represented as .
In reversible reactions, change of reactants to products and change of the products
back to reactants takes place at the same time i.e. are at equilibrium. In a reaction
like the conversion of A and B to C and D predominates at the start of the reaction.
A+B C+D
Eventually, both the forward and the backward reaction will be taking place at the
same rate. As soon as C and D accumulate, the reverse reactions start building up
until an equilibrium position or a state of ‘balance’ is reached. State of ‘balance’
means that the rate of forward reaction equals the rate of backward reaction i.e.
at state of balance;
Rate of forward reaction = Rate of backward reaction
At state of balance; the reaction is said to have reached a dynamic equilibrium
since the reactants and products are not simply coexisting but there is a constant
interchange from products to reactants and vice versa.
The following experiment also explains chemical equilibrium as a state of ‘balance’.
Experiment 3.7
To investigate change of colour of indicator in acid and alkali media as an example
of a reversible reaction.
• beakers
• phenophthalein or any other suitable indicator.
Procedure
1. Put some water in a beaker. Add three drops of phenolphthalein indicator to the
water.
• What is the colour of phenolphthalein indicator in water?
2. To another clean beaker, rinsed with sodium hydroxide solution, add about
10 cm3 of 2M sodium hydroxide solution.
3. Now, pour the phenolpthalein solution from the first beaker into the sodium
hydroxide solution in step 2 above.
• What can you conclude from the observations?
4. Get a third beaker with about 15 cm3 of 2M hydrochloric acid in it. Pour the
solution in 3 above into the beaker with the acid.
• What can you conclude from this observation?
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Phenolphthalein indicator is colourless in acid and pink in alkali. The results from
the above experiment have been summarised in Fig. 3.21 below.
Water with
phenolphthalein
indicator
The indicator changes

colour in alkali
The indicator turns to

its original colour in
acid
Fig. 3.21: Colour changes of indicator in acid/ base
Many reactions are ‘one-way only’. The starting materials react to form the product.
The products cannot easily be turned back into the starting materials.
However in reversible reaction, products can reform the reactants. In a closed
system that is if you do not let any reactants or products escape, both forward and
backward reactions can occur at the same time. Reactants make products, and at
the same time, products make reactants. Eventually, both the forward and the
backward reactions will be going on at the same rate.
When this happens, we say it has reached a state of “balance”. This is called
chemical equilibrium.
At the point of equilibrium, the rate of the forward reaction equals
the rate of backward reaction.

1. What is a chemical equilibrium?
2. Give an example of a chemical reaction which eventually attains chemical
equilibrium.
3.6 Effects of different factors on the position of equilibrium

The equilibrium position raises many interesting questions. For instance,
• What factors affect the position or ‘balance’ of chemical equilibrium?
• What is the change when some of the factors are altered?
• What is the composition of the mixture of the old and new equilibriums after
one of the conditions is altered?
127
Let us consider what happens to the position of equilibrum when concentration,
temperature and pressure are changed respectively.
1. Effect of changing concentration on the position of equilibrium
Experiment 3.8
To investigate how concentration affects the equilibrium of bromine and water
• beaker
• filter papers or any white paper
• dropper
• 2 M sodium hydroxide
• 2 M hydrochloric acid
• Liquid bromine or 1% bromine water
Procedure
1. Prepare 1% bromine water by adding 1 cm3 of liquid bromine to 99 cm3 of
distilled water and shaking the mixture well to dissolve.
Caution: This should be done in a fume chamber or open space. Bromine
vapours are poisonous.
2. Put 20 cm3 of 1% bromine water in a glass beaker. Place the beaker and its
contents on a filter paper or any white paper.
3. Add 2M sodium hydroxide solution drop by drop to the solution above while
swirling until there is no further observable colour change. Keep this solution
for procedure 4.
4. To the same solution in step 3, add 2M hydrochloric acid drop by drop while
swirling until there is no further observable colour change.
• What is the colour of 1% bromine water?
• What is the effect of adding in turns, sodium hydroxide and hydrochloric
acid to bromine water?
• What is your explanation and conclusion in this experiment?
A. Bromine water is yellow-orange in colour. When the mixture is at equilibrium,
it has bromine molecules, water molecules, hypobromite ions, bromide ions
and hydrogen ions i.e.
Br2(aq) + H2O(l) OBr–(aq) + Br–(aq) + 2H+(aq)
yellow-orange colourless
Bromine molecules make the mixture yellow-orange.
When we add sodium hydroxide solution; the OH– ions react with H+ ions in the
system to form water i.e.
OH–(aq) + H+(aq) H2O(l)
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This decreases the hydrogen ions concentration in the system. To cancel this
change, the equilibrium shifts to the right to replace H+ ions used and hence forward
reaction is favoured. This produces more hydrogen ions which are added to the
system. This shift converts the bromine molecules to hypobromite and bromide
ions and hence the change in colour of solution from yellow-orange to colourless.
Addition of hydrochloric acid provides hydrogen ions (H+), i.e the concentration
of H+ in the system is increased. To cancel this change, the equilibrium shifts to
the left. The backward reaction favours the conversion of the additional hydrogen
ions to water. In the course of this, bromine molecule are produced making the
colour of the mixture to change from colourless to yellow-orange.
Changing the concentration of any one of the components of the equilibrium
mixture disrupts the equilibrium by either changing the rate of forward or reverse
reaction. Hence the reaction adjusts itself until the rate on both directions are equal
to establish a new equilibrium.
B. Another good example that we have already discussed which demonstrates
the effect of concentration on position of equilibrium is chromate(VI) ion/
dichromate(VI) ion mixture. The addition of hydrochloric acid (HCl) increases
the concentration of hydrogen ions (H+). The equilibrium shifts to the right to
convert the added hydrogen ions to water. More dichromate(VI) ions are also
formed making the solution orange.
When hydroxide ions (OH–) are added through addition of 2M sodium hydroxide,
they react with hydrogen ions to form water. This makes the concentration of
hydrogen ions go down. The equilibrium shifts to the left to form more hydrogen
ions to replace the ones converted to water. More chromate(VI) ions are formed
making the solution yellow.

Br2(aq) + H2O(l) OBr–(aq) + Br– + 2H+(aq). What is the effect of adding
potassium hydroxide when the above system is in chemical equilibrium?
2. Effect of changing temperature on the position of equilibrium

Experiment 3.9
To investigate the effect of temperature change on equilibrium.
• thistle funnel or dropper
• flat-bottomed flask
• delivery tube
• boiling tube
• copper turnings
• concentrated nitric acid
129
Procedure
1. Put copper turnings in a flat-bottomed flask.
2. Arrange the apparatus as shown in Fig. 3.22.
Conc. nitric
Thistle funnel acid
Delivery tube
Cork
Flat-bottomed
flask Boiling tube
Nitrogen(IV) oxide
Copper turnings
Fig. 3.22: Preparation of nitrogen(IV) oxide

NB: This should be done in a fume cupboard. NO2 is poisonous.
3. Add concentrated nitric acid to the copper turnings in the flask.
4. Collect the gas in a boiling tube with some air and cork it tightly.
• What is the colour of the gas in the boiling tube?
5. Slightly warm the gas in the boiling tube and note the colour. Record this in your
notebook. Cool it in ice cold water as shown in Fig. 3.23 and record any
colour change.
Cork
NO2
Nitrogen(IV) gas
oxide gas
Boiling tube
Ice cold water
Beaker
Heat
Fig. 3.23: Effect of temperature on position of equilibrium

Concentrated nitric acid reacts immediately with the copper to form red-brown
fumes of nitrogen(IV) oxide.
Copper + nitric(V) ––––– copper(II) + water + nitrogen(IV)
acid nitrate oxide
Cu(s) + 4HNO3(conc.) –––– Cu(NO3)2(aq) + 2H2O(l) + 2NO2(g)
When air and nitrogen(IV) oxide at room temperature are heated gently then
cooled in cold water, the colour changes from dark-brown to pale yellow. This
130
is because the nitrogen(IV) oxide is converted to dinitrogen tetra-oxide. The
colour of nitrogen(IV) oxide is dark brown and that of dinitrogen tetra-oxide is
pale yellow.
Nitrogen(IV) decrease temp. dinitrogen
oxide increase temp. tetra-oxide
2NO2(g) decrease temp. N2O4(g)

(dark-brown) increase temp. (Pale-yellow)
This demonstration illustrates the effect of temperature on the position of

equilibrium. The equilibrium shifts to the right at lower temperatures favouring
forward reaction, i.e (i.e 2NO2––– N2O4). Nitrogen(IV) oxide is converted to
dinitrogen tetra-oxide and the colour of the gas changes to pale-yellow. At higher
temperature the equilibrium will shift to the left and the dinitrogen tetra-oxide will
be converted to nitrogen(IV) oxide i.e the backward reaction is favoured
(N2O4––––– 2NO2). The colour of the gas changes to dark-brown.
C. Another example which shows that increasing the temperature causes
the equilibrium of a reaction to shift in the direction that absorbs heat, is the
production of sulphur(VI) oxide (SO3) which is an exothermic reaction.
Sulphur(IV) oxide + oxygen Sulphur(VI) oxide + heat
2SO2(g) + O2(g) 2SO3(g) + heat
Heating the reaction mixture at equilibrium shifts the equilibrium to the left.
Cooling shifts the equilibrium to the right.

1. What is the effect of increasing the temperature in
(i) an endothermic reaction which is in equilibrium?
(ii) an exothermic reaction in equilibrium?
3. Effect of changing pressure on the position of equilibrium

Effects of changing pressure on the equilibrium applies only to substances that
are in gaseous form and not those in liquid or solid forms. However, the number
of moles of gases on either side of the equation must be different. If you increase
the pressure as shown in Fig. 3.24 (b), the equilibrium shifts so as to try and
reduce it.
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(a) decreasing (b) increasing
Fig. 3.24: Changing pressure
We are going to illustrate the effects of pressure on the equilibrium by considering
the reaction of nitrogen and hydrogen to form ammonia.
Nitrogen + hydrogen ammonia + heat
N2(g) + 3H2(g) 2NH3(g) ∆H = –92kJ/mol
1 mole 3 moles 2 moles
The reactants are 4 moles (2.4 × 1024 molecules) whereas the product is two moles
(1.2 × 1024 molecules). The more the molecules the higher the pressure.
(Remember 1 mole = 6.023 × 1023 molecules, i.e. Avogadro’s number L)
Reactant(s) product
(high pressure) (low pressure)
In this reaction, there is a change of pressure when the product is being formed.
Changing the pressure in a reaction like this one; which is in equilibrium is applying
a stress to the system. This imposed stress has to be reduced. Increase in pressure
will, therefore, cause the equilibrium to shift in the direction which will lower the
increased pressure. This means that forward reaction will be favoured and hence
more ammonia gas will be formed. The equilibrium therefore shifts to the right.
D. Other examples where the equilibriums shift from the left to the right with
increase in pressure include:
(1) 2SO2(g) + O2(g) 2SO3(g)
(2) 2NO(g) + O2(g) 2NO2(g)
However, in other reactions i.e where the number of moles on the right side of
the equation is higher than the left side, the equilibrium will shift from right to
left when the pressure is decreased. For example.
N2O4(g) 2NO2(g)
1 mole 2 moles
In this reactions, more product can be obtained by decreasing the pressure.
E. In other reactions where the number of moles on either side of the reaction
is the same, change in pressure will have no effect on the composition of the
mixture at equilibrium. The position of equilibrium is therefore not altered.
The following are examples of such reactions:
132
N2(g) + O2(g) 2NO(g)
CO(g) + NO2(g) CO2(g) + NO(g)
CO(g) + H2O(g) CO2(g) + H2(g)
Le Chatelier’s Principle
From previous exampes, you noticed that the addition of one or more of the
substances which appear on one side of the equation always displaces the posi-
tion of equilibrium away from that side. The temperature change also affects the
equilibrium mixture. If the reaction involves gases, changing the pressure might
affect the equilibrium as well.
Such factors which affect the position of equilibrium in

a reaction were first investigated by a French Chemist,
Henri Louis Le Chatelier. He expressed his results in
a generalised way which later came to be known as
Le Chatelier’s Principle.
Fig. 3.25: Henri Le Chatelier

1850 – 1936
Le Chatelier’s Principle
“It states that if a system in equilibrium is subjected to a stress, the equilibrium
will shift in the direction which tends to relieve that stress”
This principle can be expressed in the following different ways without necessarily
changing its meaning.
1. If a system in equilibrium is subjected to a change, the position of equilibrium
will move in such a way as to tend to eliminate the change.
2. If a system in equilibrium is subjected to a change, processes will occur which
tend to counter the change imposed etc.
Le Chatelier’s Principle can be used to predict the effect of changing concentration,
temperature or pressure in any chemical system in equilibrium. This principle has
been applied in reversible reactions in industrial processes. Let us now look at
examples of some industrial applications.
3.7 Uses of reversible reactions in industrial processes

Many industrial processes involve reversible reactions and since cost reduction
is an extremely important consideration in industry, a great deal of care is taken
when determining the conditions that affect these processes. It is important to
maximise the concentration of the desired products and minimise the ‘left over’
reactants. A set of rules can be used to predict the best reaction conditions to give
133
the highest possible yield of the products. The rules are based on the conditions
that affect the reactions involved as discussed below.
Rule 1: Based on temperature
(a) If the forward reaction is endothermic, raising the temperature favours
increased yield of the product. Lowering the temperature decreases the yield
of the product.
(b) If the forward reaction is exothermic, lowering the temperature favours
increased yield of the product. Raising the temperature decreases the yield.
Note that rule 1 applies to any reaction.
Rule 2: Based on pressure

(a) Increasing the pressure favours the side of the equilibrium with the least
number of gaseous molecules.
(b) Decreasing the pressure favours the side of the equilibrium with the most
number of gaseous molecules.
Rule 2 applies to reactions involving one or more

gaseous reactants or products only.
Rule 3: Based on the concentration of reactants

(a) If the concentration of any reactant on the left is increased then some of it must
be used up to form products on the right to maintain a balanced equilibrium
position.
(b) If the concentration of any reactant on the left is decreased then some of
the products on the right must change back to the reactants to maintain a
balanced equilibrium
Rule 3 applies to any reaction.
Rule 4: Based on catalyst

A catalyst does not affect the position of an equilibrium. It only makes the forward
and reverse reaction take place at a faster rate. In this way, it helps the equilibrium
to be established faster. But once the equilibrium has been established, it cannot
influence the final composition of the equilibrium mixture.
The following are some of the ways in which reversible reactions are applied in
industry.
(a) Manufacture of concentrated sulphuric(VI) acid (Contact process)
• In the manufacture of sulphuric(VI) acid, the main reaction that converts sulphur(IV)
oxide (SO2) to sulphur(VI) oxide(SO3) is reversible.
Sulphur(IV) oxide + oxygen sulphur(VI) oxide + heat energy
2SO2(g) + O2(g) 2SO3(g); ∆H= –197kJ/mol
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• The reaction of sulphur(IV) oxide and oxygen to form sulphur(VI) oxide is
an exothermic reaction.
• 3 moles of reacting gases form 2 moles of the product, so there is net
decrease in the number of moles on forming sulphur(VI) oxide.
• So applying the equilibrium rules, the formation of sulphur(VI) oxide is
favoured by:
1. Increasing pressure because there is a decrease of 3 moles of reacting gases to
2 moles of the products formed.
2. Lowering temperature because the reaction is exothermic.
Since the reaction is exothermic, once the process has started, no more heating
is required i.e the reaction is self-sustaining.
According to the above equation, increase in pressure will give an increased
yield of sulphur(VI) oxide (favour forward reaction). The effect is small and
the yield of sulphur(VI) oxide is good even at low pressures. Therefore 1-2
atmospheres pressure is used in practice.
• Can you predict the optimum temperature for a high yield of sulphur(VI) oxide?
• Should the system be allowed to attain equilibrium at low or high temperature?
Application of Le Chatelier’s Principle suggests that the lower the temperature the
more the equilibrium state will favour the production of sulphur(VI) oxide. But,
what about rate or time required to produce a given quantity? At low temperatures,
reaction rates are slow. A compromise temperature of about 450 – 500˚C is usually
used to give desirable yield of SO3 and a satisfactory rate of reaction.
You recall that during contact process, sulphur(VI) oxide is reacted with
concentrated sulphuric acid to form oleum. This reduces the concentration of
SO3 in the system. This removal of sulphur(VI) oxide creates stress and shifts the
equilibrium to the right.
A catalyst of vanadium(V) oxide is also used to increase the rate of reaction.
It does this by reducing the activation energy required to initiate the reaction. A
yield of about 98% is obtained when all these conditions are applied.
(b) Manufacture of ammonia (Haber process)
Ammonia gas is synthesised in the industry by reacting nitrogen gas and hydrogen
gas through a process called Haber process. The reaction is reversible as shown
below.
Nitrogen + hydrogen ammonia + heat
N2(g) + 3H2(g) 2NH3(g) ∆H = –92kJ/mol
1 mole 3 moles 2 moles
This reaction is an exothermic reaction. The four moles of ‘reactants’ (1 mole of
N2 and 3 moles of H2) form two moles of ‘product’ gas (2 moles of NH3), so there
is a net decrease in gas molecules on forming ammonia.
135
Applying the earlier discussed equilibrium rules, the formation of ammonia is
favoured by:
1. High pressure. Because we are going from 4 to 2 moles. High pressure
increases the number of collisions of gaseous particles hence higher rate of
foward reaction to form ammonia
2. Low temperatures. Because the reaction is an exothermic reaction, high
temperatures would decompose ammonia, the product we want.
Unfortunately, at low temperatures and high pressure, the rate at which equilibrium is
reached is very slow. Also, if very high pressures are used, an expensive industrial
plant will be required. In practice, ‘optimum conditions are applied’.
Theoretically, a low temperature would give a high yield of ammonia but
nitrogen is a very stable molecule and therefore not very reactive especially at low
temperatures. A compromise temperature of 400 – 450˚C is used. To speed up the
reaction, finely divided iron catalyst is used. Using the catalyst in this process does
not affect the position of equilibrium but the reaction reaches equilibrium faster.
Table 3.4 Summary of effects of changing some factors on chemical equilibrium
Factor Change Effect

Concentration Increase —for reactants • Shifts from left to right (––)
or • Favours forward reaction (––)
(decrease for products) • More products formed
Decrease —for reactants • Shifts from right to left (––)

or • Favours backward reaction (––)
(increase for products) • More reactants are formed
Increase in number • Shifts from right to left (––)

of moles on forma- • Favours reverse reaction (––)
Pressure Increase
tion of products • More reactants formed in the
reverse reaction
Decrease in number • Shifts from left to right (––)
of moles on forma- • Favours forward reaction (––)
tion of products • More products formed from
the reactants in forward reaction
Increase in number • Shifts from left to right (––)
Decrease of moles on forma- • Favours forward reaction (––)
tion of products • More products formed
Decrease in number • Shifts from right to left (––)
of moles on forma- • Favours reverse reaction (––)
tion of products • More reactants are formed
136
Temperature Increase Exothermic • Shifts from right to left (––)
reaction • Favours reverse reaction (––)
• More reactants are formed
Endothermic • Shifts from left to right (––)

reaction • Favours forward reaction (––)
• More products formed.
Decrease Exothermic • Shifts from left to right (––)

reaction • Favours forward reaction (––)
• More products are formed
• Shifts from right to left (––)
• Favours reverse reaction (––)
Endothermic
• More reactants are formed.
reaction

1. State three factors which determine the composition of equilibrium mixture.
2. Why does the catalyst have no effect on the composition of equilibrium mixture.
3. Explain how the following will affect the yield of ammonia.
(i) Increase in pressure
(ii) Increase in temperature
4. Use Le Chatelier’s Principle to explain how removal of a little of D in the
following reaction favours a higher yield of D.
A + B D
Summary
• The rate of a chemical reaction is the change in the concentration of one of
the reactants or products per unit time.
• The rate of reaction is inversely proportional to the time taken.
• Activation energy is the initial energy required by reactants for them to start
reacting chemically.
• The lower the activation energy for a reaction, the faster the reaction takes
place.
• The rates of chemical reactions are affected by concentration (or pressure in case
of gases), temperature, surface area for solid reactants and also a catalyst.
• A catalyst increases the rate of reaction by lowering the activation energy
required to initiate the reaction.
• A reversible reaction proceeds in either direction depending on the physical
conditions under which it is carried out.
• When both forward and reverse reactions take place at the same rate, the
reaction is said to be at chemical equilibrium or state of ‘balance’.
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• A catalyst affects to the same extent, the rate of the forward reaction as well
as the reverse reaction. It has no effect on the composition of the mixture at
equilibrium state.
• A catalyst makes the reaction reach equilibrium faster thereby increasing the
rate of reaction.
• means forward reaction or left to right
means reverse reaction or right to left
Revision Exercise 3
1. (a) Define the following terms.
(i) Rate of chemical reaction.
(ii) Activation energy.
(iii) Reversible reaction.
(b) 25.0 cm3 portion of 0.2M sodium thiosulphate were put into a conical
flask. The temperature of this solution was recorded. A cross was drawn
on a piece of white paper underneath the flask. An excess of 2M
hydrochloric acid was added. The time taken for the cross to disappear
was recorded. The experiment was then repeated with the solutions at
different temperatures. The results obtained were as shown in the table
below.
Temperature 19 29 40 49 60
of sodium
thiosulphate
Time(seconds) 340 250 155 90 55
(i) Plot a graph of time (vertical axis) against temperature (horizontal axis)
(ii) From your graph, estimate the reaction time at
• 25˚C
• 54˚C
(iii) From the graph, estimate the temperature at which the reaction time is
(i) 110 seconds
(ii) 65 seconds
(iv) What effect does an increase in temperature have on the rate of the
reaction? Explain your answer.
2. (a) Excess dilute nitric acid reacts more rapidly with powdered marble than
with lumps of marble. In both reactions, the rates of reaction decrease
with time. Explain these two observations.
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Vol. of CO2(cm3) produced
Time taken
(b) The above graph shows the volume of carbon(IV) oxide produced and
time taken when lumps of marble are reacted with excess 2M nitric acid.
(i) Sketch on the same axis the curve obtained when the same mass of
marble powder and excess 2M nitric acid are reacted.
(ii) Write the chemical equation for the reaction.
3. (a) State Le Chatelier’s Principle.
(b) Name three factors which may disturb a chemical equilibrium.
(c) What is the use of a catalyst in chemical reactions?
4. Explain briefly the effect of addition of aqueous potassium hydroxide on
equilibrium of the following reactions.
2CrO2–4(aq) + 2H+(aq) Cr2O72–(aq) + H2O(l)
What would happen when a few drops of dilute sulphuric acid are added to the
mixture at equilibrium?
5. The production of ammonia through the Haber process involves the following
reversible reaction.
N2(g) + 3H2(g) 2NH3(g) ∆H = –ve
(a) What does ∆H = –ve indicate?
(b) Suggest two conditions that are likely to shift the equilibrium position
from left to right.
(c) Name the catalyst used in the Haber process.
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Unit 4: Electrochemistry
Introduction
In unit 2, we learnt that energy can be transformed from one form to another. For
example, electrical energy can be converted to chemical energy. This is as a result of
the fact that chemical reactions can generate electrical energy and electrical energy
can cause chemical reactions.
We learnt about the effect of electric current on substances. We learnt that:
• A conductor (a metal or graphite) conducts electric current but it is not decomposed.
• Electrolytes are compounds which conduct an electric current in aqueous solution
or molten state and are decomposed by the current.
• In electrolytic cell, ions carry the electric current when they migrate to the electrodes.
• The cations, which are positively charged ions move to the cathode, while the
anions which are negatively charged, move to the anode.
• During electrolysis, anions are discharged by losing electrons at the anode.
Electrons, therefore leave the electrolyte via the anode.
• Electrons travel in the external circuit through the connecting wire from the anode
to the cathode where they are gained by the cations.
• Electrolysis therefore involves gain or loss of electrons.
Electrochemistry deals with the relation of electricity to chemical changes and with
interconversion of chemical and electrical energy.
4.1 Redox reactions
The term redox is an abbreviation of reduction and oxidation. The first three letters are
taken from the word reduction and the other two from the word oxidation respectively,
to form redox. Redox reactions therefore involve oxidation and reduction.
Experiment 4.1
To investigate a reaction between an iron(II) compound and hydrogen peroxide as
an example of a redox reaction.
• test tubes
• test tube rack / beaker
• boiling tube
• glass rod
• source of heat
• iron(II) sulphate or iron(II) chloride
• 2M sodium hydroxide solution / aqueous ammonia
• 2M sulphuric(VI) acid
• twenty-volume hydrogen peroxide solution
• distilled water.
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Procedure
1. Pour about 2cm3 of freshly prepared iron(II) sulphate solution into a boiling tube.
2. Divide the solution into two portions.
3. To one portion, add a few drops of sodium hydroxide.
4. To the other portion, add a few drops of aqueous ammonia.
5. Record your observations in form of a table as in Table 4.1
6. Repeat steps 1 and 2.
7. Add 1 cm3 of 2M sulphuric(VI) acid to the iron(II) sulphate solution in the test
tubes followed by about 0.5 cm3 of twenty-volume hydrogen peroxide solution
(if any effervescence occurs, it is some of the H2O2 decomposing to form O2).
9. Divide the solution into two portions placed in test tubes. Add a few drops of
sodium hydroxide solution in one test tube and a few drops of ammonia in the
other test tube. What do you observe?
10. Record your observations and conclusions as shown in Table 4.1
• What role does hydrogen peroxide play?
• Write both stoichiometric and ionic equations for the reaction.
Table 4.1 Results of experiment 4.1
Solution Addition of Addition of Conclusions
sodium hydroxide aqueous ammonia
(a) Iron(II) sulphate
solution
(b) Iron(II) sulphate
solution + dil.
sulphuric acid
+
hydrogen peroxide
(a) When sodium hydroxide solution or aqueous ammonia are added to freshly
prepared iron(II) sulphate, a green precipitate of iron(II) hydroxide is formed.
The green colour indicates the presence of iron(II), Fe2+ ions. On the other hand,
addition of sodium hydroxide solution or aqueous ammonia to acidified iron(II)
sulphate followed by hydrogen peroxide solution forms a red-brown precipitate
of iron (III) hydroxide. The red-brown colour indicates the presence of iron(III),
Fe3+ ions.
Hydrogen peroxide removed an electron from Fe2+ ions to form Fe3+ ions. When
an atom or an ion loses electrons, it is said to be oxidised.
(i) Fe2+ (aq) –––––– Fe3+(aq) + e–
The reaction is oxidation because the iron(II) ions lose electrons. It is said Fe2+ ions
have been oxidised to Fe3+ ions. Notice that the charge has increased from +2 to +3.
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The electrons lost through reaction (i) above are gained by hydrogen peroxide to
form water i.e
(ii) 2H+(aq) + H2O2(aq) + 2e– ––––– 2H2O(l)
Gain of electrons is a reduction process. Hydrogen peroxide is therefore said to be
reduced to water. Note that reaction (ii) above requires 2e– but only 1e– is obtained
from reaction(i). This means that for this reduction to take place; two iron(II)
ions must be oxidised to iron(III) ions i.e
(iii) 2Fe2+(aq) ––––– 2Fe3+(aq) + 2e–
When we add equations (ii) and (iii), we get the overall equation:
(iv) 2Fe2+(aq) + 2H+(aq) + H2O2 (aq) –––– 2Fe3+(aq) + 2H2O(l)
Equation (iv) is therefore a redox reaction. This is because both gain and loss of
electrons have occured at the same time. Oxidising agents gain electrons. In the
reaction above, H2O2 is an oxidising agent. Other examples of oxidising agents which
undergo a similar type of reaction as above include:-
• concentrated nitric(V) acid.
• acidified potassium manganate(VII).
• acidified potassium dichromate (VI).
• concentrated sulphuric(VI) acid.
• oxygen from the air slowly oxidises iron(II) to iron(III).
1. Name two other reagents that can oxidise iron(II) ions to iron(III) ions.
2. What is a reducing agent? Name the reducing agent in the redox
reaction discussed above.
Other examples of redox reactions
(a) Reaction of metals with cold water
Experiment 4.2
To investigate the reaction of sodium with water.
• pair of tongs
• knife/scalpel
• trough
• universal indicator / suitable indicator
• water
Procedure
1. Half fill the trough with cold water.
2. Add three drops of the indicator.
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3. What colour do you observe? Record the colour in your notebook.
4. Using a pair of tongs, remove a small piece of sodium from the bottle, place it
on a ceramic tile covered with a filter paper to absorb excess oil.
5. Cut a very small piece of sodium and return the rest into the bottle.
6. Drop the small piece of sodium using either a knife or a scalpel into the water.
What do you observe? Record your observations in your notebook.
As we have already learnt, alkali metals react with water liberating hydrogen. The
resulting solution is alkaline. In this particular case, sodium hydroxide is formed i.e.
2Na(s) + 2H2O(l) ––––– 2NaOH(aq) + H2(g)
This is also a redox reaction. First, water undergoes slight ionisation to form hydrogen
ions, i.e
(i) H2O(l) –––– H+(aq) + OH–(aq)
Then, sodium atoms are oxidised by losing electrons to form sodium ions i.e.
(ii) 2Na(s) –––– 2Na+(aq) + 2e– oxidation
The electrons in equation(ii) above are then picked up by H+ ions in equation (i)
reducing them to hydrogen gas i.e
(iii) 2H+(aq) + 2e– –––– H2(g) reduction
The sodium ions, Na+ from equation(ii) and the hydroxide ions , OH– from equation
(i) remain in solution forming sodium hydroxide (NaOH).
• Why do we multiply the reaction(ii) above by 2?
1. Calcium metal reacts with cold water. This is a redox reaction.
(i) Write an ionic equation for the reaction.
(ii) Which are the oxidising and reducing agents in this reaction?
(b) Reactions of metals with acids

Experiment 4.3
To investigate the reaction of magnesium with dilute hydrochloric acid.
• boiling tube
• bunsen burner / appropriate source of heat
• wooden splint
• 2M hydrochloric acid or 1M sulphuric(VI) acid
• clean magnesium ribbon
Procedure
1. Put a little of dilute hydrochloric acid or sulphuric acid provided in the boiling tube.
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2. Add the piece of magnesium. What do you observe?
3. Test the gas evolved with a burning splint. What do you observe?
When a metal reacts with an acid, the reaction is a redox reaction. The metal atoms
lose electrons, which are taken by aqueous H+ ions in the acid. The metal atoms are
oxidised while the H+ ions are reduced as shown in the following half equations.
Note that when we add the half-equations, we get final ionic equation.
Mg(s) + 2HCl(aq) –––– MgCl2(aq) + H2(g)
or
Mg(s) + H2SO4(aq) –––– MgSO4(aq) +H2(g)
Mg(s) ––– Mg2+(aq) + 2e– oxidation
2H+(aq) +2e– –––– H2 (g) reduction
Overall ionic equation: Mg (s) +2H+(aq) ––– Mg2+(aq) + H2 (g) redox
• Identify the oxidising and reducing agents in the overall equation.
1. (a) Write an ionic equation to show a redox reaction between
(i) zinc and dilute sulphuric acid.
(ii) iron and hydrochloric acid.
(b) Name the oxidising and reducing agents in (a) (i) and (ii) above.
2. Which of the following reactions are oxidation reactions, both oxidation and
reduction (redox) and which are none? Explain.
(i) K+(aq) + e– ––––– K(s)
(ii) Fe2+(aq) +2e– –––– Fe(s)
(iii) Pb2+(aq) + 2Cl–(aq) –––– PbCl2(s)
(iv) Cu+(aq) ––––– Cu2+(aq) + e–
(v) Ag+(aq) + Cu+(aq) –––– Ag(s) + Cu2+(aq)
(vi) 2Cl–(aq) –––– Cl2(g) + 2e–
(vii) Mg(s) + 2H2O(l) –––– Mg(OH)2(aq) + H2(g)
Changes of oxidation numbers during redox reactions
To be able to understand these changes, we must learn how to determine oxidation
numbers of elements and elements in compounds.
Determination of oxidation numbers
Oxidation number, also called oxidation state is determined by the electrons gained,
lost or shared by the element in a compound during bonding with other elements
present. The oxidation number exhibited by an atom of an element refers to the
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charge on the ion of that element. See Table 4.2 below.
Table 4.2 Oxidation number of some ions
Ion Oxidation number
Na+ +1
Mg2+ +2
Al3+ +3
Cl– –1
O2– –2
P3– –3
Generally, the maximum oxidation number exhibited by an atom of an element
increase across each period in the Periodic Table. For example, in the third period
of the periodic table, if atoms were to lose electrons; we have the following:
Table 4.3: Oxidation numbers of period three electrons
Ion Oxidation number
Na+ +1
Mg2+ +2
Al3+ +3
Si4+ +4
P5+ +5
S6+ +6
Cl7+ +7
To find the oxidation number of an element in a molecule or a complex ion, the
following rules are applied:
1. The oxidation number for an atom of any free (uncombined) element is zero,
thus the atoms in H2, O2, Cl2, K, Na and Fe have zero(0) oxidation number.
2. The oxidation number for any simple one-atom ion is equal to its charge, thus the
oxidation number of K+ = +1; Ca2+ = +2 and of Cl– = –1.
3. The oxidation number of hydrogen in non-ionic compound is +1.This applies to
hydrogen compounds such as H2O; HCl and CH4 among others. For the ionic metal
hydrides such as sodium hydride, NaH, the oxidation number of hydrogen is –1.
4. The oxidation number of oxygen is –2 in all compounds e.g. H2O, NO, CO2 etc
except in peroxides e.g in H2O2 where it is –1. Another exception is OF2 in which
O has +2 as its oxidation number.
5. The algebraic sum of the oxidation numbers of all atoms in the formula of a neutral
compound must be zero. For example, in H2O since the oxidation number of H =
+1 and O = –2, it follows that the oxidation state of water (H2O) is zero (0) given
by (+1 x 2) + (–2) = 0.
6. The algebraic sum of the oxidation numbers of all the atoms in a complex ion is
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equal to the charge on the ion. Thus in NH+4 ion, if we add the oxidation number
of N and the 4H atoms, the answer must be equal to +1. In SO42– , the sum of all
oxidation numbers must be equal to –2 and so on.
Example 1
What is the oxidation number of Na, Mg, O2, and N2?
Solution
Zero (0) because these are uncombined elements.
Example 2
What is the oxidation number of chlorine in
(a) Cl2?
(b) HCl?
(c) HOCl?
(d) ClO–3?
Solution
(a) Zero
• In (b) to (d), we will assign oxidation number of chlorine a value x, and write
down an algebraic equation and solve for x.
• In (b) and (c), the algebraic sum of oxidation numbers must be equal to zero.
• From the rules above, the oxidation number of H = +1 and O = –2.
(b) HCl = 0
+1 + x = 0
x =0–1
= –1
The oxidation number of chlorine is –1
(c) The oxidation number of H = +1 , O = –2
H O Cl = 0
+1 + (–2) + x = 0
x = +1
The oxidation number of chlorine is +1
(d) Rule number 6; sum of oxidation number of all atoms in a complex ion is equal
to the charge on the ion.
ClO3–
x + 3(–2) = –1
x + (–6) = –1
x = –1 + 6
=+5
The oxidation number of Cl atom in ClO3– is +5.
Examples of changes of oxidation number during redox reactions
Let us use our previous examples.
146
1. Reaction of iron(II) ions with acidified hydrogen peroxide
1. When iron(II) ions react with acidified hydrogen peroxide, iron(II) ions are
oxidised to iron(III) ions as shown in the following half equations.
(i) 2Fe2+(aq) ––––– 2Fe3+(aq) + 2e–
+2 +3
Oxidation
The oxidation number has increased by +1 from +2 for Fe2+ ions to +3 for Fe3+ ions.
An increase in oxidation state is an oxidation process. Reaction (i) is therefore an
oxidation reaction.
(ii) 2H+(aq) + H2O2(aq) + 2e– –––– 2H2O(l)
The oxidation state of oxygen has decreased from –1 in hydrogen peroxide (H2O2)
to –2 in water (H2O). A decrease in oxidation state is a reduction process. Equation
(ii) is therefore a reduction reaction.
In overall equation
Reduction
2Fe2+(aq) + 2H+(aq) + H2O2(aq) –––– 2Fe3+(aq) + 2H2O(l)

+2 –1 +3 –2
Oxidation
Reaction of sodium with water

2. The change in oxidation numbers is shown in the following equation.
Reduction
2Na(s) + 2H2O(l) ––––– 2NaOH(aq) + H2(g)
0 +1 +1 0

Oxidation
Sodium is oxidised because its oxidation state change from a lower number(0) to
a higher oxidation state (+1). The oxidation state of sodium has increased by +1.
Hydrogen is reduced since its oxidation number decreases from (+1) to (0)
3. Reaction between magnesium and dilute hydrochloric acid
We have seen that hydrogen gas is evolved in this reaction. The equation for the
reaction is:
Mg(s) + 2HCl(aq) ––––– MgCl2(aq) + H2(g)
147
Ionic equation,

Reduction
Mg(s) + 2H+(aq) ––– Mg2+(aq) + H2(g)
0 +1 +2 0
oxidation
The oxidation number of magnesium increases from 0 to +2. This is oxidation. The
oxidation number of hydrogen ions, H+, decrease from +1 to zero. This is reduction.
Note: The oxidising agent gets its oxidation number decreased while the reducing
agent gets its oxidation number increased.
1. What are the oxidation numbers of nitrogen in the following.
(i) N2O (ii) NO2 (iii) NO–3 (iv) NO
2. Determine the oxidation number of sulphur in the following.
(i) H2SO4
(ii) SO2
(iii) SO32– and SO42–
(iv) H2S
3. What is the oxidation number of manganese in the following?
(i) KMnO4 (ii) MnO–4 (iii) MnO2
4. Find the oxidation number of the underlined element and give systematic
names of the following compounds:
(i) CuSO4
(ii) FeCl3
(iii) MnSO4
(iv) Cu2O
5. What is the oxidation number of chromium, (Cr), in each of the
following compounds?
(i) CrO3
(ii) Cr2O3
(iii) Na2CrO4
(iv) Cr2O2–7
4.2 Displacement reactions as redox reactions

Displacement reactions involve reactions of metals with other metals in aqueous
solution. For example, a reaction of zinc with copper(II) sulphate solution i.e.
Zn(s) + CuSO4(aq) ––––– ZnSO4(aq) + Cu(s)
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Zinc displaces copper from copper(II) sulphate.
The metals react by donating or losing electrons. The electrons lost are gained by
the metal in solution. Therefore, the metal donating the electrons is oxidised, while
the metal in solution gaining electrons is reduced. As such, displacement reactions
can be considered as redox reactions.
The metal is the reducing agent and the substance gaining electrons is the oxidising
agent. The reducing power of the metal decrease as we go down the reactivity series.
This is the reason why the metals above in the series displace metals below them
from their salt solutions.
Below is an example of a reactivity series
Calcium most reactive
Magnesium
Zinc
Iron
Lead
Copper least reactive
The general reaction that takes place during displacement reactions occur in two
half-reactions.
(i) M(s) –––––– M2+(aq) + 2e– oxidation
(ii) M2+ (aq) + 2e– –––– M(s) reduction
Where M represents a metal
Adding equations (i) and (ii) gives the overall equation.
Oxidation

M(s) + M2+ (aq) ––––– M2+ (aq) + M(s) redox reaction

0 +2 +2 0
reduction
Let us now compare this general equation with the displacement of copper from
copper(II) sulphate solution by zinc. Zinc dissolves and in the process, it loses two
electrons. This is an oxidation reaction.
Oxidation
Zn(s) ––––––– Zn2+(aq) + 2e- oxidation

0 +2
Cu2+ ions in solution gain the electrons and copper is deposited. In the process, the
blue colour disappears. This is a reduction reaction.
149
Cu2+(aq) + 2e- ––––– Cu(s) reduction
+2 0
reduction
We add the two half equations to get the overall ionic equation as follows:
Reduction
Zn(s) + Cu2+(aq) ––––– Zn2+(aq) + Cu(s) redox reaction

0 +2 +2 0

oxidation
In this reaction, a red-brown solid (copper) is deposited and the blue colour fades.
Displacement reactions involving halogens
Halogens also displace each other from their respective salt solutions according to
their reactivity. This happens by oxidation of halide ions in the solution. For example,
chlorine is more reactive than iodine. Therefore, if we bubble chlorine through a
solution of potassium iodide, iodine is displaced. Iodide ions, I- in the solution are
oxidised (lose electrons). The electrons are gained by chlorine atoms, and become
chloride ions as shown below.
2 I– (aq) ––––– I2(g) + 2e– Oxidation
Cl2(g) + 2e– ––––– 2Cl–(aq) Reduction

Reduction
2I–(aq) + Cl2 (g) ––––– I2(s) + 2Cl-(aq) redox

–1 0 0 –1
oxidation
Note that chlorine is more reactive than bromine. Chlorine can also displace bromine
from potassium bromide solution. We therefore say that chlorine is a more powerful
oxidising agent than bromine and iodine. The order of oxidising power is the same
as the order of reactivity.
Chlorine High oxidising power
Bromine
Iodine Low oxidising power
150
1. Write both a stoichiometric and ionic equations for the reaction between
chlorine and potassium bromide solution.
2. What observations would you make during this reaction?
3. Which other halide can chlorine displace from the above reactivity series?
4. (i) Copy and fill the table below. Choose which metal will react with the metal
salt solution and put a tick (√) and which will not and put a cross (x).
(ii) Write equations for the reactions.
Metal salt solution Magnesium Copper Zinc
Magnesium sulphate
Copper(II) sulphate
Zinc sulphate
5. Aluminium is above iron in the reactivity series. Write an ionic equation to

show how aluminium displaces iron from its salt solution.
4.3 Electrochemical cell

