Senior Secondary

Chemistry
Textbook 3

S. T. Bajah
B. O. Teibo
G. Onwu
A. Obikwere

i
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© Longman Nigeria Plc 1990, 2000, 2013

First Published 1990

Reprinted 1995, 1996, 1997
New Edition 2000
Reprinted 2001, 2003, 2005
Revised 2013

National Library of Nigeria Cataloguing in

Publication Data

SENIOR Secondary Chemistry, Textbook 2

1. Chemistry – Study and teaching
(Secondary) – Nigeria
2. Bajah, S.T. II Title

QD 42.S4777 2001 540.7

ISBN 078-978-026 AACR 2

Acknowledgements
The publishers would like to thank Cadbury Nigeria Plc for per-
mission to reproduce the cover photograph. The Nigerian National
Petroleum Corporation provided the data on crude oil fractions
and the publishers are thankful for this kind gesture.

ii
 Contents

Preface vi General principles of extraction of

metals 43
1 Quantitative and qualitative analysis 1
Quantitative analysis 1 4 The alkali metals: Group 1
Titration 1 elements 46
Qualitative analysis 9 Occurrence of alkali metals 47
Physical properties of alkali metals 47
2 Petroleum 20 Chemical properties of alkali metals 49
Petroleum 20 Extraction of sodium 53
Hydrocarbons 20 Sodium hydroxide 56
Saturated hydrocarbons (The alkanes) 21 Disodium trioxocarbonate(IV) 61
Unsaturated 22 Sodium hydrogen trioxocarbonate(IV)64
Uses of petroleum fractions 25 Sodium chloride 65
Composition of oil fractions 24 Sodium trioxonitrate(V) 65
Conversion 30 Disodium tetraoxosulphate(VI) 66
Octane number 31 Sodium hydrogen tetraoxo-
sulphate(VI)
3 Chemical bonding Sodium peroxide 67
Metallic character and periodicity
Atomic properties and periodicity 5 Alkaline earth metals: Group A
Types of bonding in metallic and non- elements 71
metallic elements and compounds Occurrence of alkaline earth metals 71
Covalent bonds and bond energy Physical properties of alkaline
Chemical bonding and shapes of simple earth metals 72
molecules General chemical properties of
Properties and structure of solids alkaline earth metals 74
Reactions of alkaline earth metals
3 Extraction of metals: General with acids 75
principles 40 Reactions of alkaline earth metals
Occurrence of metals in nature 41 with non-metals 76
Reactivities of metals 41 Alkaline earth metals as reducing
Extraction of metals 42 agents 77

iii
 Preparation of amines
6 The aluminium family 87 Amides
Occurrence of aluminium 87 Nomenclature of amides
Extraction of aluminium 88 Sources of amides
The thermite process 92 Preparation of amides
Aluminium oxide (alumina) 92 Amino acids
Dialuminium(III) tetraoxosulphate(VI) 92 Sources of amino acids
Aluminium hydroxide 93 Nomenclature of amino acids
Alums 94 Preparation of amino acids
Aluminium(III) chloride 95 Esters
Nomenclature of esters
7 Tin, iron and other metals of the first Preparation of esters of alkanoic acids
transition series 99 Theory of detergency
Occurrence of tin 99 Soaps
Extraction of tin 99 Synthetic surfactants
Metals of the first transition series 101 Heavy-duty powder detergents
Complex ion formation 107 Uses of alkanoic acids and their
Iron 110 derivatives
Extraction of iron 110
Rusting of iron 113 10 Fats and oils
Compounds of iron 114 Sources of fats and oils
Copper 114 Test for fats
Extraction of copper 117 Uses of fats and oils
Copper(II) tetraoxosulphate(VI) 119 Physical properties of fats and oils
Alloys 119 Chemical properties of fats and oils
Steel 120
Manufacture of steel 121 11 Soap and detergents
Soap and detergents 179
8 Waste: Ethical, legal and social issues Soaps 179
Chemical waste Effects of hard water on soaps 181
Industrial pollution Detergents
Industrial pollutants
Effects of pollution 12 Giant molecules
Pollution control Carbohydrates
Roles of government in preventing Monosaccharides
chemical degradation Disaccharides
Ethical, legal and social issues Polysaccharides
Carbohydrates and energy in living
9 Alkanoic acids and their derivatives system
Nomenclature of alkanoic acids Fats
Sources of alkanoic acids and esters Proteins
Laboratory preparation of carboxylic acids Enzymes
Amines Nucleic acids
Nomenclature of amines
Sources of amines

iv
13 Nuclear chemistry 13
Evidence for the atomic nucleus
Radioactivity
Properties of radiation
Nuclear stability
Nuclear reactions
Nuclear fission and atomic energy
Nuclear chain reactions
Radioactive waste
Nuclear waste
Nuclear fusion
Peaceful uses of radioactivity
Radioactivity and biological systems

14 Projects
Literature projects
Chance discoveries in chemistry
Experimental Project
Test paper I Test paper II
General test papers Answers
Index

v
 Preface
Senior Secondary Chemistry is a complete course
consisting of a set of three pupils’ textbooks.
The authorship comprises university science
educators, practising classroom teachers and
school administrators.
In this Revised Edition, the contents of
the books have been enlarged to include the
requirements of the Examination Syllabus as
approved by the West African Examinations
Council. Each book is clearly graded and paced
in a way to highlight the in-depth treatment of
the contents. The selection of contents into each
book is based mainly on the prescribed Core
Curriculum and partly on experiences gathered
by the authors in their several years of teaching
at the senior secondary school level.
The approach adopted in these books is
spiral and conceptual in nature, with three major
concepts—periodicity, energy, and structure—as
the core. Furthermore, an experimental ap-
proach, with emphasis on guided discovery,
has been adopted in conformity with the West
African Examinations Council’s expressed
desire that practical work should be the basis of
teaching the course. Many experiments have
been included, widening the choice available to
schools. Each school is thus in a position to se-
lect only those experiments for which relevant
apparatuses and materials are available.
A necessary component of this course is
vi
an accompanying Teacher’s Guide. The Guide
contains very detailed background materials
derived from recent Chemical Education Jour-
nals. It is the hope of the authors that those
teachers who use our course materials will not
only be knowledgeable in chemical facts and
processes but will also develop a strong sense of
confidence in teaching Chemistry at the senior
secondary level.
As a rule, each chapter ends with a set of
review questions which will serve as a useful
guide in the review of knowledge gathered. In
compliance with the examination requirements,
three major types of questions have been pro-
vided:
i) multiple-choice type
ii) short-structured type
iii) essay type
Wherever possible, answers have been
provided to the questions. The authors duti-
fully recommend these books to all Chemistry
students and to all teachers of Chemistry. They
will find the approach relevant, meaningful and
pragmatic.
February 1997
S.T.B.
B.O.T.
G.O.
A.O.
 About the authors
Sam Tunde Bajah (Project Coordinator) was
for many years a Professor of Science Edu-
cation at the University of Ibadan, Ibadan.
He was lately Chief Project Officer, Science
Education, at the Commonwealth Secretariat,
London. An author of several science books,
Professor Bajah, who had taught Chemistry
at Hussey College, Warri and the Interna-
tional School, Ibadan, was an ex-President
of the Science Teachers’ Association of Nige-
ria (STAN) and member of the Academy of
Education in Nigeria. He was educated at the
University of Ibadan, Oxford University and
the University of South Dakota.
Ben Olanrewaju Teibo holds a doctorate
degree in Science Education and was, for many
years, a Chemistry teacher at several second-
ary schools in Nigeria, including Baptist Boys’
High School, Abeokuta and Olivet Baptist
High School, Oyo. He was a senior lecturer in
Chemical Education at the University of La-
gos. Dr Teibo is a former Provost, Osun State
College of Education, Ilesa as well as a former
Curriculum Coordinator of the Science Teach-
ers’ Association of Nigeria (STAN). He is a
member of the Nigerian Academy of Education.
He was educated at the University of Ibadan,
Oxford University and the Teachers’ College,
Columbia. Dr Teibo is currently at the Ladoke
Akintola University of Technology, Ogbomoso.
vii
Gilbert Onwu is a Professor of Chemical
Education at the University of Ibadan. He holds
a doctorate degree in chemical education and
has many years of teaching experience both
in Nigeria and in the United Kingdom where
he taught Chemistry and rose to the headship
of the Chemistry Department in a London
Comprehensive School. A member of the
Association for Science Education (ASE) and
the Science Teachers’ Association of Nigeria
(STAN), Professor Onwu was educated at the
University of London’s Goldsmith College and
the University of East Anglia, Norwich.
Ada Obikwere, who holds a B.Sc. (Hons)
degree in Chemistry, was Vice Principal, Fed-
eral Government Girls’ College Owerri for
many years and Principal, Federal Government
Girls’ College, Gusau. Mrs Obikwere has taught
Chemistry at the College of Immaculate Con-
ception, Enugu, Government Girls’ College,
Dalla Kano and Queen’s College, Lagos. Mrs
Obikwere was educated at the University of Ni-
geria, Nsukka, Ahmadu Bello University, Zaria
and at the University of Bradford, Yorkshire.
She is an active member of the Science Teachers’
Association of Nigeria (STAN). Mrs Obikwere
was the pioneer Coordinating Federal Inspector
of Education (C.I.E) for Abia State. She retired
as a Deputy Director of Education and is cur-
rently an educational consultant.
viii
 1 Quantitative and qualitative
analysis
Introduction
One of the major branches of chemistry
is analytical chemistry. This branch deals
with the identification of the individual
elements that make up a substance (quali-
tative analysis), and also the number
of each element present in a substance,
that is, the ratio to which the elements
are combined (quantitative analysis).
Other branches include organic,
inorganic, physical and biological
chemistry.
Performance objectives
At the end of this chapter, you should be
able to:
1 titrate accurately and do relevant
calculations;
2 analyse different salts for anions and
cations;
3 carry out simple tests for common
gases (oxygen, hydrogen, carbom(IV)
oxide. etc;
4 carry out simple redox titrations; and
5 test for fats oil, protein, starch, etc.
1
Quantitative analysis
Quantitative analysis involves ose of
calculations to determine the amount
or quantity of individual elements or
compounds present in a given sub-
stance. Any one of these two methods
can be used in quantitative analysis:
1 Gravimetric analysis: This method
involves the direct measurement of
the mass of the substance, using mass
spectra.
2 Volumetric analysis: This method
involves titration, a process of
measuring the volume of each of
the reacting substances which are in
solution.
Titration
During titration, the most common being
acid–base titration, a solution from a grad-
uated vessel (burette) is added to a known
volume of a second solution in a (conical
flask until the chemical reaction between
the two solutions is completed (at the end-
point), which is shown by the change in co-
lour of the substance (an indicator) added.
Experiment 1.1
Aim
To demonstrate an acid–base titration
Apparatus
Clamp and stand, pipette, burette, two conical flasks, two beakers, methyl orange
indicator.
Fig. 1.1 The titration process
Procedures
1 Set up the apparatus as shown in
Fig.1.1.
2 Use a pipette to put 25 cm3 or 20 cm3
of a base (NaOH) into a beaker; then
add 1 or 2 drops of the indicator i.e.
methyl orange. The solution becomes
yellow.
3 Put some of the acid from one of the
beakers into the burette; make it up to
the zero mark.
4 Add the acid from the burette
gradually into the base, shaking the
mixture of the two solutions after
every addition.
5 At end-point, i.e. when the reaction
is complete, there will be a colour
2
change. In this case, the yellow colour
of the indicator solution becomes
golden-brown (coppers colour).
6 Record the burette reading. The
difference between the final and the
initial burette readings gives the
volume of the acid used.
7 Repeat the titration, using another 20
cm3 or 25 cm3 of base once more or
twice, and then take the average titre
of volume used.
Recording titration values
Assuming the following values were got
from in Experiment 1.1, then they will be
recorded as in Table 1.1.
Table 1.1
Burette reading Rough (cm3) first titre (cm3) second titre (cm3)

Final reading 23.50 33.60 28.40

Initial reading 0.00 10.00
Volume used 23.50 23.60
23.50 + 23.60 + 23.40
Average titre value =
3
Precautions during titration
The burette
1 After rinsing with distilled water,
rinse the burette with the acid to be
used.
2 Remove air bubbles from the burette.
3 The burette tap must be placed
correctly to avoid leakage.
4 Avoid parallax error by taking the
burette reading with your eyes at the
same level as the meniscus.
5 Make sure the burette is filled, and
remove the funnel before taking your
readings.
6 Do not leave the funnel in the burette
while titrating.
The pipette
1 Remove air bubbles in the pipette.
5.00
23.40
= 23.50 cm3
2 Avoid parallax error.
3 Rinse the pipette with the base to be
used.
4 Do not blow out the last drop at the
tip of the pipette.
Conical flask/beakers
1 Do not rinse the titration flask with
the solution it holds, i.e. the base.
2 Make sure the beakers holding the
acid and the base solutions are well
labelled.
Choice of indicator
The accuracy of an acid–base titration
depends on the use of the right indicator.
Tables 1.2 and 1.3 give a summary of the
indicators to use for particular acid–base
titrations as well as the colours of these
indicators in solutions.

Table 1.2 Colours of inidicator in solution

Indicator Acid Alkali Neutral

Methyl orange Pink Yellow Orange

Litmus Red Blue Purple
Phenolphthalein Colourless Pink Colourless

3
Table 1.3

Acid-base titration PH at end point Suitable indicator Example

Strong acid 7 Any indicator HNO3

and strong base KOH

Strong acid and weak 5-6 Methyl orange HCl

base NaHCO3

Weak acid and 8-9 Phenolphthalein H2CO3

strong base NH4OH

Weak base and Variable Na2CO3

weak acid CH3COOH

Terms used in calculations involving a) Mass concentration: This is

volumetric analysis concentration measured in grams
of a substance dissolved in 1 dm3
1 Standard solution: A standard of solution. It is the concentration
solution is a solution with a known expressed in grams per dm3 (or
concentration. It is prepared by g/dm3), that is:
weighing a pure salt (solute), mass concentration
dissolving it in a solvent in a
Mass (grams) (g/dm 3 )
volumetric flask and then making =
volume (grams)(dm )
3

the volume up to the mark (that is

a definite volume). For example, A
solution that contains 4.0 g of NaOH
dissolved in 250 cm3 of water is a
standard solution.
2 Molar solution: A molar solution is
a solution that contains one mole of a
substance/solute in 1 000 cm3/1 dm3
of solution. For example, a solution
that contains 40 g or 1 mole of NaOH
dissoved in 1 000 cm3/1 dm3 of
solution is a molar solution because
40 g is the mass of 1 mole NaOH.
3 Concentration: Concentration can be
expressed as:
b) Molar concentration: This is the
concentration expressed in moles
per dm3 (mol/dm3 or mol/dm-3).
It is the amount of a substance
in moles present in 1 dm3 of
solution, i.e. molar concentration
mass (grams) (g)
=
volume (dm 3 )
m
C= ; m = cv
v
A molar solution contains 1 mole of a
substance in 1 dm3 of solution. For example

4
1 mole of KOH weighs 56.0 g. Therefore, Solution
dissolving 56.0 g of KOH in water and 1 molar solution of NaHCO3 contains 84 g
making it up to the mark in a 1 dm 3 of NaHCO3 in 1 000 cm3 solution.
volumetric flask will give a molar solution. 2 molar solution requires 2 x 84 g NaHCO3
Molar concentration in 1 000 cm3.
mass concentration \ 100 cm3 of 2 molar solution requires

=
molar mass
100 × 2 × 84
g/dm 3 = 16.8 g of NaHCO3
That is, mol/dm3 = 1 000
mm
Using the formula: amount (moles)
Example 1.1 molar concentration =
A solution contains 1.00 g of NaOH in 250 cm3 volume (dm 3 )
of solution. Calculate the concentration of the Then,
solution in: (a) grams per dm3; (b) mol dm-3. amount (in moles) = molar concentration
× volume (dm3)
Solution
a) From the question, we understand that = 2 mol/dm3 ×
100 dm 3
250 cm3 of the solution contains 1.00 g 1 000
of NaOH, and mass concentration is = 0.200 mole
the mass of a substance contained in
1 dm3 of solution. Hence, mass (gram)
Number of moles = molar mass
250 cm3 contains 1 g of NaOH
1×1 000 Mass (gram) = amount (in mol) × molar
1 000 cm3 of solution contain
250 mass
= 4 g of NaOH = 0.200 x 84
\ mass concentration = 4 g/dm3 = 16.8 g

b) Molar concentration Statement of equivalence

Understanding the relationship between
mass concentration reactants, that is, the acid and the base, is
= molar mass
quite helpful when solving calculations
Molar mass of NaOH = 23 + 16 + 1 = involving concentration.
40 Consider the following reaction between
4g / dm 3 tetraoxosulphate(VI) acid and potassium
\ molar concentration =
40g / mol hydroxide:
= 0.1 mol/dm3 H2SO(aq) + 2KOH(aq)→ K2SO4(aq + H2O(l)
Molar mass : 1 mol 2 mols
Example 1.2 98 56
What mass of sodium hydrogen Reacting mass 98 2 × 56
trioxocarbonate(IV), NaHCO3, will be required If the reacting masses are dissolved in 1
to prepare 100 cm3 of 2.0 molar solution? dm3 solution, then from the equation of

5
the reaction, Example 1.3 (Standardisation)
1 mol H2SO4 ≡ 2 moles KOH 23.90 cm3 of 0.125 mol dm-3 H2SO4 reacted with
That is, 98 g H2SO4 ≡ 112 g KOH 25 cm3 of X mol dm-3 NaOH solution. Calculate
1 dm3 H2SO4 ≡ 112 g KOH the concentration of the base in:
i) mol dm-3
or ii) g dm-3

98 g H2SO4 ≡ 1 dm3 2 moles KOH Solution

1 dm 1 mol H2SO ≡ 2 dm3 1 mol KOH
3
Equation of the reaction:
1 dm3 0.1 mol H2SO4 ≡ 2 dm3 0.1 mol KOH
H2SO4 + 2NaOH → Na2SO4(aq) 2Hs) + 2H2O
Therefore,
1 mole 2 moles
20 cm3 mol H2SO4 ≡ (2 × 20) cm3
× mol KOH
Amount of H2SO4 in the volume of the acid
The sign ≡ stands for equivalence and can
used in the equation =
serve as a conversion factor in calculating
volume (cm 3 ) × concentration (mol/dm 3 )
molar concentrations of solutions.
1 000
Amount in 23.90 cm3 of H2SO4 =

Calculations in volumetric analysis 23.90 × 0.125

1 000 = 0.003 of H2SO4
To standardise an unknown solution,
volumetric analysis is used. It is also used to From the equation,
calculate molar mass, molar concentration 1 mole H2SO4 reacts with 2 moles NaOH
and mass concentration, and to determine \ 0.003 moles H2SO4 reacts with 2 × 0.003
percentage purity, percentage impurity, moles NaOH
water of crystallisation and number of i) To calculate concentration of B in
ions/particles in a substance. mol dm-3
The numerical coefficient of a balanced
equation shows the number of moles of Amount in mole =
reactants and products. Consider a reaction Conc. of B in mol dm × vol. (cm 3 )
–3

between an acid A and a base B where (a) 1 000

and (b) are the number of moles of A and B
2 × 003 =
respectively; then aA + bB → products. The
following expressions can be derived: Conc. of B in mol dm –3 × 25.00 cm 3
Amount of A a 1 000
= = mole ratio
Amount of B b
2 × 003 × 1 000 = Conc. in mol dm-3 ×
amount n
Concentration (C) = = 25.00 cm3
volume v
n 2 × 0.003×1 000
i.e. C = , n = CV ; Hence, Conc. in mol dm-3 =
C V v na 25.00
∴ A a = = mole ratio
C B Bb nb = 0.24 mol dm-3

6
After actively using the formula: Solution
C AVa na Equation of the reaction:
= HCl(aq ) + KOH(aq ) → KCl(aq ) + H 2 O( l )
C B Bb nb
Where: Mole ratio 1 : 1
CA = 0.125 mol dm-3 conc. in g/dm 3
a) Conc. in mol/dm3 =
CB = 23.90 cm3 molar mass
CB = ? Molar mass of HCl = 35.5 + 1 = 36.5 g/
VB = 25 cm3 mol
5.0
Conc. in mol dm-3 = = 0.137 mol dm–3
na = 1; nb = 2 36.5
0.125 × 23.90 1 ii) Concentration of KOH in mol dm-3
=
C B × 25.00 2 C AVB 1
= =
C B BB 2
C 0.125 × 23.90 × 2
CBB =
25.00 CA = 0.137 mol dm –3 ; VA = 18.20 cm3 ;
CB = ? ; VB = 25.00 cm3
= 0.239 mol/dm3
= 0.24 mol/dm3 0.137 ×18.2 1
=
ii) Concentration in g/dm3 (mass C B × 25.5 1
concentration) of B
0.137 ×18.20
CB = = 0.10 mol dm -3
Molar concentration (mol dm-3) = 25.00
mass concentration (g / dm −3 )
Molar mass of KOH = 39 + 16 + 1
molar mass
= 56 g mol–1
Molar mass of B (NaOH) = 23 + 16
+1 = 40 Mass concentration of pure KOH =
Mass concentration g/dm3 56 g mol–1 × 0.1 mol dm–3 = 5.6 g/dm3
= 0.24 mol/dm3 × 40
Percentage purity =
= 9.6 g dm-3
Mass of pure KOH
×100
Mass of inpure KOH
Example 1.4 (Percentage purity)
6.50 g of a mixture of potassium hydroxide 5.6
= ×100 = 86.2%
(KOH) and sodium chloride (NaCl) was made 6.5
up to 1 dm3 of aqueous solution. 25 cm3 of this Mass of NaCl = mass of impure KOH
mixture was neutralised by 18.20 cm3 of a – mass of pure KOH
solution containing 5.0 g dm-3 HCl. Calculate = 6.5 – 5.6 = 0.9 g
the:
i) mass of sodium chloride impurity; Example 1.5 (Water of crystallisation, molar
ii) percentage purity of the potassium mass and solubility)
hydroxide solution. a) 23.20 cm3 of 0.050 mol dm-3 of an acid
completely neutralised 25.00 cm3 of 0.025

7
 mol dm-3 of an XCO3. YH2O containing 7.2
gdm-3 of the hydrated salt. Calculate the: 0.025 0.253
i) concentration of anhydrous salt in the 0.025 0.253
trioxocarbonate(IV); 0.025 0.025
ii) number of water of crystallisation of the 1 10
salt; \ the value of Y is 10
iii) number of moles of the trioxocarbonate- XCO3.10H2O
(IV).
b) A saturated solution of lead (II)
Solution (Note: Molar mass of anhydrous trioxonitrate (V), Pb (NO3) was prepared
XCO3 = 106 g/mol) at 22°C. 27 cm3 of this solution required
C AVB na 46 cm3 of sodium chloride, NaCl solution
Using =
C B BB nb containing 96 g/dm 3 for complete
CA = 0.050 mol dm-3 precipitation. Find the solubility of
CB = 0.025 mol dm-3 lead(II) trioxonitrate(V) at 22°C in (i)
VA = 23.20 cm3 mol/dm3 (ii) gdm-3
VB = 25.00 cm3 (Na = 23, Cl = 35.5, Pb = 207, N = 14,
O = 16)
0.050 × 23.20 na
=
0.025 × 25.00 nb Solution
0.050 × 23.20 1.16 2NaCl(aq) + Pb (NO3)2(aq) → PbCl2(aq) +
= = 1.86 2 moles 1 moles 2NaNO3(aq)
0.025 × 25.00 0.625
1.86 = mole ratio of acid to base, i.e. Molar concentration of the NaCl =
1.86 : 1, approximately 2 : 1.
96 gdm –3
\ A : B = 1.86 : 1 = 2 : 1 = 1.64
58.5 mol–3mol/dm –3
Concentration in g/dm3 of anhydrous C AVA na
=
trioxocarbonate(IV) = C BVB nb
Conc. in g/dm3 = molar conc. (mol/
where A and B represent NaCl and
dm3) × molar mass
= 0.025 × 106 Pb (NO3)2 respectively.
= 2.65 g/dm3 CA = 1.641 ; VA = 46 cm3
ii) Mass of water = mass of anhydrous
CB = ? VB = 27 cm3
– mass of hydrated
= 7.2 – 2.65 na = 2, nb =1
= 4.55 g
1.641 46 2
iii) The value of Y (XCO3.YH2O) × =
CB 27 1
XCO3 Y2
2.65 4.55 1.641 46
CB = × = 1.398 moldm–3
106 16 2 27

8
Molar concentration of Pb (NO3)2 Solution

= 1.398 mol/dm3. Using the dilution expression Co Vo = C1 V1,
Mass concentration = molar concentration Co = 1.20 moldm-3 ; Vo = ? ;
molar mass. C1 = 0.50 moldm-3 ; V1 = 1 dm3
Conc. in g/dm3 = conc. in mol/dm3 × Co Vo = C1 V1 = 1.20 x V1 = 0.050 x 1
molar mass.
0.050 × 1
Since solubility at a particular temperature V1 = = 0.042 dm 3 or 4.20 cm 3
is also expressed in moldm-3 and gdm-3, 1.2
then solubility of Pb (NO3)2 at 22°C is:
i) 1.398 mol dm-3 Qualitative analysis
ii) 1.398 × 331 = 462.7 gdm-3
Here we deal with the identification of the
Dilution principle elements or compounds present in a given
If a known volume Vo, of a standard sample of a substance.
solution of concentration, C o, is taken Preliminary tests carried out on the
and diluted with distilled water to a new substance include the following:
1 Appearance of the compound
volume, V1, its concentration decreases
Here, a substance is first indentified
to C1, although, the original amount, n,
by its structure and colour, that is,
taken remains the same, that is, amount of a) If the compound is crystalline
substance in the original solution = amount or amorphous (powdery) and
of substance in the final diluted solution. remains white even in solution,
Since n, mole = molar concentration, C × then no transition element is
Volume, V (dm3), present.
then, n = C initial × V initial = C final × V final b) A crystalline or amorphous
or Co Vo = C1 V1. compound, which is coloured
Generally, the initial concentration is always even when in solution,
greater than the final concentration. indicates the presence of a
transition metal ion.
Example 1.6 c) A black substance indicates
the presence of an oxide or a
Calculate the volume of a 1.200 mol per dm3
sulphide.
HCl that should be diluted with distilled water
See Table 1.4 for summary.
to obtain 1.0 dm3 of a 0.05 mol dm-3 HCl.

Table 1.4

Appearance Most likely compounds or ions

White or colourless Ca2+, Pb2+, Na, Zn2+, Al3+,

NH 44 , salts are present
Green Fe2+ salts are light green; Cu2+ salts are bluish-green
Brown/Yellow Fe3+; Pbo, CuO, PbO

9
2 Flame test
Some metals show characteristic colours when their sats are put in flame. Usually,
a little amount of the salt in a dry spatula is placed in the blue zone of the flame.
See Table 1.5.

Table 1.5

Colour from the flame Inference

Dark green Cu2+

Bright golden yellow Na+
Brick red Ca2+
Consistent lilac K+
Pale blue Pb2+
Light green Ba2+

3 Action of heat
The residue left when a substance is heated shows same features. Table 1.6 shows
the features shown by the residues of some sustances.

Table 1.6

Observation Inference

The residue is white when cold and ZnO

yellow when hot.
The residue makes a cracking sound Pb(NO3)2
when decomposing.
The residue is yellow when hot and
reddish-brown when cold.
The residue has water vapour which Hydrated HCO3 or OH-
condenses at upper part of test tube
Sublimation occurs Ammonium salt
The residue turns from blue to white. CuSO4.5H2O
The residue turns from blue to brown. CuCl.2H2O
The residue turns from yellow to black. FeCl3

Basically, qualitative analysis is used to 2) Identification of acid radicals

identify acid radicals (anions) and basic 3) Identification of metallic radicals
metallic radicals (cations). It involves:
1) identification of gases (evolved on Table 1.7 gives a summary of the properties
heating salts) some of common gases.

10
Table 1.7 Properties of common gases

Gas Colour/smell Action on damplitmus

paper

1) Oxygen, O2 Colourless/odourless Neutral

2) Water vapour, H2O Colourless/odourless Neutral
3) Hydrogen, H2 Colourless/odourless No action (neutral)
4) Carbon(IV) oxide, CO2 Colourless/odourless Turns blue litmus
paper red (acidic)
5) Sulphur(IV) oxide, SO2 Colourless/ burning Turns blue litmus
brown smell paper red (acidic)
6) Nitrogen(IV) oxide NO2 Reddish-brown/irritating Turns blue litmus paper
smell red (acidic)
7) Hydrogen sulphide, H2S Colourless/rotten egg Turns blue ltmus paper
smell red (acidic)
8) Chlorine, Cl2 Greenish yellow/ Turns blue litmus paper
irritating smell red, then bleaches it
9) Bromine, Br2 Reddish-brown/irritating Turns blue litmus paper
smell red, then bleaches it
10) Iodine, I2 Purple/irritating smell Turns blue litmus paper
red, then bleaches it
11) Ammonia, NH3 Colourless/pungent, Turns red litmus paper
choking, irritating blue (alkaline)
smell

Tests for acid radicals can be done in two 2 Wet test

other ways: a) The action of precipitating
1 Dry test reagents on the solution of the
a) By the action of heat on the substance
substance b) The action of oxidising agents on
b) By the action of dilute HCl on the the solution of the substance
substance
c) By the action of concentrated The following tables give a summary of
H2SO4 on the substance the tests:
Table 1.8 Action of heat on a sample of the salt

Observation Inference

If a colourless, odourless gas that turns moist Gas is acidic.

blue litmus paper red and limewater milky is Gas is CO2 from
CO32- or HCO-3
given off

11
If a colourless gas which smells of burning Gas is acidic.
sulphur and turns moist blue litmus paper red, Gas is SO2 from SO32-, S2O32- or
and decolourises acidified KMnO4 is given off SO42-.

If a reddish-brown gas, acidic to litmus, with Gas is acidic.

an irritating smell, and changes starch-iodide Gas is NO2 from NO2- or NO_3
paper blue-black (except NaNO3, KNO3.

If on heating with MnO2 powder, a greenish- Gas is chlorine,

yellow gas is evolved Cl2, from a Cl_.

If a reddish-brown gas is given off on heating Gas is bromine, Br2 from a Br_.
with MnO2

If the gas evolved on heating with MnO2 is Gas is iodine, I2 from an I_

purple or violet

If the gas is colourless, with a choking irritating Gas is alkaline.

smell, and turns moist red litmus paper blue Gas is NH3 from NH4+.

If a colourless, odourless gas, which is neutral Gas is oxygen, O2 from NO3– of

to litmus and rekindles a glowing splint is alkali metals.
given off

If water condenses on the cooler part of the Salt is hydrated.

boiling tube

Table 1.9 confirmatory tests for anions

Test Observation Inference

To about 5 cm3 of solution, add White precipitate Cl–, SO32- or SO42- present
AgNO3(aq) + dil. HNO3(aq) in drops;
and in excess + aqueous ammonia White precipitate
(NH4OH) in excess
Precipitate dissolves Cl–

Add MnO2 and then conc. H2SO4 Greenish-yellow gas Cl present; the gas is
to a sample of the salt, then with a choking smell chlorine
warm gently and acidic to litmus

12
To about 5 cm3 of salt solution, Efferverscence occurs; a Gas is acidic.
add dil. HCl or conc. H2SO4 colourless, odourless Gas is CO2
gas which turns blue from CO32-
litmus red and lime- HCO-3
water milky

Add BaCl2(aq) to the salt solution + White ppt SO2-3, SO42- present
dil. HCl(aq) solution + BaCl2(aq) + Ppt dissolves SO32- present
dil. HCl(aq) solution White ppt insoluble SO42- confirmed

Test: To about 2 cm3 of the solution of the substance add NaOH(aq) in drops, then in excess.

Observation Inference

A white, chalky ppt which is insoluble in excess Ca2+ present

NaOH(aq)

A white, gelatinous ppt soluble in excess Al3+ present

NaOH(aq)

A white, gelatinous ppt soluble in excess Zn2+ present

NaOH

A white powdery ppt soluble in excess NaOH Pb2+ present

A light-blue, gelatinous ppt insoluble in excess NaOH Cu2+ present

A dirty-green, gelatinous ppt insoluble in excess NaOH Fe2+ present

A reddish-brown, gelatinous ppt insoluble in excess Fe2+ present

NaOH

Test: To about 2 cm3 of the solution of the salt add aqueous ammonia (NH3(aq)) in drops,
then in excess

Observation Inference

No reaction visible Ca2+ present

A white, gelatinous ppt insoluble in excess
NH3(aq)

13
A white, gelatinous ppt soluble in excess Al3+ present
NH3(aq)

A white, gelatinous ppt soluble in excess Zn2+

NH3(aq)

A white, powdery ppt insoluble in excess NH3(aq) Pb2+ present

A light, blue gelatinous ppt soluble in excess CU2+ confirmed

NH3(aq) to give a deep blue solution

A dirty-green, gelatinous ppt insoluble in NH3(aq) Fe2+ confirmed

A reddish-brown, gelatinous ppt insoluble in Fe3+ confirmed

NH3(aq)

Note: To differentiate between Pb2+ and Al3+, add dil. HCl to the solution of the salt. A
white ppt confirms Pb2+ and no ppt confirms Al3+.

The confirmatory tests for cations: 2 cm3 of the solution

Test Observation Inference

Add NH4CO3(aq) White ppt is formed Ca2+ confirmed

Add NH3(aq) and then NH4Cl(aq) White ppt Al3+ confirmed

Add ammonium sulphide solution or H2S Dirty-white ppt Zn2+ confirmed

Add potassium hexacynoferrate(II) White ppt Zn2+ confirmed

solution, K4Fe(CN) 4

Add potassium tetraoxochlorate(VI) Yellow ppt Pb2+ confirmed

solution (K2CrO4)

Add potassium hexacynofferrate(II) Brown ppt Cu2+ confirmed

solution

Add K4Fe(CN)6(aq) Light blue ppt Fe2+ confirmed

Add K3Fe(CN)6(aq) Deep blue ppt Fe2+ confirmed
Add K4Fe(CN)6(aq) Deep blue ppt Fe3+ confirmed
Add potassium thiocynate Deep blood-red Fe3+ confirmed

14
Add K4Fe(CN)6(aq) Deep blue ppt Fe3+ confirmed
Add potassium thiocynate solution Deep blood-red ppt Fe3+ confirmed
(KSCN)(aq)
Add dil. HCl(aq) then NH3(aq) White ppt soluble in Ag+ confirmed
NH3(aq) or darkens
when exposed to light

Table 1.11 Test for

Test Observation Inference

Add a few drop of concentrated. Solid; chars with the Starch is present
H2SO4to a small amount of solid evolution of gases; a
in a test tube, then warm gently. black residue.

To an aqueous solution of the Solution turns blue- Starch is present

substance, add a few drops black.
of iodine.

Add 1 cm of Fehling’s reagent A brownish-red Reducing sugar

and boil for a while. precipitate is formed. is present.

Add a few drops of NaOH(aq) A purple colouration Amino acid or

to the solution of the substance is seen. protein is present.
and swirl briefly, then add a
few drops of CuSO4(aq) and
swirl the mixture.

Add few drops of millon’s A white precipitate Amino acid is

reagent to the solution and warm. which turns red after presnt.
a while.

Add a few drops of sudan(III) A distinct red Fat or oil is present.

reagent to a little amount of colouration is seen
the substance.

Example 1.7
C and D are samples of two simple salts. Carry out the following tests on them. Record your
observations and state the conclusion you draw from the result of each test.
a) i) Put half of C in a test tube and add about 5 cm3 of distilled water. Test with litmus.

15
 ii) Put the rest of C in a test tube and add about 5 cm3 of dilute hydrochloric acid.
Identify any gases evolved.
b) i) Put half of D in a test tube. Add about 5 cm3 of sodium hydroxide solution and warm.
Identify any gas evolved.
ii) Put the rest of D in a test tube and add about 5 cm3 of distilled water. Mix thoroughly.
Add about 2 cm3 of barium chloride solution followed by dilute hydrochloric acid in
excess.

Solution

Table 1.12

Test Observation Inference

a) i) C + water + litmus C dissolves to give Solution of C is alkaline.

a colourless solution which
turns red litmus paper blue.

b) ii) C + HCl(aq) Effervescence occurs colourless; Gas is acidic.

and odourless gas is evolved; gas Gas is CO2
turns moist blue litmus paper from CO2-3.
red and lime water milky.

b) i) D + NaOH(aq) Colourless gas evolved Gas is NH3 from NH4+.

+ heat with a characteristic choking
smell; turns wet red litmus
paper blue and forms dense
white fumes with concentrated
HCl acid stopper.

ii) D + water D dissolves to give a colourless

solution.

Solution of D+ White precipitate is formed SO32-, SO42- , CO32- or
BaCl2 S2- is present

+ dilute HCl Precititate dissolves. Colourless Gas is acidic.

gas with irritating smell which Gas is from SO32-.
turns moist blue litmus paper
red and changes the colour of
acidified K2Cr2 O7 solution from
orange to green is given off.

16
Example 1.8
C is a mixture of two salts. Carry out the following tests on C. Record your observations and
identify any gas(es) evolved. State the conclusion you draw from the result of each test.
a) Put all of C in a test tube and add about 10 cm3 of distilled water. Shake thoroughly and
filter. Keep both the filtrate and residue. Divide the filtrate into three portions.
i) To the first portion, add NaOH(aq) in drops, and then in excess.
ii) To the second portion, add NH3(aq) in drops, and then in excess.
iii) To the third portion, add BaCl2(aq) followed by dilute HCl.
b) Divide the residue into two portions.
i) Heat the first portion strongly in a test tube.
ii) Add dilute HCl to the second portion.

Solution 2

Table 1.13
Test observation Inrerence

a) i) C + H2O, then C partially dissolves C is a mixture of soluble

filtered to give a green residue and insoluble salts.
and a blue filtrate

ii) Filtrate + NaOH(aq) Blue, gelatinous Cu2+ present

in drops, and then precipitate insoluble
in exces NaOH in excess

iii) Filtrate + NH3(aq) in Pale blue gelatinous ppt Cu2+ confirmed

drops, and then precipitate dissolves
in excess in excess NH2 to give a
deep blue solution

iv) Filtrate + BaC12(aq) White ppt insoluble SO42- confirmed

+ dilute HCl in dilute HCl

b) i) First portion of Colour changed from

residue + heat green to black power

ii) Second portion Effervescence occurs Gas is acidic.

of residue + dilute colourless, odourless Gas is CO2
HCl gas which turns moist from CO32-.
blue litmus paper red
and lime water milky
is evolved

17
Essay-type questions
1 25.60 cm3 of potassium hydrogen
tetraoxosulphate(VI) containing
14.0 gdm -3 of KHSO 4 completely
neutralised 25 cm 3 of sodium
hydroxide solution. Calculate the:
a) concentration of the KHSO 4
solution in mol dm-3.
b) concentration of NaOH in g dm-3.
c) volume of KHSO4 (in dm3) that
would produce one mole of
sodium tetraoxosulphate(VI)
in solution.
2 25.00 cm3 of a trioxonitrate(V) acid
containing 0.095 mol dm-3 of the acid
completely neutralised 25.00 cm3
of a solution containing 13.50 g of
X2CO3.10H2O per dm3..
Calculate the:
a) concentration of the base in
mol dm-3.
b) molar mass of X2CO3.10H2O.
c) percentage by mass of X in
X2CO3.10H2O.
d) value of X in X2CO3.10H2O.
3 29.80 cm3 of an acid H2X containing
3.70 g dm-3 of H2X was titrated against
25.00 cm 3 of sodium hydroxide
containing 2.15 g dm-3 NaOH.
Table 1.14
Test
ZnCl2(aq) + HNO3 + AgNO3(aq) + NH3(aq)
in excess
ZnCl2(aq) + NaOH(aq) in drops, and
then in excess
ZnCl2(aq) + NH3(aq) in drops, and then
in excess
18
Calculate the:
a) concentration of NaOH in
mol dm-3
b) concentration of H2X in
mol dm-3
c) molar mass of the acid H2
(H = 1, O = 16, Na = 23).
The equation for the reaction is
2 NaOH(aq) + H2X(aq) → Na2X (aq) +
2H2O(i)
4 a) In a laboratory procedure for
preparing ZnCl2, a solid X was added
with stirring to dilute HCl(aq) until no
more of it dissolved. The remaining
undissolved X was removed from
the mixture. The solution of ZnCl2
obtained was concentrated to a small
volume and then put aside.
i) Suggest three substances which
X could be.
ii) What method was used to
concentrate the ZnCl2(aq)?
iii) Name the method for removing
excess X.
Observation
 iv) Write a balanced equation
between X suggested above and
dilute HCl(aq).

b) Copy and complete Table 1.14

as appropriate.

5 State what is observed when

ammonia is tested with concentrated
HCl.
6 State an indicator suitable for the
titration of:
a) dilute HCl and NaOH(aq).
b) dilute CH3COOH and KOH(aq).
c) dilute HCl and NH3(aq).
Give reasons for your answers.
7 Calculate the volume of water that
would be added to 50 cm3 of 0.10
mol dm-3 of HCl to dilute it to 0.10 mol
dm-3.