Earlier, we mentioned that a chemical reaction can generate an electric current. This
is what happens in an electrochemical cell.
We will now see how an electric current is generated by the chemical reaction by studying
an electrochemical half-cell below, which is a metal electrode dipped into an electrolyte.
A metal e.g. Zinc
Solution containing ions

of the metal; in this case,
zinc ions
Fig 4.1: An electrochemical half-cell
A metal dipped in an electrolyte as shown in Fig. 4.1 above tends to form ions.
If a metal, M, is placed in a solution containing Mn+ ions, of the same metal, the metal
atoms may lose n electrons and go into solution as positive ions i.e.
M(s) ––––– Mn+ (aq) + ne- where; n = 1,2,3
The electrons, which are released accumulate on the metal surface, which becomes
negatively charged. The metal ions in the solution increase until some start to gain
electrons on the metal surface and form atoms.
151
Mn+(aq) + ne- –––– M(s)
The two reactions above take place at the same time and at the same rate. This is
represented as shown in the following equation.
M(s) Mn+(aq) + ne–
If metal M is zinc, the equation would be written as follows:
Zn(s) Zn2+(aq) +2e-
The ease with which metals lose electrons depend on their position in the reactivity
series. A metal, which loses electrons easily, will acquire a much bigger negative
charge on its surface, whereas a metal which loses electrons less easily will have a
much smaller negative charge on its surface as shown in Fig. 4.2.
Magnesium Copper metal

metal
Magnesium Copper(II)
sulphate solution sulphate solution
Fig 4.2: Comparison of the number of electrons on metal surfaces
The electrons which are released, accumulate on the metal surface. The metal becomes
negatively charged and attracts a layer of positive ions. Two layers of opposite charges
are formed. This results in a potential difference between the metal and a solution of
the metal ions. This potential difference is reffered to as the electrode potential of the
metal. The potential difference depends on the tendency of metals to form ions. The
greater the tendency for the metal to ionise, the greater the potential difference. For
example, in Fig. 4.2, magnesium forms ions more easily than copper. The magnesium
half-cell therefore, exhibit a higher potential difference. An arrangement like we have
in Fig. 4.2 where a metal strip is dipped in its salt solution is called a half-cell. It is
not possible to measure the electrode potential of one electrode but we can measure
the difference in potential of two electrodes. This can be done by connecting the two
electrodes by a metal wire and connecting the two solutions by a salt bridge in such
a way that ions can flow between them as shown in Fig. 4.3.
Each beaker with the metal rod and salt solution is the half-cell. Two half-cells
connected through the two electrodes using a metal wire and the two solutions with
a salt bridge containing a salt solution as shown in Fig. 4.3 above is known as an
electrochemical or voltaic cell.
Now, let us see how the chemical reactions generate electrical energy in zinc–copper
electrochemical cell.
152
Voltmeter
Direction of electron flow
Switch
Metal wire
Zinc rod
Copper rod
Salt
Plug of cotton wool Plug of cotton wool
bridge
2+
(KNO3) SO2– Cu
Zn2+ NO3– 4 K+
1M Zinc sulphate 1M Copper(II)
solution Zn2+ sulphate solution
Beakers
Fig. 4.3: An electrochemical cell
In the left-hand side beaker as shown in Fig. 4.3, the zinc rod dissolves by losing
two electrons to form zinc ions, Zn2+(aq).
Zn(s) –––– Zn2+(aq) +2e-
The electrons then flow through the external wire to the right-hand side beaker. The
copper(II) ions, Cu2+(aq), take these electrons and copper metal is deposited.
Cu2+(aq) + 2e- ––––– Cu(s)
The overall reaction is as follows:
Zn(s) + Cu2+(aq) ––––– Zn2+(aq) + Cu(s)
The overall reaction is an oxidation-reduction reaction. Oxidation always occurs at
the anode and reduction always occurs at the cathode of an electrochemical cell.
The Zn(s)|Zn2+(aq) half-cell is therefore the anode, and the Cu2+(aq)|Cu(s) half-cell
is the cathode.
The electrons are transported by the ions (anions) present in the solution up to the
electrode and through the wire to the other electrode. Look at Fig 4.3 and see how the
Zn2+(aq) and SO42- ions move into the salt bridge, while K+ and NO–3 ions diffuse
out of the salt bridge into the solution. Since electricity is a flow of electrons, the
arrangement as in Fig. 4.3 is called an electrochemical cell. The potential difference
between the two metal electrodes is measured by a voltmeter. It gives the voltage of
the cell, also known as the electromotive force (e.m.f). It is measured in volts and
given the symbol, E. The e.m.f of zinc - copper cell is 1.10V. The e.m.f varies with
temperature, concentration of the solution and state of the metal used.
153
The electrochemical cells as shown in Fig. 4.3 can be described by a line notation
as illustrated below.
Zn(s) Zn2+(aq) (1M) Cu2+(aq), (1M) Cu (s)
metal conducting ions in contact salt ions in contact metal conducting in

in left-hand with metal in bridge with metal in right-hand beaker.
beaker. left-hand right-hand
beaker. beaker.
Note: By convention, (i) the half-cell of the more reactive metal is placed on the left
hand side. (ii) Hydrogen electrode, if part of the cell is placed on the left.
It is very important to follow the above shorthand notation of the cell. The line
notation is based on the following conventions:
• | – A single vertical line represents a change in state or a phase between the metals
and their ions e.g. Zn(s)|Zn2+(aq).
• Within a half- cell, the reactants are written before the products e.g. zinc metal
(reactant) dissolves to form zinc ions (product), in the other half-cell, copper(II)
ions, Cu2+, (reactant) gain, electrons to form copper metal, Cu(s), (product).
• Concentrations of aqueous solutions are written in brackets after the symbol of
the ion (sometimes the concentrations are omitted).
• || – A double vertical line or a double dotted vertical line indicates the salt bridge
or a porous barrier connecting the half-cells.
• By convention, the more electropositive electrode (one that does not ionise
easily) is put on the right-hand side.
The e.m.f. of the cell is given by:
E cell = E (right-hand side electrode) – E (left-hand side electrode)
Or simply,
E cell = E RHS – E LHS.
The salt bridge can be a U-tube filled with electrolyte e.g.KNO3, NaNO3 or a
filter paper soaked in the electrolyte. It serves two main functions.
I. Completes the circuit by allowing ions carrying charge to move from one half-
cell to the other.
II. It provides positive ions (cations) and negative ions (anions) to replace those used
up at the electrodes and balance the charges on ions formed at the electrodes. For
example, at the cathode, Cu2+ ions gain electrons to form copper metal Cu(s) at
the cathode. This leaves many negative sulphate, SO42- ions. If CuSO4 solution
was used in the second half-cell, potassium, K+ ions from the salt bridge flow to
balance the increased negative charge at the cathode.
What happens when the electrochemical cell is used to do work?
154
• The zinc electrode becomes thinner and thinner as zinc atoms are oxidised to
Zinc ions (Zn2+), which go into solution.
• The copper electrode becomes thicker and thicker as copper(II) ions, Cu2+ in
the solution are reduced to copper metal which get deposited on the electrode.
• The concentration of Zn2+ ions at the anode increases and the concentration
of the Cu2+ ions at the cathode decreases.
Over a period of time, all the zinc dissolve and the cell eventually has to be replaced.
Experiment 4.4
To measure the voltage, (e.m.f.) of an electrochemical cell using different electrodes.
• beakers
• filter papers
• voltmeter capable of measuring positive and negative voltage 0-3V with zero
– centre.
• metal electrodes - copper, zinc, iron, magnesium, aluminium, silver.
• the respective metal salt solution of the above metals
Procedure
1. Assemble the apparatus as in Fig. 4.4
V Connecting wire
Copper rod Magnesium rod
Salt
bridge
Copper(II) sulphate (KNO3) Magnesium sulphate
Beakers
Fig. 4.4: Measuring the e.m.f of an electrochemical cell
2. Use copper electrodes throughout the experiment in the left-hand beaker.
3. In the beaker on the right-hand side, use an electrode of a different metal, which
must be inserted in its own electrolyte.
4. Note the voltage shown by the deflection in the voltmeter. Note whether the
deflection is –ve or +ve.
5. Record the voltage in your notebook. Indicate the voltage with (–) or (+) sign.
6. Arrange the list of the metals plus their voltage in your notebook, starting with
most negative (smallest value) and end with most positive (largest value).
7. Repeat procedure 4 and 5 using the different metals in their salt solutions.
8. What do you conclude?
• From your knowledge of reactivity series, which is the most reactive metal?
155
The list you have obtained is called electrochemical series. The most reactive metal
has the largest negative (-ve) voltage. This is the metal that loses electrons most easily.
We can conclude that the voltage difference is a measure of how easily metals lose
electrons forming ions. It also shows the strongest reducing agent. We are going to
discuss the electrochemical series in detail later in this unit.
1. State briefly what you understand by the following terms.
(i) electrode potential.
(ii) half-cell.
(iii) electromotive force.
2. (i) How is a salt bridge represented?
(ii) Write the line notation of cell made of the following metals
(a) Fe2+(aq) + 2e– ––––– Fe(s) – 0.44V
2+ –
(b) Pb (aq) + 2e ––––– Pb(s) – 0.13V
Standard electrode potentials

It has already been mentioned that it is impossible to measure the electrode potential of a
single half-cell. This implies that the electromotive force (e.m.f) can only be measured for
complete circuits with two electrodes. To measure the e.m.f of a single electrode, usually
a reference electrode is used as the second electrode. The e.m.f of the electrode of interest
is therefore the e.m.f value between the reference electrode and that particular electrode.
This reference electrode is also referred to as the standard electrode. Hydrogen has
been chosen as the standard electrode. The standard hydrogen electrode (Fig. 4.5) is
the reference electrode and is assigned electrode potential value of zero.
The measured e.m.f value between the electrode of interest and the standard
hydrogen electrode at standard conditions is referred to as the standard electrode
potential denoted by Eθ.
Note: The other half cells are usually compared to this standard half-cell (Fig. 4.5).
Hydrogen gas
in at 25˚C and
1 atm pressure
Bubbles of hydrogen
Platinised gas escaping
platinum
electrode
1M solution of
H+ ions
Fig 4.5: The standard hydrogen half-cell
156
The hydrogen half-cell
The standard hydrogen half-cell consists of the following:
• Hydrogen gas at 1 atmosphere pressure and 250C temperature.
• Platinised-platinum electrode immersed in1M H+ ions solution.
The platinised-platinum electrode is coated with finely divided platinum (i.e. it
is platinised). This increases the surface area so that a lot of hydrogen gas can be
adsorbed on the platinum and an equilibrium is established between the adsorbed
layer of H2 (g) and H+ ions in the solution as shown in the equation below.

1
2 H2(g) H+(aq) + e– Eθ = 0.00 volt
The standard electrode potential, Eθ, for the reference electrode is taken as zero. The
superscript θ denotes standard conditions. Where standard conditions are:
• 25˚C temperature
• 1 atm pressure
• hydrogen electrode immersed in 1 M H+ ion solution
• 1M concentration of ions in the solution of the other half-cell.
The inert platinum electrode acts as the connection between hydrogen gas H2 (g) and
hydrogen ions, H+ in the solution. The hydrogen electrode is represented as follows:
Pt(s) H2(g)|H+(aq)
Let us now see how the standard electrode potential of various metals can be
determined.
The standard electrode potential of zinc
e– flow
Hydrogen gas at
25˚C and 1 atm
Salt bridge
Zinc electrode
Platinum electrode
1M H+ions Zinc ions (Zn2+)
Fig. 4.6: Measuring the standard electrode potential of Zn(s) | Zn2+(aq) half-cell
In Fig. 4.6, zinc is placed in 1M Zn2+ ion solution and connected to standard hydrogen
half-cell. The cell diagram is represented as
Pt(s), H2(g) | H+(aq) || Zn2+(aq) | Zn(s) Eθ= –0.76 volts
157
Thus the standard electrode potential, Eθ, for zinc is – 0.76V.
Zinc loses electrons more readily than hydrogen. Therefore, zinc is the negative electrode.
Zinc reduces H+ions in aqueous solution to hydrogen gas (H2) by donating electrons i.e.
Zn(s) –––––– Zn2+(aq) + 2e- Eθ = +0.76V
2H+(aq) + 2e- ––––– H2(g) Eθ = 0.00V

The overall reaction of the cell is obtained by adding the two equations above i.e
Zn(s) + 2H+(aq) ––––– Zn2+(aq) + H2(g) Eθ = + 0.76V
Note: The two electrons cancel out as they occur on both sides of the equation.
The standard electrode potential for the half- cell Zn2+(aq) | Zn(s) is – 0.76V
(b) The standard electrode potential of copper
When the hydrogen electrode is connected to a copper electrode, the electrons flow
in the opposite direction as shown in Fig. 4.7.
The electron flow is from left half-cell to the right half-cell in the external circuit i.e.
from the hydrogen electrode to the copper electrode. This is because copper does
not lose electrons as readily as hydrogen i.e copper is lower than hydrogen in the
reactivity series. In this case, copper is the positive electrode. The standard electrode
potential, Eθ of copper is +0.34V. The cell can be represented as:
Pt(s) H2(g) | H+(aq) || Cu2+(aq) | Cu(s) Eθ = +0.34V
e– flow
H2gas at 25˚C
and 1 atm
Salt bridge
Copper electrode
Platinum electrode
1M H+ions 1M Cu2+(II) ions
Fig. 4.7: Measuring the standard electrode potential of Cu(s) | Cu2+(aq) cell
Note that the positive e.m.f. of the cell tells us that the right-hand side electrode is positive.
We can therefore define the standard electrode potential as follows:
The standard electrode potential, Eθ, is the potential of that half-cell relative
to a standard hydrogen half-cell under standard conditions.
158
Standard electrode potentials, Eθ, provide a measure of the relative oxidising
and reducing power of different species. Electrode systems are written showing
particles
gaining electrons. Gain of electrons is reduction; hence sometimes they are referred
to as reduction potentials. When all the redox systems are arranged in order of the
magnitude of their standard electrode potentials starting with the highest to the lowest,
the arrangement is called, the electrochemical series. Table 4.4 is an example of
electrochemical series. Notice that the relative value of Eθ gives a measure of the
strengths of the oxidising and reducing agents.
Table 4.4 Electrochemical series
Reaction Eθ, volts
+ -
K (aq) + e K(s) – 2.92 Strongest reducing
2+ -
Ca (aq) + 2e Ca(s) – 2.87 agent
Na+(aq) + e- Na(s) – 2.71
Mg2+(aq) + 2e- Mg(s) – 2.36
3+ -
Al (aq) + 3e Al(s) – 1.66
Zn2+(aq) + 2e- Zn(s) – 0.76 Reducing power
2+ -
Fe (aq) + 2e Fe(s) – 0.44 increases
Ni2+(aq) + 2e- Ni(s) – 0.25
Pb2+(aq) + 2e- Pb(s) – 0.13
+ –
2H (aq) + 2e H2(g) 0.00
Cu2+(aq) +2e- Cu(s) +0.34
I2(s) + 2e- 2I- +0.54
+ -
Ag (aq) + e Ag(s) +0.80 Oxidizing power
- -
Br2 (l) + 2e 2Br (aq) +1.09 increases
- -
Cl2(g) + 2e 2Cl (aq) +1.36
MnO4- (aq) + 8H+(aq) + 5e- Mn2+(aq) + 4H2O(l) + 1.51
F2 (g) + 2e- 2F-(aq) +2.87 Strongest oxidizing
agent
Note
The table only shows the conventional way of listing standard electrode potentials,
whether they are metals or non-metals. During calculations, if we reverse the equation
for a metal, the sign in front of the Eθ value will also change. For example:
Zn2+(aq) + 2e- ––––– Zn(s) Eθ = -0.76V
To show that zinc reacts by donating electrons, we reverse the equation as follows.
Zn(s) ––––– Zn2+(aq) + 2e- Eθ = +0.76V.
Note the following about the Eθ values in Table 4.4:
• The more negative the Eθ value, the more reactive the metal. It gives electrons
easily, hence it is a powerful reducing agent. It is also relatively difficult for the
159
ions formed to gain electrons. For example, if this metal is potassium(K) it is
difficult for potassium(K+) ion to gain electrons.
• The more positive the Eθ value is, the less reactive the metal. The metal atoms do
not donate electrons easily.An example of this is iron(Fe)
• For non-metals, the more +ve the Eθ value, the more readily that element gains
electrons. Since electrons are removed from another species, those elements are
strong oxidising agents. In Table 4.4. fluorine has the largest positive Eθ value;
+2.87V. It is the strongest oxidising agent in the table. It gains electrons most easily.
F2 (g) + 2e- ––––– 2F–(aq) Eθ = +2.87V.
To make it easy for us to understand, let us put some of the Eθ values in Table 4.4 in
a number line as shown below.
| | | | | | | | | | | |
-2.92 -1.66 -0.76 -0.44 -0.13 0.00 +0.34 +0.54 +0.80 +1.09 +1.36 +2.87volts
K Al Zn Fe Pb H2 Cu I2 Ag Br2 Cl2 F2
Best reducing agent Best oxidising agent
Increasing ease of loss of electrons Increasing ease of gain of electrons
Increasing strength of reducing agent Increasing strength of oxidising agent
Fig. 4.8: Some electrode potentials on the number line
What is the use of electrode potentials?
• to calculate e.m.f of a cell.
• to predict whether or not a redox reaction will occur.
Sample calculations using Eθ values
Place the Eθ values in a number line as shown above. Check the Eθ value on the right
hand side, (RHS) and subtract the Eθ value on the left hand side (LHS).
By convention, the e.m.f of the cell is obtained from the following relationship.
Eθ cell = Eθ(RHS electrode) – Eθ(LHS electrode)
Note: If the final value above is +ve, it indicates that the reaction will occur.
Example 1
Calculate the e.m.f. of an electrochemical cell, Zn(s) | Zn2+(aq) || Cu2+ | Cu(s). Refer
to Table 4.4 for Eθ values.
Solution
–0.76 0.00 +0.34
Cu is on the RHS and Zn on the LHS of the number line, therefore e.m.f of the cell
= EθCu - EθZn
= +0.34 – (-0.76) V
= +1.10 V
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Note: Whenever, you choose a pair of electrodes to construct a cell, you will always
have one on RHS and the other on LHS on the number line irrespective of whether
they both have positive values or negative values or one has a positive value and
the other, a negative value.
Remember the following:
• the more reactive a metal is, the more negative the Eθ value and is always placed
on the LHS when we draw an electrochemical cell.
• oxidation-reduction reactions that have a positive overall cell potential are
spontaneous.
Example 2
A student wanted to find out whether a reaction would occur or not. The student set
up the experiment as shown in Fig. 4.9.
Copper(II) Zinc sulphate

sulphate solution solution
Zinc Copper
(a) (b)
Fig. 4.9: Displacement of metals from their salt solutions
• Using the standard electrode potentials, Eθ, given on Table 4.4, explain in which
beaker the reaction took place and state the observations the student made. Write
an ionic equation for the reaction.
Solution
The problem demands that we use Eθ values to solve it.
From Table 4.4, the half-reactions given are:
Zn2+(aq) + 2e- ––––– Zn(s) Eθ = -0.76V.
Cu2+(aq) + 2e- ––––– Cu(s) Eθ = +0.34V.
The –ve Eθ value indicates that this metal loses electrons easily. These electrons are
taken up by Cu2+ ions(oxidising agent).This is the equation we must reverse first
then add up the two equations as follows:
Zn(s) ––––– Zn2+(aq) + 2e- Eθ = +0.76V
Cu2+(aq) + 2e- ––––– Cu(s) Eθ = + 0.34V
Overall reaction:- Zn(s) + Cu2+(aq) –––– Zn2+(aq) + Cu(s) Eθ = +1.10V
The reaction will take place in beaker (a) because the overall Eθ value is positive, i.e
+1.10V. Cu2+ ions are reduced by zinc and displaced from the solution as copper.
Observation: The blue colour fades and a red-brown solid, which is copper is
deposited. The ionic equation for the reaction is the same as overall equation above.
161
Ionic equation
Zn(s) + Cu2+(aq) ––––– Zn2+(aq) + Cu(s)
Now, let us reverse the half reaction of copper in beaker (b)
Cu(s) ––––– Cu (aq)+2e- Eθ = -0.34V
Zn2+(aq) + 2e- ––––– Zn(s) Eθ = –0.76V
Overall equation Cu(s) + Zn2+(aq) ––––– Cu2+(aq) +Zn(s) Eθ = - 1.10V
The reaction cannot take place because Eθ value is negative, i.e.–1.10V.
A negative final Eθ means that the reaction is not possible. In this case, it means
copper cannot displace zinc from its salt solution.
Example 3
Can chlorine displace iodine from a solution of potassium iodide?
Use electrode potentials given in the equation below to answer the question.
Cl2 (g) + 2e- ––––– 2Cl-(aq) Eθ = +1.36V
I2(s) + 2e- ––––– 2I-(aq) Eθ = +0.54V
Solution
+1.36V is a greater value than + 0.54V. This means Cl2 accepts electrons more readily
than I2 (see the ‘number line’ below).
We reverse the 2nd equation and add the two equations.
Cl2 (g) + 2e- ––––– 2Cl- (s) Eθ = +1.36V

-
2I (aq) ––––– I2(s) + 2e Eθ = - 0.54V
-
Overall equation: Cl2 (g) + 2I-(aq) ––––– 2Cl-(aq) + I2(s) Eθ = +0.82V

The answer has a positive value. Therefore, chlorine can displace iodine from
potassium iodide solution.
• Alternatively, we can put the values on a number line and subtract the smaller
value (on LHS) from the greater value (on RHS) as shown below:
| | |
0.00 +0.54 +1.36
H2 I2 Cl2
θ θ θ
E = E RHS – E LHS
Eθ = Eθ Cl2 – Eθ I2
= +1.36 – 0.54
= +0.82V
• Now, show that iodine cannot displace chlorine from potassium chloride solution.
162
Use the electrode potentials in Table 4.4
1. Which of the following species can be reduced by Ni?
I2, Cu2+, Fe2+
2. Calculate the standard e.m.f of each of the following cells.
(a) Ag(s) | Ag+ || Cu2+(aq) | Cu(s)
(b) Fe(s) | Fe2+(aq) || Cu2+(aq) | Cu(s)
(c) Zn(s) | Zn2+(aq) || Ni2+(aq) | Ni(s)
3. The letters A,B,C,D, and G given below do not represent actual symbols of elements.
Use the Eθ values given to answer the questions that follow.
Electrode reaction Eθ (volts)
A2+(aq) + 2e- –––– A(s) -2.90
B2+(aq) + 2e- –––– B(s) -2.38
C+(aq) + e- –––– 1/2C2(g) 0.00
D2+(aq) + 2e- –––– D(s) +0.34
1 G (g) + e- –––– G –
(aq) +2.87
2 2
(i) Which element is likely to be hydrogen? Give a reason for your answer.
(ii) Which element is the strongest reducing agent? Give a reason for your answer.
(iii) Write the representation of a cell obtained when A and D are combined and
calculate e.m.f. of that cell.
4.4 Electrolysis
Electrolysis, as we learnt in Form 2, is the decomposition of a compound by passing
an electric current through it. The compound being electrolysed is called electrolyte.
The electrolyte is a compound which when in solution or molten form, conducts an
electric current and is decomposed by it.
In preparing electrolytes for electrolysis; we either melt solid compounds or
dissolve them in water.
The role of water in electrolysis
Water is a good solvent. This is because its molecules are polar i.e. its oxygen molecule
is partially negative whereas hydrogen atom is partially positive. Because of this,
the oxygen atoms are attracted by the positive ions on the surface of solid while the
hydrogen atoms are attracted by the negative ions on the surface of the solid. The
solid in this case is the ionic compound being disssolved. The attraction between
the water molecules and the ions in the solid may be so intense that it overcomes
the forces of attraction holding the ions in the solid together. When this happens,
the solid dissolves. The ions then become free to move in the aqueous solution and
therefore, can conduct an electric current during electrolysis.
163
Water is a weak electrolyte. It is only slightly dissociated. Its molecules dissociate
into hydrogen ions (H+) and hydroxide ions (OH–) i.e.
H2O(aq) H+(aq) + OH–(aq)
During electroysis, the hydrogen ions(H+) are attracted to the cathode and hydroxide
ions (OH–) to the anode. They compete with the ions from dissolved salt for discharge
at the respective electrodes but, at each electrode, only one type of ions get discharged.
This is called preferential discharge. Now let us see how this preferential discharge
is influenced by certain factors.
Selective discharge during the process of electrolysis
When two or more cations, e.g. Na+ and H+, or anions e.g. Cl–, OH– and SO42– migrate
to the same electrode, one is selected and is discharged preferentially. To understand
this, let us carry out the following experiment.
Factors affecting preferential discharge

We are already aware that during electrolysis, certain ions are preferentially
discharged at their respective electrodes. There are factors which influence the ions
to be discharged. The following are some of the factors.
1. Position of the metal in the electrochemical series
The ease of discharge of ions during electrolysis depends on their position in the
electrochemical series. Metals in this series are placed in an increasing order of their
ability to lose electrons whereas non-metals are placed in an increasing order of their
ability to gain electrons. The most reactive metals e.g. potassium release electrons
easily to form ions. These cations require more energy to gain back electrons i.e. to
be reduced and therefore, are more difficult to discharge. Ease of discharge therefore
increases down the electrochemical series as shown in Table 4.9.
Table 4.9 The ease of discharge of ions during electrolysis of various solutions
Cations (+ve ions) anions (–ve ions)
Ease of K+ SO42–
discharge Na+ NO3– Ease of discharge of
of cations Ca2+ Cl -
anions increases
increases Mg2+ Br - downwards
downwards Zn2+ I -
Fe2+ OH-
Pb2+
H+
Cu2+
Ag+
164
2. Concentration
We have seen that ions lower in the electrochemical series will preferentially be
discharged under normal conditions. However, if the ion that requires more energy
to discharge is present in greater concentration than the other one lower in the
electrochemical series, it will be discharged preferentially. For example, in electrolysis
of dilute sodium chloride solution OH- ions are discharged preferentially to give
oxygen since Cl– ions are present in low concentrations. But, if the concentration
of Cl– ions is much higher than OH– ions, the Cl– ions are discharged first to give
chlorine as seen in the electrolysis of brine.
Note that the number of Cl– ions in the solution gradually decreases as their
discharge continues. When they are no longer more than OH– ions, the OH– ions
will be discharged preferentially to produce oxygen, because they are lower in
electrochemical series than Cl– ions and are easier to discharge.
3. Nature (type) of electrode
The choice of electrodes during electrolysis can alter the order of discharge of the
ions. For example, if a copper electrode is used as the anode during electrolysis of
copper (II) sulphate solution, neither OH– nor SO42– ions, are discharged. Instead, the
copper electrode dissolves. But if we change and use graphite as the anode, OH- ions
are discharged and we get oxygen. In this case, we say that the nature of the electrode
i.e. whether active or inert, has influenced preferential discharge of ions.
Another example where the type of electrode can change the order of discharge of
ions is in the electrolysis of concentrated sodium chloride solution using a mercury
cathode. Na+ ions are discharged instead of H+ ions, which should be the case if we
consider the position of sodium in the electrochemical series. Sodium metal forms
an amalgam with mercury in the process.

1. Name the factors that affect preferential discharge.
2. (a) Two students set up an electrolytic cell and electrolysed copper(II) sulphate
solution using carbon electrodes. What did they see at the anode?
(b) They repeated the experiment again, but this time they used copper electrodes
instead of carbon. What difference did they notice between their two experiments?
Electrolysis of dilute sodium chloride

Experiment 4.5
To investigate preferential discharge in the electrolysis of dilute sodium chloride solution.
• beaker
• carbon (graphite) rods
165
• wooden splint
• connecting wires fitted with crocodile clips
• dry cells (1.5V) with cell holder/ battery
• stirrer
• bulb/ ammeter
• test tube rack with test tubes
• distilled water
• sodium chloride
Procedure
1. Set up the apparatus as in Fig 4.10
Battery
Oxygen gas
Connecting
Switch wire
Hydrogen gas
Graphite
anode (inert) Graphite
cathode (inert)
Dilute sodium
chloride solution
Fig. 4.10: Electrolysis of dilute sodium chloride solution
2. Half-fill the beaker with a dilute solution of sodium chloride.

3. Switch on the current. What do you observe on the electrodes?
4. What is the colour of the gas collected at the
(a) anode? (b) cathode?
5. Test the gases collected with a glowing and burning splints.
6. Copy Table 4.7 in your notebook and record your observations.
Table 4.4: Electrolysis of dilute sodium chloride solution
Gas collected at Colour Test with glowing/ burning
splint
Anode
Cathode
A colourless gas, which re-lights a glowing splint, is collected at the anode. The gas
is therefore oxygen. At the cathode, a colourless gas is collected which burns with
a ‘pop’ sound. This gas is therefore hydrogen.
Now, let us see how these gases are formed at the respective electrodes. We start
by finding out which ions are present in the electrolyte, then see how they migrate
and finally find out which ones are selectively discharged.
166
Ions present
From sodium chloride Na+(aq), Cl- (aq)
From water H+(aq), OH- (aq)
The positive ions (cations), Na+ and H+ migrate to the cathode. The negative ions,
(anions) Cl- and OH-, migrate to the anode. This is because they are attracted by the
oppositely charged electrodes.
At the cathode At the anode

Ions present Na+(aq), H+(aq) Ions present Cl-(aq), OH-(aq)

Both ions move to the cathode. H+ ion Both ions move to the anode. OH- ion
is discharged in preference to Na+ ion is discharged because it is lower in
because it is lower than Na+ion in electrochemical series
the electrochemical series. It gains OH- is discharged by losing an electron
an electron to form H atom.

H+(aq) + e– ––––– H (g) OH– (aq) –––– OH (g) + e-

The hydrogen atoms combine to form Four OH– ions are discharged, the OH
H2(g) molecules. groups interact to form one mole of
H(g) + H(g) ––––– H2(g) oxygen and two moles of water as
shown below, releasing 4 electrons
Therefore; which move to the cathode.
2H+(aq) + 2e– ––––– H2(g) Overall reaction
But the 4e–s produced at the anode 4OH– (aq) –––– O2 (g) + 2H2O(l) + 4e–
must react hence overall equation is
4H+(aq) + 4e– ––––– 2H2(g)
Note: The 4e– released at the anode must be taken up by H+ ions. So, we must multiply
the last equation under cathode by 2 to get the overall equation.
Finally, Na+ and Cl– ions remain in solution forming sodium chloride; solution of
higher concentration.
Experiment 4.5
To investigate preferential discharge in the electrolysis of dilute sulphuric(VI) acid.
• a standard set up of apparatus used for electrolysis of water, called Hofmann
voltameter is shown in Fig 4.12 (a) or we can use a set up as shown in Fig.
4.12 (b) if apparatus (a) is unavailable.
• sulphuric(VI) acid.
• water.
167
Procedure
1. Put some dilute sulphuric acid in a beaker.
Reservior Oxygen
Connecting
(1 vol)
Battery wire
Oxygen Hydrogen Switch
(1 vol) gas (2 vols)
Hydro-
Dilute
Platinum gen gas
sulphuric
anode (2vols)
acid
Platinum Platinum Platinum
electrode electrode cathode
Dilute
sulphuric
Battery acid
(a) Hofmann voltameter (b) Alternative set-up
Fig. 4.12: Electrolysis of dilute sulphuric acid

2. Assemble the apparatus as shown in Fig 4.12 (b).
4. What do you observe at the electrodes? Record your observations in your
notebook.
5. At which electrode do we collect more gas?
6. Test the gases collected with a burning and a glowing splint. Record the results
in your notebook.
7. What can you conclude?
Ions present
From sulphuric(VI) acid, H+(aq), SO42– (aq)
From water H+(aq), OH– (aq)
Ions H+(aq) Ions SO42- (aq), OH- (aq)

H+ions moves to the cathode Both ions move to the anode.
and gain an electron to form OH- ion is lower in the electrochemical series
H atom. and is therefore discharged preferentially to
SO42– ion by loss of one electron.
H+(aq) + e- ––––– H (g)
Since hydrogen is a diatomic gas, OH- (aq) ––––– OH (g) + e-
the atoms combine to form a The OH(g) ions interract to form 1 mole of O2
hydrogen molecule. and 2 moles of water
Overall ionic equation.
168
H (g) + H (g) –––– H2 (g) 4OH-(aq) –––– 2H2O(l) + O2 (g) + 4e–
The 4e– from the anode are Note
taken up by H+ ions giving OH- (aq) ions come from water i.e.
2 moles of hydrogen gas. H2O (l) OH–(aq) + H+(aq)
–
when the OH are discharged, the equilibrium
Overall ionic equation is disturbed. Forward reaction is favoured and
more water dissociates to replace the discharged
4H+(aq) + 4e- –––– 2H2(g) OH–(aq) ions. As a result, more and more
discharge takes place.
This also increases the concentration of H+ (aq)
ions at the cathode. More H+ ions are
therefore discharged at the cathode.
The volume of hydrogen liberated at the cathode is twice the volume of oxygen
produced at the anode. Explain why.
• Bromophenol blue turns yellow in acidic solutions and blue in alkaline solutions.
What would happen if we added an indicator such as bromophenol blue into
this apparatus?
OH– ions are being used up but water ionises to replace them. At the cathode, H+
ions are being used up but more are being replaced by ionisation of water molecules.
Therefore, the indicator should turn yellow at the cathode because of presence of H+
ions and blue at the anode because of presence of OH- ions.

1. During electrolysis of dilute sulphuric(VI) acid, at which electrode does oxidation
take place?
2. In the electrolysis of water, at which electrode will hydrogen be produced?
Give a reason for your answer.
Electrolysis of magnesium sulphate solution

Experiment 4.6
To investigate preferential discharge in the electrolysis of magnesium sulphate solution.
• battery/dry cells
• carbon electrodes
• beaker
• bulb
• magnesium sulphate solution
169
Ions present
From water, H2O(l) ––––– H+(aq), OH- (aq)
From magnesium sulphate, Mg2+(aq), SO42- (aq)
Procedure
1. Set up the apparatus as shown in Fig. 4.13 below.
Oxygen gas Battery
Connecting
Switch wire
Hydrogen gas
Platinum
anode Platinum
cathode
Magnesium sulphate
solution
Fig. 4.13: Electrolysis of magnesium sulphate

2. Half-fill the glass beaker with magnesium sulphate solution.
4. Test the gases produced at the cathode or anode using both glowing or lighting
splint.
5. Record your observations.
What would you observe on the electrodes?
Name the product at the:
(i) cathode
(ii) anode
Write ionic equations to show how the products are formed at the:
(i) cathode
(ii) anode
During electrolysis of magnesium sulphate solution, the movement of ions is as follows.
Anode Cathode
OH– and SO42– ions migrate here H+ and Mg2+ions migrate here
OH– ions are preferentially H+ ions gain electrons and are
discharged because they are discharged preferentially to Mg2+ ions
lower in the electrochemical because they are lower in the
series. Oxygen is liberated electrochemical series forming
as shown in the equation below hydrogen gas.
4OH–(aq) ––– 2H2O(l) + O2(g) + 4e– 2H+(aq) + e- –––– H2(g). Account for
the 4e–s from the anode.
170
Electrolysis of brine
Experiment 4.7
To investigate preferential discharge in the electrolysis of brine (concentrated sodium
chloride solution).
• The apparatus is the same as in experiment 4.5 and the set up is as in Fig. 4.11
or glass cell fitted with inert electrodes such as platinum or carbon as in
Fig 4.11 below.
• 1M sodium chloride solution.
Procedure
1. Set up the apparatus as in Fig. 4.11
Chlorine gas Hydrogen gas
Conc. sodium Glass cell

chloride
solution (Brine)
Carbon cathode
Carbon anode
Switch
Battery
Fig. 4.11: Electrolysis of brine

2. Half-fill the beaker or glass cell with 1M sodium chloride solution.
4. Note the colour of the gas collected at the anode and the cathode
5. At which electrode is a gas with a smell produced?
6. Test the gas produced at each electrode with a burning splint.
At which electrode does the gas burn with a “pop” sound?
When the circuit is completed, bubbles are observed at the electrodes. A green-yellow
poisonous gas which has a choking irritating smell is collected at the anode. This gas
bleaches moist litmus papers and therefore the gas is chlorine. At the cathode, a
colourless gas which burns with a ‘pop’ sound is collected. This gas is therefore
hydrogen.
Ions present
From sodium chloride Na+(aq), Cl- (aq)
171
Na+(aq), H+ Cl- (aq), OH- (aq)
H+ ions are discharged in preference to Although OH- ion is lower in the
Na+ ions because H+ ion is lower in electrochemical series than Cl-, the
electrochemical series than Na+ ion. concentration of Cl– ions at the
2H+(aq) + 2e- ––– H2 (g) cathode is greater than the OH- ions.
Therefore, Cl- ions are discharged in
preference to OH- ions
2Cl-(aq) –––– Cl2 (g) + 2e-
Note the following
(a) The concentration has determined the product at the cathode.
(b) H+ and Cl- ions are discharged leaving Na+ and OH- ions. Finally, sodium
chloride solution is converted to sodium hydroxide solution.
• What would be formed if the chlorine produced was allowed to react
with sodium hydroxide solution?
• Write an ionic equation for the reaction.
Chlorine would react with sodium hydroxide solution to form sodium hypochlorite
which is a bleaching agent, and sodium chloride.
Ionic equation.
Cl2 (g) + 2OH-(aq) ––––– Cl– (aq) + OCl– (aq) + H2O (l)

1. Write the equations that occur at the electrodes during the electrolysis
of dilute and concentrated sodium chloride solution.
2. How would you identify the product at the anode in each case?
Electrolysis of dilute sulphuric(VI) acid

Electrolysis of dilute sulphuric acid is also called the electrolysis of water. By itself,
water is a very poor conductor of electricity because it is a weak electrolyte. We
therefore add an electrolyte to water to provide more ions that flow through the
solution thereby completing the electric circuit. Sulphuric acid is a strong electrolyte
and when added to water, it provides ions.