19
 2 Petroleum
Introduction
About two hundred years ago, people
depended almost entirely on plants
for both energy and useful chemicals,
including drugs. Today, in some parts of
the developing world, wood is still the
predominant fuel for domestic cooking.
Plants continue to be used for their
medicinal properties. One problem,
however, is that plants require large areas
of land and long periods of time to renew.
Today’s ever increasing demand for
fuel is met by a mix of wood, peat, coal,
and petroleum products (gasoline, diesel
fuel, furnace oil, petroleum gases, etc.).
Petroleum products provide about half
the energy needs of the industrialised
countries. A major segment of the chemical
industry depends, for its raw materials, on
petrochemicals (ethene, propene, butene,
benzene, toluene, xylen, etc.). Through
modern chemical technology, the chemical
industry uses these petrochemicals to
produce drugs, plastic, and many other
kinds of useful products.
The word petroleum means rock oil.
Crude oil is a complex mixture of liquids
known as hydrocarbons (compounds
containing carbon and hydrogen only). In
this chapter, we shall discuss how crude
20
petroleum is separated into fractions by
distillation in modern refineries, and the
uses of the fractions.
Performance objectives
At the end of this chapter, you should be
able to:
1 state the main classes of hydrocarbons;
2 describe the formation of crude oil;
3 demonstrate crude oil as a complex
mixture of hydrocarbons;
4 use fractional distillation to separate
petroleum into its fractions;
5 list the properties and uses of the
different fractions of petroleum; and
6 explain the term ‘octane number’ as
applied to gasoline.
Hydrocarbons
Hydrocarbons, as the name implies,
are compounds of only two elements:
hydrogen and carbon. There are many
such organic compounds. Fortunately,
chemists have come to our rescue by
developing a basis for the grouping of these
hydrocarbons into a number of chemically
similar groups or families, so that we need
to learn only about the families rather than
about individual members.
 In Book 2, you will have learnt more
about the composition and chemical prop-
erties of these families of hydrocarbons.
Hydrocarbons are usually classified into
two main classes or groups, namely satu-
rated and unsaturated hydrocarbons.
of carbon atoms to combine with one
another to form ‘chains’ of carbon atoms
which gives rise to the alkane series
of compounds. Some other saturated
hydrocarbons can be represented by the
formulae:

Saturated hydr0carbons (The alkanes) H H H H H

The compounds in a family of organic | | | | |
compounds are known as a homologous H—C—C—H H—C—C—C—H
series. Several hydrocarbons belong to the | | | | |
family known as the alkane. The alkanes ßH H H H H
are well known because they are present C2H6 CH3CH2CH3
in gas and petroleum products, such as
ethane; propane;
petrol (gasoline) and paraffin wax. All
the compounds in this series have similar
H H H H
chemical properties and composition. But
| | | |
there is a gradual change in the physical
H—C—C—C—C—H
properties of the compounds as the
| | | |
number of carbon atoms in the molecules
H H H H
increases.
CH3CH2CH2CH3
Methane, or marsh gas, is the first mem-
ber (with the smallest number of carbon at- (normal butane)
oms) of the long alkane series of hydrocar-
bons. The molecule of methane consists of Ethane, propane and normal butane
one atom of carbon to which four atoms of molecules, with two, three and four carbon
hydrogen are bonded. Since a carbon atom atoms respectively, are correspondingly
is never found to combine with more than the second, third and fourth members of
four atoms of hydrogen, the carbon is said the alkane series after methane. A large
to be saturated, and methane is referred to number of such compounds is known.
as a saturated hydrocarbon. In saturated It should be observed that the difference
hydrocarbons, therefore, the bonds of the between any two consecutive alkanes is
carbon atoms are single, covalent bonds. CH2. The alkanes can be represented by
The molecule can be represented by the the general formula: CnH2n + 2 where n is
line formula: an integer or whole number,
H e.g. CH4 : methane n = 1,
| C2H6 : ethane n = 2,
H — C — H, or, more simply, by the C3H8 : propane n = 3 and so on.
| formula CH4 The alkanes are relatively inert
H compounds. They generally burn in air to
give out much energy, as well as carbon
As we said earlier, it is this property (IV) oxide and water. For example,

21
CH4 + 2O2 → CO2 +2H2O + energy
2C2H6 + 7O2 → 4CO2 + 6H2O + energy
Many common fuels contain alkanes.
Unsaturated hydrocarbons
Apart from the saturated hydrocarbons,
there are other hydrocarbon compounds
which contain a lower proportion of
hydrogen atoms and are, therefore, said
to be unsaturated. One such unsaturated
family of hydrocarbons is known as the
alkene series. Thus, if two hydrogen atoms
are taken away from each of the compounds
of the alkane series, hydrocarbons are
obtained which can be represented by the
general formula, C2H2n.
H H H H H
| | | | |
C = C C= C– C– H
| | | |
H H H H
C2H4 ethene C3H6, propene
Ethene is the first member of the alkene
family. The names of alkenes are obtained
by taking the name of the corresponding
alkane and changing the ending to ‘ene’.
All alkenes have similar chemical
properties because they all have one
double bond per molecule. The double
bond makes them more reactive than the
alkanes, by providing the molecules with
‘spare’ bonds which can be used to add on
more atoms to the alkene molecules. It is
the so-called ‘spare’ bonds that confer on
alkenes the term ‘unsaturated’.
Formation of crude oil
Some 500 million years ago, marine life
flourished in coastal waters. The animals
died and were silted over by continental
rivers. In time, earth piled up, and the dead
22
marine life got buried to greater depths.
In the absence of air, anaerobic microbial
action initiated the conversion of marine
life to crude oil. The action was completed
by the geochemical agents: heat and time.
Scientists estimate that temperatures at
burial sites 2 km below the ground could
be around 100°C.
Geochemical agents also converted
sand into sandstone, and clay into shale.
Sandstone is porous and spongy. It allowed
the oil to move upwards through it, until it
encountered some impervious rock which
halted the upward movement. Here the oil
got trapped, together with its associated
gas. Very often, tectonic foldings also
occurred, and the oil accumulated in the
basis which were formed. Geologists use
seismic soundings to locate the humps in
the rock beds. These are the points where
oil wells are most profitably located.
Composition of crude oil
Although crude oil from different oil
fields may vary greatly in composition, it
consists essentially of a complex mixture
of hydrocarbons. Crude petroleum
is generally a thick (viscous), black,
yellow or brown liquid which shows a
green fluorescence. Quite often, crude
petroleum oils contain some impurities
of oxygen, nitrogen and sulphur. These
impurities are known as contaminants.
The most troublesome contaminants
are organic sulphur compounds. Some
of Nigeria’s petroleum is known to be
relatively sulphur-free, which makes it
very marketable. Countries like Saudi
Arabia and Venezuela have oils with a high
sulphur content.
Exploration of oil
The decision as to where to prospect for
oil is made by geologists. Geologists use
seismometers to study the underlying
layers of the earth’s crust, and from the
information obtained, decide where
the oil ‘caps’ are located, for drilling.
Successful test drillings hit the ‘caps’ direct.
Because petroleum is a mixture of several
hydrocarbons, it is always associated with
gas (see Fig. 2.1). When a well is carefully
bored through the impervious rock cap, the
gas pressure could be sufficient to force the
oil to the surface. The gas sits on top of the
crude oil and is called natural gas. crude oil
Natural gas is mainly methane, CH4.
As the principal constituent of natural gas,
methane is of great importance to the fuel
industry as a source of energy.
Petroleum as main energy source
Many oil-producing countries refine
a large amount of their petroleum to
produce gasoline and fuel oils. These
provide energy for automobiles and
heavy machinery. However, the burning of
petroleum for energy is not an acceptable
policy. For instance, Dimitri Mendeleev, a
Russian chemist, is reported to have stated
that burning petroleum for energy could be
likened to ‘burning bank notes’ in a stove
to keep warm.
Again, the Swedish scientist, Arrhenius,
has alerted us about an impending energy
crisis if fossil fuels, which took millions of
years to build up, are recklessly being used.
Only about 6 per cent of the world’s
annual production of crude oil is applied
towards the manufacture of chemicals.
The rest, about 94 per cent, is burnt as
23
sea level
drill pipe
recovery
sea bed
recent sedimentary
deposits
intermediate strata
of sedimentary rock
cap rock
natural
gas
Fig. 2.1 Section through an oil well
fuel. This is wasteful because oil is more
valuable for its chemical contents than for
its energy contents. When processed for
its chemicals, crude oil acquires an added
value. When converted into polymers and
plastics, crude oil is worth five times more
than when burnt for energy.
When converted into agricultural
chemicals or photosensitive materials,
such as x-ray films, crude oil is worth 100
times more than when burnt for energy.
More than 90 per cent of industrial organic
chemicals come from petroleum and
natural gas.
Scientists are looking for alternative
sources of energy and have indeed
succeeded in producing petroleum
from coal. Friedrich Bergius, a German
chemist was the first to hydrogenate coal
successfully to produce petroleum.
Coal(s) + H2(g) → Petroleum
 Any country which can successfully and
economically produce synthetic petroleum
in sufficient quantity may no longer
depend on importing petroleum.
Transportation of oil
As a source of fuels, crude oil is more
convenient than coal. As it is mainly a
mixture of liquids, it is easier to handle,
process and transport than coal, which is
a solid.
Transportation of crude oil between
countries or points can be by water
in supertankers or by pipeline. Sea
transportation of oil in supertankers is
cheaper than transportation by pipeline.
Fractional distillation of oil
Distillation takes place in a tall steel tower
known as a fractionating tower. First, the
crude oil from the oil field is heated in a
furnace and the vapour led into a high
fractionating tower near the bottom end
of the column (see Fig. 2.2). The tower is
divided by a series of plates with holes,
covered by bubble traps or caps, at which
condensation of the vapour takes place.
The vapours rise up the column until they
are cool enough to condense.

Refining of oil

Crude oil must be refined to make useful

fuels and chemicals. The crude petroleum
taken from the oil fields to refineries
is processed in three stages: separation,
conversion and purification. The first two
stages will be treated in this book.

Sepearation
The first step in refining is the separation
of the oil into fractions, i.e. into its various
components by distillation. Since petroleum
is a mixture of liquids with different boiling
points, the various liquids can be separated
by fractional distillation. This method is so-
called because it uses the differences in
boiling points to split the mixture into two
or more parts which can then be separated
off. Fig. 2.2 Refining of crude oil
Let us see how the separation of
petroleum is done on an industrial scale, Vapours of substances with higher
i.e. at a refinery. boiling points (i.e. the heavier fractions)

24
condense at the lower bottom trays of
the column, while the vapours of the Composition of oil fractions
more volatile substances (i.e. the lighter
fractions) bubble through the liquid and Table 2.2 shows the composition of typical
condense at successively higher levels. oil fractions in three crude oils from
Overflow pipes, known as ‘down spouts’, different sources.
keep the liquid at a constant level in each The table also shows that the
tray, with excess of liquid running down approximate demand by the consumers
to the tray below. Provision is thus made for each reaction is quite different from
for dense liquids to ‘sink’ through the the proportions produced from the initial
floor of the section. By separating off the distillation. Some fractions are over-
condensed liquids at different heights of produced and others under-produced. It
the tower, a series of ‘fractions’ of different would thus be necessary for the refineries
boiling points is obtained.
to carry out some conversion processes,
The composition of the fractions is as
i.e. the second stage in refining, so as to
shown in Table 2.1.
produce the various oil products in the
Table 2.1 amounts required by the consumers, i.e.the
industrial and domestic users.
Name of Boiling Range of
fraction range °C carbon atoms Conversion
Conversion is the second stage in the
Natural gas, or 30 C1— C4 refining process. It involves three main
liquid petroleum processes, namely cracking (involving
gas (LPG) the breaking up of larger molecules into
smaller ones), polymerisation (in which
Naphtha or 30–200 C4— C12 small molecules join together to form
straight-
larger ones), and reforming (a process in
run gasoline
which atoms are rearranged into different
molecular structures). These processes
Kerosene or
are designed to convert over-produced or
heater oil 200–300 C12— C15
unwanted fractions into the products in
Gas oil, diesel high demand. Over a period of years, the
oil, 300–400 C15— C25 demand for any particular product can
lubricating oil vary a great deal.

Residual oil,
paraffin, 400 C25
asphalt (tar)

25
Table 2.2 Crude oil fractions

Fraction Number of Percentage of each fraction from the Approximate %

carbon atoms initial distillation demand for each
in the molecules fraction

Oil from Oil from Oil from

North sea Persian Nigeria
Gulf

Gas 1–4 2 2 2 4
Gasoline 5–6 8 5 6 22
Naphtha 6 – 10 10 9 7 5
Kerosene 10 – 14 14 12 14 8
Gas oil 14 – 19 21 17 28 23
Fuel oil Over 35 45 55 39 38

Take kerosene as an example. This was
the most important fraction extracted from
crude oil at the beginning of this century.
It was used for lighting kerosene lamps
and the rest of the oil was wasted. With
the invention of the internal combustion
engine, the demand for the gasoline
(petrol) fraction grew while the demand
for kerosene fell because people started
using electricity for lighting. However, in
the mid-fifties, the demand for kerosene
increased once more because it became the
main ingredient for the blending of fuel,
particularly of aviation fuel for jet engines
and rockets.
Nowadays, in modern refineries,
unwanted fractions are no longer wasted,
instead, they are converted into the
products in high demand. For example,
large molecules can now be split (cracked)
to give smaller molecules while smaller
molecules can be linked (polymerised)
to give larger molecules, according to
demand. Both cracking and polymerisation
are used to increase the yield of gasoline
from crude oil.
Cracking consists essentially of heating,
under pressure (at about 800°C), the higher
hydrocarbons in the C20– and–above range
to decompose them to smaller molecules,
i.e. lower hydrocarbons. For example,
these days, gasoline (C5– C6) is needed
more than lubricating oils (C19 and above).
To increase the yield of gasoline (C5– C6)
fraction, the large molecules (of say the
C19 and above range) are broken down to
smaller molecules (C5– C10 fractions) by this
process of cracking.
There are two types of cracking :
thermal and catalytic. The above example
is known as thermal cracking where
the higher hydrocarbons are heated to
a high temperature in order to break
them up into smaller molecules. When
this is done in the presence of steam,
it is known as hydro or steam cracking.

26
Hydro-cracking is undertaken to produce methane, ethane, propane, butane, ethene,
chemical feedstocks, such as ethane, which etc. Propane and butane gases, when
can be polymerised and dehydrogenated liquefied under pressure, are distributed
to very many chemical products, like in high-pressure tanks and cylinders and
naphthalenes. sold as bottled gas, for cooking. Apart
Catalytic cracking involves the use of from adding an odouriser, such as ethyl
a catalyst, silica-alumina, at a reduced mercaptan (CH 3 CH 2 SH) to alert the
temperature. It is used to convert higher consumer to a leak in the system, nothing
boiling fractions of crude oil to high-grade else is required to make this product.
motor spirit, i.e. gasoline.
Cracking, however, starts right from
the naphtha fraction (C 6–C 10) which is
the supplier of chemicals from oil. The
naphatha fraction is cracked to give
reactive hydrocarbon gases, such as
ethene, C2H4 and propene, C3H6. These
are in turn used as the starting materials
for making chemical products, such as
solvents, detergents, industrial chemicals,
agricultural chemicals, plastics and
synthetic rubbers.
Polymerisation joins small molecules of
the hydrocarbon gases in the C1–C4 range
to produce molecules in the C5–C8 range.
Fig. 2.3 A cylinder of cooking gas
Thus, both cracking and polymerisation
are used to increase the yield of gasoline
(petrol) from crude oil. Polymerisation can
also convert ethene to butene, C4H8, for use Napththa
as chemical feedstocks. Naphtha is the old name for straight-run
Reforming rearranges the atoms in gasoline. Modern gasoline is naphtha which
molecules. Reforming is used to help has been subjected to secondary reactions
and to which additives have been added.
improve the quality of petrol by converting
Naphtha contains mainly straight-chain
linear or straight-chain alkanes to branched,
aliphatic hydrocarbons and cycloaliphatics.
chain and cyclic hydrocarbons which yield
The proportion of aromatic hydrocarbons
better or high-performance fuels.
is very small. The refiner converts the
straight-chain hydrocarbons to branched-
Uses of petroleum fractions chain and aromatic hydrocarbons, because
these are the ones that burn well in internal
Petroleum gas combustion engines.
The most volatile fractions during the first Traditionally, three types of chemical
distillation of crude oil are the gas fractions. reactions are performed on the naphtha:
They consist chiefly of the hydrocarbons:

27
1 polymerisation (oligomerisation), catalytic reforming. The reforming tower
2 alkylation, and contains a catalyst system comprising
3 catalytic reforming platinum or rhenium supported on
Polymerisation is the term used by alumina at 500°C. The alumina effects
commercial refiners. It is a misnomer, the isomerisation to cycloaliphatics and
however, because in practice, trimers of the platinum or rhenium dehydrogenates
propene are the main products. These are to alkylbenzenes. For example, this kind
oligomers and not polymers. of treatment will convert n-heptane to
toluene.
3CH3CH2CH3
(propane) CH3 CH2CH2CH2CH2CH2CH3
↓ HF or H2SO4/catalysts n-heptane
CH3CHCH2CHCH = CHCH3 (octane no. = 0 cat/500°C; 20 atm
| |
CH3 CH3 C6H5CH3 + 4H2
(C9 – trimer) toluene
The olefin oligomers are then hydrogenated (octane no. = 120.1)
to give stable products. It can be seen that this treatment raises the
Alkylation involves reactions, such as octane number of the fuel dramatically
that between isobutane (2-methylpropane) from zero to 120.
and propene or butene: The catalytic reforming process also
CH3 provides the chemical industry with all the
| aromatics it requires. These are benzene,
CH3CHCH3 + CH2 = CHCH3 toluene and the xylene, known in industry
as the BTX petrochemicals.
HF or H2SO4 /catalysts at 50°C As engine makers sought to get more
CH3
power by raising the compression ratio,
| CH3
they found that the fuel exploded in the
|
cylinder, instead of burning smoothly.
CH3CHCHCH—CH3
2,3,-dimethylpentane This defect was called ‘knock’. Dr Thomas
(major product) Midgeley solved the problem of ‘knock’ in
1921 by adding small amounts of tetraethyl
The major product is 2,3-dimethylpentane. lead (C2H5)4Pb into the gasoline. Lead cured
Minor products include the problem of ‘knock’ but created other
2,2,4-trimethylpentane. The products are problems. Lead got deposited in the valves.
known in industry as alkylates. This new problem was cured by adding
The third refinery reaction is catalytic small amounts of 1,2-dibromoethane
reforming. The standard practice in (C2H4Br2). The bromine atoms reacted with
American refineries is to subject all the the lead and removed it as particles in the
naphtha used in producing gasoline to exhaust gases.

28
 Further improvements in gasoline
additives technology became necessary
after the Arab Oil Embargo of 1973. The U.S.
Congress imposed on car manufacturers
a minimum performance of 11.7 km/
litre (27.5 miles per U.S. gallon), effective
1985. In addition, the Environmental
Protection Agency, through the Clean Air
Act, imposed limits of particulate lead
emissions from car exhausts not to exceed
1.5 µg/dm3 also by 1985.
Research showed that tetraethyl lead
could be replaced by oxygen-containing
compounds such as ethers and alcohols.
This is the non-leaded gasoline which
is now mandatory in the United States,
Canada, Japan and Europe. The most
Fig. 2.4 A kerosene lamp
effective ‘oxygenate’ is methyl tertiarybutyl
ether (MTBE).

CH3 Demonstration experiment

| To produce a sample of kerosene:
H3C–O–C– CH3
| materials:
CH3
Other important oxygenates are ethanol
and methanol.
Kerosene
This is the fraction which boils over
between 200°C and 300°C. In the early
days, it was used mainly for lighting and
space–heating in the cold countries. Then it
contained C9 -H3 molecules. In 1955, the jet
engine appeared and the kerosene fraction
was modified to serve a dual purpose, as jet
fuel. No additives or colouring is needed
for kerosene.
1 The teacher will need the following
A sample of Bonny Light crude, or
other named blend, distillation flask,
500 cm3 or 250 cm3 air condenser,
thermometer 0–360°C; two 100 cm3
beakers, fire extinguisher (carbon(IV)
oxide type).
Set up the apparatus, as shown in Fig.
2.5.
2 Measure out some 300 cm3 of crude oil
and place it in the 500 cm3 distillation
flask (150 cm3 in 250 cm3 distillation
flask).
3 Heat the flask until the temperature
rises to 200°C.
4 Remove the beaker and its contents,
which is the naphtha fraction (30° –

29

200 °C), and replace with another
beaker.
5 Continue heating until the
temperature gets to 300°C. What is
collected to this point is the kerosene
fraction (200°–300°C).
6 Pour the kerosene into a clean and
dry 150 × 25 mm boiling tube and
pass it round the class to observe
the mobility (viscosity), colour and
smell. About 40 cm3 (20 cm3 for 250
cm3 flask) should be obtained.
Diesel oil
The fraction which boils over between
300°C and 400°C, has many names and
many uses: gas oil, diesel oil, or heating oil.
This fraction is also used as lubricating oil
for some machines.
30
Residual oils
All that remains undistilled after 400°C is
known as residual oils. The type of paraffin
wax recovered from this fraction is called
microcrystalline wax. The crystals are
much smaller than those obtained from
condensates. It is harder than ordinary
paraffin wax and melts in the range
87°–92° compared to 40°–52° for paraffin
wax. The hydrocarbon molecules are in
the range C40–C60 with relative molecular
masses in the range 580–850. Branched-
chain hydrocarbons predominate in
microcrystalline wax. In paraffin wax,
straight chain molecules in the C 26–C35
range predominate.
The residual oil can also be burnt by
heavy diesel engines used in ships. Used
in this way, it is known as ‘bunker fuel’.
It must be preheated, to flow more freely
into the ship’s engines. No additives are
needed.
The asphaltic tar is used in paving
roads. Other products such as white oils,
liquid paraffin, and petroleum jelly used
in cosmetic formulations, are produced
by subjecting the residual oil to vacuum
distillation.
Impact of automobiles and electric
light on kerosene production
At the beginning of the twentieth century,
the history of petroleum took a new turn.
Two new technologies emerged then,
and these had an effect, not only on the
petroleum industry, but on the entire
modern society. The two technologies were
the electric light and the gasoline-powered
automobiles. The petroleum refiners were
now able to sell kerosene for lighting, and
gasoline for motor fuel.
 With the increase in the population
of automobiles, the demand for gasoline
sky- rocketed. While about 4 dm 3 of
kerosene could last a household for one
week, automobiles dissipated about 4 dm3
of gasoline in a matter of minutes. At the
same time, electric light was replacing
kerosene lanterns in the cities. As a result,
there was a large demand for gasoline by
1910 and a surplus of kerosene.
In 1910, William Burton and his
colleagues at Standard Oil Co. (Indiana),
started looking for ways of converting the
surplus kerosene to the easily marketable
gasoline. The kerosene molecule was
approximately twice the size of the gasoline
molecule, and perhaps could be ‘cracked’
into smaller molecules.
The equation which follows is ideal for
cracking a 16-carbon molecule into two
smaller molecules with 8 carbons each:
C16 H 34 700°C
 → C 8 H16 + C 8 H18
Burton and his colleagues heated
kerosene in crude pressure cooker-type
reactors to 700°C. What was obtained in
practice, was a mixture which contained
methane, ethene, propene and molecules in
the C5– C8 range. During the 1920s, Burton’s
batch process was gradually replaced by
a continuous process invented by C.P.
Dubbs. This time, kerosene was heated
while it flowed past through pipes.
Octane number
The major components of the automobile
engine fuel, gasoline, are the C7 (heptane),
C8 (octane) and C9 (nonane) hydrocarbons.
These hydrocarbons may occur as straight-
31
chain or branched-chain molecules, as in
the following examples:
a) H H H H H H H
| | | | | | |
H– C– C– C– C– C– C– C– H
| | | | | | |
H H H H H H H
n-heptane, C7H16 (A straight-chain
molecule)
b) H
|
H– C– H H H H
H | | | | |
H– C – C –– C – C – C C H
| | | | |
H H
H– C– H H– C– H
| |
H H
2, 2, 4-trimethyl pentane, C8H18 (a branched-
chain molecule, formerly known as isooctane)
It has been observed that straight-
chain alkanes do not burn smoothly
in combustion engines. They burn too
rapidly and generate an explosion in the
cylinder, thereby upsetting the normal
up-and-down motion of the pistons.
This phenomenon, known as ‘knocking’
in internal combustion engines, is an
abnormal ‘pinking’ sound commonly
called ‘engine knock’,
The straight-chain hydrocarbon
n-heptane (C7H16), the worst offender, is
rated zero, while 2, 2, 4-trimethyl pentane,
C 8 H 18 (iso-octane), a branched-chain
hydrocarbon, is rated as 100 on a scale for
describing the burning characteristics of
gasolines. This rating is called the octane
number.
 The octane number is a measure of the
value or performance of the fuel in the
engine, and the rating depends on the
percentage composition of branched-chain
(iso-octane) to straight-chain hydrocarbons
in the fuel. The percentage of 2, 2, 4-trimethyl
pentane in a fuel is its octane number. For
example, the gasoline with octane number
89, is equivalent to a fuel made up of 89
per cent 2, 2, 4-trimethyl pentane (iso-
octane) and 11 per cent n-heptane. Almost
all automobiles run well on any gasoline
whose rating is between 89 and 100.
Cetane number
Diesel fuel consists of hydrocarbon
CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2 CH3
cetane
(cetane no. = 100)
CH3
a-methylnaphthalene
(cetane no. = 0)
Experiment 2.1
Procedure
1 Set up the distillation apparatus as
shown in Fig. 2.6.
2 Place about 25 cm3 of the mixture
provided in a 125 cm 3 Erlenmeyer
32
molecules in the C15– C18range. Straight-
chain hydrocarbons are preferred for use
as diesel. A cetane scale is used to rate diesel
fuels. Cetane (a- hexadecane) is rated 100
while a-methylnaphthalene is rated zero.
Mixtures of these two reference fuels are
used to determine the cetane number.
The cetane number, therefore, is the
volume per cent of n-cetane in alpha-
methylnaphthalene which ignites similarly
to the fuel being measured. Diesel fuels
have cetane numbers around 40. The
typical diesel engine operates on a
compression ratio of 16:1, as compared
with 9:1 for a typical gasoline engine.
conical flask and add two or
t h re e p i e c e s o f b o i l i n g c h i p s .
3 Place the test tube (a receiving
container) in an ice-water bath.
This will help minimise the loss of
vapour. Make sure the mercury bulb
of the thermometer is positioned
just below the opening in the air
condenser tube. This placement is
important for accurate temperature
readings, because the amount of
mixture in the container is small.
4 Clamp the flask in the water
bath so that the flask just
touches the surface of the water.
Make sure that all stopper connections
 thermometer
water bath
heat
Fig. 2.6
are tight and that the surface of the
water just touches the bottom of the
flask. Before starting the distillation,
have your teacher check your
apparatus.
5 Start heating the water bath gently and
watch the temperature reading.
6 Record the temperature every 30
seconds. When the temperature
becomes steady, it indicates that one
of the liquids in the mixture is boiling
and you should see liquid beginning
to collect in the test tube.
7 Record the steady temperature over
the period. (Note: Because water will
boil off in the water bath, you will have
to adjust the flask to keep the bottom
touching the water level).
33
delivery tube
test tube
cold water bath
a fraction
8 When the temperature begins to rise
again, all of the first fraction (liquid)
should be almost completely distilled
and the droplets entering the test tube
should stop.
9 Remove the first test tube receiver
and label it A. Replace with another
clean dry test tube and collect the next
fraction while noting the temperature.
Label the test tube B. Continue the
procedure until there are only a few
cubic centimetres of mixture in the
flask. (Note: if one of the liquids in
your mixture has a boiling point
higher than that of water, it will be
necessary for you to remove the water
bath and heat the flask directly with
the burner. Why?)
Never heat to dryness.
Questions
1 H o w m a n y d i ff e re n t l i q u i d s
(fractions) were in your mixture?
2 What were the boiling points of the
liquids?
3 What was the relative percentage
composition of each liquid? (Use a
graduated cylinder to measure the
volume of each liquid.)
4 Were the fractions collected over
definite temperatures, over a short,
or wide range of temperature?
5 Does the process involve a chemical
reaction or a physical process?
6 What other uses can be made of
different methods of separation,
such as distillation and fractional
distillation?
Other products of the petroleum
industry
We shall now consider some products,
which are not petroleum fractions as such,
but are nevertheless, important products of
the petroleum industry.
Natural gas
Natural gas is found either by itself, or
in association with crude oil. It is a clean
fuel which, in some countries, is metered
directly into residential houses for cooking.
Industrial users of natural gas in Nigeria
include the Power Holding Company of
Nigeria (PHCN). PHCN uses natural gas to
run its thermal stations at Afam, Sapele and
Egbin. Potential industrial users include
glass factories in Aba, Port Harcourt,
Ughelli and Lagos, together with the
cement plant in Shagamu.
34
Engine oils
Engine oils are base oils to which additives
have been added. Additives seek to prevent
or ameliorate the following problems:
1 sludge formation
2 varnish formation (gum)
3 viscosity increase (thickening)
4 piston deposit formation
Some of these problems can be cured by
base oils only. Others must be cured by
additives.
Engine oils are classified according to
their viscosity. Thus, we have SAE 10, SAE
30 and SAE 50. Lower numbers indicate
lower viscosity oils. Engine oils contain
additives which help to keep the engine
clean.
Grease
Grease is a base oil thickened with metallic
soaps to make it semi-solid. The major
advantage of this lubricant is that it stays
where it is placed, and slowly bleeds into
the part it is meant to lubricate. Two parts
of the grease determine its operating
temperature. These are its base oil and its
thickener.
Paraffin wax
Paraffin wax contains straight-chain
hydrocarbons in the C 26–C 35 range. It
is usually separated into three melting
point ranges: 40°C– 42°C; 45°C– 47°C and
50°C–52°C corresponding to soft, medium,
and hard waxes. These grades are used for
such diverse purposes as the manufacture
of cosmetics, and together with stearic
acid, for the manufacture of candles. No
additives are needed. Paraffin wax is
obtained by dewaxing the distillate, and
from natural gas condensates.
Oil shale
Oil shale is a rock (not necessarily shale)
containing finely-divided organic matter
called kerogen. The kerogen content of
different shales varies widely, but generally
can be said to be in the range of 12–16 per
cent. Kerogen is a structural material whose
main building blocks are polycyclic clusters
with a low degree of unsaturation.
Gasification
Kerogen can be converted into gas by
retorting at atmospheric pressure and
temperatures above 700°C. The residual
carbon can be reacted with steam, leading to
complete gasification. Hydrogen sulphide
formed by the decomposition of organic
sulphur compounds reacts with alkaline
earth oxides, thereby removing a potential
pollutant.
Experiment 2.2 Distillation of a
petroleum sample
Procedure
In Experiment 2.1, you were able to separate
a liquid mixture into its component parts
through a physical process. You will now
distil a crude oil sample, so as to determine
whether crude oil is a pure substance or a
complex mixture.
1 Examine carefully the colour, odour,
texture and viscosity (how easily it
flows) of the oil and note down your
observations.
2 Set up the distillation apparatus as in
Experiment 2.1.
3 Place about 25 cm3 crude oil and a
0°–360° range thermometer in a round-
bottomed flask and heat the flask
directly with the burner, i.e. without
35
the use of a water bath.
4 Heat the mixture slowly and watch the
thermometer. Note the temperature
every 30 seconds.
5 Collect fractions boiling roughly at
the following temperature ranges
in labelled, clean, dry test tubes
(receivers):
a) room temperature to— 30°C
b) 30° C– 200°C
c) 200°C – 300°C
d) 300°C – 400°C
6 Label the distillates and residue.
Exercise
1 Note the colour and odour of the
different fractions and the residue.
Compare them.
2 How easily can you pour each
fraction and the residue?
3 Do you think crude oil is a single
substance or a mixture? State your
reasons.
Summary
This chapter has taught the following:
• Compounds consisting of only two
elements, hydrogen and carbon, are
known as hydrocarbons, e.g. alkanes
and alkenes.
• Hydrocarbons are mainly classified as
saturateand unsaturated hydrocarbons.
• Petroleum is a complex mixture of
hydrocarbons.
• Fractional distillation is used to separate
a mixture into fractions.
• T h e c o m p o u n d s o b t a i n e d f ro m
distillation of petroleum are all
hydrocarbons. The individual
 hydrocarbons found in petroleum exist
normally as gases, liquids or solids.
• Refining of oil involves the three
successive stages of separation,
conversion and purification.
• Cracking is a process used in oil
refining to break up large hydrocarbon
molecules into smaller ones in order to
get the best value from crude oil. The
reaction takes place in the liquid phase
and involves heat and catalysts. There
are three types of cracking: thermal,
catalytic and hydrocracking.
• Polymerisation is a reaction by which a
very large number of small molecules
are joined together to make a large
molecule.
• Reforming rearranges the atoms in
molecules. It converts linear alkanes to
branched-chain and cyclic hydrocarbons.
• The octane number is a rating scale used
to measure the value or performance
of a given gasoline fuel in the car
engine. The rating depends on the
percentage composition of branched-
chain (especially iso-octane) to straight-
chain hydrocarbons in the fuel. The
scale rates n-heptane as 0 and 2, 2,
4-trimethylpentane as 100.
• Additives are substances which help to
improve the quality of gasoline.
• Fuels release energy when they burn
in air or oxygen. Fuels which contain
carbon and hydrogen give carbon
(IV) oxide and water on complete
combustion.
36
Review questions
Multiple-choice questions
1 Which method is often employed in the
separation of the hydrocarbons found
in petroleum?
A Catalytic cracking
B Polymerisation
C Fractional distillation
D Hydrogenation
2 Hydrocarbons are organic compounds
that contain
A carbon and oxygen.
B carbon, hydrogen and oxygen.
C carbon and sulphur.
D hydrogen and carbon only.
3 Which statement is correct? Petroleum
is
A a complex mixture of petrol and oil.
B carbon, hydrogen and oxygen.
C carbon and sulphur.
D a mixture of hydrocarbons.
4 Petrol (gasoline) contains the paraffin
hydrocarbons
A C6– C10.
B C1– C4.
C C5– C6.
D C14– C19.
5 Which one of these statements is
correct? Cracking is
A another form of polymerisation.
B conversion of long-chain
hydrocarbons to short-chain ones.
C the production of unsaturated
molecules from saturated ones.
D distillation of crude petroleum to
obtain kerosene.
Short-structured questions
1 a) State the products of the distillation
of petroleum in order of their boiling
points, starting with the lowest.
 b) Octane is a saturated hydrocarbon.
Explain what is meant by hydrocarbon
and saturated.
c) Give any industrial use of a branched-
chain isomer of octane.
2 a) Oils with high sulphur content are
usually cheaper than low-sulphur
crudes. Why?
b) The fractionating column of an
oil refinery is sometimes as high
as sixty metres. This is because
_________________.
c) What functions do ‘bubble caps’ in a
fractionating tower perform during
the first distillation of oil?
d) Why is the second stage in the oil
refining process necessary?
3 a) State the two classes of hydrocarbons.
b) Fuels burn to release the following
products: ____________
c) Polythene (polyethene) is made
by joining together many ethene
molecules.
i) What is this process called?
ii) How is the process made use of
in the oil industry?
4 At the beginning of this century,
kerosene fraction was much in demand,
but since the mid-fifties, the demand for
other fractions has increased.
a) What is responsible for the changes
in demand of these fractions? Give
examples.
b) How do the oil companies try to
cope with changes in demand?
c) With the relatively smaller use of
the kerosene fraction as fuel, what
do you think happens to the excess
kerosene produced? Give reasons
for your answer.
5 The first stage in the refining process
is the separation of oil in which a
37
hydrocarbon mixture is separated into
fractions at similar boiling temperatures.
Each fraction contains substances of
similar molecular size.
a) What is the meaning of similar
molecular size?
b) What is the usual name for this
separation using different boiling
points? Is this process a chemical
change? Give reasons for your
answer.
Essay-type questions
1 a) Describe briefly, with an illustrated
example, how crude oil is thought
to have been formed.
b) State how the processes of catalytic
cracking are used to provide a range
of hydro carbon fuels.
2 a) List the main fractions, including
their ranges of molecular size and
boiling points, obtained from the
distillation oil crude oil.
b) State the main uses of each fraction.
3 An oil refinery has to separate, convert
and then purify crude oil. Describe
briefly what is involved in each of
these three stages. Give appropriate
examples.
4 What is meant by these terms: cracking,
polymerisation, reforming, purification and
octane number. Illustrate your answers
with reference to petroleum.
5 Read the following passage carefully
and answer the questions below.
a) Let us suppose that it has been
discovered that amounts of
lead (Pb) in the air of cities have
increased dramatically. Most of
the lead comes from the exhaust
fumes of vehicles using petrol
that contain lead compounds. Oil
 companies have for many years Fig. 2.7. The different fractions are
added these lead compounds summarised in Table 2.3.
as anti-knock agents because
they are the cheapest and most
practical way of increasing the
octane rating of the fuel. Without
them, the oil industry would
have to use different and more
expensive plants to improve the
cheap chemical to replace these
lead compounds.
However, lead is only one of
a number of pollutants put out
by the automobile engine. Carbon
(II) oxide (CO) accounts for 6% of
Fig. 2.7
exhaust gases, oxides of nitrogen
0.04% and sulphur (IV) oxide (SO2)
0.006%.
i) Why are lead compounds Table 2.3
added to petrol?
ii) What is meant by the term Fraction Boiling point range °C
octane rating?
iii) How could the oil industry 1 30–70
avoid the use of lead 2 70–120
compounds in petrol? 3 120–170
iv) Would the price of petrol be 4 170–250
affected by the removal of 5 250–360
lead compounds from petrol?
How? i) Complete the diagram (Fig. 2.7)
v) Why is lead in the atmosphere by drawing a thermometer in
thought to be dangerous? the correct place for taking the
vi) How can lead be prevented temperature measurements.
from being deposited in the ii) What name is given to this process
car engine? for refining crude oil?
vii) Which other pollutants are iii) What was the purpose of the cold
found in exhaust fumes and water?
what proportion do they make iv) Give two differences in physical
up? properties other than boiling point
b) An experiment was carried out to between fraction 1 and fraction 5.
separate crude oil into fractions, v) F r a c t i o n 2 c o n t a i n s t h e
using the apparatus shown in hydrocarbon octane, C8H18. What is
the structural formula for octane?

38
 Give one use of a branched-chain
isomer of octane.
vi) Give one use for the mixture of
hydrocarbons in fractions 2 and 4.
6 What action would you suggest
your country should take to be self-
sufficient in petroleum and petroleum
products?

39
 3 Extraction of metals: General
principles
Introduction
In Book 2, we defined the periodic table
as an organisational chart of elements
following a particular pattern. You will
recall that the basic features of the periodic
table are as follows:
1 Elements in the same vertical
column form a group. They all
have the same number of valency
electrons.
2 There are eight main groups
represented by figures I, II, III, IV, V,
VI, VII and 0.
3 Group I elements are called alkali
metals, and Group II elements are
called alkaline-earth metals.
4 Elements intervening between
Groups II and III are called transition
elements.
From the periodic table, you can easily
identify those elements which are metals.
Metals are very useful, and their importance
lies in their physical properties, especially
their mechanical strength. Man depends
on metals to carry out certain important
activities in life. For example, there is the
day-to-day use of the cutlass, hoe, cutlery,
and alloys used for aircraft and missiles.
Most metals do not occur as free
elements, but are found combined with
40
other elements to form ores from where
they are extracted.
In this chapter, we shall study the
extraction of metals and relate the method
and ease with which the extraction is done
to the chemical properties of the metal. A
metal, as you already know, is an element
which ionises by electron loss. For example,
Mg → Mg2+ + 2e-
Al → Al3+ + 3e-
Hydrogen is a non-metal, although it
ionises by loss of electrons. Hydrogen is
thus an exception to this definition.
Performance objectives
At the end of this chapter, you should be
able to:
1 state the relative abundance of
metals in nature;
2 arrange the metals in order of their
chemical activity;
3 explain extraction of metals in
simple terms;
4 state the general principles of
extraction of metals; and
5 relate the reactivities of metals to
extraction methods.
Occurrence of metals in nature The majority of metals are usually
found as minerals in combined forms of
Metals are widely distributed in the earth’s more or less definite chemical composition.
crust either as compounds or in the free These minerals are often mixed with earthy
metallic form. More than 80 of the known material and so are called ores.
elements are metals. The form in which
a metal exists in nature is related to its Reactivities of metals
reactivity.
The very reactive metals, for example Metals, as we already know, are elements
sodium and potassium, are usually with few valency electrons, and these
found combined with other elements. electrons are comparatively readily given
For example, they are found as chlorides, up so that they form positively-charged
or carbonates which are very stable ions. Metals can be arranged in a series
compounds. Moderately reactive metals, according to their comparative tendencies
such as zinc and lead, are usually found as to give up their valency electrons, i.e.
oxides or sulphides while the least reactive according to their electropositivity, which
metals are usually found in an uncombined in turn determines their chemical activity.
state, for example gold, which is found This series is known as the activity series or
almost entirely as a free metal. electrochemical series.

Table 3.1 Positions of the common metals in the activity series.

Action with concentrated acids

Metal Electro- Chemical Combustion Action with Action with HCl H2SO4 NHO3 Action with
positivity activity water dilute acids other metallic
salts

Potassium K Displace
hydrogen from
React to form
cold water
Sodium Na Burns readily Displace hydrogen and React React to
Calcium Ca in air to form hydrogen from a salt (Al to form formNO2 Each metal
the oxide steam at read reacts only hydrogen React to will displace a
heat with dilute anda salt SO2 No metal lower in
HCl) reaction the series form
Magnesium Mg Forms a solution of
Decreasing chemical activity

Aluminium Al NO lower metal

No reac-
Decreasing electropositivity

Zinc Zn
tion
Iron Fe
Form the
Tin Sn oxide when Do no react
heated in air with cold No reaction
water or steam (Pb reacts
with dilute No
Lead Pb HNO3 to form Reaction
Copper Cu the oxides of
Mercury Hg Nitrogen No No
Reaction reaction

Silver Ag No action
Gold Au

41
Table 3.2 The gradation in some of the properties of metals and their compounds

Reaction of the oxide Charater of Solubility Solubility

Metal Solubility Heating With carbon with hydrogen Hydroxide Carbonate Nitrate(V) of suphide of chloride

Potassium K Dissolve Not reduced Not reduced Soluble: Soluble in Soluble in

Decomposed Soluble in
to form when heated when heated stable to heat water; stable to the nitrate water water (except
Sodium Na hydroxides to heat (III) and O2 PBCl2 which
Insoluble by heat is insoluble
Calcium Ca Stable to (CaOH)2 is Insoluble in cold water
Magnesium Mg heat in water; but slightly
sparingly Decomposed Insoluble
Aluminium Al soluble: decomposed to the oxide, in water; soluble in
decomposed to the oxide NO2 and O2 soluble in warm water)
to the oxide and CO2 by heat. dilute HCI
Zinc Zn
Insoluble Reduced by heat by heat
to the (Al2(CO3)3
Iron Fe metal when Reduced does not
Tin Sn heated to the exist
metal when
heated Unstable or
Lead Pb not formed Insoluble in
Decomposed
Copper Cu Decom- to the Metal; wat er
posed to NO2 and O2
Mercury Hg
the metal by heat

Hydroxides
Silver Ag do not exist
Gold Au

The activity series of metals shows a Extraction of metals

gradual change in the chemical activity of
the metals. The chemically active metals
form very stable compounds because
of their great activity. The ores formed
are usually chlorides or carbonates, e.g.
potassium, sodium and calcium. Base
metals, such as zinc, iron and copper, form
compounds of intermediate stability. Their
ores are usually oxides and sulphides; and
sometimes carbonates.
Noble metals, such as silver and gold,
usually occur in the free state, but they
also form compounds that are easily
decomposed. Tables 3.1 and 3.2 show
the position of the common metals in the
activity series and the gradation in some
of the properties of these metals and their
compounds. The tables are useful aids in
remembering some of the reactions of the
metals and of their compounds.
The extraction of metals is basically a
reduction process in which a reducing
agent or and electron donor must be
present to supply the electrons to the
metallic ions. The method of extraction of
a metal from its ore depends on the ease
with which compounds of the metal can
be reduced to the metal.
Normal reducing agents, e.g. carbon
and hydrogen do not reduce compounds
of the chemically active metals; so, such
compounds have to be reduced by
electrolysis. Ores of the base metals can
be decomposed to their oxides, and such
oxides can then be reduced by carbon.
General principles of extraction of
metals
The method chosen for the extraction of
a particular metal is dependent on the
stability of its ore. The more common

42
methods used in the extraction of metals
are as follows:
1 Electrolytic process
This is used to extract the more
electropositive metals, e.g. potassium,
sodium, calcium and magnesium
from their ores which are mainly
very stable chlorides and carbonates.
During electrolysis, oxidation and
reduction processes take place. The
cathode acts as a reducing region by
supplying electrons to the metallic
ions in the electrolyte, thus resulting
in the deposition of the free metal.
Electrolytic processes are expensive
to instal and maintain. Thus, they are
used only when chemical reduction is
not sufficient.
2 Chemical reduction
This is used to obtain the less
electropositive metals, e.g. lead, tin,
iron and zinc from their ores. Two
methods are available.
The first method involves reducing
oxides of metals with coke or carbon II
(oxide.
Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g)
Table 3.3 Common methods of extraction of metals in relation to their positions in the activity
series
Metal Symbol Reactivity Most commo ore
Potassium K Chlorides
Sodium Na Very reactive
Calcium Ca Electrolysis of fused
43
The second method involves oxidation
of the sulphide to the oxide followed
by reduction of the oxide by coke.
2PbS(s) + 3O2(g) → 2PbO(s) + 2SO2(g)
2PbO(s) + C(s) → 2Pb(s) + CO2(g)
During the heating process, the coke
combines with the oxide ions to
release the electrons necessary for the
reduction of the lead ions.
a) C + O2- → CO + 2e-
b) Pb2+ + 2e- → Pb
c) 2Pb2+ 2O2- + C(s) → 2Pb(s) +
CO2(g)
3 Thermal reduction
Here, the metals are obtained from their
ores by heating. For example, mercury
is obtained by heating mercury(II)
sulphide in air.
HgS(s) + O2(g) → Hg(s) + SO2(g)
In the case of platinum, the ore
is first converted to ammonium
hexachloroplatinate(IV) which is then
reduced to platinum by heating.
Table 3.3 gives a summary of the
extraction methods.
Method of extraction
Electrolysis of fused
hydroxides or chlorides
chlorides
Magnesium Mg Carbonates
Aluminium Al Oxides Electrolysis of oxide
Zinc Zn Moderately oxides Reasting of carbon-
nates and sulphides
to form oxides: reduction
Iron Fe reactive carbonates and
sulphides
Tin Sn
Lead Pb
Copper Cu Least sulphides Roasting in air
Mercury Hg reactive Heating in air
Silver Ag Fee element Mined as free elements
Gold Au

Summary • Metals are arranged in series

This chapter has taught the following:
• Metals are found in nature either
as compounds known as ores or in
the free state. The reactive metals
are found as compounds while the
unreactive metals are found in the
free state, e.g. gold.
• Metals are widely distributed in the
earth’s crust.
• The ores of reactive metals are usually
chlorides and carbonates.
• Less reactive metals, e.g. zinc, iron
and copper are found as oxides and
sulphides, and sometimes, carbonates.
• Extraction of metals is a reduction
process in which the metallic ions
receive the required number of
electrons from an electron donor (i.e.
a reducing agent) and so form the
metal, e.g. Na+ +e- → Na
• The methods of extraction of metals
are the electrolytic process, chemical
reduction and thermal reduction.
according to their reactivities, i.e.
comparative electropositivities. This
series is known as the activity series
or electrochemical series.
Review questions
A Multiple-choice questions
1 In the periodic table, elements are
arranged in order of their
A electronic configuration.
B structural natures.
C molecules.
D atomic numbers.
E isotopes.
2 The elements intervening between
Groups II and III of the periodic table
are collectively known as
A non-metals.
B metals.
C lanthanides.
D halogens.
E transition elements.