Electrolysis of copper(II) sulphate
Experiment 4.8
To investigate how nature of electrode affects preferential discharge
172
Electrolysis of copper(II) sulphate solution using inert electrodes
Inert electrodes are substances like carbon (graphite) or platinum. They take no part
in electrolysis except to carry electrons to and from the electrolyte.
• battery/dry cells
• carbon rods
• beaker
• bulb (6V) or ammeter
• Copper (II) sulphate solution
Procedure
1. Half-fill a beaker with copper(II) sulphate solution.
2. Set up the apparatus as shown in Fig. 4.14.
Switch
Bulb
Crocodile clips
Carbon anode
(inert)
Carbon cathode (inert)
Beaker Copper(II) sulphate

solution
Fig. 4.14: Electrolysis of copper(II) sulphate using inert electrodes

3. Switch on the current and after a short while, observe what happens on the
carbon electrodes at the:
(i) anode
(ii) cathode
4. Record your observations in your notebook.
5. What do you conclude?
Ions present
From copper (II) sulphate, Cu2+(aq), SO42–(aq)
From water H+(aq), OH–(aq)
• Cu2+(aq), H+(aq) both move to the • SO42– (aq), OH– (aq) both move to the
cathode. anode,
• Cu2+ ions gain electrons, to form • OH– ions preferentially lose electrons
copper which appears as a brown being lower in the electrochemical series.
173
deposit, at the cathode i.e They combine to form water and oxygen
Cu2+ ions are preferentially
discharged.
Ionic equation: Ionic equation.
Cu2+(aq) + 2e– –––– Cu(s) 4OH–(aq) ––– 2H2O(l) + O2 (g) + 4e–
Account for the 4e–s from the anode. Bubbles of oxygen gas are observed at
the anode.
Copper(II), Cu2+, ions, give copper(II) sulphate solution the blue colour. As they are
discharged and deposited at the cathode as copper solid, the colour of the solution fades
and if we continue with electrolysis the solution finally turns colourless and acidic.
• If we continue passing electricity in the colourless solution what would be the
product at:
(i) cathode?
(ii) anode?
Note
Further electrolysis of the colourless solution would give the same products as
electrolysis of dilute sulphuric acid.
Experiment 4.9
Electrolysis of copper(II) sulphate solution using copper electrodes.
• as in experiment 4.8 but using copper electrodes
• balance (sensitive)
• distilled water
• propanone
Procedure
1. Put copper(II) sulphate solution in a beaker.
2. Clean the copper electrodes until they shine.
3. Weigh the electrodes and record the mass in your notebook as in Table 4.7 below.
4. Set up the apparatus as in Fig. 4.15 and switch on electric current.
Battery
Copper anode
loses mass Copper cathode
gains mass
Copper(II) sulphate
solution
Fig. 4.15: Electrolysis of copper(II) sulphate using copper electrodes
174
5. After 10 minutes, note the colour of the electrolyte and rinse the electrodes with
distilled water.
6. Dip the electrodes in propanone and then let propanone dry.
7. When dry, re-weigh the electrodes.
8. Record the mass after the experiment as shown in Table 4.7.
• Why must electrodes be cleaned before electrolysis?
• Why must the electrodes be washed with distilled water and propanone
after electrolysis?
Table 4.5: Results of electrolysis of copper(II) sulphate solution using copper
electrodes
Before passing After passing
electricity electricity
Colour of copper(II)
sulphate solution
Mass of electrodes
Change in mass of
electrodes
The electrodes must be cleaned to remove any oxide that might be on the surface.
The electrodes are washed with water and propanone to ensure they are completely
dry.
Ions present:
From copper(II) sulphate,Cu2+(aq), SO42- (aq)
Cu2+(aq), H+(aq) SO42-(aq) , OH-(aq)
These ions move to the cathode. Cu2+ These ions move to the anode. We would
ions are lower in electrochemical expect OH– ions to be oxidised. But
series and are preferentially discharged because of the nature (type) of
by gaining electrons to form a brown electrodes used i.e copper; none of the
solid which is copper. ions is discharged. Instead,copper,
electrode dissolves i.e.
Cu2+(aq) + 2e– ––––– Cu(s) Cu(s) ––––– Cu2+(aq) + 2e–
Copper is deposited on Copper is an active electrode and it
the cathode as shown in Fig. 4.15 and it therefore gets dissolved. This process
causes an increase in mass of cathode. is called electrode ionisation and it
causes a decrease in mass.
175
Note: Copper(II), Cu2+, ions make copper(II) sulphate solution blue. For each ion
removed at the cathode, it is replaced when copper dissolves at the anode. Therefore,
the solution remains blue and the concentration of the solution remains constant.
When we electrolyse copper(II) sulphate solution using copper electrodes, the mass
of both electrodes change. The anode loses mass while the cathode gains mass. The
loss in mass at the anode is equal to the mass gained at the cathode (see Fig. 4.16).
Remember that metals are always formed at the cathode. This is the reason why even
if we use carbon (graphite) as the cathode, the metal will still be deposited on it.
Battery
Anode Cathode
gain in mass
Loss in
mass Copper(II) sulphate solution
Fig. 4.16: Loss in mass at the anode is equal to gain in mass at the cathode
Table 4.6 Summary of electrolysis of some aqueous solutions

Electrolyte Electrodes Reaction at the anode Reaction at the cathode
- –
Dilute sulphuric(VI) graphite/platinum 4OH (aq)–– 2H2O(l)+O2(g) +4e 2H+(aq)+2e- –– H2(g)
acid (water)
Dilute sodium
chloride. graphite/platinum 4OH-(aq) –– 2H2O(l)+O2 (g) +4e- 2H+(aq)+2e- ––– H2(g)
Concentrated sodium
chloride (brine) graphite/platinum 2Cl–(aq) ––– Cl2 (g) +2e– 2H+(aq)+2e– ––– H2 (g)
Magnesium sulphate graphite/platinum 4OH–(aq) ––– 2H2O(l) + O2(g)+4e– 2H+(aq)+2e– ––– H2 (g)
Copper(II) sulphate carbon/platinum 4OH–(aq) ––– 2H2O(l)+O2(g)+4e– Cu2+(aq)+2e– ––– Cu(s)
Copper(II) sulphate copper Copper dissolves Copper deposited
Cu(s) ––– Cu2+(aq) + 2e– Cu2+(aq)+2e–––– Cu(s)
Quantity of electricity
We have seen that when we pass electricity through an ionic compound in molten or
solution form, it is decomposed and we get products at the electrodes. Experiments
have shown that the mass or volume of elements of the products formed depends on
the following factors:
1. amount of electricity passed.
2. length of time taken to pass the steady current.
3. charge on the ions of the element making electrolyte.
176
The quantitative laws relating the amount of
electricity passed during electrolysis, to the mass or
volume of elements formed at the electrodes were
first formulated by Michael Faraday.
Fig. 4.17: Michael Faraday

(1716-1867).
The coulomb
The coulomb is the practical unit used to measure the quantity of electricity or charge.
An electric current is produced in the opposite direction to the flow of electrons in
a circuit.
By definition, one coulomb (1 C) of charge is transferred if a current of 1-ampere
(1 A) flows through a circuit for 1 second (1 s)
i.e. 1C = 1 amp/sec or (As–1)
Generally, if Q coulombs of electricity flow along a wire for (t) seconds, the electric
current (I),produced is given by :
Q
I = we can re-arrange the equation to get Q as:-
t
Q = I × t
(Charge in) Current in time in
coulombs Amperes
OR
coulombs amperes × seconds
C = A × s
In this section, we are going to look at these laws and learn how to use them in
determining the quantity of substances deposited during electrolysis.
Example
Calculate the quantity of electricity passed when a current of 0.6 ampere flow for
50 minutes.
Solution
Q = It Or C=A×s
Substituting values given
C = 0.6 × (50 × 60)
= 1800 C
177
Therefore,the quantity of electricity passed is 1800 C
1. In an experiment, a total of 4,820 coulombs were passed. x amps were passed
for 161minutes. Find the value of x.
2. During the electrolysis of a molten binary compound, a current of 2 amperes
was allowed to flow. If a total of 3600 C were passed, how many minutes was
the compound electrolysed?
3. A student bought a torch bulb marked 0.25A. How much charge flows if the
student uses the torch for 15 minutes?
Farady’s first Law of electrolysis

Experiment 4.10
To determine the amount of copper liberated during electrolysis using different
quantities of electricity.
• sensitive balance (electrical/digital)
• 2 strips of copper electrodes (same size)
• battery / dry cells 6V
• rheostat (variable resistant)
• emery paper
• ammeter /stop clock
• copper(II) sulphate solution
Procedure
1. Set up the circuit as shown in Fig 4.18.
2. Fill the beaker to about two-thirds with dilute copper(II) sulphate solution.
Battery
Ammeter Rheostat
Copper anode
Copper cathode
Copper anode Deposited copper
dissolves Copper(II) sulphate
solution
Fig. 4.18: Investigating the amount of copper deposited by different quantities of
electric current
1. Clean the copper electrodes with emery paper until they shine.
2. Weigh the electrode attached to the cathode.
178
3. Place both electrodes into the solution.
4. Start the stop clock/stopwatch and simultaneously, complete the circuit by closing
the switch.
5. Adjust the rheostat to obtain a steady current of about 0.2 to 0.5A.
6. Switch off the current after every fifteen minutes.
7. Record the current passed (in amperes) and time (in seconds) in a table similar
to Table 4.7.
8. Remove the cathode electrode from the electrolyte, rinse it with distilled water,
then dip it in propanone or ethanol and let it dry.
9. Weigh the cathode and determine the change in mass. Record this as mass of
copper deposited in Table 4.7.
10. Repeat the experiment using different quantities of electricity as shown in Table
4.7.
Current (A ) time(s) Quantity of electricity Mass of copper
(15min × 60s) Q = It deposited (g)
0.5 600 300 0.098
1.0 600 600 0.196
1.5 600 900 0.392
2.0 600 1200 0.784
Draw a graph of copper deposited against quantity of electricity from the results in
Table 4.7 above.
• What relationship do you notice between the quantity of electricity passed and
the mass of copper deposited?
When the quantity of electricity is doubled, the mass deposited is also doubled. The
relationship between the amount of copper deposited and the quantity of electricity
passed can be shown graphically as shown in Fig 4.19.We get a straight line, which
passes through the origin. This indicates that the mass of copper deposited is directly
proportional to the quantity of electricity passed.
179
0.20
Mass of 0.15
copper
deposited 0.10
0.50
0.0
200 400 600 800 1000 1200
Quantity of electricity (coulombs) (Q)
Fig. 4.19: Graph of mass of copper deposited against quantity of electricity passed
The famous scientist Michael Faraday did much of his work on electrolysis. He
expressed the results of the many experiments he did in the law named after him.
Faraday’s first law of electrolysis can be stated as follows.
The amount of substance consumed or produced at one of the electrodes
during electrolysis is directly proportional to the amount of electricity that is
passed through the electrolytic cell.
From the above experiment, we have seen that it is possible to measure the mass of
an element produced at an electrode during electrolysis. From such experiments, we
can work out the quantity of electricity that would give 1 mole to the element.
Example
A student set up an experiment for the electrolysis of copper(II) sulphate solution.
A current of 0.5A was passed through the circuit for 3860 seconds. A mass of 0.64
g of copper was deposited.
(i) Which electrode gained mass?
(ii) How many coulombs are needed to deposit one mole of copper?
(R.A.M of Cu = 64)
Solution
(i) The cathode gained mass
(ii) Quantity of electricity(Q) = Current × time
(in amps) (in seconds) i.e
Q = It
= 0.5 × 3860
= 1930 C
This means 1930C of electricity deposited 0.64 of copper.
However, we know that 1 mole of copper has a mass of 64 g. From the relative atomic
mass (RAM) given we then say:
If 1930 C can deposit 0.64g of copper
x C would deposit 64g of copper.
180
Cross multiply and solve for x.
x = 1930 C × 64 g
0.64 g
= 193,000 C
OR
Working from mole conversions:-
1 mole of Cu = 64 g
y mole of Cu = 0.64 g.
Cross multiply and solve for y.
y = 0.64 g = 0.01mol
64 g
1930C deposited 0.01 mol
x C would deposit 1 mol
x = 1930 C × 1 mol
0.01 mol
= 193,000 C

1. A current of 2.0 amperes was passed through molten sodium chloride for a
period of 161 minutes. 4.6g of sodium were deposited at the cathode. How
many coulombs of charge would give 1 mole of sodium? (Na = 23)
2. During electrolysis, a current of 1A was passed through molten lead(II) bromide
for 1930 seconds. 2.07g of lead were collected.
(i) On which electrode was lead deposited? Give a reason.
(ii) Write an ionic equation to show how lead was formed.
(iii) Calculate the quantity of electricity that would deposit 1 mole of lead.
(Pb = 207)
We have seen how to work out the quantity of electricity (charge) needed to deposit 1
mole of an element. Now, let us see how we use the quantity of electricity (coulombs)
to work out the charge of an ion.
Determining charges carried by ions using quantity of electricity used
The charge on an ion, whether a cation or anion, depends on its valency. It depends on
the number of electrons lost, for cations or number of electrons gained, for anions.
The Faraday’s Constant
It has been found through many experiments that when molten compounds and
aqueous solutions are electrolysed, the quantity of electricity needed to produce one
mole of atoms of any element is always 96500 coulombs or a multiple of 96500C.
For example, in the previous example, it was found that 193,000C of electricity
181
were required to deposit 1 mole of copper. This is twice 96500C i.e. (96500C × 2) =
193000C. This is also true with other elements. Table 4.8 shows how much charge
is required to produce one mole of some of the atoms
Table 4.8 The charge needed to produce 1 mole of different elements.
Element Ion Charge on ion Charge needed to Number of
produce 1 mole Faradays
(C)
Ag Ag+ +1 96500 1F
Na Na+ +1 96500 1F
H H+ +1 96500 1F
Cu Cu2+ +2 193000 = 2 × 96500 2F
Mg Mg2+ +2 193000 = 2 × 96500 2F
Al Al3+ +3 289500 = 3 × 96500 3F
Br Br- -1 96500 1F
Note that 96,500 coulombs is called the Faraday’s constant. It’s symbol is F.
It was named in honour of Michael Faraday.
Now, let us analyse the equations for discharging some ions in Table 4.8 that would
take place at the electrodes.
(i) Ag+ (aq) + e– –––– Ag (s)
1 mol of Ag+ ion requires 1 mole of electrons or 1F to deposit 1 mole of Ag atoms
(ii) Cu2+(aq) + 2e– –––––– Cu(s)
1 mole of Cu2+ ions requires 2 moles of electrons or 2F to deposit 1 mole of
copper atoms.
(iii) Al3+(aq) + 3e– ––––– Al(s)
1 mole of Al3+ ions requires 3 moles of electrons or 3F to deposit 1 mole of Al atoms.
We can put the relationship in Table 4.8 to read
1F = 1 mole of electrons = 96500C.
Using this relationship, we can calculate the charge on an ion as shown in the
following examples.
Example 1
During electrolysis of copper(II) sulphate solution, a current of 0.5A was passed for
a period 3860s.The amount of metal deposited was 0.64g.
(i) Calculate the charge carried by the metal ion.
(ii) Write an ionic equation for the reaction.
(R.A.M of Cu = 64, 1F = 96500C)
182
Solution
Quantity of charge = current × time (in seconds)
(Q) (I) (t)
= 0.5 × 3860
= 1930 C
So, 1930 coulombs deposited 0.64 g of copper
x coulombs would deposit 64 g of copper.
x = 1930 × 64
0.64
= 193000 coulombs
1F = 96500 C
y F = 193000 C
y = 193000 C
96500 C
= 2F
2F is the same as 2 moles of electrons.
The charge on the ion is +2.
Ionic equation
Cu2+(aq) + 2e– –––– Cu(s)
Example 2
During electrolysis of an aqueous solution of a salt of metal M, a current of 2.0A was
passed for 32 minutes 10 seconds.The mass of metal M deposited was 2.24g.
(i) On which electrode was the metal deposited?
(ii) Calculate the quantity of charge needed to deposit 1 mole.
(iii) Calculate the charge carried on the ion.
(iv) Write an ionic equation to show how the ions of M are discharged at the
electrode. (R.A.M of metal M is 112)
Solution
(i) At the negative electrode (cathode).
(ii) Quantity of charge = current × time (in seconds)
Q = It
On substituting the values = 2.0 × {( 32 x 60) + 10}s
= 2.0 × 1930
= 3860 coulombs
3860 coulombs deposited 2.24g
x coulombs would deposit 112g
183
x = 3860C × 112g
2.24g
= 193000 coulombs
193000 coulombs are needed to deposit 1 mole
(iii) 1F = 96500C
yF = 193000 C
y = 193000 C
96500 C
= 2F
Since 1F = 1 mole of electrons, 2F means 2 moles of electrons were required.
Therefore, the charge on the ion is +2.
(iv) M2+ (aq) + 2e- ––––– M(s)

1. A current of 1.0 A was passed through molten lead(II) bromide for 1930
seconds. The amount of lead deposited was 2.07g. What is the charge on
lead ions? Show how you arrive at your answer. (Pb = 207, 1F= 96500C)
2. A current of 10.0 A is passed through molten sodium chloride for
a period of 4.0 hours.
i. How many moles of sodium metal will form on the cathode?
ii. How many grams of sodium metal will be deposited?
iii. How many Faradays are used in this electrolysis?
(1F = 96500C, Na = 23.0)
4.5 Applications of electrolysis

The process of electrolysis has many applications.
1. Extraction of metals
Extraction of metals by the process of electrolysis is known as electro-metallurgy.
This process is used to extract highly reactive metals such as sodium, magnesium
and aluminum from their molten ionic compounds, e.g.
• Sodium is extracted from molten sodium chloride.
• Aluminum is extracted from molten bauxite (hydrated aluminum oxide, Al2O3.2H2O).
2. Refining of metals
Copper is an excellent conductor of electricity. It is therefore used widely as a
conductor in various electrical appliances and electrical lines. Copper extracted from
its ores is not pure enough to be used for electrical wiring. It must first be purified.
184
It is purified (refined) using electrolysis as shown in Fig. 4.20 before use.
Battery
Impure copper
Pure copper
anode gets thinner
(cathode)
Copper(II) sulphate
solution
Sludge
Fig 4.20: Refining impure copper
During refining of copper, the following must be done:
• the cathode must be made of thin sheet of pure copper.
• the anode is made of impure copper.
• the electrolytic solution must contain copper (II) ions e.g. copper (II) sulphate
solution.
(a) At the anode
The copper atoms lose electrons and enter into solution as ions.
Cu(s) ––––– Cu2+(aq) + 2e–
(b) At the cathode
The positively charged Cu2+ ions are attracted to the cathode (- ve) , accept two electrons
and get discharged. They then get deposited on the pure cathode as copper solid.
Cu2+(aq) + 2e– ––––– Cu(s)
Thus, the impure block at the anode dissolves and pure copper is deposited at the
cathode. The impurities from the anode drop to the bottom of the cell as sludge. This
sludge contains valuable metals like silver and gold.
3. Electroplating of metals
Electroplating is a process whereby a thin layer of desired material is applied on a required
metal of interest. Electroplating is mostly done on stainless steel to prevent rusting. It is
also done on some objects to make them look shiny and attractive. Fig. 4.21.
Examples
(i) Most metal objects are made of iron or steel. To prevent rusting, they are
nickel–chromium plated e.g. bicycle handlebars, car rims, among others.
(ii) Silver or gold plating is done e.g, on spoons, plates and jewellery items to
improve their appearance.
(iii) ‘Tin cans’—Cans made of steel are electroplated using a thin layer of tin to
prevent them from rusting.
185
Battery
Switch
Pure metal anode Cathode (item to be coated;

e.g. silver in this case, a spoon)
Silver salt solution
Fig. 4.21: Conventional electrolytic cell that can be used for electroplating
To coat the item, the following procedure is used.
• First, the item to be electroplated is thoroughly cleaned.
• An electrolyte whose ions are required to be deposited is selected.
• Direct current (DC) is used instead of alternating current( AC).
• The item to be coated must be made the cathode. Metal for coating must be
made the anode.
Manufacture of sodium hydroxide, chlorine and hydrogen
The main raw material is concentrated sodium chloride (brine). Electrolysis of brine
yields sodium hydroxide, chlorine and hydrogen. Fig. 4.22 shows the set-up for the
electrolysis process.
In this industrial process, mercury is made to flow along the cell as shown in Fig. 4.22.
This mercury acts as the cathode from where sodium is discharged.
2Na+(aq) + 2e- ––––– Na(l)
Graphite is made the anode because it is an inert electrode hence resists corrosion
by chlorine which is discharged and collected at the anode i.e.
2Cl- (aq) –––– Cl2(g) + 2e-
Cl2 out +ve
Spent brine Fresh brine

out
Brine
Mercury
Flow of mercury Graphite anodes

Sodium/Mercury amalgam –ve
Fig. 4.22: The flowing mercury cell for the manufacture of sodium hydroxide, chlorine
and hydrogen
Sodium formed at the cathode dissolves in mercury forming sodium-mercury
186
amalgam (NaHg). The amalgam is reacted with water to form sodium hydroxide
solution and hydrogen gas.
2NaHg (l) + 2H2O (l) –––– 2NaOH(aq)+ H2 (g) + 2Hg(l)
sodium-mercury
amalgam
The mercury produced is recycled. Chlorine, sodium hydroxide and hydrogen are
packaged in readiness for use.
Note: Mercury is a toxic heavy metal. It can cause heavy- metal poisoning to animals
and humans. We should therefore ensure that all measures are taken to ensure no mercury
finds its way to the environment through the effluents from industries or any other means.

1. Name the reagent we should change in Fig 4.22 in order to prepare
potassium hydroxide.
2. Give three applications of electrolysis.
3. A student wanted to coat a steel knife with chromium. On which electrode
should the knife be attached, the positive electrode or negative electrode?
Projects
• Investigate more electroplating processes.
• Prevention of rusting (cathodic protection). This is used to protect corrosion in
underground pipes made of steel. Pieces of zinc or magnesium alloy are connected
to the buried pipes at intervals. Zinc or magnesium will corrode in preference to
steel because they are more reactive.
• Investigate various types of cells, e.g. dry cell, car battery.
Summary
• Redox reactions involve transfer of electrons.
• Oxidising agents accept electrons. Strong oxidising agents have a high affinity
for electrons.
• Reducing agents donate electrons. Strong reducing agents donate electrons more
easily.
• Oxidation number is the charge on the ion.
• An electrochemical cell generates electricity by a chemical reaction.
• The electron-losing substance gets oxidised and the electrode where this occurs
is the anode.
• The electron–accepting substance gets reduced and it is the cathode.
• The “pressure” the electrons exert measured between the anode and cathode of
a cell is the electromotive force (e.m.f) or the cell voltage.
• A positive cell voltage means that the cell reaction will proceed spontaneously,
with electron flow from anode to cathode.
187
• A negative cell voltage means that the forward reaction is not feasible but the
reverse reaction is spontaneous.
• By convention, half-cell reactions are written as reductions, and the corresponding
electrode (reduction) potentials, E, measures the relative tendency for that
reduction to take place.
• A large negative electrode potential value indicates a strong tendency toward
oxidised state (great tendency for example for metal to lose electrons).
• A high positive electrode potential value indicates a strong tendency towards
reduction (ease of accepting electrons by non-metals).
• When one half-reaction is added to another to get a complete cell reaction, the
corresponding electrode potentials are also added. Although the half-cell reaction
may be multiplied by stoichiometric constant (number to balance electrons), the
corresponding electrode potential value is not multiplied.
• The standard hydrogen electrode half-cell is used as the reference electrode. It is
assigned an electrode potential value of zero and is used to get standard electrode
potentials of other elements.
• In an electrolytic cell, ionic compounds conduct when molten or dissolved in water.
• Liquids or solutions can either be electrolytes (conductors) or non-electrolytes
(non-conductors).
• An electrolytic cell consists of anode (positive electrode) and cathode (negative
electrode).
• Positive ions (cations) move towards the cathode while negative ions (anions)
move to the anode.
• The products of electrolysis appear at the electrodes where ions are discharged
by either gaining or losing electrons.
• Generally, metals and hydrogen are produced at the cathode.
• Preferential discharge of ions is influenced by position of the element in the
electrochemical series. This can be changed by concentration of the electrolyte
or type of electrode used.
• The amount of substance consumed or produced at one of the electrodes during
electrolysis is directly proportional to the amount of electricity passed through
the electrolytic cell.
• The quantity of electricity needed to produce one mole of atoms of any element
is always 96500 coulombs or a multiple of 96500C.
• 96500 coulombs is called the Faraday’s constant. 1 mole of electrons = 96500C.
• In an electrolytic cell, a battery or source of D.C is necessary.
• When anode is made of an active electrode like copper, it dissolves.
• Electrolysis is used industrially to extract or purify metals e.g. copper and
aluminium. It is also used in the manufacture of sodium hydroxide, hydrogen
and chlorine.
• Electroplating is a process whereby a thin layer of desired material is applied on
188
the surface of another metal. It is used to produce a protective layer to prevent
corrosion or a decorative layer to make the article attractive.
• In aqueous electrolytes, some water molecules ionise to provide additional H+
and OH– ions. When both are discharged, H+(aq) produce H2(g) and OH–(aq)
produce O2(g).
Revision Exercise 4
1. Explain what you understand by the following terms:
(i) oxidation
(ii) reduction
(iii) electrolysis
(iv) weak electrolyte
2. (a) In terms of electron transfer, explain the meaning of oxidising and
reducing agents.
(b) Study the following half-reactions together with their respective standard
electrode potentials, then answer the questions that follow:
Eθ/Volts
Zn2+(aq) + 2e– Zn(s) –0.76
Fe (aq) + 2e
2+ –
Fe(s) –0.44
Br2(l) + 2e– 2Br–(aq) +1.36
Fe3+(aq) + 2e– Fe2+(aq) +0.77
Ce4+(aq) + e– Ce3+(aq) +1.61
(i) Which substance in the table above is the
• strongest oxidising agent?
• strongest reducing agent?
• weakest reducing agent?
(ii) Choose the best substance from the table which can be used to convert
bromide ions to bromine molecules (Br2) molecules. Write a balanced equation
for this reaction.
(iii) Choose a pair of substance that you can use to construct a cell so that it
gives the highest e.m.f. Calculate the e.m.f of the cell.
Represent the cell in shorthand notation.
3. (a) What is the oxidation number (state) of manganese in the following
substances?
(i) Mn2O7
(ii) MnO4–
(b) What is the oxidation number of germanium in GeCl4?
4. Calculate the oxidation number of the underlined elements on each side of the
equation and state whether the element has undergone oxidation or reduction.
C2O42–(aq) –––– 2CO2(g) + 2e–
189
5. Calculate the standard e.m.f of each of the following cells. Use standard electrode
potentials in Table 4.4
(i) Fe(s) |Fe2+(aq) ||Cu2+(aq) | Cu(s)
(ii) Zn(s) |Zn2+(aq) ||Pb2+ |Pb(s)
(iii) Cu(s) |Cu2+(aq) || Ag+(aq) | Ag(s)
6. A student set up an electrochemical cell as represented below.
Pb(s) | Pb(NO3), (1.0M) || SnCl2(aq), (1.0M) | Sn(s)
The student used a salt bridge to connect the two half-cells. The standard
electrode potentials for the metals used are indicated below.
Eθ/Volts
Pb (aq) + 2e ––––– Pb(s)
2+ –
– 0.13
Sn2+(aq) + 2e– ––––– Sn(s) – 0.14
(a) Which line represents the salt bridge?
(b) What is the function of that salt bridge?
(c) Name the reference electrode against which other standard electrode
potentials are measured.
(d) Calculate the e.m.f. of the cell.
(c) In the external circuit, will the electrons flow from Pb to Sn or Sn to Pb.
Explain your answer?
7. Draw a labelled diagram of a simple electrochemical cell, which has zinc and
copper immersed in their respective electrolytes. Show the direction of electron
movement. Briefly state how the cell generates an electromotive force.
State how such a cell will finally fail to generate power.
8. During electrolysis of molten bauxite, aluminium is deposited on the cathode. If a
current of 0.15 A flowed for 31/2 hours, what is the mass of the metal deposited?
(1F = 96500C, R.A.M of Al = 27)
9. During electrolysis of water acidified with sulphuric acid, two gases were
produced at the electrodes.
(a) Name the gas produced at the anode?
(b) Calculate the volume of the gases at s.t.p produced when a current of 0.025
A is passed for 4 hours. (1 Faraday = 96500C)
10. A current of 5.0A was passed through molten anhydrous calcium chloride,
(CaCl2), for 10 minutes using inert graphite electrodes. Calculate the mass of
each product liberated at each electrode.
11. Calculate the quantity of electricity required to deposited one mole of each of
the following:
(i) copper
(ii) aluminium
190
Unit 5: Metals
5.1 Extraction of metals
5.2 General method of extracting metals
Metals can be extracted from minerals found in form of rocks together with other
materials eg.soil, sand etc in the earth’s crust. A mineral is the useful part of the
rock. Rocks from which metals can be extracted are called ores. Extraction of
metals from their ores involves the following general processes.
• Removing the ore from the ground (mining)
• Concentration of the ore
• Reduction of the ore to metal
Fig. 5.1: General process of extracting metals

1. Getting the ore from the ground
The ore can be located near the surface of the earth or deeper into the earth’s
crust. If the ore is near the surface, open-cast mining or quarrying is used. If it
is deeper into the earth’s crust, then deep mining is used. Machines like excavators,
crawlers, bulldozers, etc. are used during this process.
2. Concentration of the ore
The ore after mining is in lump form. It has to be crushed first into powder form.
It is then concentrated. Concentrating the ore increases the percentage of the
mineral or metal in it.
The methods used to concentrate the ore depends on the differences in physical
or chemical properties between the mineral and the waste material found in the
ore. These methods include froth floatation and chemical leaching.
(a) Froth floatation
This method is used when the percentage of mineral in the ore is too small. In
this process, the ground ore is mixed with water and oil and air blown into the
191
mixture. Separation is possible because of the different densities of the materials.
This imparts an oil coat in every grain of the ore making it hydrophobic (‘water
hating’). This creates two layers. A froth forms on top with most of the minerals
and the waste materials or impurities at the bottom. The top layer with the metal
of interest is removed and dried in readiness for further processing.
(b) Chemical leaching
The crushed ore is first dissolved in a chemical where only the ore can dissolve.
The solution is then separated from the insoluble materials (which in this case,
are considered to be impurities) and finally, the purified ore is crystallised out of
the solution.
3. Reduction of the ore to metal
Once the ore has been concentrated, the metal of interest has to be extracted from
the ore. The method of separation of the metal from the ore depends on the position
of the metal in the electrochemical series. There are two major methods of obtaining
the metal from the ore.
• Reduction by carbon– for moderately reactive metals with less negative
electrode potentials e.g. zinc, iron etc.
• Electrolysis– for very reactive metals with high negative electrode poten-
tials e.g sodium, potassium, calcium and aluminium.
Reduction by carbon cannot work for metals higher in electrochemical series
than carbon. This is because carbon cannot displace the highly reactive met-
als from their ores. However, electrolysis can be used to separate these metals
from their fused ores. Note that the more reactive the metal is, the harder it is
to extract. This is because they are very stable in their compounds.
The following is a summary of the way metals can be obtained from their
concentrated ores depending on their position in the electrochemical series.
Note: The arrow indicates increase in ease of extraction.
Metal Extraction method

Difficult
Potassium (K)
to extract
Sodium (Na)
Lithium (Li)
Electrolysis
Calcium (Ca)
Magnesium (Mg)
Aluminium (Al)
Zinc (Zn)
Iron (Fe) Reduction by carbon
Tin (Sn)
Lead (Pb)
192
These metals can be found
uncombined in which case they
Copper (Cu) are simply picked and washed as
Silver (Ag) free metal. Copper and silver are
Gold (Au) often found as ores but they are
Platinum (Pt) extracted by roasting the ore. Easy to
to extract
The flow chart illustrated in Fig. 5.2 shows how the method used to extract
metals depends on the answers to some important questions. Study the flow chart
carefully and predict the method used to extract sodium, aluminium, zinc, iron,
copper and lead. Explain how you arrived at your choice.
193
Is
the ore
YES near the NO
surface?
Use open Use deep

cast mining mining
or quarrying
Is
NO it a low
grade
ore?
YES
Use a method involving

concentrating the ore
Is
YES the ore an
oxide?
NO
Is
the ore a
sulphide/
carbonate?
YES
Roast the ore in
air to form the
oxide
Can the
oxide be NO Electrolysis
reduced by used to extract Metal
carbon the metal
YES
Reduce the oxide
with coke to extract Metal
the metal
Fig. 5.2 A flow chart on the general method of extraction of metals
194
Although metals have many uses and benefits, there are also side effects associated
with metals especially during mining. Some of these benefits and side effects
are summarised in Table 5.1 below.
Table 5.1 Summary of benefits of mining and effects on the environment
Benefits Side effects
• Creates employment. Mining and quarrying can affect the

environment particularly the ecology
• Produces useful materials for use of the area. They leave very big holes
in different industries the metals on the ground surface. The holes can
especially. be ugly and dangerous especially after
rain when they are filled with water.
The extraction process may produce
• Creates wealth for the company waste materials that are dangerous
and country as a whole. to the environment and need to be
disposed off.
Displacement of people and their
properties

1. Name the process involved in the extraction of metals from their ores.
2. List the two methods of concentration of ores.
3. There are two methods of extracting the metal depending on their position
in the electrochemical series. Name the two methods.
4. Explain the effect of mining on the environment.
5.3 Extraction of sodium, aluminium, iron, copper and zinc from

their ores
Sodium
Occurrence
Because of its reactivity, sodium metal does not occur as a free element but in
combination with other elements in form of ionic compounds. It occurs chiefly
as sodium chloride, which is found in large quantities in sea water, in salted
lakes and as salt deposits which have formed after evaporation of brine. This is
because many sodium compounds are soluble in water. Sodium is found in Lake
Magadi as a double salt i.e. Na2CO3.NaHCO3.2H2O (Trona). It is also found in
other parts of the world e.g. in Chile where it occurs in deposits of sodium nitrate
195
known as Chile saltpetre. Sodium occurs in many other forms as summarised
in Table 5.2 below:
Table 5.2: Occurrence of sodium
Common name Chemical form Formula
Rock salt Sodium chloride NaCl
Chile saltpetre Sodium nitrate NaNO3
Glauber’s salt Sodium sulphate Na2SO4.10H2O
Washing soda Sodium carbonate Na2CO3.10H2O
Trona Sodium sesquicarbonate Na2CO3.NaHCO3.2H2O
Borax Sodium borate Na2B4O7.10H2O
Extraction process of sodium

The metal does not occur naturally because of its reactivity. These compounds
of sodium are so stable that the metal can only be extracted by electrolysis. It is
extracted by electrolysis of molten sodium chloride in a Down’s cell; hence the
process is commonly referred to as the Down’s process.
Downs process
This process takes place in a Down’s cell shown in Fig. 5.3 below.
Chlorine gas
Molten sodium Molten sodium

metal out metal out
Steel cathode Steel cathode – surrounds

the anode
Graphite anode
Molten sodium chloride
Steel gauze with CaCl2 added to it
Fig. 5.3: Down cell for the extraction of sodium

The cell consists of:
• an iron box lined with fire-brick. This iron box contains the mixture of salts
to be electrolysed.
• a carbon (graphite) anode.
• a circular steel cathode from which metallic sodium rises into the receiver.
• steel gauze for separating sodium and chlorine as these can react to form
sodium chloride.
196
To obtain molten sodium chloride, temperatures of upto 800˚C are required in the
cell. This high temperatures are expensive to attain and maintain and also, at this
temperatures fused salt is very corrosive, therefore; there is need to reduce the
melting point of sodium chloride. To do this, calcium chloride (CaCl2) is added to
sodium chloride. This reduces the melting point of sodium chloride to 600˚C. At
this temperature; the reaction proceeds satisfactorily.
In molten state, sodium chloride occurs in ionic form i.e.
NaCl(s) ––––– Na+(l) + Cl–(l)
Na+ ions migrate to the cathode whereas Cl– ions migrate to the anode. These ions
are then discharged as shown in Table 5.3 below in their respective electrodes to
give sodium metal and chlorine gas respectively.
Table 5.3. Reactions at the electrodes in Down’s cell
• The product obtained is sodium • The product obtained is chlorine gas
metal.
• 2Na+(l) + 2e– ––– 2Na(l) • 2Cl–(l) ––– Cl2(g) + 2e–
NB: Sodium has low melting point. NB: Chlorine gas reacts with sodium
In the hot cell, sodium is formed as a very vigorously to form sodium
liquid. This liquid sodium is collected chloride. It is important to keep the
and solidified and can be stored for chlorine gas away from the sodium in
use. It floats on brine due to low the cell. This is done using the steel
density where it is tapped off. guaze as shown in the Fig. 5.3.

Sodium is extracted from its mineral by electrolysis. Answer the following
questions concerning extraction of sodium.
(a) What is the main mineral from which extraction takes place?
(b) What has to be done to the mineral before it is electrolysed?
(c) What are the materials used as the negative and positive electrodes?
(d) What is the reaction at the negative electrode?
(e) What is the reaction at the positive electrode?
(f) How is the metal extracted from the electrolysis apparatus?
(g) Why does chlorine have to be separated from the rest in the electrolysis
apparatus?
Aluminium
Occurrence
Aluminium is also a very reactive metal and therefore does not occur freely. It is
found in compounds with other elements in the forms shown in Table 5.4. These
are some examples of aluminium ores.
197
Table 5.4: Aluminium ores
Natural Chemical name Formula
Bauxite Hydrated aluminium oxide Al2O3.2H2O

Feldspar Potassium aluminium silicate K2O.Al2O3.6SiO4
Clay (kaolin) Aluminum silicate Al2Si2O7 . 2H2O
Ruby Aluminium oxide Al2O3
Extraction process of aluminium

Aluminum is extracted from its chief ore bauxite. Extraction involves concentra-
tion of the ore and electrolysis.
Concentration of the ore
Mining of bauxite is done through open cast method. The bauxite has a lot of
impurities which include mud and other chemical impurities. The chemical
impurities include:
(i) iron(III) oxide
(ii) silicon(IV) oxide (sand)
The impurities are removed during the process of concentration. This is done in
the following steps:
Step 1 Removal of iron(III) oxide
The bauxite ore is first heated at 160˚C with concentrated sodium hydroxide
solution under a pressure of about 4 atms.
• The aluminium oxide dissolve in concentrated sodium hydroxide to form
sodium aluminate.
Aluminium + sodium + water –––– sodium
oxide hydroxide aluminate
Al2O3(s) + 2NaOH(aq) + 3H2O(l) –––– 2Na[Al(OH)4](aq)
Note: Aluminium oxide reacts with concentrated sodium hydroxide because it
is amphoteric in nature.
• Silicon(IV) oxide also dissolves in concentrated sodium hydroxide because it
is an amphoteric oxide.
Silicon(IV) oxide + sodium hydroxide –––– sodium silicate + water
SiO2(s) + 2NaOH(aq) –––– Na2SiO3(aq) + H2O(l)
• Iron(III) oxide is not an amphoteric oxide and therefore does not dissolve in con-
centrated sodium hydroxide. The undissolved impurities which include iron(III)
oxide and others like mud are removed by filtering off from the solution to obtain
a filtrate containing aluminate and silicate ions. The filtrate is then cooled and is
ready for the next step.
198
Step 2: Formation of aluminium hydroxide
There are two ways which can be used in this step:-
1. Treating the filtrate with carbon(IV) oxide gas which precipitates
aluminium hydroxide leaving the silicate in solution.
carbon(IV) oxide
Sodium –––––––– Aluminium + sodium
aluminate hydroxide hydroxide
CO2
Na[Al(OH)4] (aq) ––––––– Al(OH)3(s) + NaOH(aq)
2. The filtrate can be diluted with water, then agitated in air to enhance hydrolysis
of the aluminate ions and finally seeded with freshly prepared aluminium
hydroxide.
Step 3: Roasting of Aluminium hydroxide
Aluminium hydroxide is then roasted at temperatures of about 1000˚C to give
aluminium oxide and water.
1000˚C
Aluminium –––––– Aluminium + water
1000˚C
hydroxide oxide
2Al(OH)3(s) –––––– Al2O3(s) + 3H2O(l)
Step 4: Electrolysis of aluminium oxide
The aluminium oxide is first melted and then electrolysed. Aluminium oxide is
composed of aluminium ions, Al3+ and oxide ions, O2–. When the aluminium oxide
is in molten state, the ions are free to move towards the electrodes.
However, aluminium oxide has a high melting point (2050˚C). Therefore a lot
of energy is required to melt it. Also, aluminium oxide does not dissolve in water
which would otherwise be used as a solvent to separate the ions. These properties
pose some challenges in the process of electrolysis. To solve these problems, the
purified aluminium oxide is dissolved in molten cryolite (Sodium aluminium
fluoride, Na3AlF6). This produces a suitable electrolyte at a lower temperature,
about 900˚C –– 1000˚C. The cryolite does not decompose during this process.
Electrolysis of aluminium oxide takes place in Hall’s cell illustrated in Fig. 5.4.
199
Battery
Carbon anodes
Molten aluminium
oxide dissolved in
cryolite
Molten aluminium 1000˚C Carbon cathode forms the

lining of the cell
Molten aluminium is tapped

of from the cell
Fig. 5.4: Hall’s cell for electrolysis of aluminium oxide

The electrolysis of aluminium oxide starts as soon as it melts. In the molten
aluminium oxide, ions are free to move between the electrodes. The aluminium
ions move to the cathode, whereas the oxide ions (O2–) move to the anode. The
aluminium(Al3+) ions gain three electrons forming an aluminium atoms. The oxide
ions lose two electrons to form oxygen molecules (O2).
The reactions taking place at the electrodes are as follows:
Al3+(l) + 3e Al(l) 2O2–(l) O2(g) + 4e–
Multiply 1st equation by 4 and 2nd by 3 to balance the number of electrons at the
cathode and anode:
4Al3+(l) + 12e– 4Al(l) 6O2–(l) 3O2(g) + 12e–
Overall equation
4Al3+(l) + 6O2–(l) 4Al(l) + 3O2(g)
Oxygen is released at the anode and metallic aluminium settles to the bottom
of the cell and it is tapped off at intervals. Fresh aluminium oxide is continually
added as the reaction proceeds so that the process becomes continuous and the
cryolite is not used up.
Note: The oxygen gas produced at the anode reacts with the carbon anodes to
produce carbon(IV) oxide or carbon(II) oxide. This reaction burns away the
anodes. The anode must therefore be replaced quite often.
This process requires high input of electrical energy and therefore, it is only
economical in countries where electricity is cheap and readily available. The
following flow chart is a summary of the process involved in the extraction of
aluminium.
200
Aluminium ore + impurities Crushing Powdered alu-
(bauxite, Al2O3.2H2O) minium ore
Fe2O3(s) and SiO2(s)
Heating to
remove
water
Impure
bauxite (Al2O3)
Fe2O3, SiO2
Heating
with conc.
NaOH
Sodium aluminate
Na[Al(OH)4](aq) with
impurities, Na2SiO3(aq)
and Fe2O3(s)
Filter to
remove
impurities
Sodium aluminate(III)
solution
Na2SiO3(aq)
Treat with
carbon(IV)
Na2SiO3(aq) oxide to
precipitate
Aluminium
hydroxide
and filter
A1(OH3)
Heat, 1000˚C
Molten dissolve in
cryolite Pure bauxite (Al2O3)
Al2O3(l)
in cryolite
Electrolysis
Pure
aluminium
Fig.5.5: Flow chart of extraction of aluminium

201
1. Name the chief ore of aluminium and give its chemical formula.
2. Why is electrolysis chosen as the method of extraction of aluminium
from its ore?
3. What is the name of the compound used to lower the temperature of
aluminium oxide in the Hall’s cell?
4. Draw and label the cell used in extraction of aluminium.
5. List the three stages in the extraction of aluminium.
6. Write equations for the reactions occurring at the cathode and the
anode of the cell.
7. Why is the anode replaced regularly?
Iron
Occurence
Iron occurs in the earth’s crust in various compounds as shown in the Table 5.5
below
Table 5.5 Ores of iron
Common name Chemical name Formula
Iron pyrites Iron(II) sulphide FeS2
Siderite Iron(II) carbonate FeCO3
Magnetite Tri-iron tetra-oxide Fe3O4
Haematite Iron(III) oxide Fe2O3
The most abundant ores which are normally used for extracting iron are
magnetite and haematite.
Extraction process of iron
Iron extraction involves the following steps.
Step 1: Preparation of the ore
The ore (haematite) is first crushed after which it is heated. The process of heating
removes water and other impurities with low melting points. This gives iron
ore with about 30 – 95% of iron(III) oxide depending on the quality of the ore.
The other remaining percentage are impurities such as silica (SiO2) and alumina
(Al2O3). These are the main impurities.
Note: Remember that iron is manufactured by reduction of its oxide in the blast
furnance. In a situation where sulphide and carbonate ores are used, they should
be first converted to the oxide by roasting in air as follows
Iron(II) + oxygen ––––– iron(III) + sulphur(IV)
sulphide oxide oxide
202
4FeS2(s) + 11O2(g) ––––– 2Fe2O3(s) + 8SO2(g)
Iron(II) + oxygen ––––– iron(III) + carbon(IV)
carbonate oxide oxide
4FeCO3(s) + O2(g) ––––– 2Fe2O3(s) + 4CO2(g)
Step 2: Reduction of the oxide to iron
This is carried out in the blast furnance as shown in Fig. 5.6 below.
Iron ore + coke + limestone
Hot waste gases out
Hot waste
(recycled to heat the furnace)
gases out
1000˚C
1500˚C
1900˚C
hot air
Tuyéres Tuyéres
(blast of hot air) (blast of hot air)
Molten slag out
Molten iron out
Fig. 5.6: Blast furnance for reduction of iron(III) oxide

The raw materials are fed into the blast furnace. This is done through hoppers at
the top of the furnance. The raw materials are:
• iron ore –(mainly haematite, iron(III) oxide).
• coke –which is a cheap form of carbon made from coal.
• limestone –which is used to remove wastes.
At the bottom of the furnace, there are nozzles or tuyéres. The iron ore, coke and
limestone are heated by blowing hot air into furnance through tuyéres. Inside the
furnaces, the following reactions take place.
1. At the base of the furnace, blasts of hot air at about 600˚C are driven into the
furnace. The coke burns in the hot compressed air to form carbon(IV) oxide
gas. This reaction is an oxidation reaction. It is also an exothermic reaction.
The heat evolved raises the temperatures from 600˚C to about 1600˚C.
Carbon + oxygen ––––––––– carbon(IV)
oxide
C(s) + O2(g) –––––––––– CO2(g) ∆H = – 394kJ/mol
203
2. As the carbon(IV) oxide rises up the furnace, it reacts with more coke reducing
it to carbon(II) oxide gas. This reaction is endothermic.
1600˚C
Carbon(IV) + carbon ––––– carbon(II)
oxide oxide
1600˚C
CO2(g) + C(s) ––––-–– 2CO(g) ∆H = +173 kJ/mol
3. The carbon(II) oxide formed then reduces the iron(III) oxide to iron. This
reaction takes place at the upper part of the furnace at temperatures of about
600–700˚C.
600 –700˚C
Iron(III) oxide + carbon(II) –––––––––– iron + carbon(IV)
oxide oxide
600 –700˚C
Fe2O3(s) + 3CO(g) –––––––––– 2Fe(s) + 3CO2(g)
The iron produced settles to the bottom of the furnace and melts at about 1539˚C.
4. The limestone helps in the removal of the sandy impurities which include
acidic impurities in the ore to form a liquid slag. To accomplish this, the
limestone is decomposed in the blast furnace to calcium oxide and carbon(IV)
oxide.
800˚C
Calcium ––––––– calcium + carbon(IV)
800˚C
CaCO3(s) ––––––– CaO(s) + CO2(g)
The carbon(IV) oxide formed when limestone decomposes helps to increase the
yield of iron by producing more carbon(II) oxide when it is reduced by the coke
higher up in the furnace at a temperature of about 700˚C.
700˚C
C(s) + CO2(g) ––––– 2CO(g)
The calcium oxide formed from decomposition of limestone combines with the
impurities to form slag.
i.e. Calcium + silicon(IV) ––––– calcium
oxide oxide silicate(slag)
CaO(s) + SiO2(s) ––––– CaSiO3(l)
Aluminium + calcium ––––– Calcium
oxide oxide aluminate (slag)
Al2O3(s) + CaO(s) ––––– CaAl2O4(l)
5. The molten slag formed by the impurities is less dense than the molten iron.
Because of this, it floats on the surface of the iron. The slag on top of the
iron is important because it prevents the re-oxidation of the iron to iron(III)
oxide by the hot air at the base of the furnace. The slag and the iron can then
be tapped off separately at different levels as shown in Fig. 5.6.
204
The iron obtained directly from the blast furnace is known as ‘pig’ or ‘cast iron’.
Cast or pig iron contains about 90 – 95% of iron. The remaining percentage are
other impurities, mainly carbon, silicon, manganese, sulphur and phosphorus.
These impurities make the iron brittle which limits its usefulness. For example,
it cannot be welded and has low strength. The impurities also lower the melting
point to about 1200˚C as compared to 1535˚C for pure iron, known as wrought
iron.
Wrought iron is the purest form of commercial iron. It is 99% iron. It contains
less than 0.1% carbon. It is not brittle like cast iron. It can be shaped by hammering
and can be welded.
The slag can be used in the manufacture of road making material such as cement,
lightweight building materials and also fertilisers.
Self assessment exercise 5.4

1. List three major ores of iron and write their chemical formulae.
2. Name the raw materials required for the extraction of iron.
3. Which is the best method of extraction of iron? Explain.
4. Which is the reducing agent in the blast furnace? Explain with chemical
equations.
5. Why is limestone (calcium carbonate) used in the extraction of iron?
Explain with equations.
6. Name the waste materials produced in the extraction of iron. How are
these wastes disposed? Does it cause any danger to the environment
if not well disposed? Explain.
Zinc
Occurrence
Zinc occurs in the earth’s crust in the forms shown in Table 5.6.
Table 5.6: zinc ores
Common name Chemical name Formula
Zinc blende Zinc sulphide ZnS
Red zinc ore Zinc oxide ZnO
Calamine Zinc carbonate ZnCO3
Extraction process of zinc

The main form of zinc ore is zinc blende (zinc sulphide). Zinc blende generally
contains quite considerable amount of impurities e.g. lead(II) sulphide, silica
among others, which have to be removed during the extraction process.
Step 1: Concentration of the ore
This is done to increase the percentage of zinc in the ore. The ore is concentrated
205
by froth flotation. In froth flotation, the ore is added to a detergent bath followed
by agitation of the mixture. The conditions in the bath are carefully controlled so
that zinc sulphide floats while the impurities sink.
Step 2: Roasting of the ore in air
After froth flotation, the ore is roasted in air. Zinc sulphide will react with air to
form zinc oxide and sulphur(IV) oxide.
Zinc + oxygen ––––– zinc + sulphur(IV)
2ZnS(s) + 3O2(g) ––––– 2ZnO(s) + 2SO2(g)
Zinc ––––– zinc + carbon(IV)
ZnCO3(s) ––––– ZnO(s) + CO2(g)
Impurities of lead(II) sulphide will also react with oxygen to form lead(II) oxide
and sulphur(IV) oxide.
Lead(II) + oxygen ––––– lead(II) + sulphur(IV)
2PbS(s) + 3O2(g) ––––– 2PbO(s) + 2SO2(g)
Step 3: Reduction of zinc oxide using coke
The mixture of zinc oxide and lead(II) oxide impurities are heated with coke in
a fire clay retort at about 1300˚C.
This temperature has to be maintained to prevent re-oxidation to zinc oxide.
At this stage, the carbon reduces zinc oxide and lead(II) oxide to zinc and lead
metals respectively.
Zinc + carbon ––––– zinc + carbon(II)
oxide oxide
ZnO(s) + C(s) ––––– Zn(s) + CO(s)
Lead(II) + carbon –––– lead + carbon(II)

oxide oxide
PbO(s) + C(s) –––– Pb(s) + CO(s)
The zinc produced in this case has a boiling point of 907˚C which is lower than
1300˚C, the temperature of the furnace. Because of this, the zinc is present in
vapour form and leaves the furnace at the top. It is rapidly cooled in the condenser
and collected as molten zinc.
Molten lead and molten slag formed from silica impurities and the added
limestone settle to the bottom of the furnace and are tapped off.
The mixture of zinc and zinc oxide which condenses and collects at the upper
part of the condenser is purified by distillation. This process produces zinc which
is more than 99.97% pure.
206
Crush ore
Zinc sulphide (ZnS) Powdered ore
Froth
flotation
Concentrated ore
(ZnS)
Roast in air
Reduction of Sulphur(IV)
oxide with oxide released
carbon
Zinc metal (Zn) Zinc oxide (ZnO)
Fig. 5.7: Flow chart for extraction of zinc

Note: Where there are cheap supplies of electricity, zinc is extracted by electrolysis.
In this method, zinc oxide is dissolved in sulphuric acid. Zinc sulphate solution
is then electrolysed using aluminium cathode and lead anode.

1. Name and give the chemical formulae of two major ores of zinc.
2. Why is electrolysis not chosen as the method of extraction of zinc from the ores?
3. List the raw materials required in the extraction of zinc.
4. What impurities does zinc blende contain?
5. Explain with equations, how zinc oxide is formed from their sulphides.
Copper
Occurrence
Copper is found in nature in many different forms. Most often, it occurs in chemi-
cal combination with sulphur and oxygen. Table 5.7 shows a list of copper ores.
Table 5.7 Copper ores
Natural form Chemical name Formula
Red copper ore(cuprite) Copper(II) oxide CuO
Copper pyrites Copper iron disulphide CuFeS2
Malachite Basic copper carbonate Cu(OH)2 .CuCO3
Purple copper ore Copper iron sulphide Cu3FeS3
Copper glance/chacocite Copper sulphide Cu2S
Atacamite Basic copper chloride CuCl2 .3Cu(OH)2
Chrysocolla Silicate mineral CuSiO3.2H2O
207
Extraction process of copper
Most of copper that we use is extracted from copper pyrites CuFeS2. The extraction
process involves the following steps.
• Concentration of the ore.
• Reduction of copper ore.
• Refining of copper by electrolysis.
Step 1: Concentration of copper ore
The ore is concentrated by froth flotation. The finely divided ore is mixed with
oil and stirred with soapy water in a large tank. Compressed air is then blown
through this mixture as shown in Fig. 5.8.
Air
Water + oil + ore + detergent Water + oil + ore + detergent

mixture mixture
Froth separation
Light sulphide particles

in froth suspension
Rocky Desired product

material out
Water + detergent + oil
out for recycling
Fig. 5.8: Concentrating copper ore
The oil-coated particles of the ore float on top of the tank. They form a froth that
can be skimmed off. Most of the rocky impurities, including silicon(IV)oxide
settle at the bottom of the tank. In this way, the fraction of copper in the ore is
raised from 20% to 40%.
Step 2: Reduction of copper ore
The second step is reduction of the copper ore through different stages.
1. The copper ore is further concentrated by roasting in air. This process is carried
out in large flat furnaces to create large surface area. The air reacts with copper
iron sulphide to form copper(I) sulphide, iron(II) oxide and sulphur(IV) oxide.
Copper iron + oxygen –––– heat copper(I) + iron(II) + sulphur(IV)
sulphide sulphide oxide oxide
2CuFeS2(s) + 4O2(g) –––– Cu2S(s) + 2FeO(s) + 3SO2(g)
2. Silicon(IV) oxide (silica) is added to the mixture of copper(I) sulphide and
iron(II) oxide which reacts to form iron(II) silicate as slag. The slag, (iron(II)
208
silicate) floats on the surface of the mixture and is continually tapped off. The
equation for the reaction is as follows.
Iron(II) + silicon(IV) –––– iron(II)
oxide oxide silicate
FeO(s) + SiO2(s) –––– FeSiO3(l)
(Slag)
3. The copper(I) sulphide is then strongly heated in a furnace with controlled sup-
ply of air. Some of copper(I) sulphide is converted to copper(I) oxide, Cu2O,
which then reacts with the remainder of copper(I) sulphide to form copper
and sulphur(IV) oxide. The copper(I) oxide is reduced to blisters of copper
and sulphur(IV) oxide. The equations for the reactions are as follows.
Copper(I) sulphide + oxygen ––––– copper(I) oxide + sulphur(IV) oxide
2Cu2S(s) + 3O2(g) ––––– 2Cu2O(s) + 2SO2(g)
Copper(I) oxide + copper(I) sulphide ––––– Copper + sulphur(IV) oxide

2Cu2O(s) + Cu2S(s) ––––– 6Cu(s) + SO2(g)
The copper produced in this process is called blister copper. This is because when
the liquid copper metal formed is cooled, it starts to solidify and in the process,
release bubbles of sulphur(IV) oxide gas which gives it a blistered appearance.
The blister copper produced is 95% to 97% pure. The copper produced by this
method can be used for making boilers and pipes only. For copper to be used for
electrical wiring, it must be refined or purified by electrolysis.
Step 3: Refining copper by electrolysis
To obtain pure copper (100%), the refining is done through electrolysis. A cell
is set up using copper electrodes. The impure copper is made the anode and the
pure copper the cathode. The electrolyte is copper(II) sulphate solution to which
sulphuric acid has been added. On passing the current, electrolysis takes place and
the impure copper (anode) dissolves. Copper(II) ions, Cu2+ are formed. These ions
are discharged on the pure copper cathode. The cathode gains mass as copper is
deposited on it as shown in Fig. 5.9 below.
Anode Copper(II) sulphate solution

(impure copper) (blue)
Cathode
Sludge (pure copper)
Fig. 5.9: Purification of copper by electrolysis
209
From Fig. 5.9 shown, the cathode gets bigger as the anode gets smaller and smaller.
This is because of the reactions shown below.
Table 5.8
Cu2+(aq) + 2e– ––– Cu(s) Cu(s) –––– Cu2+(aq) + 2e–
Note: Cu2+ ions are discharged Note: The copper anode gets
to form copper metal. The cathode dissolved to form copper(II) ions,
therefore gains mass as copper is Cu2+. The anode loses mass as
deposited in it copper dissolves. Impurities are
dropped below the electrode.
The blue colour of the copper(II) sulphate solution does not change because the
concentration of the Cu2+ ions remains the same. This is because as they get used
up at the cathode, they are replenished at the anode.
The impurities from the anode settle at the bottom of the cell as illustrated in
Fig. 5.9. These impurities are known as sludge. Sludge contains precious metals
such as gold, silver and platinum. These metals can be purified from the sludge.
Chief ore Crush Powder Froth Concentrated ore

(copper pyrite) copper ore floatation
Roasting
in air
SO2 released
SiO2(s) Cu2S + FeO
FeSiO3(l)
slag
Copper(I) sulphide
Cu2S
Strongly heated in
furnance with air
(controlled)
SO2 released
Blister Separation
copper Copper(I) oxide (Cu2O)
+
Blister copper
Purification by Cu2O reacts with
electrolysis
remaining Cu2S
Purification by
Pure electrolysis Blister
copper copper SO2 released
Fig. 5.9: Flow chart for extraction of copper

210
1. Name and give the formulae of four principle ores of copper.
2. What are the raw materials for:
(i) extraction of copper from copper pyrite?
(ii) refining of copper metal?
3. What is the reducing agent in the blast furnace?
4. Write an equation for (3) above.
5. In the purification of copper by electrolysis,
(i) what are the cathode and anode made of?
(ii) draw a labelled diagram to illustrate the process.
(iii) the anode loses mass and the cathode gains mass during the
purification process. Explain with equations.
5.4 Properties of metals

We will start by discussing the physical properties of the metals whose extraction
we have discussed above.
Physical properties of some metals
The physical properties of these metals are as summarised in Table 5.9 below.
Table 5.9 Physical properties of metals
Metal Melting Boiling Density Thermal Electrical Malleability Ductility
Point(˚C) Point(˚C) g/cm3 Condu- Condu-
tivity tivity
Sodium 98 883 0.97 good good malleable ductile
Aluminium 660 2467 2.70 good good malleable ductile
Zinc 420 907 7.14 good good malleable ductile
Iron 1535 2750 7.86 good good malleable ductile
Copper 1085 2572 8.96 good good malleable ductile
From Table 5.9, what can you conclude about the physical properties of the given
metals? Explain your observations.
Melting and boiling points
Metals generally have high melting and boiling points. This is due to the strong
metallic bonds between the fixed positive ions embedded in the ‘sea’ of deloca-
lised electrons.
However, sodium is an exception with a low melting point of 98˚C. This is be-
cause of the few delocalised electrons which decrease the strength of the metallic
bond. Recall that sodium has a valency of one. So, only one electron is released
per atom to the delocalised ‘sea’ of electrons. The same applies to other metals
in group I of the periodic table.
211
Density
Metals have high densities because of their structures except sodium and group I
metals. The observed different densities in metals is due to different arrangements
of atoms in their structures. Again, density increases with increasing atomic number.
This is because the mass of an atom increases as the atomic number increases.
Thermal conductivity
Metals are the best conductors of heat. This is due to the free or delocalised elec-
trons in their structure. When one end of the metal is heated, the heat is felt on
the other end when the kinetic energy of the delocalised electrons is increased.
This cause them to vibrate, move and hit other nearby electrons resulting in the
transfer of heat. This process will continue until the free electrons transfer the
heat to the colder end.
Electrical conductivity
Electrical conductivity is similar to heat conduction but the electrons move along
the wire instead of just vibrating. A flow of electrons in a metal atom pushes the
electrons nearest to it so that the entry of one electron pushes out another electron at
the opposite end of the metal. This leads to conduction of electrical current.
Ductility and malleability
• Most metals are ductile i.e. they are capable of being drawn out into wires.
The atoms within a metal are arranged in layers. Ductility involves slipping
of these layers of atoms over each other when the metal is pulled or hit. This
results in the formation of wires as shown in Fig. 511.
Metal rod Atoms in the metal rod
Before
After
Fig. 5.11: Ductility in metals

• Most metals are also malleable i.e. they are capable of being hammered into
thin sheets. The hammer exerts strong forces on the layers of atoms in the
structure of the metal. Because of this property, metals can be bent and moulded
into different shapes. This is illustrated in Fig. 5.12 below.
Metal rod Atoms in the metal rod
Before
After
Fig. 5.12: Malleability in metals

212
1. List four general properties of metals.
2. Why does sodium have lower melting point compared to other metals?
3. Metals are known to be good conductors of heat and electricity. Explain.
4. Metals are said to be malleable and ductile. Explain the meaning of
these terms.
Chemical properties of some metals
(I) Reaction of metals with air
Experiment 5.1
To investigate reaction of metals with air.
• source of heat
• pair of tongs
• knife
• ceramic tile
• filter paper
• sodium
• aluminium foil
• iron
• copper
• zinc granules
Procedure
1. Place all the requirements on the bench.
2. With a pair of tongs, remove a small piece of sodium from the bottle and place
it on the ceramic tile covered with filter paper to remove most of the oil. Cut
a small piece and return the rest into the bottle. What do you notice on the
freshly cut surface?
3. Hold the small piece with a pair of tongs.
4. Heat the sodium metal as illustrated in Fig. 5.13 below.
5. Repeat this procedure using aluminium foil, iron, copper and zinc granules.
6. Record your observations and conclusions in your notebook.
Metal
heat
Fig. 5.13: Burning metals in air
• What do you conclude about the reactivity of these metals with air?
213
Sodium
Sodium burns in air with a yellow flame to form two oxides i.e sodium oxide;
and sodium peroxide.
Sodium + oxygen –––– sodium oxide
4Na(s) + O2(g) –––– 2Na2O(s)
Sodium + excess oxygen ––––– sodium peroxide
2Na(s) + O2(g) –––– Na2O2(s)
Aluminium
Aluminium burns in air to form aluminium oxide. This can only occur when the
aluminium is cleaned well to remove the oxide layer. Freshly-cut aluminium im-
mediately acquires the thin coating of the oxide which prevents any further reaction.
Aluminium + oxygen –––– aluminium oxide
4Al(s) + 3O2(g) –––– 2Al2O3(s)
Iron
When iron is heated strongly in air, it burns slowly to form tri-iron tetroxide.
Iron + oxygen –––– tri–iron tetroxide
3Fe(s) + 2O2(g) –––– Fe3O4(s)
Copper
Copper does not burn in air but when heated, the surface of the red-brown copper
metal turns black due to formation of copper(II) oxide. Finely divided copper
burns with a blue flame.
Copper + oxygen –––– copper(II) oxide
2Cu(s) + O2(g) –––– 2CuO(s)
Zinc
When zinc is heated in air, it burns with blue-green flame to form a smoke of zinc
oxide. The oxide is yellow when hot and white when cold. Zinc tarnishes very
slowly in air because of formation of zinc oxide coating which prevents further
reaction.
Zinc + oxygen –––– zinc oxide
2Zn(s) + O2(g) –––– 2ZnO(s)
1. Describe the reaction of sodium, aluminium, iron, zinc and copper in air.
2. Write equations for reactions in 1 above.
3. What would be the pH of the solution when an oxide of sodium is
dissolved in water? Write an equation for the reaction.
4. Aluminium is high in the electrochemical series. Why is it difficult
for it to react with air?
214
(II) Reaction of metals with water
Experiment 5.2
To investigate reaction of metals with water.
• trough
• pair of tongs
• ceramic tile
• knife
• filter paper
• sodium
• aluminium
• iron
• copper
• zinc
Procedure
1. Half fill the trough on the bench with water.
2. Add three drops of universal indicator as shown in Fig. 5.14(a). You can also
test with red and blue litmus papers.
3. With a pair of tongs, remove a small piece of sodium from the bottle and
place it on the ceramic tile covered with filter paper to remove excess oil.
4. With a knife, cut a small piece of sodium and return the rest to the bottle.
5. Hold the sodium tightly with a pair of tongs [Fig. 5.14(b)] and drop it into
the trough with water [Fig. 5.14(c)].
6. Hold each of the rest of the metals with the pair of tongs and drop it into a
trough of water and indicator as shown in Fig 5.14
• What do you observe in each case?
• Record your observations and conclusions in your notebook
• Arrange the metals in order of their reactivity in water.
• Does aluminium react with water as expected by virtue of its position in
the reactivity series? Explain.
(a) (b) tongs (c)

troughs
sodium
water
Fig. 5.14: Reaction of metals with water

215
7. Now, react the following metals Al, Fe, Cu and Zn with steam by putting a
piece of each metal in steam as shown in Fig. 5.15.
Record your observations and conclusions in your notebook.
moist
sand metal ribbon hydrogen
gas
heat heat
water
Fig. 5.15: Reaction of metals with steam

Sodium
When sodium is dropped in water, it darts around the surface of the water with a
hissing sound and melts. The colour of the indicator changes because of formation
of sodium hydroxide solution which is alkaline in nature.
Sodium + water ––––– sodium + water

hydroxide
2Na(s) + 2H2O(l) ––––– 2NaOH(aq) + H2(g)
Aluminium
Aluminium reacts very slowly with water to form aluminium hydroxide and hydro-
gen. It will react faster with steam to form hydrogen gas and aluminium oxide.
Aluminium + water ––––– aluminium + hydrogen

hydroxide
2Al(s) + 6H2O(l) ––––– 2Al(OH)3(aq) + 3H2(g)
Aluminium + steam ––––– aluminium + hydrogen
oxide
2Al(s) + 3H2O(g) ––––– Al2O3(s) + 3H2(g)
Note: Before this reaction is carried out, the aluminium oxide layer on the surface
of aluminium has to be cleaned. Explain why?
Iron and zinc
Iron and zinc do not react with cold water but react with steam to form their cor-
responding oxides and hydrogen gas.
Iron + steam –––– iron(III) oxide + hydrogen
2Fe(s) + 3H2O(g) –––– Fe2O3(s) + 3H2(g)
Zinc + steam –––– Zinc oxide + hydrogen
Zn(s) + H2O(g) –––– ZnO(s) + H2(g)
216
Copper
Copper does not react with both cold water and steam.
1. Among sodium, aluminium, iron, zinc and copper, which metals
react with steam and which metals react with cold water? Explain.
2. Write equations for the above reactions.
3. What nature of solutions are formed from the above reactions?
(III) Reaction of metals with chlorine

Experiment 5.3
To investigate the reaction of metals with chlorine.
• source of chlorine gas
• delivery tube
• clamp stand
• source of heat
• deflagrating spoon
• gas jars
• sodium
• aluminium
• iron
• copper
• zinc
Procedure
1. Set up the apparatus to prepare dry chlorine in the laboratory.
2. Heat sodium metal in a deflagrating spoon and insert the burning sodium into
a gas jar of chlorine as shown in Fig. 5.16 below. Repeat the same procedure
for aluminium.
deflagrating spoon
gas jar of
chlorine
burning metal in
chlorine
burning metal
Fig. 5.16: Reaction of sodium and aluminium with chlorine

3. In the case of iron, copper and zinc, place the metal in a combustion tube.
4. Pass a steady stream of chlorine gas over heated metal as shown in Fig. 5.16.
5. Heat the metal until the reaction starts and then remove the bunsen burner.
217
concentrated
hydrochloric
acid
metal
excess chlo-
rine
heat
potassium
manganate(VII)
Fig. 5.17: Reaction of iron, copper and zinc with chlorine
• What do you observe for each of the metals above?

• Record your observations and conclusions in your notebook.
• From your conclusions, predict the reactivity of these metals.
Sodium
Heated sodium metal reacts vigorously with chlorine to form white salt of
sodium chloride.
Sodium + chlorine –––– sodium chloride
2Na(s) + Cl2(g) –––– 2NaCl(s)
Aluminium
Heated aluminium burns in chlorine gas to form a white solid of aluminium
chloride which sublimes in the cooler parts of the apparatus.
Aluminium + chlorine ––––– aluminium chloride
2Al(s) + 3Cl2(g) ––––– 2AlCl3(s)
Iron
Strongly heated iron glows red hot. Red hot iron reacts with chlorine to form a
brown solid of iron(III) chloride which sublimes to the cooler side of the apparatus.
Iron + chlorine –––– iron(III) chloride
2Fe(s) + 3Cl2(g) –––– 2FeCl3(s)
Copper
Hot copper reacts with chlorine to form green copper(II) chloride.
Copper + chlorine –––– copper(II) chloride
Cu(s) + Cl2(g) –––– CuCl2(s)
218
Zinc
Hot zinc reacts with chlorine gas to form white solid of zinc chloride.
Zinc + chlorine –––– zinc chloride
Zn(s) + Cl2(g) –––– ZnCl2(s)
1. What observations are made when heated sodium, aluminium, iron,
zinc and copper are inserted to gas jars of chlorine?
2. Write equations for the above reactions.
(IV) Reaction of metals with dilute hydrochloric acid

Experiment 5.4
To investigate the reaction of metals with dilute hydrochloric acid.
• test tubes
• test tube racks
• splint
• source of heat
• labels
• aluminium
• iron
• copper
• zinc
• dilute hydrochloric acid
Note: Do not attempt this experiment with sodium because it is explosive.
Procedure
1. Put about 20 cm3 of dilute hydrochloric acid into test tubes placed in a test
tube rack.
2. Add separately small amounts of aluminium, iron, copper and zinc into each
of the test tubes with dilute hydrochloric acid as shown in Fig. 5.18 below
and test for hydrogen gas.
Add the
(a) metals to
separate (b)
tubes
Test gas evolved with a
burning splint
(c)
Fig. 5.18: Reaction of metals with dilute hydrochloric acid
219
• What conclusions can you make from your observations?
• Arrange the metals according to their reactivity starting from the most reactive
to the least reactive.
• Where would you place sodium in your arrangement? Explain.
Sodium
• Sodium reacts explosively with dilute hydrochloric acid to form a salt and
hydrogen gas.
Sodium + hydrochloric –––– sodium + hydrogen
acid chloride
2Na(s) + 2HCl(aq) –––– 2NaCl(aq) + H2(g)
Aluminium, iron and zinc
• Aluminium, reacts very slowly with dilute hydrochloric acid to form a salt
and hydrogen. This is due to the oxide coating.
• Iron and zinc reacts readily with dilute hydrochloric acid to form their respective
salts and hydrogen.
Aluminium + hydrochloric –––– aluminium + hydrogen
acid chloride
2Al(s) + 6HCl(aq) –––– 2AlCl3(aq) + 3H2(g)
Iron + hydrochloric ––––– iron(II) + hydrogen
acid chloride
Fe(s) + 2 HCl(aq) ––––– FeCl2(aq) + H2(g)
Zinc + hydrochloric –––– zinc + hydrogen
acid chloride
Zn(s) + 2HCl(aq) –––– ZnCl2(aq) + H2(g)
Copper
Copper does not react with dilute acids.

1. Explain why it is not advisable to react sodium with dilute hydrochloric
acid in the laboratory.
2. Why does aluminium react much faster when the mixture is warmed but
reacts very slowly when it is not warmed?
3. When aluminium, iron, zinc and copper are reacted with dilute hydrochloric
acid, which one of these metals will not react?
4. Write chemical equations for the metals that react with dilute hydrochloric
acid in 3 above.
220
(V) Reaction of metals with concentrated nitric and sulphuric acid
Experiment 5.5
To investigate the reaction of metals with concentrated nitric and sulphuric acid.
• test tubes
• test tube racks
• splint
• source of heat
• labels
• aluminium
• iron
• zinc
• copper
• concentrated nitric acid
Note: Sodium is extremely reactive with concentrated acids. Do not attempt this
reaction in the laboratory.
Procedure
1. Follow the procedure as in experiment 5.4 but instead of using dilute
hydrochloric acid, use concentrated nitric acid.
2. Repeat the same procedure with concentrated sulphuric acid.
• What do you observe in each of the above reactions?
• What conclusions can you make from the above observations?
• Write equations for the above reactions.
Sodium
Sodium would be extremely explosive when reacted with both concentrated
nitric and sulphuric acid. However, it reacts to form nitrate and sulphate salts
respectively.
2Na(s) + 2HNO3(aq) ––––– 2NaNO3(aq) + H2(g)
2Na(s) + H2SO4(aq) ––––– Na2SO4(aq) + H2(g)
Aluminium
Aluminium reacts with hot concentrated sulphuric acid to form salt, water and
sulphur(IV) oxide.
Aluminium + Conc. sulphuric(VI) –––– aluminium + water + sulphur(IV)
acid sulphate oxide
2Al(s) + 6H2SO4(l) –––– Al2(SO4)3(aq) + 6H2O(l) + 3SO2(g)
Aluminium does not react with concentrated nitric acid. This is because
concentrated nitric acid is a strong oxidizing agent and it will produce an
221
insoluble aluminium oxide on the surface of the metal which will prevent any
further reaction from taking place.
Iron
Iron is oxidised by concentrated sulphuric acid to form iron(III) sulphate, in the
process, it is itself reduced to sulphur(IV) oxide.
Iron + conc. sulphuric(VI) –––– iron(III) + water + sulphur(IV)
acid sulphate oxide
2Fe(s) + 6H2SO4(l) –––– Fe2(SO4)3(aq) + 6H2O(l) + 3SO2(g)
Again, concentrated nitric acid does not react with iron. This is because concentrated
nitric acid being a strong oxidizing agent, produces a thin coating of tri-iron tetroxide
(Fe3O4) on the surface of the iron and prevents any further reaction from taking place.
Zinc
Concentrated sulphuric acid oxidises zinc to form zinc sulphate, water and
sulphur(IV) oxide.
Zinc + Conc. sulphuric(VI) –––– zinc + water + sulphur(IV)
acid sulphate oxide
Zn(s) + 2H2SO4(l) –––– ZnSO4(aq) + 2H2O(l) + SO2(g)
Concentrated nitric acid oxidises zinc to form zinc nitrate, water and nitrogen(IV)
oxide.
Zinc + conc. nitric –––– zinc nitrate + water + nitrogen (IV)
acid oxide
Zn(s) + 4HNO3(l) –––– Zn(NO3)2(aq) + 2H2O(l) + 2NO2(g)
However, zinc reacts with 50% concentrated nitric acid to give nitrogen(II) oxide
instead of nitrogen(IV) oxide.
Zinc + 50% conc –––– zinc + water + nitrogen(II)
nitric(V) acid nitrate oxide
3Zn(s) + 8HNO3(aq) –––– 3Zn(NO3)2(aq) + 4H2O(l) + 2NO(g)
Copper
Concentrated sulphuric acid oxidises copper and is itself reduced to sulphur(IV)
oxide.
Copper + conc. –––– copper(II) + water + sulphur(IV)
sulphuric(VI) sulphate oxide
acid
Cu(s) + 2H2SO4(l) –––– CuSO4(aq) + 2H2O(l) + SO2(g)
Concentrated nitric acid oxidises copper metal to copper(II) nitrate while itself is
reduced to nitrogen(IV) oxide.
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Copper + conc nitric(V) –––– copper(II) + water + nitrogen(IV)
acid nitrate oxide
Cu(s) + 4HNO3(l) –––– Cu(NO3)2(aq) + 2H2O(l) + 2NO2(g)
Again, when 50% solution of nitric acid is used, nitrogen(II) oxide is formed
instead of nitrogen(IV) oxide.
Copper + 50% conc. nitric(V) –––– copper(II) + water + nitrogen(II)
acid nitrate oxide
3Cu(s) + 8HNO3(aq) –––– 3Cu(NO3)2(aq) + 4H2O(l) + 2NO(g)

1. What is observed when
(i) zinc is reacted with concentrated nitric acid?
(ii) copper reacts with concentrated sulphuric acid?
2. Write chemical equations for the reactions in 1 above
3. Aluminium reacts with concentrated nitric acid slowly and immediately stops.
Explain.
5.5 Uses of some metals

The uses of metals are based on their physical and chemical properties.
Sodium
• Sodium metal is used in the preparation of tetraethyl lead, PbEt4, an important
anti-knock reagent in leaded petrol (gasoline). Leaded petrol is being phased
out in many countries because of pollution problems.
• It is used in table salt in form of sodium chloride. Note that taking too much
salt can be harmful to your health.
• Sodium vapour is used in lamps for street lighting.
• Sodium metal is used in the reduction of organic esters, and in the preparation of
organic compounds.
• Sodium is a powerful reducing agent and therefore, it is used to reduce
titanium(IV) chloride to titanium metal used in the manufacture of rockets.
• Manufacture of sodium peroxide, which is a bleaching agent.
• Sodium is used in the manufacture of sodium cyanide used in gold extraction.
• Sodium compounds including “common salt” (sodium chloride, NaCl), “soda ash”
(sodium carbonate, Na2CO3), “baking soda” (sodium hydrogencarbonate,
NaHCO3), and “caustic soda” (sodium hydroxide, NaOH) are important in
paper, glass, soap, textile, petroleum, chemical and metal industries where
they are used in various processes.
Aluminium
• Aluminium can be alloyed to make duralumin by adding copper and smaller
amounts of magnesium, silicon and iron. The alloy is stronger, has low density
hence lighter and as such, is used in the manufacture of aircraft components.
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• It is used in greenhouses and window frames since it has good anti-corrosion
properties.
• It is used in overhead power lines because it is a good conductor and is light
• It can be used to make machinery parts where lightness and strength are
required.
• In the manufacture of explosives e.g. a mixture of ammonium nitrate and
aluminium powder is explosive.
• Manufacture of aluminium paint. This is used in coating radiators, storage
tanks and other metal works.
• It is used in jewellery, for example, corundum is widely used in making gems
such as sapphires, rubies and oriental amethysts.
• Aluminium foil is used in wrapping foodstuffs.
• Some aluminium compounds are used in sewage treatment.
Zinc
• Zinc (about 20 – 45%) can be combined with copper to form an alloy called
brass. Brass is easy to work with and is a good conductor of electricity. As
such, it finds its use in electrical appliances. Zinc can also form alloys with
many other metals. For example, nickel and silver used as typewriter metal.
Also commercial bronze, spring brass, soft solder, and aluminum solder all
contain zinc.
• To galvanize metals such as iron so as to prevent corrosion. Typically, this
involves dipping the object to be coated in molten zinc for a short period of time
so that zinc covers the whole surface. Zinc protects any exposed iron sacrificially
because of the relative positions of zinc and iron is the electrochemical series.
Note: Electroplating and painting can be done to serve the same purpose.
• Zinc metal is used in batteries, roof cladding, and to protect iron structures
from corrosion by attaching zinc as sacrificial anodes. Zinc metal is also used
in lightweight coins.
• A compound of zinc oxide (ZnO) is used in the manufacture of paints, rubber
products, cosmetics, pharmaceuticals, floor coverings, plastic printing inks, soap,
textiles, electrical equipment, and other products. It is also used in ointments.
• A compound of zinc sulphide (ZnS) is used in making luminous dials, X–ray
and TV screens, paints and flourescent lights.
Copper
• Copper is low in the reactivity series. This means that it doesn’t corrode easily.
This is important for its use in the making of pipes, electrical cables, saucepans
and radiators. However, it also means that it is good for decorative use. Jewel-
lery, statues and parts of buildings can be made from copper, brass or bronze
and remain attractive for thousands of years.
• Copper is effective at stopping the growth of many micro-organisms. This is
important for its use in domestic water systems. Its value and unreactive nature
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is an advantage to use of copper for making currency coins. Copper is also
reckoned to reduce the painful bone inflammation caused by arthritis. Many
people wear copper bracelets to reduce the effects of the disease.
• Copper can be joined easily by soldering or brazing. This is useful for pipework
and for making sealed copper vessels.
• Copper is a ductile metal. This means that it can be shaped into pipes and
drawn into wires. Copper pipes are lightweight because they can have thin
walls. They don’t corrode and they can be bent to fit around corners. The pipes
can be joined by soldering and they are safe in fires because they don’t burn
or support combustion.
• Copper and copper alloys are tough. This means that they are well suited for
being used in tools and weapons. Imagine the joy of ancient man when he
discovered that his carefully formed arrowheads no longer shattered on impact.
The property of toughness in copper and copper alloys is what makes those
arrow heads not to shatter. As such, copper is widely used in modern world to
make tools which are required not to shutter.
• Copper is non-magnetic and non-sparking. Because of this, it is used in
special tools and military applications.
• Copper and its alloys, such as brass, are used for jewellery and ornaments. They
have an attractive golden colour which varies with the content. They have a
good resistance to tarnishing making them last a long time.
1. (a) Why is sodium a powerful reducing agent?
(b) Give two properties which makes aluminium suitable for use in
overhead power lines
2. (a) List three uses of zinc
(b) List four uses of copper.
5.6 Some alloys and their uses

As we have learnt, different metals have different properties. For example, we saw that
the metals vary in their melting and boiling points; density, malleability and ductility
among other properties. If these different properties of metals are mixed; we can
come up with metals of intermediate property which could serve certain purposes
better. For example; mixing of metals improves the appearance, strength, resistance
to wear or corrosion and lower the melting points of the final product. If one or
more metals are mixed, we call them alloys. Alloys are formed by mixing molten
metals together and allowing them to cool. Table 5.10 shows examples of some
alloys and their uses.
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Table 5.10 Some alloys and their uses
Alloy Composition Properties Used to make
Brass 70% Copper • harder than pure • utensils
copper • screw
30% Zinc • ‘gold’ coloured • radiators
Bronze 90% Copper • harder than pure • machinery
10% Tin copper • decoration work
Steel Stainless steel
74% Iron • tough • cutlery
18% Chromium • does not corrode • surgical
instruments
8% Nickel • kitchen sinks
Tungsten steel
95% Iron • tough • edges of
5% Tungsten • hard even at high high-speed
temperatures cutting tools

Manganese steel
87% Iron • tough • drill bits
13% Manganese • springy • springs

Mild steel
0.3% Carbon • stronger and harder • car bodies
than pure iron • axles
99.7% Iron • it is not brittle • bridges
Medium steel
99.55% Iron • tougher than
mild steel • car springs
0.45% Carbon • chains
High–carbon steel
iron 98.5% • hard • chisels
carbon 1.5% • brittle • cutting tools
• razor blades
Cast iron
95.5% Iron • easily molded • gear boxes
4.5% Carbon • engine blocks
• brake discs
Duralumin 95% Aluminium • strong • parts of airplanes
4% Copper • light weight • rockets
smaller amounts • cans
of other elements • foils
• kitchen utensils
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1. What is an alloy?
2. Name two alloys of copper.
3. What are the compositions of duralumin and brass?
4. State the properties of duralumin and cast iron.
5. Name the various steel in alloys.
6. What is the purpose of making alloys?
7. Pure copper is used for household wiring rather than a copper alloy.
Suggest one reason for this.
8. Suggest one reason why alloys are used in aircraft structures rather than
pure aluminium.
5.7 Pollution effects of the industrial production of metals on the

environment
One of the problems of metal extraction is balancing ecological, environmental,
economical and social advantages and disadvantages. In this section, we will
explore some of the problems caused by metal extraction which alter the composition
of the air, contaminate water sources, pollutes the land and creates noise pollution.
Air pollution
For decades, mining companies have been striving to minimize the environmental
impact of recovering base metals such as copper from sulphide ores. The
traditional extraction methods of smelting generates harmful gases containing
sulphur(IV) oxide, some of which escapes into the atmosphere (5 –15%) while
the rest is converted to sulphuric acid. In other industries, waste gases such
as carbon(II) oxide are emitted to the atmosphere. Some gases form acid rain
which has a lot of negative effects on the environment. Also, harmful smoke
and fumes are usually produced from factories. They have offensive smell and
cause respiratory diseases. In some cases, the smoke can fill the surrounding
environment during the night. The soot becomes visible during sunrise and affects
visibility. This can cause road and air accidents. Pollution control measures
have been put in place by environmental control agencies and governments
to eliminate this problem. Currently, there are two primary methods used by
industries and power plants to reduce the amount of pollutants released into the
atmosphere. These include, installation of scrubbers and electrostatic precipitators.
• Scrubbers– are designed to remove the various gases like sulphur(IV) oxide
from the plant emission. They are considered to be very effective.
• Electrostatic precipitators– are designed to remove visible soot from the
emissions.
• Emissions control equipment to capture particulates. Air emissions in
these industries also include particulates. Particulate air emissions usually
include iron and copper(II) oxide and other metal oxides (as dust particles).
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Water pollution
Outflow pipes from metal processing plants directly pour their waste into the
rivers and lakes. This outflow has chemical wastes, (eg arsenic, cyanide, phenols,
oil, acid etc. Though treated to remove dangerous polluting substances before it
is released, not all pollutants get eliminated. When such pollutants find their
way to rivers, lakes and even oceans, it can cause harm to aquatic plants and
animals. If waste is continually dumped into an area where there is water, the
water may never recover. This situation has occurred in some rivers of the world.
Such rivers have been called ‘dead’ rivers.
Many industries use water for cooling machines and materials. The resulting
hot water is usually released into streams and lakes. This increases the water
temperatures resulting in decrease in the amount of oxygen that can dissolve
in the water. This affects the aquatic animals such as fish. To control the above
situations, liquid wastes from plants are treated and reused so that minimal amount
is released to the rivers, streams and oceans.
Land pollution
Land pollution resulting from metal extraction is due to chemical waste disposal
and mining. Chemical pollutants from solid waste resulting from mining of min-
erals and industries settle on land and contaminate the soil. These wastes can be
harmful to animals and plants living in the soil. When these chemicals contami-
nate crops and these crops are eaten by animals and even humans, it can lead to
deformities and even death.
Extraction of large quantities of mineral resources from mines create several
problems. If the mines are underground, subsidence is a problem. If, however,
they are open-cast mines or quarries, wasteful land are formed. Quarries and
open trenches resulting from open-cast mining can be reclaimed by a process
called “landfill”. Governments have put in place policies requiring mining
companies to restore the land to the standard in which they were initially.
Noise pollution
The major noise pollution from the industries are from the vehicle operations within
the plants, noise and vibrations relating to the operation of the rail network etc.
Effect of noise
• Reports by the World Health Organisation (WHO) suggests that noise can
affect human health and well-being in a number of ways, including annoyance
reaction, sleep disturbance, interference with communications, performance
effects, effect on social behaviour and hearing loss.
• Exposure to noise is also associated with a range of possible physical effects including
colds, changes in blood pressure, cardiovascular changes, increased general
medical treatment cost, problems with the digestive system and general fatigue.
• It can cause deafness with prolonged exposure to high noise levels. The amount
of deafness depends on the amount of exposure.
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Techniques used to reduce noise pollution
• Buildings are designed and constructed with details to minimise noise
impacts in sensitive areas.
• Sealing walls closest to the noise source.
• Create awareness about noise pollution.
• Strengthen laws and governmental efforts to control noise pollution.
• Establish networks among environmental, professional, medical,
and non governmental organisations working on noise pollution issues.