44
3 A metal is an element which ionises by
A proton reactions.
B electron loss.
C electron gain.
D sharing of electrons.
E nuclear reaction.
4 The process of extraction generally
involves
A oxidation-reduction reaction.
B combination reaction.
C displacement reaction.
D neutralisation reaction.
E double decomposition reaction.
5 Chemical reduction is used to obtain
A highly electropositive metals from
their ores.
B highly electronegative metals from
their ores.
C less electropositive metals from
their ores.
D less electronegative metals from
their ores.
E none of the above.
C Essay-type questions
1 What are the principles underlying
the extraction of metals? Explain,
using examples.
2 How would you differentiate between
an alkali metal trioxocarbonate(IV)
salt and an alkalineearth metal
trioxocarbonate(IV) salt?
3 How does electropositivity of metals
change along the electrochemical
series? Relate this change to their
chemical reactivity and give adequate
explanation for your answer.
4 Give a summary of the reaction of
metals along the activity series with
concentrated acids such, as hydrogen
chloride acid, tetraoxosulphate(VI)
acid and trioxonitrate(V) acid. Give
examples.
5 Discuss the behaviour of metallic
oxides in terms of solubility, the
action of heat and their reactions with
carbon. Give examples.

B Short-structured questions
1 Give the possible ores of the following
metals:
a) sodium
b) calcium
c) aluminium
d) iron
e) lead
2 For each of the ores named in (1) above,
give the method of extraction.
3 What is a metal? Give an example of a
redox reaction involving a metal ion.
4 Arrange the following metals in
increasing order of their reactivity:
copper, sodium, zinc, lead, gold,
calcium and aluminium.
5 Give two examples of ores that can be
reduced to the metal, using carbon.

45
 4 The alkali metals: Group I
elements
Introduction
The elements in Group I of the periodic table
are collectively known as alkali metals. They
are lithium, sodium, potassium, rubidium,
caesium and francium. Francium is a short-
lived radioactive element about which little
more need be known at this stage.
In the periodic table, the Group 0
elements precede the Group I elements.
The two groups differ from each other in
a remarkable way. Group 0 elements are
unreactive non-metals while the Group I
elements are reactive metals.
On moving diagonally across the
periodic table, elements in different groups
show certain similarities. For example,
the Group II elements are also highly
electropositive metals and have a close
relationship with the alkali metals. The
properties of lithium and its compounds
are markedly different from those of the
other alkali metals. The lithium compounds
resemble the magnesium compounds in
many respects. This is an example of a
diagonal relationship.
46
Performance objectives
At the end of this chapter, you should be
able to:
1 explain the similarities of the alkali
metals in terms of the electronic
structure of the atoms of the
elements;
2 investigate some of the physical
properties, e.g. lustre, appearance
and hardness of the alkali metals;
3 explain other physical properties
and relate them to the behaviour of
the metals in the group;
4 give examples of chemical proper-
ties of the group;
5 state the occurrence of some of the
metals in nature;
6 explain the chemistry involved in
the extraction of sodium;
7 give the compounds of sodium;
8 state the properties of a given
sodium compound;
9 carry out simple experiments to
investigate the properties of alkali
metals;
10 give the names and symbols of all
the alkali metals; and
11 write the electronic structures of the
alkali metals.
Occurrence of alkali metals
The alkali metals are reactive and highly
reducing. Thus, they do not exist naturally
as the pure metals, or as oxides which are
deliquescent. Sodium and potassium are
relatively abundant while the other alkali
metals are relatively rare.
Sodium is found as sodium chloride
in sea water, and as solid deposits in the
ground. Huge compounds of sodium
can be found in North America, France,
Germany, China, Cheshire and South
Durham. Sodium trioxonitrate(V) is found
in the deserts of Chile. Sodium also occurs
in sodium sesquicarbonate (trona) and in
other minerals, such as borax.
Potassium is found in sea water and as
carnalite. Lithium, rubidium and caesium
occur in a few rare aluminosilicates.
Physical properties of alkali metals
Table 4.1 shows the properties of the alkali
metals.
Table 4.1 Properties of the alkali metals
1 In the outermost shell of the atom of
each alkali metal, there is only one
electron, the loss of which converts
the atom into a unipositve ion. This
unipositive ion now has the same
electronic configuration as the noble
gas which immediately precedes it
in the periodic table. For example,
Na → Na+ + e-
2.8.1 2.8
Recall that 2.8 is also the
electronic configuration of neon, a
noble gas in Group 0.
Due to the tendency to assume a
noble gas structure, the outermost
electron in the atom of the alkali
metal atom experiences a greatly
reduced electrostatic attraction from
the positively charged nucleus.
Also, the outermost electron is
located some distance away from
the preceding inner shell which
has a complete octet of electrons.
As a result, the atom of the alkali
metal has a larger radius than any
of the atoms of elements in the same
period.
The radius of an atom is the

Element Symbol Atomic Electronic Relative Atomic Ionic First

number configuration atomic radius radius ionisation
mass (Å) (Å) energy
(KJmol-1)
Lithium Li 3 2.1 6.94 1.33 0.60 518.82

Sodium Na 11 2.8.1 22.99 1.57 0.95 493.24

Potassium K 19 2.8.8.1 39.096 2.03 1.33 418

Rubidium Rb 37 2.8.18.8.1 85.48 2.16 1.48 401.28

Caesium Cs 55 2.8.18.18.8.1 132.91 2.35 1.69 376.2

Francium Fr 87 Radioactive (223) ____ ____ ____

47
 distance of closest approach to Table 4.2
another atom in a given bonding
situation. At this distance, the inter- Element Atomic Ionic Density
nuclear repulsions and the inter- radius radius in gcm-3
electronic repulsions just balance in mm in mm
the nuclear–electron attractions.
Li 0.157 0.074 0.535
Thus, the sizes of the atoms are not
Na 0.191 0.102 0.971
determined directly by the size of K 0.235 0.1384 0.862
the nucleus, which is very small, but Rb 0.2507 0.149 0.532
by the effective volume of the outer Cs 0.272 0.170 0.90
electron cloud. Within the alkali
group, the atomic radius increases Also ionic radius, which is the
with increasing atomic number, space occupied by an ion in any
a factor which tends to reduce direction, in the lattice of an ionic
ionisation energies. solid increases down the group.
2 Ionisation energy decreases pro- 3 Table 4.3 gives the standard
gressively down the group as far electrode potential of the alkali
as caesium which is, therefore, the metals. The standard electrode
easiest to ionise, i.e. the ease of potential is a quantitative measure
electron loss increases down the of the tendency of reactants in their
group; so also do the reactivities of standard states to form products in
the metals. their standard states for a particular
reaction. It is also known as the
reduction potential E0.
Table 4.3

Element Standard M+/M Boiling point Melting point Electronegative

electrode (K) (K) EN
potential (E°)
(volts)

Li -3.02 1 615 454 1.15

Na -2.71 1 156 371 1.6
K -2.92 1 033 336 0.19
Rb -2.99 959 312 0.9
Cs -3.02 942 302 0.85

Electrode potential tables are usually example, the electrode potential of sodium
written for half-reactions relative to the is presented as:
hydrogen electrode, in order to present the Na+(aq) + e → Na(s) E0 = -2.71
information as efficiently as possible. For

48
4 Electronegativity decreases down
the group due to the screening
effect of inner electron shells on the
outermost electrons.
5 Alkali metals are said to be strongly
electropositive (this is used to des-
cribe how easily atoms tend to give
up electrons).
6 The alkali metals have large atomic
volumes and increasing screening
effect down the group. The atoms
of each element do not exert great
attractive force amongst themselves.
Consequently, the metals have
low melting points, low boiling
points, relatively low energies of
sublimation, weak metallic bonding
and low densities.
7 The atoms of the alkali metals are
held in closely-packed structures by
weak metallic bonds because there
is only one bonding electron per
atom. The metallic bonds become
weaker as the atomic size increases.
Therefore, the melting point de-
creases down the group.
8 The alkali metals, as expected,
are good conductors of heat and
electricity due to the presence of
delocalised electrons. Conductivity
is reduced if impurities are pre-
sent. At low temperature, the
conductivity is high because the
atoms vibrate very little and there is
no resistance at all.
Experiment 4.1
Aim
Investigating some characteristic physical
properties of alkali metals and ions
49
Procedure
1 Cut small pieces of lithium and sodium
metal with a pen knife.
2 Examine the lustre and note the hardness
of each metal. Does potassium need
cutting? Why?
3 Pick up small pieces of lithium, sodium
and potassium with a platinum wire
one at a time and heat in a bunsen flame.
Record the colours of the different
metals.
Lithium, sodium and potassium have
metallic lustre. Lithium is the hardest
member, and the property of hardness
decreases down the group. Sodium
is soft enough to be cut with a knife
while potassium is putty-like and can be
moulded. Each member of the alkali metals
burns with a characteristic flame colour
when heated:
Lithium - crimson
Sodium - bright yellow
Potassium - lavendar lilac
Rubidium - lilac
Caesium - bright blue
Chemical properties of alkali metals
Experiment 4.2
Aim
Investigating the chemical properties of
alkali metals
Materials required
Small pieces of lithium, sodium and
potassium. In addition, your teacher will
supply you with watch glasses, small glass
trough, water, dilute acids, hard glass,
tubes and stream of hydrogen.
 Procedure

Place a small piece of lithium, sodium and potassium separately in watch glasses in
a fume cupboard for one or two days. What do you observe?

Table 4.4 Summary of physical properties of alkali metals

Property Li Na K Rb Cs
Lithium Sodium Potassium Rubidium Caesium

Atomic number 3 11 19 37 55
Electron configuration (outer) 1s22s1 2p63s1 3p64s1 4p65s1 5p66s1
Isotopes (in order of abundance) 7,6 23 39,41,40 85,87 133
Relative atomic mass 6.94 22.99 39.096 85.48 132.91
Metalic radius (A) 1.55 1.90 2.35 2.48 2.67
Ionic radius (Å) 0.60 0.95 1.33 1.48 1.69
Atomic radius (Å) 1.33 1.57 2.03 2.16 2.35
Density (gcm-3) 0.54 0.97 0.86 1.53 1.90
First ionisation energy (kJmol-1) 518.32 493.24 418 401.28 376.2
Electronegativity A/R 1.15 1.0 0.9 0.9 0.85
Electrode potential (E0) -3.02 -2.71 -2.92 -2.99 -3.02
Enthalpy of sublimation (kJmol-1) 1 52.3 108.47 89.95 85.69 78.71
Melting point (K) 454 371 336 312 302
Boiling point (K) 1 615 1 156 1 033 959 942
Abundance (parts per million 65 28 300 25 900 310 7
(p.p.m.))
Flame Criosme Bright Lavender Lilac Bright blue
yellow lilac
Physical state Hardest Softest
Metallic bonding Weak Decreases
m. bonding down the
group
Atomic volume (cm3mol-1) 13.1 23.1 95.5 55.8 71

Exposure to dry air
Lithium is less reactive in dry air because
it is stable in dry air at room temperature.
Sodium and potassium, however, form
their corresponding higher oxides.
2Na(s) + O2(g) → Na2O2(s)
Sodium peroxide (pale yellow)
K(s) + O2(g) → KO2(s)
Potassium super oxide (yellow solid)
The reactions are more violent when heat
is applied. Both rubidium and caesium
react more vigorously, catching fire in
the process. Caesium, is however, more
reactive than rubidium. So the degree of
reaction with dry air increases down the
group.

50
Exposure to damp air
Lithium, sodium and potassium tarnish
easily when exposed to damp air because
they are readily oxidised by atmospheric
oxygen to form their oxides. These oxides
react with water vapour in the air to
form the corresponding hydroxides
which slowly absorb atmospheric
carbon(IV) oxide to form crystals of
hydrated trioxocarbonate(IV) salts of the
corresponding metals. Taking sodium as
an example:
4Na(s) + O2 (g) → 2Na2O(s)
Na2O(s) + H2O(g) → 2NaOH(aq)
2NaOH(aq) + CO2(g) → Na2CO3(s) + H2O(l)
Generally,
4 X + O2 → 2X2O (X being an alkali metal)
X2O + H2O → 2XOH
2XOH + CO2 → X2CO3 + H2O
The tarnishing property increases down
the group. Rubidium and caesium react too
vigorously with damp air. Due to their high
reactivity, lithium, sodium and potassium
are kept under paraffin oil, toluene or
naphthalene while rubidium and caesium
are kept in vacuo.
Reaction of alkali metals with cold water
Experiment 4.3
Aim
Investigating the reaction of alkali metals
with cold water
Procedure
1 Put a small piece of lithium metal into
a glass trough of cold water.
51
2 Test the resulting solution with litmus
paper.
3 Record your observations.
4 Repeat the experiment using a small
piece of sodium metal.
5 In both cases, test any gas being given
off, using a fairly long lighted paper on
the surface of the resulting solutions.
The reactivity of the alkali metals with
water increases down the group.
1 Lithium floats and reacts least
explosively with water.
2 Sodium darts about on the surface of
the water and gradually melts to a
silvery ball. The reaction is violent.
3 Potassium, rubidium and caesium
actually melt and catch fire.
Thus, all the alkali metals react
with cold water, liberating hydrogen.
The resulting solution is the soluble
metallic hydroxide which turns red
litmus paper blue.
2Na(s) + 2H2O(I) → 2NaOH(aq) + H2(g)
Ionically,
2Na(s) + 2H2O(l) → 2Na+ + 2OH-(aq) + H2(g)
2K(s) + 2H2O(l) → 2KOH(aq) + H2(g)
The reaction of an alkali metal with
water is a redox reaction in which
the metal is the reducing agent or the
electron donor.
Reaction with dilute acids
Carefully repeat experiment 4.3 using,
in turns, dilute acids such as hydrogen
chloride acid and trioxonitrate(V) acid.
The alkali metals react vigorously with
the dilute acids liberating hydrogen gas
and forming the corresponding salts. The
reactivity generally increases down the
group from lithium to caesium.
2Na(s) + 2HCl(aq) → 2NaCl(aq) + H2(g)
Ionically,
2Na(s) + 2H+(aq) → 2Na+(aq) + H2(g)
2K(s) + H2SO4(aq) → K2SO4(aq) + H2(g)
2Na(s) + 2HNO3(aq) → 2NaNO3(aq) + H2(g)
Reaction with hydrogen
Pass a stream of hydrogen gas over
heated lithium, sodium and potassium
respectively. This should be done in a hard
glass tube, as shown in Fig. 4.1. Record all
your observations.
The reactivity of the metals with
hydrogen increases down the group.
All the metals, when heated, react with
hydrogen to form the corresponding
hydrides. The hydrides formed are ionic
compounds with high melting points and
boiling points which increase down the
group.
2Li(s) + H2(g) → 2Li+ H-(s)
2Na(s) + H2(g) → 2Na+ H-(s)
2K(s) + H2(g) → 2K+ H-(s)
alkali metal
hydrogen
heat
Fig. 4.1 Reacting hydrogen with some alkali metals
52
Reaction with nitrogen
Set up the apparatus as in Fig. 4.1, passing
nitrogen over heated pieces of lithium,
sodium and potassium respectively. Then
dissolve the different products formed in
water and test with litmus paper. Record
all your observations as usual.
Only lithium reacts when heated with a
stream of nitrogen to form lithium nitride
which dissolves in water to give lithium
hydroxide due to hydrolysis.
Li3N(s) + 3H2O(l) → 3LiOH(aq) + NH3(g)
The solution turns red litmus paper blue.
Why?
Sodium, potassium, and caesium
only react with nitrogen under an electric
arc in a discharge tube. They do not react
under ordinary laboratory heating.
The reactivity decreases down the group
from lithium to caesium.
Reaction with halogens
The alkali metals react violently with
the halogens, hence the reactions are not
usually carried out in ordinary laboratories.
uncombined
hydrogen

Reactivity increases down the group with
the formation of the corresponding halides.
2Na(s) + Cl2(g) → 2NaCl(s)
2Cs(s) + F2 → 2CsF(s)
(caesium fluoride)
2Li(s) + Br2(g) → 2LiBr
(lithium bromide)
Reaction with sulphur
When alkali metals are heated respectively
w i t h s u l p h u r, t h e c o r re s p o n d i n g
monosulphides are formed. Reactivity
decreases down the group when alkali
metals react with non-metals, such as
sulphur, carbon and nitrogen.
2Li(s) + S(s) → Li2S(s)
(lithium monosulphide)
2Na(s) + S(s) → Na2S
(sodium monosulphide)
Reaction with mercury
All the alkali metals dissolve in mercury,
forming the corresponding amalgams
which are used as reducing agents.
Li(s) + Hg(l) → Li/Hg(I)
Na(s) + Hg(l) → Na/Hg(l)
Reaction with ammonia solution
All the alkali metals dissolve in liquid
ammonia and some amines to form blue
solutions. At higher concentrations, the
solutions are copper-coloured and are
better regarded as liquid metal solutions.
If no impurities are present, the alkali
metal (except lithium) can be recovered
unchanged by evaporation of the ammonia.
Na(s) + NH3(l) → Na+NH-2 +
Anomalous nature of lithium
The anomalous nature of lithium occurs
because it is unexpectedly much less
electropositive than sodium. Some of the
important differences between lithium and
other alkali metals are listed as follows:
1 Lithium reacts only very slowly
with water.
2 In air, lithium forms the normal
oxide whereas the other alkali
metals form higher oxides.
Li(s) + O2(g) → Li2O(s) (lithium oxide)
2Na(s) + O2 → Na2O2(s) (sodium peroxide)
3 Lithium reacts with nitrogen to
form the nitride. Other alkali metals
do not form nitrides.
6Li(s) + N2(g) → 2Li3N(s) (lithium nitride)
4 Lithium hydride is more stable than
other hydrides and, with ethyne,
lithium carbide forms more easily.
5 Lithium compounds are more
covalent. Thus, the halides are more
soluble in organic solvents than the
halides of other alkali metals.
6 Some lithium salts are less
stable than those of other
alkali metals. For example,
Li 2CO 3(s) 7273 K Li 2O (s) + CO 2(g)
With sodium and other alkali
metals, there is no reaction below
1 073 K. Solid LiNO3 and NaNO3
are stable trioxonitrates(V), but
on heating, they decompose to the
dioxonitrates(III).
2LiNO3(s) → Li2O(s) + 2NO2(g) + 12 O2(g)
NaNO3(s) → NaNO2(S) + 12 O2(s)
Lithium hydroxide forms the oxide
on gentle heating.
2LiOH(s) → Li2O(s) + H2O(I)
1
2
H2(g) Sodium hydroxide and other
hydroxides of alkali metals do not
decompose.
53
7 Lithium resembles magnesium,
an alkaline earth metal, in those
§
properties in which it differs from
other alkali metals. This is called
diagonal relationship.
Extraction of sodium
Extraction is the chemical isolation of
metals from their ores. Generally, alkali
metals are extracted by the electrolysis of
their chlorides. The extraction of sodium
is typical.
Sodium is extracted commercially by
the electrolysis of molten sodium chloride,
using the Downs cell. Fig. 4.2 shows the
Downs cell which consists of an iron box
lined with brick. The graphite anode is
separated from the circular steel cathode by
a steel wire gauze so that the products of
electrolysis do not mix and can be collected
separately.
chlorine gas
sodium
metal
iron cathode
carbon (graphite) anode
Fig. 4.2 The Downs cell
54
The fused sodium chloride is placed in
the cell and maintained in the molten state
by heat from an electric current of up
to 30 000 amperes. An excess of calcium
chloride is usually added to lower the
melting point of the sodium chloride to
about 873 K. Fused sodium chloride melts
at about 1 073 K which is close to the
boiling point of sodium which is 1 106 K.
The molten sodium collects in the
cathode apartment where it rises to the top
and is tapped off via a pipe. The gaseous
chloride is guided by a hood and collected
from another pipe. Fused sodium chloride
contains sodium and chloride ions.
NaCl → Na+ + Cl-
At the Cathode, the Na+ ions receive an
electron each to become metallic sodium.
Hence, the sodium ion is said to be reduced
at the cathode.
Na+ + e- → Na
The chloride ions give up an electron each
to become atomic chlorine which then pair
sodium chloride feed
iron gauze diaphragm
fused sodium chloride
up to form gaseous chlorine molecules. 2 With air and plentiful supply of
Hence, the chloride ion is said to be oxygen
oxidised at the anode. It burns with a golden yellow flame
2Cl- - 2e- → Cl2(g) to form the higher oxides.
or Cl- - e- → Cl 2Na(S) + O2(g) → Na2O2(s)
Cl + Cl → Cl2(g) (sodium peroxide)

Sodium is always stored under

Physical properties of sodium paraffin oil, toluene or naphthalene
Appearance – sodium is a because of its great reactivity with the
silvery soft solid atmospheric gases.
with a metallic
3 Reaction with cold water
lustre.
Sodium reacts very vigorously with
Flame colour - bright yellow
cold water. The reaction may even be
Electrode potential - 3.02 volts
explosive because of the large amount
Melting point - 371 K
of heat evolved.
Boiling point - 1 156 K
This is another reason why it is stored
Density - 0.97 gcm-3
under oil.
Outer electronic
2Na(s) + H2O(I) → 2NaOH(aq) + H2(g)
configuration - 2p63s1
First ionisation energy - 493.24 kJmol-1 4 Reaction of sodium with ammonia
Sodium reacts with ammonia,
Chemical properties of sodium liberating hydrogen and forming
1 With air and limited supply of sodamide.
oxygen 2Na(s) + 2NH3(g) → 2NaNH2(s) +H2(g)
a) Sodium metal tarnishes rapidly
5 Reaction with dilute acids
when exposed in air because it is
It reacts explosively with dilute acids,
readily oxidised by atmospheric
liberating hydrogen gas and forming
oxygen to form the sodium
a salt. (It is not advisable to carry out
oxide.
this experiment in the laboratory.)
4Na(s) + O2(g) → 2Na2O(s) 2Na(s) + 2HCl(aq) → 2NaCl + H2(g)
b) Sodium oxide then reacts
with moisture to form sodium 6 Reaction with non-metals
hydroxide. Sodium combines directly on heating
with most non-metals except boron,
Na2O(s) + H2O(I) → 2NaOH(aq)
carbon and nitrogen.
c) Sodium hydroxide then reacts
3Na(s) + P(s) → Na3P(s)
with carbon(IV) oxide present
(trisodium phosphide(III)
in the air to form sodium
2Na(s) + S(s) → Na2S(s)
trioxocarbonate(IV).
(disodium sulphide)
2NaOH(aq) + CO2(g) → Na2CO3(aq)
2Na(s) + Cl2(g) → 2NaCl(s)

+H2O(I) (sodium chloride)

55
Uses of sodium
1 It is used to prepare sodium peroxide
which is used in hospitals to clean
wounds.
2 It is used in making alloys, e.g. as an
alloy with lead in the preparation
of lead(IV) tetraethyl which is an
antiknock agent in petrol.
3 It is used in the preparation of
important compounds, such as
sodamide and sodium cyanide used
in the extraction of gold from its
compounds.
4 It is used in sodium vapour lights
which give a bright yellow colour for
street lighting.
5 As a heat conductor in nuclear
reactors, sodium acts as a coolant
which conducts heat away from the
system, bringing cooling effects.
6 It is used as a reducing agent in the
extraction of titanium. Sodium and
ethanol mixture is used as a reducing
agent in organic chemistry. Sodium
amalgam (in water) is also used as a
reducing agent in organic chemistry.
spent brine
amalgam
Fig. 4.3 Mercury cathode cell
56
Sodium hydroxide
This is commonly known as caustic soda.
Laboratory preparation of sodium
hydroxide
Sodium hydroxide can be prepared in
the laboratory by adding excess calcium
hydroxide (slaked line) to sodium
trioxocarbonate(IV) solution (washing
soda) in a beaker.
The mixture is heated until the double
decomposition reaction is complete. A
white solid of calcium trioxocarbonate-
(IV) is formed and this is filtered off.
The solution left behind is concentrated
to dryness in an iron dish to give fused
sodium hydroxide.
Na2CO3(s) + Ca(OH)2(aq) → 2NaOH(aq) +
CaCO3(s)
Sodium hydroxide solution is also
produced in the laboratory by the action
of sodium on water. A dilute solution of
the hydroxide is obtained in this reaction.
chlorine
brine
mercury
2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g)
Commercial production of sodium
hydroxide
Two electrolytic methods are used in the
manufacture of sodium hydroxide. These
methods are:
1 Mercury cathode cell method, and
2 Diaphragm cell method.
The mercury cathode cell method
Fig. 4.3 shows the mercury cathode cell
which is made up of graphite anodes which
dip into a concentrated solution of brine. A
layer of mercury, which acts as the cathode,
covers the floor of the cell.
brine in
hydrogen
out
graphite anode
brine
Fig. 4.4 Diaphragm cell
Chemistry of the reaction
Concentrated brine solution contains the
ions Na+ Cl- and H+ OH-.
The concentration of sodium and chloride
ions is higher than the concentration of
hydrogen and hydroxide ions. At the
cathode, sodium ions, being more easily
discharged than hydrogen at the mercury
cathode, form a solution of sodium in
mercury. This solution is known as sodium
amalgam. Note that Sodium amalgam
is not a compound of definite atomic
proportions, hence it is represented as Na/
Hg.
Na+ + e- → Na(s)
Na(s) + Hg(I) → Na/Hg(I)
+ve
chloride out
–ve
spent brine out
steel net cathode
porous
diaphragm
sodium
hydroxide
solution
57
 The sodium amalgam is allowed to
flow into a reservoir which contains
water. The amalgam reacts with the water
decomposing it to form sodium hydroxide
solution, and hydrogen gas is liberated.
2Na/Hg(I) + 2H2O (I) → 2NaOH + H2(g)+ 2Hg(I)
The sodium hydroxide solution so
obtained is concentrated by heating in iron
pans to obtain fused sodium hydroxide
from which pellets or flakes are obtained.
The mercury produced is returned to the
electrolytic cell to pass through the process
again.
Diaphragm cell method
In the diaphragm cell method, sodium
chloride solution is put into a porous
asbestos vessel. Carbon rods serve as the
anode while the cathode is a steel net used
in covering the outer surface of the asbestos
(Fig. 4.4). The solution oozes through the
asbestos vessel to the cathode as electrical
contact is made.
Chemistry of the reaction
At the cathode, hydrogen ions are
discharged. The sodium ions left behind
in the solution form sodium hydroxide
with hydroxyl ions. The sodium hydroxide
is then drained off from the solution. At the
anode, chlorine ions are discharged; they
form chlorine molecules which are allowed
to escape through a tube as shown in
Fig. 4.4. The reaction is as follows:
H2O(l) → H+(aq) + OH-(aq)
NaCl(aq) → Na+(aq) + Cl-(aq)
Na+(aq) + OH-(aq) → NaOH(aq)
2Cl-(aq)-2e → Cl2(g)
2H+(aq) + 2e → H2(g)
58
Physical properties of sodium hydroxide
1 Sodium hydroxide is a white cry-
stalline solid. Its crystals deliquesce
when exposed in air to form sodium
hydroxide solution.
2 It readily dissolves in water with
evolution of heat, giving a strong
alkaline solution. It is also soluble in
ethanol.
3 Sodium hydroxide solution, as a
strong alkali, turns red litmus paper
blue.
Experiment 4.4
Aim
Investigating the physical properties of
sodium hydroxide
Procedure
1 Put a few sodium hydroxide pellets in
a watch glass for a few minutes and
record your observations.
2 Put some of the pellets in water and in
ethanol. What are your observations?
3 With litmus papers, test the product
obtained in (1) and record your
observations.
Chemical properties of sodium hydroxide
1 Sodium hydroxide is a strong electro-
lyte which ionises completely in
solution.
NaOH(aq) → Na+(aq)+OH-(aq)
2 It is a typical base, neutralising all
acids however weak to form the
appropriate salt and water.
NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(I)
2NaOH(aq) + H2SO4(aq) → Na2SO4(aq) +
2H20(l)
 NaOH(aq) + HNO3(aq) → NaNO3(aq) +
H2O(I)
Ionically,
H3O+(aq) + OH-(aq) → 2H2O(I)
or H+(aq) + OH- (aq) → H2O(I)
3 Sodium hydroxide reacts with acidic
oxides to form normal or acid salts.
For example, it reacts with sulphur(IV)
oxide, SO2 to form the sulphate(VI) or
the hydrogen sulphate(IV) of sodium.
2NaOH(aq) + SO2(g)→ Na2SO4(aq) + H2O(I)
NaOH(aq) + SO2(g) → NaHSO3(aq)
4 Sodium hydroxide, when exposed,
readily absorbs carbon(IV) oxide, a
weak acidic oxide, to form sodium
trioxocarbonate(IV).
2NaOH(aq) + CO2(g)→ Na2CO3(aq) +
H2O(I)
5 When warmed together with any
ammonium salt, sodium hydroxide
solution liberates ammonia gas. The
ammonia gas given off turns moist
red litmus paper blue. This is the test
for ammonium salts.
NH4Cl(3) + NaOH(aq) → NaCl (aq) + NH 3 (g)
(ammonia)
+ H2O(I)
NH4NO3(s) + NaOH(aq) → NH3(g)+
NaNO3(aq) + H2O(I)
6 Sodium hydroxide reacts with
soluble salts of iron, tin, copper,
zinc, aluminium and lead to form
their insoluble hydroxides by double
decomposition. The precipitates
produced by compounds of iron
and copper do not dissolve in excess
sodium hydroxide solution.
FeSO4(aq) + 2NaOH(aq) → Fe(OH)2(s) +
Na2SO4(aq)
FeCl3(aq) + 3NaOH(aq) → Fe(OH)3(s) +
59
3NaCl(aq)
CuSO4(aq) + 2NaOH(aq) → CU(OH)2(s)
+ Na2SO4(aq)
Ionically,
Fe2+(aq) + 2Na+OH-(aq) → Fe(OH)2(s) +
2Na+(aq)
Cu2+(aq) + 2Na+ OH-(aq) → Cu(OH)2(s) +
Na2SO4(aq)
The hydroxides of zinc, lead, aluminium
and tin dissolve in excess sodium hydroxide
solution and are said to be amphoteric.
ZnSO4(aq) + 2NaOH(aq) → Zn(OH)2(s) +
Na2SO4(aq)
Zn(OH)2(s) + 2NaOH(aq) →
Na2Zn(OH)4(aq) +
(sodium zincate solution)
2H2O(I)
Ionically,
Zn(OH)2(s) + 2OH-(aq) → Zn(OH)2-4(aq)
7 Aluminium and zinc readily
dissolve in hot concentrated sodium
hydroxide solution to form sodium
aluminate and sodium zincate
respectively with the evolution of
hydrogen gas.
2Al(s) + 2NaOH(aq) + 6H2O(I) →
2NaAl(OH)4 + 3H2(g)
Zn(s) + 2NaOH(aq) + 2H 2O(I) →
Na2Zn(OH)4(aq) + H2(g)
8 Cold dilute sodium hydroxide
solution reacts with chlorine gas
to produce sodium chloride, water
and a pale yellow solution of
sodiumoxochlorate(I) .
2NaOH(aq) + Cl2(ag) → NaCl(aq) + H2O(I)
+ NaClO(aq)
(sodiumoxochlorate(I))
Hot concentrated sodium hydroxide
solution reacts with chlorine gas to
 form sodium chloride, water and
sodium trioxochlorate(V)
6NaOH(aq) + 3Cl2(g) → 5NaCl(aq) +
3H2O(I) + NaClO3(aq)
9 Sodium hydroxide reacts with a
variety of other non-metals, such as
the halogens, phosphorous, sulphur
and silicon to form sodium salts.
4F(g) + 4NaOH(aq) → 4NaF(aq) + 2H2O (I)
+ O2 (g)
10 Concentrated and dilute sodium
hydroxide solutions, as well
as molten sodium hydroxide,
react with glass to form sodium
trioxosilicate(IV) .
SiO2(s) + 2NaOH(s) → Na2SiO3(s) + H2O(g)
This explains why glass stoppers
become glued to reagent bottles
containing the sodium hydroxide
and why burette taps tend to stick
after the solution has been used in
the burette. Thus, sodium hydroxide
is stored in bottles with rubber
stoppers.
Experiment 4.5
Aim
To investigate the chemical properties
of sodium hydroxide
Reaction with acids
Watch your teacher prepare 2 M hydrochloric
acid and 2 M sodium hydroxide solution.
Add 2 or 3 drops of methyl orange
indicator to 20 cm3 or 25 cm3 of the 2 M
sodium hydroxide prepared, then add 2
M hydrochloric acid until the first colour
change is obtained. Repeat the experiment,
using 1 M H2SO4 (tetraoxosulphate(VI)
acid). Pass sulphur(IV) oxide into a test tube
60
containing some of the sodium hydroxide
solution. Record all your observations.
Reaction with sodium hydroxide with
ammonium salts
Prepare solutions of the following:
ammonium chloride, diammonium
tetraoxosulphate(VI), and ammonium
trioxonitrate(V). Add about 5 cm 3 of
sodium hydroxide solution to about 5 cm3
of the already prepared ammonium salt
solutions in test tubes. Warm gently. Test
the gas given off with moist litmus paper.
Identify the gas evolved.
Precipitation of insoluble hydroxides
Using different test tubes, prepare solutions
of iron(II) tetraoxosulphate(VI), iron(III)
chloride, zinc tetraoxosulphate(VI), lead(II)
trioxonitrate(V) and tin(II) chloride.
To each of the solutions so prepared,
first add a few drops of bench sodium
hydroxide solution and then excess. Record
all your observations.
Reaction with metals
Place a piece of aluminium foil and zinc
metal in two different beakers. Add hot
concentrated sodium hydroxide solution
to each beaker. Record your observations.
The experiment should be carried out in a
fume cupboard.
Reaction with non-metals
Prepare some chlorine gas and pass into
two different test tubes containing cold
dilute sodium hydroxide solution and hot
concentrated sodium hydroxide solution
respectively. What do you observe?
Uses of sodium hydroxide
In the laboratory it is used:
1 as a strong alkali in the neutralisation ammoniacal
of acids to form mineral salts; brine
2 as an analytical agent; waste gas
3 as a precipitating agent in the
preparation of insoluble metallic
hydroxides; and
4 for absorbing carbon(IV) oxide gas.
In industry, it is used in:
1 the manufacture of soap;
2 the manufacture of artificial silk
(rayon);
3 the manufacture of paper;
4 the extraction of aluminium from its
ores;
5 the refining of petroleum;
6 the bleaching of cotton textiles; and
7 making certain compounds, such as
phosphine, sodium methanoate, and
sodium trioxochlorate(V) .

Sodium trioxocarbonate(IV) carbon(IV)

In reality, this is a salt but we are treating it
here as an alkali in order to show the uses
of alkalis. Sodium trioxocarbonate(IV) is
often called a milk alkali because it has an
alkaline reaction with indicators.
Production of Sodium trioxocarbonate
(Solvay process)
Sodium trioxocarbonate(IV) is produced
industrially by the Solvay process or
ammonia-soda process. The raw materials
used are sodium chloride and limestone.
The basic reaction takes place between
carbon(lV) oxide and concentrated brine
saturated with ammonia. The limestone is
heated to give carbon(IV) oxide which is
then forced up the tower (Fig. 4.5).
CaCO3(s) → CaO(s) + CO2(g)
Concentrated brine, saturated with
ammoniacal brine, is poured down the
oxide sludge of
NaHCO3 in
NH4Cl solution
Fig. 4.5 The Solvay process
Solvay tower where it comes in contact
with carbon(IV) oxide forced up the tower.
The perforated metal plates in the tower
break the ammoniacal brine solution into
a fine spray, thus causing effective contact
between the brine and the ascending
carbon(IV)oxide. Ammonium hydrogen
trioxocarbonate(lV) is first formed and
sodium hydrogen trioxocarbonate(IV) is
produced later.
NH3(g) + H2O(I) + CO2(g) → NH4HCO 3 (aq)
NH4HCO3(aq) + NaCl(s) → NH4Cl(s) +
NaHCO3(aq)
Sodium hydrogen trioxocarbonate(IV),
being insoluble, is precipitated at the

61
bottom of the tower, filtered, dried and
then heated to give anhydrous sodium
trioxocarbonate(IV) and soda ash.
2NaHCO3(s) → Na2CO3(s) + H2O(I)+CO2(g)
Crystals of sodium trioxocarbonate(IV) are
obtained by dissolving anhydrous sodium
trioxocarbonate(IV) in hot water followed
by the process of crystallisation.
Na2CO3(s) + 10H2O(l) → Na2CO310H2O(s)
(washing soda)
The Solvay process is economical
and can be made to be continuous.
The carbon(IV) oxide produced in the
decomposition of sodium hydrogen
trioxocarbonate(IV) is used again in the
tower. More ammonia gas is produced by
the action of heat on ammonium chloride
and slaked lime. The slaked lime is
obtained by the reaction between calcium
oxide, produced in the decomposition of
calcium trioxocarbonate(IV) and water.
CaO(s) + H2O(l) → Ca(OH)2(s)
Ca(OH)2(s) + 2NH4Cl(s) → 2NH3(g) + 2H2O(1)
+ CaCl2(s)
The only waste product in the Solvay
process is calcium chloride.
Laboratory preparation of sodium
trioxocarbonate(IV)
Sodium trioxocarbonate(IV) can be
prepared in the laboratory by passing
carbon(IV) oxide into sodium hydroxide
solution until a white solid of sodium
trioxocarbonate(IV) is formed. This is
filtered off.
2NaOH(aq) + CO2(g) → Na2CO3(s) + H2O(l)
Physical properties of Sodium
trioxocarbonate(IV)
1 The anhydrous sodium trioxo-
carbonate(IV) is a white powder
62
while the hydrated salt is in the form
of large colourless crystals.
2 Both forms of sodium trioxo-
carbonate(IV) are soluble in water.
3 The solution of sodium trioxo-
carbonate(IV) in water turns red
litmus paper blue.
Chemical properties of sodium
trioxocarbonate(IV)
1 A solution of sodium trioxo-
carbonate(IV) in water is alkaline
to litmus because it hydrolyses to
form a strong alkaline solution. The
trioxocarbonate(IV) acid produced is
too weak to have any dominant effect
on the litmus.
Na2CO3(s) + 2H2O(1) → H2CO3(aq) +
2NaOH(aq)
This reaction also explains why sodium
trioxocarbonate(IV) is generally used
in acid – base titration as a base even
though it is classified as a salt.
2 Sodium trioxocarbonate(IV) is
unaffected by heat. It does not
decompose on heating.
3 Dilute acids liberate carbon(IV)
oxide from sodium trioxo-
carbonate(IV) to form the corres-
ponding salt.
Na2CO3(s) + H2SO4(aq) → + Na2SO4(aq)
+H2O(l) + CO2(g)
Na2CO3(s) + 2HCl → (aq) 2NaCl(s) + H2O(1)
+ CO2(g)
4 Sodium trioxocarbonate(IV) solu-
tion precipitates carbonates from
the solutions of most metallic salts
(ammonium and potassium are
exceptions).
 CaSO4(aq) + Na2CO3(aq) → CaCO3(s) + Experiment 4.6
Na2SO4(aq)
MgSO4(aq) + Na2CO3(aq) → MgCO3(s) +
Na2SO4(aq)
Salts of zinc, copper, iron and metals
below sodium in the activity series
have their basic carbonates precipitated
from their solutions.
The formation of the basic carbonates
involves the hydrolysis of sodium
trioxocarbonate(IV) with water.
Na 2 CO 3(s) + 2H 2 O (l) → H 2 CO 3(aq) +
2NaOH(aq)
The products of hydrolysis then react
with the metallic salt in solution.
H2CO3(aq) + 2NaOH(aq)+ 2FeCl2(aq)→
FeCO3(s) + Fe(OH)2 + 2NaCl(aq)
+ 2HCl(aq)
H2CO3(aq) + 2NaOH(aq) + 2CuSO4(aq) →
CuCO3(s).Cu(OH) 2 (aq) + Na2 SO4(aq)
+ H2SO4(aq)
H2CO3(aq) + 2NaOH(aq) + 2ZnCl2(aq) →
ZnCO3(s).Zn(OH)2(s) + 2NaCl(aq)
+ 2HCl(aq)
Experiment 4.5
Aim
To investigate the physical properties of
sodium trioxocarbonate(IV)
Procedure
Examine a little quantity of anhydrous
sodium trioxocarbonate(IV) and hydrated
sodium trioxocarbonate(IV) -10-water in
different watch glasses. Add water to some
of the anhydrous salt in a test tube and test
the solution with litmus
paper. Record your observations.
63
Aim
Investigating the chemical properties of
sodium trioxocarbonate(IV)
Procedure
Put a small quantity of the anhydrous
sodium trioxocarbonate(IV) in a test
tube and heat strongly. Record your
observations.
Reaction with acid
Put a small quantity of sodium
trioxocarhonate(IV) in a test tube and add
some dilute hydrochloric acid. Pass the
gas liberated into lime water. Record your
observations.
Reaction with metallic salts
In a test tube, prepare solutions of iron(II)
chloride, magnesium tetraoxosulphate(VI)
and copper(II) tetraoxosulphate(VI). To
each solution so prepared, add sodium
trioxocarbonate(IV) solution. Record all
your observations as usual.
Reaction of sodium trioxocarbonate(IV)
with air
Weigh a sample of washing soda (hydrated
salt Na2CO3.1OH2O) and leave it exposed
for some days. Weigh the sample again.
Record your result and give explanations
for your observation.
Washing soda effloresces in air to
produce a layer of fine white powder
around the crystals. The salt loses nine of
its ten molecules of water of crystallisation.
Thus there is a loss in mass at the end of
the experiment due to the water molecules
lost.
Na2CO3.1OH2O → Na2CO3.H2O(s) + 9H2O(g)
Experiment 4.7
Aim
To investigate some properties of sodium
hydrogen trioxocarbonate(IV)
Procedure
l a) Put a small quantity of sodium
hydrogen trioxocarbonate(IV) in a
test tube and heat strongly.
b) Test the product (if any) with moist
blue litmus paper.
c) Record all your observations and,
using equations where possible,
draw inferences.
2 Prepare dilute solutions of
iron(II) chloride and magnesium
tetraoxosulphate(VI).
Place about 2 cm 3 of each of the
solutions in separate test tubes. To each
of the solutions in the test tube, add
about equal volumes of sodium hydrogen
trioxocarbonate(IV) solution.
Record all your observations and draw
inferences.
Your teacher will supply you with 2 cm3
of the following:
a) Iron(II) chloride solution,
b) Zinc(II) chloride.
To each of these solutions in a test tube,
add about 4 cm 3 of sodium hydrogen
trioxocarbonate(IV).
Record all your observations and draw
inferences.
Uses of sodium trioxocarbonate(IV)
1 In the manufacture of detergents.
2 To soften hard water.
3 As a cleansing agent.
4 In making soap.
5 In the manufacture of glass.
64
6 As an alkali in volumetric analysis.
7 As a precipitating agent for metallic
trioxocarbonates in qualitative analysis.
Sodium hydrogen trioxcarbonate(IV)
I n d u s t r i a l l y, s o d i u m h y d r o g e n
trioxocarbonate(IV) is manufactured in
the Solvay process. In the laboratory, it is
prepared by passing carbon(IV) oxide into
a strong solution of sodium hydroxide until
the sodium hydrogen trioxocarbonate(IV)
separates out.
2NaOH(s) + 2H2O(l) + 2CO2(g) → 2NaHCO3(s)
+ 2H2O
Properties of sodium hydrogen
trioxocarbonate(IV)
Sodium hydrogen trioxocarbonate(IV)
is less soluble in water than sodium
trioxocarbonate(IV) and decomposes on
heating to sodium trioxocarbonate(IV),
carbon(IV) oxide and water.
2NaHCO3(s) → Na2CO3(s) + 2CO2(g) + H2O(l)
It is decomposed by all acids, for example,
NaHCO3(s) + HCl(aq) → NaCl(aq) + H2O(l)
+ CO2(g)
Uses of sodium hydrogen trioxo-
carbonate(IV)
1 In the manufacture of baking powder.
When mixed with tartaric acid and
heated, it gives carbon(IV) oxide
which makes the cake and loaf of
bread rise.
2 As a health salt for indigestion caused
by excess acid in the stomach.
3 In fire extinguishers.
4 In the precipitation of normal
trioxocarbonates of some metals, e.g.
 2NaHCO3(aq) + FeCl2(aq)→ FeCO3(s) +
2NaCl(aq) + H2CO3(aq)
2NaHCO3(aq) + ZnCl2(aq) → ZnCO3(s) +
2NaCl(aq) + H2CO3(aq)
Sodium chloride
Sodium chloride is the so-called common
salt which is in daily use in every home. It
occurs naturally as a solid in the form of
rock salt deposits in Cracow, Poland and
certain other parts of the world, and as a
solution in seawater. This is why seawater
tastes salty.
Extraction of sodium chloride
In the solid form, sodium chloride is mined
directly. In solution form, it is pumped up
through a hole drilled in the ground. The
brine so obtained is concentrated by passing
it through series of vacuum evaporators.
Common salt obtained in this way contains
small quantities of magnesium chloride
as impurity. Commercial sodium chloride
contains hygroscopic impurities, and so, it
absorbs water and dissolves in water.
To k e e p s a l t d r y, m a g n e s i u m
trioxocarbonate(IV) is added in small
quantities. This is because magnesium
trioxocarbonate(IV) is non-deliquescent.
Also magnesium trioxocarbonate(IV) will
react with the hygroscopic impurities to
form non-hygroscopic products.
Uses of sodium chloride
1 As table salt in our diet because
it supplies necessary mineral
substances.
2 In preserving and seasoning food.
3 In the production of sodium
65
trioxocarbonate(IV) by the Solvay
process.
4 As an industrial source of sodium and
chlorine.
5 As a ‘salting-out’ agent in the
manufacture of soap.
6 In the manufacture of bleach.
7 For glazing pottery.
Sodium trioxonitrate(V)
Sodium trioxonitrate(V) occurs naturally
in mineral deposits in Chile. It is known
commercially as Chile saltpetre.
Properties of sodium trioxonitrate(V)
Sodium trioxonitrate(V melt at 589 K
(316°C) and decomposes on further
heating to give oxygen and sodium
dioxonitrate(III), NaNO2.
2NaNO3(s) → 2NaNO2(s) + O2(g)
Uses of sodium trioxonitrate(V)
1 Sodium trioxonitrate(V) is used as a
fertiliser.
2 It is used in the manufacture of
other chemicals, such as sodium
dioxonitrate(III), NaNO2, which is
used extensively in the manufacture
of aniline dyes.
Sodium tetraoxosulphate(VI)
Sodium tetraoxosulphate(VI) is prepared
in the laboratory by neutralising dilute
tetraoxosulphate(VI) acid with an
appropriate amount of sodium hydroxide,
followed by crystallisation.
2NaOH(aq) + H2SO4(aq) → Na2SO4(aq) +
2H2O(l)
NaOH(aq) + H2SO4(aq) → NaHSO4(aq) + H2O(l)
 I n i n d u s t r y, s o d i u m t e t r a o x o -
sulphate(VI) is manufactured by heating
sodium chloride with tetraoxosulphate(Vl)
acid.
2NaCl(s) + H2SO4(aq) → Na2SO4(s) + HCl(g)
Sodium tetraoxosulphate(VI) is known
as Glauber’s salt commercially. Sodium
tetraoxosulphate(VI) crystallises as
Na2SO4. 10H2O. It forms alums and double
sulphates.
Uses of sodium tetraoxosulphate(VI)
1 Sodium tetraoxosulphate(VI) is used
in the glass manufacturing industry.
2 It is used as a purgative, under the
patent name, Glauber’s salt.
3 Sodium tetraoxosulphate(VI) is used
to treat wood-pulp for papermaking.
Sodium hydrogen tetraoxo-
sulphate(VI)
Sodium hydrogen tetraoxosulphate(VI) is
prepared in the laboratory by the reaction
between sodium trioxocarbonate(IV) and
excess tetraoxosulphate(VI) acid.
Na2CO3(s) + 2H2SO4(aq) → 2NaHSO4(aq)
+ CO2(g) + H2O(l)
It is also prepared by neutralising dilute
tetraoxosulphate(VI) acid with an
appropriate amount of sodium hydroxide.
NaOH(aq) + H2SO4(aq)→ NaHSO4(aq) + H2O(1)
In industry, sodium hydrogen tetraoxo-
suphate(VI) is produced as a by-product in
the manufacture of hydrogen chloride as
shown in the reaction:
66
NaCl(s) + H2SO 4(aq) → NaHSO4(aq) + HCl(g)
Sodium hydrogen tetraoxosulphate(VI)
crystallises as a monohydrate NaHSO4.
H2O.
Properties of sodium hydrogen
tetraoxosulphate(VI)
Sodium hydrogen tetraoxosulphate(VI) is
a salt and behaves as a dilute solution of
tetraoxosulphate(VI) acid. It reacts with
sodium chloride when heated to give
hydrogen chloride.
NaCl(S) + H2SO4(aq) → NaHSO4(aq) + HCl(g)
Sodium peroxide
This is a pale-yellow solid which is formed
when sodium metal burns in plentiful
supply of air.
2Na(S) + O2(g) → Na2O2(s)
Reactions of sodium peroxide
It forms sodium hydroxide solution with
water.
2Na2O2(s) + 2H2O(l) → 4NaOH(aq) + O2(g)
Hydrogen peroxide is formed when
sodium peroxide reacts with ice-cold water
and dilute acid:
Na2O2(s) + 2H2O(l) → H2O2(aq) + 2NaOH(aq)
Na2O2(s) + 2HCl(aq) → H2O2(aq) + 2NaCl(aq)
Sodium peroxide is used as a cleansing
agent.
Summary
This chapter has taught the following:
• Lithium, sodium, potassium,
rubidium, caesium and francium
occupy the Group IA of the periodic
 table and are commonly referred to as
the alkali metals.
• General notes on the family:
a) They all have one valency electron.
b) They are all strongly electro-
positive.
c) They tend to lose their single
outer electron due to relatively
low first ionisation energies and
form ions.
d) They form ionic compounds.
e) Nearly all their salts are soluble
in water.
f) Their oxides are basic.
g) They impart characteristic colour
to the flame.
h) They exhibit physical properties
which show gradation down the
group.
• The metals (except lithium) are
highly reactive and are powerful
reducing agents, reacting with air,
water and most non-metals. They
form white crystalline ionic salts
with high melting and boiling points.
• Lithium shows properties which
differ from those of the other
members of the group. Lithium
shows a diagonal relationship with
magnesium. Its compounds are more
covalent.
• Sodium is a very reactive element,
reacting with air, water and with some
non-metals to form corresponding
compounds.
• Sodium is very useful in the
preparation of many important
compounds. It is also useful as a
reducing agent and as a conductor
of heat and electricity.
• Sodium hydroxide, an important
compound of sodium, is prepared
67
on a small scale in the laboratory.
Industrially, it is produced by the
electrolysis of concentrated sodium
chloride solution (brine), using: (a)
mercury cathode cell or
(b) diaphragm cell.
• Sodium hydroxide is a white,
crystalline, deliquescent solid,
soluble in water with production of
heat.
• Sodium hydroxide is useful as a
precipitating agent, precipitating
insoluble metallic hydroxides from
solutions of their salts in qualitative
analysis.
• Sodium trioxocarbonate(IV) is
produced industrially by the Solvay
process using ammoniacal brine and
limestone. It is also prepared on a
small scale in the laboratory.
• Sodium trioxocarbonate(IV) is not
decomposed by heat, but it reacts
with air, acid, water and metallic
salts.
• Other important compounds of
sodium are:
a) Sodium hydrogen trioxo-
carbonate(IV) and sodium
chloride (common salt). They
are both useful in everyday
life and in the manufacturing
industry.
b) Sodium trioxonitrate(V), used
as fertiliser, and in industry.
Sodium tetraoxosulphate, used
in the manufacture of glass.
c) Sodium hydrogen tetraoxo-
sulphate(VI).
d) Sodium peroxide.
 6 Sodium hydroxide is
Review questions
A manufactured by the Solvay
process.
A Multiple-choice questions
B a strong alkali used in
1 Alkali metals form
precipitating insoluble metallic
A the first column of s-block elements
hydroxides.
in the periodic table.
C used to season food.
B the second column of s-block
D important in the manufacture of
elements.
rubber.
C the s and p-blocks of elements in
E a by-product in the production of
the periodic table.
calcium metal.
D the p-block elements in the
7 Which sodium salt is most likely to be
periodic table.
used as a fertiliser?
E the d-block elements in the
A Sodium trioxonitrate(V)
periodic table.
B Sodium sulphide
2 Sodium metal
C Sodium cyanide
A has a very high density.
D Sodium hydrogen trioxo-
B is a strong reducing agent.
carbonate(IV)
C is stored under water.
E Sodium tetraoxo-
D is extracted as an impurity in
sulphate(VI)
the electrolysis of brine.
8 Sodium trioxocarbonate(IV) is
E ionises by electron loss.
A used in the baking industry.
3 Sodium is prepared industrially by
B used in most laundry detergents.
A oxidation of sodium hydroxide.
C decomposed by heat.
B heating sodium trioxo-
D a product of the Haber process.
carbonate(IV).
E found naturally in nature.
C the electrolysis of brine.
9 In a saturated solution of brine,
D reduction from molten sodium
A no sodium chloride is
chloride.
dissolving.
E heating the sodium oxide.
B no sodium chloride is
4 Sodium compounds colour a flame
evaporating.
A brick-red.
C there is no net change in the
B violet.
amount of sodium chloride in the
C bright yellow.
solution.
D scarlet.
D no ions exist.
E blue.
E none of the above obtains.
5 Pure sodium chloride is
10 Electronegativity of a substance
A deliquescent.
describes
B cubic in crystalline structure.
A the tendency of an atom to become
C found in seawater.
negatively-charged.
D used for preservation of food.
B the tendency of an atom to become
E found in seashells.
positively-charged.