1. (i) What are the main causes of water pollution in the extraction of metals?
(ii) How could this pollution be reduced or prevented?
2. (i) What makes a substance a waste material in the extraction of metals?
(ii) What is meant by the word “toxic”?
(iii) List some of the toxic wastes in 2(i) above.
3. A piece of paper can take 20 days to decompose. Steel can take 100 years and
some plastics take over 500 years. What are the implications of these figures?
4. When is a body of water said to be polluted?
6. (i) What is noise pollution?
(ii) What are the causes of noise pollution in industries?
(iii) What are the effects of noise pollution?
Projects
• Analysis of ores
• Construction of a mini-blast furnace
• Carrying out iron-smithing
Summary
• General methods used for the extraction of metals from their ores are
—Concentration of the ore
—Reduction of the ore
—Purification of the ore
• The method of extraction of a metal from its ore depends on the position of
the metal in the electrochemical series.
• Metals high in the electrochemical series like sodium and aluminium are
stable compounds and are extracted by electrolysis.
• Metals low in electrochemical series like zinc, iron, tin, lead, copper etc
are first converted to oxides through heating (If their ores are not already
in oxides) and then reduced to metals by heating with carbon.
• Metals at the bottom of the electrochemical series like mercury and silver have
been found at times as “free” metals. When in compound form, they can be
converted to oxides first and then reduced to metal by heating with carbon.
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• Sodium is extracted by electrolysis of fused sodium chloride, sodium is
deposited at the cathode and chlorine gas is liberated at the anode.
• Aluminium is extracted by electrolysis of molten aluminium oxide. Pure
aluminium is deposited at the cathode and oxygen is liberated at the anode.
• The extraction of iron is carried out in a blast furnace. Iron is extracted by re-
duction using carbon as the reducing agent. The slag formed from impurities
is used in making road surfaces. It can also be used to make various forms of
special steel for different uses.
• Zinc is extracted from zinc blende which is one of the chief ores of zinc. It is
extracted by reduction using carbon as the reducing agent. Zinc can be purified
by electrolysis.
• Copper can be extracted in two ways: by reduction using carbon as a reducing agent
or by electrolysis of copper sulphate as the electrolyte and using copper electrodes.
• Extraction of metals can cause air, water, land and noise pollution. Measures
should be put in place to make sure that the environment is protected.
Revision Exercise 5
1. (i) What is the use of carbon(II) oxide in the extraction process of iron?
(ii) Give the role played by limestone during the process of extraction of iron.
(iii) Explain how carbon(II) oxide is formed in the extraction process of iron.
(iv) State five uses of iron metal.
2. The following figure is a Down’s cell used in the extraction of sodium.
Name the parts labelled— (i) K (ii) L
(iii) What is the use of calcium chloride in the Down’s
L K process?
(iv) Write down the equations that occur at the:
(a) cathode. (b) anode.
(v) Why is sodium collected at the top and not at
the bottom of Down’s cell?
(vi) Give three uses of sodium and three of chlorine gas.
3. (a) Give five uses of aluminium.
(b) Why is aluminium not extracted by reduction using carbon?
(c) Below is a diagram used for electrolysis of aluminium oxide in the
extraction of aluminium. Name parts labelled A, B, C, D and E.
B C (d) Write down the reactions that occur

A at the anode and cathode.
D (e) What is an amphoteric oxide?
E
4. (i) Name three major copper ores.

(ii) Name the method used to concentrate copper ore before extraction.
230
(iii) What are the reactants in the reduction stage in the extraction of copper?
(iv) (a) What are the products formed when copper(I) sulphide is heated
strongly in a blast furnace?
(b) Write the equation of the reaction.
(v) Copper produced during the extraction process is 95–97% pure. To produce
pure copper, electrolysis of the blister copper is carried out.
(a) What metal is used as the cathode during this process?
(b) Name the electrolyte used.
(c) Write the equations of the reactions at each electrode.
(vi) (a) What does the term concentration mean in extraction of copper?
(b) What is roasting in this process?
(c) What role does refining process serve during extraction of copper?
5. (i) Explain formation and pollution effects of acid rain caused by
sulphur(IV) oxide.
(ii) What is the name given to the negative electrode in any electrolysis
apparatus?
(iii) State 2 advantages and 2 disadvantages of mining.
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Unit 6: Organic Chemistry II
(Alkanols and Alkanoic acids)
Introduction
In Form 3, we learnt that hydrocarbons are compounds which contain carbon and
hydrogen only. We also learnt that the hydrocarbons are grouped into families which,
form homologous series. The members in the same homologous series have similar
physical and chemical properties. Some of the homologous series that we learnt
about include:
• Alkanes –– are saturated hydrocarbons with a general formula CnH2n+2
• Alkenes –– are unsaturated hydrocarbons with a double bond with a
general formula CnH2n.
• Alkynes –– are unsaturated hydrocarbons with a triple bond with a
general formula CnH2n–2 where n = 1, 2, 3, … …
We are going to learn about other examples of homologous series which contain oxy-
gen in addition to carbon and hydrogen i.e. alkanols and alkanoic acids. Members of
these series also show similarity in their physical and chemical properties.
6.1 Alkanols
Alkanols are organic compounds. They are also known as alcohols. The alkanols
form a homologous series with -OH as the functional group. They may be regarded
as being derived from an alkane by replacing one of the hydrogen atoms with an
-OH group. They are saturated organic compounds.
General formula and nomenclature of alkanols

The general formula of alkanols is ROH, where R is an alkyl group. Alkyl group is
the name given to the group of atoms remaining when one of the hydrogen atom of
an alkane is removed. For example
When we remove one hydrogen atom from
• Methane (CH4), we get methyl (CH3) group.
• Ethane (CH3 CH3), we get ethyl (CH3CH2) group and
• Propane (CH3CH2CH3), we get propyl (CH3CH2CH2) group etc.
In this case methyl, ethyl and propyl are examples of alkyl groups and can be repre-
sented by letter R as described above. To get the number of carbon and hydrogen
atoms, represented by R in the general formula, we use another formula CnH2n + 1OH,
where n is the number of carbon atoms which can be 1, 2, 3, 4 etc.
232
Nomenclature
The names of members of this homologous series are obtained by replacing the
suffix -e of the corresponding alkane by -ol. For example, when n = 1 in alkanes,
the name is methane. In this example, if we replace the suffix -e in methane with
-ol, the name becomes methanol. It is the first member of the family of alkanols.
We can use the general formula CnH2n+1 OH to find the structural formula of each
member of this family as follows. For methanol n = 1, we substitute in the formula
to get C1H(2×1)+1OH which gives CH3OH. This is the molecular formula of methanol.
Methanol is almost the same as methane in structure. The difference is that we replace
one of the hydrogen atoms with hydroxyl group, –OH
H H
H C H or CH4 ; H C OH or CH3OH
H H
Methane Methanol
Note: The hydroxyl group can replace any of the four hydrogen atoms in methane.
When n = 2, the molecular formula becomes C2H(2×2)+1OH or C2H5OH. The name of
this alkanol is derived from ethane, where one hydrogen atom is replaced by –OH
as shown below.
H H H H 2 1
H C C H
2
1
or C 2H 6 H C C OH or CH3CH2OH
H H H H
Ethane Ethanol
When n=3, the molecular formula will be C3H7OH. The name is propan-1-ol and
the structure is as shown below.
H H H
3 2 1
or CH3CH2CH2OH
32 1
H C C C OH
H H H
Propan-1-ol


1. Write the formula of alkanols where n = 6,7,8,9 and 10
2. Name the alkanols in (1) above
3. Draw the structures of the alkanols in (2) above. Compare your answers
with some given in Table 6.1.
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Table 6.1 Names, formulae and structures of some alkanols
Name Molecular formula Structural formula
H
Methanol CH3OH H - C - OH
H
or
CH3OH
H H
Ethanol C2H5OH H - C - C - OH
H H
or
CH3CH2OH
H H H
Propan-1-ol C3H7OH H - C - C - C - –OH
H H H
or
CH3CH2CH2OH
H H H H
Butan-1-ol C4H9OH H - C - C - C - C -OH
H H H H
or
CH3CH2CH2CH2OH
H H H H H
Pentan-1-ol C5H11OH H - C - C - C - C - C - OH
H H H H H
or
CH3CH2CH2CH2CH2OH
Note:
The IUPAC rules demand that the position of the –OH group be included in the name. This
is why the, number 1 is included in propan-1-ol, to show that functional group is attached
to first carbon of the straight-carbon chain. The same applies to all other alkanols.
234
The alkanols as a homologous series
• Members of this series contain-OH as the functional group.
• All the names of alkanols end with -ol.
• They have a general formulae ROH or CnH2n+1OH
• Each member differs from the preceding one by a –CH2– group (methylene
group).
• They show gradual change in physical properties such as melting points and
boiling points.
• They have similar chemical properties.
Preparation of alkanols
In general, alkanols can be prepared in two ways.
1. Hydrolysis of alkenes.
2. Fermentation of carbohydrates e.g. starch and sugars such as glucose, etc.
We are going to discuss the preparation of ethanol to represent how all other alkanols
can be prepared.
1. Preparation of ethanol by hydrolysis of ethene
Ethanol is produced in large quantities, from hydrolysis of ethene. Ethene to be used
in this process is produced by cracking long chain alkanes which are broken down
into an alkene and shorter alkane. The ethene produced is mixed with steam and passed
over a phosphoric acid catalyst at a temperature of about 300˚C and 60 atmospheres
pressure to produce ethanol.
ethene + water 300˚C ethanol
–––––
300˚C CH CH OH(g)
CH2 = CH2 (g) + H2O (g) ––––– 3 2
2. Preparation of ethanol by fermentation of glucose

Experiment 6.1
Preparation of ethanol in the laboratory by fermentation of glucose.
• delivery tube
• cork
• conical flask
• boiling tube
• glucose or any other sugar solution
• yeast
• calcium hydroxide solution
Procedure
1. Place sugar solution mixed with yeast in a conical flask.
235
2. Connect a delivery tube with a tight fitting cork to the conical flask and boiling
tube containing calcium hydroxide solution as illustrated in Fig. 6.1
Delivery tube
Cork
Clamp
Conical flask
Boiling tube
Yeast + sugar Calcium hydroxide

solution solution
Fig. 6.1: Fermentation
3. Keep the apparatus for about 3 to 4 days.

• What do you observe in the above experiment after 4 days ? Explain your
observations.
• What is the role of yeast in this process?
• What do you conclude from the above observations?
• What happens to the calcium hydroxide after 4 days? Write equations for
the reactions that take place.
• Calcium hydroxide acts as fermentation lock in the above experiment.Why
do we need a fermentation lock?
• What gas is produced in the above experiment? Explain with equations.
4. Pure ethanol is obtained by fractional distillation of the mixture formed.
The reactions whereby sugars are converted to alcohol are referred to as fermentation
reactions. Ethanol is prepared in the laboratory by the fermentation of glucose or any
other sugar solution using enzymes in yeast. Yeast is a single-celled fungus which
contains a number of enzymes including maltase and zymase. The enzymes break
down carbohydrates e.g. starch into glucose. The enzyme zymase, then catalyses
the fermentation of glucose into ethanol and carbon(IV) oxide. The following are
the reactions that take place.
diastase maltose
Starch + water –––––––
2(C6H10O5)n (s) + H2O(l) ––––––– C12H22O11(aq)
Maltose is then hydrolysed into glucose molecules.
Maltose + maltase glucose
water ––––––––
C12H22O11(aq) + H2O(l) –––––––– 2C6H12O6(aq)
Glucose is finally converted to ethanol and carbon(IV) oxide.
236
zymase
Glucose ––––– ethanol + carbon(IV) oxide
C6H12O6(aq) ––––– 2C2H5OH(aq) + 2CO2(aq)
The ethanol produced during fermentation is toxic to the enzymes. It kills the yeast at
concentrations greater than 15% by volume. To increase the alcoholic concentration
from fermented liquids, they are distilled to produce spirits. For example, distillation
of wine produces brandy which is about 40% ethanol. Brandy is an example of a spirit.
Spirits are alcohols with high alcoholic content.
Ethanol is an intoxicating substance in alcoholic beverages. It damages the liver
and causes behavioural change.
The first member of the alkanol series is methanol and is much more toxic than
ethanol. It is added to industrial alcohol to make it undrinkable. Unfortunately, a few
people drink it and the final result is blindness, death or both. Methylated spirit is
ethanol where a small amount of methanol has been added to make it undrinkable.
A purple dye is often added too, to discourage people from attempting to drink it.
Note:
The first fraction from the distillation of solution from fermented sorghum or maize
meal which are used for making local brews contains mainly methanol. Pure ethanol
is harmful. Ethanol is a social drink. Abuse of ethanol is a major drug problem in
most countries including Kenya. We should avoid abuse of alcohol.
1. Using a chemical equation, explain how ethanol is prepared
from hydrolysis of ethene.
2. Which gas is produced in the process of fermentation of carbohydrates?
3. What happens to the calcium hydroxide after 4 days in experiment 6.1?
Explain with an equation.
4. Write equations to explain the process of fermentation from starches.
Properties of alkanols
Generally, alkanols are neutral and are poor conductors of electricity. The first three
are soluble in water i.e. are completely miscible with water. The rest are immiscible.
The trends in physical properties of alkanols are summarised in Table 6.2.
237
Physical properties of alkanols
Table 6.2: Trends in physical properties of alkanols
Name Melting point Boiling point Density Solu-
0
C 0
C g cm-3 water
Methanol -98 65 0.791 Soluble

Ethanol -117 78.5 0.789 Soluble
Propan-1-ol -127 97 0.803 Soluble
Butan-1-ol -89.5 117 0.810 Fairly soluble

Pentan-1-ol -79 138 0.814 Slightly soluble
Hexan-1-ol -51.6 157 0.814 Slightly soluble
Heptan-1-ol -34 176 0.822 Slightly soluble
Octan-1-ol -15 195 0.825 Slightly soluble
Nonan-1-ol -7 212 0.827 Slightly soluble

Decan-1-ol 6 228 0.829 Slightly soluble
From Table 6.2, the melting and boiling points of alkanols increase with increase in
relative molecular mass. As the molecular mass increases, intermolecular forces of
attraction between molecules increase. As these forces increase, more energy to separate
the molecules is needed. This makes the melting and boiling points to increase. Apart
from that, there is hydrogen bonding between the oxygen atom and hydrogen atom
that forms when two molecules of alkanols come close to each other.
R1 O
O H
R2
H
Hydrogen bonding
Fig. 6.2: Two molecules of alkanol joined through hydrogen bond

Because of these hydrogen bonds, alkanols have higher melting points than
hydrocarbons of the same molecular mass. In order to break the hydrogen bonds,
238
more heat energy is required, hence raising the melting point. A lot more energy is
also needed to make the constituent alkanol molecule to leave the liquid and form a
gas. So, the boiling points are also much higher.
The densities increase with increase in relative molecular mass. This is because of the
increase in intermolecular forces of attraction between molecules, making them very
close to each other. This reduces the volume occupied by the molecule and from
the formula D = M , the density increases.
V
1. Explain the trends in melting and boiling points of the first 10 alkanols.
2. Compare the melting and boiling points of alkanols to those of alkanes with
the same number of carbon atoms. Give reasons for your answer.
Chemical properties of alkanols

Alkanols form a homologous series with similar chemical properties.Experiment
6.2 gives us the chemical properties of ethanol. This information can be applied to
the other alkanols.
Experiment 6.2
To determine the chemical properties of ethanol.
• bottle tops/evaporating basins
• test tubes
• beaker
• universal indicator
• blue and red litmus papers
• sodium metal
• ethanoic acid
• acidified potassium dichromate(VI)
• acidified potassium manganate(VII)
239
Procedure: As shown in Table 6.3
Table 6.3 Investigating chemical properties of ethanol
Procedure Observations Conclusions

1. Place a few drops of ethanol into a bottle
top and ignite.
2. Place about 2-3 cm3 ethanol in a test tube.
Add about 3 drops of universal indicator.
Test with blue and red litmus papers.
3. Place about 2-3 cm3 of ethanol in a test
tube.Add a very small piece of sodium
metal.Test for any gas produced with a
burning splint.
4. Place about 2-3 cm3of ethanol in a test tube.
Add an equal amount of ethanoic acid. Add
two drops of concentrated sulphuric acid and
heat. Pour the resulting mixture into about
70cm3 of water in a beaker. Smell the product.
5. Place about 2-3 cm3of ethanol in a test tube.
Add about 5 cm3 of acidified potassium
manganate(VII) to the test tube.Warm gently.
6. Repeat procedure 5 but add acidified
potassium dichromate(VI).
• What colour changes occur on the indicators?
• What is the pH of ethanol?
• Which gas is produced when sodium reacts with ethanol?
• Write the equations for reactions in 3, 4 and 5 above.
1. Combustion of ethanol
When ethanol is ignited in plentiful supply of air or oxygen, it burns with almost
an invisible blue flame to produce carbon(IV) oxide and water.
Ethanol + oxygen ––––– carbon(IV) oxide + water
C2H5OH(l) + 3O2(g) ––––– 2CO2(g) + 3H2O(l)
2. Reaction of ethanol with sodium
When sodium metal reacts with ethanol, it forms a compound called sodium ethoxide.
Effervescence occurs and a colourless gas which burns with a ‘pop’ sound is
produced. The gas is hydrogen.The reaction is similar to the reaction of sodium with
240
water but is much slower and less vigourous.
Ethanol + sodium ––– sodium ethoxide + hydrogen
2C2H5OH(l) + 2Na(s) ––– 2C2H5ONa(aq) + H2(g)
Ethanol also reacts with other metals e.g. potassium to produce the corresponding
ethoxide and hydrogen gas.
Note: This reaction is also possible with other alkanols. The general equation of the
reaction is:
2R–OH(aq) + 2M(s) –––– 2ROM(aq) + H2(g)
Where, R – alkyl group of the reacting alkanol.
M – metal reacting with the alkanol e.g. potassium or sodium.
3. Reaction of ethanol with concentrated sulphuric acid
Concentrated sulphuric acid reacts with ethanol at 180˚C to form ethene and water.
This is a dehydration reaction. This is the reverse of the reaction used to produce
ethanol from ethene.
Conc. sulphuric(VI)
Ethanol acid
––––––––––– ethene + water
heat
Conc. H2SO4, 180˚C
C2H5OH(l) ––––––––––– C2H4(g) + H2O(l)
dehydration
Note: At 140˚C another organic compound known as ether is formed.
4. Ester formation
Alkanols react with alkanoic acids (to be discussed later in this topic) to form
compounds called esters. For example, ethanol reacts with ethanoic acid in the
presence of a few drops of concentrated sulphuric acid (catalyst) to form a substance with
characteristic sweet and fruity smell called ethyl ethanoate. This substance is an ester.
Ethanol + ethanoic acid Conc. ethyl ethanoate + water
H2SO4
Conc.
CH3CH2OH(l) + CH3COOH(aq) CH3COOCH2CH3 + H2O
H2SO4 (Ester)
The process of ester formation is called esterification. Esterification process is
reversible and the ester formed can be reverted back to the parent alkanol and alkanoic
acid as shown in the reaction above. This process is called ester hydrolysis.
Note: The name of the ester is derived from the reactants; in this case, the respective
alkanol and alkanoic acid. In our example above; the name comes from ethanol and
ethanoic acid respectively.
241
Oxidation of ethanol
When acidified potassium dichromate(VI) is added to ethanol, its colour changes
from orange to green. When acidified potassium manganate(VII) is added to ethanol,
the purple colour changes to colourless. Potassium dichromate(VI) and potassium
manganate(VII) are oxidising agents. They oxidise ethanol to ethanoic acid. The
oxidation of ethanol is a two step process.
1. Ethanol is first converted to ethanal.This is a slow process.
Ethanol + oxygen––––– ethanal + water
Cr2O72–(aq)
C2H5OH(l) + [O] ––––––– CH3CHO(l) + H2O(g)
H+(aq)
from oxidizing
agent
2. Then rapid conversion of ethanal to ethanoic acid.

Cr2O72–(aq)
Ethanal + oxygen ethanoic acid
H+(aq)
Cr2O72–
CH3CHO(aq) + [O] CH3COOH(aq)
H+(aq)
Note:
• If ethanol is allowed to come into contact with air, it can be oxidised by oxygen in
the air to dilute ethanoic acid. This dilute ethanoic acid is commonly referred to
as vinegar. The souring of ethanol was the original method of making vinegar.
• Oxygen of the air slowly oxidises ethanol in beer. If the bottle is not tightly corked
and a lot of carbon(IV) oxide escapes, ethanol is oxidised making the beer go ‘flat’.
CH2 = CH2 CH3COOCH2CH3
+
Ethene /H ethyl ethano-
excess OH
conc. H2SO4 CO ate
CH 3
180˚C
CH3CH2OH Cr
2 O 2
Ethanol or 7 /H +
Na M
nO –
4
/H +
CH3CHO
ethanal Cr O 2–
CH3CH2O–Na+ 2 7
Sodium ethoxide H+
CH3COOH
ethanoic acid
Fig. 6.3: Summary of some reactions of ethanol
242
1. How does the reactivity of sodium with ethanol compare with sodium in
water? Which gas is produced?
2. Write an equation for the reaction between ethanol and ethanoic acid in the
presence of concentrated sulphuric acid.
3. What do you observe when acidified potassium dichromate (VI) is added to
ethanol?
4. Explain with equations what happens when ethanol is burned in air.
Uses of ethanol
1. Used as a solvent e.g. it is a good solvent for iodine.
2. Used in the manufacture of varnishes,ink,glues and paints.
3. Used in the manufacture of deodorants, perfumes etc. because it evaporates quickly.
4. Ethanol is used in alcoholic drinks, e.g. beer, wines and spirits.
5. As an antiseptic in specified concentrations.
6. As a fuel when it is blended with gasoline to form gasohol. On small scale,
ethanol in form of methylated spirit is used in spirit lamps.

1. State the physical properties of ethanol.
2. Explain the following reactions with the help of equations
(i) Burning of butan-1-ol in air.
(ii) Reaction of propan–l–ol with sodium metal. Name the organic
compound produced.
(iii) Reaction of butan-1-ol with ethanoic acid and propan-1-ol with
butanoic acid. Name the esters formed.
(iv) Oxidation of pentan-1-ol with acidified potassium dichromate(VI).
3. List three uses of ethanol
4. Draw the structures of
(i) Octan-1-ol
(ii) Hexan-1-ol
5. What is the functional group of an alkanol?
6. Write the molecular formula and draw the structures for
(i) Pentan–l–ol
(ii) Heptan-l–ol
7. Why is it dangerous to drink methylated spirit?
8. Why do alkanols make good fuels?
9. Ethanol (C2H5OH) can be made by fermentation of glucose (C6H12O6).
Carbon(IV) oxide is also formed
(a) Write a balanced equation for the fermentation of glucose.
243
(b) Yeast must be added to glucose solution in order for fermentation to
occur. Explain why yeast is needed.
(c) If the temperature during fermentation is increased to 70˚C, the reaction
slows down and then stops completely. Explain why this happens.
(d) An increase in temperature from 25˚C to 35˚C will increase the rate of
reaction. Explain this using collision theory of particles.
10. Methanol, CH3OH and ethane CH3CH3, have almost the same molecular mass.
Explain why the b.p of methanol is 65˚C while that of ethane is –88.6˚C.
6.2 Alkanoic acids

Alkanoic acids are organic acids which are sometimes called carboxylic acids. They
are so called because they have a carboxyl group as their functional group. They
may be regarded as being derived from alkanes by replacing one of the hydrogen
atoms with a–COOH group. Alkanoic acids form homologous series with a general
formula R–COOH where R is an alkyl group or H in case of the first one. We use
the general formula CnH2n+1COOH to calculate their molecular formula.
General formula and nomenclature of alkanoic acids

The systematic name of a carboxylic acid comes from an alkane with the corresponding
number of carbon atoms. The –e in the name of alkane is replaced with -oic acid. Let
us name and draw the structures of the first three alkanoic acids.
• The first member of the series is methanoic acid with the formula HCOOH. In
methanoic acid, R is represented by H while for the rest of the members, R is
represented by an alkyl group. The structure of the carboxyl group is
O O
or C
C – OH OH
The structure of methanoic acid is therefore,
O
H C OH
• The second member of the alkanoic acid is ethanoic acid, which has two carbon
atoms. Since one of the carbon atoms is already attached to the functional group,
the value of n in the general formula CnH2n+1COOH is l. When we subtitute, we
get the molecular formula for ethanoic acid as follows.
244
C1H(2 × 1) +1COOH
CH3COOH
The structural formula is represented as

H O
H C C OH
H
Ethanoic acid
For the third member; n = 2 we substitute in CnH(2n+1)COOH i.e.

C2H(2 × 2)+1 COOH
hence we get C2H5COOH as the molecular formula. This can also be written as
CH3CH2COOH
It
is called propanoic acid and its structural formula is as follows.
H H O
H C C C OH
H H
Propanoic acid
Table 6.5 below shows examples of alkanoic acids with upto 10 carbon atoms.
Table 6.5 The first 10 alkanoic acids
Name Molecular formula Structural formula

O
Methanoic acid HCOOH H — C — OH
or
HCOOH
H O
Ethanoic acid CH3COOH H — C — C — OH

H
or
CH3COOH
245
H H O
Propanoic C2H5COOH H — C — C — C — OH
acid H H
or
CH3CH2COOH
H H H O
Butanoic H – C – C – C – C – OH
C3H7COOH
acid H H H
or CH3CH2CH2COOH
H H H H O
Pentanoic C4H9COOH H – C – C – C – C – C – OH
acid H H H H
or CH3CH2CH2CH2COOH
H H H H H O
Hexanoic C5H11COOH H – C – C – C – C – C – C – OH
acid
H H H H H
or CH3CH2CH2CH2CH2COOH
H H H H H H O
Heptanoic C6H13COOH H – C – C – C– C – C – C – C – OH
acid H H H H H H
or CH3CH2CH2CH2CH2CH2COOH
H H H H H H H O
Octanoic C7H15COOH H – C – C – C – C – C – C – C – C –OH
acid
H H H H H H H
or CH3CH2CH2CH2CH2CH2CH2COOH
246
H H H H H H H H O
Nonanoic C8H17COOH H – C – C – C – C – C – C – C – C – C –OH

acid H H H H H H H H
or CH3CH2CH2CH2CH2CH2CH2CH2COOH
H H H H H H H H H O
Decanoic C9H19COOH H – C – C – C – C – C – C – C – C – C – C –OH

acid
H H H H H H H H H
or CH3CH2CH2CH2CH2CH2CH2CH2CH2COOH
The alkanoic acids as a homologous series

The alkanoic acids are another homologous series of organic compounds with the
following characteristics
• They have the functional group -COOH attached to the hydrocarbon chain
• The members have a general formula CnH2n+1COOH or RCOOH, where n =
0, 1, 2, ……
• Members of the series differ from the next by a _CH2_ group.
• They have similar chemical properties.
• They show a gradual increase in physical properties such as melting
points,boiling points and density.

1. Name alkanoic acids with the following carbon atoms; 4,5,6,7,8,9.
2. Draw the structures of the above alkanoic acids.
3. Write the formulae of the above alkanoic acids.
Preparation of alkanoic acids

Alkanoic acids can be prepared by oxidation of the corresponding alcohol in two
steps. The oxidising agents are:
• acidified potassium dichromate(VI)
• acidified potassium manganate(VII)
The corresponding alcohol is mixed with excess acidified potassium dichromate(VI)
and warmed.
The first step forms an alkanal and water as shown in the following general equation.
247
R represents an alkyl group
acidified
(i) Alkanol + oxygen alkanal + water
potassium
dichromate(VI)
RCH2OH(l) + [O] Cr2O72–/H+ RCHO(aq) + H2O(l)

From oxidising
agent
The second step involves further oxidation of alkanal to alkanoic acid i.e.
acidified potassium
(ii) Alkanal + oxygen –––––––––––––– Alkanoic acid + water
dichromate(VI)
Cr2O2–7 /H+
RCHO(aq) + 2[O] ––––––––– RCOOH(aq) + H2O(l)
Therefore, the overall reaction is:

acidified
Alkanol + oxygen Alkanoic acid + water
potassium
dichromate(VI)
RCH2OH(l) + 2[O] Cr2O72–/H+ RCOOH(aq) + H2O(l)
Example: Preparation of ethanoic acid

Ethanoic acid is prepared by warming a mixture of ethanol and excess acidified
potassium dichromate(VI) or excess acidified potassium manganate(VII).
Step I
This involves the conversion of ethanol to ethanal as shown below. This is a slow
process.
acidified
Ethanol + oxygen ethanal + water
(from oxidizing potassium
agent) dichromate(VI)
CH3CH2OH(l) + [O] Cr2O72–/H+ CH3CHO(aq) + H2O(l)

or MnO4–/H+
OR
H H H O
2 –
Cr2O 7
/H+
H — C — C — OH(l) + [O] H — C — C — H(aq) + H2O(l)
or MnO–4/H+
H H H
248
Step II
In this step, the ethanal is oxidised to ethanoic acid. This reaction takes place at
a much faster rate.
acidified
Ethanal + oxygen potassium chromate(VI) ethanoic acid
Cr2O2–
7
/ H+
CH3CHO(l) + [O] CH3COOH(aq)
or MnO–4/H+
OR
H O H O
2–
Cr2O7 /H +
H — C — C — H(l) + [O] H — C — C — OH(aq)
or MnO–4/H+
H H
General equation for the preparation of alkanoic acids

acidified
Alkanol + oxygen alkanoic acid + water
potassium
(from oxidizing
dichromate(VI)
agent)
Eventually, the orange colour of potassium dichromate (VI) turns green as the oxida-
tion progresses or if we use potassium manganate(VII), the purple colour turns colour-
less. The acid is obtained from the mixture by distillation at its boiling point while
testing the distillate. Distillation is stopped when the distillate is no longer acidic.

1. Name the chemical reagents required in the preparation of butanoic acid.
2. Write down an outline of the procedure required in the above preparation.
3. Write step by step equations for the preparation of butanoic acid.
4. Write a general word equation for the preparation of butanoic acid.
5. List the characteristics of homologous series of alkanoic acid.
Properties of alkanoic acids

Physical properties of alkanoic acids
• The first ten straight chain alkanoic acids are liquids at room temperature.
• The first few members like methanoic and ethanoic acids are soluble in water.
The rest are insoluble and actually float in water. The solubility of alkanoic
acids generally decreases with increasing molecular mass.
• Table 6.5 shows the physical properties of some alkanoic acids.
249
Table 6.5 Trends in physical properties of alkanoic acids
Name Melting point Boiling point Density Solubility in water

0
C 0
C g/cm-3
Methanoic acid 8.4 101 1.220 Soluble
Ethanoic acid 16.6 118 1.049 Soluble
Propanoic acid -20.8 141 0.992 Soluble

Butanoic acid -8 164 0.964 Soluble
Pentanoic acid -19 187 0.939 Slightly soluble
Hexanoic acid -3 205 0.927 Slightly soluble
Heptanoic acid -10.5 223 0.920 Slightly soluble
Octanoic acid 16 239 0.910 Slightly soluble

Nonanoic acid 11 253 0.907 Slightly soluble
Decanoic acid 31 269 0.905 Slightly soluble
As shown in the table above, the boiling and melting points of the alkanoic acids
increase gradually as the length of the hydrocarbon chain increases except for a few
discrepancies in the melting points . The increase is due to the following reasons.
• As the length of the hydrocarbon increases, the weak intermolecular forces
(van der Waals forces) are increased.
• There is also formation of hydrogen bonds between the alkanoic acid molecules.
This is brought about by the partial positive and negative charges on the H and O
atoms of the carboxyl group(-COOH). These charges enable the molecules to
attract each other and form strong hydrogen bonds.
d2– d+
O H O
R C C R
d+ d2–
O H O
hydrogen bonding between

molecules of alkanoic acids
250
1. Describe the trend in melting and boiling points of the first ten alkanoic acids.
2. Compare the answer in (1) above with their corresponding alkanes. Explain
their differences.
3. Compare the solubility of the first four alkanoic acids in water with those of
alkanes. Explain the differences.
Chemical properties of alkanoic acids

Alkanoic acids are another homologous series of organic compounds that have
similar chemical properties. In these series, we will learn about the properties of
ethanoic acid as a representative of alkanoic acids. Ethanoic acid is a colourless
liquid with a sharp smell.
Experiment 6.3
To investigate the chemical properties of ethanoic acid.
• test tubes
• droppers
• beaker
• universal indicator or litmus papers
• spatula
• test tube holder
• source of heat
• calcium carbonate
• magnesium ribbon
• ethanol
• ethanoic acid
• sodium hydroxide solution
• phenolphthalein indicator
Procedure
Copy Table 6.6 in your notebook. Follow the procedures as outlined in the table and
record your observations and conclusions in the spaces provided.
251
Table 6.6 Investigating chemical properties of alkanoic acids
Procedures Observations Conclusions
1. Place about 2cm3 of ethanoic acid in a test
tube.Add a few drops of universal indicator
or test with litmus papers.
2. Place about 2cm3 of ethanoic acid in a
test tube. Add a small piece of clean
magnesium ribbon and test for any gas
produced.
tube. Add a spatula endful of calcium
carbonate and test for any gas produced.
4. Place about 2cm3 of ethanoic acid in a
test tube. Add an equal amount of ethanol
followed by two drops of concentrated
sulphuric acid.Warm the mixture gently
and pour the resulting mixture into a
beaker with about 60cm3 of cold water.
Smell the product.
tube.Add two drops of either phenolphtha-
lein or methyl orange indicator. Then add
2cm3 sodium hydroxide solution to the
mixture drop by drop until there is colour
change.
When we dissolve mineral acids in water, they dissociate into their respective ions.
For example, HCl produces hydrogen ion H+, as well as the chloride ion Cl– on
dissolution in water. Similarly, when an alkanoic acid is dissolved in water, it dis-
sociates to form hydrogen ion, H+ and carboxylate anion, RCOO– as illustrated in
the following general equation.
R COOH(aq) H+(aq) + RCOO–(aq)
OR
O O
R C H+(aq) + R C
OH(aq) O–(aq)
Carboxylic acid Carboxylate anion
252
Note: The functional group, –COOH donates the H+ ion, not the alkyl group rep-
resented by R.
Ethanoic acid is said to be a weak acid. It partially dissociates into ions in water.
Ethanoic acid hydrogen ion + ethanoate ion
CH3COOH(aq) H+(aq) + CH3COO–(aq)
An aqueous solution of ethanoic acid has a pH of about 4.7
A solution of ethanoic acid will show characteristic reactions of a dilute acid as follows:
1. Reaction of ethanoic acid with carbonates
Ethanoic acid will react with carbonates to produce a salt, carbon(IV) oxide
and water. For example, it reacts with calcium carbonate to give calcium etha-
noate, carbon(IV) oxide and water.
Calcium + ethanoic acid –––– Calcium + carbon(IV) + water
carbonate ethanoate oxide
CaCO3(s) + 2CH3COOH(aq) –––– (CH3COO)2Ca(aq) + CO2(g) + H2O(l)
Note that for an organic salt formula, the metal is written last. But, when naming
the salt, we start with the metal.
2. Reaction of ethanoic acid with metals
Ethanoic acid reacts with reactive metals like magnesium to produce a salt
and hydrogen gas. To understand this, let us first start with a reaction that we
are familiar with.
Mg(s) + 2HCl(aq) –––––– MgCl2(aq) + H2(g)
Magnesium displaces hydrogen from the acid to form magnesium chloride.
In organic acids, the metal displaces hydrogen from the carboxyl group (–COOH)
of the alkanoic acid as shown in the following general equation.
Mg(s) + 2RCOOH(aq) ––––– (RCOO)2 Mg(aq) + H2(g)
displaces H
Now, let us look at the reaction of magnesium with ethanoic acid.

Magnesium + ethanoic acid ––––– magnesium ethanoate + hydrogen
Mg(s) + 2CH3COOH(aq) ––––– (CH3COO)2Mg(aq) + H2(g)
Note that the metal displaces hydrogen in the –COOH group and not the other
hydrogens.
3. Reaction of ethanoic acid with bases
Ethanoic acid reacts with bases to form salt and water. In experiment 6.3, it reacted
with sodium hydroxide as follows:
253
Sodium hydroxide + ethanoic acid ––––– sodium ethanoate + water
NaOH(aq) + CH3COOH(aq) ––––– CH3COONa(aq) + H2O(l)
4. Reaction of ethanoic acid with ethanol
In general, when organic acids are reacted with alkanols, they form esters in the
process of esterification as we had seen earlier. Ethanoic acid will react with
ethanol in the presence of a few drops of concentrated sulphuric acid to form
ethyl ethanoate. Concentrated sulphuric(VI) acid is a catalyst for the reaction.
Ethanoic acid + ethanol ethyl ethanoate + water
(ester)
H +
CH3CO OH (aq) + CH3CH2O H CH3COOCH2CH3(l) + H2O(l)
Ethyl ethanoate is one example of an ester.

Note: Always remember that the first part of the ester is derived from the acid
while the second part is derived from the alcohol. In writing the name of the esters,
we start with alcohol part and end with the acid part.
The process of esterification
In esterification, the hydroxyl group from the acid combines with the hydrogen atom
from the hydroxyl group of alcohol to form water and the remaining parts combine
to form the ester.
Ethanol + ethanoic acid ethyl ethanoate + water
H H H O H O H H
H-C-C-O H + H-C-C H-C-C-O-C-C-H + H 2O
H H H OH H H H
Esters have the general formula RCOOR¢. In the above example, R represents
CH3- from ethanoic acid and R¢ represents CH3CH2- from ethanol.
H O H H
H-C-C-O-C-C-H
H H H
R R¢
The general structure of an ester is represented as
254
O
R-C-O-R or R - COOR
R and R´ represent akyl groups which are not necessarily equal in carbon chain
length, but depends on the acid and alcohol used.
Esters form a homologous series of compounds that have strong pleasant smells.
Esters are responsible for many of odours in flowers and flavours in fruits. Flowers
and fruits have natural esters. For example, the fruity smell of a banana is because
of a particular ester; the fruity smell of a pineapple is because of another ester and
so on. They have also been used in food flavourings and perfumes.
We have seen that an alcohol and an organic acid react to produce an ester and
water through the process of esterification. Earlier, we also learnt that an alkali and
a mineral acid react to form salt and water in a neutralisation process. The differ-
ences between esterification and neutralisation reactions are listed below. Table 6.7
summarises the differences between these two important processes.
Table 6.7 Comparison of esterification and neutralisation
Esterification Neutralisation
1. The reaction is slow. 1. Fast or instantaneous.
2. Reaction is reversible. 2. Irreversible.
3. Forms esters and water. 3. Forms salts and water.
4. Heat or catalyst required. 4. No heat or catalyst required.
5. The esters formed are 5. Salts formed are ionic, in
molecules and in water solution form they are
they do not conduct electrolytes.
electricity.
When esters are boiled with alkalis, they break up. During hydrolysis, we get the acid
and alcohol used to form the same ester. This process is called ester hydrolysis.
Example
You are given the following ester to hydrolyse, CH3COOCH2CH3.
Determine the acid and the alcohol that were used to form it.
Solution
There are 2 things to remember before you solve this problem.
(a) The first portion of the ester is from the acid.
(b) The last portion is from the alcohol.
The oxygen atom bridging the two portions is from the alcohol.
Let us start with the last part of the ester.
(a) Cut the molecule as shown below, leaving the alcohol part with an oxygen
255
atom and the acid part also with an oxygen atom.
….…
CH3CO OCH2CH3
We know that the alcohol ends with –OH.
Add a ‘H’ atom on the alcohol part.
HOCH2CH3
Write the formula in the usual way to get the alcohol used.
CH3CH2OH
Name the alcohol i.e. ethanol
(b) The acid must end with OOH.
In the acid part, we already have one ‘O’ atom. Add the remaining O and H
atoms to get the acid.
CH3COOH
Name the acid i.e ethanoic acid.