68
 C the tendency of an atom to lose
electrons.
D the reduction process.
E the repulsion of an element for
electrons in a particular
situation. 5
B Short-structured questions
1 Use the electronic structures of the
alkali metals to explain the following
observations.
a) The metals have similar physical
properties.
b) The metals have low melting and
boiling points. hydroxide is added in drops and then
c) The metals have low densities.
d) A l l t h e e l e m e n t s i m p a r t a
characteristic colour on the flame.
2 Give reasons for the following:
a) The first three alkali elements are
stored under paraffin.
b) The rest of the elements in the
group are stored in vacuo.
c) Sodium is used as a coolant in
nuclear reactors.
3 a) Name the two types of cells used
in the manufacture of sodium
hydroxide, and give the electrodes
used in the two cells respectively.
b) Using equations only, show how
sodium hydroxide reacts with
tetraoxosulphate(VI) acid.
c) List two important uses of sodium
hydroxide in industry.
4 Sodium trioxocarbonate(IV) is
produced industrially.
a) Name the process.
b) Give the raw materials used for
this industrial production.
c) Give the chemistry of the reaction
69
leading to the formation of the
sodum trioxocarbonate(IV) in the
last stage, using equations only.
d) Name the only waste product in
this process.
Give two uses of each of the following
sodium compounds:
a) sodium chloride
b) sodium trioxonitrate(V)
c) sodium trioxocarbonate(IV)
C Essay-type questions
1 Describe with equations what
happens when a solution of sodium
in excess to the following solutions:
a) calcium chloride
b) aluminium trioxonitrate(V)
c) iron(III) chloride
d) iron(II) tetraoxosulphate(VI)
e) copper(II)tetraoxosulphate(VI)
2 a) Describe in detail how you can
obtain a pure sample of sodium
chloride from a named source.
b) Why is the common salt purchased
in the market deliquescent?
3 Using the trioxocarbonate(IV) salts of
metals, describe the decreasing activity
of metals arranged in order of the
activity series.
4 Describe how you would prepare
crystals of sodium trioxocarbonat(IV)
10-water in the laboratory. Give two
important uses of the salt.
5 a) H o w i s s o d i u m h y d ro x i d e
obtained by the mercury cathode
cell?
b) Using equations only, show how
sodium hydroxide reacts with
chlorine.
 5 Alkaline earth metals:
Group IIA elements
Introduction
Group IIA of the periodic table consists
of the elements beryllium, magnesium,
calcium, strontium, barium and radium.
Radium is radioactive and its chemistry is
very similar to that of barium. The elements
are collectively known as the alkaline earth
metals.
Alkaline earth metals form the second
column of s-block in the periodic table.
They are more electronegative but less
basic than the alkali metals. There is a
marked diagonal relationship between
beryllium and aluminum, between lithium
and magnesium, and between magnesium
and scandium.
Performance objectives
At the end of this chapter, you should be
able to:
1 give the names and symbols of all
the alkaline earth metals;
2 write the electronic structures of the
alkaline earth metals;
3 give the similarities existing between
Group I and Group II metals;
4 explain why there are physical and
chemical similarities between the
members of the Group II metals.
70
5 investigate some of the physical and
chemical properties of members of
the group through experiments;
6 state the occurrence of some of the
metals in nature;
7 give the chemistry involved in the
extraction of calcium as a member
of the group;
8 state the properties of a given
calcium compound;
9 state the uses of calcium and
compounds of calcium; and
10 explain the nature of cement, mortar
and plaster, and give their uses.
Occurrence of alkaline earth metals
The alkaline earth metals are too reactive
to occur free in nature. All the elements
occur as carbonates and sulphates. Calcium
occurs as trioxocarbonate(IV), CaCO3, in
limestone, marble, chalk, argonite, coral
and calcite. It occurs as sulphate(VI) in
gypsum, CaSO4.2H2O, and the anhydrite,
CaSO4.. Magnesium occurs as sulphate in
MgSO4. 2H2O, and MgSO4.7H2O (Epsom
salt). Barium also occurs as sulphate in
BaSO4.
Calcium occurs as the phosphate ,
3Ca2 (PO4)2, as fluoride in CaF2 (fluospar),
and as double carbonate in dolomite,
(CaCO3.MgCO3). Magnesium and barium
also occur as the carbonate in BaCO3 and
MgCO3) respectively.
Magnesium and calcium compounds,
formed by the weathering of igneous rocks,
are found in all soils and in most fresh
waters as hydrogen carbonates, sulphates
and chlorides, causing hardness of water.
For example, Epsom salt, MgSO4.7H2O,
was isolated from spring water at Epsom
in Surrey, England in 1965. Magnesium is
found in the green compound, chlorophyll
in green plants. Calcium is found in bones
as the double salt 3Ca3(PO4)2. CaCO3.H2O
and as calcium trioxocarbonate(IV), CaCO3
in eggshells and seashells.
Beryllium is found in small quantities as
silicate minerals, phenacite (Be2SiO4) and
beryl (Be3Al2S6O8). Beryllium is not very
abundant, probably because it is difficult
to extract.
Strontium is less abundant, but occurs
as concentrated ores. Radium is extremely
scarce. More is known of its radioactivity
than its chemistry.

Physical properties of alkaline earth metals

The detailed electronic configurations of these elements are as follows:

Be 4 – 1s2 2s2
Mg 12 – 1s2 2s2 2p6 3s2
Ca 20 – 1s2 2s2 2p6 3s2 3p6 4s2
Sr 38 – 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2
Ba 56 – 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2
Ra 88 – 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f14 5d10 6p6 7s2

Table 5.1 Electronic structures of the atoms of the alkaline earth metals

Element Symbol Atomic number Electronic configuration

Beryllium Be 4 2.2

Magnesium Mg 12 2.8.2

Calcium Ca 20 2.8.8.2

Strontium Sr 38 2.8.18.8.2

Barium Ba 56 2.8.18.18.8.2

Radium Ra 88 2.8.18.32.18.8.2

71
1 Each of the metals has two valency
electrons in the outermost shell (Table
5.1), the loss of which converts the
atom into a stable bivalent cation M2+.
The M2+ cations are large and have a
noble gas electronic configuration.
2 Except for barium, the alkaline earth
metals have closely-packed metallic
structures at room temperature.
3 They have stronger metallic bonding
and so are harder, but become
increasingly soft as the atomic number
increases, i.e. down the group. Thus,
they are better conductors of heat and
electricity than the alkali metals.
4 The ionisation energies decrease down
the group as the atomic radii of the
last four metals are large. Thus, the
metals are highly electropositive but
less electropositive than alkali metals.
5 The alkaline earth metal salts are usually
less soluble than the corresponding
alkali metal salts.
6 The metals are denser and more
metallic. They have smaller atomic
volumes than those of the alkali metals
because of high nuclear charge from
beryllium to barium.
7 The metals have higher melting points
than the alkali metals.
8 Like the alkali metals, when heated,
three of the members impart colour to
the flame: calcium imparts brick red,
strontium crimson, and barium green.
9 Calcium and magnesium have a
whitish-grey appearance, beryllium
is very hard while barium is very soft
due to increase in atomic radii.
72
Table 5.2 Physical appearance of alkaline earth
metals
Metal Physical appearance
Be Silvery grey
Mg Silvery white
Ca Silvery whitel
Sr Silvery yellowish
Ba Silvery yellowish
Ra Silvery white
10 Electrode potential decreases down the
group, hence the chemical properties
increase down the group with barium
being the most reactive and magnesium
the least reactive in the group.
11 Beryllium has abnormal chara-cteristics
and a diagonal relationship with
aluminium. For example, beryllium
has a very high melting point, 1 553 K
(1 280°C) and a low density.
Experiment 5.1
Aim
To Investigate some of the physical
properties of the alkaline earth metals
Procedure
1 Examine pieces of magnesium and
calcium. Note the hardness of each
metal. Try to cut each with a knife.
Compare the hardness with that of
alkali metals.
2 Place a tiny piece each of magnesium
and calcium in a deflagrating spoon
and in turn heat each in a Bunsen
burner flame. Note the time it takes for
 the metal to melt and also the colour it
imparts to the flame.
General chemical properties of
alkaline earth metals
1 The most important chemical fact about
the Group IIA elements is that, in the
solid state, they form colourless, large
ionic compounds in which they exhibit an
oxidation state of +2.
2 All the metals tarnish in air, forming a film
of oxide, the speed of the reaction increasing
from beryllium to barium.

Table 5.3 Summary of physical properties of alkaline earth metals

Property Beryllium Magnesium Calcium Strontium Barium

Atomic number 4 12 20 38 56
Outer electronic 1s2 2s2 2p6 3s2 3p6 4s2 4p6 5s2 5p6 6s2
configuration
Atomic mass 9.012 24.312 40.08 87.62 137.34

Metallic radius (Å) 1.12 1.60 1.97 2.15 2.22

Ionic radius (Å) 0.31 0.65 0.99 1.13 1.35

Covalent radius (A) 0.89 1.36 1.74 1.91 1.98

Atomic volume 4.9 14.0 26 33.7 39.3

(cm3 mol-1)

Boiling point (K) 3 243 1 380 1 760 1 607 1 413

Melting point (K) 1 553 923 1 124 1 062 993

Enthalpy of sublimation 322 150 177 163 176

or atomisation (kJmol-1)

Density (gcm-3) 1.55 1.74 1.55 2.6 3.5

Electronegativity 1.5 1.25 1.05 1.0 0.95

(A/R)

Ionisation energy 900 738 590 549 502

(kJmol-1)

Electron affinity - 66 - 67
(kJmol-1)

73
Electrode potential (V) -1.85
Abundance (p.p.m.) 6 20 900
parts per million
Common coordination 2, 4
number
Flame colour
B a r i u m i s s o re a c t i v e t h a t ,
when divided finely, it inflames
spontaneously in air at ordinary
temperatures. In the case of beryllium
and barium, the film of oxide is
protective, preventing further
reaction from taking place. With the
other alkaline earth metals, the film
of oxide is non-protective so that
the action proceeds to completion.
For this reason, it is essential to
store strontium and barium under
paraffin.
3 All the metals burn brilliantly when
heated in air, forming the oxide along
with some nitride. The proportion of
nitride found increases as the group
is descended.
2Mg(s) + O2(g) → 2MgO(s)
2Ca(s) + O2(g) → 2CaO(s)
4 Beryllium does not react at all
with water, cold or hot, because of
the insolubility of its hydroxide.
Magnesium reacts very slowly with
cold water and slowly with boiling
water. Beryllium does not react with
steam, even at red hot, but burning
magnesium burns brilliantly in
steam to form the hydroxide and
hydrogen.
-2.37 -2.87 -2.89 -2.90
36 300 150 430
6 6 6 6
White Brick red Crimson Green
Generally, the reaction with water
increases from beryllium to barium.
Calcium reacts moderately quickly
with cold water, strontium more
quickly and barium vigorously.
Ca(s) + 2H2O(l) → Ca(OH)2(aq) + H2(g)
5 Generally, alkaline earth metals
react with acids as shown in the
equation:
M + 2H+ → M2+ + H2
Reactions of alkaline earth metals
with acids
Alkaline earth metals react with both
dilute and concentrated acids. We shall
consider the reactions of the metals with
hydrochloric acid, trioxonitrate(V) acid and
tetraoxosulphate(VI) acid.
Reactions with dilute hydrochloric acid
Beryllium reacts, when heated with
hydrochloric acid, to give hydrogen. All the
other metals react at room temperature to
give hydrogen. Reactivity increases down
the group.
Ca(s) + 2HCl(aq) → CaCl2(aq) + H2(g)
Ba(s) + 2HCl(aq) → BaCl2(aq) + H2(g)
74
Reactions with dilute trioxonitrate(V) acid Be(s) + 2NaOH(aq) + 2H2O(l) → Na2Be(OH)4(aq)
Dilute trioxonitrate(V) acid does not react
+ H2(g)
with beryllium. All the other alkaline earth Ionically,
metals react with the dilute acid to produce Be(s) + 2OH- + 2H2O(l) → (Be(OH4)2-(aq) + H2(g)
hydrogen.
The other metals do not react appreciably.
However, the hydrogen produced
Beryllium hydroxide is amphoteric in
is quickly oxidised to water due to the
nature.
oxidising power of trioxonitrate(V) acid.

Reactions with concentrated trioxo-

Experiment 5.2
nitrate(V)
Beryllium is rendered passive with
Aim
concentrated trioxonitrate(V) acid.
To investigate the reactions of alkaline
Magnesium reacts vigorously to give
earth metals with air/oxygen
oxides of nitrogen.

3Mg +8HNO3 → 3Mg(NO3)2 + 4H2O + 2N Procedure

Ionically, l In a watch glass, put small pieces each
3Mg + 8H+ + 2NO_ → 3Mg2+ + 4H2O of magnesium and calcium and expose
for 48 hours. What do you observe?
Reactions with dilute tetraoxosulphate(VI) 2 Heat each exposed metal in a
acid deflagrating spoon and, in turns, lower
All the metals, except beryllium, react to the metals into a jar of oxygen. Record
give hydrogen. The reactivity decreases your observations.
down the group. The insoluble sulphates
are correspondingly produced.
Experiment 5.3
Ca(s) + H2SO4(aq) → CaSO4(s) + H2(g)
Ba(s) + H2SO4(aq) → BaSO4(s) + H2(g)
Aim
To investigate the reactions of alkaline
Reactions with concentrated tetraoxo-
earth metals with water
sulphate(VI) acid
Cold concentrated tetraoxosulphate(VI)
Procedure
acid has little or no action on beryllium or
1 Put pieces of magnesium and calcium
magnesium, but when heated, sulphur(IV)
in a trough containing water. What do
oxide is evolved and the sulphate of the
you observe? Compare this reaction
metal formed.
with that of alkali metals.
2 Test the resulting solution with litmus
Reactions with alkali
paper. What is your observation?
Beryllium reacts with NaOH to liberate
hydrogen, forming sodium beryllate in
solution.

75
Experiment 5.4
Aim
To investigate the reactions of alkaline
earth metals with acids
Procedure
1 To a piece of calcium in a test tube add
dilute hydrochloric acid,
2 Repeat the experiment 2, using
dilute tetraoxosulphate(VI) acid,
dilute trioxonitrate(V) acid and the
concentrated acids.
3 Carry out these experiments with a
piece of magnesium.
4 Write down all your observations.
Experiment 5.5
Aim
To investigate the reactions of the alkaline
earth metals with alkali
Procedure
1 Place pieces of magnesium and
calcium in different test tubes.
2 To each test tube, add sodium
hydroxide solution. Record your
observations.
Reactions of alkaline earth metals
with non-metals
The alkaline earth metals are powerful
reducing agents. They combine directly and
often vigorously, at suitable temperatures,
with the highly electronegative non-metals,
i.e. oxygen, the halogens, nitrogen, sulphur,
phosphorous and carbon.
76
Reactions with hydrogen
All the metals, except beryllium, form
hydrides, MH2, by direct combination.
Calcium and barium combine with
hydrogen, forming calcium hydride and
barium hydride respectively. Barium
hydride is more covalent than ionic. The
other alkaline, earth metals form ionic
hydrides.
Ca(s) + H2 (g) → CaH2(s)
(Calcium hydride)
Ba(s) + H2(g) → BaH2(s)
(Barium hydride)
Reactions with halogens
The metals all combine directly with the
halogens at an appropriate temperature,
forming halides, MX2. These may also be
formed by the action of halogen acid or the
trioxocarbonate.
Mg(s) + Cl2(s) → MgCl2(s)
Ca(s) + Cl2(g) → CaCl2(g)
Ba(s) + F2(g) → BaF2(s)
Reactions with nitrogen
By contrast with the alkali metals, the
alkaline earth metals burn in nitrogen to
form nitrides, M3N2.
3Ca(s) + N2 (g) → Ca3N2(s)
2Mg(s) + N2 (g) → Mg3N2(s)
Reactions with sulphur
Alkaline earth metals react with sulphur,
forming the corresponding sulphide.
Be(s) + S(s) → BeS(s)
Ca(s) + S(s) → CaS(s)
Mg(a) + S(s) → MgS(s)
Reactions with carbon
Ionic carbides, MC 2 are formed by heating
the metals or their oxides with carbon.
Ca(s) + 2C2(s) → CaC2(s)
Mg(s) + 2C(s) → MgC2(s)
Calcium carbide, CaC2(s), is the best known.
It reacts with water and liberates ethyne.
CaC2 + 2H2O → Ca(OH)2 + C2H2
(ethyne)
In all, the reactions of alkaline earth
metals with non-metals increase down the
group.
Alkaline earth metals as reducing
agents
The metals are all powerful reducing
agents. Calcium and magnesium may
reduce almost any oxide, leaving the free
element. Calcium is more effective as a
reducing agent at high temperatures.
Burning magnesium continues to burn
in steam, carbon(II) oxide, carbon(IV)
oxide, sulphur(IV) oxide, nitrogen(II) oxide
and nitrogen(IV) oxide, reducing them to
hydrogen, carbon, sulphur and nitrogen
respectively. When heated, magnesium
reduces the oxides of silicon, sodium,
potassium, rubidium and caesium to the
free elements.
Similarities between lithium and
magnesium
Lithium resembles magnesium in the
following ways:
1 They both have small atomic and ionic
radii.
2 They both form nitrides when heated
in molecular nitrogen.
3 They form normal oxides on burning.
77
4 Their hydroxides, carbonates and
nitrates decompose much more easily
on heating, forming oxides.
5 Their hydroxides are not deliquescent
and are much less soluble in water.
6 Their fluorides and carbonates are
sparingly soluble in water.
7 Their hydrogen carbonates are more
soluble than their carbonates.
8 Their hydrogen carbonates are known
only in solution, being too unstable to
exist in the solid state.
Calcium
Extraction of calcium
Calcium is manufactured by the electrolysis
of fused anhydrous calcium chloride. In the
electrolytic cell, the calcium chloride is
mixed with calcium fluoride to lower the
melting point of the former.
The anode is a graphite vessel lined with
iron. The cathode is an iron rod which just
touches the surface of the electrolyte.
Calcium hydroxide cannot be used as
an electrolyte in this process because it
decomposes to calcium oxide and water
on heating. The calcium oxide formed
only becomes white-hot on further heating
and does not melt. Indeed, it is one of the
refractory substances known.
Chemistry of the reaction
The following reactions occur during the
extraction process:
At the cathode
The calcium ions receive two electrons each
to become reduced to metallic calcium.
Ca2+ + 2e- → Ca
The metallic calcium so formed collects at
the bottom of the cathode which is then
raised slowly as the metal accumulates.
At the anode
The chloride ion gives up an electron to
become atomic chlorine. Two chlorine
atoms then combine to form a chlorine
molecule which is then liberated.
Cl- – e- → Cl
Cl +Cl → Cl2
2Cl- → Cl2+ 2e-
Physical properties of calcium
1 Calcium is a soft silvery-white metal
with a melting point of 1 124 K (851°C)
and a boiling point of 1 760 K (1 487°C).
2 It has a density of 1.55 gcm-3.
3 It is a good conductor of heat and
electricity.
Chemical properties of calcium
The chemical properties of calcium are
given in the following reactions.
1 Reaction with air
It tarnishes rapidly on exposure to air
due to the formation of a white film
of calcium oxide or quicklime on the
surface of the metal.
2Ca(s) + O2(g) → 2CaO(s)
In the presence of moisture, the oxide
absorbs moisture to form the hydroxide.
CaO (s) + H2O(1) → Ca(OH)2(s)
The hydroxide formed then reacts
with carbon(IV) oxide to form calcium
trioxocarbonate(IV).
Ca(OH)2(aq) + CO2(g)→ CaCO3(s) + H2O(l)
78
Calcium burns with a brick-red flame
when heated in air to form the oxide.
2 Reaction with water
Calcium decomposes in water, slowly
producing calcium hydroxide and
hydrogen.
Ca(s) + 2H2O(l) → Ca(OH)2(aq) + H2 (g)
3 Reaction with dilute acids
Calcium reacts vigorously to displace
hydrogen from dilute acids.
Ca(s) + 2H+(aq) → Ca2+(aq) + H2(g) ,
e.g.
Ca(s) + 2HCl(aq) → CaCl2(aq) + H2(g)
4 Reaction with ammonia
When ammonia is passed over heated
calcium, the nitride is formed and
hydrogen gas is liberated.
3Ca(s) + 2NH3(g) → Ca3N2(s) + 3H2(g)
5 Reaction with non-metals
Calcium combines directly with
c h l o r i n e , s u l p h u r, c a r b o n a n d
hydrogen, when heated, to form the
corresponding compounds.
Ca(s) + Cl2(g) → CaCl2(s)
Ca(s) + 2C(s) → CaC2(s)
Calcium reacts with nitrogen in
an electric furnace as shown in the
equation below.
3Ca(s) + N2(g) → Ca3N2(s)
Uses of calcium
1 Calcium is used in the extraction of
uranium.
2 It is used as a deoxidant.
3 Calcium is used as a dehydrating agent
in the preparation of pure ethanol.
4 It is used in the manufacture of
hydrolith (CaH2), which is a source of
hydrogen gas.
5 It is used to remove impurities of
sulphur from petroleum.
Calcium oxide (quicklime)
Calcium oxide (CaO) is a white, amorphous
powder called quicklime. Quicklime
has many industrial applications.
Preparation of calcium oxide
Calcium oxide is prepared from two main
sources:
1 limestone
2 seashells
Preparation of calcium oxide from
limestone
It is prepared in industry by heating
calcium trioxocarbonate(IV) in a lime kiln.
The lime kiln is fed with alternate charges
of limestone (CaCO3) and coal or coke (C).
Modern kilns are kept at the required
working temperatures in the region of
1 273 K (1 000°C) using producer gas (a
mixture of nitrogen and carbon (II) oxide
produced by passing air over heated
coke) as a fuel. The trioxocarbonate(IV)
gradually decomposes into calcium oxide
and carbon(II) oxide.
Preparation of calcium oxide from
seashells
Seashells are made up of calcium
trioxocarbonate(IV). Seashells give off an
effervescence of carbon(IV) oxide gas when
a dilute acid is added to them. Calcium
oxide can thus be prepared by strongly
heating seashells. A thermal decomposition
similar to the reaction in the kiln takes
79
place, with the formation of calcium oxide
and carbon(IV) oxide.
Properties of calcium oxide
1 Calcium oxide is a white amorphous
powder.
2 It is hygroscopic.
3 It does not decompose or melt
on heating, even to a very high
temperature.
4 It is a strongly basic oxide which reacts
vigorously with acids to form the
corresponding calcium salts.
5 Quicklime is a very reactive compound.
It reacts violently with water to produce
slaked lime (the reaction is exothermic).
CaO(s) + H2O(l) → Ca(OH)2 + Heat
When more water is added to slaked
lime, and filtered, limewater is obtained
as the filtrate.
6 Calcium oxide reacts with silica to form
trioxosilicate(IV) compounds. Thus, it
is used in many metallurgical processes
to remove silica as waste or slag.
CaO(s) + SiO2(s) → CaO.SiO2 (CaSiO3)(s)
Uses of calcium oxide
1 Calcium oxide is used to make
refractory bricks for furnace linings.
2 It is used in the production of slaked
lime and limewater.
3 It is used in agriculture as a base to
neutralise soil acidity.
4 Calcium oxide is used as a drying
agent.
5 Calcium oxide is used in the
manufacture of bleaching powder.
6 In the extraction of iron, calcium oxide
is used to remove silica impurities.
7 Calcium oxide is used in the
manufacture of cement, mortar and
plaster.
Cement, mortar and plaster
Cement
Cement is produced by heating a mixture
of limestone and clay (clay contains
aluminium trioxosilicate(IV)) to a high
temperature of about 1 273 K (1 000°C)
in a rotating kiln. The product, known
as clinker, is then ground into very fine
powder. This is cement powder. The
equation for the reaction is given as:
4CaCO3(s) + Al2Si2O7(s) → 2CaSiO3(s) +
Ca2Al2O5(s) + 4CO2(g)
Cement is thus a complex mixture
of anhydrous calcium trioxosilicate(IV),
anhydrous calcium aluminate and free
lime.
When sand and water are added
to cement, a hard-setting product is
obtained. Concrete is produced when
gravel, sand and water are mixed with
cement. Concrete is used for constructing
bridges, pillars, floors, etc.
Mortar
Mortar is made by mixing approximately
one part of slaked lime and three or four
parts of sand.
Water is added to the mixture to
obtain a thick paste. The paste is then
exposed to the air. The calcium hydroxide
formed absorbs carbon (IV) oxide from
the atmosphere at the same time as it uses
the water. The carbon (IV) oxide converts
the calcium hydroxide into calcium
trioxocarbonate(IV).
80
Ca(OH)2(s) + CO2(g) → CaCO3(s) + H2O(1)
This reaction represents the hardening or
setting process. The mortar then becomes
hard.
Mortar cannot be used for construction
under water because evaporation is
essential for the setting (hardening)
process. The sand is not involved in the
chemical reaction but it helps to prevent
the mortar from cracking as it sets.
Plaster
This is formed when a binder is added to
a mortar, e.g. fibre. It is made by partial
dehydration of gypsum, CaSO4.2H2O(s). Its
formula is (CaSO4).2H2O(s).
Calcium hydroxide or slaked time
Industrially, calcium hydroxide, Ca(OH)2,
is obtained by the action of water on
calcium oxide. The calcium oxide is
prepared by roasting limestone.
CaO(s)+ H2O(1) → Ca(OH)2(aq)
In the laboratory, calcium hydroxide
is prepared by adding sodium hydroxide
solution to a solution of any soluble salt of
calcium, e.g. calcium chloride.
CaCl2(s) + 2NaOH(aq) → Ca(OH)2(aq) +
2NaCl(aq)
Properties of calcium hydroxide
1 Calcium hydroxide is a white powder
which dissolves slightly in water to
give an alkaline solution of limewater.
Unlike most solids, its solubility
decreases with increase in temperature.
Milk of lime is slaked lime suspended
in water.
2 Calcium hydroxide decomposes at 753
K (480°C) to give calcium oxide and
water.
Ca(OH)2(aq) → CaO(s) + H2O(l)
3 It neutralises acids to give salts and
water.
Ca(OH)2(aq) + 2HCl(aq) → CaCl2(S) +
2H2O(l)
4 It liberates ammonia from ammonium
salts.
Ca(OH)2(aq) + 2NH4Cl(s) → CaCI2 (s) +
2NH3(g) + 2H2O(l)
5 Bleaching powder is produced when
chlorine gas is passed over dry slaked
lime.
Ca(OH)2(s) + Cl2(g) → CaOCl2(s) + H2O(l)
When a cold solution of calcium
hydroxide, Ca(OH)2, is saturated with
chlorine gas, the products are calcium
chloride, calcium monooxochlorate(I)
and water.
2Ca(OH)2(aq) + 2Cl2(g)→ CaCl2(aq) +
Ca(OCl)2(aq) + 2H2O(l)
When a hot solution of calcium
hydroxide, Ca(OH) 2 , is saturated
with chlorine, the products formed
a re c a l c i u m c h l o r i d e , c a l c i u m
trioxochlorate(V) and water.
6Ca(OH)2(aq) + 6Cl2(g) → Ca(ClO3)2(aq) +
5CaCl2(aq) + 6H2O(l)
6 When carbon(IV) oxide is passed into
limewater for a short time, the solution
becomes milky due to the formation of
insoluble calcium trioxocarbonate(IV).
Ca(OH)2(aq) + CO(g) → CaCO3(s) +
H2O(l)
This is the test for carbon(IV) oxide gas.
When carbon(IV) oxide is passed for
81
long time (i.e. in excess) into limewater,
the milkiness disappears due to
the formation of calcium hydrogen
trioxocarbonate(lV), which is soluble
CaCO3(s) + H2O(l) + CO2(g) →
Ca(HCO3)2(aq)
Uses of calcium hydroxide
In industry, calcium hydroxide is used in
1 the production of bleaching powder.
2 the softening of water by Clark’s process.
3 the manufacture of glass.
4 the recovery of ammonia from
ammonium chloride (Solvay process).
5 the purification of coal gas.
6 the purification of sugar.
7 in agriculture to neutralise acidic soil.
Whitewash
This is a solution of slaked lime. As it dries,
it absorbs carbon(IV) oxide from the air
and turns white due to the formation of
calcium trixocarbonate(IV), CaCO3. It is
used in the preliminary painting of new
buildings, goalposts and in lining tracks.
Calcium trioxocarbonate(IV)
The occurrence of calcium trioxo-
carbonate(IV), CaCO3, has already been
discussed. It occurs naturally as deposits
in the form of chalk, marble and limestone.
Calcium trioxocarbonate(IV) is also found
in eggshells and seashells.
Note: Blackboard chalk is calcium
tetraoxosulphate(VI) and should not be
mistaken for calcium trioxocarbonate(IV).
Laboratory preparation of calcium
trioxocarbonate(IV)
1 Pure calcium trioxocarboate(IV) can be
 prepared in the laboratory by double 3 In the form of limestone, it is used as:
decomposition. For example, a) a building stone;
Na2CO3(aq) + CaCl2(aq) → CaCO3(s) + b) a raw material in the manu-facture
of quicklime;
2NaCl(aq)
c) a raw material in the manu-facture
It is obtained as a white solid.
of cement; and
2 Calcium trioxocarbonate(IV) is also
d) a source of carbon(IV) oxide
produced when carbon(IV) oxide is
in the manufacture of sodium
passed for a short time into limewater.
trioxocarbonate(IV) by the Solvay
Ca(OH)2(aq) + CO2(g) → CaCO3(s) + H2O(l)
process.
4 It is used in blast furnaces for the
Properties of calcium trioxocarbonate(IV)
smelting of iron.
1 It is insoluble in water but dissolves
5 As whitening (for painting houses and
in water containing carbon(IV) oxide
lining tracks), it is employed in the
to give soluble calcium hydrogen
production of distempers and putty.
trioxocarbonate(IV).
CaCO3(s) + CO2(g) + H2O(1) →
Ca(HCO3)2(aq) Calcium chloride
2 It decomposes when heated to about
873 K (600°C) to produce calcium oxide Laboratory preparation of calcium
and carbon(IV) oxide. chloride
Calcium chloride, CaCl 2, is prepared
CaCO3(s) → CaO(s) + CO2(g)
in the laboratory by the action of
3 It reacts with dilute acids, except
dilute hydrochloric acid on calcium
H2SO4, to liberate carbon(IV) oxide. For
trioxocarbonate(IV).
example,
CaCO3(aq) + 2HCl(aq) → CaCl2(aq) + CaCO3(s) + 2HCl(aq) → CaCl2(aq) + H2O(l) +
CO2 (g)
H2O(l) + CO2 (g)
4 Calcium trioxocarbonate(IV) dissolves
Properties of calcium chloride
in water containing dissolved carbon(IV)
1 The anhydrous form of calcium
oxide to produce calcium hydrogen
chloride is a white powder.
trioxocarbonate(IV). Dissolved calcium
2 It has the typical reactions of a chloride.
hydrogen trioxocarbonate(IV) is the
3 It is very deliquescent, absorbing
cause of temporary hardness in water.
moisture from the air to form hydrated
calcium chloride.
Uses of calcium trioxocarbonate(IV)
1 It is used in the preparation of penicillin CaCl2(s) + 5H2O(g) → CaCl2.5H2O(s)
and streptomycin, used as medicines in A solution is obtained when enough
hospitals. moisture has been absorbed.
2 It is widely used as a source of
carbon(IV) oxide in fire extinguishers. Use of calcium chloride
Calcium chloride is mainly used as a

82
drying agent in desiccators and in drying
towers.
Calcium(II) dicarbide
Calcium(II) dicarbide (calcium carbide), is
prepared in industry by heating a mixture
of calcium oxide (CaO) and coke (C) in
an electric furnace between 2 273 K and
2 773 K (2 000°C and 2 500°C).
CaO(s) + 3C(s)→ CaC2(s) + CO(g)
Uses of calcium(II) dicarbide
1 Calcium(II)dicarbide is used in the
manufacture of the extremely important
fertiliser, nitro-lime, by heating it with
nitrogen.
CaC2(s) + N2(g) → CaCN2(s) + Cl(s)
(nitro-lime)
CaCN2 is calcium cyanamide.
2 It is used in the manufacture of ethyne,
which is a useful raw material in the
paint, plastic and cosmetic industries.
CaC2(s) + 2H2O(1) → Ca(OH)2(aq) + C2H2(g)
(ethyne)
Calcium tetraoxosulphate(VI)
Calcium tetraoxosulphate(VI) occurs
naturally as gypsum, CaSO4.2H2O, and
as the anhydrite, CaSO4. When gypsum
is carefully heated, plaster of Paris,
2CaSO4.H2O(s)or (CaSO4)2.H2O(s) is obtained.
The equation for this reaction is:
2CaSO4.2H2O(s) → (CaSO4) 2.H2O(s)+3H2O(l)
Properties of calcium tetraoxosulphate(VI)
Calcium tetraoxosulphate(VI) is a white,
non-deliquescent solid. Its solubility
increases with rise in temperature to a
83
maximum of 313 K (40°C), after which the
solubility falls.
Uses of calcium tetraoxosulphate(VI)
1 Calcium tetraoxosulphate(VI) is used
in making plaster of Paris, which is
used in orthopaedic hospitals to set
broken bones.
2 The anhydrite is used as a source
of sulphur in the manufacture of
tetraoxosulphate(VI) acid.
Calcium hydrogen tetraoxo-
sulphate(IV)
Calcium hydrogen tetraoxosulphate(IV),
Ca-(HSO3)2, is of industrial importance. It
is prepared by the action of sulphur(IV)
oxide on milk of lime.
Ca(OH)2(aq) + 2SO2(g) → Ca(HSO3)2(s)
Use of calcium hydrogen tetraoxo-
sulphate(IV)
It is used in bleaching wood pulp, an
important raw material in the manufacture
of paper.
Calcium trioxonitrate(V)
Calcium trioxonitrate(V) is prepared in
the laboratory by the action of dilute
trioxonitrate(V) acid on chalk (chalk is the
soft form of calcium trioxocarbonate(IV),
CaCO3).
CaCO3(s) + 2HNO3(aq) → Ca(NO3)(aq) + H2O(l)
+ CO2(g)
On filtering and crystallisation, white
crystals of calcium trioxonitrate(V),
Ca(NO 3 ) 2 , are formed. The nitrate of
calcium is usually hydrated and has the
formula Ca(NO3).4H2O(s).
Calcium trioxonitrate(V) can also be
prepared by reacting calcium, calcium
oxide or slaked lime with trioxonitrate(V)
acid.
Properties of calcium trioxonitrate(V)
1 Calcium trioxonitrate(V) is a typical
nitrate.
2 It decomposes on heating to form the
oxide, nitrogen(IV) oxide and oxygen.
2Ca(NO3)2(s) → 2CaO(s) + 4NO2(g) + O2(g)
3 The anhydrous form, Ca(NO 3) 2, is
hygroscopic.
Use of calcium trioxonitrate(IV)
When quicklime has been added to it,
calcium trioxonitrate(lV) is used as a
fertiliser.
Summary
This chapter has taught the following:
• The alkaline earth metals have two
electrons in their outermost shells and
eight electrons in their penultimate
shells (except beryllium which has 2).
Alkaline earth metals, therefore, show
a positive electrovalency of 2 and form
stable, bivalent cations M2+, with a
noble gas electronic configuration.
• General trends in physical properties
are similar to those of the alkali metals.
For example, the metals decrease
in melting point, boiling point and
hardness down both groups. Beryllium
is the only metal with a low density
and a high melting point.
• Alkaline earth metals form colourless,
largely ionic compounds in the solid
state in which they all show only the
+ 2 oxidation state.
• All the metals tarnish in air, forming a
film of oxide. The speed of the reaction
increases from beryllium to barium.
All the metals burn brilliantly when
heated in air to form the oxide and
some nitrides.
• They all react with water. The rate of
reaction increases from beryllium to
barium. Beryllium does not react with
steam, even when red hot. Magnesium
burns brilliantly in steam, forming the
hydroxide and liberating hydrogen.
• The metals are powerful reducing
agents, combining directly, vigorously
and at suitable temperatures with the
highly electronegative non-metals,
such as oxygen, the halogens, nitrogen,
sulphur, phosphorus and carbon.
• The metals do not occur free in nature
because they are very reactive.
• They are found in nature as the
trioxocarbonate(IV) salts,
tetraoxosulphate(VI) salts,
tetraoxophosphate(VI) salts, fluorides
and chlorides.
• Calcium is extracted by the electrolysis
of fused calcium chlorid,e using a
graphite anode and an iron cathode.
Calcium fluoride is added to reduce
the melting point of calcium chloride.
• Calcium is a grey metal, malleable,
ductile and a good conductor of heat
and electricity.
Review questions
A Multiple-choice questions
1 One product of the reaction between
chlorine and calcium hydroxide is

84
 A calcium chloride.
B bleaching powder.
C calcium monoxochlorate(I).
D calcium trioxochlorate(V).
E any of the above depending on
reacting conditions.
2 When magnesium ribbon is burnt in
steam, the white ash produced is
A magnesium hydroxide.
B magnesium hydride.
C magnesium metal.
D magnesium oxide.
E magnesium peroxide.
3 Which of the following metals does not
react with water?
A Potassium
B Calcium
C Beryllium
D Magnesium
E Sodium
4 Which of the following is stable to heat?
A Calcium trioxocarbonate(IV)
B Mercury oxide
C Sodium trioxocarbonate(IV)
D Ammonium chloride
E None of the above
5 Copper tetraoxosulphate(VI) is used
A in alloys like brass and bronze.
B to prevent iron from rusting.
C for killing bacteria.
D in a test for sulphur(VI) oxide.
E as a solvent.
B Short-structured questions
1 Write the materials used in the
production of:
a) cement
b) plaster
c) concrete
d) whitewash
e) mortar
85
2 Using equations only, show how the
following react with water:
a) Calcium
b) Calcium oxide
3 Give the compounds produced when
the following are heated:
a) Calcium trioxocarbonate(IV)
b) Calcium trioxonitrate(V)
c) Magnesium trioxocar- bonate(IV)
4 Give two important uses of the
following:
a) calcium hydroxide
b) calcium oxide
c) calcium tetraoxosulphate(VI)
5 Using equations only, give one chemical
reaction each of calcium and two
compounds of calcium.
C Essay-type questions
1 Describe how you would obtain
quicklime (calcium oxide) from:
a) marble
b) limestone
c) seashells
2 Give three forms in which calcium
occurs in nature. Describe how calcium
is extracted from one of the ores and
give the chemistry of the reaction.
3 a) What happens when dilute
hydrochloric acid is added to old
mortar?
b) A substance A decomposed on
heating to give carbon(IV)oxide
and a solid substance B which
is white and highly refractory.
Solid B reacts exothermically
with water to give another solid
C. When carbon(IV) oxide is
passed into a solution of C,
it gives a white precipitate D
which dissolves when an excess
of carbon(IV)oxide is passed
 into it, to give a solution E.
When solution E is heated, a
white precipitate F is obtained.
Suggest reasonable names for
substances A, B, C, D, E and F.
Which of these substances are the
same? Write balanced equations
to represent each stage of the
reaction.
4 Describe the preparation of each
o f t h e f o l l o w i n g f ro m c a l c i u m
trioxocarbonate(IV):
a) bleaching powder
b) calcium carbide
c) calcium tetraoxosulphate(VI)
State and explain one use for each
compound.
5 Explain the term ‘diagonal relationshipʼ.
Give and explain the diagonal
relationship between lithium and
magnesium.