1. Methanoic acid is added to the same volume of ethanol in the presence of
concentrated sulphuric acid and warmed.
(i) What is the name of the ester formed ?
(ii) Write an equation for the reaction in (i).
2. Write equations and name the products in the following reactions
(a) propanoic acid and potassium.
(b) ethanoic acid and potassium hydroxide.
(c) methanoic acid and lead carbonate.
(d) butanoic acid and magnesium oxide.
(e) butan-1-ol and ethanoic acid heated in the presence of
concentrated sulphuric acid.
3. What is the functional group in an alkanoic acid?
4. Write the molecular formula and structural formula for butanoic and
heptanoic acids.
5. Ethanoic acid is a weak acid. Explain.
6. Explain why the boiling point of ethanoic acid (118˚C) is higher than that of
propan-1-ol (b.p. 97˚C) and yet they have the same molecular mass.
7. Which ester forms from the reaction between methanol and ethanoic acid? Write
a word equation for the reaction.
8. Describe with equations, the reaction between ethanoic acid and sodium metal.
9. The following ester, HCOOCH3 was hydrolysed. Write the formula and names
of the organic acid and alcohol used to form the ester.
256
Uses of ethanoic acid
Ethanoic acid is one of the world’s most important chemicals. It serves as an
intermediate in the production of various products as indicated below.
• It is used in the manufacture of a wide range of polymers e.g. ethyl ethanoate
which is used in adhesives and others for films, paints, textiles and paper.
• Ethanol is used in production of ethanoic anhydride used in the manufacture of
pharmaceuticals like aspirin, bleaching agents in detergents; agro-chemicals
(like herbicides) and dyes.
• It is used in the manufacture of butyl ethanoate which is used in the production
of many paints, dyes, adhesives and ink.
• Chloroethanoic acid is used in the production of wallpaper, adhesives,
herbicides, pharmaceuticals and cosmetics.
6.3 Detergents
Detergents are cleaning agents which are used to improve the cleaning properties
of water. Water has a high surface tension and does not wet greased surfaces well.
Water also does not dissolve grease. To be able to remove such substances using
water, we need to add compounds to the water to enable it to wet and soak the clothes
between the fibres, separate grease and any other dirt from the fibres and suspend
the grease or dirt in the water so that it can be washed away. Any substance that
has the above characteristics is called a detergent. Detergents are not only used in
cleaning clothes,they are also applied in cleaning dishes, vehicles, walls of houses
among very many other things.
There are two types of detergents:
1. Soapy detergents
2. Soapless detergents
Soapy detergents
Soap is a mixture of the salts of medium-chain and long-chain alkanoic acids. For
example, if we react an 18 carbon-chain alkanoic acid, for example octadecanoic
acid, CH3(CH2)16COOH, with sodium hydroxide we will get a salt (soap) and water.
Generally ,
Alkanoic acid + sodium hydroxide ––––––– salt + water
(soap)
RCOOH(aq) + NaOH(aq) ––––––– RCOO–Na+(aq) + H2O(l)
salt (soap)
We can react octadecanoic acid with sodium hydroxide to form sodium octadecanoate.
CH3(CH2)16COOH + NaOH(aq) ––––––– CH3(CH2)16COO–Na+(aq) + H2O(l)
(soap)
257
However,soaps are made by reacting esters with concentrated sodium hydroxide
solution.
Experiment 6.4
Laboratory preparation of soapy detergents.
• 100cm3 beaker
• coconut oil, castor oil or animal fat
• sodium hydroxide solution
• sodium chloride
• retort stand and clamp
• wire gauze
• filter paper
• filter funnel
• source of heat
Procedure
1. Pour about 4cm3 of castor oil or place about 40g of animal fat into 100cm3
beaker.
2. Add about 15cm3 of 4M sodium hydroxide solution.
3. Boil the mixture for about 10-15 minutes stirring and adding small amounts of
distilled water. The distilled water should make up for evaporation.
4. Add about four spatula full of sodium chloride and stir well.
5. Allow the mixture to cool.
6. Filter off the solid.
7. Wash the solid residue with distilled cold water.
8. Place the solid residue in a clean dry beaker.
• What did you observe in every stage of the above procedure?
• What can you conclude from the above observations?
9 Place a small piece of the solid residue in two separate test tubes.
(i) In one test tube, add about 5cm3 of warm distilled water and shake well.
(ii) In the other test tube, add warm tap water and shake well.
• What do you observe from each test tube? Explain your observations.
• What would happen if you had added warm sea water? Explain
your answer.
Soapy detergents are prepared by hydrolysing vegetable oil or animal fat using an
alkali (concentrated sodium hydroxide solution). This reaction is an example of
saponification reaction. Sodium chloride is added to help in precipitating the soap.
It does this by reducing the solubility of the soap in a process called salting out.
258
Fats and oils are esters of long-chain alkanoic acids called fatty acids and glycerol,
an alcohol with three hydroxyl (–OH) groups. They occur naturally in plants and
animals.
An example of an ester found in fats and oils is a structure as shown below. Note that
the structure has ‘3 parts’ of a long alkanoic acids numbered as 1, 2 and 3.
1. C17H35COO – CH2
2. C17H35COO – CH
3. C17H35COO – CH2
fatty acid part glycerol part
When a fat is boiled with sodium hydroxide solution, it is hydrolysed to give glycerol
(propan-1,2,3-triol) and soap (sodium octadecanoate) i.e.
This part gives glycerol
C17H35 CO O – CH2 CH2 – OH

3NaOH boil 3C17H35 COO–Na+ + CH – OH
C17H35 CO O – CH +
sodium
octadecanoate CH2 – OH
C17H35 CO O – CH2 (soap) (Glycerol)
(fat) propane–1,2,3 – triol
NB: Each part of the acid formed reacts with NaOH to form the salt i.e sodium
octadecanoate (C17 H35 COO– Na+) which is the soap. This is neutralisation.
3C17H35 COOH + 3NaOH –––– 3C17 H35 COO–Na+ + 3H2O

Sodium octadecanoate
(soap)
Soaps can be prepared using the general method which can be represented by the
following equation:
Fat or oil + sodium hydroxide –––––– soap + glycerol
259
CnH2n+ 1 COO – CH2 CH2 – OH
CH – OH
CnH2n+ 1 COO – CH2 + 3NaOH –––– 3CnH2n+1COO–Na+ +
(alkali) (soap) CH2 – OH
CnH2n+ 1 COO – CH2
Fat or oil Propane–1,2,3-triol

(glycerol)
Note that soap is the sodium salt of the fatty acid.
The general formula for ordinary soap is CnH2n+1COO–Na+.
• We can summarise the process of making soap by alkaline hydrolysis in a flow chart
as shown below. It involves hydrolysis, neutralization, salting and addition of
perfumes or colours.
Fat or vegetable
Alkali
oil
Boil Sodium chloride
Filter
Residue Filtrate
Colouring agents
and perfumes are Propane-1,2,3-triol
Soap
added according to (glycerol)
market demands
Fig. 6.4: Flow chart for the preparation of soap

1. What is saponification reaction?
2. List the reagents required for the preparation of a soapy detergent (soap).
3. What is observed when the reagents in 2 above are added together and
heated?
4. What is the purpose of adding sodium chloride when preparing soap?
5. Write a chemical equation for the formation of soap from animal fat.
260
Mode of action of soapy detergents
Detergents help water to soak into clothes when they are being washed. The detergent
forms a thin layer on top of the water. This layer breaks down the strong forces of
attraction between water molecules on the surface.
Assume our soap has a structure as shown below.
CH3(CH2)16 COO–Na+. We can represent this structure as RCOO–Na+ or
COO–Na+
non–polar Polar R or represent the long carbon chain.
‘tail’ ‘head’
We say that detergents reduce the water surface tension. This causes the water to
spread out more easily as illustrated in Fig.6.5 below
• • • • •
• • • • • • • •
Na+
• • • Water • Na+ • •
• • • • • • • • •• Na
+
• • • Na+ • • • • •
+
• Na+ • • •
Na
Na+ • • • • • • • • • • • • •
• • • • • •
• Grease on fibre • • • • • Grease on fibre • • • • •
• •
• • • •
Fabric • • • ’tails’ enter into grease Fabric
• •
• • • •
(a) • • • • (b) •
• ••
Na+ • Na+• •• • • •
• • • •• • • •
• • • • Water •
• • • • •
Na+
detergent Na+ • • •
• • grease droplets
• • (micelle) float in
• •• Na+•
•
•
•
•
polar non-polar Clean fibre water
‘head’ ‘head’ grease is lifted from the fibre Fabric
(c)
Fig. 6.5: How soap removes grease or oil from fabrics

1. The ‘tail’ of soap molecule is non-polar. We can regard it as a grease-loving end
hence gets attracted by grease. The ‘head’ of the soap molecule is polar. It is
attracted by water molecules.
• When we are washing, soap molecules dissociate in water. The long non-polar
hydrocarbon chain (‘tail’) of the soap molecule dissolves in grease or oil. The
polar end (‘head’) of the molecule is attracted by water molecules.
2. When the solution is stirred or agitated, the grease is lifted from the cloth fibre
and surrounded completely by soap anions as shown in Fig. 6.5(c) thereby
removing the dirt from the clothes effectively.
3. Once the grease has been lifted up from the fabric by the detergent, it floats and
spreads throughout the water as tiny droplets of an emulsion which makes the
water cloudy. Rinsing with fresh water removes the grease emulsion.
The droplets cannot mix because they repell each other due to the –vely charged
anions on their surfaces.
261
Pollution effect of soapy detergents
Detergents are used in everyday life in homes, industries, offices, hotels among many
other places. Soapy detergents are biodegradable. This means they can be broken
down by micro-organisms like bacteria in the water or in the soil. Such detergents
sometimes find their way into our rivers, lakes and oceans.When bacteria decompose
biodegradable detergent wastes, they use oxygen and produce carbon(IV) oxide and
water. On land there is plenty of oxygen but in water, the amount of oxygen is lim-
ited. Bacteria can multiply quickly and soon oxygen levels decrease. Low oxygen
levels in water have an adverse effect on aquatic animals (e.g. fish) and plants .These
aquatic animals move to another area or die.

1. What is pollution?
2. What is water pollution?
3. Explain the effect and remedies of water pollution by soapy detergents.
Water hardness and soapy detergents

Water hardness
Water hardness is caused by presence of Ca2+ and Mg2+ ions in water.
Experiment 6.5
To investigate the effect of water hardness on soapy detergents
Apparatus and chemiclas
• test tubes
• sea water (if available)
• calcium sulphate or magnesium sulphate
• distilled water
• soapy detergent (soap)
• dropper
Procedure
1. Place about 15-20 cm3 of distilled water in a test tube.
2. To another test tube, place 15-20 cm3 of sea water. In the absence of sea water,
dissolve 1/2 spatula of calcium sulphate in about 15-20 cm3 of water.
3. To each test tube, add about 3-4 drops of soapy detergent.
4. Shake the mixture well
• Explain your observations and conclusions from the above experiment.
From experiment 6.5, you have observed that it was difficult for soap to produce
lather in the test tube with sea water or the water with dissolved calcium sulphate.
262
You must have seen bits of white scum floating in the water or on the sides of the
container when you used soapy detergent.
Many compounds dissolve in water without any chemical change but have a lot of
consequences. Some of these dissolved substances make the water hard.This means
that the water does not readily form a good lather with soap and causes formation of
scum. Distilled water or pure water contains no dissolved solid impurities and lathers
easily with soap.
Hard water is caused by dissolved magnesium and calcium hydrogencarbonates
and calcium and magnesium sulphates. The hard water is formed when natural
waters flow through rocks containing calcium and magnesium compounds. For
example:
• chalk or limestone which contains mainly calcium carbonate CaCO3.
• or gypsum rock deposits which are mainly calcium sulphate (CaSO4) and
magnesium salt mainly magnesium sulphate (MgSO4.7H2O).
These calcium and magnesium salts are washed out of rock formations.They then
dissolve in acid rain forming the compounds which cause hardness in water.
We have learnt about two types of hardness in water namely:
1. Temporary hardness
2. Permanent hardness
Temporary hardness is caused by dissolved calcium hydrogencarbonate and magnesium
hydrogencarbonate and permanent hardness is caused by dissolved calcium sulphate
and magnesium sulphate. Hard water forms scum from the dissolved calcium and
magnesium compounds. The scum is a precipitate formed when calcium and
magnesium ions react with soap. After using more soap than would otherwise be
required, lather does form when all the calcium and magnesium ions have been
precipitated. For example
Calcium + Soap ––––––– calcium + Sodium

sulphate octadecanoate sulphate
(Scum)
CaSO4(aq) + 2C17H35COONa(aq) –––––– (C17H35COO)2Ca(s) + Na2SO4(aq)

Ionic equation
Ca2+(aq) + 2C17H35COO–(aq) ––––––– (C17H35COO)2Ca(s)
Magnessium ions are precipitated in the same way.
Using hard water can increase costs because more soap is needed. However, hard
water can be made soft by removing the dissolved calcium and magnesium ions.
1. If it is due to hydrogencarbonates, it is removed by boiling.
The following experiment was done by some students in a certain school.
263
Add Add
little a lot of
Lather
soap soap
Slightly (a) (c)

acidic water
Add
Boil little Lather
soap
Hard
water
(b) (d)
Fig. 6.6: Effect of hard water on soapy detergent
(i) What do you expect to observe in test tube (a) and (b). Explain.
(ii) Predict observations made in (c) and (d). Explain your observations.
(iii) What conclusions can you make from these observations?
2. Temporary hard water caused by calcium hydrogencarbonate can be removed by
boiling.
3. On addition of sodium carbonate as washing-soda crystals it dissolves and
precipitates out the calcium and magnesium ions as insoluble carbonates.
4. The hardness of water can also be removed by an ion exchange column. Ion
exchange polymer resin columns hold sodium ions. These ions can be replaced
by calcium and magnesium ions when hard water passes down the column.
Sodium ions do not make water hard.
Note: Permanent water hardness cannnot be removed by boiling while temporary
hardness can be removed by boiling.
1. If the water in your home is hard, how can that affect the cleaning of your clothes?
2. How can you remove or decrease the hardness of water so that the soap can be
effective?
Soapless detergents
Because of the problems associated with soapy detergents e.g not lathering easily in
hard water, chemists have made molecules which have similar structures, but improv-
ing some of their characteristics to produce better cleaning agents. Such agents are
called soapless detergents. Unlike soapy detergents, they do not form scum with hard
water. Soapless detergents are made from by-products of crude oil distillation.
Experiment 6.6
Preparation of soapless detergents.
264
• teat pipette
• beaker
• stirring rod
• olive oil
• tap water/any other hard water, e.g. sea water
• distilled water
Procedure
1. Place about 15 cm3 of olive oil in a beaker.
2. Place the content of the beaker in ice cold water.
3. Stir the content with glass rod as you carefully add concentated sulphuric acid
drop by drop using a dropper.
4. When the yellow oil turns brown, stop adding the acid.
5. Add about 25 cm3 of 6M sodium hydroxide solution.
Dropper Beaker
6M NaOH
Olive oil Soapless

detergent
Beaker Ice
Acidic organic
compound
Fig. 6.7: Preparation of soapless detergent

6. Place about 5 cm3 of the product into two separate test tubes.
(i) To one of the test tubes, add distilled water and shake well.
(ii) To the other test tube, add tap water or sea water (or water made hard by addition
of MgSO4 and shake well.
• What do you observe in (i) and (ii) above?
• What is the purpose of adding sodium hydroxide solution?
• What do you conclude from your observations?
• Record all your observations and conclusions in your note book.
Sodium hydroxide solution is added to neutralise the excess acid during the reaction.
Soapy and soapless detergents are very similar in structure despite the different
methods of preparation. Both have a long hydrocarbon chain attached to an ionic
group. In soapy detergents, the ionic group is –COO– and in soapless detergents, it
is –OSO3–.
265
O
C Soapy
O Na + detergent
long hydrocarbon chain
ionic group
(or ‘tail’ non-ionic)
C - O - S - O– Na+ Soapless
detergent
long hydrocarbon chain O
(or ‘tail’ non-ionic) ionic group
The olive oil has a double bond. Concentrated sulphuric acid adds to the double bond to
form a compound called alkyl hydrogensulphate. This alkyl hydrogensulphate then
reacts with sodium hydroxide to form a sodium alkyl sulphate which is the soapless
detergent. This reaction is comparable to the reaction of ethene with sulphuric acid. When
ethene is reacted with concentrated sulphuric acid, it forms ethyl hydrogensuphate.
ethene + conc. sulphuric acid ethyl hydrogensulphate
H H H H
C=C + conc. H2SO4(l) H - C - C – OSO3H
H H H H
The above product is then neutralised by the sodium hydroxide solution, the hydrogen
in hydrogensulphate is replaced by a sodium atom to form sodium ethylsulphate.
Ethyl + sodium ––––––– sodium + water

hydrogensulphate hydroxide ethylsulphate
H H H H
H - C - C - OSO3H + NaOH(aq) H - C - C - OSO3–Na+ + H2O
H H H H
The sodium ethylsulphate is equivalent to the soapless detergent.

• Ethyl hydrogensulphate can also be made from alcohols. Let us consider the following
familiar reaction of ethanol and sulphuric acid to form ethyl hydrogensulphate.
266
Ethanol + conc. sulphuric acid ethyl hydrogensulphate
H H H H
H – C – C – OH + conc. H2SO4(aq) H – C – C – OSO3H
H H H H
When the ethyl hydrogensulphate is neutralised by sodium hydroxide, sodium
ethyl sulphate is formed
Ethyl + sodium –––––– sodium + water
hydrogensulphate hydroxide ethylsulphate
H H H H
H – C – C – OSO3H + NaOH(aq) H – C – C – OSO–3Na+ + H2O
H H H H
Industrial manufacture of soapless detergent

The principles that we have discussed above are used in the manufacture of soapless
detergents.Alcohols of long chain hydrocarbons of 12 to 18 carbon atoms are used.
They are reacted with sulphuric acid to form alkyl hydrogensulphate.
Alcohol + conc. sulphuric acid ––––– alkyl hydrogensulphate
R - OH(l) + conc. H2SO4 ––––– R - OSO3H(aq)
R-represents an alkyl group.
The alkyl hydrogensulphate is then neutralised by sodium hydroxide to form
sodium alkylsulphate which is the soapless detergent we require.
Alkyl + sodium ––––– sodium + water
hydrogensulphate hydroxide alkylsulphate
R - OSO3H(aq) + NaOH(aq) ––––– R - OSO–3Na+ + H2O(l)
Soapless detergent
The actual structure of the part of a soapless detergent represented by R can be a
complex as shown in the following soapless detergent.
CH3(CH2)11 O –– OSO3– Na+.
non-polar end polar end
267
Note that the polar end of a soapless detergent has OSO3– group while that of a soapy
detergent has – COO– group.
Examples of soapless detergents include: Omo, Toss, Sunlight among others.

1. Write an equation for the preparation of soapless detergents?
2. What is the difference between soapy and soapless detergents?
3. What is the effect of hard water on soapless detergents?
Mode of action of soapless detergents

The mode of action of soapless detergents is the same as that of a soapy detergent.
The hydrocarbon tail which is grease-loving will dissolve in fats, grease or oil while
the ionic head which is water-loving dissolves readily in water.
O
O - S - O - Na+
grease loving ‘tail’ water loving ‘head’
The tails of molecules of detergents stick into the greasy dirt and attraction between
water molecules and the detergent molecules lifts the dirt from the fibre as illustrated
in Fig. 6.5 (c). Agitation of the solution helps to lift the dirt. The grease is then
suspended in the solution with repulsive forces between detergent anions, preventing
grease from returning to the material. Grease spreads through the water as tiny droplets.
This is an emulsion and makes water look cloudy. On rinsing, the emulsion is
washed away.
Note: Whereas soap forms scum with calcium and magnesium ions in hard water,
soapless detergents do not.
Pollution effects of soapless detergents
Soapless detergents have very serious effects on the environment. They are not
biodegradable like the soapy detergents, that is, they are not broken down into
harmless chemicals by the micro-organisms. They, therefore, tend to persist in water,
sewage treatment and cause foaming in rivers and streams.
Advantages of soapless detergents over soapy detergents
• They do not form scum with hard water.
• They are made from petroleum products, hence save animal fats and vegetable
oils to be used for human consumption.
268
Disadvantages
Soapless detergents are non-biodegradable, hence pollute the environment.

1. What is a detergent?
2. Differentiate between soapy detergents and soapless detergents.
3. When hard water is used in cleaning, it forms a lot of scum with soap.
(a) With the help of equations, explain how temporary hard water is formed.
(b) What is scum? Explain using equations how it is formed.
(c) Detergents are needed to make things clean when washing with water.
With the help of an illustration, explain how a detergent cleans.
4. (a) What is water pollution?
(b) When is water said to be polluted ?
(c) How do detergents cause water pollution?
(d) What are the effects of water pollution caused by detergents?
6.4 Polymers and fibres

Polymers and fibres are giant molecules. Polymers vary in strength and flexibility.
Polymers which do not stretch readily are suitable for use as fibres. They occur natu-
rally or may be made artificially in industries by joining small units, called monomers.
The process by which they are formed is called polymerisation. Polymers and fibres
can be classified into two groups.
(a) Natural polymers and fibres.
(b) Synthetic polymers and fibres.
Natural polymers and fibres
All living things contain polymers. Proteins,carbohydrates,wood and natural rubber
are all polymers.These polymers are formed in nature i.e. they are not man-made
polymers. Examples of some natural polymers/fibres are:
• Starch
• Cellulose e.g. cotton, wool, paper, silk.
• Proteins
• Glycogen
• Fats
• Rubber
Synthetic polymers and fibres
These are polymers and fibres that are man-made.They include
• Polythene
• Polychloroethene(PVC)
• Polyphenylethene(Polystyrene)
• Terylene
269
• Nylon
• Perspex (artificial glass)

1. What is a natural polymer and fibre?
2. Name four
(i) natural polymers and fibres.
(ii) synthetic polymers and fibres.
Sythetic polymers are made by polymerisation. There are two kinds of polymerisation:
• addition polymerisation.
• condensation polymerisation.
Addition polymerisation of some synthetic polymers
Addition polymerisation involves joining monomers, which are unsaturated molecules
like ethene, chloroethene and phenylethene etc. During polymerisation of ethene
for example, the double bonds between the carbon atoms are broken down enabling
many molecules of ethene to join to each other to form a large molecule called
poly(ethene). It is commonly called polythene. Polythene is therefore an addition
polymer. This can be summarised in the following equations.
high pressure
ethene polythene
heat,catalyst
H H H H H H
Monomers
C=C + C=C + C=C
(Ethene)
H H H H H H
H H H H H H
Double bond •C- C• •C- C•
+ + • C - C • + …………
broken
H H H H H H
H H H H H H
Uniting of
monomers •C -C- C -C- C -C•
H H H H H H
Polyethene (polymer)
270
Note that at each end of the polymer, there is a lone electron indicating that more
monomers can be joined to form a longer polymer. In this way, a very long chain of
carbon atoms is formed.The chain may contain over 50,000 carbon atoms or less. If
n molecules of ethene combine, the process can be written as.
H H H H
n C=C C - C
H H H H n
Polyethene
2. Polychloroethene (Polyvinylchloride) PVC
Polychloroethene is made from monomers called chloroethene. It is also formed
by addition polymerisation.
H H H H H H
Monomer
(chloroethene) C=C + C=C + C=C
H Cl H Cl H Cl
H H H H H H
Double bond
•C- C• + •C- C • + • C - C • +………
broken
H Cl H Cl H Cl
Uniting H H H H H H
monomers • C- C- C -C -C -C•
H Cl H Cl H Cl
Polychloroethene (polymer)
Again, if n-molecules of chloroethene combine we get;
H H H H
n C=C C- C
H Cl H Cl n
Polychloroethene (PVC)
271
3. Polyphenylethene is also formed by addition polymerisation.
H C6H5 H C6H5 H C6H5
Monomer
(phenylethene) C=C + C=C + C=C
H H H H H H

Double bonds
•C- C • + • C- C • + • C – C • + …………
broken
H H H H H H
Uniting
monomers • – C – C – C – C – C – C –•
H H H HH H
Polymer (polyphenylethene)
n–molecules combine as follows
H C6H5 H C6H5
n C=C C– C
H H H H
n
Note that C6H5 can be represented as Polyphenylethene
(polystyrene)
Table 6.8 Summary of polymers formed by addition polymerisation
Formula of Name of Reaction
Name of polymer monomer monomer conditions Part of polymer chain
H H Low temperautre H H H H
Polyethene C C Ethene (gas) and pressure, C C C C
(high density form) special catalyst
H H H H H H
H H 60 ˚C, high H H H H
Polychloroethene pressure,
C C C C C C
(PVC) Chloroethene H2O2 catalyst
H Cl H Cl H Cl
H H Catalyst, heat H H H H
Polyphenylethene
(Polystyene) C C Phenylethene C C C C
H C6H5 (styrene) H C6H5 H C6H5
272
Condensation polymerisation
This is the formation of a single molecule by the combination of two or more mol-
ecules. This process usually is accompanied by elimination of a simple molecule
e.g. water or hydrogen chloride. For example, if we want to join the boxes below,
we can do that by giving off a simple water molecule as shown.
HO –- A ––– H + HO –– B ––– H + HO –– A –– H + HO – B – H
Condensation polymerisation
HO –– A –– B –– A –– B –– H + 3H2O
“Poly AB”
Nylon and terylene are made by condensation polymerisation.
Let us consider condensation polymerisation of nylon. Nylon is a polymer of
1,6-diaminohexane and hexane-1,6-dioyl dichloride.
The structure of 1,6-diaminohexane is
H H H H H H H H
N – C –C – C – C – C – C – N
H H H H H H H H
1,6-diaminohexane
H
which can be represented as H for simplicity while the structure of
hexane-1,6-dioyl dichloride is
O H H H H O
C–C–C–C– C – C
Cl H H H H Cl
Hexane–1,6– dioyl dichloride
which we can be represented as Cl Cl
When a molecule of1,6-diaminohexane reacts with a molecule of hexane–1,6–di-

oyl dichloride, the two join by eliminating a hydrogen chloride molecule.
H H + Cl Cl H Cl + HCl
‘polymer’
273
This process can occur again and again forming a long polymer which is called
nylon.
H Cl
longer polymer
Now, let us see how nylon is polymerised using actual monomers.
H H H H H H H H O H H H H O
… + N - C- C -C- C - C- C - N + C - C - C - C - C - C +……
H H H H H H H H Cl H H H H Cl
Hexane–1,6– dioyl dichloride
H 1,6-diaminohexane H O O
… + N - CH - CH - CH - CH - CH - CH - N - C - CH - CH - CH - CH - C…+
2 2 2 2 2 2 2 2 2 2
nylon
bond joining the HCl
two monomers

1. Name two methods of preparing polymers and fibres.
2. With equations, describe the preparation of
(i) polyphylethene
(ii) nylon
3. Write equations for the formation of polystyrene from styrene.
4. Name the monomer that forms cellulose.
Properties of synthetic polymers

Although different polymers have unique characteristics, many synthetic polymers
have the following properties.
• They do not corrode in air or water.
• They are thermal insulators.
• They are electrical insulators.
• They do not decompose easily.
• They are relatively light.
• Some synthetic polymers are soft and malleable while others are very strong.
• They are cheap to produce.
• Some are transparent.
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Table 6.9 Properties and uses of specific synthetic polymers
Name of Trade name Properties Uses
polymer of polymer
Polyethene Polythene • tough Used in making

• durable • pipes and plastic bags
• bowls and bottles
• packaging material
• insulation for electric
wiring
Polychloroethene Polyvinyl chloride • tough Used in making

(PVC) • durable • crates and boxes
• plastic rope
• artificial leather
• water pipes
• insulation for electrical
wires
Polyphenylethene Polystyrene • light Used in making
• poor • insulation material
conductor • packaging(foam)
of heat • ceiling tiles
• clothes
• plastic model kits
Terylene Terylene • light Used in making

( a polyester) • tough • clothing e.g.
• durable shirts and trousers
• sails and ropes
• plastic model kits
Nylon Nylon • light Used in making

• tough • ropes
• durable • clothings
• carpets
Perspex Perspex • strong Used in making

• transparent • safety glass
• reflectors
• contact lenses
• false teeth
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Table 6.10 Summary of monomers and their respective polymers
Monomer Polymer Trade
Name
H H H H
C=C C -C Polythene
H H H H n
Ethene Poly(ethene)
H Cl H Cl
Polyvinyl
C=C C -C chloride
H H H H n (PVC)
Chloroethene Polychloroethene
H C6H5 H C6H5
C=C C - C Polystyrene
H H H H n
Phenylethene Polyphenylethene
HO - CH2 - CH2 - OH
Ethane-1,2-diol O O
O + O --- O – C – C6H5 – C–O –CH2–CH2--- Terylene
C - C6H5 - C
OH OH
Terylene
benzene–1,4–dicarboxylic acid
H H
NCH2CH2CH2CH2CH2CH2N
H H O O
H H
hexane–1,6–diamine --N–(CH2)6–N–C–(CH2)4–C-- Nylon–6,6
and
O O Nylon
CCH2CH2CH2CH2C NB: The C and H are written as
Cl Cl (CH2) where n is 6 or 4 as in the
hexane–1,6–dioyl dichloride diagram.
276
O
H C - O - CH3 Polymethyl-2-meth-
ylpropanoate Perspex
C=C
H CH3
Methyl 2-methylpropanoate
F F Polytetrafluoro- PTFE,
C=C ethene ‘Teflon’
F F
Tetrafluoroethene
6.5 Advantages and disadvantges of synthetic and natural poly-

mers and fibres
The advantages and disadvantges of synthetic and natural polymers and fibres
have been summarised in Table 6.11 and 6.12 below.
Table 6.11 Advantages and disadvantages of synthetic polymers and fibres.
• They are light and therefore • They have comparatively low
portable. strength.
• They are soft, and easy to manufacture. • They have poor heat resistance.
• They can be made into complicated • They have poor weather resistance.
shapes more easily i.e. are malleable. • They have low dimensional stability.
• They are good insulators and • They are not biodegradable hence
thermal radiators. difficult to dispose.
• They are resistant to corrosion • Some synthetic polymers give
from acids, alkalis,water and air. off poisonous gases e.g. carbon(II)
• They are colourful and attractive. oxide when they are burnt.
• They are cheap and therefore affordable. • They increase carbon(IV) oxide in
the atmosphere when they burn.
Carbon(IV) oxide causes global
warming.
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Table 6.12 Advantages and disadvantages of natural polymers and fibres
• They are biodegradable and can easily be disposed. • Cannot be moulded into
• They do not burn readily. complicated shapes like
• Do not produce poisonous gases when the burn. synthetic polymers.

1. State three advantages and disadvantages of
(i) synthetic polymers and fibres.
(ii) natural polymers and fibres.
2. What is a biodegradable and non-biodegradable material?
3. List two examples of each in (2) above.
4. What problems do synthetic polymers and fibres cause in the environment?
5. Suggest four ways to deal with pollution of the environment by synthetic
polymers and fibres.
Rubber
You probably have seen rubber. An example of rubber is the one you use to erase while
drawing. Rubbers are plastic materials which are elastic. Rubber can be natural or synthetic.
Natural rubber
Natural rubber is a polymer of 2–methylbut–1,3– diene i.e.
H CH3 H
H CH3 H
C = C – C = C C C = C – C
H H H H H H
n
(2-methylbut-1,3-diene) natural rubber (n = 100–5000)
Natural rubber is obtained from rubber trees. The trees produce a milky substance
called latex. Latex is a mixture of rubber and water. The latex is collected from
incisions in the trunks of rubber trees then taken to the factory for processing to
produce rubber. During processing, acid is used to coagulate the rubber. The solid
rubber can then be made into different shapes for different uses. Pure rubber is
soft and sticky. However, its physical properties can be improved or modified by
heating with sulphur. The process by which rubber is heated with sulphur is known as
vulcanisation of rubber. The sulphur atoms form cross-links between chains of rubber
molecules decreasing the number of double bonds in the polymer. Vulcanised rubber is
harder, tougher and less flexible. It also has a wide range of applications in industries.
278
CH3
CH2 CH2 C CH CH2 Sulphur atoms
S forming cross-links
S
CH2 CH2 CH2 CH CH2 n
Vulcanised rubber
Some uses of vulcanised rubber

Vulcanised rubber is used to make tyres, valves, shoes and for flooring. Name other
uses of vulcanised rubber.
Synthetic Rubber
Because of disadvantages associated with the physical properties of natural rubber i.e.
being soft and sticky; a tougher rubber was necessary. Synthetic rubber is made in such a
way that it resists action of oils, solvents and abrasion. An example of synthetic rubber
is polybutandiene shown below.
Cl H Cl H H
n CH2 = CCH = CH2
Catalyst
C C C –– C
n
2–chlorobuta–1,3–diene H H H H
Poly–2–chlorobutan–1,3–diene

1. State three uses of sythentic rubber.
2. What is vulcanisation of rubber?
3. Name two processes of strengthening rubber.
Disposal of synthetic polymers

Plastic waste like polythene bags,drinks containers and coffee wrappers litter our
environment within the cities and on the country side. Cattle and other domestic
animals have been choked after swallowing plastic materials. The problem is made
worse by the fact that plastic articles are non-biodegradable i.e. cannot be broken down
by micro-organisms like bacteria. They do not decompose like paper, wood among
other natural polymers. So, we should avoid careless disposal of these wastes.
279
How then do we dispose off these wastes?
1. Dumping in holes underground.
2. Destroyed by burning.
3. Produce biodegradable plastics. Biodegradable plastic bags are already available
in some parts of the world.
4. Recycling the plastics.
Note: The safest methods are the ones named in number 3 and 4 above.
• Explain why methods 1 and 2 above are not recommended for disposal of plastics?
Plastics are non-biodegradable and will stay underground for a very long time. Burning
plastics can produce toxic gases into the atmosphere and also carbon(IV) oxide
which causes global warming.

1. What is polymerisation ?
2. How many products are formed from an
(i) addition polymerisation?
(ii) condensation polymerisation?
3. An addition polymer is made from a monomer Q shown below.
Draw part of the polymer chain that forms and name the polymer.
F F
C = C
F F
Q
4. The molecular mass of a polymer does not have a fixed value. Explain.
5. Ethene is used in the manufacture of the plastic poly(ethene). Ethene is heated
under high pressure in the presence of a catalyst. Many ethene molecules join
together to form a giant molecule poly(ethene). The diagram below shows how
the polymer is formed.
H H H H
Catalyst
n C=C C –C
H H H H n
(i) What is the name given to this reaction?

(ii) Describe how ethene molecules join together to form poly(ethene).
6. What enviromental effects do plastics have?
280
H H H H
(i) 7. The following are two addition
C C C C polymers. Write the formulae and
names for the monomers.
H O H O n
(ii) CH2 ––– CH –– CH2 –– CH
Cl Cl n
Cl H
8. Write an equation to represent polymerisation of
1–chloroprop–1–ene whose structure is as shown C C
below. What is the name of the polymer formed? H CH3
Summary
• Organic Chemistry is the study of the chemistry of the compounds of carbon.
• The oxides of carbon (CO2 and CO); carbonates; hydrogencarbonates and carbides
of metals are not in form of chains or rings. Therefore, these compounds are
studied under Inorganic Chemistry.
• A homologous series is a group of similar compounds which have a similar
general formula and hence have similar chemical properties.
• Alkanols have a general formula of CnH2n+1OH, where n = 1, 2, ……
• Alkanoic acids have a general formula of CnH2n+1COOH, where n = 0, 1, 2, ……
• Graphical formula shows the individual atoms in a molecule and the way they
are arranged.
• Structural formula shows the arrangement of the atoms in the molecule.
• Molecular formula shows only the number of atoms of the different elements in
the molecule of the compound, and not how they are arranged.
• All alkanols have a hydroxyl group (–OH) on one of the carbon atoms as the
functional group.
• All alkanoic acids have a carboxyl group (–COOH) on one of the carbon atoms
as the functional group.
• The process of converting fatty acids to soap is known as alkaline hydrolysis.
• The process of converting esters to form soaps is known as saponification.
• Polymerisation is the process of combining simple molecules (monomers) of
the same or different kind to form a more complex and large one (polymer).
• Addition polymerisation is the combination of similar molecules or pairs of
dissimilar molecules to produce one product only.
• In condensation polymerisation, the process is accompanied by the removal of
small molecules like water, ammonia or hydrogen chloride between monomers
to form a polymer.
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• Synthetic polymers and fibres should be discouraged for the sake of our natural
environment, which they heavily pollute.
Projects
1. Petroleum products are common in all countries of the world. Visit an oil refinery
if possible and discuss with the chemists about all the processes involved in
getting various products from crude oil. Write a detailed report.
2. Visit a brewery if possible and have a serious discussion with the chemists on
the brewing process. Write a report on this and in it, include the economic and
social impact of beer consumption in Kenya.
Revision Exercise 6
1. (a) Write down the formula for ethanol and draw its structural formula.
(b) Ethanol is produced by fermentation of sugar solutions.
(i) Name the other product of fermentation.
(ii) Give two other conditions which are necessary before fermentation
takes place.
(iii) How can the dilute solution of ethanol produced by fermentation be
concentrated?
(iv) State two uses of ethanol.
2. Write the structural formula of each of the following substances.
(a) C3H7OH
(b) CH3COOH
(c) Butanoic acid
(d) Hexan–l–ol
3. The boiling points of the first six alkanols are given in the following table
Number of C atoms 1 2 3 4 5 6
Boiling points 64˚C 78˚C 97˚C 117˚C 132˚C 154˚C
(a) What conclusion can be drawn from the information given in the table above?
(b) The boiling points of the first six alkanes are much lower compared to those
of the alkanols of same number of carbon atoms given in the table above.
Explain.
4. Two alkanols X and Y have the same composition by mass: carbon 60%, hydrogen
13.3% and the rest is oxygen. Their relative molecular mass is 60.
(a) Determine the empirical formula and the molecular formula of compound X
and Y.
(b) Write two structural formulae for the two isomers.
(c) Name the two isomers.
5. Write the structural formula for ethanol and hexan–1–ol. Why is it necessary to
282
write‘l’ in hexan–1–ol? Why is there no number included in the name ethanol?
6. (a) Which organic acid and alkanol could be used to make
(i) ethyl methanoate?
(ii) methyl butanoate?
(b) What is the general name for substances named in (i) and (ii) above?
(c) Write the chemical equations for (a) (i) and (ii) above to show how
they are formed.
7. The following scheme represents the manufacture of a cleaning agent Y.
Conc H2SO4 NaOH(aq)
R O COOH R O SO3H Cleansing agent Y
H2SO4
(a) Draw the structure of Y and state the type of cleansing agent to which Y belongs.
(b) State one disadvantage and one advantage of using Y as a cleansing agent.
H H H H
–– C –– C –– C –– C ––
O H O H n
8. The following formula represents a portion of a polymer.

(i) What is the name of the polymer
(ii) Give one disadvantage of continued use of the polymer.
9. (a) Give the names of the following compounds
(i) CH3CH2CH2CH2CH2OH
(ii) CH3CH2CH2CH2COOH
(iii) CH3CH2CH2CH2 – O – CCH3
O
(b) Study the scheme given below and answer the questions that follow.
Step 1 Step III
CH = CH –––––––––– C2H5OH –––––––– ethylethanoate
Step
II
[ CH2 –– CH2]n
(i) Name the regents in step I, II and III.

(ii) Write an equation for the reaction in step I.
(iii) Explain one disadvantage of the continued use of items made from
compounds formed in step II.
283
Unit 7: Radioactivity
Introduction
Atoms are made up of positively charged nucleus, surrounded by negatively
charged mobile electrons. The nucleus of the atom is in turn made up of positively
charged protons and neutrons which are neutral. Usually, atoms of the same
element have the same number of protons and neutrons. However, there are other
atoms of the same elements which have same number of protons but different
number of neutrons. These are called isotopes. Depending on the number of
protons and neutrons; isotopes can be stable or unstable. Unstable isotopes emit
radiations to become stable. This process is called radioactivity.
7.1 Stability of isotopes and other nuclides

We have seen that isotopes are atoms of the same element which have different
numbers of neutrons in their nuclei. Nuclides on the other hand refer to all
atoms of the same element irrespective of whether they differ in the number of
protons, neutrons or both. All isotopes are therefore nuclides but not all nuclides
are isotopes. Stability of nuclides depend on the stability of their nuclei. Protons
in the nucleus repel each other because of their like positive charges. The proton
repulsion forces tend to split the nucleus. The proton-neutron attraction forces
prevent the tendency to split the nucleus. It is reinforced by the neutron forces of
attraction. Therefore, the nucleus to some extent is stable.
As the number of protons in an atom increases (increase in atomic number),
the repulsion between protons rapidly increases. If the atom does not have a
larger proportion of neutrons to counteract the increasing number of protons, the
nucleus becomes unstable. This instability can make the nucleus to disintegrate
to form a stable product (nuclide). This however depends on the position of the
element in the periodic table. Elements above Bismuth (atomic number 83) in the
periodic table, have insufficient neutrons in their nuclei. They can easily undergo
spontaneous and uncontrollable disintegrations to become stable.
To summarise, when the ratio of neutrons (n) to protons (p) equals to one, i.e. np = 1,
the nucleus is stable. When np < 1, the nucleus is unstable. The nuclear reaction
which takes place in this case converts a proton to a neutron by capturing an electron
(b-particle) from the same nuclide, thereby raising np ratio. When np > 1, the
nucleus is also unstable. The nuclear reaction which takes place in such a case
involves conversion of a neutron(n) to a proton by emitting an electron thereby
lowering np ratio.
For most elements with low atomic numbers e.g. below 20, this ratio is 1. This
means that in their nuclei, the number of neutrons is equal to the number of protons.
284
This can be seen in elements like 126C, 147 N and 168O. Above atomic number 20, the
stable nuclei have more neutrons than protons. The neutron to proton ratio reaches
206 238
about 1.5 with heavy elements like Pb,
82 92 U etc.
The stability of nuclides can be illustrated by plotting a graph of the number
of neutrons against the number of protons for the various nuclei as shown in Fig.
7.1 below. Study this figure and note which nuclide lie along the
• straight line.
• shaded region.
• region X and Y.
Dotted region
Ratio = 1.5
120 X
Y Straight line
100
Number of neutrons
Ratio = 1.4
80
60
Ratio = 1.2
40
20
20 40 60 80 100 120 140

Number of protons
Fig. 7.1: Nuclear stability in nuclides
Straight line
Nuclides falling along this line are non-radioactive. Their np = 1 and are therefore
stable. Note that nuclides with upto 20 protons (atomic number 20) and less fall
within this line and are therefore stable.
Shaded region
The shaded region forms the band of stability. Nuclides that lie within this region
are stable. Any nuclide not lying in this region like those in regions X and Y are
radioactive and undergo decay until an atom is formed which is within the band
of stability.
Region X
This region is situated to the left of the band of stability. Nuclides have too many
neutrons than the protons and therefore np > 1. As such, this region constitutes
of unstable nuclides.
285
Region Y
This region is situated to the right of the band of stability. Nuclides here have too
many protons than the neutrons and therefore, n < 1. As such, this region
p
constitutes unstable nuclides.
7.2 Radioactivity
The nuclei of elements like Bismuth and many others which are after Bismuth
in the periodic table are unstable and undergo the process of radioactivity.
Henri Becquerel in 1896 found out that if the element uranium was placed in a
photographic plate wrapped in thick black paper, the photographic plate ‘fogged’
when developed i.e. an image of the uranium crystal appeared on the plate though
there was no light reaching it. He suggested that rays which could pass through
the wrapped paper were produced. He called these rays radiations. Radiations are
therefore penetrating rays produced by radioactive atoms undergoing radioactivity.
The radiations were produced due to the splitting up or decay of unstable isotopes;
a process referred to as radioactivity.
Radioactivity can therefore be defined as the spontaneous splitting up of atoms of
unstable nuclei accompanied by the release of charged particles and/or gamma
rays.
The rate at which this splitting up occurs is termed as the activity of the
radioisotope. This activity is measured using an instrument called Geiger Muller
counter (GM-tube) shown in Fig. 7.2 below.
ratemeter
GM tube
Radioactive
source
Fig. 7.2: Geiger-Muller (G.M) counter
The GM–tube is usually connected to a ratemeter from where the readings are
made. The ratemeter gives counts per unit time which can be taken as the activity
of the radioisotope.
Because of the cosmic rays in the atmosphere and radiations from radioacitve
materials in rocks, soils, water, air and our bodies, the GM counter records slightly
higher counts per unit time than the normal activity of the radioisotope. This means
that it can also record counts in the absence of any visible radioactive substance.
These radiations from the atmosphere and natural radioactivity of the earth, air and
our bodies is called background radiation. The counts contributed by background
radiations should be subtracted when recording the counts of the radioactive
substance to get the final count. This is called corrected count. For example: if
286
the counts are 10 per second in the absence of any radioactive substance and 100
counts per second when the GM counter is directed to a radioactive substance,
the corrected count is (100 – 10) = 90 counts per second.
Note:
The process of radioactivity or nuclear reactions in general, unlike chemical
reactions, are unaffected by the purity of the element, temperature, pressure or
the nature of the compound of the element.
Define the following terms
(i) radioactivity.
(ii) nuclide.
Types of radiation
When an unstable nucleus decays, several types of radiations are emitted. These
include:
• a – (alpha) particles
• b – (beta) particles
• g – (gamma) rays
Table 7.1 shows the characteristics of these types of radiations.
Table 7.1 Characteristics and properties of radiations
a-particles b-particles g-rays
(alpha–particles) (beta–particles) (gamma –rays)
Characteristics
• a– particles are made

• b-particles are streams of • g –rays are waves not
of 2 protons and 2 neu- particles.
electrons
trons
• They are negatively • They have no mass
• they are positively and no charge
charged
charged.
• They are represented by • Gamma rays are
• are represented by the 0 always represented
4 the symbol –1e
symbol 2He2+ i.e by the sign
corresponds to a helium g
nucleus.
–
g
Properties
e–
An illustration of An illustration of An illustration of
emission of a–particle emission of b–particle emission of g–rays
287
Properties • They have very low • They have a higher • They are invisible like
penetrating power and penetrating power X-rays.
can be shielded or than a–particles. They • They have no mass or
stopped by thin sheets can penetrate a thin charge.
of paper. sheet of paper but can • They have very high
• They readily ionise be shielded or stopped penetrating powers
gases when they col- by an aluminium compared to a and
lide with them. This is foil. The denser the b–particles.
because of their high shielding material, the • They ionise gases but
ability to cause ejec- greater its shielding not as well as a and b–
tion of electrons from power. particles do.
atoms present in gases. • They move at high • The path of g–rays is
• The path of a–particles speed and ionise gases not affected by a mag-
is slightly affected by a but not as well as netic field.
magnetic field. a–particles.
• The path of b-particles
is greatly affected by a
magnetic field.
! Caution ! Caution ! Caution
Alpha–particles can Beta–particles can Gamma–rays are
be shielded by a sheet be stopped by thin the most penetrating
of paper or by human sheet of aluminium , when compared to the
skin. some particles can be other two radiations.
However, if radioiso- stopped by human skin This type of radiation
topes that emit alpha– but not all. They can causes damage to your
particles are inhaled, cause serious problem internal organs. To
ingested or enter your to your health if they protect yourself from
body through a cut in enter the body. They these rays, you need a
your skin, they can be can be absorbed into block of lead wall.
very harmful. your bones and cause
damage.
Penetrating power of radiations from a radioactive element

The penetrating power of a–particles, b– particles and g – rays have been illustrated
in Fig. 7.3 below.
a–particles b–particles
g–rays
Sheet of Sheet of Block of

paper aluminium lead
Fig. 7.3: Penetrating power of different types of radiations
Note that g–rays have the highest penetrating power, followed by b-particles and
then a–particles.
288
The effect of electric field on radiations
Figure 7.4 below is an illustration of what happens when the various types of
radiations are subjected to an electric field.
Photographic plate
Gamma (g) rays
a–particles b–particles
Negative plate Positive plate
Radioactive
source Lead block
Fig. 7.4: Effects of electric charges on radiations
• What is the use of the lead block?

• What is the use of the photographic plate?
• What do you notice about the extent of deflections?
• What are your conclusions from this illustration?
Excessive exposure to radiations is very harmful to living things. Lead block is
used as a shield against these radiations. These radiations leave a mark on the
photographic plate, which can be developed later. The photographic paper is used
as a detector for the radiations.
a–particles are attracted by the negatively charged plate. b–particles are attracted
by positively charged plate while g-rays are unaffected. The deflection of
b–particles is more than that of a–particles. This is because a–particles are heavier
than b–particles. Since the a–particles are attracted to the negatively charged plate,
they are, positively charged. The b–particles are negatively charged because they
are attracted by the positively charged plate. g–rays have no mass or charge and
therefore are unaffected by the electric charges.

1. What makes the atoms of an isotope stable?
2. Give the names of three main radiations emitted from radioisotope.
3. State two main differences between g–rays and b–particles.
Half-life (t1/2)
We have learnt that radioactive isotopes decay and emit either a–particles,
b–particles or g–rays. The decay occurs at different rates. Some will take few
microseconds, some minutes or hours while others will take thousands of years.
The rate of decay of a radioactive isotope is a characteristic of the isotope and is
measured by its half-life. This is expressed as t1/2.
289
A half-life(t1/2) is the time required for one-half of the initial
number of atoms of a radioisotope to decay.
After one half life, half of the original radioactive atoms would have decayed. The
other half remains unchanged. After two half lives, only a quarter of the original
radioative atoms remain etc.
For short-lived radioisotopes, the half-lives can be determined by plotting the
activity of a sample against time. The graph of activity against time is referred
to as a decay curve. An example of this is as shown in Fig. 7.5 below.
Activity in counts per minute
80
40
20
10 20 30
Time (min)
Fig. 7.5: Decay curve

Fig. 7.5 shows that the activity of a radioisotope decreases by the same fraction
in successive equal time intervals. It falls from 80 to 40 counts per minute in 10
minutes, then from 40 to 20 in the next 10, 20 to 10 in the third 10 minutes and
so on. Half life (t1/2) can also be defined as the time taken for the activity of a
radioisotope to fall to half its original value.

10 min 10 min 10 min
80 ––––– 40 ––––– 20 ––––– 10 and so on
The half-life for this example is 10 minutes.
Example, Half-life of radium
Radium has a half-life of 1620 years. This means that if we start with 1 g of radium,
0.5 g of it will have disintegrated (decayed) by the end of 1620 years. After another
1620 years, half of what remains will have disintegrated, leaving 0.25 g
and so on. In other words, a given mass (M) of radium, will be reduced to M in
2
1620 years. This mass of M will be reduced to M in another 1620 years and then
2 4
to M in another 1620 years and so on. It means that the initial amount makes no
8
difference in half-life. 1 kilogram of a radioactive substance is reduced to
290
1 kilogram in exactly the same time as 1 gram is reduced to 1 gram. Half-lives
2 2
of elements range from billions of years to a fraction of a second as shown in
Table 7.2 below.
Table 7.2 Half-lives of some selected elements
Element Half-life
238 (Uranium) 4.5 ´ 109 years
U
92
229 Ra (Radium) 1620 years
88
32 P (Phosphorus) 14 days
15
210Po (Polonium) 0.0002 second

84
Worked Examples
Example 1
A radioactive substance has a half-life of 2 hours. What fraction of the substance
will remain after 6 hours have passed?
Here is a suggestion of how to do this. Simply count on your fingers as follows
• Thumb: It represents the original
rs
s
our
ou
substance. 1
2h
2h
1
• First finger: After one half-life (2hrs)
1 4
8
2 2
3 1
2 of the original substance is left.
urs
1
• Second finger: After two half-lives
2 ho
(4hrs), half of the 12 that was left

0 1
decay so 4 that is left.
• Third finger: After three half-lives
(6hrs) 1 of the 14 was left
2
decay so that 18 is left.
Fig. 7.6: Using fingers of the hand
to calculate the remaining fraction of radioactive atom
In this example, for a substance with a half-life of 2 hours, 1 of the original atoms
8
will remain after 6 hours have passed.
Example 2
A radioactive substance gave corrected count of 240 counts per second. After 6
hours, it gave a corrected count of 30 counts per second. Calculate its half-life.
Solution
Let the half-life be x hours
291
x hr x hr x hr
240 ––––– 120 –––––– 60 –––––– 30
3x = 6 hours
x = 2 hours
Therefore, half-life = 2 hours.
Example 3
An a–emitting gas has a half-life of 20 minutes. What fraction is left after 1 hour?
Solution
1 hour = 60 minutes
After 20 minutes, the fraction left = 1 . After 40 minutes, the fraction left
2
= 1 ´ 1 =1
2 2 4
After 60 minutes, the fraction left = 1 ´ 1 = 1
4 2 8
in
in
1
6m
4m
Example 4 4 1
1 8 in
If the half-life of a radioisotope is 2 minutes, 2 2 8m
3 1
what fraction of its initial activity value will 1
16
in
4
2m
have remained in 8 minutes?

We can solve this using fingers of the hand
as follows: 0
Example 5
Nitrogen–13 emits b–particles and decays to
carbon–13 with half-life of 10 min. Assume
a starting mass of 2 g of nitrogen–13. 1
Therefore, the fraction = 16
(a) How long is six half-lives?
(b) How many grams of that isotope will remain after six half-lives?
Solution
(a) One half-life is 10 min
Six half-lives = (6 ´ 10) min
= 60 min
(b) Starting mass of nitrogen –13 = 2g

After 10 min the mass = (2 ´ 12 )g = 1 g
1
After 20 min the mass = (1 ´ 2 )g = 0.5 g
“ 30 min “ “ = (0.5 ´ 12 )g = 0.25 g
“ 40 min “ “ = (0.25 ´ 12 )g = 0.125 g
292
“ 50 min “ “ = (0.125 ´ 12 ) g = 0.0625 g
“ 60 min “ “ = (0.0625 ´ 12 )g = 0.03125 g
\ 0.03125 g will remain after 6 half-lives.

1. (i) In an experiment done at a school to find the half-life of a
radioactive element, the count-rate fell from 200 counts per second to 25
counts per second in 75 minutes. Calculate the half-life of the radioactive
element.
(ii) What do you understand by “background radiation”? State two sources
of this radiation.
2. A radioisotope has a half-life of 10 minutes. The GM counter records 20
counts per minute(cpm) without this radioisotope placed in front of it. With
this radioisotope in front, it registers 400(cpm). Calculate the count rate after
20 minutes.
3. A radioactive substance gave uncorrected count of 260 counts per second. After
6 hours, it gave a corrected count of 30 counts per second. Calculate the half-
life of this substance assuming a background radiation of 20 counts per second.
4. 348 grams of a radioisotope X was reduced to 48 grams after 270 days.
Determine the half-life of X.
Changes in nuclei resulting from radioactive decay

When a radioactive element emits radiations, a new element is formed. Just as we
have chemical equations in chemical reactions, we can also have equations involving
nuclear reactions. Nuclear reactions, involve decay processes, either a–particles,
b–particles or gamma (g) rays are emitted. This leads to formation of new elements.
(a) a-particle decay
An a–particle is positively charged and that is why it is deflected towards the
negative pole in an electric field. Studies have shown that it has a charge of +2
and a mass of four (4). Recall that helium has two electrons in its only energy
level and that it can lose these to form just a helium nucleus with a charge of +2.
The mass of He nucleus remains four (4) due to the presence of 2 protons and 2
neutrons. The helium nucleus is therefore similar to an a – particle. As such; an
a– decay is said to occur by emission of a helium nucleus. An element undergoing
a–decay therefore has its mass reduced by a value of four (4) and its atomic
number reduced by two(2).
Let us take an example of a parent nuclide X of mass number A and atomic
number Z for us to see how this happens.
293
Y +
A A–4 4
X 2
He
Z Z–2
Parent Daughter a–particle
nuclide nuclide (helium nucleus)
The following nuclear equations show specific examples of this type of decay.
238 234 4
U92 90
Th + 2 He
Uranium–238 Thorium–234 a–particle
226 222 4
Ra Rn + 2
He
88 86
Radium–226 Randon–222 a–particle
210 206 4
Po Pb + 2
He
84 82
Polonium–210 Lead–206 a–particle
Assuming that more than one a – particle is emitted in a decay process, for example
5 a -particles. To get the mass number and atomic number of the resultant daughter
nuclide, multiply the mass number and the atomic number of the helium nucleus
by the number of a– particles emitted then subtract each of these from the mass
and atomic numbers of the parent nuclides respectively. For example,
4
Y
227 207
99 89
Z + 52 He
Loss in mass number = 5 ´ 4 = 20

The mass number of Z = 227 – 20 = 207
Loss in atomic number = 5 ´ 2 = 10
The atomic number of Z = 99 – 10 = 89
(b) b– decay 0
b–particle is an electron (–1e). Therefore, when an element decays by the emission
of a b – particle, it turns into the next element in the Periodic Table. A neutron
changes into a proton and an electron is emitted. Atomic number increases by one.
There is no change in mass number. For example, assuming a parent nuclide X
with mass number A and atomic number Z, giving rise to a daughter nuclide Y.
Y +
A A 0
X e
Z Z +1 –1
The following nuclear reactions show specific examples of this kind of decay.
23 23 0
Na 11
Mg
12
+ e
–1
Sodium–23 Magnesium–23 b–particle
294
234 234 0
Th90
Pa + e
91 –1
Thorium–234 Protactinium–234 b–particle
Again, if more than one b–particle is emitted; for instance 3 b–particles, multiply
0
by 3 ( e ). We then raise the atomic number of the parent nuclide by 3 to get the
–1
atomic number of the daughter nuclide. The mass number does not change because
the mass of electron is negligible.
Y
207 207 0
79 82
Z + 3–1e
Note:
Gamma(g) rays have no charge and mass. Their emmission therefore have no
effect on the mass and atomic numbers of resultant daughter nuclide.
Radioisotopes can also undergo natural continuous decay to form various unstable
isotopes. In the process of decay, b–particles and a–particles are emitted. An
238
example of such an isotope is U as shown below, to form a stable isotope of
206 92
lead, i.e. Pb .
82
238 a 234 b 234 b 234
a 230 a 226
92
U 90
Th Pa U Th Ra
91 92 90 88
a, g
222
86
Rn
a
210 b 210 a 214 b 214 b 214 a, g 218
83
Bi 82
Pb 84 Po 83
Bi Pb 84
Po
82
b
210
84
Po
206
82
Pb Fig. 7.7 The Uranium–238 decay series
Worked example
232
Below is a part of a radioactive decay series which starts with 90 Th . Identify the
particles emitted in all the six stages.
295
232 1 228 2 228 3 228 4 224
90 Th 88 Ra 89 Ac 90 Th 88 Ra
5
212 7 216 6 220
82 Pb 84 Po 86 Rn
Solution
Stage 1
232 228
90 Th –––– 88 Ra
The mass number has gone down by 4 and the atomic number by 2. Therefore,
an a–particle has been emitted.
Stage 2
228 Ra –––––– 228Ac
88 89
The mass number has not changed but the atomic number has increased by 1.
Therefore, a b–particle has been emitted.
Do the same for the other stages.
232
1. The isotope 90Th decays by a–particle emission.
(a) What is the atomic number and mass number of the element resulting
from this decay?
(b) If the resulting element is radium, Ra, write down the nuclear equation.
2. Complete the following nuclear equations
209 205 4
Bi 81
Tl + He
83
239 238 1
92
U U+ 0
n
239 0
U Np +–1 e
93
3. Write down, in words, the changes represented by the following nuclear equations.
(a) 14 14 0
6
C N+ e
7 –1
(b) 1
n 1 0
0 1
H + –1e
296
(c) 28
Al
28
Al + g
27 27
4. A chemist bombarded nitrogen–14 with a – particles and obtained an isotope

of oxygen and one proton. Write the nuclear equation for this nuclear reaction.
7.3 Nuclear fission and fusion

Nuclear fission
We have learnt that nuclear reactions involve the emission of small particles such
as a–particle, b–particle or g–rays. However, when the nuclei of certain isotopes
are bombarded with neutrons, they split up. For example, when uranium-235 is
bombarded with neutrons, it is split into two smaller fragments. The process releases
two smaller nuclei, two or three neutrons and a large quantity of energy.Uranium
is said to have undergone fission. This has been illustrated in Fig. 7.8 below.
Fission products
Neutron to bombard Neutron

uranium nucleus
Smaller Energy
fragments Neutron
Neutron
Stable uranium Unstable
nucleus nucleus
Small stable
nuclei
Fig. 7.8: Nuclear fission
Nuclear fission is the splitting of a heavy unstable nucleus into two

approximately equal parts with stable nuclei.
The following reaction is an example of nuclear fission reaction involving U–235

1 235 90 144 1
0
n + 92
U 38
Sr + 54
Xe + 30n + Energy
Note: The total sum of the superscripts on the right and left sides of the arrow
should be equal. The same should apply for the total sum of the subscripts.
The following are other examples of nuclear fission reactions.
1. Fast moving a–particles can collide with the nuclei of an element like nitrogen
instead of being deflected away by this positive nucleus. When this happens,
a nuclear reaction takes place.
297
14
N +
4 fission
He ––––––
17
O + H
1
7 2 8 1
Nitrogen –14 a– particle oxygen– 16 proton
This nuclear equation shows that nitrogen – 14 has been split by the force of the
moving a– particle to produce oxygen – 17 and one proton.
2. A fast moving neutron can collide with the nuclei of an element like aluminium
– 27 and its nucleus split to form sodium – 24 and an a–particle.
27 1 fission 24 4
13
Al + n –––––– 11Na + 2He
0
Aluminium–27 neutron Sodium –24 a– particle
(fast moving)
3. Slow moving neutrons split aluminium–27 to form aluminium–28 and g–rays
27 1 fission 28 + g
Al
13
+ 0
n ––––––– 13Al
Aluminium–27 neutron Aluminium–28 gamma rays
(slow)
Fission unleashes enormous amounts of energy. It is an exothermic reaction. For
example, 1 kg of uranium–235 releases an amount of energy equal to that generated
in an explosion of 20,000 tons of dynamite.
Nuclear fusion
Fusion occurs when two nuclei combine to produce a nucleus of heavier mass. It
is the opposite of fission. Fusion of two nuclei is not, however, at all easy. They
are both positively charged and therefore repel each other. However, at high
temperature, nuclei may have sufficient energy to enable them to overcome the
repulsive forces and combine. A good example is in solar fusion. Here, hydrogen
nuclei are fused to make helium nuclei. It is one of the reactions by which the sun
produces energy. This can be illustrated using the following equation.
2 3 4 1
H + H He + 0n
1 1 2
This reaction absorbs a lot of energy. One of the difficulties is to raise the temperature
sufficiently to start the reaction. Once the reaction was started, enough heat would be
generated to keep it going. Infact, this reaction takes place only at temperatures that
exceed 40,000,000˚C. The following are other examples of nuclear fusion reactions.
Example 1
2 1 3
H H fusion
1
+ 1 2
He
Deuterium hydrogen Helium–3
(proton)
298
Sometimes in nuclear fusion, particles like b–particle, neutron or protons can be
emitted.
Example 2
2 2 3
H H fusion He +
1
n
1
+ 1 2 0
Deuterium Deuterium Helium–3
Example 3
1 4
4 1H fusion He + 2–10e
2
four Helium 2b–particles
hydrogen atoms
(protons)
Example 4
2 2 3 1
1
H + 1
H fusion H+ 1
H 1
Deuterium Deuterium Tritium hydrogen
(proton)
Self-Assessment exercise 7.5
1. The two nuclear equations below represent either nuclear fission or fusion.
14 4 17 1
N +7
He 2 O+ 8
H
1
2 1 3
1 H + 1
H He
2
Describe in words, what has happened in the two nuclear reactions.
Nuclear reaction as a source of energy

Nuclear reactions like nuclear fission and fusion liberate very large amounts of
energy. Fusion reactions occurring in the sun have provided the earth with energy
for billions of years. During nuclear fission, enormous amounts of energy are
released. Much of this energy generated from controlled nuclear reactions is in
form of heat. The heat is used to generate steam to drive turbines. The spinning
turbines generates electricity that can be used for domestic and industrial purposes.
When the nuclear reactions are not controlled, the energy produced is enormous
and instantaneous. Atomic bombs that were used in wars were devices that start
uncontrolled nuclear chain reactions. In atomic bombs, the enormous release of
energy causes a vast explosion accompanied by enormous release of heat and
light. The explosion sound will definitely rupture the eardrums of the population
around. The heat will roast people, animals and plants. The light will definitely
299
make survivors blind. The heat cause strong winds due to heating of air, which
will knock down buildings, trees, vehicles, dams among other things.
Note
Apart from the emission of radiations, nuclear reactions differ sharply from
chemical reactions in several other ways as shown in Table 7.3.
Table 7.3 Differences between chemical and nuclear reactions

Chemical reactions Nuclear reactions
1. Involve valency 1. Involve the nucleus
(outer energy level) (protons and neutrons)
electrons in an atom. of an atom.
2. Rate of reaction is dependent 2. Rate of reaction is
on external factors such as independent of
pressure, concentration external factors
temperature and purity or purity of the
of the substance. substance.
3. No new elements are formed. 3. New elements are formed.
4. Little amount of energy 4. Involve large amounts
are either released or consumed. of energy.
5. There is no change in mass 5. There is change in mass of
of reacting substances. reacting substances.
6. Some changes are reversible 6.Changes are irreversible.

(i) Mg(s) + 2HCl(aq) MgCl2(aq) + H2(g)
24 24 0
(ii) Na Mg + e
11 12 –1
State three major differences between reactions (i) and (ii) above.
7.4 Applications of radioactivity and radioisotopes

(a) In chemistry
A radioisotope can be used to follow the course of a particular atom in a chemical
reaction. For example:
1. It has been found that the oxygen of the water formed in an esterification
reaction comes from the hydroxyl group of the alcohol. Radioactive oxygen
atom (O*) can be used to trace the movement of oxygen i.e.
CH3COOH + H*OC2H5 ––– CH3COO*C2H5 + H2O
300
2. In the photosynthesis process, the oxygen released comes from the water.
6CO2 + 12H2O* ––– C6H12O6 + 6H2O + 6O*2
(b) In medicine
1. Penetrating radiations like g–rays can be used in the treatment of malignant
tumors and cancer. The main problem with these rays is that because of long
exposure required, surrounding healthy tissues may be destroyed in the process.
2. Radioactive iodine–131 is used to study the working of the thyroid gland.
3. Instruments and equipments in hospitals and dispensaries can be sterilised
by exposing them to g–rays for a short time.
(c) Carbon–dating
The carbon atoms involved in the oxygen–carbon(IV) oxide cycle of living animals
and plants are kept at low but constant level of radioactivity by the production of the
radioactive carbon–14 from nitrogen–14 atoms in the atmosphere.
14 14 1
1
7
N + n C + H
6
0 1
So, when the animals or plants are living, there is incoming and outgoing carbon–14.
The rate of intake is equal to the rate of outgoing of carbon–14 keeping the quantity
of C–14 in the body constant.
When they die, the oxygen – carbon(IV) oxide cycle no longer operates in them.
They no longer replace carbon–14 or any other carbon isotope atoms in their cells.
Thus the carbon – 14 content which decay to nitrogen–14 starts reducing in their
cells. This is because the carbon–14 decays to nitrogen–14 i.e.
14 14 0
6
C N + –1e
7
By comparing the carbon–14 content of ancient organic remains with present

similar substances, the age of the remains can be estimated. Also, radioactivity
of the radioactive C –14 starts reducing with time. The activity of the carbon–14
at present can be compared to that in the ancient organic remains to estimate
their age. For example, the activity of carbon–14 from the wooden beam taken
from the tomb of an Egyptian Pharaoh is about half of carbon–14 in the wood of
the living trees. Since the half-life of a carbon–14 atom is 5600 years, the age of
wood with half the activity of currently-living wood is about 5600 years. Fossils
up to 24,000 years old have been dated by this method.
(d) In agriculture
All isotopes of a given element, as we have discussed before, have the same
electronic arrangement and therefore exactly the same chemical properties. For
24
example, radioactive sodium atom, Na is chemically similar to ordinary
11
301
23
sodium atom, 11
Na . It is therefore possible to explore the courses of many
chemical changes in soil, animals, fertilisers and plants by using a reagent in
which one of the elements is a radioisotope. The radioisotope chosen must have
a reasonable half-life. For example, if small quantities of sodium phosphate
32
containing radioactive phosphorus, P (half-life of 14 days) are added to an
15
animal’s diet or soils, this phosphorus takes part quite normally in the various
metabolic processes of the animal or the plant respectively. By examining various
parts of the body of the animal or parts of the plant for radioactivity from time to
time using a GM counter, it is possible to trace the route of the phosphorus through
the animal’s body or plant and its final disposition. These studies help in improving
livestock, poultry and crops, thereby reducing poverty by improving farm produce.
(e) Preservation
g–rays can be used to kill bacteria in tinned foods like fish, fruits, beans etc. These
tinned foods last for a long time and can be used in our country and also exported to
earn the country foreign exchange. g–rays can also be used to kill pests in stored grains.

(i) State three uses of radioisotopes.
(ii) What is carbon-dating?
7.5 Pollution effects of radioactivity

The three types of radiations from radioactive materials end up in air, water and
soil. The importance of air, water and soil cannot be over-emphasised. Man breathe
in air, drink water and eat food crops grown on soil. The crops may get some of
radioisotopes in soils, water and air.
These crops have some of these radioisotopes as a result of their use of air, water
and nutrients from soil. People and animals are exposed to these radioisotopes when
they eat food from such crops.
Let us now discuss the dangers of each radiations.
Dangers from a –radiation
• Alpha radiation is not able to penetrate human skin. However, materials
emitting a–particles (a –alpha) can be harmful to humans if the materials are
inhaled, swallowed, or absorbed through open wounds. They cause damage
to cells and body organs.
Dangers from b – radiations
• If high levels of beta-emitting contaminants are allowed to remain on the
skin for a prolonged period of time, they may cause skin injury.
They penetrate human skin to the “germinal layer” where new skin cells are usually
produced. This may interfere with the process of production of new skin cells.
302
• Beta-emitting contaminants may be harmful if inhaled or swallowed or
absorbed through open wounds.
Gamma g–rays
Gamma radiations are able to penetrate into human tissue. They readily penetrate
most materials and are sometimes called “penetrating” radiations. When they do
this, they cause damage to body tissues and organs and can also lead to mutations
which can cause permanent change of the body structure of both plants and animals.
When radiation passes through cells, it causes the cell molecules to disintegrate.
If radiation passes through the nucleus of the cell, it damages the vital DNA
molecules which stores the genetic information for building the cell. As a result,
the cell may either die or fail to divide. In some cases, the damaged DNA molecule
may carry faulty genetic information into future generations. The following disasters
further demonstrate the effect of radiations in the environment.
(a) Titanium mining in Kwale

Titanium is the ninth most abundant element on earth. It is present in igneous rocks
and in the sediments derived from them. Titanium deposits have been discovered in
Kwale district in Kenya. Natural titanium consists of five isotopes with atomic masses
from 46 to 50 that are stable. A few unstable isotopes are also known to exist.
Although tests of titanium in Kwale for radioactivity have proved to be negative,
it still calls for proper planning for its mining. This is because it is suspected to
be radioactive. This will help avoid occurrence of disasters like the Chernobyl
disaster. Careless disposal of radioactive wastes could cost many lives.
(b) Chernobyl disaster

This great disaster occurred on April 26, 1986 in the nuclear power plant at
Chernobyl. Chernobyl is located 128 km northwest of Kiev in Ukraine, part of
the former Soviet Union.
The cause of the disaster was a malfunction within the plant that caused the
radioactive core to melt down and get exposed. Large amount of radioactive
materials were left over. Many of the details of the accident are still unknown.
Some people believed the accident was caused because the operators were over
confident in their decision making. Others said that there was a flaw in the design
of the reactor and others blamed the accident on the safety systems. Further
investigations showed that all the three factors were involved.
The disaster at Chernobyl affected people all over Ukrain and also affected various
areas around the world due to the radiation leak. The effects of the accident were
therefore both local and worldwide. Wind carried the huge masses of radioactive
particles all over the world. Ukraine and Europe were greatly affected by the
disaster because bans had to be put on many goods and commodities from these
regions. This hurt the areas economically. Even the United States received a good
share of radiations as a result of this explosion.
303
The accident caused 31 deaths. All but two of these deaths were the result of exposure
to radiations. The other two occurred from the result of thermal burns or falling
debris. Up to 200 people were hospitalized due to the radiation exposure. Due to the
nature of radiation exposure, many of the medical effects may not be reversed until
many years after the accident. These medical problems may include cancer,
birth defects, and skin diseases. It is estimated that 6500 people may die from
cancers caused by the radiation from this disaster. It has been estimated that it
will take approximately 30 years for the affected areas to recover from this disaster.
Protection against radiations
The concepts of personal protection against the dangers of radioactivity are
simple. These are:
• Do not handle any radioactive material unnecessarily.
• Use the correct handling equipment, e.g. tongs.
• If you must work with radioactive substances, do not go near them unnecessarily.
• If you have to work near radioactive substances, do so for as short a time as possible.
• When working with radioactive substances, use shields to protect yourself.
Such shields are made of special glass or lead block.
Note
The best protection consists of maximum distance, shielding and minimum time
of exposure. Damage from radioactive substances is proportional to the amount of
radiation received. This depends on the power of the source, the type of radiation,
the time of exposure and the proximity to the source. There is therefore tight control
on the use of radioactive substances, training in the correct use of handling devices
and lead shielding sheets.
Global effort of reducing environmental pollution from radioactivity
There are two personalities worth mentioning for their effort in sensitising human
race the importance of pollution free world. They include Linus C. Pauling, an
American, who won 1962 Nobel Peace Prize for working energetically to awaken
the conscience of societies to its new responsibilities in a nuclear age and Prof.
Wangari Maathai, a Kenyan who also won 2004 Nobel Peace Prize for pioneering
and fighting for sustainable environmental practices.
Linus C. Pauling, Prof. Wangari Maathai

Fig. 7.9: Important personalities involved in fighting environmental pollution
304
The treaty on the non-proliferation of nuclear weapons is a landmark international
treaty whose objectives are to prevent the spread of nuclear weapons and weapons
technology, to foster the peaceful use of nuclear energy and to further the goal of
achieving general and complete disarmament of nuclear weapons.
From what we have learnt, every individual should be responsible for maintaining
a pollution free environment. Let us all work towards achieving this goal.
Summary
• Radiations from radioactive material include a–particles, b–particles and g–rays
•
4
a-particles are nuclei of helium atoms ( 2He ) and are positively charged.
0
b–particles are streams of fast-moving electrons ( –1e) and therefore negatively
charged. g–rays are invisible rays like X–rays and therefore they have no mass
or charge.
• a–particles are the least penetrating. The most penetrating are g–rays followed
by b–particles.
• a–particles have the greatest ionising power, followed by b–particles and
g–rays in that order.
• When the a–particle leaves the nucleus of an atom, the mass number(superscript)
of the resulting nucleus will be less by 4, and the atomic number (subscript)
will be less by 2.
• When a b–particle leaves the nucleus of an atom, the mass number of the
resulting nucleus will not change but the atomic number will increase by 1.
• In a nuclear equation, the sum of mass number and atomic number on the
two sides of the arrow must be equal.
• The splitting of an atomic nucleus of an element to form two or more atomic
nuclei of different elements is called nuclear fission. Nuclear energy is
released in this process.
• The process of combining two or more atomic nuclei of same elements or
different elements to form nucleus of a heavier mass is called nuclear
fusion. Nuclear energy is also released in this process.
• “Fall-out” consists of radioactive fission products which have escaped into
the atmosphere.
• Radioactive “fall-out”, accidental or from careless disposal of nuclear
materials, may cause irreparable damage to mankind, animals, plants and in
general to our natural environment. So watch out!
Revision Exercise 7
1. (i) Define the terms
(a) half-life
(b) nuclear fission
(c) carbon-dating
(ii) State the three types of radiations from a radioisotope.
305
2. (i) Name two main differences in properties between a–particles and
b–particles.
(ii) Why is a b – particle deflected more than an a– particle by electric charges?
3. The activity of carbon–14 found in a timber in a Pharoah tomb in Egypt was
found to be half of that found in the same timber from the present trees. The
half-life of carbon–14 is 5600 years. What is the age of the timber found in
the tomb?
4. Complete the following nuclear equations by putting the respective mass
numbers and atomic numbers for A,B, C and D.
238 4
(a) 92
U A+ He
2
238
(b) 92
U B+ g– rays
241 0
(c) Pu C+ –1
e
94
7 1 4
(d) 3
Li + 1
H D+ 2
He
5. (i) Name two main differences between a chemical reaction and a nuclear
reaction.
(ii) What is “background radiation?
6. Which radiations W, X, Y and Z have been emitted in:
14 14
(i) C 7
N +W
6
1 1 2
(ii) H+ n H +X
1 0 1
1 95 139
La + n + Y
235 1
(iii) U+ n Mo +
92 0 42 57 0
238 234
(iv) U Th + Z
92 90
7. Explain briefly the effects of nuclear bomb to the environment.
306
Model Test Papers
Model Test Papers A (80 marks)
Paper 1 Time 2hrs
1. Element X has an atomic number 16 and mass number 32.
(a) How many neutrons are in the nucleus of the atom of X? (1 mark)
(b) Draw the structure of the ion of X. (2 marks)
(c) Write the formula of the ion of X. (1 mark)
2. Write the half equations for the reactions that occur at the following electrodes
when molten lead(II) bromide is electrolysed using carbon electrodes
(a) Cathode (2 marks)
(b) Anode (2 marks)
3. Three metals X, Y and Z form oxides XO, YO and ZO. Hot powered Y will
remove oxygen from XO but not from ZO. Arrange the metals in order of
reactivity starting with the most reactive. (1 mark)
4. (a) Write the formula of the two compounds which cause permanent water
hardness. (2 marks)
(b) Write the two chemical equations for the reactions which occur during
the removal of permanent hardness using sodium carbonate. (2 marks)
5. Given the equation N2O4(g) 2NO2(g) ∆H = +Ve
What would be the colour changes made and the effect of increasing tem-
perature on the equilibrium mixture? (3 marks)
6. If isotope 232
90
Th decays to 216
82
Pb as a result of x alpha-particles and
y beta-particles emission.
(a) Find the numerical value of x and y. (1 mark)
(b) Write the nuclear equation. (2 marks)
7. The diagram below represents a paper chromatogram of pure W, X, Y and
Z. A mixture of M contains W and Z only. Indicate on the diagram the
chromatogram of M. (2 marks)
solvent front
W Y
X Z
W X Y Z M
307
8. Study the following electrode potentials, Eθ
Fe2+(aq) + 2e– –––– Fe(s) Eθ = – 0.44V
Cu2+(aq) + 2e– –––– Cu(s) Eθ = + 0.34V
Ag+(aq) + e– –––– Ag(s) Eθ = + 0.80V
Zn2+(aq) + 2e– –––– Zn(s) Eθ = – 0.76V
Mg2+(aq) + 2e– –––– Mg(s) Eθ = – 2.36V
1
/2Cl2(g) + e–
–––– Cl (aq) Eθ = + 1.36V
–
(a) Name
1
(i) the strongest reducing agent. ( 2 mark)
1
(ii) the strongest oxidising agent. ( mark)
2
(b) Calculate the e.m.f of a cell made by combining Mg and Cu half-cells.
(2 marks)
9. When zinc is burnt in oxygen, the compound formed reacts with both dilute
hydrochloric acid and sodium hydroxide solution.
(a) Write the chemical equation of the reaction of zinc and oxygen. (1 mark)
(b) What property of the compound formed between zinc and oxygen
makes it possible to react with both dilute hydrochloric acid and
sodium hydroxide solution? (2 marks)
10. Study the set-up below and answer the questions that follow
Copper(II) Anhydrous
oxide copper(II) sulphate
hydrogen
Dry burning
hydrogen
gas
heat heat
(a) What is observed in the combustion tube after the experiment? (2 marks)
(b) Write the equation for the reaction between the oxide and hydrogen
gas. (2 marks)
(c) Explain why after the reaction, hydrogen is continuously passed through
the combustion tube until it cools down. (1 mark)
11. Determine the relative atomic masses of the following elements whose
isotopic mixture occur in the proportions given. (2 marks)
38
Ar, 0.06%
40
Ar, 99.6%
36
Ar, 0.34%
18 18 18
308
12. The flow diagram represents the isolation of nitrogen from the atmosphere.
CO2
N2
N2 Step 1 Step 2 N2 Step 3
O2 N2
O2 H2O
H 2O
H2O
(a) State what happens in steps1 and 2. (1 mark)

(b) Name the substances which can be used in step 1 and 2 respectively.
(2 marks)
13. Sulphur is soluble in ethanol but not in water. Sodium chloride is soluble
in water but not in ethanol. Sand is insoluble in both ethanol and water.
Explain briefly how you would obtain sand from a mixture of all three.
(2 marks)
14. An element X has a relative atomic mass of 44. When a current of 0.5 amperes
was passed through the molten chloride of X for 32 minutes and 10 seconds,
0.22 g of X were deposited at the cathode.
Determine the charge on an ion of X. (3 marks)
(1 Faraday = 96500 Coulombs)
15. Using a suitable example, explain what is an unsaturated hydrocarbon.
(2 marks)
16. Under certain conditions, methane reacts with steam to form carbon(II)
oxide and hydrogen only. Calculate the total volume of gas that can be
formed when 200 cm3 of steam reacts completely with methane. (2 marks)
17. 24.0 cm3 of a solution of 0.1M KOH were exactly neutralized by 30 cm3 of
a solution of sulphuric acid. Find the molarity of the acid. (3 marks)
18. A compound has an empirical formula C3H6O and a relative formula mass
of 116
(a) Determine its molecular formula. (1 mark)
(b) Calculate the percentage composition by mass of each element given in
the compound. (C = 12.0 H = 1.0 O = 16) (2 marks)
19. Copper is extracted from its ores by a process of froth floatation and then
roasted in air to produce copper(I) sulphide.
(a) What is froth floatation? (1 mark)
(b) State two properties of duralumin that makes it more suitable than pure
aluminium in aeroplane construction. (2 marks)
309
20. Calculate the amount of zinc in grams that would remain if 1.96 g of the
metal were reacted with 100 cm3 of 0.2 M hydrochloric acid. (3 marks)
(Zn = 65.0, H = 1.0, Cl = 35.5)
21. Describe how the value of x in the compound, CuSO4• xH2O can be deter-
mined. (3 marks)
22. (a) Diammonium phosphate is a nitrogenous fertilizer. Calculate the
percentage of nitrogen in the fertilizer. (N = 14, H = 1.0, P = 31.0, O =
16.0) (2 marks)
(b) State one physical property that makes solid diammonium phosphate
a good fertilizer. (1 mark)
23. (a) Name two crystalline allotropes of carbon. (2 marks)
(b) Draw the structures of diamond and graphite. (2 marks)
(c) With reference to the structure, explain why graphite conducts
electricity whereas diamond does not. (1 mark)
24. In the manufacture of detergents, phosphates are added. Explain the effect
of phosphates on the environment. (2 marks)
25. Hydrogen and chlorine react as shown in the equation below.
H2(g) + Cl2(g) 2HCl(g) ∆H = –185 kJ
In terms of bond energies explain why the ∆H is negative. (2 marks)
26. (a) ‘Sacrificial protection’ is one method that is used to protect iron from
rusting. State briefly how it prevents rusting. (2 marks)
(b) Give another method for preventing rusting apart from painting,
oiling or greasing. (1 mark)
27. (a)
Nitrogen, oxygen and argon are obtained from liquid air by fractional
distillation.
State the physical property that makes this possible. (1 mark)
(b) Arrange the gases in (a) in order of how they distil, starting
with the first. (1 mark)
(c) Give one industrial use of oxygen. (1 mark)
28. (a) When a hydrocarbon fuel is burnt, one of the main products is
slightly acidic gas R. What is the name of the gas R? (1 mark)
(b) State two processes in which gas R is produced in nature. (2 marks)
310
Paper 2 80 marks Time 2hrs
1. The grid below represents part of the periodic Table. Study it and answer
the questions that follow. The letters do not represent the actual symbols of
the elements.
Y C D E
F G
H
(a) Name the elements (letters) that can form anions with a charge of –1.
Give a reason for your answer. (2 marks)
(b) What type of structure would the oxide of C have? Give a reason.
(2 marks)
(c) How does the reactivity of H compare with that of E? Give a reason.
(2 marks)
(d) 1.3 g of Y reacts completely with 1.21 dm of chlorine when heated
3
at s.t.p. (Molar gas volume at s.t.p = 22.4 dm3).