86
 6 The aluminium family
Introduction
The aluminum family comprises elements
in Group IIIB of the periodic table. These
elements are boron, aluminum, gallium,
indium and thallium. All the elements in
the aluminum family, except boron, are
fairly reactive metals. Boron is a non-metal
and is classed as a metalloid.
Elements in this group have three
electrons in their valency shell. They are
the first elements with valency electrons
in more than one orbital- s2p1. Members of
this family show an oxidation state of +3
because one electron is readily promoted to
the p orbital when the atom is in an excited
state, giving the s1p2 configuration.
s2 p1 s1 p2
↿ ↿ ↿ ↿

atom at the atom at the
ground state excited state
The elements of Group IIIB are more
electronegative than the corresponding
elements of Group IIA. A strong diagonal
relationship exists between boron and
silicon and between beryllium and
aluminum.
87
Performance objectives
At the end of this chapter, you should be
able to:
1 give examples of naturally occurring
aluminum ores;
2 describe how aluminum is extracted
from its ore;
3 explain the chemistry involved in (2)
above;
4 give examples of the physical and
chemical properties of aluminum as a
typical member of the group;
5 describe the chemistry of aluminum
as a typical element;
6 name the compounds of aluminum;
and
7 state the uses of aluminum com-
pounds.
Aluminium
Occurence of aluminium
Aluminium is the third most abundant
element in the earth’s crust and it is the
most abundant metal. Aluminium has
great affinity for oxygen and so it is not
found free in nature. It occurs widely as
silicates in clay and rock from which it can
be extracted.
 The most important minerals in which
aluminium occurs are:
1 Bauxite (hydrated oxide, Al2O3.2H2O )
2 Corundum (oxide, Al2O3)
3 Spinel (aluminate, MgO.Al2O3)
4 Cryolite (fluoride, Na3AlF6)
5 Kaolin or china clay (complex silicate,
Al 2Si 2O 7.2H 2O) or mica or feldspar
(K2Al2Si6O16)
Extraction of aluminium
Aluminium is extracted by the electrolysis
of a solution of aluminium oxide in fused
cryolite. Pure aluminium oxide is obtained
from bauxite, which is the most important
ore, containing 50-70 per cent of aluminium
oxide. The extraction proceeds in two
stages:
Stage 1: Purification of bauxite to produce
alumina
The first stage in the extraction of aluminium
involves the purification of crude bauxite to
obtain pure, anhydrous aluminium oxide.
The chief impurities are oxides of iron,
silicon and titanium.
The processes involved in this stage are:
1 Roasting of bauxite in air to convert
iron(II) to iron(III).
2 The residue obtained from (1) above is
then finely powdered.
3 Powdered aluminium oxide is dissolved
under pressure in hot concentrated
sodium hydroxide solution. The
aluminium oxide forms sodium
aluminate solution,
(NaAl(OH)4)(aq).
Al2O3(s) + 3H2O(l) + 2NaOH(aq) → electrolyte.
2NaAl(OH)4(aq)
88
4 The solution is filtered. The filtrate is
the sodium aluminate while the residue
contains the insoluble iron(III) oxide,
silicon oxide and other impurities
which do not dissolve during this
process.
5 The filtrate is diluted with water
and cooled. Freshly prepared, pure
aluminium hydroxide crystals are then
added to ‘seed’ the filtrate, that is, to
induce the precipitation of aluminium
hydroxide.
NaAl(OH)4(aq) → Al(OH)3(s) + NaOH(aq)
6The aluminium hydroxide so
precipitated is filtered off, washed,
dried and heated strongly to yield pure
aluminium oxide or alumina.
2Al(OH)3(s) → Al2O3(s) + 3H2O(l)
The sodium hydroxide is recovered and
used again.
Stage 2: Reduction of alumina by
electrolysis
In the second stage, electrolysis of the pure
aluminium oxide (aluminia) is carried out.
The aluminium oxide is mixed with molten
cryolite (NaAlF 6) which serves as the
solvent. A temperature of about 1 273 K (1
000°C) is maintained. The aluminium oxide
dissolved in the molten cryolite forms the
electrolyte used in the electrolytic cell, as
shown in Fig. 6.1.
The electrolytic cell is a rectangular
iron box, lined with graphite. The graphite
lining serves as the cathode. The anode is
made of carbon rods which dip into the
Reaction at the electrodes
At the cathode, the aluminum ions gain
 Carbo anodes

Crust of
solified
electrotrolyte

Al2O3 Cathode iron

dissoved in tank
molten cryolite

Carbon lining molten

of iron tank) aluminium

Fig. 6.1 Electrolytic cell for the extraction of aluminium

three electrons each (that is, they are g) Atomic mass: 27

reduced) to become deposited as aluminum h) Electrode potential (E°):
metal. - 1.66V
2Al3+ + 6e- → 2Al i) Common oxidation state: + 3
At the anode, the oxygen ions donate two j) Outer electronic configuration:
electrons each, and in the process, are 3s2 3pl
oxidised to atomic oxygen which then pair
up to form oxygen molecules: Chemical properties of aluminium
2O2- → O2(g) + 4e- 1 When a piece of aluminium sheet
or 2O2- → 4e- → O2(g) is exposed to moist air, it acquires a
The oxygen gas is liberated. thin continuous coating of aluminium
oxide, which prevents further attack of
Physical properties of aluminum the metal by atmospheric oxygen, water
1 Aluminium is a silvery-white metal. or steam under normal conditions.
2 It is ductile and malleable. Thus, it can Aluminium is thus said to be corrosion-
be made into foil, wire and sheets. free.
3 It is a good conductor of both heat and 2 Aluminium metal burns in air at about
electricity. 1 073 K (800°C) to form the oxide and
4 Other physical properties are: nitride.
a) Melting point: 933 K (660°C) 4Al(s) + 3O2(g) → 2Al2O3(s)
b) Density: 2.70 g cm-3 2Al(s) + N2(g) → 2AlN(s)
c) Boiling point: 2 723 K (2 450°C) (aluminium nitride)

d) Ionic radius M3+: 0.50 Å 3 Mercury forms amalgam, Al/Hg, with

e) Metallic radius: 1.43 Å aluminium. The pure aluminium in
f) Atomic number: 13 the amalgam reacts immediately with
the moist air, forming aluminium

89
 hydroxide which appears as an
overgrowth on the metal.
4 Aluminium reacts slowly with dilute
hydrochloric acid. It does not react
with dilute tetraoxosulphate(VI) acid,
or trioxonitrate(V) acid, dilute or
concentrated. This is probably because
of the formation of a protective layer
of aluminium oxide. The aluminium
metal is said to have been rendered
passive whenever this happens.
5 With concentrated hydrochloric acid,
aluminium reacts rapidly, forming the
chloride and liberating hydrogen.
2Al(s) + 6HCl(aq) → 2AlCl3(aq) + 3H2(g)
6 Aluminium reacts with hot concentrated
tetraoxosulphate(Vl) acid to liberate
sulphur(IV) oxide.
2Al(s) + 6H2SO4(l)→ Al(SO4)3(aq) + 6H2O(l)
+ 3SO2(g)
Here, alumimium behaves as
a reducing agent, reducing the
tetraoxosulphate(Vl) acid to
sulphur(IV) oxide. The aluminium is
oxidised to the sulphate.
7 Aluminium dissolves in alkalis, such
as sodium hydroxide solution, to form
a soluble complex salt and liberates
hydrogen gas.
2Al(s) + 2NaOH(aq) + 6 H2O(l) →
2NaAl(OH)4(aq) + 3H2(g)
8 Aluminium oxide is said to be amphoteric
because it reacts with both acids and
bases to form salts. Washing soda
attacks aluminium. This is why alkalis
are not stored in aluminium containers.
9 When a few drops of ammonia solution
are added to a solution containing
aluminium ions, a white, gelatinous
90
precipitate, which is insoluble in excess
aqueous ammonia, is formed.
Al3+(aq) + 3OH-(aq) → Al(OH)3(s)
Zinc salts give a white, gelatinous
precipitate with ammonia solution,
but the precipitate is soluble in excess
of the reagent. Also, lead(II) salts
give a similar reaction with ammonia
solution, but unlike aluminium,
lead(II) salts give a white precipitate
with concentrated hydrochloric acid.
10 Aluminium reacts with sodium
trioxocarbonate(IV) as represented by
the following equation:
2Al (s) + 2Na 2 CO 3(aq) + 4H 2 O (l) →
2NaHCO3(aq) + 2NaAlO2(aq) + 3H2(g)
Aluminium carbonate does not
exist. When a solution of sodium
trioxocarbonate(IV) is added to the
solution of an aluminium salt, e.g.
aluminium(III) tetraoxo-sulphate(VI),
aluminium hydroxide is precipitated
and carbon(IV) oxide liberated.
Al2(SO4)3(aq) + 3Na2CO3(aq) + 3H2O(l) →
3Na2SO4(aq) + 2Al(OH)3(s) + 3CO2(g)
11 Aluminium metal, when placed in
mercury(II) chloride solution, displaces
the mercury (since aluminium is higher
in the electrochemical series). The
mercury then forms amalgam, Al/Hg,
with the aluminium. The aluminium in
this form is no longer protected by its
film of oxide, thus it reacts with water
in the solution to liberate hydrogen gas.
12 When heated, aluminium combines
directly with non-metals, such as
sulphur, nitrogen, carbon, phosphorus,
and also with halogens.
 The reaction is accompanied by
evolution of heat.
2Al(s) + 3Cl2(g) → 2AlCl3(S)
2Al(s) + 3S(s) → Al2S3(s)
(aluminium sulphide)
Aluminium sulphide cannot be
prepared in solution because it is
hydrolysed by water to produce
aluminium hydroxide and hydrogen
sulphide.
Al2S3(s) + 6H2O(l) → 2Al(OH)3(s) + 3H2S(g)
Experiment 6.1
Aim
To investigate the reaction of aluminium
with air
Procedure
Expose a clean piece of aluminium foil
to moist air for several days. Notice the
changes.
Experiment 6.2
Aim
To investigate the reactivity of pure
aluminium
Procedure
Take a small piece of aluminum metal and
carry out the following activities. Note
your observations.
1 Clean the metal with emery paper.
2 Rub its surface with mercury.
3 Leave the amalgamated aluminum
for several minutes.
4 Note your observations and record.
91
Experiment 6.3
Aim
To investigate the reaction of aluminum
with acids
Procedure
1 Cut some pieces of aluminum foil.
Place some pieces in five different test
tubes.
2 To each test tube, add
(a) dilute hydrochloric acid,
(b) dilute tetraoxosulphate(VI) acid,
(c) dilute trioxonitrate(V) acid,
(d) concentrated hydrochloric acid,
(e) concentrated tetraoxosulphate(VI)
acid and
(f) concentrated trioxonitrate(V) acid.
3 Test for the evolution of hydrogen in
each case.
Experiment 6.4
Aim
To investigate other reactivities of
aluminum
Procedure
Cut two pieces of aluminum metal.
1 Put one piece of aluminum in
a test tube containing sodium
trioxocarbonate(VI) solution and
warm.
2 Put the second piece of aluminum
in another test tube containing
mercury(II) chloride solution.
3 In both cases (1) and (2), test the gas
evolved for hydrogen, using a lighted
splint.
Uses of aluminium
1 Aluminium is used in making pans,
kettles and teapots. It is also used as foil
for wrapping foods and confectionery
and for milk bottle tops.
2 Aluminium, because of its light weight,
is used to replace copper as a conductor
of electricity. For example, overhead
cables in the grid system are made
of aluminium wires twisted round
reinforcing steel wires.
3 Aluminium is used to build the
bodies of vehicles, such as buses, and
in constructing railway coaches. Its
lightness renders it readily useful in
building prefabricated houses.
4 Aluminium forms alloys with other
elements. Such alloys are used in
the aircraft, motorcar and building
industries.
5 Aluminium powder is used in making
paints and explosives.
6 As a reducing agent, aluminium is used
a) i n r e m o v i n g o x y g e n a n d
nitrogen from iron and steel, thus
preventing blow-holes in castings;
and
b) in the preparation of iron,
chromium, man gan es e an d
titanium from their respective
oxides.
The thermite process
Aluminium has a very strong affinity
for oxygen. A large quantity of heat is
evolved whenever oxygen combines with
aluminium. The heat of such a reaction,
estimated at 3 273 K, is used in the thermite
process for welding.
For example, the welding of steel rails
on site is carried out by packing a mixture
92
of aluminium powder and iron(III) oxide
around the joint to be welded and igniting
the mixture with a fuse. The aluminium
powder reduces the oxide to the metal.
The heat of the reaction melts the iron so
formed. The molten iron formed is used
to join the rails. This is an example of the
thermite process.
Other metallic oxides, as mentioned,
can be reduced to their metals in this way,
using a vessel. The metals so formed collect
on the floor of the vessel.
Aluminium oxide (alumina)
Aluminium oxide is made by heating
the hydrated oxide, the hydroxide, the
trioxonitrate(V) or the tetraoxosulphate(VI)
salts. The hydrated oxide is called bauxite,
Al2O3.2H2O while the crystalline form of
aluminium oxide is called corundum.
2Al(OH)3(s) → Al2O3(s) + 3H2O(l)
Properties of aluminium oxide
1 Aluminium oxide is a very refractory
white solid.
2 It is insoluble in water.
3 It is amphoteric, reacting with acids to
form salts, and with aqueous alkali to
form aluminates.
Uses of aluminium oxide
1 Aluminium oxide is used in the
manufacture of aluminium.
2 It is used as a furnace lining.
3 It is a constituent of cement.
4 It is used as an abrasive.
5 It is used as an adsorbent in
chromatography.
6 It is used as a catalyst-support in
organic preparations.
7 It is used as coloured jewels when
mixed in small proportions with other
metals. For example, ruby is alumina
containing traces of chromium oxide;
blue sapphire is alumina containing
traces of titanium and iron.
Aluminium(III) tetraoxosulphate(VI)
Industrial preparation
I n d u s t r i a l l y, A l u m i n i u m ( I I I )
tetraoxosulphate(VI), Al2(SO4)3, is prepared
by:
1 heating bauxite, Al 2O 3, with dilute
tetraoxosulphate(VI) acid. The
product contains some iron(III)
tetraoxosulphate(VI).
Experiment 6.5
Aim
Laboratory preparation of aluminium(III)
tetraoxosulphate(VI)
Procedure
1 Dissolve a piece of aluminum in con-
centrated tetraoxosulphate(VI) acid in
a beaker. Warm.
2 Dilute the resulting solution slightly
and crystallise the salt from solution.
Physical properties of aluminium(III)
traoxosulphate(VI)
1 Aluminium(III) tetraoxo-sulphate(VI)
is a colourless, crystalline, ionic solid.
2 It is readily soluble in water.

Al2O3(s) + 3H2SO4(aq) → Al2(SO4)3(aq) + Chemical properties of aluminium(III)

3H2O(l)
2 heating the complex aluminium
silicate, kaolin, which contains silicate
and aluminium anions.
I n t h e l a b o r a t o r y, h y d r a t e d
Aluminium(III) tetraoxosulphate(VI) is
prepared by the action of concentrated
tetraoxosulphate(VI) acid on aluminium
metal.
tetraoxosulphate(VI)
1 When dissolved in water, the solution
has an acid reaction because of partial
hydrolysis in which (Al(H2O)6)3+ ions
are produced.
2 When heated strongly, aluminium(III)
tetraoxo-sulphate(VI), Al 2 (SO 4 ) 3 ,
decomposes to give the oxide, oxygen
and some sulphur(IV) oxide.

2Al(s) + 6H2SO4(aq) → Al2(SO4)3(aq) + SAI 2 ( (SO

2Al SO 4 )3()s ) heat
 2A1O
→2Al 2
O 3( s+ 6SO 2( g ) ++ 30
) +6SO 3O
2 4 3(s) 2 3(s) 2(g) 2(g)
6H2O(l) + 3SO2 (alumina)

3 It forms double salts (alums) with other

Aluminium(III) textraoxosulphate(VI)
sulphates.
is also prepared by the reaction of the
oxide or hydroxide of aluminium with
Uses of aluminium(lII) tetraoxo-
tetraoxosulphate(VI) acid.
sulphate(VI), Al2(SO4)3
2Al(OH)3 + 3H2SO4 → Al2(SO4)3 +6H2O 1 Aluminium(III)tetraoxo-sulphate(VI),
Al2(SO4)3, is used in the manufacture
of paper.

93
 2 It is used as a mordant in the dyeing
of cloths.
3 It is added to water to purify it for
human consumption.
Aluminium hydroxide
The gelatinous, white precipitate formed
when sodium hydroxide solution is added
in drops to a solution of aluminium(III)
tetraoxosulphate(VI) is aluminium
hydroxide.
Al2(SO4)3+ 6NaOH(aq) → 2Al(OH)3(s) +
3Na2SO4(aq)
When freshly precipitated, aluminium
hydroxide is readily soluble in acids and
alkali hydroxides because it is amphoteric.
When excess alkali is added, the resulting
product is an aluminate.
Al(OH)3(s) + NaOH(aq) → NaAl(OH)4(aq)
Ionically, the above equation is represented
as:
excess
Al(OH)3+3+++OH
A1(OH) OH
- alkali
 (
→ (Al(OH) )
AI ( OH 4 4))
Generally, aluminium hydroxide
precipitate is formed when ammonia
solution or sodium hydroxide is added
to a solution of an aluminium salt. The
aluminium hydroxide thus precipitated
is soluble in excess sodium hydroxide
solution, forming hydroxy-aluminate ions
which are insoluble in excess ammonia
solution.
When excess acid is added to the
aluminium hydroxide, the resulting
product is the corresponding aluminium
salt.
2Al(OH)3(s) + 3H2SO4(aq) → Al2(SO4)3(aq) +
6H2O(l)
94
Experiment 6.6
Aim
To prepare aluminium hydroxide
Procedure
1 Prepare a solution of alumi-nium(III)
tetraoxosulphate(VI).
2 To the aluminium(III) tetraoxo-
sulphate(VI) solution prepared,
carefully add sodium hydroxide
solution, drop by drop. Observe the
precipitate aluminium hydroxide
being formed.
3 Divide the precipitate so formed and
the solution into three portions. To
the first portion, add more sodium
hydroxide solution in excess and
shake. Observe what happens.
To the second portion, add dilute
teraoxosulphate(VI) acid.
4 To the third portion, add ammonia
solution. Record your observations.
5 What inferences can you draw from
this experiment?
Properties of aluminium hydroxide
1 It is very slightly soluble in water.
2 It is amphoteric but, if left standing,
changes its structure to a form which
is insoluble in acids or alkalis.
3 It decomposes on heating to give the
oxide and water.
4 During precipitation, the gelatinous
aluminium hydroxide has a great
power of absorbing molecules and ions
from solution, e.g. Co2+and Ni2+. This
can be shown with coloured ions and
dyes.
Uses of aluminium hydroxide
1 Aluminium hydroxide is used in the
dye industry as a mordant. It performs
the function of absorbing the dye and
binding it firmly to the cloth.
2 Cloth may be made waterproof by
precipitating aluminium hydroxide in
its fibres.
3 It is used in the manufacture of alumina
and other chemicals.
Alums
Alums are hydrated, ‘double’ tetraoxo-
sulphate(VI) salts, with the general formula
Y2I SO .X III(SO ) .24H O
4 2 4 3 2
where YI is a monovalent cation, usually
one of K+, Na+ or NH4+, and XIII is a trivalent
cation, usually one of Fe3+, Al3+ or Cr3+
Preparation of alums
All alums can be made by mixing
equimolecular masses of the tetraoxo-
sulphate(VI) salts concerned. The alums
crystallise out with each cation being
associated with six molecules of water of
crystallisation. They all have octahedral
shapes.
Preparation and properties of potash alum
Potash alum is the common alum used
daily in homes and industries. It has
the formula K 2SO 4.Al 2(SO 4) 3.24H 2O, or
KAl(SO4)2.12H2O. Potassium aluminium
tetraoxosulphate(VI) - 12-water is the
chemical name for potash alum.
Potash alum can be prepared by
adding a mixture of potassium
tetraoxosulphate(VI) solution and
aluminium(III) tetraoxosulphate(VI)-18-
water solution in the ratio of their relative
95
molecular masses. The resulting solution is
then evaporated, cooled and crystallised.
Alums exhibit the properties of their
composite salts. The crystals have an
octahedral shape and can grow on crystals
of other alums to form giant crystals.
Experiment 6.7
Aim
To Preparate potash alum
Procedure
1 Dissolve enough aluminum foil in
some potassium hydroxide (caustic
potash) solution until a small excess
of the undissolved foil is observed.
2 Filter the solution.
3 Add dilute tetraoxosulphate(VI)
acid to the filtrate until it becomes
acidic (test with litmus).
4 The acidified filtrate in (3) is
concentrated, and then cooled to
obtain alum crystals.
The reactions involved in Experiment
6.7 can be represented as:
2Al(s) + 2KOH(aq) + 6H2O(l) → 2KAl(OH)4(aq) +
3H2(g)
2KAl(OH)4(aq) + 4H2SO4(aq) → K2SO4 + Al2(SO4)3
(alum) + 8H2O(l)
Aluminium(III) chloride
Anhydrous aluminium(III) chloride is
prepared by passing dry chlorine gas
or hydrogen chloride gas over heated
aluminium.
2Al(S) + 3Cl2(g) → 2AlCl3(S)
2Al(s) + 6HCl(g) → 2AlCl3(s) + 3H2(g)

Preparation of the hydrated form of
aluminium(III) chloride is discussed in
Experiment 6.8.
Experiment 6.8
Aim
To prepare aluminum (III) chloride
Procedure
Dissolve aluminum foil in concentrated
hydrchloric acid in a beaker. Obtain
aluminium(III) chloride crystals by
evaporating and cooling the solution. Test
and identify the gas given off.
Aluminium(III) chloride crystals
prepared in this way are colourless,
deliquescent and ionic. On crystallisation,
the hexahydrate crystals are formed in
solution.
2Al(S) + 6HCl(aq) → 2AlCl3(s) + 3H2(g)
2AlCl3(aq) + 6H2O(l) → 2AlCl3.6H2O(s)
Anhydrous aluminium(III)
chloride cannot be made by heating the
hydrated salt in air. This is because the
hydrated aluminium(III)chloride when
heated becomes hydrolysed, resulting
in aluminium hydroxide and finally
aluminium oxide.
2AlCl3(s) + 6H2O(I) 2Al(OH)3(s) + 6HCl(aq)
Note
Hydrolysis of aluminium(III) chloride
gives an acid, hydrochloric acid (acid
hydrolysis) while hydrolysis of sodium
trioxocarbonate(IV) gives an alkali (alkali
hydrolysis).
96
Properties of aluminium(llI)chloride
1 The anhydrous aluminium(III)chloride
is a deliquescent, white, volatile solid.
It is soluble in most organic solvents
and is hydrolysed by water, giving an
acidic solution and the hydroxide.
2 Aluminium(III) chloride prepared in
the laboratory is yellowish in colour
due to the presence of iron(III)chloride
impurities.
3 When heated, it sublimes at 456 K
(183°C); giving aluminium(III)chloride
molecules Al2Cl6.
Uses of aluminium(III) chloride
1 Aluminium(III) chloride is used as
a catalyst in organic synthesis, for
example, in Friedel-Craft’s reaction for
making toluene.
2 Aluminium(III) chloride is used
in cracking and polymerisation of
petroleum.
Summary
This chapter has taught the following:
• Aluminium belongs to the Group IIIB
elements. It has atomic number of 13
and outer electronic configuration of
3s23pl. Thus, it is an example of a p
orbital element.
• Aluminium occurs most abundantly
as the hydrated oxide, bauxite.
• It is extracted by purifying the
oxide. The pure oxide obtained is
then dissolved in molten cryolite
and electrolysed to produce pure
aluminium.
• Pure aluminium is a light, silvery-
white metal. It is ductile, malleable,
and has moderate tensile strength.
 It is a good conductor of heat and C clay.
electricity. D impurities in petroleum.
• When exposed, it readily tarnishes in E rock deposits.
air due to the formation of a layer of 3 As a reducing agent, aluminium is
the oxide which renders it passive. used in
Aluminium has a great affinity for A the Solvay process.
oxygen and this makes the metal a B the thermite process.
great reducing agent. This reducing C Downs cell.
property is made use of in the thermite D blast furnaces.
process. E Friedel-Craft’s reaction.
• Aluminium metal reacts with acids, 4 Which of the formulae below represents
non-metals and alkalis to form various potash alum?
products. A KHAl(SO4)2.12H2O
• Aluminium is used B KAl(SO4)2.12H2O
a) in the electrical industry. C KAl(SO4)3.12H2O
b) in the building industry. D K2Al(SO4)3.12H2O
c) in making alloys. E KAl2(SO4)3.12H2O
d) as aluminium powder in paints. 5 Aluminium hydroxide is
e) as a reducing agent. A a gelatinous, green precipitate in
• Some important compounds of colourless solution.
aluminum are: B used in the dye industry as a
a) aluminium oxide mordant.
b) a l u m i n i u m ( I I I ) t e t r a o x o - C not decomposed by heat.
sulphate(VI) D very soluble in water.
c) aluminium hydroxide E not amphoteric.
d) alums, e.g. potash alum
e) aluminium(III) chloride B Short-structured questions
1 Aluminium occurs in nature in more
Review questions than one ore.
a) Give the names of at least three
A Multiple-choice questions ores of aluminium.
1 Aluminium is normally extracted from b) Give the formula for each ore
A hydrated aluminium oxide. written in (a)
B aluminium tetraoxosulphate(VI). c) Write an equation for the
C aluminium chloride. purification of one of the ores.
D aluminium trioxonitrate(V). d) How is pure aluminium obtained
E aluminium hydroxide. from the purified ore?
2 Aluminium compounds are abundant 2 Write the name and formula of one of
in the form of the products formed when aluminium
A sand. metal reacts with
B decaying animal and vegetable a) (i) air, (ii) moist air.
matter. b) a named acid.

97
 c) sodium hydroxide solution.
d) ammonia solution.
e) a named non-metal.
3 Aluminium forms alums.
a) Write the general equation for
alums.
b) What type of crystals do alums
form?
c) Write the name and formula of
potash alum.
4 Aluminium hydroxide is a compound
of aluminium.
a) What compound of aluminium
is formed when the hydroxide is
heated?
b) State the name and use of the
compound formed.
c) Write one important use of
aluminium hydroxide in
industry.
d) How does aluminium hydroxide
react with
i) sodium hydroxide?
ii) a named acid?
e) What property of aluminium
hydroxide is exhibited in (di)
and (dii) above?
5 Aluminium oxide is an important
compound of aluminium.
a) Write the name and formula of its
hydrated form.
b) Which method can you use to
obtain pure aluminium metal
from its oxide?
c) State the condition under which
aluminium oxide dissolves
readily during the extraction of
aluminium.
98
d) What property of the oxide
is being made use of in this
extraction process?
C Essay-type questions
1 a) Give the name of the main ore of
aluminium in nature.
b) How is pure aluminium extracted
from the above named ore?
c) G i v e t h e c h e m i s t r y o f t h e
extraction process.
d) Aluminium sheet does not rust.
Explain.
2 Write a brief note on the thermite
process.
3 a) How would you prepare a sample
of potash alum?
b) Give two chemical properties
of aluminium(III)tetraoxo-
sulphate(VI). What are its uses?
4 a) Name the products obtained in
the hydrolysis of aluminium(III)
chloride. Write the equation for
the reaction.
b) Compare this with the hydrolysis
of sodium trioxo-carbonate(IV).
c) With the aid of a well-labelled
diagram and equation, show how
anhydrous aluminium chloride is
prepared.
5 a) Write the names and formulae of
three compounds of aluminium
that you know.
b) Describe the preparation of any
one of them.
c) Give three chemical properties
and two industrial uses of the
example you have chosen.
 7 Tin, and metals of the first
transition series

9 describe the chemistry of copper;

Introduction
10 give the uses of copper;
11 describe the chemistry of iron;
In the periodic table, tin is located in the
12 prepare anhydrous iron(III)
5th period and is a member of the Group
chloride;
IVA elements. Tin does not belong to the
13 explain the chemistry involved in
first transition series, but we shall study
the rusting of iron and how rusting
its chemistry along with the metals of the
can be prevented; and
first transition series. This is because tin is a
14 carry out experiments to show the
valuable industrial metal just like metals of
oxidation of zinc by acid.
the first transition series which are of great
industrial application.
Occurrence of tin
Performance objectives
Tin occurs as tinstone or cassiterite (SnO2),
At the end of this chapter, you should be
also known as tin(IV) oxide. Large deposits
able to:
of the ore are found in Malaya and some
1 describe the chemistry of tin metal;
quantity is also found in Jos, Plateau State
2 explain polymorphism and enan-
of Nigeria.
tiotropy as exhibited in tin metal;
3 explain how tin is mined, using a
Extraction of tin
Nigerian source as an example;
4 give the uses of tin metal;
After mining, the tin ore is powdered
5 explain what a transition metal is;
and washed free of impurities by strong
6 list the elements of the first transition
currents of running water.
metals;
The ore is then roasted in air to remove
7 give the physical properties of the
impurities, such as sulphur and arsenic
first transition elements as related
oxides. Tin(IV) oxide so obtained is then
to their electronic structures;
reduced to tin by heating it with coke or
8 describe the common chemical
anthracite in a reverberatory furnace.
properties of the first transition
SnO2(s) + 2C (s) à Sn(s) + 2CO(g)
elements;

99
Physical properties of tin
1 Tin metal exists in three allotropic
forms. Allotropy of solids is
caused by differences in structure.
This phenomenon is referred to as
polymorphism.
The three allotropic forms of tin
are grey tin, white tin, and brittle tin.
Grey tin is a grey powder formed at
low temperatures below 286 K (13°C).
It is less dense than white tin and
its formation is accompanied by an
increase in volume. White tin is the
well-known form of the metal. It is
stable at temperatures between 286 K
(13°C) and 433 K. Brittle tin is formed
at temperatures above 433 K (160°C).
The different forms of tin are
reversible at different temperatures.
Tin, therefore, exhibits enantiotropy.
2 The other physical properties of tin are:
a) Atomic number: 50
b) Outer electronic configuration:
4d105s25p2
c) Atomic mass: 118.69
d) Atomic radius (Å): 1.62
e) Ionic radius M2+ (Å): 1.12
ore + anthracite
hearth
air
Fig. 7.1 Reverberatory furnace
100
f)Boiling point: 2 543 K (2 270°C)
g)Melting point: 505 K (232°C)
h)Density (gcm-3): 7.3
i)Electrode potential M2+/M(V):
- 0.136
j)Common oxidation numbers: II, IV
k)1st and 2nd ionisation energies
kJmol-1 AR: 2.119
1st + 2nd + 3rd + 4th IE; 8.989
l) Electronegativity A/R; 1.7
Chemical properties of tin
1 Tin reacts with air or oxygen when
heated to form tin(IV)oxide.
Sn(s) + O2(g)- SnO2(s)
2 Tin does not react with either water or
steam.
3 Tin combines directly with non-metals
when heated to form the corresponding
products.
Sn(s) + 2Cl2(g) → SnCl4(s)
Sn(s) + 2S(s) → SnS2(s)
(tin sulphide)
4 Tin reacts with hot concentrated
trioxonitrate(V)acid to give the
hydrated oxide. Hot concentrated
flue
 tetraoxosulphate(VI)acid reacts with
tin to give tin(IV) oxide, sulphur(IV)
oxide and water.
Sn(s) + 2H2SO4(aq) → SnO2(s) + 2SO2(g) +
2H2O(l)
5 With alkalis, tin reacts very slowly.
Uses of tin
1 Tin is handy in the plating of steel
containers used in preserving food, e.g.
milk cans.
2 Tin is used in making alloys, for
example, bronze solder consists of tin
and lead.
Fig. 7.2 Food items in steel containers
Metals of the first transition series
Transition metals are those metals whose
unique chemical properties are related
to incomplete inner orbitals. They are
characterised by the expansion of the d-
sub-level in the penultimate orbital, that
is, the orbital next to the outermost orbital.
101
Transition metals have variable positive
oxidation states. The oxidation state varies
from +2 (+1 for transition metals in Group
IB) up to a maximum that is equal to the
group number to which the elements
belong.
The metals show other transition
properties, such as coloured ions, complex
ion formation, paramagnetism, catalytic ability
and other known metallic properties.
The ten elements in Period 4 of the
periodic table, starting from scandium to
zinc, form the first transition series (Table
7.1). In all the elements, either the five 3d
orbitals or the 4s orbitals are partially filled
(Table 7.2).
Physical properties of metals of the first
transition
1 All the transition elements are typical
metals. For example, iron, copper, zinc
and the others are hard solids which
are malleable, tough and ductile. These
possess good mechanical properties.
2 They are good conductors of heat and
electricity.
3 The presence of the 3d single electrons
makes the elements closely packed
due to inter-atomic bonding. Thus, the
metals have
a) high melting and boiling points;
b) high densities; and c) low
atomic volumes.
4 They have magnetic property because
the single 3d electrons are electrical
in nature. As the electrons spin in
their orbitals, they develop magnetic
property. Thus, finely divided iron,
manganese, cobalt and nickel are
Table 7.1 Metals of the first transition series

Period 4

Atomic Sc Ti V Cr Mn Fe Co Ni Cu Zn

numbers 21 22 23 24 25 26 27 28 29 30

Table 7.2 Electronic configuration of metals of the first transition series

Element Atomic number Electronic configuration

Scandium Sc 21 1s2 2s2 2p6 3s2 3p6 3d1 4s2

Titanium Ti 22 1s2 2s2 2p6 3s2 3p6 3d2 4s2
Vanadium V 23 1s2 2s2 2p6 3s2 3p6 3d3 4s2
Chromium Cr 24 1s2 2s2 2p6 3s2 3p6 3d5 4s1
Manganese Mn 25 1s2 2s2 2p6 3s2 3p6 3d5 4s2
Iron Fe 26 1s2 2s2 2p6 3s2 3p6 3d6 4s2
Cobalt Co 27 1s2 2s2 2p6 3s2 3p6 3d7 4s2
Nickel Ni 28 1s2 2s2 2p6 3s2 3p6 3d8 4s2
Copper Cu 29 1s2 2s2 2p6 3s2 3p6 3d10 4s1
Zinc Zn 30 1s2 2s2 2p6 3s2 3p6 3d10 4s2

Fig. 7.3 shows the energy level diagram

ferromagnetic because they are strongly
attracted by a bar magnet.
Titanium and chromium are weakly
attracted by a bar magnet, and so are
paramagnetic. Scandium and zinc are
repelled by a bar magnet and so are
said to be diamagnetic metals. However,
they are good conductors of heat and
electricity.
5 The s and d electrons do not differ
much in energy. For this reason, the
difference in ionisation energies is
relatively small. This leads to the
occurrence of various stable oxidation
states for each of the elements.
of an atom while Table 7.3 shows the
electronic configuration of some elements.
We shall carefully study Fig. 7.3 and
Table 7.3 to enable us to understand fully
the chemical properties of the transition
metals.
The energy level diagram shows
1 the main shells and subshells (orbitals);
2 the different energy levels of shells
K,L,M and N (1,2,3 and 4) and the
energy levels of subshells s,p,d, and f;
and
3 the maximum number of electrons
which each shell and each sub-shell
can contain, for example, an s sub-shell
can hold 2 electrons, a p sub-shell 6, a

102
 d sub-shell 10 and an f sub-shell 14.
(14e–) In the elements having atomic numbers
4f
1 to 18, the electrons are filled normally
(10e–) into the sub-shells as shown in Table
N(32e–) 4d
7.3. Argon is a noble gas because it has
n=4 (6e )–
4p 8 electrons in its outermost shell. The
(10e–) 3d next element, potassium, has an atomic
M(18e–) 2(e–) 4s number of 19 and the nineteenth electron
n=3 3p
(6e–) goes into the 4s sub-shell. This is because
3p
the 4s sub-shell is lower in energy than
Energy

(6e–) the 3d sub-shell (Table 7.4) even though

L(8e )
– 2p
(2e–) all the sub-shells in the third shell, M, are
n=2 2s not yet completely populated. For calcium,
element number 20, another electron is
added to the 4s energy level. For element
K(2e–) (2e–)
1s number 21, scandium, the 21st electron
n=1
goes into the next available energy level,
shell sub-shell
the 3d sub-shell. This is because the 4s
Fig. 7.3 Energy level diagram of an atom
shell is fully occupied. This movement
of the 21st electron into the 3d sub-shell

Table 7.3 Electronic configuration of some elements

Electronic configuration
Element Atomic K L M N Shell
number
1s 2s 2p 3s 3p 3d 4s 4p 4d 4f Sub-shell

Argon 18 2 2 6 2 2 2 2

Potassium 19 2 2 6 2 2 2 2 1

Calcium 20 2 2 6 2 2 2 2 2

Scandium 21 2 2 6 2 2 2 2 1 2

Titanium 22 2 2 6 2 2 2 2 1 1 2
Vanadium 23 2 2 6 2 2 2 2 1 1 1 2

affects the chemistry of all the elements configuration of the first transition metals
from scandium to zinc. Thus, the outer 4p explain why the metals have similar
orbitals of the elements from scandium to physical properties.
zinc are not filled because of their higher
energy levels, while the inner 3d orbitals Chemical properties of metals of the first
or sub-shells are preferentially filled since transition series
they are at lower energy levels. 1 The metals unlike alkali metals do
The similarities in the electronic not react with cold water. They are

103
Table 7.4 Summary of physical properties of the first transition metals
*(II) to refers to couple M2+/M

Property Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nicket Copper Zinc

Atomic Number 20 21 22 23 24 25 26 27 28 29 30

Outer electro-
nic structure 3d°4s2 3d14s2 3d24s2 2d34s2 3d54s1 3d54s2 3d64s2 3d74s2 3d84s2 3d104s1 3d104s2

Configuration
M2+ 3d°4s° — 3d2 3d3 3d4 3d5 3d6 3d7 3d8 3d9 3d10

Configuration
M3+ — 3d°4s° 3d1 3d2 3d3 3d4 3d5 3d6 3d7 3d8 —

Relative atomic
mass 40.08 44.956 47.90 50.942 51.996 54.938 55.847 58.933 58.710 63.54 65.37

Atomic volume
(cm–3mg–1) 26 14.55 10.81 8.39 7.24 7.62 7.10 6.77 6.59 — —

Density (gcm–3) 1.54 3.1 4.43 6.67 7.188 7.21 7.869 8.70 8.902 8.94 7.13

Melting point (K) 1118 1814 1933 2163 2130 1517 1808 1768 1728 1356 693

Boiling point (K) 1760 3104 3560 3653 2943 2235 3023 3134 3003 2840 1180

*Electrode (11)-0.28 (1)+0.52

potential (V) (11)-2.87 (111)-2.1 (111)-1-2 (11)-1.2 (11)-0.91 (11)-1.18 (11)-0.44 (111)+0.4 (11)-0.25 (11)+0.34+ (11)0.76

Metalic radius Å 1.97 1.64 1.47 1.35 1.30 1.35 1.26 1.25 1.25 1.28 1.37

Ionic radius (Å) 2+ 3+ 3+ 4+ 3+ 4+ 2+ 3+ 2+ 3+ 2+ 3+ 2+ 3+ 2+ 3+ 1+ 2+ 2+

0.99 0.81 0.76 4.68 0.74 0.60 0.84 0.69 0.80 0.66 0.76 0.64 0.74 0.64 0.74 0.62 0.96 0.69 0.74

thus less reactive. However, they react 2Zn(s) + O2(g) → 2ZnO(s)

with steam when heated to redness to 4Cr(s) + 3O2 (g) → 2Cr2O3(s)
liberate hydrogen. For example, Iron reacts with oxygen to form three
Zn(s) + H 2O(g) → ZnO(s) + H2(g) types of oxides: iron(II) oxide Fe O,
3Fe(s) + 4H2O(g)- → Fe3O4(s) + 4H2(g) iron(III) oxide, Fe 2 O 3 and iron(II)
2 When exposed to air, transition diiron(III) oxide, Fe3O4.
metals slowly oxidise to form the 4 When heated in a Bunsen flame, they
corresponding oxide. Copper forms are stable to heat and do not burn.
the oxides the trioxocarbonate(IV) and 5 Iron, cobalt and nickel liberate
the hydroxide. Chromium forms the hydrogen from dilute hydrochloric
oxide, CrO, and the trioxide, CrO3. In acid, tetraoxosulphate(VI)acid and
damp air, iron rusts to form a reddish- trioxonitrate(V) acid because they
brown layer of hydrated iron(III) oxide, are higher than hydrogen in the
Fe2O3.3H2O. electrochemical series.
3 When heated to red hot, transition 6 Chromium, manganese and copper
metals burn in oxygen to form the do not react with dilute acids. With
corresponding oxides. For example, concentrated acids, these transition
zinc burns with a blue green flame, metals react to form the corresponding
forming white, solid zinc oxide. salts. However, copper reacts to form
Chromium burns to give green, solid blue copper(II)trioxonitrate(IV) solution
dichromium(III) oxide.

104
 with either dilute or concentrated
trioxonitrate(V) acid.
7 Metals of the first transition series
have variable oxidation states as
shown in Table 7.5. The trend in the
oxidation states of the transition metals
follows the increasing number of 3d
and 4s electrons. With the exception
of scandium, all the elements show
an oxidation state of +2. This can be
associated with the loss of the two
outermosts electrons from the neutral
atom. By losing all the three valency
electrons, an atom of scandium gains the
very stable electronic configuration of
Table 7.5 Variable oxidation states of metals of the first transition series
Element Sc Ti V Cr
Maximum +3 +4 +5 +6
oxidation –
+3 +4 +3
numbers
+2
+2
8 Metals of the first transition series form
coloured ions in aqueous solutions.
Coloured ions are formed by metals
with incomplete d-orbitals. Thus most
compounds of the transition metals are
coloured.
The colour of the compounds of
transition metals may be explained
by the presence of 3d electrons. The
energy needed to raise 3d electrons to
a higher energy level happens to be
equal to the energy found in certain
component colours of the visible
105
argon and this accounts for its readiness
to form the Sc3+ ion. Similarly, loss of the
4s electrons from a zinc atom exposes
the fairly slable 18-electron structure
and this limits further ionisation. As
the neutral copper atom has only one
4s electron before exposing this same
18-electron structure, copper is able to
form copper(I) compounds.
It should be noted that from scandium
to manganese, the highest oxidation state
of each element is its group number. In the
higher oxidation states, the compounds
formed are covalent.
Mn Fe Co Ni Cu Zn
+7 +6 +4 +4 +2 +2
+6 +3 +3 +2 +1 –
+4 +2 +2
+3
+2
white light. When light interacts with
an atom, the energy of the light can
be transferred to the atom only if the
energy corresponds to that amount
needed to raise an electron to a higher
energy level.
Therefore, when white light
is beamed on the compound of a
transition element, some of the colour
components are absorbed by the
excited 3d electrons. The remaining
light is now deprived of some of its
colour components and no longer
 appears white. For example, some
cobalt compounds which absorb red
light acquire blue colouration because
the white light is deprived of its red
component. For this reason, blue glass
is often made by the addition of cobalt
compounds to glass.
Table 7.6 shows the characteristic
colours of some compounds.
Colourless ions are formed by metals with
completely filled d-orbitals or completely
empty d-orbitals. Coloured ions are formed
by metals with incomplete d-orbitals. For
example, scandium and zinc do not form
coloured ions because they cannot absorb
colours from white light.
Experiment 7.1

Aim
Table 7.6 Characteristic colours of some To investigate the effect of water on metals
compounds of transition metals of the first transition series

Ion Colour Compounds in Procedure

which ions exist 1 Place some pieces of copper, zinc and
iron into three different test tubes.
Mn4+ Black MnO2
2 Add cold water to each test tube.
Mn7+ intense purple KMnO4 3 Observe and record what happens in
Fe2+ Black FeO each test tube.

Fe3+ Reddish-brown Fe2O3 Experiment 7.2

Fe 2+
Green FeSO4
Aim
Fe3+ from colour-
To investigate the action of acids on metals
less to yellow Fe2(SO4)3.YH2O
of the first transition series
Cr6+ Yellow K2CrO4
Procedure
Cr6+ Yellow K2CrO4
1 Place pieces of iron, copper and zinc
Cr6+ Deep orange K2Cr2O7 into different test tubes.
Co2+ Blue CoCl2.6H2O 2 Add dilute hydrochloric acid and warm
gently.
Co2+ Pink CoSO4.7H2O 3 Repeat experiment using:
as double salt a) dilute tetraoxosulphate(VI) acid
in (NH4)2SO4 b) concentrated hydrochloric acid
Cu1+ Orange yellow Cu2O c) concentrated tetraoxosulphate(VI)
acid
Cu2+ Black CuO
4 Record all your observations.
Cu2+ Green CuCl2.2H2O
Cu2+ Blue CuSO4.7H2O

106
Complex ion formation or
3+
Metals of the first transition series form NH3 NH3
complex compounds. Complex compounds
Cr NH3
are those compounds which contain a central
atom or a central ion closely surrounded NH3 NH3 NH3
by a cluster of other ions or molecules. The
surrounding ions or molecules are called
Experiment 7.3
ligands which are usually bonded to the
nuclear atom.
Aim
Complex compounds, also called
To prepare tetraamine copper(II)hydroxide,
complexes or complex ions, are often referred
[Cu(NH4)4](OH)2
to as coordination compounds. The number
of ligands is referred to as the coordination
Precedure
number. The nuclear atom and ligands are
1 Prepare a solution of copper(III)
usually capable of independent existence
tetraoxo-sulphate(VI) in a test tube.
as stable species.
2 Add ammonia solution in drops and
The formation of complex ions is due
then in excess.
to the presence of vacant orbitals in the
3 Write down your observations.
transition metals. Also, the small size
and the comparatively high charge of
A pale blue precipitate of copper(II)
the ions of transition metals favour the
hydroxide is formed when drops of
acceptance of a lone pair of electrons
ammonia solution are added to copper(II)
from the ligand molecule or ion. For
tetraoxosulphate(VI) solution.
example, in the electronic configuration of
chromium(III) ion, Cr3+, given below, each CuSO 4(aq) + 2NH4OH(aq)- → Cu(OH)2(s) +
arrow represents an electron occupying (NH4)2SO4(aq)
that particular orbital.
When excess ammonia is added, the pale
↑ ↑ ↑ blue precipitate dissolves and a deep blue
3d 45 4p solution of tetraamine copper(II) hydroxide
is formed.
Cu(OH)2(aq) + 4NH3(aq)→ (Cu(NH3)4)(OH)2(aq)
There Cu
2+
are two 3d, one 4s and three 4p

orbitals completely empty and able to
The copper(II) ion Cu2+ has no electrons
accept a share of six pairs of electrons.
in its outermost shell. It has four vacant
Thus, chromium(III) ion, Cr3+, can form an
orbitals with which it can take 8 electrons
ammonia complex.
as shown.
Cr3+ + 6NH3 → Cr(NH3)3+6 1





Cu2+
3d-orbitals (3d )
9
4s 4p

107
When a solution of copper(II) tetraox-
osulphate(VI) is prepared, the 8 electrons
are supplied by 4 lone pairs of electrons from
4 molecules of water. The hydrated ion
formed is [Cu(H2O)4]2+, hydrated copper(II)
ion. When ammonia solution is added
in excess to the solution, the ammonia
displaces the water molecules and forms a
coordinate covalent compound, tetraamine
copper(II) ion, which is deep blue in colour
in water molecule with 2 lone pairs of
electrons.
NH
3
:O:
H H
i)
H H
O
:
H H
:O Cu O:
H acid down the side of the tube.
O H
H H
:
ii) Hydrated copper(II)ion
NH3 2+
NH3 Cu
NH3
iii) Tetraamine copper(II) ion
The higher the oxidation state, the
greater the tendency to form complex
salts. Thus the transition metals with
higher oxidation states form more stable
complex compounds than those with
lower oxidation states. This is also true for
transition metals with variable oxidation
states. For example, cobalt(II) ion, Co2+ does
not form a stable complex with ammonia,
whereas the cobalt(III) ion, Co 3+ does,
forming [Co(NH3)6]3+.
Experiment 7.4
Aim
To carrty out brown ring test
Procedre
1 Place about 2 cm3 of a solution of a
trioxonitrate(V) salt (for example, Zn
(NO3)2) in a test tube.
2 Acidify the solution with about two
drops of dilute tetraoxosulphate(VI)
acid.
3 Add 2 cm3 of freshly prepared iron(II)
2+ tetraoxosulphate(VI) solution and
shake very well.
4 Hold the test tube in a slanting position
and carefully pour a continuous stream
of concentrated tetraoxosulphate(VI)
5 Keep the tube to stand as in Fig. 7.4.
6 Record all your observations.
test tube
mixed solutions of trioxonitrate(V)
and iron(II) tetraoxosulphate(VI)
brown ring
concentrated
tetraoxosulphate(VI) acid
Fig. 7.4 Brown ring test
When iron(II) tetraoxosulphate(VI) is
dissolved in water, the hydrated pale-green
iron(II) ion, [Fe(H2O)6]2+, is formed. The
108
concentrated tetraoxosulphate(VI) acid
reacts with the trioxonitrate(V) solution,
producing some nitrogen(II) oxide, NO.
The hydrated iron(II) ion reversibly
absorbs the nitrogen(II) oxide, which
then displaces one molecule of water,
and the ion, [Fe(H 2O) 5NO] 2+ produced
is responsible for the brown colouration
observed, that is, the brown ring.
[Fe(H2O)6)2+ + NO → [Fe(H2O)5NO)2+ + H2O
(pale green) (brown)
Other complexes of interest are:
1 Tetrapotassium hexacyanoferrate(II),
K 4 Fe(CN) 6 , a yellow-crystal. It is
produced when excess potassium
cyanide solution is added to a solution
of iron(II)tetraoxosulphate(VI). The net
charge on the complex ion is -4, that is,
(Fe(CN6)-4.
2 Intense brown-red iron(III) complex,
(Fe(SCN)2+, produces dark-red crystals
of hydrated iron(III) thiocyanate,
Fe(SCN)3.3H2O. It is produced when
thiocyanate solution is added to
iron(III) salt solution.
Uses of complex compounds of transition
elements
1 They are used in the extraction of
metals, such as aluminium and gold.
2 They are used in electroplating, for
example, silver plating. The electrolytes
used contain the silver complex iron,
_
Ag(CN)2(aq) in order to obtain a uniform
coherent layer of the plated material.
_ _
Ag(CN)2(aq) → Ag+ (aq) + 2CN (aq)
3 The compounds are used in softening
of water, for example, polyphosphates.
4 They are used in analytical chemistry,
for example, industrial determinations
109
of metal ions.
5 Insoluble, coloured, neutral complexes
are used as pigments (colouring agents)
in the paint manufacturing industry.
6 The complexes of iron, magnesium
and copper are essential for life. For
example, chlorophyll is a complex
compound of magnesium; and
haemoglobin is a complex compound
of iron, known as iron porphyrin.
Catalytic ability of transition metals
Catalytic ability is one of the chemical
properties of the transition metals. Most
of the common catalysts are found among
the transition metals and their oxides.
Examples include vanadium, chromium,
iron, nickel, manganese and platinum.
Catalytic ability is possible because
electron redistribution among reacting
particles is fast. This redistribution is
facilitated by the large number of valency
electrons and also by the available d
orbitals within the atoms of the transition
metals.
Examples and uses of some catalysts
1 Finely divided nickel is used to catalyse
a) theproduction of ethane from
ethene.
b) the hydrogenation of oil to
margarine fat.
C 2 H 4 + H 2 Nickel
→,C 2 H 6
(ethene) catalyst (ethane)
−CH = CH − + H 2 → −CH 2 − CH 2 −
Nickel
(a section of unsaturated catalyst (a section of
saturated fat)
oil)
2 Manganese(IV) oxide is used to catalyse
the decomposition of potassium
 trioxochlorate to oxygen.
2KClO 3(s) Catalyst
MnO
 2
 → 2KCl(s) + 3O 2( g )
3 Vanadium(V) oxide is a catalyst in
the contact process for producing
tetraoxosulphate(VI) acid in industry.
4 Finely divided iron is used as catalyst
in the manufacture of ammonia by the
Haber process.
N 2( g ) + 3H 2( g ) Catalyst
Fe
 → 2NH 3( g )
Iron
Occurrence of iron
Iron is the second most abundant metal in
nature. It commonly occurs as:
1 Haematite (iron(III)oxide, Fe2O3)
2 Magnetite-lodestone (iron(II)
diironoxide, Fe3O4)
3 Limonite (hydrated iron(III)oxide,
Fe2O3.3H2O)
4 Siderite (iron(II) trioxocarbonate(IV),
FeCO3)
5 Iron pyrite-firestone (iron(II)
persulphide, FeS2)
In Nigeria, iron occurs as haematite and
as magnetite. Large deposits are found in
Ajabonoko and Itakpe hills between Okene
and Lokoja. The Ajaokuta Steel and Iron
Complex is served by these deposits.
Extraction of iron
The ores used for the production of iron are
the haematite and magnetite. The first main
stage is smelting, which is the reduction of
iron oxide with carbon. Smelting is carried
out in a blast furnace. The product obtained
is a very impure iron called pig iron or cast
iron.
The blast furnace is a cylindrical steel
structure lined with fire brick. It is usually
110
about 30 metres high and 6 metres wide.
The oxide ores are broken into pieces, about
the size of a fist.
Siderite (FeCO3) is also used to produce
iron. However, it is first roasted outside
the furnace to convert it to iron(III) oxide.
Also iron pyrite, FeS2, and chalcopyrite,
CuFeS2, are first burnt in air and converted
to iron(III) oxide,
4FeS2(g) + 11O2(s) → 2Fe2O3(s) + 8SO2(g)
The iron(III) oxide, coke and limestone
are fed into the furnace through the charger.
Hot air is passed into the furnace from its
base through the air pipes or (tuyeres). The
reactions within the furnace are as follows:
1 The coke burns in the oxygen present
in the hot air to form carbon(IV) oxide
with the production of heat.
C(s) + O2(g) → CO2 (g) + Heat
2 As the carbon(IV) oxide moves up
the furnace, it is reduced by coke to
carbon(II) oxide.
CO2 (g) + C(S) → 2CO(g)
3 The carbon mono(II) Oxide so formed
reduces the iron(III) oxide to iron;
which then collects at the bottom of the
furnace.
Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g)
4 Limestone in the mixture decomposes
at high temperature to give calcium
oxide and carbon(IV) oxide.
CaCO3(s) → CaO(s) + CO2(g)
5 The calcium oxide produced reacts
with silicon(IV) oxide present as
impurity in the ore to form calcium
trioxosilicate(IV), CaSiO3, known as
slag.
CaO(s) + SiO2(s) → CaSiO3(l)
 ore, coke, and
hopper for
limestone in
filling furnace

damper

3Fe2O3 + CO 673

873 hot stack gases

Fe2O + CO2 24% CO to
stoves for heating

823
FeO + CO

1 273

1 573

2c + O2
1 773

hot air in
tuyeres from stove

slag out molten pig

iron out

Fig. 7.5 Blast furnace for extracting iron

The molten slag formed is less dense Types of Iron

than iron, so it forms a layer over the
iron and protects it from oxidation.
The slag is run out at the bottom of the
furnace, as shown in Fig 7.5.
The slag is allowed to harden, and
then crushed and used for building
roads. The iron so obtained is hard and
brittle.
Pig iron
This is the iron obtained straight from the
blast furnace. It is hard and brittle because
it contains impurities. The impurities
present consist of between 2 and 5% of
carbon and other elements, such as sulphur,
phosphorus, manganese and silicon.

111
Cast iron
Cast iron is obtained by melting pig iron,
mixing it with steel scrap and then cooling
it to form moulds. Cast iron has a lower
melting point than pure iron.
Wrought iron
Wrought iron is the pure form of iron. It
contains about 0.2 per cent carbon. It is
produced from cast iron by removing the
impurities. The process takes place in a
reverberatory furnace in which haematite
is mixed with cast iron. The haematite
(Fe2O3) serves as the oxidiser, oxidising the
impurities to their oxides.
3C(s) + Fe2O3(s) → 2Fe(s) + 3CO(g)
Physical properties of pure iron
1 Iron is a silvery metal.
2 It has a density of 7.9 gcm-3.
3 It has a melting point of 1 803 K (1
530°C).
4 It can be easily magnetised.
5 It is malleable and ductile.
red-hot iron nail
steam
heat
Fig. 7.6 Action of steam on hot iron
112
Chemical properties of iron
1 When iron is exposed to moist air, it
rusts gradually due to the formation of
reddish hydrated iron(III) oxide, Fe2O3.
YH2O, where Y represents the number
of molecules of water. Y is yet to be
determined accurately. The layer of
oxide formed does not render the iron
passive as for aluminium. The rusting
process continues until all the iron
has been converted to the oxide. This
shows that the oxide layer is porous
and does not prevent further corrosion
of the metal from taking place.
4Fe(s) + 3O2(g) + YH2O(l) → 2Fe2O3.YH2O(s)
2 When heated in air, finely divided iron
burns at high temperature, combining
with oxygen to form iron(II)diiron(III)
oxide, Fe3O4, magnetic iron oxide.
3Fe(s) + 2O2(g) → Fe3O4(s)
3 Iron(II)diiron(III)oxide and hydrogen
are produced when steam is passed
over red-hot iron.
3Fe(s) + 4H2O(g) → Fe3O4(s) + 4H2(g)
The reaction is reversible.
hydrogen
water
4 Iron combines with chlorine and other
non-metals. Iron combines directly
with dry chlorine gas when heated,
to form anhydrous iron(III) chloride.
With sulphur, iron(II) sulphide is
formed, whereas with hydrogen
chloride gas, iron(II) chloride is formed
and hydrogen gas liberated.
2Fe(s) + 3Cl2(g) → 2FeCl3(s)
Fe(S) + S(s) → FeS(s)
Fe(s) + 2HCl(g) → FeCl2(s) + H2(g)
Phosphorous and carbon also
combine with iron directly when
heated, but nitrogen does not combine
with iron even when heated.
5 Iron dissolves readily when dropped
into test tubes containing dilute
tetraoxosulphate(VI) acid and
dilute hydrochloric acid, forming
the corresponding iron(II) salts and
liberating hydrogen gas.
Fe(s) + H2SO4(aq) → FeSO4(aq) + H2(g)
Fe(s) + 2HCl(aq) → FeCl2(aq) + H2(g)
When dilute trioxonitrate(V) acid
is added to pieces of iron in a test
tube, series of complex reactions
take place leading to the formation
of several products, such as iron(II)
trioxonitrate(V), ammonium
trioxonitrate(V), ammonia and even
oxides of nitrogen.
Experiment 7.5
Aim
To investigate the effects of moist air on
iron
Procedure
1 Put some pieces of pure iron in a beaker.
2 Place the beaker where it will be in
contact with moist air for some days.
3 Examine the pieces of iron in the beaker
and record your observations.
Uses of iron
Cast iron is used for making pipes, railings,
radiators, lamp posts, retort stands, fancy
cast-iron work, piping, cylinder blocks and
many other things, where the brittle nature
of the iron does not matter.
Wrought iron is malleable; so it is used
to make ornamental gates, horse shoes,
door knockers, iron chairs, etc. It is too soft
for most other purposes.

layer of palm
oil or kerosine desiccator
dry air
distilled
water
iron nails
boiled
distilled
iron nails water

iron nails
anhydrous
A B calcium
chloride

Fig. 7.7 Investigating the conditions necessary for rusting

113
Rusting of iron
Iron is moderately reactive. When exposed
to moist air, it rusts and forms the brown
hydrated oxide, Fe2O3.YH2O. This oxide is
non-coherent and permeable. Thus, it does
not protect the metal from further reaction.
Experiment 7.6
Aim
To investigate the conditions necessary for
rusting
Procedure
1 Select two test tubes laelled A and B
and get some clean unused iron nails
ready. Preparea desiccator.
2 Into test tbe A containng distilled water,
put a few unsed, clean iron nails; then
exposed the test tube to air.
3 Into test tube B, put some distilled
water, boil for a few minutes to drive
off and dissolved gases. Then quickly
place few claan, unsed nails in the test
tube and seal off the furface of the
water by adding a layer of palm oil or
kerosine, to ensure that no air dissolves
in the water.
4 Into the desiccator, put a few unused,
clean iron nails, as shown in Fig7.7.
Leave the experiment to stand for about
five days.
5 Carefullyexaminethenals in the test
tubes and the deciccator and record all
your observations.
In the experiment, the nails in test tube A
are seen to be covered with a reddish brown
layer, which is hydrated iron(III) oxide,
Fe2O3.YH2O or rust. In test tube B and the
114
desiccator, the nails do not rust. This is
because test tube B has water but no air.
The desiccator has dry air but no water.
The conclusion, therefore, is that rusting of
iron occurs in the presence of both air and
water. Further investigation has shown
that one-fifth of the air present is used up
during rusting. This confirms that it is the
oxygen in the air which is important and
used during rusting of iron.
Prevention of rusting
There are several methods for protecting
iron from rusting. We shall outline a few
of such methods.
1 Application of a protective layer, e.g.
paint, tin, or zinc, by electroplating.
2 Galvanisation, which consists
of coating the iron metal with a
layer of zinc metal. Zinc is more
electropositive than iron and so
is oxidised first. Zinc metal only
tarnishes in air and moisture. Thus
zinc acts as a protector for steel and
iron. Galvanised iron is used for
making roofing sheets. Tin is also an
uncreative metal and can be used in
galvanisation. Cans used for food are
light iron sheets coated with tin.
3 Greasing is another method of
preventing rusting and it is used on
iron surfaces to prevent them from
rusting.
Compounds of iron
We have already seen that iron exhibits
two different oxidation states. In each
of these oxidation states, corresponding
compounds are formed. A summary of the
compounds formed is given in Table 7.7.
Table 7.7 Compounds of different oxidation states of iron

Compounds of iron Oxidation state of iron

Iron(II), Fe2+ Iron(III), Fe3+

oxidation state 2 oxidation state 3

1 Oxides FeO Fe2O3; Fe3O4 is a mixed oxide

2 Chlorides FeCl2 FeCl3
3 Hydroxides Fe(OH)2 Fe(OH)3
4 Tetraosulphate(VI) salts FeSO4 Fe2(SO4)3
5 Complex ion formed in (Fe(H2O)6)2+ (Fe(H2O)6)3+
solution ion ion

Iron(II) compounds are reducing agents Properties of iron(II)tetraoxosulphate(VI)

and are converted to the iron(III) state by 1 The hydrated form is efflorescent.
losing one electron per atom. When exposed to air, it effloresces
Fe2+ – e- → Fe3+ and turns yellow due to atmospheric
or oxidation, to basic iron(III) tetraoxo-
sulphate(VI). The solution of iron(III)
Fe2+ → Fe3+ + e-
tetraoxosulphate(VI) is also slowly
Iron(III) compounds are oxidising agents
oxidised by oxygen in the air to form
and can be changed to iron(II) by gaining
iron(III) tetraoxosulphate(VI), and then
an electron.
iron(III) hydroxide precipitate.
Fe3+ + e → Fe2+ 2 Heat decomposes iron(II) tetraoxo-
sulphate(VI).
Iron(II) compounds
FeSO4.7H2O(s) → FeSO4.H2O(s) + 6H2O(l)
Generally, iron(II) compounds are prepared
by the action of suitable dilute acids on FeSO 4.H2O (s) → FeSO4(s) + H2O(l)
iron. 2FeSO4(s) → Fe2O3(s) + SO2(g) + SO3(g)

3 Iron(II) tetraoxosulphate(VI)
Iron(II)tetraoxosulphate(VI)
Fe(s) + H2SO4(aq) → FeSO4(aq) + H2(g)
Green crystals of hydrated iron(II)
tetraoxosulphate(VI) -7- water
(FeSO 4 .7H 2 O) are obtained from the
aqueous solution by crystallisation.
FeSO4(aq) + 7H2O(l) → FeSO4.7H2O(s)
(green)
solution turns purple potassium
tetraoxomanganate(VII) colourless.
The iron(II) ions in this reaction
are oxidised to iron(III) ions. This
means that iron(II) ions are acting
as a reducing agent while the
manganate(VII) solution is acting as
an oxidising agent.

115
 Also, iron (II) ions give a pale-
blue precipitate with potassium
hexacyanoferrate(II) solution, and a
dark-blue precipitate with potassium
hexacyanoferrate(III).
Iron(II) hydroxide
A green, gelatinous precipitate of iron(II)
hydroxide is formed by double decomposition
when iron(II) ions react with sodium
hydroxide or ammonia solution.
FeSO4(aq) + 2NaOH(aq) → Fe(OH)2(s) + chloride undergoes oxidation to form
Na2SO4(aq)
FeSO4(aq) + 2NH4OH(aq) → Fe(OH)2(s) +
(NH4)2SO4(aq)
The green, gelatinous precipitate of iron(II)
combines with oxygen from the air, in
the presence of water, to produce a red
or misty-brown precipitate of iron(III)
hydroxide.
4Fe(OH)2(aq) + O2(g) + 2H2O(l)→ 4Fe(OH)3(s)
(iron(III) hydroxide)
Iron(II) chloride
Anhydrous Iron(II) chloride can be
produced by direct combination of iron
iron filings
dry
chlorine
heat
Fig. 7.8 Preparation of anhydrous iron(III) chloride
116
with chlorine in a combustion tube.
2Fe(s) + 3Cl2 (g) → 2FeCl3(s)
The hydrated form of the chloride can also
be prepared by using dilute hydrochloric
acid and the oxide of the metal.
FeO(s) + 2HCl(aq) → FeCl2 (aq) + H2O(l)
The anhydrous iron(II) chloride is
produced by the action of hydrogen
chloride gas on iron. It is a white, crystalline
solid. On heating, the hydrated iron(II)
iron(II) oxide. This is why anhydrous
iron(II) chloride is not prepared from
hydrated iron(II) chloride.
Fe(s) + 2HCl(s) → FeCI2(s) + H2(g)
Experiment 7.7
Aim
To preparate anhydrous iron(III)chloride
Procedure
1 Set up the apparatus as shown in Fig.
7.8.
solid rust or
iron (III) chloride
to fume
cupboard
2 Place the apparatus in a fume cupboard.
3 Reapeat the experiment, using other
non-metals, such as sulphur and
hydrogen chloride gas.
4 Record your observations.
Properties of iron(II) chloride
1 The anhydrous iron(II) chloride is a
white crystalline solid which is soluble
in water.
2 It is deliquescent, that is, when exposed
to air it absorbs water, dissolves in it
and forms a solution.
Iron(II) sulphide
Iron(II) sulphide is prepared by heating
iron filings and sulphur.
Fe(s) + S(s) → FeS(s)
Properties and uses of iron(II) sulphide
Iron(II) sulphide is a greyish-black
compound in the form of plates or hard
sticks. It is used for generating hydrogen
sulphide in Kipp’s apparatus by the
reaction:
FeS(s} + 2HCl(aq) → H2S(g) + FeCl2(aq)
Iron(III) compounds
Iron(III) compounds are produced when
iron(II) compounds are oxidised by mild
or strong oxidising agents.
Diiron(III)tetraoxosulphate(VI), Fe2(SO4)3
Diiron(III)tetraoxosulphate(VI) is prepared
by heating iron(II) tetraoxosulphate(VI)
with concentrated tetraoxosulphate(VI)
acid.
2FeSO4(s) + 2H2SO4(aq) → Fe2(SO4)3(aq) +
SO2(g) + 2H2O(l)
117
Diiron(III)tetraoxosulphate(VI) undergoes
hydrolysis when dissolved in water, giving
a strong acid.
Fe2(SO4)3(s) + 6H2O(aq) → 2Fe(OH)3(s) +
3H2SO4(aq)
Iron(III) hydroxide, Fe(OH)3
Iron(III) hydroxide is obtained by the
action of sodium hydroxide or ammonia
solution on any iron(III) salt.
Fe2(SO4)3(aq) + 6NH4OH(aq)→ 2Fe(OH)3(s)
(brown, gelatinous precipitate)
+ 3(NH4)2SO4(aq)
FeCl3(aq) + 3NaOH(aq) → Fe(OH)3(s) +
3NaCl (aq)
Properties of iron(III) compounds
1 Iron(III) salts are reduced by sulphur(IV)
oxide and other reducing agents, such
as hydrogen sulphide to form iron(II)
salts.
2FeCl3(aq) + H2S(g) → 2FeCl2(aq) + 2HCl(aq)
+ S(s)
2 Potassium hexacyanoferrate(II) reacts
with iron(III) salts to give ‘prussian
blue’.
3 Potassium or ammonium thiocyanate
gives a deep red colouration with
iron(II) salts.
Iron(III) oxide, Fe2O3
Iron(III) oxide occurs in nature as haematite.
In the laboratory, it can be prepared by
heating iron(II) tetraoxosulphate(VI)or
iron(II) hydroxides.
2FeSO4(s) → Fe2O3(s) + SO3(g) + SO2(g)
2Fe(OH)3(s) → Fe2O3(s) + 3H2O(g)
Properties of iron(III) oxide
1 Iron(III) oxide can be reduced to the
metal by carbon(II) oxide, as in the blast
furnace, or by hydrogen.
2 Iron(III) oxide is a reddish-brown basic
oxide.
Iron(II)diiron(III)oxide
Commonly known as magnetite, iron(II)-
diiron(III) oxide occurs in nature as a black
magnetic oxide. It is produced by:
1 burning iron in oxygen at high
temperatures.
3Fe(s) + 2O2(g) → Fe3O4(s)
2 passing steam over red-hot iron.
3Fe(s) + 4H2O(g) → Fe3O4(s) + 4H2(g)
Properties of magnetite (Fe3O4)
I Under suitable conditions, magnetite
is reduced to the metal and water by
hydrogen.
Fe3O4(s) + 4H2(g) → 3Fe(s) + 4H2O(l)
2 It is black, solid and magnetic.
Uses of iron(III) oxide
I Iron(III) oxide is used as a pigment.
2 It is a major source of iron metal.
Copper
Occurrence of copper
Copper occurs as:
1 Copper pyrites (CuFeS2, which is the
main source of copper).
2 Cuprite (Cu2O).
3 Malachite (CuCO3.Cu(OH)2).
4 Chalcocite (Cu2S).
5 Bornite (Cu2S.CuS.FeS).
118
Extraction of copper
Copper is extracted from the sulphide,
Cu 2 S, which is often combined with
CuFeS2. The process involves:
1 crushing of the mined rock, using
suitable machinery;
2 removal of impurities through flotation,
in which air is blown into a large tank
containing a mixture of the crushed ore
and water;
3 roasting the ore to remove some of the
sulphur, such as sulphur(IV) oxide;
2CuFeS2(s) + 4O2 g) → Cu2S(s) + 2FeO(s)
+ 3SO2(g)
4 smelting the roasted ore in a non-
oxidising furnace and removing the
iron(II) oxide as iron trioxosilicate(IV);
FeO(s) + SiO2(s) → FeSiO3(s)
5 reduction of copper(I) sulphide(Cu2S)
to copper in a Bessemer converter by
air blasted into the converter.
2Cu2S(s) + 3O2(g) → 2 Cu2O2(s) + 2SO2(g)
2Cu2O(s) + Cu2 S(s) → 6Cu(s) + SO2(g)
The copper produced in this way is the
crude form.
Copper of high purity can be obtained
from the crude form by electrolysis, using
copper(II) tetraoxosulphate(VI) as the
electrolyte. The crude copper is the anode
e e
CuSO4
impure solution
copper
pure
anode copper
slime
Fig. 7.9 Obtaining pure copper by electrolysis
while pure copper is used as the cathode.
The impure copper goes into solution,
while pure copper is deposited at the
cathode, leaving the impurities in the
solution. Some silver and gold are collected
at the anode as valuable impurities.
Reactions at the electrodes are as follows:
1 at the anode,
Cu(s) → Cu2+ + 2e-
2 at the cathode,
Cu2+ + 2e- → Cu(s)
Physical properties of copper
Copper is a red, soft metal with a chara-
cteristic lustre. It is malleable and ductile.
Copper is an excellent conductor of heat
and electricity. It has a density of 8.95 gcm-3,
melting point of 1 353 K (1 080°C) and
relatively high tensile strength.
Chemical properties of copper
1 Copper has weak electropositive
property, hence it is low on the activity
series. It is very stable in pure air.
2 When exposed to moist air for a long
time, copper becomes covered with
a green coating of basic copper(II)
tetraoxosulphate(VI), CuSO4.3Cu(OH)2
and the carbonate, Cu2(OH)2CO3, is also
formed. The basic copper(II) chloride,
CuCl2.3Cu(OH)2 is also formed when
copper is exposed to moist sea air.
3 Copper forms black copper(II)
oxide when heated in air at a high
temperature.
2Cu + O2(g) → 2CuO(s)
Copper(I) oxide, Cu2O, is formed in
the inner layer, while black copper(II)
oxide (CuO) layer is on the outer
surface.
119
4 Copper is lower than hydrogen in
the electrochemical series, hence it
cannot displace hydrogen gas from
acids. It does not react with non-
oxidising acids, such as hydrochloric
acid and other dilute acids. With
concentrated tetraoxosulphate(VI)
acid, copper is oxidised to copper(II)
tetraoxosulphate(VI), while the acid is
reduced to sulphur(IV) oxide, (SO2).
Cu(s) + 2H2SO4 → CuSO4(aq) + 2H2O(l) +
SO2(g)
5 Dilute trioxonitrate(V), reacts with
copper to give the trioxonitrate(V) and
the acid is reduced to nitrogen(II)oxide
(NO).
3Cu(s) + 8HNO3(aq) → 3Cu(NO3)2(aq) +
4H2O(l) + 2NO(g)
With hot, concentrated trioxo-nitrate(V)
acid, nitrogen(IV) oxide is formed.
Cu(s) + 4HNO3(aq) → Cu(NO3)2(aq) +
2H2O(l) + 2NO2(g)
6 Copper(II) ions form a blue, gelatinous
precipitate with sodium hydroxide
solution. The precipitate is insoluble
in excess of the alkali.
Cu2+(aq) + 2NaOH(aq) → Cu(OH)2(s) +
2Na+(aq)
7 Copper(II) ions form blue precipitate
with a few drops of ammonia solution.
The precipitate dissolves in an excess of
the ammonia solution to give a deep-
blue solution.
Cu2+(aq) + 2OH-(aq) → Cu(OH)2(s)
(blue precipitate)
Cu(OH) 2(s) + 4NH + 4(aq) + 4OH - →
[Cu(NH3)4]2+(aq) + 2OH-(aq) + 4H2O(l)
 8 When heated in a non-luminous
flame, copper(II) ions burn with a
characteristic bluish-green colour.
Uses of copper
1 Copper is used as a conductor for
making electric wires, since it is ductile.
2 In metalwork, copper is used in
plumbing, roofing and other building
operations.
3 Copper is used in making alloys, such
as brass, nickel and bronze.
Copper(II)tetraoxosulphate(VI)
This is the most important compound
of copper. It exists as the anhydrous
white powder, and as the blue hydrated
crystals with five molecules of water of
crystallisation. The anhydrous white
compound easily forms the hydrated
tetraoxosulphate(VI).
CuSO 4 .5H 2 O(s) 303
 K ( 30°C )
→ CuSO 4(s) + 5H 2 O( l )
Uses of copper(II)tetraoxosulphate(VI)
1 In agriculture as fungicide for
controlling diseases in potatoes, apples,
grapes and other crops.
2 To prevent timber rot.
Table 7.8 Composition and uses of alloys
Stainless steel Composition
1 Steel 98-99.5% Fe;
0.15-1.5% carbon
120
3 In oil refineries.
4 To control algae and other micro-
organisms in reservoirs.
5 In the rayon industry.
6 As an electrolyte in galvanic cells and
in eletroplating.
Alloys
When two or more metals are mixed
or combined to make an entirely new
substance, such a substance is called an
alloy. An alloy is usually more useful than
the pure metal. For instance, bronze is an
alloy of copper and tin, but bronze is more
useful than either copper or tin.
Sometimes, an alloy contains a substance
which is a non-metal. For example, steel is
an alloy of iron and carbon.
In making an alloy, the components
are mixed in the desired proportions,
melted together and solidified. Thus, the
components do not undergo any chemical
change. Also, the elements in an alloy
must be soluble in each other and must
not separate from one another even when
cooled and solidified. Examples of alloys,
their composition and uses are presented
in Table 7.8.
Properties and uses
Steel is hard and almost free from other
impurities. It is used in building and
construction industries, for example, in
the construction of bridges, and making
of farm equipment, vehicle bodies and
other machines.
 2 Stainless steel 90-95% Fe; Stainless steel is hard and resistant to
5-10% Cr, Ni corrosion. It is used in making cutlery,
tools and surgical instruments.

3 Duralumin 90-95% Al; Duralumin is very light and stronger

3-5% Cu; than aluminium. It is used in
3-5% Mg constructing aircraft, ships, buses, rail
coaches and piston heads.

4 Brass 60-80% copper ; Brass is stronger, more malleable,

20-40% zinc more attractive and of lower melting
point than copper. It is used in making
moving parts of clocks and watches,
nuts, bolts, rods, tubes, musical
instruments, ornaments and for general
metal work.

5 Bronze 90-95% copper; Bronze is stronger and has greater

5-10% tin resistance to chemical attack than
copper. It is more attractive in
appearance than copper. It is used in
making medals, coins, sculptures and
for general metalwork.

Steel chromium content is as high as 18 per

cent. Manganese, cobalt, tungsten,
Steel is an alloy of iron containing from 0.15 vanadium and silicon can also be
to 1.5% carbon. Steel is almost free from alloyed with steel to produce other
other impurities, such as silicon, sulphur kinds of steel.
and phosphorous. Steel can be grouped
into two types:
Manufacture of steel
1 Carbon steel, which is classified
There are three main processes used in the
according to the percentage of carbon
manufacture of steel: Bessemer process,
present, into low, mild, medium and
process, Linz-Donawitz (L-D), and Siemens
high-carbon steel.
Werner proces.
2 Alloy steel, which is formed when
other elements are added to the
1 Bessemer process
molten steel to produce desirable
This is a process of converting cast iron into
properties. For example, stainless
steel. The process was invented by Henry
steel contains a good percentage of
Bessemer, an English metallurgist. In this
chromium metal. In some cases, the
process, the Bessemer converter is used.

121
 heat-resistant
brick linings
horizontal
axle
Fig. 7.10 Bessemer converter
Molten pig-iron from the blast furnace
is poured into the Bessemer converter,
an egg- shaped vessel. The converter
rotates on a horizontal axis and, during
the addition of the molten pig-iron, the
converter is kept in a horizontal position.
The converter is then turned to an
upright position and a blast of hot air is
blown into the molten pig-iron through the
perforated base of the converter.
Impurities, such as carbon and sulphur,
are oxidised to their respective gaseous
products and burnt away. Manganese and
silicon react with the lining of the converter
to form slag. Also, phosphorous(V)oxide
reacts with the lining of the converter to
form slag.
All the slag formed is easily removed. In
this way, pure iron is produced. Depending
on the type of steel required, calculated
amounts of manganese, carbon, etc. are
added to the pure iron.
2 Linz-Donawitz (L-D) process
This is a modification of the Bessemer
122
molten
pig-iron
air
process. It is a new method of producing
steel, and accounts for the major proportion
of steel produced today. In the L-D process,
molten pig-iron and some scrap steel are
fed into the blast furnace. A blast of oxygen
is passed through the mixture. The non-
metallic impurities are oxidised and burnt
off.
Basic slag is produced by the addition of
powdered lime. The L-D process does not
require the use of large quantities of scrap
steel it is rapid and produces quality steel.
3 Siemens-Werner process
This is a process of making steel invented
by Siemens-Werner, a German electrical
engineer. An adaptation of Siemens-Werner
process became known as the open-hearth
process which uses a shallow rectangular
furnace lined with limestone or dolomite,
CaCO3.MgCO3.
In this process, calculated quantities
of pig-iron, scrap steel and haematite are
heated together in a rectangular furnace.
When hot air and fuel are blasted into the
furnace, the haematite supplies the oxygen
for the oxidation process. Non-metallic
impurities are converted to their oxides.
blast of oxygen
Fig. 7.11 Blast furnace for the
Uses of steel
1 In the form of stainless steel, it is used
in the manufacture of cutlery.
2 Steel is used in the building and
construction industry, for example,
in building bridges, farm equipment
and so on.
3 Steel is used for making drilling and
cutting implements.
4 It is used in industry for making
motor vehicle bodies and parts.
5 Steel is used in the manufacture of
equipment requiring toughness and
great tensile strength.
Summary
This chapter hastaughtthefollowg:
• The main ore of tin is cassiterite (SnO2)
123
The open-hearth process is rather slow
but it allows for control and produces the
best quality steel.
scrap steel
+
molten iron
or tin(IV)oxide. Tin is extracted from
its ore by a reduction process in which
tin(IV)oxide is heated with coke and
anthracite. Tin exhibits enantiotropy
and reacts with air or oxygen when
heated to form tin(IV)oxide. Non-
metals combine directly with tin when
heated, forming the corresponding
products. Tin reacts with both hot,
concentrated trioxonitrate(V)acid and
hot tetraoxosulphate(VI) acid. Tin
reacts slowly with alkalis. Tin is used
in tin-plating to prevent rusting. Some
alloys are made of tin.
• The ten elements in Period 4 of the
periodic table, starting from scandium
to zinc, form the first transition series.
Transition metals are characterised by
the expansion of the d sub-level in the
 orbital next to the outermost orbital.
Transition metals have variable
positive oxida-tion states.
• Coloured ions, complex ion for-
mation, paramagnetism and catalytic
ability are known metallic properties
of the transition metals. All transition
elements are typical metals with
similar physical properties:
a) They are hard solids which are
tough and ductile.
b) They are good conductors of heat
and electricity.
c) They have
i) high melting and boiling points;
ii) high densities;
iii) low atomic volumes; and
iv) magnetic property, because
the single 3d orbital electrons
become magnetic as they spin.
• Transition metals do not immediately
react with cold water, but they react
with steam to liberate hydrogen. When
exposed to air, transition metals slowly
oxidise to form the corresponding
oxides. When heated in a bunsen flame,
they are stable to heat and do not burn.
• Iron, cobalt and nickel liberate
hydrogen from dilute hydrochloric,
tetraoxosulphate(VI) and
trioxonitrate(V) acids because they
are higher than hydrogen in the
electrochemical series.
• Chromium, manganese and copper
do not react with dilute acids. The
transition metals react to form the
corresponding salts.
• Iron is the second most common metal
in nature. It commonly occurs as
haematite, Fe2O3; magnetite or lodestone,
Fe 2O 4, limonite, Fe 2O 3.H 2O, siderite,
FeCO3 and iron pyrite (firestone), FeS2.
124
Iron is extracted from its ore in the blast
furnace by the reduction of iron oxide
with carbon. The product is impure iron
called pig iron or cast iron.
• When exposed to air, iron rusts by
forming Fe2O2.YH2O. Iron combines
directly with non-metals, such as
sulphur and chlorine when heated. Iron
displaces hydrogen whendissolved
in dilute tetraoxosulphate(VI) and
hydrochloric acids.
• Water, and air are necessary for rusting
of iron. Methods for preventing rusting
include
a) the application of a protective layer,
such as paint or by electroplating tin
and zinc.
b) galvanisation, which involves
coating the iron with other less reactive
metals.
c) greasing.
• Copper occurs as copper pyrite, CuFeS2;
cuprite, Cu 2 O; malachite, CuCO 3 .
Cu(OH)2; chalcocite, Cu2S; bornite, Cu2S.
CuS.FeS. Extraction of pure copper
from its crude form is by electrolysis.
• When exposed to moist air for a long
time, copper becomes covered with
green coating of CuSO4.3Cu(OH)2. It is,
however, stable in pure air.
• Copper cannot displace hydrogen from
acids.
• Copper(II) ions form a blue, gelatinous
precipitate with sodium hydroxide
solution which is insoluble in excess
of the alkali. Copper(II) ions form
blue precipitate with a few drops of
ammonia solution. The precipitate
dissolves in an excess of the ammonia
solution to give a deep-blue solution.
• Copper(II) tetraoxosulphate(VI) is used
as fungicide for controlling diseases in
 potatoes, grapes, etc; to prevent timber
rot and to control algae and other
microorganisms in reservoirs.
• An alloy is a metallic substance prepared
by adding other metals or non-metals
to a basic metal so as to obtain certain
desirable qualities.
• Steel contains a definite percentage of
carbon. Three processes for producing
steel are the Bessemer process, Linz-
Donawitz (L-D) process and the
Siemens-Werner open-hearth process.
Review questions
A Multiple-choice questions
1 Which of the following reactions occur
during the extraction of tin from its
oxide?
A Hydrolysis
B Oxidation–reduction
C Hydraulic
D Electrolytic
E Reverberation
2 Most compounds of transition
metals are coloured. Which of these
compounds will give intense purple
colour in aqueous solution?
A K2Cr2O7
B FeSO4
C KMnO4
D CuCl2.2H2O
E CoCl2.6H2O
3 The brown ring test is used to detect
the presence of
A Cr6+.
B Mn4+.
C Fe2+ .
D Co2+ .
E Cu+1.
125
4 The reaction,
FeSO4(aq) + 2NaOH(aq) → Fe(OH)2SO4(aq)
is best described as
A double decomposition.
B fission reaction.
C crystallisation reaction.
D hydrolysis reaction.
E deliquescence.
5 The reaction,
Fe3O4(s) + 4H2(g) → 3Fe(s) + 4H2O(l)
is an example of
A hydration.
B precipitation.
C rusting.
D ionisation.
E reduction reaction.
B Short-structured questions
1 The three allotropic forms of tin are:
a) ___________________________
b) ___________________________
c) ___________________________
2 Using equations only, show what
happens when sulphur and chlorine
combine with tin. State under what
condition this reaction takes place.
3 List four chemical properties of
transition metals.
4 Complete the following equations.
a) C2H4(g) + 4H2(g) ?→ C2H6(g)
b) Fe2O3(s) + CO(g) → Fe(s) + 3CO2(s)
c) 2CuFeS2(s) + O2(s) → Cu2S(s) +
FeO(s) + 3SO2(g)
d) Cu(s) + 4HNO3(aq) → Cu(NO3)2(aq)
+ __?____ + ____?___
5 Complete the following statement:
Copper(II) ions form a blue
(i) precipitate with (ii) solution which
is (iii) in excess of the alkali.
C Essay-type questions
1 Using the valency bond approach,
draw the electronic configurations of
the following:
a) Cr(NH3)6 3+
b) Cu(NH3)4 24
+

2 Account for the economic usefulness

of extracting iron from its ore. Explain
chemically why iron rusts.
3 How is pure copper produced in
industry? How would you produce
copper(II) tetraoxosulphate(VI) in the
laboratory? What are the six uses of the
compound?
4 What are the common physical and
chemical properties of the transition
metals? What advantages can you take
of these properties? How would you
test for iron(II) ion in the laboratory?
5 What are alloys and how are they
produced in industry? Name five alloys
you know. What use can we make of
any two of the alloys?