(i) Write a balanced chemical equations for the reaction between Y
and chlorine gas. (2 marks)
(ii) Determine the atomic mass of Y. (2 marks)
2. The set-up was used by a student from Sky High School to prepare and
collect dry hydrogen gas.
acid
hydrogen
solid N liquid B
(a) Identify three mistakes in this set-up. (3 marks)

311
(b) Name liquid B. (1 mark)
(c) Suggest a possible solid which can be used as solid N in the set-up.
(1 mark)
(d) Name a suitable catalyst in this reaction. (1 mark)
(e) Hydrogen produced can be passed over heated lead(II) oxide to
determine one main property of this gas
(i) What property of hydrogen is determined in 2(e) above? (1 mark)
(ii) Write down the chemical equation in 2e(i). (2 marks)
(iii) Name the black solid that can be turned to red-brown when hydrogen
is passed over it when it is hot. (1 mark)
3. The following is a list of reagents used in the preparation of some sub-
stances in the laboratory. Copper carbonate, copper(II) oxide, dilute hydro-
chloric acid, magnesium, sodium hydroxide and dilute sulphuric acid
(a) Name the reagent which would react with dilute sulphuric acid and
give off.
(i) carbon(IV) oxide. (1 mark)
(ii) hydrogen. (1 mark)
(b) What name is given to the reaction between aqueous sodium hydroxide
and the two acids in separate boiling-tubes? (1 mark)
(c) Write an ionic equation for the reaction between copper(II) oxide and
dilute hydrochloric acid. (2 marks)
(d) Name two reagents from the above list that can be used to prepare
magnesium sulphate. (2 marks)
(e) Write a chemical equations for reaction 3(d). (2 marks)
(f) Sulphuric acid forms two salts of sodium when it reacts with aqueous
sodium hydroxide. Name the anions in the two salts. (2 marks)
4. An electric current was passed through copper(II) sulphate solution for a
long time using carbon rods as electrodes as shown in the set-up below. A
gas that re-lights a glowing splint was produced at electrode Z.
Z Y
Copper(II) sulphate
solution
(a) Which of the electrodes is

(i) anode? (1 mark)
(ii) cathode? (1 mark)
(b) State the observation made at electrode Y. Give a reason for your
observation. (2 marks)
312
(c) State the observation in the electrolyte after a long time. Give a reason
for your answer. (2 marks)
(d) Write an ionic equation for the reaction at electrode Y. (2 marks)
(e) Why is copper(II) sulphate used in this experiment in solution form
and not crystals? (1 mark)
(f) What observations would be made at electrodes Z and Y if the
electrolyte is concentrated sodium chloride solution? Give reasons.
(3 marks)
5. (a) Describe the chemical processes involved in the manufacture of
hydrochloric acid from the reaction of chlorine and hydrogen. (2 marks)
(b) suggest an ideal location for this plant in Kenya. Give reasons. (2 marks)
(c) state two environmental effects the plant would have. (2 marks)
(d) name two uses of hydrochloric acid. (2 marks)
(e) describe with the help of chemical equations, the observations made
when dilute hydrochloric acid is reacted with
(i) marble chips. (2 marks)
(ii) zinc metal. (2 marks)
(iii) iron(II) sulphide. (2 marks)
(iv) aqueous silver nitrate solution. (2 marks)
6. During an experiment, sulphur(IV) oxide gas was found to diffuse through
a porous material at a rate of 25.00 cm3 per minute. When the experiment
was repeated under the same conditions with another gas G, G was found to
diffuse through the same porous material at a rate of 26.26 cm3 per minute
(a) Determine the molecular mass of gas G. (O = 16.0, S = 32.0). (2 marks)
(b) Further investigations showed that gas G consisted of 82.7% by mass
of carbon and the rest was hydrogen. Determine the molecular formula
of gas G (H= 1.0, C = 12.0). (2 marks)
(c) Name the homologous series to which gas G belongs. (1 mark)
(d) Draw and name two possible isomers of gas G. (3 marks)
(e) One mole of gas G was burned in excess air.
Write the chemical equation for the reaction that occurred. (2 marks)
7. The table below gives the formulae of some carboxylic acids and their
boiling points.
Acid Boiling point, ˚C
HCOOH 101
CH3COOH 118
CH3CH2COOH 141
CH3CH2CH2COOH 187
CH3CH2CH2CH2COOH 205
313
(a) (i) Name the acid with the formula CH3CH2COOH (1 mark)
(ii) Write the formula of the alkanol that can be oxidised to give
CH3CH2CH2CH2COOH (1mark)
(iii) On the graph paper provided, plot a graph of boiling point against
the number of carbon atoms of the carboxylic acids. (3 marks)
(iv) Explain giving reasons the shape of the graph. (2 marks)
(b) Explain the observations which you would make if you reacted sodium
hydrogencarbonate with aqueous solution of HCOOH. (2 marks)
(c) Calculate the volume of 0.2 M sodium hydroxide solution which
would be required to react completely with a solution containing 3.0g
of CH3COOH. (2 marks)
(C= 12.0, H = 1.0, O = 16.0)
1
Paper 3 practical Time 2 4 hours 40 marks
1. You are provided with the following reagents.
• Solution X of a dibasic acid of the formula H2A made by dissolving
1.225 g of H2A in water to make 250 cm3 of solution.
• Solution Y, which is sodium hydroxide solution made by dissolving 2 g
of sodium hydroxide in water to make 500 cm3 of solution.
You are required to determine the mass represented by A in the formula
H2A of the dibasic acid.
Procedure
1. Pipette 25.0 cm3 of solution Y into a 250 cm3 conical flask.
Add 2 to 3 drops of phenolphthalein indicator.
2. Fill the burette with solution X and titrate. Record your results in the
table given.
1 2 3
Final burette reading (cm3)
Initial burette reading (cm3)
Volume of solution X used (cm3)

(4 marks)
3. Repeat the titration procedure to get three accurate readings
(a) Calculate the average volume of solution X used. (1 mark)
(b) The equation of the reaction is
2NaOH(aq) + H2A(aq) ––––––– Na2A(aq) + 2H2O(l)
Calculate the molarity of sodium hydroxide, solution Y. (1 mark)
314
(c) Calculate the number of moles of sodium hydroxide in 250 cm3 of
solution Y. (1 mark)
(d) Calculate the number of moles of sodium hydroxide in 25.0 cm3 of
solutions. (1 mark)
(e) Calculate the molarity of solution X. (1 mark)
(f) Calculate the relative formula mass of H2A, the dibasic acid. (1 mark)
(g) Calculate the mass represented by A in the formula H2A of the dibasic
acid. (1 mark)
2. You are required to determine the enthalpy of displacement of copper from
copper(II) sulphate solution using zinc metal.
Procedure
• Transfer 50 cm3 of 0.2 m copper (II) sulphate solution into a lagged
beaker.
• Record the initial temperature of copper(II) sulphate solution in the
table below.
• Add 0.6 g of zinc power supplied and carefully stir with the thermometer
• Record the highest temperature of the mixture.
Table of results
˚C
Final temperature
Inital temperature
Change in temperature
(2 marks)
(a) Calculate the change in temperature. (1mark)

(b) Write the ionic equation of the reaction. (2 marks)
(c) Calculate the enthalpy of the reaction. (3 marks)
(density of solution 1 g/cm3, specific heat capacity 4.2 kJ/kg/K)
(d) Calculate the molar heat of displacement. (3 marks)
3. You are provided with solid M, which is a mixture of two salts. Carry out
tests below and record your observations and inferences in the table. Iden-
tify any gas(es) produced.
(a) Put a spatula endfull of solid M into a dry test tube and heat strongly.
Test for any gas produced using litmus papers.
315
Observations Inferences
(2 marks) (2 marks)
(b) Place the remainder of solid M in a boiling tube. Add distilled water
and shake well.
(1 mark) (1 mark)
(c) Divide the above solution into four equal portions

(i) To the first portion, add sodium hydroxide solution dropwise until
in excess.
(2 marks) (1 mark)
(ii) To the second portions add ammonia solution dropwise until in

excess
(2 marks) (1 mark)
(iii) To the third portions add lead(II) nitrate solution and warm
316
(1 mark) (1 mark)
(iv) To the fourth portions add barium nitrate solution.
(1 mark) (1 mark)
Model Test Papers B

Paper 1 Time 2 hrs 80 marks
1. Give two reasons why luminous flame is not used for heating purposes in
the laboratory. (2 marks)
2. A given sample of ink is a mixture of red dye, blue dye and orange dye.
The blue dye is more adsorbed than the rest and the red dye is the least
sticky.
(a) Complete the paper chromatogram below to show how the dyes are
separated. (2 marks)
Solvent front
Ink spot
(b) The dyes above are soluble in propanone. Describe how a pure
sample of red dye can be obtained. (1 mark)
3. One of the chemical compounds used in Pan paper industry at Webuye is
hydrated calcium hypochlorite. Explain its role. (1 mark)
317
4. Excess iron was allowed to rust in 2dm3 of moist air and the volume of air
remaining was measured at atmospheric pressure on daily basis. The results
obtained were as follows.
Day 0 1 2 3 4 5 6 7 8 9
Volume 2000 1900 1800 1730 1670 1630 1610 1610 1610 1610
of air
(cm3).
(a) Explain briefly why the volume of air is decreasing. (1 mark)

(b) On which day was the reaction complete? Explain. (1 mark)
(c) What is the percentage by volume of oxygen in the air? (Show clearly
how you arrive at your answer). (1 mark)
5. An element P forms an ion P2+. This ion contains 18 electrons
(a) Give the group of this element in the Periodic Table.
Explain your answer. (2 marks)
(b) Write the formula of the compound which would be formed if P reacts
with bromine. (1 mark)
6. Study the following equilibrium equation.
2A2(g) + B2(g) 2A2B(g) ∆H = –197 kJ/mol
(a) Suggest two ways of increasing the yield of A2B. (2 marks)

(b) On the grid provided below, draw a labelled energy level diagram for
the forward reaction. (2 marks)
Energy
Reaction progress
7. Calculate the mass of silver chloride which would be precipitated when a
solution containing 3.4 g of zinc chloride is reacted with excess silver nitrate
solution. (3 marks) (Zn = 65; Cl = 35.5; Ag = 108)
8. The set-up below shows the electrolysis of aqueous copper(II) sulphate
solution. Carbon electrodes are used.
318
Gas X
Carbon electrode B Carbon electrode A
Copper(II) sulphate
solution
(a) Write an ionic equation to show the formation of gas X. (2 marks)
(b) Why does the colour of copper(II) sulphate solution change during the
experiment. (1 mark)
9. (a) State Gay-Lussac’s law. (1 mark)
(b) 30 cm3 of a hydrocarbon which is gaseous reacted completely with 90 cm3
of oxygen. 60 cm3 of carbon(IV) oxide were produced. Given that
all volumes of the gases were measured at the same conditions of
temperature and pressure, determine the formula of this hydrocarbon.
10. Explain why aluminium is used for manufacturing utensils such as sufurias
or cooking pans. (1 mark)
11. (a) Define oxidation and reduction in terms of:
(i) Oxidation number (1 mark)
(ii) Electron transfer (1 mark)
2–
(b) Calculate the oxidation number of chromium in Cr2O7 . (2 marks)

12. (a) What is observed when hydrogen sulphide gas is reacted with lead(II)
nitrate solution? (1 mark)
(b) Write an ionic equation for the reaction in 12(a) above. (2 marks)
13. A polymer has the following structure
CH2 – CH – CH2 – CH – CH2 – CH

| | |
CH3 CH3 CH3
n
(a) Draw the structural formula of the monomer. (1 mark)
(b) A sample of the polymer is found to have a relative molecular mass of
4116 g.
Determine the number of monomers in the polymer (H= 1.0, C = 12.0)
(2 marks)
319
14. (a) 100 g of a radioisotope was reduced to 12.5 g after 81 days. Calculate
the half-life of this radioisotope. (2 marks)
212
(b) X decays by beta emission.
80
What is the mass number and the atomic number of the element
produced after decay? (1 mark)
15. Explain the effects of releasing nitrogen(IV) oxide to the environment. Use
chemical equations where possible.
16. (a) Name two cations that cause water hardness. (1 mark)
(b) Identify the following cleansing agents. (2 marks)
O
||
(i) C –– O– Na+
(ii) CH3– CH6CH2 OSO3+ Na–
State one advantage of using the cleansing agent in 16b(ii) above. (1 mark)
17. Study the set-up below and use it to answer the questions that follow
Copper(II) Anhydrous
oxide copper(II) sulphate
hydrogen
Dry burning
hydrogen
gas
heat heat
(a) Why is excess hydrogen burnt at the end of the tube? (1 mark)
(b) What is observed in the combustion tube? (2 marks)
(c) Write an equation for the reaction in the combustion tube. (2 marks)
18. The table below gives information on three substances A, B, and C. Study it
an answer the questions that follow.
Substance Melting Boiling Electrical
Point ˚C Point˚C Conductivity
A 98 824 Conducts in solid
and molten states
B –117 80 Does not conduct in
any state.
C 658 1320 Conducts in molten
and aqueous states.
320
(a) What type of bonding is in C? (1 mark)
(b) Which substance is likely to be sodium? Explain. (2 marks)
19. An oxide of M contains 48% oxygen by mass. What is the empirical for-
mula of the oxide? (M = 26, O = 16). (2 marks)
20. A white solid produces a red-brown gas and oxygen when heated. The hot
solid residue is brown but turns yellow on cooling.
(a) What is the cation and anion in this white solid? (2 marks)
(b) Write the chemical equation for the reaction. (2 marks)
(c) Name the two products formed when the red-brown gas is bubbled into
water. (2 marks)
21. Explain why the pH value of 0.1M hydrochloric acid is lower than that of
0.1M carbonic acid. (2 marks)
22. Name the following compounds.
(a) CH3CH = CHCH3 (1 mark)
(b) CH3CH2CH2C = CCH3 (1 mark)
23. Using excess pieces of magnesium ribbon and 1M sulphuric acid, describe
how you can prepare a sample of magnesium sulphate crystals. (3 marks)
24. Explain why an alkanol has a higher boiling point than an alkane of the
same molecular mass. (2 marks)
25. (i) State Graham’s law of diffusion. (1 mark)
(ii) Hydrogen diffuses through a porous plug in 80 seconds. The same
volume of gas W diffuses the same aperture in 300 seconds.
Calculate the molecular mass of gas W. (3 marks)
26. A certain compound was analysed and the results obtained are in the table
below. Study it and answer the questions that follow.
Tests Observations
1. Add few drops of acidified barium No ppt formed
nitrate solution to 1st portion. No bubbles seen
2. To the 2nd portion, add lead(II) A white ppt
nitrate solution.
3. To the 3rd portion, add sodium A green ppt
hydroxide solution.
(a) Identify the;

(i) cation present (1 mark)
(ii) anion present (1 mark)
321
(b) Write an ionic equation to show how the green precipitate was
formed. (2 marks)
27. Draw two isomers of butyne and name them. (4 marks)
28. Explain why concentrated sulphuric acid turns sucrose (sugar) to
a black mass. (2 marks)
Paper 2Time 2Hrs 80 marks

1. (a) The grid below represents part of the periodic table. Study it and answer
the questions that follow. The letters do not represent the actual symbols
of the element.
M
N S
Q O P
R
(a) What name is given to the group of elements to which Q and R

belongs? (1 mark)
(b) Which letter represents the element that is least reactive? (1 mark)
(c) What type of bond is formed when N and P react? Explain. (2 marks)
(d) Write the formula of the compound formed when elements Q and S
react. (1 mark)
(e) Using dot(•) and cross (x) draw a diagram to represent the compound
you have named in (d) above. (2 marks)
(f) Write the electron arrangement and the symbol of ion of Q. (1 mark)
2. (i) Use the standard electrode potentials for elements A, B, C, D and F
given below to answer the questions that follow. The letters do not
represent the actual symbols of the element
A2+(aq) + 2e– –––– A(s) Eθ = – 2.90 V
B2+(aq) + 2e– –––– B(s) Eθ = – 2.38 V
2C+(aq) + 2e– –––– C2(g) Eθ = 0.00V
D2+(aq) + 2e– –––– D(s) Eθ = + 0.34 V
322
1
/2F2(g) + e– –––– F(aq) Eθ = + 2.87 V
(a) Which element is likely to be hydrogen? Give reasons for your

answer. (2 marks)
(b) Calculate the Eθ value of the electrochemical cell obtained when the
half-cells of elements B and D are combined. (2 marks)
(c) Draw a fully labelled diagram to show how you can electroplate a
copper coin with silver. (4 marks)
3. The figure below is used to investigate the effect of carbon(II) oxide on
copper(II) oxide. Study it and answer the questions that follow.
Copper(II) oxide
Z
Carbon(II) oxide
Glass Heat A
wool B
Calcium hydroxide
solution
(a) Name two chemicals that may be used to produce carbon(II) oxide gas.
(2 marks)
(b) Write the chemical equation for 3(a) above. (2 marks)
(c) State the observations made in apparatus A and B at the end of the
experiment. (1 mark)
(d) Write the chemical equation for the reaction in apparatus A. (2 marks)
(e) State the oxidising and reducing agents for 3(d) above. (1 mark)
(f) Write balanced chemical equations for the two reactions taking place
in apparatus B, one after a short time and the other after a long time.
(4 marks)
4. (a) What is observed when dry ammonia gas is passed over hot copper(II)
oxide in a combustion tube? (1 mark)
(b) Write a chemical equation for the reaction in 4(a). (2 marks)
(c) Ammonia gas can be reacted with a certain reagent to produce
ammonium sulphate.
(i) Write the chemical equation to show how ammonium sulphate is
formed. (2 marks)
(ii) Mention one use of ammonium sulphate. (1 mark)
(iii) Calculate the percentage by mass of nitrogen in ammonium
sulphate. (2 marks)
(iv) Ammonium phosphate and sodium nitrate are used as fertilizers.
Which is the faster acting fertilizer? Explain your answer. (2 marks)
323
5. 4.0 g of magnesium carbonate having some impurity of magnesium sulphate
were dissolved in 250 cm3 of 1M HCl. 25 cm3 of the resulting solution
was found to require 28.8 cm3 of 0.6 M NaOH for complete neutralization.
(a) Calculate the number of moles of sodium hydroxide in 28.8 cm3.
(2 marks)
3
(b) Calculate the number of moles of HCl in 250 cm of 1M solution.
(2 marks)
(c) Determine the percentage purity of the magnesium carbonate. (2 marks)
6. (a) Write an ionic equation for the reaction between iron(II) sulphide and
dilute hydrochloric acid. (2 marks)
(b) Why is it not advisable to prepare large quantities of hydrogen sulphide
gas in a closed laboratory? (1 mark)
(c) Write a chemical equation for the reaction that would occur if hydrogen
sulphide gas is burned in excess air. (2 marks)
(d) Sulphur(IV) oxide reacts with oxygen as shown below
2SO2(g) + O2(g) 2SO3(g)
Calculate the volume of air required to convert 6.4 g of sulphur(IV) oxide
completely into sulphur(VI) oxide at room temperature. (4 marks)
(O = 16.0, S = 32.0, molar gas volume at r.t.p = 24 dm3. Air contains 20%
by volume of oxygen)
(e) Explain what would happen to the equilibrium in 6(d) if carbon(II)
oxide was injected in. (2 marks)
7. (a) Metals are said to be ductile, malleable and they corrode in the air.
(i) Explain the meaning of the terms in italics. (3 marks)
(ii) Give the names of the ores used in the production of iron and
aluminium. (2 marks)
(iii) Name the method used to extract aluminium. (1 mark)
(b) What is the environmental effect of obtaining the ores of the metals
named in a(ii) from their large reserves in the earth. (2 marks)
(c) Name an alloy of aluminium and give one of its uses. (2 marks)
8. An aqueous solution of hydrogen peroxide decomposes according to the
equation:
2H2O2(l) 2H2O(l) + O2(g)
This reaction is fast at 20˚C in the presence of manganese(IV) oxide.
(a) What is the role of manganese(IV) oxide in? (2 marks)
(b) Sketch graphs on the grid given, showing how the volume of
oxygen (vertical axis) varies with time when:
324
(i) 0.5 g of manganese(IV) oxide is mixed with 100 cm3 of 0.2M
hydrogen peroxide solution, label the curve A. (1 mark)
(ii) The same experiment is repeated at 30˚C, label the curve B.
(1 mark)
Volume of oxygen
Time
(c) (i) Write the equation for the manufacture of ammonia, using
equilibrium arrows. (2 marks)
(ii) Explain how the increase in pressure affects the position of the
equilibrium. (1 mark)
(iii) The reaction in c (i) above is exothermic, what is the effect of
raising temperature on the equilibrium? (1 mark)
(d) Explain how some human activities have interfered with the natural
phenomenom of maintaining the earth’s temperature to a level
necessary to support life. (4 marks)
9.When excess iron filings were dissolved in dilute sulphuric acid, a pale
green solution was obtained and a colourless gas evolved. The solution
was filtered and divided into two portions.
(a) Write an equation for the reaction. (2 marks)
(b) (i) To the first portion aqueous ammonia was added until in excess.
State the observation. (1 mark)
(ii) Write an ionic equation for the reaction in (i) above. (2 marks)
(c) (i) To the second portion of the filtrate dilute sulphuric acid was
added followed by a few drops of concentrated nitric acid and
the mixture warmed. State and explain the observations made
during the addition of concentrated nitric acid. (2 marks)
(ii) Write an ionic equation for the reaction in c(i). (2 marks)
(d) Give the name of the acid whose formula is CH3CH2CH2CH2COOH
(1 mark)
325
1
Paper 3 practical Time 2 4 hours 40 marks
1. You are provided with the following reagents
• 0.1 M sulphuric acid, labelled M
• Carbonate solution containing 13.8 g dm–3 of X2CO3, labelled N
• Methyl orange indicator
You are required to:
— Calculate the formula mass of X2CO3
— Calculate the relative atomic mass of X in X2CO3
Procedure
1. Fill the burette with sulphuric acid, solution M.
2. Pipette 25.0 cm3 of carbonate solution into a conical flask and add 2-3
drops of methyl orange indicator.
3. Titrate the carbonate solution with the acid and record your results in a
table similar to the one given below.
1 2 3
Final burette reading (cm3)
Initial burette reading (cm3)
Volume of acid used (cm3)
(4 marks)
4. Repeat the titration procedure to get three accurate readings.

(a) Calculate the average volume of acid used (cm3). (1 mark)
(b) Calculate the molarity of X2CO3 used in the reaction. (1 mark)
(c) Calculate the formula mass of X2CO3. (1 mark)
(d) Calculate the relative atomic mass of X (C = 12, 0 = 16). (1 mark)
2. You are required to determine the heat of neutralisation of solution C by
solution D.
Procedure
• Measure 50 cm3 of solution C and transfer to a lagged beaker.
• Record the temperature of solution C.
• Rinse the thermometer.
• Measure 50 cm3 of solution D.
• Record the temperature of solution D.
• Add solution D to solution C and stir carefully with the thermometer.
• Record the highest temperature of the mixture.
• Record your results in the table below.
326
˚C
Temperature of solution C
Temperature of solution D
Highest temperature of the mixture
Change in temperature, ∆T
(4 marks)
(a) Calculate the average temperature of solution C and solution D. (1 mark)
(b) Write the ionic equation of the reaction. (1 mark)
(c) Calculate the heat of reaction. (Specific heat capacity = 4.2 kJ Kg–1 K–1,
density of solution 1 g/cm3) (2 marks)
(d) Calculate the molar heat of neutralisation. (4 marks)
3. You are provided with solid P which is a mixture of two salts. Carry out
the tests below and record your observations and inferences in the tables.
Identify any gas(es) produced.
(a) Heat a spatula end full of mixture P in a test tube
(2 marks) (2 marks)
(b) Dissolve part of mixture P in about 10 cm3 of distilled water
(1 mark) (1 mark)
(c) Filter the mixture and retain both the filtrate and the residue. Divide the
filtrate into two equal portions.
(i) To the first portion, add sodium hydroxide solution dropwise until
excess

327
(2 marks) (2 marks)
(ii) To the second portion, add potassium iodide solution
(1 mark) (1 mark)
(d) To the residue, add dilute nitric acid. Divide the resulting solution into
two equal portions.
(1 mark) (1 mark)
(i) To the first portion, add aqueous sodium hydroxide dropwise until
in excess
(2 marks) (1 mark)
328
(ii) To the second portion, add aqueous ammonia dropwise until in excess.
(2 marks) (1 mark)
329
GLOSSARY
Activated complex: An unstable arrangement of atoms that exists momentarily at
the peak of the activation energy barrier. It represents an intermediate or transitional
structure formed during the course of a reaction.
Activation energy: The minimum energy colliding particles must have in order
to react.
Addition polymerization: The process that occurs when unsaturated monomers
add to each other forming a polymer.
Alkanols: Organic compounds made of a hydrocarbon group and one or more
hydroxyl group (OH) e.g. ethanol (C2H5OH).
Alloy: A material composed of two or more metals physically combined e.g.
bronze or brass.
Alpha particle(a): A positively charged particle emitted from certain radioactive
nuclei. It consists of two protons and two neutrons and is identical to the nucleus
of a helium atom, 4 He2+.
2
Alpha radiation: A stream of alpha particles emitted from a radioactive isotope.
Amphoteric: Capable of acting either as an acid or as a base, e.g. Zinc oxide is
an amphoteric oxide.
Amphoteric hydroxide: A metal hydroxide which reacts with an acid or base
producing salts in both cases, Al(OH)3 , Zn(OH)2 , Pb(OH)2 are amphoteric
hydroxides.
Amphoteric oxide: A metal oxide which reacts with an acid or a base producing
salts in both cases PbO, ZnO, Al2O3 are amphoteric oxides.
Aqua regia: A mixture of concentrated nitric acid and concentrated hydrochloric
acid (it is capable of reacting with gold).
Atomic bomb: An explosive device whose vast source of energy is a nuclear
fission reaction, e.g. uranium atomic bomb that was dropped in Japan during the
2nd world war.
Basic solution: Any solution in which the hydroxide ion (OH–) concentration is
greater than the hydrogen ion (H+) concentration.
Beta particle (b): A fast-moving electron emitted from certain radioactive
nucleus; it is formed when a neutron changes into a proton.
Beta radiation: A stream fast-moving electrons (beta particles) emitted from a
radioactive isotope.
Blast furnace: A tall cylindrical chamber in which iron(III) oxide is reduced to
iron using coke (carbon), limestone and a blast of hot air.
330
Bond dissociation energy: The amount of energy required to break a bond
between atoms. It is usually expressed in kJ per mol of substance.
Bronze: An alloy composed of copper and tin. Small amounts of zinc, lead and
other metals may be added to give it special properties.
Brass: An alloy of copper and zinc.
Cathode: The negatively charged electrode at which reduction (gain of electrons)
takes place during electrolysis. In primary or secondary cells, it is the electrode
from which electrons emerge.
Chain reaction: A reaction which is self-sustaining because the products of one
step of the reaction assists in starting further reaction, e.g. uranium nuclear fission
is started by a neutron. The fission causes the production of more neutrons.
Chemical equilibrium: It is a state of “balance” in which forward and reverse
reactions are taking place at the same rate; no net change in the amounts of reactants
and products occurs in the chemical system.
Condensation polymer: A polymer formed by condensation reaction; for example,
nylon which is produced by a condensation reaction between 1,6-diaminohexane
and hexanedioic acid.
Condensation reaction: A reaction in which a simple molecule (for example,
water or ammonia) is produced when reactant molecules join together to form a
polymer.
Contact process: A process for making sulphuric acid in which the sulphur(IV)
oxide and oxygen come into contact in the presence of a catalyst.
Cross-linking: The formation of side covalent bonds linking different polymer
chains and therefore increasing the rigidity of the plastics. Thermosetting plastics
usually contain many cross-links. See vulcanization of rubber also.
Detergent: Any substance in liquid or solid form which removes dirt physically
from clothes, hands, utensils, e.g. Omo a cleansing agent.
Dissociation: The separation of the ions of an ionic substance when it dissolves
in water.
Denatured alcohol: Ethanol to which a poisonous substance has been added to
make it unfit for human consumption.
Electrochemical cell: A device that converts chemical energy into electrical
energy.
Electrochemical process: The conversion of chemical energy into electrical
energy or electrical energy into chemical energy. In an electrochemical cell,
chemical energy is converted into electrical energy.
331
Electrochemical series: A table of metals or non-metals arranged in order of
descending ease of losing electrons for metals or gaining electrons for non-metals.
Electroplating: The process of coating the surface of a metallic surface with a
metal using electrolysis process, e.g. electroplating iron with zinc.
Endothermic reaction: A chemical change in which energy is absorbed, the
energy content of the products is higher than the energy content of the reactants
∆H has a positive value.
Enthalpy: The amount of heat that a substance has at a given temperature and
pressure.
Equilibrium position: The relative concentrations of reactants and products of
a reaction that has reached equilibrium; it indicates whether the reactants or products
are favoured in the reversible reaction.
Esters: A family of organic compounds formed by esterification i.e. the reaction
of an alkanol with alkanoic acid. They are characterised by strong and pleasant
tastes and smells.
Esterification: The process of producing an ester by the reaction of an alkanoic
acid and an alkanol.
Excess reagent: A reagent in a quantity that is more than sufficient to react with
another or any reactant that remains after a reaction stops.
Exothermic reaction: A chemical change in which energy is released in form
of heat; the energy content of the products is less than the energy content of the
reactants i.e. ∆H as a negative value.
Faraday’s constant: The quantity of electricity transferred by one mole of
electrons (6.0 ´ 1023 electrons). It has a value of 96500 C/mol.
Fermentation: The production of ethanol from sugars by the action of yeast or
bacteria. It is usually accompanied by evolution of heat and carbon(IV) oxide gas.
Fission: The break-up of a nucleus into medium-mass nucleus accompanied by
the release of neutrons and a large amount of energy.
Froth floatation: A method commonly used to enrich sulphide ores of copper
and lead by separating ore from gangue. Crushed ore is mixed with water and
oil is blown through the mixture. The more pure ore is obtained as a froth which
floats.
Functional group: The atom or group of atoms responsible for the characteristic
chemical reactions of an organic compound. The chemistry of an organic compound is
determined by its functional group.
Fussion: A reaction in which two light nuclei combine to produce a heavier and
more stable nucleus accompanied by the release of a large amount of energy.
332
Gamma-ray or radiation(g): High energy electromagnetic radiation, like X-ray,
emitted by certain radioactive nuclei. They have no mass or electrical charge.
Gangue: The worthless sand and rock contained in freshly mined ore.
Geiger counter: A gas-filled metal tube used to detect the presence of radioactive
radiations.
Half-cell: The part of a voltaic cell in which either oxidation or reduction occurs.
It consists of a single electrode immersed in a solution of its ions.
Heat of combustion: The heat released during a chemical reaction in which one
mole of a substance is completely burned in oxygen.
Heat of neutralisation: The heat change which takes place when one mole of
hydrogen ions in solution is completely neutralised by one mole of hydroxyl ions
in a solution of alkali.
Heat of solution: The heat absorbed or evolved when one mole of a substance
is dissolved in a stated number of moles of water.
Ionizing radiation: Radiation which has enough energy to produce ions by
knocking off electrons from the atoms it strikes.
Ion exchange resin: A resin which can exchange ions for positive ions, or one
which exchange hydroxide ions for negative ions.
IUPAC system: An internationally accepted system of naming compounds
proposed by the International Union of Pure and Applied Chemistry (IUPAC).
Le Chatelier’s principle: When stress is applied to a system at equilibrium, the
system changes to reduce the stress.
Limiting reagent: Any reactant that is used up first in a chemical reaction; it
determines the amount of product that can be formed in the reaction.
Nuclear equation: An equation representing changes in the nuclei of atoms.
Nuclear fission: The splitting of an atomic nucleus of an element to form two
or more atomic nuclei of different elements or another element and particle(s)
like b- particles, neutrons, protons, etc. Energy is released in this type of reaction
(nuclear energy).
Nuclear fussion: The process of combining two or more atomic nuclei of the
same element or different elements to form an atomic nucleus of same or different
element. Nuclear energy is released in this type of reaction.
Nuclear reactor: A set-up in which the controlled fission of radioactive material
produces new substances for economic use, e.g. Chernobyl nuclear reactor.
Ore: A mineral used for commercial production of a metal.
Oxidation: There are three definitions of oxidation:
333
• A reaction in which oxygen is added to an element or compound or hydrogen
is removed from an element or compound.
• A reaction involving the loss of electrons from an atom, molecule or ion.
• A reaction in which oxidation number of an element is increased.
[It is brought about by an oxidising agent].
Oxidation number or state: It is the apparent charge that an atom of an element
has when in a molecule or ion.
Oxidation-reduction reaction: A reaction that involves the loss or gain of
hydrogen or oxygen or transfer of electrons between reactants during a chemical
change.
Oxidising agent: The atom, radical or ion which gives out oxygen or takes up
hydrogen or takes up electron(s) during a chemical reaction. In the reaction the
oxidising agent is reduced.
Permanent hardness: Hardness caused by the sulphates or chlorides of calcium
and magnesium and can only be removed by addition of chemical softeners like
Na2CO3 but not by boiling.
pH scale: A scale with a range from 1 to 14, used for expressing the acidity or
alkalinity of a solution. A neutral solution has a pH of 7
Pig iron: The form of iron obtained from the blast furnace. It contains high carbon
content and other impurities making it brittle.
Plastic: Synthetic material which can be shaped while soft into required form
and then hardened to produce a durable finished article, e.g. polyethene.
Radioactive fall-out: Radioactive fission products which have escaped into the
atmosphere.
Radioactive decay: The process in which unstable nucleus emits radiations.
Radioactivity: The spontaneous uncontrollable decay (disintegration) of unstable
nucleus of an atom with the emission of beta or alpha particles and gamma-rays
producing a nucleus of different atomic number. This process is accompanied by
release of energy.
Radioisotopes: Isotopes that have unstable nuclei and undergo radioactive decay.
Reaction rate: A measure of how fast a reaction takes place. [Particular reactions
may be affected by the following factors the surface area of the solid reactants,
the concentration of aqueous reactants or pressure of gaseous reactants, the
temperature of the reactants, light and the use of a catalyst].
Redox reaction: Short form for Reduction–oxidation reaction.
Reduction: There are three definitions of reduction
334
• A reaction in which oxygen is removed from an element or compound or
hydrogen is added to an element or compound
• A reaction involving gain of electrons by an atom, molecule or ion.
• A reaction in which oxidation number of an element is decreased. [It is
brought about by a reducing agent].
Reducing agent: The atom, radical or ion which takes up oxygen or gives out
hydrogen or gives out electrons during a chemical reaction. In the reaction, the
reducing agent is oxidised.
Reversible reaction: A reaction in which the conversion of reactants into products
(forward reaction) and the conversion of products into reactants (backward reaction)
are possible depending on the physical conditions in which it is carried out.
Roasting: A process used to purify sulphide ores by heating the ore with air.
Salt bridge: A tube or porous material containing a conducting solution used
to connect the half-cells in a voltaic cell; it allows the passage of ions from one
half-cell to the other but prevents the solutions from mixing completely.
Saponification: The process of making soap by hydrolysis of an ester with a
hot aqueous alkali.
Slag: The fused waste material from a smelting process; it is usually composed
of silicates.
Smelting: A process in which impurities are removed from an ore by melting.
Soapless detergents: Cleansing agent which do not contain a carboxylate ion as
its polar end, but have –OSO3–Na+.
Soaps: Cleansing agent which contain a carboxylate ion as its polar end. [They
are formed by a process called saponification].
Solubility: The mass in grams of a substance that will saturate 100 g of a solvent
at a particular temperature.
Solubility curve: A graph showing how the solubility of a substance in a solvent
changes with temperature.
Specific heat capacity: The quantity of heat required to raise the temperature
of 1 g of a substance by 1˚C.
Spontaneous reaction: A reaction that takes place without application of external
energy (heat or light), e.g. nuclear reactions, neutralization of a strong acid/strong
base.
Standard electrode potential: Electrode potential of the metal when it is in
contact with 1 molar solution of its metallic ions at 25˚C when measured using a
standard hydrogen electrode as the reference.
335
Standard hydrogen electrode potential: This is the electrode potential when
one atmosphere of hydrogen gas is in contact with 1 mole of hydrogen ions. It is
arbitrarily taken as zero.
Strong acid: An acid that is completely (or almost completely) dissociated to
form ions in aqueous solution e.g. sulphuric acid.
Strong base: A base that completely dissociates into metal ions and hydroxide
ions in aqueous solution e.g. sodium hydroxide solution.
Strong electrolyte: A solution in which a large portion of the solute exists as
ions.
Temporary hardeness: Hardness of water caused by the hydrogencarbonate of
calcium and magnesium, which can be removed by boiling the water.
Thermochemical equation: A chemical equation that includes the amount of
heat produced or absorbed during the reaction. ∆H is –ve for exothermic reaction and
+ve for endothermic reaction.
Thermoplastics: Plastics which soften when heated. They can be re-moulded
e.g. polyethene, PVC and nylon.
Thermosetting plastics: Plastics which do not soften on heating but only harden
and decompose. They cannot be re-moulded, e.g. Backelite.
Water softener: A chemical substance which is added to hard water to remove
hardness, e.g. sodium carbonate
Water softening: The Process by which hardness is removed from water.
Weak acid: An acid that partially dissociates into ions in aqueous solution e.g.
ethanoic acid.
Weak base: A base that partially dissociates in aqueous solution e.g. ammonium
hydroxide.
Weak electrolyte: A solution in which only a fraction of the solute exists as ions.
Zincate: A salt of zinc hydroxide when it acts as a feeble acid.
336
Appendix I
Atomic numbers and relative atomic masses of some elements
Element Symbol Atomic number Relative atomic mass

Aluminium Al 13 27
Argon Ar 18 40
Barium Ba 56 127
Beryllium Be 4 9
Boron B 5 11
Bromine Br 35 80
Calcium Ca 20 40
Carbon C 6 12
Chlorine Cl 17 35.5
Chromium Cr 24 52
Copper Cu 29 63.5
Fluorine F 9 19
Gold Au 79 197
Helium He 2 4
Hydrogen H 1 1
Iodine I 53 127
Iron Fe 26 56
Krypton Kr 36 84
Lead Pb 82 207
Lithium Li 3 7
Magnesium Mg 12 24
Manganese Mn 25 55
Mercury Hg 80 207
Neon Ne 10 20
Nickel Ni 28 59
Nitrogen N 7 14
Oxygen O 8 16
Phosphorus P 15 31
Potassium K 19 39
Silicon Si 14 28
Silver Ag 47 108
Sodium Na 11 23
Sulphur S 16 32
Tin Sn 50 119
Vanadium V 23 51
Zinc Zn 30 65
337
APPENDIX II x x is the Relative Atomic Mass (RAM)
338
Z Z is the symbol of the element
Periodic table y
y is the Atomic Number of the element
Name
Groups
I II III IV V VI VII O
Periods 1
H 4
1 He
1
Hydrogen
2
Helium
7 9 11 12 14 16 19 20
2 3
Li B C O F Ne
4 Be 5 6 7N 8 9 10
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
23 24 27 28 31 32 35.5 40
3 Na Mg Transition metals Al Si P S Ar
11 12 13 14 15 16 17 Cl 18
Sodium Magnesium Aluminium Silicon Phosphorus Sulphur Chlorine Argon
39 40 54 48 51 52 55 56 58.9 59 64 65 70 73 75 79 80 84
4 19 K 20 Ca 21 Sc 22 Ti 23 V 24 Cr 25
Mn Fe Co 28 Ni 29 Cu 30 Zn 31 Ga Ge As Se Br Kr
26 27 32 33 34 35 36
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germenium Arsenic Selenium Bromine Krypton
86 88 89 91 93 96 99 101 103 106 108 112 115 119 122 128 127 131
5 Rb Sr Y Zr Nb Mo Tc Cd
37 38 39 40 41 42 43 44 Ru 45 Rh 46 Pd 47 Ag 48 49 In 50 Sn 51Sb 52 Te 53 I 54 Xe
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium palladiun Silver Cadmium Tin Antimony Tellurium Iodine Xenon
Indium
133 137 175 178 181 184 186 190 192 195 197 201 204 207 209 210 210 222
6 Cs Ba Lu Os
55 56 71 72Hf 73Ta 74 W 75 Re 76 77 Ir 78 Pt 79 Au 80 Hg 81 Tl 82 Pb 83 Bi 84 Po 85At 86 Rn
Caesium Barium lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury Thallium Lead Bismuth Polonium Astatine Radon
223 226 257 261 262 266 264 269 268 271 272 285 289 Uup 292
7 Lr Rf Db Uun Uuu Uut Uuo
Sg 107 Bh 108Hs 109Mt 111 Uuh Uns 118
87Fr 88 Ra 103 104 105 106 110 112Uub 113 114 Uuq 115 116
Francium Radium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Ununniliam Ununnium Ununbium unnuqnabium ununhexium 117 ununoctium
257 140 141 144 147 150 152 157 159 163 165 167 169 173
Lanthanides La Ce Pr Nd 61 Pm Sm Eu Dy Ho 68 Er
57 58 59 60 62 63 64
Gd 65 Tb
66 67 69 Tm 70 Yb
Lanthanum Cerium Praseodymium Neodymium Promethium Erbium
Samarium Europium Gadolinium Terbium Dysprosium Holmium Thulium Ytterbium
Actinides 227 232 231 238 237 242 243 247 249 251 254 253 256 254
Ac Th Pu Am Cm Bk
89 90 91Pa 92U 93Np 94 m 95 96 97 98Cf 99 Es 100 Fm 101Md 102No
Actinium Thorium Protactinum Uranium Plutoniu
Neptunium Americium Curium Berkelium Carlifonium Einsteinium Fermium Mendelevium Nobelium

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Longhorn Secondary

Longhorn Publishers (U) Ltd.,

Longhorn Publishers (T) Ltd.,

© George Ngaruiya • Joan Kimaru • Paul Mburu, 2005

All rights reserved. No part of this publication may be

First published 2005

ISBN 9966 49 565 7

Illustrations by Timothy Maleche

Unit 1: Acids, Bases and Salts.............................................................................................. 1

Unit 7: Radioactivity..................................................................................... 284

Acid + base salt + water

As we learnt earlier, there are several methods of salt preparation and

1.2 Strong and weak acids and bases

HCl(aq) ––––– H+(aq) + Cl–(aq)

HNO3(aq) ––––– H+(aq) + NO–3(aq)

H2SO4(aq) ––––– 2H+(aq) + SO42–(aq)

A weak acid is one which is only slightly or partially dissociated in aqueous

(b) Strong and weak bases

NH3(g) + H2O(l) NH4OH(aq) NH4+(aq) + OH–(aq)

Self-assessment exercise 1.3

Substance being tested Colour obtained pH Indicate whether

5. Classify the solutions into strong or weak acid and base.

Increase in hydrogen Increase in hydroxide

Self-assessment excercise 1.4

1.3 Electrical conductivity of weak and strong acids and bases

Fig. 1.1: Investigating the electrical conductivity in acids and bases

1.4 Characteristics of amphoteric oxides and hydroxides

(b) Lead(II) oxide + sodium + water –––– sodium

(c) Lead(II) hydroxide + nitric(V) acid ––– Lead(II) nitrate + water

(d) Lead(II) hydroxide + sodium hydroxide –––– Sodium plumbate

• Aluminum hydroxide is showing acidic property.

Table 1.5: Summary of properties of amphoteric oxides and hydroxides

Self-assessment exercise 1.6

delivery tube hydrogen chloride

Fig. 1.2: Preparation of hydrogen chloride solution in water or

• Why do we take the precaution of using the funnel?

Table 1.6: Determining the properties of hydrogen chloride in different

Put dry blue litmus paper

Give the reason for the conclusions you have made.

Cl– ion HCl molecule

NH4+ ion NH3 molecule

Self-assessment exercise 1.7

Na+ moves here

If ammonium hydroxide was used instead of sodium hydroxide, ammonium

NH4+ moves here

2. Potassium + sulphuric(VI) ––– potassium + water

2KOH(aq) + H2SO4(aq) ––– K2SO4(aq) + 2H2O(l)

2K+ move here

NaOH(aq) + H2SO4(aq) –––– NaHSO4(aq) + H2O(l)

Na+ moves here

1.7 Precipitation reactions in salt preparation

1.8 Reactions of cations in aqueous solutions with sodium hydroxide

Cation in Observations on addition of sodium hydroxide solution

Cation in Addition of aqueous ammonia

1.9 Test for cations

Zn2+(aq) + 2OH–(aq) –––– Zn(OH)2(s)

Al3+(aq) + 3OH–(aq) –––– Al(OH)3(s)

Pb2+(aq) + 2OH–(aq) –––– Pb(OH)2(s)

Cu2+(aq) + 2OH–(aq) –––– Cu(OH)2(s)

Predicting precipitate reactions

Table 1.14 Solubility of ionic salts

Nitrates (NO–3) All None

1.10 Reactions of cations in aqueous solutions with chloride,

Pb2+ White White White White