126
 8 Waste: Ethical, legal and
social issues
Introduction
Much waste in modern times results from
various kinds of chemical activities. So,
it has become necessary that students in
their final year of senior secondary school
should get acquainted with the problem.
This would enable them to play an active
role in society towards containing waste.
In an attempt to achieve this objective,
we shall, in this chapter, study the topic
under the following sub-topics:
1 Chemical waste
2 Industrial pollution
3 Roles of government in preventing
chemical degradation:
a) Legislation
b) Setting of minimum standards
c) Enforcement of laws and
standards
Performance objectives
At the end of this chapter, you should be
able to:
1 state the adverse effects of chemical
waste on the environment;
2 list some industrial pollutants;
3 state ways of preventing chemical
degradation; and
127
4 identify the role of government in
preventing and fighting chemical
degradation.
Chemical waste
Chemical waste is waste that results from
harmful chemicals (mostly produced by
large factories).
Industrial waste is waste from industrial
activities, such as those of factories, mills
and mines. Much industrial waste (like
fibres produced in agriculture and logging)
is neither hazardous nor toxic.
Hazardous waste is any waste that
poses considerable or potential threat
to man or the environment. This could
be gaseous, liquid or solid. Hazardous
waste cannot be disposed of by common
means like other by-products of everyday
life, hence, it is considered a special type
of waste. Treatment and solidifying the
waste might be possible, depending on the
physical state of the waste.
Chemical waste, industrial solid waste,
toxic waste and solidwaste in towns or
cities are forms of industrial waste.
Industrial pollution
Pollution, in modern day definition, is the
introduction of contaminants into a natural
environment that causes harm, discomfort,
disorder, or instability to living organisms.
Pollution can either be caused by
chemical substances or energy (noise, heat
or light).
Forms of pollution
1 Light pollution: Over-illumination, light
trespass and astronomical interference
are considered as light pollution.
2 Air pollution: This is the release of
harmful chemicals and particulates
into the atmosphere. It results from
both natural and man-made activities.
3 Noise pollution: This includes noise
from motor vehicles, aircraft, as well
as industrial noise.
4 Litter: This results from dropping
used wrappers and other materials/
substances indiscriminately.
5 Soil pollution: This includes the release
of chemicals on the soil either by oil
spill or underground leakage. Burning
of natural vegetation and spraying
of pesticides and herbicides are also
sources of soil pollution.
6 Radioactive pollution: This refers to the
presence of radioactive contamination
which results from nuclear power
generation and also from research for
weapons.
7 Thermal pollution: This involves a
temperature change in natural water
bodies caused by human activities.
Industrial pollutants
Industrial pollutants are waste materials
that pollute air, water or soil. The severity
of a pollutant depends on:
1 its chemical nature;
2 the persistence; and
3 the concentration of the material.
128
Major sources of industrial pollution
include combustion from chemical plants
and release of by-products from oil
refineries, petrochemical plants and
coal-fired power plants. Other sources of
chemical pollution include nuclear waste
disposal activity, as well as waste from
incinerators, large livestock farms, plastic
factories and other heavy industries.
Effects of pollution
1 Bad air quality can result in the death
of many organisms, including humans.
Respiratory disease, heart disease and
throat inflammation can result from
ozone pollution. Contamination of
drinking water may lead to the death
of millions of people (water pollution).
Oil spills can cause skin rashes and
irritation.
2 Noise pollution can result in hearing
loss, stress, sleep disturbance and high
blood pressure.
3 Chemical and radioactive substances
can cause cancer as well as birth
abnormalities.
Pollution affects the environment
in a number of other ways, such as the
following:
1 Nitrogen oxides from the air are
released by rain, and fertilises the
land, but can alter the composition
of the species in the ecosystem.
2 Sulphur(IV) oxide and nitrogen(IV)
oxide are released in the atmosphere
as acid rain and can reduce the pH
value of the soil.
3 Smog and haze can lower the amount
of sunlight received by plants to
carry out photosynthesis.The soil
eventually becomes infertile and
unsuitable for plants.
Pollution control
Pollution control means the control of
emissions and effluents into the air, water
or soil. If there is no pollution control, the
waste products from combustion, heating,
mining, transportation, agriculture and
other human activities will degrade the
environment.
It is better to prevent pollution and
minimise waste than to control pollution.
Pollution control devices include the use
of:
1 waste collection systems;
2 scrubbers
3 sewage treatment; and
4 industrial waste water treatment.
Recycling, if practised, is another effective
way of controlling pollution.
Sustainability, whichhere refers to
the ability to maintain pollution control
over a long period of time, is also very
vrcialin polution control. Developing
an ethical framework for decision making
first is credited to the Greek physician,
Hippocrates (460–377 BC, who studied the
effects of food, occupation and climate on
causes of disease. Also Bernardo Ramazzini
(1633-1714), an Italian physician, examined
the health hazards of chemicals, dust,
metals and other agents encountered by
workers.
Aldo Leopold, who is considered by
many to be America’s first biochemist,
summarised ethical responsibilities in a
simple statement in 1949 where he said that
‘A thing is right when it tends to preserve
the integrity, stability and beauty of the
biotic community. It is wrong when it
tends otherwise.’ It can be deduced from
this ethical statement that exposing people,
particularly children, to harmful agents
129
robs them of their integrity, stability and
beauty.
Students of chemistry are thus concerned
with issues of integrity and honesty in the
conduct and interpretation of toxicological
studies, i.e. studies of poisons and their
effects on people and the environment
generally. In addition, toxicologists must
adhere to rules and regulations regarding
the use of animals and humans in scientific
studies.
Roles of government in preventing
chemical degradation
Many nations all over the world have
enacted legislation to regulate various
types of pollution and try to reduce the
adverse effects of pollution in order to
protect the environment from severe effects
of pollution.
Ethical, legal and social issues
Advances in science and technology have
produced great benefits but have also
opened the door of undesirable hazardous
side effects, that affect both man and his
environment.
The area of science which deals with the
understanding and evaluation of the effects
of chemical and physical agents on health
and environment is toxicological science
(toxicology). The impact of toxicological
science on society has grown tremendously
in the last 100 years.
Despite increased scientific data and
understanding, decision making has
become increasingly difficult and complex.
It is thus important to consider the ethical,
legal and social issues that confront
toxicologists, public health professionals
and the government.
Ethical issues
An ethical toxicologist should consider the
following fundamental principles on waste
management:
1 Dignity, which includes respect for
the autonomy of human and animal
subjects.
2 Veracity: This refers to adherence to
transparency and presentation of all
the facts so that all parties can discover
the truth.
3 Justice: This includes an equitable
distribution of the costs, hazards and
gains of pollution control.
4 Integrity: An honest and straightforward
approach is required in waste control
decisions.
5 Responsibility: To acknowledge the
fact that one is accountable to all
parties involved is also a necessary
precondition for effective waste
management.
Legal issues
A wide range of laws and regulations that
shape the role of toxicology in society have
existed for a long time. For instance, in 82
BC, the Roman Emperor Sulla, passed one
of the first laws dealing with toxicology.
This law was intended to deter intentional
poisoning because it was discovered that
some women then were poisoning their
men to acquire their wealth. Again, the
chief chemist, United States Department
of Agriculture, Peter Collier (1880) was
moved to recommend the passage of a
national food and drug law, due to food
poisoning. In 1938, the Federal Food,
Drug and Cosmetics Act was adopted
130
following an incident in which the elixir,
Sulfanilamide, containing the poisonous
solvent diethylene glycol, killed 107
people, many of whom were children.
The need to control chemical
contamination was brought to light in
1976 when the US Congress passed the
Toxic Substance Control Act (TSCA) to
‘prevent unreasonable risks of injury to
health or environment associated with
the manufacture, processing, distribution
in commerce, use or disposal of chemical
substances.’ This Act became largely
ineffective following court decisions. They
are now trying to pass chemical policy
legislation. However, Europe has moved
forward with a system that requires testing
and evaluation of chemicals before their
introduction into the market, that is, the
Registration, Evaluation and Authorisation
of Chemicals (REACH).
Social issues
Public health professionals and
toxicologists perform an important role in
protecting and promoting public health.
There has been an extra focus on ethical
and social issues related to children’s
health. In the US, for instance, the Society
for Toxicology Code of Ethics indicates that
toxicologists should be thoughtful public
health advocates.
Professional codes of ethics are also
often based on the following social
responsibilities:
1 To share and use knowledge.
2 To promote the health and well-being
of children.
3 To maintain the right of all persons to
reach and maintain their full potential.
Summary
This chapter has taught the followings:
• Chemical waste is waste from harmful
chemicals (mostly produced by large
factories).
• Industrial waste results from industrial
activities, such as those of factories,
mills and mines.
• Industrial pollutants are waste materials
that pollute the air, water or soil.
• Pollution can be controlled by sewage
treatment, water treatment, scrubbing,
dust collection and recycling.
Review questions
A Multiple-choice questions
1 Chemical waste, industrial solid waste
and toxic waste are forms of
A domestic waste.
B industrial waste.
C company waste.
D office waste.
E spiritual waste.
2 The following are forms of pollution
except
A noise pollution.
B air pollution.
C light pollution.
131
D vehicle pollution.
E water waste.
3 Pollution can be controlled by
A sewage treatment.
B hair treatment.
C washing.
D sweeping.
E dancing.
4 These are effects of pollution except
A bad air quality.
B stress.
C hearing loss.
D hair growth.
E loss of soil fertility.
B Short-structured questions
1 Name four chemical industries in
Nigeria.
2 List six forms of pollution.
3 Define the following:
a) Chemical waste
b) Industrial waste
c) Hazardous waste
C Essay-type questions
1 State the impact of any local chemical
industry on the environment.
2 Suggest ways of reducing the chemical
degradation of the environment caused
by the local industry.
3 Describe the ways government can
prevent environmental degradation.
 9 Alkanoic acids and their
derivatives

Introduction The four atoms, therefore, have a partial

charge. Reactions of carboxylic acids occur
Organic acids contain the functional group, at charge centres.
– COOH, known as the carboxyl group.
O Performance objectives

R C At the end of this chapter. you should be

O H
(carboxylic acid)
As a group, they are known as the carboxylic
acids. If R is an alkyl group, the carboxylic
acid is further described as an alkanoic
acid.
The carboxyl functional group is a
combination of the carbonyl group, – C= O,
and the hydroxyl group, – OH, on the same
carbon atom. The carbon-oxygen bond is a
strongly polar bond in which the oxygen
atom has acquired a partial negative charge
and the carbon atom a partial positive
charge. The hydroxyl group is also strongly
polar, with the oxygen partially negative
and the hydrogen partially positive. The
bond polarities in the carboxyl group can
be shown in several ways.
O
δ- O carboxylic acids are named alkanoic acids
Cδ
+
C naming of acids follows the names of the
or
δ- δ+ O H
O H
able to:
1 identify the functional groups in
alkanoic acids and amides;
2 identify alkanoic acids, alkanoates
and amides;
3 prepare an alkanoate;
4 describe the preparation of
selected vegetable oils by catalytic
hydrogenation;
5 identify the functional groups in
amino acids; and
6 describe the formation of peptide
linkage between amino acid
functional groups.
Nomenclature of alkanoic acids and
esters
In the IUPAC nomenclature, straight chain
while their esters are named alkanoates. The
compounds from which they are derived.
The acid group is
In naming acids, we determine the name of

132
 O Names of unsaturated carboxylic acids
are derived from names of corresponding
C
alkenes and alkynes. The longest chain,
which contains both the carbonyl and the
O H
multiple bond, is chosen as the parent
the alkane, drop the ending -e and add the compound. A number indicates the lower-
ending -oic, as in pentanoic acid. numbered carbon of the multiple bond. The
carbonyl carbon is numbered 1.
CH3CH2CH2CH2CH3
(pentane) O 4
CH3 – 3CH = 2CH –1C – OH

CH3CH2CH2CH2C O
(pentanoic acid) (but-2-enoic acid)
O H
Other functional groups are named as CH2 = CH – COOH
substituents. The longest carbon chain, (propenoic acid)
(acrylic acid)
which contains the carbonyl group, is
chosen as the parent compound. The Dicarboxylic acids have the ending dioic.
carbonyl carbon is numbered 1. The longest chain, which includes both
carboxyl carbons, is chosen as the parent
Cl H compound. Numbering commences at
O
one carbonyl carbon and ends at the other
4
CH3 3C 2C 1C carbonyl carbon.

O H O
H OH O
­­­(3-chloro-2-hydroxybutanoic acid) C
6
CH
5 4
CH 3
CH CH 1C
2

OH H O O H

(hexanedioic acid)
3
CH3 2
CH COOH
1

(2-hydroxypropanoic)
(lactic acid)

Table 9.1 Some naturally-occurring saturated carboxylic acids

Number Formula IUPAC Name Comom

of carbon name
atoms

1 HCOOH Methanoic Formic

2 CH3COOH Ethanoic Acetic
3 CH3CH2COOH Propanoic Propionic

133
4 CH3(CH2)2COOH Butanoic Butyric
5 CH3(CH2)3COOH Pentanoic Valeric
6 CH3(CH2)4COOH Hexanoic Caproic
12 CH3(CH2)10COOH Dodecanoic Lauric
14 CH3(CH2)12COOH Tetradecanoic Myristic
16 CH3(CH2)14COOH Hexadecanoic Palmitic
18 CH3(CH2)16COOH Octadecanoic Stearic
20 CH3(CH2)18COOH Eicosanoic Arachidic
22 CH3(CH2)20COOH Docosane Behenic

Table 9.2 Some naturally-occurring unsaturated carboxylic acids

Number
of carbon Formula IUPAC name Common
atoms name

16 CH3(CH2)5OH=CH(CH2)7COOH Hexadec 9-enoic Palmitoleic

18 CH3(CH2)7CH=CH(CH2)7COOH Octadec-9-enoic Oleic
18 CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH Octadec-9,12- Linolenic
dienoic
20 CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7COOH Octadec-9,12,15-
trienoic Linolenic

The naming of esters follows from the Sources of alkanoic acids and esters
name of the acid. An ester is prepared from
an alkanol and an acid, and is named as Alkanoic acids and their derivatives –
such. The alcohol is named first, and then esters, amides, halides and anhydrides –
the acid, using the ending -ate, as in pentyl are widely distributed in nature. They are
ethanoate. all found in living organisms.
Man arrogates to himself the invention
of chemical weapons. This is not strictly
O true. Animals actually embarked on
chemical warfare long before man gave
­ CH3 – C – O H + HO – CH2CH2CH2CH2CH3 it a thought. From experience, children
(ethanoic acid) (pentan–1–ol) now know that, when disturbed, wasps
and bees could be very unfriendly. The
O beetle, Galerita janus, uses a spray of
methanoic acid as a defence mechanism.
CH3C – O – CH2(CH2)3CH3 Methanoic acid was in fact first isolated
(pentyl ethanoate) by distilling white ants. From the base of
its tail, the whip scorpion, Mastigoproctus

134
giganteus, sprays a mixture which is 84% HO – CH – COOH
ethanoic acid, CH3COOH, 5% octanoic |
acid, CH3(CH2)6COOH, and water. Other HO – CH – COOH
classes of chemicals are contained in the (tartaric acid)
venom pouches of many animals and
insects. Butanoic acid, CH3CH2CH2COOH), is
present in human sweat and has a putrid
odour. Every individual sweats out a
characteristic blend of carboxylic acids.
Sweat from the feet of an individual has
a characteristic blend of carboxylic acids.
In crime detection, dogs can be trained to
sniff and recognise a particular blend of
carboxylic acids.
Vegetable oils and animal fats are both
Fig. 9.1 Beetle Galerita janus spraying
naturally-occurring esters of glycerol with
long chain carboxylic acids (C12 to C24). If
the triester is liquid at room temperature, it
is called an oil. If the triester is solid at room
temperature, it is called a fat. In shape, these
triesters resemble the head of a pitchfork,
with the three long acyl residues as the
prongs.

Fig. 9.2 A scorpion Mastigoproctus giganteus firing

Ethanoic acid (CH3COOH), is present

in vinegar to about 7%. Lemons are well-
known to contain citric acid while tartaric
acid is present in grapes. Sour milk is
known to contain lactic acid.
CH2 — COOH H
| |
HO C — COOH CH3 – C – COOH
| |
CH2 — COOH OH

(citric acid) (lactic acid)

Fig. 9.3 Sniffing dog with a guide

135
 O
O
CH2 – O – C – (CH2)16CH3 CH3CH2CH2C
O
O CH3
CH – O – C - (CH2)16CH3
O (methyl butanoate)
(pineapple)
CH2 – O – C – (CH2)16CH3
(glyceryl trioctadecanoate) Laboratory preparation of carboxylic
(glyceryl triestearate) acids

We shall consider a few general methods

for the preparation of carboxylic acids.

Oxidation of primary alkanols

Primary alkanols are oxidised by suitable
reagents to alkanoic acids.
O

R – CH2OH + [O] R–C + H2O

Fig. 9.4 A pitchfork head H

Esters of the smaller carboxylic acids
are volatile compounds, with somewhat
sweet odours, which are characteristic
fragrances of many flowers and fruits.
These fragrances attract the insects and
animals which are responsible for the
pollination of flowers and dispersal of their
seeds. The chief ester constituents present
in some fruits and leaves are shown below:
O acid from ethanol.
⎟⎟
O O
R–C + [O] R—C
H OH
Suitable oxidising agents include sodium
heptaoxodichromate(VI), (Na 2 Cr 2 O 7 ),
and potassium tetraoxomanganate(VII),
(KMnO4). We shall illustrate this general
method by preparing a solution of ethanoic

CH3(CH2)3CH2 – O – C – CH3 Class experiment 9.1

(pentyl ethanoate)
(banana) Aim
To prepare a solution of ethanoic acid from
ethanol

136
Procedure
1 Dissolve 6 g of sodium heptaoxodichro-
mate(VI) powder in about 5 cm3 of
water and carefully add 4 cm 3 of ethanol and water
concentrated tetraoxosulphate(VI)
acid.
2 Transfer the mixture to a round
water
bottomed flask and set up the apparatus
as shown in Fig. 9.5(a). The dropping
funnel contains a mixture of 2 cm3
ethanol and 4 cm3 water.
3 Allow the ethanol-water mixture water
to drop slowly into the flask, while
swirling the flask and its contents to dilute
ensure thorough mixing. water tetraoxosulphate(VI) acid
4 When all the ethanol-water mixture bath and sodium
has been added, bring the water-bath heptaoxodichromate(VI)
to boil and keep it boiling for about
15 minutes. The oxidising agent is in
excess and the reaction proceeds as
shown: Fig. 9.5(a)

thermometer

water
outlet

Liebig condenser

impure
mixture
of ethanoic
acid cold water
ethanoic
acid
heat

Fig. 9.5(b)

137

The alkyl magnesium bromide, called a
3CH3CH2OH + 2Cr2O2-7 + 16H+ →3CH3COOH+ Grignard reagent, reacts with carbon(IV)
4Cr3+ + 11H2O oxide to form the magnesium salt of a
Any ethanol produced is returned to carboxylic acid which is hydrolysed to
the reaction flask. form the acid.
5 Arrange the apparatus for distillationH 3 – CH 2 – CH 2 – Mg – Br + CO 2 dry
 ice
→
(Fig. 9.5(b) and collect about 10 cm 3 CH 3
–CH 2
–CH 2
–Mg–Br + CO 2
of the distillate. This is a solution of
ethanoic acid. O

Hydrolysis of nitriles CH3CH2CH2-C-Mg-Br

In an acid-catalysed reaction, nitriles react (bromomagnesium butanoate)
with water to yield the corresponding acid.
O H3O+ O

CH 3 CH 2 C = N + 2H 2 O H
O+
3
→ CH 3 CH 2 C – NH 2 CH3CH2CH2-C-OH + Mg2+ + Br-
(propanonitrile) (propanamide) (butanoic acid)
H3O+
­
CH3CH2COOH + NH+4
(propanoic acid) Physical properties of carboxylic acids
From alkyl halide through an alkyl
Alkanoic acids are colourless liquids or
magnesium halide
low-melting white waxy solids. They
Primary, secondary and tertiary alkyl
constitute a homologous series, whose
halides react with metallic magnesium
series formula is CnH2n+lCOOH. The C1- C4
in dry ether to form an alkyl magnesium
acids are soluble in water in all proportions.
halide.
The solubility in water decreases after C4
CH 3 – CH 2 – CH 2 Br + Mg dry
 ether
→ as the number of carbon atoms increases.
(propyl bromide) Beyond C8, the alkanoic acids are practically
insoluble in water.
CH3-CH2-CH2-Mg-Br The small alkanoic acids are soluble
(propyl magnesium bromide) in water because of the high polarity of
their carboxyl functional groups, and their
ability to form hydrogen bonds.
Table 9.3 Some physical properties of small alkanoic acids

Name Formula Melting point Boiling point Solubility in

in K in K g/100 g of water

Methanoic HCOOH 281 373.5

Ethanoic CH3COOH 290 391

138
Propanoic CH3CH2COOH 251 414

Butanoic CH3(CH2)2COOH 267 437

Pentanoic CH3(CH2)3COOH 239 460 3.7

Hexanoic CH3(CH2)4COOH 270 478 1.0

The boiling points of alkanoic acids Ethanoic acid is the chief component of
are higher than the boiling points of vinegar. Citric acid is found in citrus fruits,
many other compounds with comparable while tartaric acid is present in grapes.
relative molar mass. This is because of
the carboxyl group to carboxyl group Reactions of carboxylic acids
hydrogen bonding. Table 9.4 shows the
boiling point of ethanoic acid which We shall now discuss a few reactions of
has a relative molar mass of 60, and the carboxylic acids.
boiling points of other classes of organic
compounds with comparable relative Acidity of carboxylic acids
molar masses as ethanoic acid. Extensive The bonds which make up the carboxyl
hydrogen bonding is also noticeable among group are all polar covalent. This creates
amides and this is responsible for the high four centres with partial charge.
boiling point of ethanamide.
Pure ethanoic acid [mp 290 K (17°C), bp O
39 K (118°C)] is a good solvent of medium
or R C
polarity which is mildly corrosive to the
skin. O H
The more volatile acids, ethanoic and
O
propanoic, have a pungent, biting odour.
C4 to C6 acids have a rancid butter odour. R
δ+
C
Carboxylic acids are responsible for the
sour taste associated with certain foods. O
δ–
H
δ+
Table 9.4 Boiling points of selected compounds, showing dependence on dipolar interactions and
hydrogen bonding

Class Compound Formula Rmm* bp.(K)

Amide Ethanamide O 59 494

CH3 – C– NH2

Acid Ethanoic acid O 60 391

CH3 – C– OH

139
 Alkanol Propan-1-ol CH3 – CH2– CH2 – OH 60 370

Ketone Propanone O 58 329

CH3 – C– CH3

Alkanal Propanal O 58 322

CH3 – CH2– C –H

Alkanoate Methyl O 60 304

Methanoate
CH3 – O –C– H

Alkane Butane CH3 – CH2– CH2 – CH3 58 272.5

*Rmm: Relative molar mass

For most carboxylic acids, the equilibrium
The carboxylic acid ionises as follows: constant for this reaction is in the order of
R-COOH + H2O  R-COO– + H3O+ 10-5.
Thus, pKa = 5. When the group attached to
The acidity equilibrium constant for this the carboxyl group is electron-withdrawing,
reaction is written as follows: ionisation is enhanced. If the group is
[RCOO – ][H 3 O + ] electron-releasing, ionisation is impeded
Ka =
[RCOOH][H 2 O] and the acid strength decreases. Table 9.5
If the concentration of water is taken as shows the effect on pKa values when an
unity, then, electronegative group, such as chlorine or
Ka =
[RCOO – H][H 3 O + ] CH3, is substituted with hydrogen on the
[RCOOH] carbon chain of ethanoic acid.

Table 9.5 pKa values of selected carboxylic acids

Acid pKa value Acid pKa value

CH3COOH 4.75 HCOOH 3.75

ClCH2COOH 2.85 CH3CH2COOH 4.87
Cl2CHCOOH 1.48 ClCH2CH2COOH 3.98
Cl3CCOOH 0.70 CH3CHClCOOH 2.83

140
 Aqueous solutions of carboxylic fizzes because carbon(IV) oxide is given off
acids turn blue litmus red and react when aspirin reacts with sodium hydrogen
with magnesium with the evolution of trioxocarbonate(IV). When put in water,
hydrogen. Carboxylic acids dissolve in aspirin becomes a soluble salt, the form in
sodium hydroxide solution, forming which it can easily be absorbed.
a salt. They also dissolve in sodium
trioxocarbonate(IV) solution with the O O
evolution of carbon(IV) oxide. OCCH3 OCCH3
Mineral acids will displace volatile NaHCO3
carboxylic acids (methanoic and ethanoic) +CO2
H2O
from their salts. The acids are recovered on C OH C O–Na+
distillation of the reaction mixture.
O O
Formation of salts [acetylsalicylic acid [sodium acetylsalicylate
Carboxylic acids are only slightly dissociated (aspirin) water-insoluble] (water-soluble)]
in aqueous solutions. Of the one thousand
molecules in ethanoic acid, for example, Formation of esters
only about four molecules dissociate When a carboxylic acid is heated with an
into ethanoate ions and hydrogen ions. alkanol, in the presence of concentrated
Carboxylic acids are, therefore, weak acids. tetraoxosulphate(VI) acid acting as catalyst
and dehydrating agent, an ester is formed.
H2O + RCOOH  RCOO– + H3O+
O H
In contrast, almost all of the inorganic acids CH3 CH2 C +H C H
—hydrochloric acid (HCl), trioxonitrate(V)
(propanoic acid)
acid (HNO3) and tetraoxosulphate(VI) acid O H OH
(H 2SO 4)—are strong acids. This means (methanol)
that the inorganic acids are completely
dissociated in water. O
Addition of a base removes H 3 O + ,
shifting the equilibrium to the right, CH3 CH2 C + H 2O
converting the acid to the carboxylate ion (methyl propanoate)
O CH3
and forming a salt.
An important application of the
Formation of amides
formation of salts by carboxylic acids is
A compound in which the – OH group
that the otherwise insoluble compounds
of an acid is replaced by — NH2 is called
are solubilised through the formation of
an N-substituted amide. Amides can be
salts. The pain-relieving drug ,aspirin, is
produced from the reaction of ammonia,
sometimes packaged in a mixture of citric
or an amine, with an ester.
acid and sodium hydrogen trioxocarbonate-
(IV), the so-called Alka-Seltzer. The mixture

141
 O is the basic structural element in the long-
chain molecules which make up proteins
CH3 C + NH2 — CH2CH3
and enzymes of living matter. Hydrogen
O CH3 bonding between two amide groups helps
(methyl ethanoate) to determine the protein structure.

Formation of acid chlorides

When the –OH group of the carboxylic acid
is replaced by a chloride group, the product
O
is known as an acid chloride. As a group,
CH3 C + CH3OH they are known as acyl chlorides.

N CH2CH3 O

R C + PCl5
H
(N-ethyl ethanamide) O H
(alkanoic acid)

O O
CH3 C + NH3 R C + HCl + POCl3

O CH3 Cl
(methyl ethanoate) (acyl chloride)

O The R – C – is the acyl group. For

example,
CH3 C + CH3OH
(methanol) O
NH2
(ethanamide) CH3 C + PCl5

Note the similarity of the two reactions. O H

Amides are of special importance because (ethanoic acid)
the amide group,

O O

C CH3 C + HCl + POCl3

NH– Cl

142
Other halogenating agents, such as SOCl2 lithium(I) tetrahydridoaluminate(III),
(thionyl chloride) and PBr3 (phosphorus (LiAlH4) will reduce carboxylic acids to the
tribromide) react similarly. corresponding primary alkanol.
O
Decarboxylation
The elimination of a molecule of CO 2 R C + 4H+ + 4e–
[carbon(IV) oxide] from a molecule of a
carboxylic acid is known as decarboxylation. O H (from
(alkanoic acid) reducer)
This is achieved by heating the carboxylic
acid with soda lime. Soda lime is calcium
oxide slaked with sodium hydroxide R — CH2 OH + H2O
solution. Therefore, decarboxylation is alkanol

preceded by salt formation.

Dehydration
R – COO–Na+ + Na+OH– → R – H + Na2CO3 The elimination of one molecule of water
from a molecule of an alkanoic acid is
Oxidation known as dehydration. Methanoic and
Carboxylic acids are not readily oxidised, ethanedioic acids are the only alkanoic
being themselves the end products of an acids which are readily dehydrated.
oxidation sequence. Methanoic acid warmed with concentrated
Primary alkanol → alkanal → alkanoic tetraoxosulphate(VI) acid is dehydrated to
acid. carbon(II) oxide.
However, there are two exceptions to HCOOH conc.H
 SO
→ CO + H 2 O
 2 4

this general rule:

On heating, ethanedioic acid is dehydrated
1 Methanoic acid and methanoates
by concentrated tetraoxosulphate(VI)
are readily oxidised by potassium
acid to a mixture of carbon(II) oxide and
tetraoxomanganate(VII) to form
carbon(IV) oxide.
carbon(IV) oxide.
HCOOH → CO2 + 2H+ + 2e- COOH
COO
(accepted by | | conc.H
 SO
→ CO + CO 2 + H 2 O
 2 4

oxidiser)
COOH
COOH

2 Ethanoic acid and ethanoates

are also oxidised to carbon(IV) Amines
oxide by warm potassium Amines are related to ammonia, in the
tetraoxomanganate(VII) . same way that alkanols are related to water.
COOH Amines are formally derived from ammonia
| → 2CO2 + 2H+ + 2e- by replacing the hydrogen atoms, one at a
COOH (accepted by
time, with carbon-containing groups. The
oxidiser)
amine functional groups, therefore, are R –
Reduction NH2, R2NH and R3N.
Carboxylic acids are difficult to reduce. These functional groups impart a basic
Powerful reducing agents, such as character to organic molecules. Thus when

143
an organic molecule is called a base, it of nitrogen to the parent compound. The
means that the organic molecule contains names of the smaller groups are placed as
an amine group. prefixes.
Amines are classified into primary, CH3CH2CH2CH2CH2 – N(CH3)2
secondary or tertiary amine. (N, N–dimethylpentylamine)

H R R An ammonium salt, which has four

carbon groups attached to the nitrogen, is
R N R N R N called a quarternary salt.
H H R (CH3)4N+ Cl-
(primary (secondary (tertiary
(tetramethylammonium chloride)
amine) amine) amine)
Salts of amines are named by changing
The terms primary, secondary and tertiary amine to ammonium for the cation and
actually refer to the degree of substitution adding the name of the anion as in
of the hydrogen atom. N-methylammonium bromide.
+
Nomenclature of amines CH3 NH2—CH2CH3 Br-
-

(N-methylethylammonium bromide)
In the IUPAC system, primary amines are
named by adding amine to the name of the Sources of amines
parent alkyl group or to the name of the
parent hydrocarbon after removing the Small amines occur in living organisms
ending -e. as compounds of large molecules.
CH3 Ethanolamine and the choline cation,
found in phosphoglycerides, are good
CH3CH2CH2CH2–NH2 CH3(CH2)3CH–NH2 examples.
(butylamine or (hexyl-2-amine or
butan- 1-amine) hexan-2-amine) HO— CH2 -— CH2 — NH2
(ethanolamine)
Symmetrical secondary and tertiary HO ­— CH2 — CH2 — +N(CH3)
amines, with simple hydrocarbon groups, (choline cation)
use the prefix di- or tri- to designate the Larger amines are found in nucleic acids,
number of groups. DNA, RNA and in many co-enzymes.
(CH3CH2CH2)3N NH2 O
(tripropyl amine) CH3
N HN
N
Secondary and tertiary amines, which
have a mixture of alkyl groups, are named, O N
using the largest alkyl group as the H
N N
base name. The other groups are then (adenine) H
designated by their alkyl group names. (nitrogen base H (thymine)
in nucleic acids, (base in DNA)
The N indicates the position of attachment DNA, and RNA)

144
 O Narcotics, analgesics and opiates
A narcotic is a drug which depresses the
C central nervous system, thereby reducing
NH2
pain. An analgesic is a chemical or drug
which can relieve pain. Narcotics are,
N therefore, analgesics with a difference.
(nicotinamide) Narcotics are addictive. In larger doses,
part of co-enzyme narcotics will induce sleep, coma or even
NAD+
death.
Larger multicyclic amines are present Opiates are drugs which contain opium,
in some plants. These multicyclic amines and are used to induce sleep or to deaden
are called alkaloids and include many that pain. Opiates are derived from the dried
have marked physiological effects on man juice of poppy, a plant which belongs to
when orally administered. An alkaloid the family of papaveraceae. Opium contains
should contain at least one nitrogen atom. some twenty alkaloids with morphine as
the principal constituent. Other opiates
Alkaloids are sub-divided into two main
include codeine and heroin.
groups:
1) narcotics: powerful painkillers which NCH3
numb the senses;
2) hallucinogens: which alter or distort
our perception of reality.
Serotonin occurs naturally in the human
brain. Serotonin helps to transfer signals
from one brain cell to another. Lysergic HO O OH
Acid Diethylamide (LSD) does not occur (morphine)
naturally. Other hallucinogens occur
NCH3
naturally in South and Central America.
O H

C N(CH2CH3)2

N
N CH3O O HO
(codeine)
CH3
(LSD) NCH3

HO CH2CH2NH2 H

O O
N
H O C CH3
CH3 C O O
(serotonin) (heroin)

145
Stimulants Another synthetic stimulant is
Stimulants are drugs which help people amphetamine which produces effects similar
avoid drowsiness and to stay alert. to those of cocaine. Amphetamine affects
Nicotine and caffeine are good examples of the central nervous system by mimicking
stimulants. Nicotine is found in tobacco the action of epinephrine, a drug formerly
while caffeine is present in coffee and tea. called adrenalin. The amphetamines are
There is a very dangerous stimulant habits forming and long-term use could
known as cocaine, an alkaloid extracted cause damage to the brain.
from the leaves of the coca plant, a shrub
H
native to Peru and Bolivia. Natives chewed
the leaves of the coca plant as mere H CH2CHNH2
stimulants. Trouble started when chemists CH3
began to extract cocaine with solvents, and H
to produce the hydrochloride which is H
thousands of times more dangerous than
(amphetamine) H
cocaine.
Cocaine produces an intense stimulation,
OH H
making the user talkative, confident, active H
and euphoric. With larger doses, the user HO O CH2 N
of cocaine may experience hallucinations CH3
and is likely to become confused, anxious, H
and even hostile. When the effect of the HO H
drug wears off, the feeling of power and
H
elation is usually followed by progressive
(epinephrine)
depression.
O
CH3
N Preparation of amines
N
H We shall consider a few general methods
for preparing amines.
O N N
From alkyl halides
(caffeine) CH3
In the laboratory, amines can be prepared
from alkyl halides in the presence of excess
O
ammonia. The halogenoalkane is mixed
COCH3 H H with an ethanoic solution of ammonia.
O CH3CH2CH2–Br + NH3
NCH3 O C H CH3CH2CH2 – NH3Br–
+
NH3
(cocaine) H H CH3CH2CH2 – NH2 + NH +4 Br –

146
By the reduction of nitriles in the presence of excess ammonia, will
Nitriles give primary amines on reduction convert to primary amines.
with powerful reducing agents, such as
lithium(I) hydridoaluminate(III), (LiAlH4), R – OH + NH 3 Hl 
2O
→ R – NH 2 + H 2 O
3

in ether. This is the common laboratory This method is preferred in industry

method of preparation. This method is because all the starting materials are readily
not used in industry because the reducing available from petrochemical feedstock.
agent is very expensive.
CH3CH2CH2C ≡ N Physical properties of amines
(butanonitrile)
Most amines are liquids but the smallest
amines are gases. Gaseous amines include
LiAlH4 H2O
monomethylamine, dimethylamine, trim-
H ethylamine and ethylamine.
The gaseous and volatile amines have
CH3CH2CH2C NH2 strong odours characteristic of dead fish.
The common names for l,4-butanediamine
H and l,5-pentaneamine are putrescine and
(butylamine) cadaverine respectively. These terms
aptly describe the odours of these two
By the reduction of nitroalkanes compounds which are produced in dead
This is the preferred industrial method animals when bacteria convert amino acids
for the preparation of amines because into amines. Larger amines possess odours
nitroalkanes are readily available from which are less unpleasant than the odours
hydrocarbon sources in the petroleum of putrescine and cadaverine.
industry. Trioxonitrate(V) acid readily The smaller amines are soluble in water,
converts alkanes to nitroalkanes. Using the solubility decreasing with an increase in
nickel as catalyst, the nitroalkanes are then the alkyl chain size.
reduced by hydrogen in the vapour phase. Primary and secondary amines are
excellent hydrogen-bond donors and
R – NO 2 + 6[H] Ni
→ R – NH 2+2H
2H22O
acceptors. The boiling points of amines are,
therefore, higher than the boiling points
From primary alkanols of compounds with comparable molar
Primary alkanols, passed over aluminium- masses, except for alkanols, acids and
(III) oxide catalyst at 623K (350°C) and amides.
Table 9.6 Transition temperatures of amine and some other compounds
Class Compound RMM* mp.K bp.K

Amine CH3CH2CH2 – NH2 59 -190 332

Alkanol CH3CH2CH2 - OH 60 -146 370
Acid CH3COOH 60 290 391
Amide CH3CONH2 59 355 494
* RMM: Relative molar mass

147
Reactions of amines Reactions with dioxonitrate(III) acid
Primary amines, such as ethylamine, will
We shall now discuss a few reactions of react with dioxonitrate(III)acid, (HNO2), to
amines. form ethyldiazonium compounds.
R – NH2 + HNO2 → R – N ≡ N + OH– + H2O
Amines as organic bases (diazonium ion)

Amines, like ammonia, have a lone pair of
electrons on the nitrogen atom.
N N N N
H H H H H H
H H H H
Since alkyl groups are electron-releasing,
the strength of the bases will increase in
the following order:
NH3 < R – NH2 < R2NH < R3N
All the species shown can go into co-
ordination with the hydrogen ion.
H H
H N: + H+  H N
H H
Strong acids displace the equilibrium to
the right while strong bases displace the
equilibrium to the left. Aliphatic amines
will give an alkaline solution in water.
+
R – NH 2 + H 2 O 
 R – N H 3 + OH

–
Dioxonitrate(III)acid is unstable and must
be generated in situ from a mixture of
sodium dioxonitrate(III), (NaNO2), and
hydrochloriC acid. The reaction vessel
H H must be kept in an ice bath at 273 K (zero
°C). This prevents the decomposition of the
diazonium compound.
If properly controlled, reactions of this
type are important in the synthesis of
some dyestuffs. If the reaction mixture
is not iced, then decomposition of the
diazonium compound follows, and the
primary amines will finally yield a mixture
of alkanols and alkenes, with the evolution
+
of nitrogen.
+
H CH3 CH2 – N = N
H2O CH3CH2OH + H+
(ethanol)
+
[CH3 CH2]
N2 +

The base strength of the amine is reflected CH2 ≡ CH2 + H+

in the equilibrium constant for this reaction. (ethene)
Alkylation of amines
Table 9.7 Base strengthS of selected amines Like ammonia, the amines are alkylated to
Name Formula Kb at 298 give N–substituted derivatives.
H
K/mol dm–3
|
Ammonia NH3 1.8 × 10-5 CH3– N – CH3 + C2H5Br
Ethylamine CH2CH2NH2 5.4 × 10-4 CH3– N – Ch3 + HBr
Diethylamine (CH2CH2)2NH 1.3 × 10-3 |
C2H5
(N, N–dimetylethylamine)

148
Successive alkylations lead to the formation have the hydrogen replaced by an acyl
of quaRternary ammonium salts. group.
R –C–
CH3 – N – CH3 + CH3Br |
| O
C2H5
O
CH3 ⎪⎪
| CH2H5 – N – C2H5 + CH3 – C – O – C– CH3
| (ethanoic
CH3 – N – CH3 + Br anhydride)
H
| C2H5 –N – C2H5 + CH3COOH
C2H5 | (ethanoic acid)
(trimethylethylammonium bromide) C=O
|
Organic chemists sometimes
CH3
manipulate these alkylations in such a
(N,N dimethylethanamide)
way that one of the groups is a long-chain
alkyl group.
+
(C 6 H 5 CH 2 )N(CH 3 )2 Cl – Amides
|
C12 H 25
A compound in which the -OH group
tetraalkylammonium chloride
(tetraalkylammonium chloride)
of a carboxylic acid is replaced by -NH2
In tetraalkylammonium chloride, there group is called an amide. When -OH is
are two methyl groups, one benzyl group replaced by -NHR, the product is called a
and one dodecyl group; the latter is also nitrogen-substituted amide. This is always
known as the laury group. The structure abbreviated to N-substituted amide. The
of tetraalkylammonium chloride qualifies amide functional group is as follows:
it for a cationic surfactant, with a hydrophilic
head and a long hydrophobic tail. O
Surface active molecules, called C
surfactants, spontaneously gather at liquid NH2
surfaces and always reduce the surface Within the functional group, the
tension of water. Surfactants are often covalent bonds are strongly polar. This
called invert soaps because their structure gives rise to several reactive centres.
is the opposite of the natural surfactants, δ–
of the sodium octadecanoate or sodium O O
strearate type, which is usually anionic.
C or C
Acylation of amines δ+
Primary and secondary amines, which still N H N H
have hydrogen on the nitrogen atom, will
H H

149
 The electron density around the nitrogen Sources of amides
atom is considerably reduced because the
electron-withdrawing oxygen is attached Amides are extremely stable compounds
to the same carbon as nitrogen. On the which are found in both natural and
other hand, the electron density around synthetic products. Naturally-occurring
the oxygen atom increases. amides are found as excretions of various
animals, being products of protein
breakdown. Urea, a diamide of carbonic
Nomenclature of amides acid, is excreted in human urine because it
is water-soluble. Land reptiles and birds,
Amides are named as derivatives of which have liquid waste system, excrete
carboxylic acids. Decide which is the parent amides in the form of uric acid, which is not
carboxylic acid. Drop the ending –oic of the soluble in water. Spiders excrete amides
parent carboxylic acid and replace with the as guanine. Uric acid and guanine are cylic
ending -amide. amides.
O O O
CH2 C CH3 C O H H
C
N C
H 2N C NH2 C O
OH NH2 C C
(ethanoic acid) (ethanamide) O N N

(urea) H H
Substituents on nitrogen are designated by
the prefix N-. (carbamide) (uric acid)

O O
CH 3 – C N – CH 3 H N
C
| N C
H ( N –methylethanamide ) C H
(N–methyletthanamide) C C
N N
H2N
Substituents on the carbon chain are H
numbered in the same way as in acids. (guanine)

CH33
CH O
| | Preparation of amides
CH33(CH
CH (CH22)7 → CHC
CHC
NH 2 We shall now discuss a few methods of
preparing mides.
( 2–methyldecanamide )
2–methyldecanamide)
From esters, acylhalides or acid
anhydrides
When esters, acylhalides or acid anhydrides
are treated with concentrated ammonia

150
solution, or better, liquid ammonia, amides
1 R – C = N + H+ → +C = N – H
are obtained.
(from acid)
O O H H
CH 3 – C + NH 3 → CH 3 – C + CH 3 OH
O+
O – CH 3 NH 2
2 R – C = N – H + H2O → R – C = N – H
+

( methylethanoate ) methylethanoate )

O H H H
CH 3 – C + H 2 N – CH 2 CH 3
O +
O
O – CH 3 ↓
3 R – C = N – H → R – C = N – H + H+
O
CH 3 C
N – CH 2 CH 3 + CH 3 OH O–H O
4
| (N–ethylethanamide)
R – C = N – H → R – C – NH 2
H
O O Dehydration of ammonium salts of
CH 3 – C + NH 3 → CH 3 – C + HCC carboxylic acids
Cl NH 2 When an ammonium salt of a carboxylic
ethanoyl chloride)
acid is heated, two reactions are possible.
(ethanamide)

O O
RCOOH + NH 3
CH 3 – C + NH 3 → CH 3 – C + CH 3 COOH +

O – C– CH 3 NH 2 R – COO – NH 4 O
| R –C + H2O
O (ethanamide)
(ethanoic anhydride) NH 2

Excess carboxylic acid, added during the

By partial hydrolysis of nitriles
heating, displaces the first equilibrium to
Partial hydrolysis of nitriles is achieved
the left, enabling a good yield of the amide
by dissolving the nitrile in concentrated
to be obtained.
tetraoxosulphate(VI) acid. The mixture is
then poured into water. The acid acts as a
Physical properties of amides
catalyst.
The separation of charges within the
O amide group makes amides strongly
R – C ≡ N + H2O → R – C polar. As a result, simple amides tend
NH 2 to be non-volatile. With the exception of
methanamide, a liquid with a high boiling
point, most unsubstituted amides are
Full hydrolysis yields the carboxylic
crystalline solids at room temperature.
acid. This reaction could be visualised as
The strong attraction between molecules
proceeding in stages.
of such small molar masses is due to the

151
number and strength of the – N – H .. O = weak acids. Let us consider the polarities
hydrogen bonds. These hydrogen bonds of the bonds which make up the amide
bind the molecules together in crystals. functional group.

O H R δ–
R –C N – H .....O = C O O
N – H ..... O = C
H R N – H..... C or C
H δ+ δ–
N H N H

N
H H
N–H
O=C Ordinarily, the nitrogen atom is electron-
R withdrawing. On the same carbon atom to
which nitrogen is attached, the effect of
the electron-withdrawing oxygen is to
Table 9.8 Melting points and boiling points reduce the electron density on the nitrogen
of some amides atom and also on the hydrogen atom.
Therefore, positive charges appear on both
Name Formula mp.K b.p.K the nitrogen atom and on the hydrogen
O atom. The nitrogen atom of the amide is,
Methanamide H – C 275 K 466 K therefore, less basic than the hydrogen
NH2 atom of the amide.
O The atoms of oxygen, nitrogen and
Ethanamide
CH3 – C
355 K 495 K hydrogen, which possess partial charges,
NH2 are responsible for the extensive hydrogen
O bonding in amides,
Propionamide
CH – CH2-C 352 K 486 K
3

NH2 Hydrolysis in amides

O When amides are heated with sodium
Carbamide
H –N–C– NH
2 2
406 K Decom- hydroxide solution, the carboxylate ion is
poses formed and ammonia liberated.

O O
Reactions of amides OH–
R C + H2O R C + NH3

We shall now discuss a few reactions of NH2 O–Na+

amides.

The alkaline hydrolysis is visualised to

Acidity and basicity of amides
proceed as follows:
Amides are very weak bases and also very

152
 R R Reduction with decarboxylation
R
HO– + C = O HO C O– C + NH3
When an amide is first treated with bromine
and dilute potassium hydroxide followed
NH2 NH2 O O–
by warming with concentrated potassium
hydroxide, the amide is converted to an
Hydrolysis proceeds faster when amides amine less one carbon atom which is lost
are treated with hot tetraoxosulphate(VI) in the form of carbon(IV) oxide.
acid. However, this time, the products are
O
carboxylic acid and ammonium ion. R –C + Br2 + 4KOH
+ +
NH ↓
CH 3 – C – NHCH 3 + H 3 O → CH 3 COOH + CH 3 NH 3 2

R – NH 2 + 2kRr + K 2 CO 3 + 2H 2 O
O (ethanoic R–NH2+ 2KBr + K2CO3 + 2H2O
(N-methylethanamide) acid)

+
This reaction is known as the Hoffmann
CH 3 – C – NHCH 3 + H 3 O + → CH 3 COOH + CH 3 NH 3 reaction, which provides a route, in organic
O (methytl ammonium ion) synthesis, for descending the homologous
series.
Reduction in amides
Primary amides can be reduced to primary Class experiment 9.2
amines with sodium and ethanol, or with
lithium(I) tetrahydriodoaluminium(III) Aim
in ether. To Prepare ethanamide and demonstrate
O H some typical reactions of amides
R –C + 4[H] → R – C – NH 2 + H 2 O
Procedure
NH 2 H
1 Gradually add 15 g of finely powdered
Reaction with dioxonitrate(III) acid diammonium trioxocarbonate(IV) to 50
When amides are treated with a solution of cm3 of glacial ethanoic acid in a 150 cm3
dioxonitrate(III) acid, the carboxylic acid is round-bottom flask. Shake the mixture
formed with the evolution of nitrogen. The during the addition. This ensures a
dioxonitrate(III) acid is generated in situ steady evolution of carbon(IV) oxide.
from a mixture of sodium dioxonitrate(III) 2 When all the trioxocarbonate(IV)
crystals and dilute hydrochloric acid. The has been added and the evolution of
reaction mixture must be maintained at a carbon(IV) oxide has ceased, fit a reflux
temperature above 283 K (10° C). air condenser to the flask and set up for
reflux as shown in Fig. 9.6.
O 3 Boil gently for 30 minutes. At the end
R –C + HO – N = O of this period, the dehydration of
NH 2 ↓ the ammonium ethanoate should be
complete.
O 4 Now, remove the air condenser and
R–C + N2 + H2O fit a fractionating column. A four-pear
fractionating column may be used.
O–H

153
 A glass-packed column containing
about 12 cm of glass sections is better.
Set the apparatus for distillation. The
thermometer fitted should read to 633
K (360°C).
5 Now distil the liquid through the
column very slowly, so that a drop
of distillate passes over every three
seconds. This should continue until the
temperature reads 443 K (170°C). If this
operation is carried out carefully, water
and excess ethanoic acid should distil
over, leaving almost pure ethanamide
in the flask.
6 Now, quickly transfer the molten
contents of the flask to a smaller 50 cm3
flask and, again, set up for distillation.
The air condenser, this time, is a short
glass tube, about 30 cm long and 12 mm
in internal diameter.
7 Distil the ethanamide carefully at such
a rate that none escapes condensation,
and none crystallises in the air.
Should crystallisation occur in the air
condenser, play a small flame on it to
melt the solids. Collect the fraction
between 488 K and 498 K (215°C and
225°C).
Ethanamide is thus obtained as a
colourless crystalline solid which has
the characteristic smell of mice. This
odour is caused by small amounts of
N-methylethanamide, CH 3CONHCH 3,
present as an impurity. The ethanamide
should be recrystallised from propanone
(acetone). This time, it is odourless and
has a melting point of 355 K (82°C) and
a boiling point of 496 K (223°C). Use the
product obtained for the exercises which
follow:
1 To a little of the solid, add about 1 cm3
of bench sodium hydroxide solution.
Observe whether any ammonia is given
off in the cold. Now warm the mixture.
What do you observe?
2 Heat a little of the solid with about
1 cm3 of bench hydrogchloric acid in a

thermometer

air condenser

air condenser
four-pear
fractionating
column
water +
excess ethanoic
acid
ammonium
ethanoate
and glacial reation mixture
ethanoic acid from stage 1

STAGE 1 STAGE 2
heat
heat

Fig. 9.7 Preparation of ethanamide

154
 test tube. Waft the fumes from the test
tube towards you. What is the odour
of the fumes?
3 Add a few crystals of sodium
dioxonitrate(lII) to 1 cm 3 of bench
hydrochloric acid. Now add a little
solid ethanamide. What do you
observe?
4 Dissolve a little solid ethanamide
in about 2 cm3 of ethanol. Then add
a small pellet of sodium. When the
reaction has subsided, smell to detect
the odour of ethylamine.
Amino acids
Amino acids are derivatives of carboxylic
acids in which one hydrogen atom of the
alkyl chain has been replaced by an amino
group, -NH2. All the amino acids, obtained
from the hydrolyzates of the proteins of
animals and the higher plants, have the
R R
+ polyamides found in animals and in the
H2N C COOH or H3N – C – COO–
H H
amino group attached to the same carbon
atom to which the carboxyl group is also
attached. The structure of such amino
acids, known ordinarily as a-amino acids,
can be shown as follows:
We have discussed the behaviour of the
carboxyl group and also the behaviour of
the amino group. Now, we shall discuss
those reactions in which the two functional
groups take part separately, and also
jointly.
Owing to the proximity of the two
functional groups, the a-amino acid is able
to exist in three forms, depending on the
155
pH of the medium. These three forms are
the acid condition, the neutral condition
and the basic condition.
+
OH – +
H 3 N CH 2 COOH 


– H+
 H 3 N CH 2 COO
 –
(acid condition) (neutral condition)
O+ OH –
N 2 NCH 2 COO –
(basic condition)
In the neutral condition, the amino acid
exists as a zwitterion. The term, zwitterion
is taken from the German word zwei, which
means two. The neutral condition is called
the isoelectric pH, or simply the isoelectric
point.
Sources of amino acids
The amino acids of the most general
biological importance are those which
compose the proteins, the macromolecular
higher plants. Individual amino acids
are obtained from these proteins by acid
hydrolysis of the amide linkages.
The 20 amino acids found in proteins are
all a-amino acids. Many of these have other
functional groups as well, such as another
amino group, another carboxyl group,
hydroxyl or thiol group. All α-amino acids,
however, have an amino group on carbon
number 2.
We can arrange these α-amino acids
from proteins into groups, according to the
nature of R in the structure which follows:
R
+
H 3 N – C – COO –
H
R may be non-polar, polar-uncharged or a O
NH 2 O NH2
charged-group. All the natural a-amino
3 2
acids have the same arrangement of the HO – C H 2 – C H – C
four groups, R, H, NH3+ and COO– round
O –H
the a–carbon.
[2–amino–3-hydroxypropanoic
acid (serine)]
Nomenclature of amino acids

O NH O
Amino acids are named simply as 5 4 3 2 1
C – C H2 – C H2 – C H – C
derivatives of carboxylic acids. Examples
include the following:
H–O O–H
O
O (2-amino-1,5-pentadiamine
5 4 3 2 1
H2N – C H2 – C H2 – C H2 – C H2 – C (glutamic acid))
(5–aminopentanoic acid) OO
–H–H

Table 9.9 Amino acids obtained from proteins

Name R– Isoelectric point

Non-polar R groups
Glycine(Gly) O
H– 5.97

Alanine(Ala) CH 3 — 6.02

CH 3 CH –
Valin(Val) 5.97
CH 3

CH 3 CH CH
CH2 _–
Leucine(Leu) 6.02
CH 3

CH 3 CH 2 CH –
Isoleucine(Ile) 5.98
CH 3

Phenylalanine(Phe) – CH2– 5.48

Methionine(Met) CH
CH3 – S –CH 2 CH 2 – 5.74

156
Tryptophan(Trip) – CH 2 – 5.88
N – CH 2 –
NH
H

Proline(Pro) CH3COO –
6.30
(entire structure shown) CH COO – 2

N+ H2

Glutamine(Gin) 5.70

Polar-uncharged groups

Serine(Ser) HOCH2– 5.68

CH 3 CH –
Threonine(Thr) 5.60
OH
Cysteine(Cys) HSCH2– 5.02

Tyrosine(Tyr)
OH 5.67
CH 2
+
H 3 N – C – COO –
OH
OH
CH
CH 22
+
H +N – C – COO –
H 33N – C – COO –

Asparagine(Asn)
O NH 2 5.40
C
CH 2
+
H 3 N – C – COO –

157
 Glutamine(Gin) 5.70
NH – CCH 2 CH 2 –
O
Charged R-groups
Negatively-charged
Aspartic acid(Asp) –OOCCH2– 2.98

Glutamic acid(Glu) –OOCCH2CH2– 3.22

Positively-charged +
Lysine(Lys) H 3 N(CH 2 )4 – 9.74

+
H 2 N = C – NH – (CH3)
(CH3)3 —
Arginine(Arg) 3 –
10.76
NH 3

NH
Histidine(His) NH
NH 7.59

HN –HN
HN – CH
CH 2 –– CH – –
2 2

Preparation of amino acids

In the laboratory, when alkanals are treated Hydrolysis with dilute hydrochloric acid
with cyanide ions in the presence of yields the amino acid.
ammonium ions, aminonitriles are formed.

O NH 2 NH 2
+
R –C + NH 4 + CN → R – C – C ≡ N + H 2 O
–

R – C – C ≡ N + 2H 2 O + H +
H H

(alkanal) H
NH 2
NH2 R – CNH
– COOH
2

| |
H COOH
R—C­
R–C–C– ≡ N + H2O |
| H
H
(amino acid)

158
Class experiment 9.3
Aim
To prepare glycine in the laboratory
Procedure
1 Add 15 g of chloroethanoic acid to
300 cm 3 of concentrated ammonia
solution contained in a 500 cm3 conical
flask. Cork the flask loosely. Set it aside
at room temperature until the next day.
2 Transfer the contents of the flask into
a suitable distillation flask. Using the
laboratory filter, set up the apparatus
for distillation under reduced pressure.
Heat the distillation flask, using a water
bath. Reduce the volume of the mixture
to about 30 cm3.
3 Transfer the 30 cm3 of solution in the
distillation flask into a conical flask
of 500 cm3 capacity and add 10 cm3 of
water bath
Fig. 9.8 Preparation of glycine
159
water and 250 cm3 of methanol. Whilst
stirring, cool the flask in iced water.
Leave the set-up for one hour. During
this period, the precipitation of glycine
should be complete.
ClCH2COOH + 2NH3
(chloroethanoic acid)
H2N — CH2COOH + NH4Cl
4 Filter off the glycine through a Buchner
funnel, at the filter pump. T
5 Transfer the residue to a beaker and
wash it with 80 cm3 of methanol. Filter
again.
6 Wash the glycine inside the funnel
with a little ether. When the ether has
drained off, dry the glycine by placing
it between filter papers.
Pure glycine is crystalline, colourless
and melts at 503-504 K (230-231°C) with
decomposition.
to filter pump
Physical properties of amino acids
NH 2 H
2-amino acids, better known as a-amino
acids, are crystalline solids. They are salt- CH 2 COOH + O = C
like and ionic, because of the formation of (amino acid)
the zwitterion H
+ 2 1 (methanal)
H 3 N – C H 2 – C OO –
CH 2
The physical properties of the a-amino
acids confirm the ionic character of the N
compounds. The melting points are high,
above 200°C, indicating strong electrostatic CH 2 COOH + H 2 O
attractions within the crystal lattice. These
acids are more soluble in water than in less
Amino acids cannot normally be titrated
polar solvents, such as ether.
directly against alkalis but this titration
is now possible with the removal of the
Reactions of amino acids
basic -NH2.
We shall now discuss a few reactions of
Class experiment 9.4
amino acids.

With sodium trioxocarbonate(IV)
Amino acids are soluble in sodium
trioxocarbonate(IV) solutions, and on
heating, evolves carbon(IV) oxide. This is
a reaction of the carboxyl function.
With dioxonitrate(lll) acid
Amino acids react with dioxonitrate(III)
acid to give nitrogen and the corresponding
hyroxycarboxylic acid.
NH 2 OH
CH 2 COOH + HONO → CH 2 COOH + N 2 + H 2 O
This is a typical reaction of the amino
group.
Reaction with methanal
Methanal converts the basic -NH2 group of
the amino acid to a neutral = CH2 group.
Aim
Demonstrate Sorensen’s reaction
Procedure
1 Dissolve 0.2 g of glycine in a few cm3 of
water contained in a test tube labelled
A. Add two drops of phenolphthalein,
and then very dilute sodium hydroxide
solution drop by drop until the solution
just turns pink.
2 In a second test tube, B, place 2 cm3
of 40 per cent formalin solution. Add
two drops of phenolphthalein, and
then dilute sodium hydroxide until the
mixture just turns pink.
3 Now, pour the contents of B into the
contents of A and note the immediate
decolourisation of the phenolphthalein.
The solution is now acid. Observe
that several drops of dilute sodium

160
 hydroxide solution will now have to O
be added before the pink colour is
restored. The reaction of amino acids
with methanal is known as Sorensen’s C C
reaction.

Formation of peptide links C NH

The amino group of one molecule of an
amino acid reacts with the carboxyl group
of a neighbouring molecule to form a
dimer.
Esters
R 1
O H R 2
O
When an alcohol reacts with a carboxylic
H2N – C – C + N–C–C acid, an ester and water are formed. For
example, when pentan-1-ol and ethanoic
H O – H H H O – H acid react, pentylethanoate and water are
formed.
R1 O H R2 O
O H
H2N – C – C – N – C – C
CH 3 – C – O – H + HO – C – (CH 2 )3 CH 3 
 CH 3 –

H H O H

(peptide H
link)
(ethanoic acid) (pentan-1-ol)
The dimer produced still has free -NH2

group and -OCOOH group which H can take O
part in further couplings, leading to the
formation of a polymer.
CH – C – O – H + HO – C – (CH 2 )3 CH 3 
  CH 3 – C – O – (CH 2 )3 CH 3 + H 2 O

This3 kind of polymer is not easily
(pentylethanoate) (water)
formed under laboratory conditions.
However, the enzymes in livingH organisms
are able to produce the polymer on a This reaction is called an esterification
regular basis. Proteins constitute one reaction and is a reversible reaction, quite
example of such natural polymers. The analogous to the neutralisation reaction
links between the individual amino acids between a mineral acid and a base, which
are called the peptide links. produces a salt and water only.

HCl + NaOH 
 Na + Cl + H 2 O

+ –

(acid) (base) (salt) (water)

161
Alkanoates are the esters of straight-chain
carboxylic acids.
The ester functional group contains the
polar carbonyl group, C = O and two C - O
single bonds attached to the same oxygen
atom.
O Oδ
–
st
–C or → – C
O C_ Oδ – Cδ –
– +
All the bonds which make up the functional
group are polar. This creates four centres
with partial charge on the atoms. Charged
reagents could attack at any of the points.
However, the carbonyl group is the usual
site of reaction because of its strong polar
nature.
Nomenclature of esters
Esters are named as alkyl derivatives of
carboxylic acids.
CH 3 CH 2 C – O – CH 2 CH 2 CH 2 CH 2 CH 3
R –C
O
(– C – O – CH 2 )
O could be used as the catalyst. Side reactions
Divide the ester into two portions. The
portion which does not carry the - COO
is named as the alkyl radical. The portion
which contains the – COO is named as the
carboxylate radical. Combining the two
162
parts, our example above is named pentyl
propanoate.
Preparation of esters of alkanoic acids
We shall now consider a few methods for
the preparation of esters of alkanoic acids.
Direct reaction between a carboxylic acid
and an alcohol
The direct reaction of an alkanoic acid and
an alkanol requires an acid catalyst in order
to proceed at a practical rate. Dry hydrogen
chloride is used as the acid catalyst. Dry
hydrogen chloride is passed into the cold
mixture of the alkanoic acid and alkanol
until the mixture is saturated. The mixture
is then boiled under reflux for about 30
minutes.
O O
R –C + HO - R1 → R – C + H2O
O–H O – R1
O O
+ HO - R 1 → R – C + H2O
O–H O – R1
Concentrated tetraoxosulphate(VI) acid
could occur, such as the dehydration of the
alkanol to the corresponding ether.
Reaction of an alcohol with an acid
chloride or acid anhydride
Acyl chlorides ad anhydrides react readily
with alcohols to give esters.
 O hydrogen bonding. As a result, esters boil
at considerably lower temperatures than
R – C + HO – R1 their parent alkanoic acids. Esters also boil
at a lower temperature when compared
Cl with the boiling points of acids and amides
(acyl chloride)
of comparable molar masses.
O
The smaller ester molecules are liquids,
R–C + HCl with the lower members being very
volatile. The lower members are also
O — R1 soluble in water. The pleasant smell of
many fruits is attributed to the volatile
O O esters, for instance, pentyl ethanoate
R—C C — R + HO — R1 in bananas. The solubility of methyl
methanoate in water is 30 g per 100 g of
O water. Solubility decreases as the relative
(acid anhudride)
molar mass of the esters increases.

O O
Reactions of esters of alkanoic acids
R – C +R–C

O — R1 OH We shall now consider a few reactions of

esters of alkanoic acids.

Physical properties of esters of Hydrolysis

alkanoic acids When esters are refluxed with either
aqueous alkali or dilute mineral acids,
Esters of alkanoic acids do not possess the esterification reaction is reversed. For
free - OH groups. Molecules of esters alkaline hydrolysis, the salt of the acid is
cannot, therefore, associate through formed. Alkaline hydrolysis is visualised
to proceed as follows:
Table 9.10 Boiling points of some esters
Name Formula bp.K
R R R R
Methyl methanoate HCOOCH3 305
HO – + C = O → HO – C – O –
Ethyl methanoate HCOOCH2CH3 326

O – R1 O – R1
Methyl ethanoate CH3COOCH3 329

Ethyl ethanoate CH3COOCH2CH3 350 RR R

Propyl ethanoate CH3COOCH2CH2CH3 374 HO – C = O + R1 O → – O – C – O + R1 OH

163
 Reaction with ammonia O
When an ester is treated with concentrated
ammonia solution, the alcohol and the
amide of the carboxylic acid are formed R –C
on heating. O
O – R1 + 4H → R – CH 2 OH + R1 – OH
O O
R –C

R –C + NH 3 → R – C + R1 – OH
O – R1 + 4H → R – CH 2 OH + R1 – OH

O – R1 NH 2
The reduction can also be achieved
O O
through treatment with lithium(I)
tetrahydridoaluminate(III), (LiAIH4). This
R –C + NH 3 →supplies
+ R1—OH R – C hydride + Rions
1
– OH
H–, followed by
hydrogen chloride acid which liberates the
alcohols.
O – R 1
NH 2
NH2
Reaction with hydrogen bromide and
hydrogen iodide
The reaction is visualised to proceed as
Dry hydrogen bromide and dry hydrogen
follows:
iodide attack esters, breaking them down
H HR R H HR R H toRthe carboxylic acid and R forming a
halogenoalkane, e.g.,
H – N: + C = O → H – N + – C – O – → H – N + – C = O + R1 O → H 2N – C = O + R1 – OH
O
H O–R 1
H O–R 1
H
CH 3 – CH 2 – C O
H HR R R
(methyl propanoate)
O – CH 3 + HBr → CH 3 CH 2 – C
– C – O → H – N – C = O + R O → H 2N – C = O + R – OH
– + 1 1
(propanoic acid)
O O
O–R 1
H
H R CH 3R– CH
R 2 –C O
(methyl propanoate)
O – CH 3 + HBr → CH 3 CH 2 – C
→ H – N – C = O + R O → H 2N – C = O + R1 – OH
+ 1 + CH 3 Br
(propanoic acid)
OH
H Reduction
Sodium and ethanol will reduce an ester
to two alcohols.

164
Class experiment 9.5
Aim
To preparate ethyl ethanoate
Procedure
1 In a 250 cm 3 round-bottom flask,
thoroughly mix 50 cm3 (40 g) of absolute
ethanol and 50 cm3 (52 g) of glacial
ethanoic acid.
2 Slowly add 10 cm3 of concentrated
tetraoxosulphate(VI) acid with cooling
and shaking.
3 When the mixture becomes
homogenous, fit the flask with a reflux
water condenser and set up for reflux
as shown in Fig. 9.8. Boil the mixture
gently for 10 minutes.
4 Now change the condenser from reflux
position to distillation position. Distil
off about two-thirds of the mixture.
5 Transfer the distillate to a separating
funnel. Add 25 cm 3 of 30 per cent
sodium trioxocarbonate(IV) solution.
6 Cork the separating funnel and shake
carefully in order to neutralise and
remove the free ethanoic acid. During
the shaking, keep your hand on the
stopper of the separating funnel.
Pressure will build up inside the
separating funnel as a lot of carbon(IV)
oxide is generated.
7 Release the presssure in the funnel
by inversion and opening the tap
momentarily. This should be repeated
as often as is necessary.
8 Now, allow the two layers in the
separating funnel to separate. Carefully
run off and reject the lower aqueous
layer.

thermometer

water
water

water

ethanol and
ethanoic acid and reaction water
tetraoxosulphate(VI) mixtures
acid from stage 1

heat heat
Stage 1 Stage 2
Fig. 9.9. Preparation of ethyl ethanoate

165
 9 Prepare a solution of 25 g of anhydrous
calcium chloride in 25 cm3 of water and
add to the ethyl ethanoate in the funnel.
The calcium chloride will remove any
unreacted ethanol present.
10 Allow the mixture to separate and
again run off and reject the lower
aqueous layer.
11 Then run the ethyl ethanoate into a
small conical flask, add a few lumps of
anhydrous calcium chloride and shake
occasionally.
12 The liquid should be dry after about
20 minutes. Filter the liquid into a
100 cm 3 distilling flask attached to
a water condenser. A few pieces of
An equilibrium is established. If the water
can be removed from this equilibrium
mixture, then, by Le Chatelier’s principle,
the equilibrium is displaced to the right,
and a good yield of the ester is obtained.
Concentrated tetraoxosulphat(VI) acid
is used as a dehydrating agent to eliminate
the water. The acid also acts as a catalyst in
this reaction. Unfortunately, concentrated
tetraoxosulphate(VI) acid also promotes a
side reaction, dehydrating some ethanol
to produce ether. In this method, ether is
always present as an impurity.
2C2H5OH → C2H5 – O – C2H5 + H2O
(ether)

anti-bumping granules or unglazed

Class experiment 9.6
porcelain should be added to make
boiling smooth.
Aim
13 Fit a 373K (100oC) thermometer to the
To preparate ethaoic acid from ethyl
flask, and place the flask in a cold water
ethanoate
bath. Bring the water in the bath to boil.
Ether should distil off at 308 K (35°C)
Procedure
to 313 K (40°C).
1 Place 5 cm3 of ethyl ethanoate in a 100
14 Reject the distillate collected before 333cm3 round-bottomed flask, and add 50
K (60oC). Collect the portion distilling cm3 of ten per cent sodium hydroxide
between 74°C and 79oC. solution. Add also some anti-bumping
Pure ethyl ethanoate is a colourless granules or unglazed porcelain. Fit the
liquid which boils at 350 K (77oC), and has flask with a reflux water condenser and
a pleasant apple-like odour, and is slightly set up for reflux.
solube in water. 2 Boil the mixture gently for 30 minutes
over wire gauze. Now disconnect the
Discussion reflux condenser and set up for direct
When ethanol and ethanoic acid are mixed, distillation.
ethyl ethanoate and water are formed. 3 Re-heat the liquid and collect the first
10 cm3 of the distillate. This should
consist of a dilute aqueous solution of
CH COOH + HOC 2 H 5 
3
  CH COOC
 H5 + H 2 O
ethanol.
2 3

4 The residual liquid in the flask is a dilute



alkaline solution of sodium ethanoate.

In order to liberate the acid, pour out
H + HOC 2 H 5 
 CH COOC 2 H 5 + H 2 O
 3
the residual liquid into a small beaker.
Add dilute tetraoxosulphate(VI) acid

166
 until the mixture is definitely acid to
litmus paper. Pour the mixture back
into the distillation flask. Distil off
about 20 cm3. This is a dilute solution
of ethanoic acid.
Discussion
The reaction which leads to the formation
of esters from a mixture of an alkanol and
an alkanoic acid is a reversible reaction.
When esters, such as ethyl ethanoate and
water, are shaken together, hydrolysis
slowly occurs and, ultimately, equilibrium
is established.
CH3COOC2H5 + HOH

CH3COOH + C2H5OH
If we boil the ester under reflux with
a dilute aqueous solution of sodium
hydroxide, the equilibrium is displaced to
the right, as the sodium hydroxide removes
the ethanoic acid as fast as this is formed.
If we reflux the ester with
tetraoxosulphate- (VI) acid, the acid
catalyses the hydrolysis. In the presence of
a large quantity of water, the equilibrium is
displaced to the right and the reaction goes
practically to completion.
If the ester hydrolysed is a triglyceride
of fatty acids, alkaline hydrolysis will yield
the sodium salts of the fatty acids which
are soaps. The general process of alkaline
hydrolysis of esters by which soap is
obtained is frequently called saponification.
Uses of alkanoic acids and their
derivatives
We shall now discuss some uses of alkanoic
acids and their derivatives.
167
Production of vegetable oils
Vegetable oils are obtained from the
so-called oil seeds, such as cotton seed,
palm kernels, groundnuts, sunflower,
beniseed, and soya beans. The seeds are
shredded, heated up and pressed while
hot. Alternatively, an organic solvent, such
as hexane, is used to extract the oil.
Vegetable oils are added to meals
as energy-giving compounds, and are
widely used for frying potato chips, yams,
plantain, eggs, akara balls, etc.
Production of margarine
Vegetable oils are treated with hydrogen
at 473K (200°C) and 2-5 atmosphere,
usually with finely divided nickel acting
as a catalyst. The double bonds present in
the vegetable oils are hydrogenated. The
resulting product is a solid fat. The process
is known as the hardening of vegetable oils.
Vitamins A and D are added to the solid fat
and this is sold as a substitute for butter,
under the name of margarine.
Manufacture of varnishes
Linseed oil, a polyunsaturated vegetable
oil, is ground together with a pigment,
such as iron(III) oxide, Fe2O3 and a drier,
such as lead(II) oxide. This mixture is
called a varnish. When painted on wooden
furniture, it dries to a hard, opaque,
protective film. The lead(II)oxide assists
the oxygen of the air to react with the
double bonds present in the vegetable oil.
This gives a hard film through a process of
oxidation and polymerisation.
Manufacture of linoleum
Powdered wood cork is mixed with linseed
oil and lead(II)oxide acting as a drier. This
is then rolled into sheets. When drying is
complete, the sheets are printed over to
give linoleum.
Production of Jojoba wax
Jojoba (pronounced ho-ho-ba) oil is
hydrogenated to give a solid white wax
with melting point 338-341 K (65°-68°C).
It is the hardest wax after Carnauba wax.
Jojoba oil contains mainly cetyl plamitate
and esters of cetyl alcohol with high molar
mass fatty acids.
Jojoba wax is used in cosmetics and
polishes where it acts as a substitute for
spermacetti, the solid fraction obtained by
pressing whale oils. Whale oils are now
scarce because of controls imposed on
international whaling.
Manufacture of fungicides and bacte-
ricides
The destructive distillation of ricinoleic
acid, which occurs as a glyceride ester in
castor oil, yields undecylenic acid.
CH3(CH2)5CHOHCH2CH = CH(CH2)7CO2H
CH3(CH2)5CHO + CH2 = CH(CH2)8CO2H
(heptanal) undecylenic acid
(dec-9-ene-1-carbonxylic
acid)
Undecylenic acid has powerful
fungicidal and bactericidal properties. A
loose complex of undecylenic acid and
ethanolamine, used as an anti-dandruff
agent in shampoos, is sold under the name
of Loramine SBU 185.
Manufacture of cosmetics
The use of alkanoic acids and their
derivatives in the manufacture of cosmetics
168
is illustrated by the manufacture of an all-
purpose cream:
a) Measure out the following
into a 50 cm3beaker:
propan-2-yl tetradecanoate 3 cm3
(iso-propyl myristate)
medicinal paraffin 11 cm3
beeswax 4g
petroleum jelly 2.5 g
b) Into another beaker, measure out the
following:
distilled water 8.5 cm3
sodium tetraborate (III) 0.25 g
c) Heat both beakers to 348 K (75°C)
over an asbestos gauze. Allow all
ingredients to dissolve.
d) Stir the aqueous solution slowly, into
the oil and allow to cool to 313 K
(40°C).
Perfume and colour can now be added
if they are required.
Olive oil, beeswax, octadecanoic
acid (stearic acid), lanolin (wool grease),
spermacetti, and astor oil, are all widely
used in the manufacture of cosmetics. A
cosmetic product is usually an emulsion
of one or more of these in water.
Manufacture of polish
An ester wax, such as beeswax, is heated
to 348K (75°C) in turpentine. This is done
in the presence of an emulsifier. Stir to give
a stable emulsion. The mixture is allowed
to cool to 318 K (45°C). Colour mixes are
then added. The emulsion is then poured
into moulds. This type of polish is the
commonest for shoes and furniture and is
known as solvent-paste polish.
Other waxes that can be used include
Carnauba, jojoba, sugar cane, raffia, and
fossil montan.
 methanal is known as the Sorensen's
Summary
reaction.
• Alkanoates are the esters of straight-
This chapter has taught the following:
chain carboxylic acids.
• Organic acids contain the functional
• Jojoba wax is the hardest known wax
group known as the carboxyl group.
after the Carnauba wax. Jojoba wax is
• Animals actually embarked on chemical
used in cosmetics and in polish.
warfare long before man gave it a
thought.
• The naming of acids follows the names
Review questions
of the compounds from which they are
derived.
A Multiple-choice questions
• Carboxylic acids are responsible for the
1 The functional group of an ester is
sour taste associated with certain foods.
A – COOH.
• Hydrogen bonding between two amide
B – COO – .
groups helps to determine the protein
C – CHO.
structure.
D –C–.
• Decarboxylation is the elimination of
⎪⎪
a molecule of carbon(IV) oxide from a
molecule of carboxylic acid. O
• Amines are related to ammonia in the 2 An ester is prepared by the reaction of
same way that alkanols are related to A a carboxylic acid and a ketone.
water. B an alcohol and an aldehyde.
• Small amines occur in living organisms C an alcohol and a carboxylic acid.
as compounds of large molecules. D a carboxylic acid and an aldehyde.
• A narcotic is a drug which depresses 3 What is the name of the compound
the central nervous system. whose structural formula is shown?
• An analgesic is a drug which can relieve H H H
pain. I I I
• Opiates are drugs which contain H – C – C – C –C – OH
opium. Opiates are used to induce sleep I I I
and to deaden pain. H H H
• Stimulants are drugs which help people A Ethylethanoate
avoid drowsiness and to stay alert. B Butanol
• Amides are extremely stable C Butanal
compounds which are found in both D Butanoic acid
natural and synthetic products. 4 Which of the following constitutes the
• Amino acids are derivatives of weakest interaction?
carboxylic acids in which one hydrogen A Hydrogen bonding
atom of the alkyl chain has been B Van der Waals forces
replaced by an amino group. C Covalent bonding
• The reaction of amino acids with D Ionic bonding

169
5The reaction A C2H5NH2
O B CH3CONH2
⎪⎪ C CH3COOH
CH3 + H – C – OH D CH3COOC2H5
10 Which of the following functional
O groups is the peptide linkage?
⎪⎪
H – C – O – CH3 + H2O A O
is best described as
A saponification. –C– O–
B neutralisation.
C hydrolysis. B O
D esterification.
6 Which compound is most readily C C
oxidised to a carboxylic acid?
A CH3CHO
B CH3CH2Cl C NH
C CH2 = CH2
D CH3OCH3
7 Which of the following functional
groups is that of a carboxylic acid?
–C –O – C–
A R–C–R C
⎪⎪
C
O D
⎪⎪
B R – C – OH

C R–O–C
O
D ⎪⎪ 11 Which of the structures shown is not a
R–C–O–R surfactant molecule?
8 Which of the following compounds
will not react with phosphorous(V) A CH 3 (CH 2 )16 COO – Na +
chloride?
A C2H5OH B CH2(CH2)10CH3
B H2O
C CH3COOH
D CH3COOC2H5 HO3S
9 Which of compounds A-D turns damp
red litmus paper blue and forms salts C CH 3 (CH 2 )16 COOC 2 H 5
with mineral acids?
O H

–C–N 170
 D f)
(C 2 H 5 CH 2 ) N(CH 3 )2 Cl – CH 3 – N – CH 3

C12 H 25 CH 3

H
B Short-structured questions
1 Give IUPAC names to the following g) N
structures:
a) CH – CH – COOH
3 CH3

CH 3 H H
O
h) +
CH 3 CH 2 N – CH 2 CH 3 + Cl –
– – –

b) CH 3 – (CH 2 )3 – CH 2 – O – C – CH 3
CH 2 – CH 3

c) CH – O – C – CH – CH – CH 2 Draw the structural formula for each

3 2 2 3

of the following compounds:

O a) methyl methanoate
b) diethylamine
CH 3 CH 3 c) hexane-1,6-diamine
d) d) tetramethylammonium chloride
CH
e) N,N- dimethyl propanamide
f) benzene-1,4-dicarboxylic acid
+
g) aspartic acid
H 3 N – C – COO – h) lysine
3 Arrange the following acids in order of
H increasing acid strengths:
CH3COOH, ClCH2COOH,
C Cl2CHCOOH and Cl3CCOOH
e) 4 As a rule, alkanoic acids are not readily
CH 2 oxidised, being themselves the end
products of an oxidation sequence.
CH 2 There are, however, two exceptions
to this general rule. Write down the
+
reactions for these two exceptions.
H 3 N – C – COO – 5 What products would you expect to be
formed when water is eliminated from
H a) a molecule of methanoic acid,
HCOOH?

171
 b) a molecule of ethanedioic acid
(COOH)2?
6 Complete the following by filling in the
blanks:
Esters are the products of ______
reactions between_____ and _____.
They are named by regarding them
as alkyl or aryl derivatives of _____
acids. Thus, the name is obtained from
a stem indicating the_____ from which
the ester is derived, with the suffix -yl,
followed by a stem indicating the _____
with the suffix -ate.
7 Predict the formulae of the products of
the following reactions by completing
the equations:
a) CH3CH2COOH + PBr3
b) C6H5COOH + LiAlH4
c) CH3COOH + Ca(OH)2(aq)
8 Although the carboxyl group contains
both the carbonyl function and the
hydroxyl function, carboxylic acids do
not exhibit some of the characteristic
reactions of aldehydes and ketones.
Which are these? Give reasons why this
is the case.
C Essay-type questions
1 How would you carry out the following
conversions in the laboratory?
a) CH2= CH2 to CH3COOH
b) CH3COOH to CH3CONH2
c) CH3CHO to CH3COOCH2CH3
d) CH3COOH to CH3COOCH2CH3
2 Illustrate, with examples and equations,
the
a) oxidation reactions of carboxylic
acids.
b) reduction reactions of carboxylic
acids.
c) dehydration reactions of carboxylic
acids.
172
3 How do you account for the following
observations?
a) Propanamide is a solid at 352
K (79°C) whereas propanoic
acid is a liquid with mp.251 K
(-22°C).
b) The amides of carboxylic acids
are much weaker bases than
ammonia.
4 How and under what conditions do
the following pairs of compounds
react?
a) E t h y l a m i n e a n d p r o p a n o i c
anhydride
b) Propanamide and thionyl chloride
(SO2C12)
c) Propanamide and bromine
5 Explain the mechanisms of acid-
catalysed and alkaline hydrolysis of
esters.
6 Wr i t e b r i e f n o t e s o n t h e
following:
a) The acid-base characteristics of
amino-acids
b) The isoelectric point of an amino
acid
7 What reactions show clearly the
presence of
a) a n a m i n o g r o u p i n a m i n o
acids?
b) a carboxyl group in amino
acids?
8 How do you account for the following
observations?
a) Methylamine is more soluble in
water than ammonia.
b) The bond angles in water, ammonia
and diethylamine are 104°, 107°,
and 108° respectively.
c) Ethylamine boils at 290 K (17°C)
whereas propane boils at 231 K
(-42°C).
 10 Fats and oils
Introduction
Fats and oils (animal fats and vegetable
oils) are both naturally-occuring esters of
glycerol with long-chain carboxylic acids.
Industrially, fats are obtained from
the adipose tissues of animals, or from
certain seeds and fruits, such as linseed,
cottonseed, and soya beans.
Fats have the highest calorific value of
all classes of foods and are an important
source of energy for homoeothermic
animals. In order to liberate their energy, fats
are first broken down to some intermediate
products. These intermediate products
then enter the Krebs cycle, giving rise to
ATP molecules.
Performance objectives
At the end of this chapter, you should be
able to:
1 identify sources of fats and oils;
Table 10.1 Names, sources and main producers of some oils
Name Source
Palm oil Oil palm
Palm kernel oil Oil palm
173
2 differentiate between fats and oils;
3 state the physical and chemical
properties of fats and oil;
4 explain saponification, using relevant
equations;
5 test for fats; and
6 state the uses of fats and oils.
Sources of fats and oils
Fats and oils are evenly distributed round
the world. Man depends on them for
cooking, as a source of energy-giving
food, and in the manufacture of soap. At
a point in the past, man depended on oils
and fats for tallow candles and for lighting
lamps. World trade in fats and oils runs into
billions of dollars annually. Table 10.1 gives
the names, sources and main producers of
some oils.
Fats and solids, are mainly found in
animals while oils are liquid and are mainly
of plant origin.
Main producer
Malaysia, Cote d’Ivoire, Nigeria
Malaysia, Cote d’Ivoire, Nigeria
 Coconut oil Coconut palm Malaysia, Nigeria

Oil of arachis Arachis Nigeria

(groundnut oil) (groundnut)

Soya bean oil Soya bean USA, Nigeria

Cotton seed oil Cotton USA, Egypt, Nigeria
Olive oil Olive tree North Africa, Spain
Castor oil Castor plant Nigeria, Malaysia
Sunflower oil Sunflower Kenya, Zambia
Corn oil Maize USA, Nigeria
Rice oil Rice Japan, Thailand, USA

(a) Coconut palm (b) Castor oil plant

(c) Groundnuts

Fig. 10.1 Sources of commercially-used oils

174
Table 10.2 gives the names, sources and main producers of some important fats.

Table 10.2 Names, sources and main producers of some important fats.

Name Source Main producers

Tallow Sheep, cattle USA, Argentina, Australia, Europe

Lanolin (Wool Sheep Australia, Argentina, England

grease)

Lard Pigs USA, China

Cocoa butter Cocoa Brazil, Cote d’Ivoire, Ghana,

Nigeria

Industrially, fats are used chiefly for 3 R’COOH + CH2OH RCOOCH2

the manufacture of soaps and detergents. (fatty acid)
(water)
Test for fats CHOH RCOOCH + 3H2O

Put a drop of fat on a piece of filter paper.

A rather permanent greasy spot is formed. CH2OH RCOOCH2
The filter paper becomes permanently alkanol ester
translucent.
The alkyl group, ‘R’ of the fatty acids
Chemistry fats and oils
may be the same or different.
Fatty acids can be grouped into saturated
Fats and oils belong to the group or
or unsaturated fatty acids. A unsaturated
family of organic compounds known as
fatty acid has one or more carbon-carbon
lipids. Fats and oils are complex mixtures
bonds, in double its hydrocarbon chain.
of esters of glycerol (a trihydric alkanol)
Fats consist of a higher proportion of
that is, glyceryl trialkanoates. Glyceryl
esters of saturated fatty acids while oils
trialkanoates are the oils and fats of plant
consist of a higher proportion of esters of
and animal origins.
unsaturated fatty acids.
Fats are simple lipids, which are solid
at ordinary temperatures. Many naturally-
occurring fats are carboxylic acid esters of
propane-1,2,3-triol (glycerol). Most of the
carboxylic acids present in fats have an

175
even number of carbon atoms. In general,
however, fats are glycosides of saturated
fatty acids.
The carboxylic acids that are obtained
by hydrolysis of naturally occurring fats
and oils usually have unbranched chains
with an even number of carbon atoms. The
most common carboxylic acids obtained
from fats and oils are the C14 – C16 and C18-
acids The table 10.3.
A fat from a particular source is
generally not a single compound but
usually a mixture of esters. For instance,
animal fat contains tristearin, the ester
of propane-1,2,3-triol, together with
octadenoic acid. Table 10.3 shows some
common fatty acids.
Chemical properties of fats and oils
Saponification reaction:
The alkaline hydrolysis of fats and oils
(glyceryl alkanoates) which produces
glycerol and a mixture of salts of long-
chain carboxylic acids (soaps) is known
as saponification.
These salts of long-chain carboxylic
acids are popularly known as soaps. In
other words, soaps are the sodium or
potassium salts of fatty acids.

Table10.3 Some common fatty acids

Saturated fatty acid Common name IUPAC name

CH3(CH2) 12 CO2H Myristic acid Tetradecanoic acid

CH3(CH2) 14 CO2H Palmtic acid Hexadecanoic acid
CH3(CH2) 16 CO2H Stearic acid Octadecanoic acid

Unsaturated fatty acid Common name IUPAC name

CH3(CH2)5 (CH2) 7 CO2H Palmtic acid Cis-9-bexahexadecenoic acid
\ /
C=C
/ /
H H

CH3(CH2)7 (CH2)7 CO2H Oleic acid Cis-9-octadecenoic acid

\ /
C=C
/ /
H H

176
 O O
CH2OCR CH2OH
O O
CHOCR’ + 3NaOH CHOH
O O
CH2OCR’ CH2OH
Carboxylate Glycerol
Chemical properties of fats and oils
Hydrogenation reaction of oils
The low melting point of oils is due to the
fact that they are made up of esters formed
largely from unsaturated fatty acids.
Hydrogenation of an oil produces a solid
fat. Vegetable oils are hydrogenated until
a semi-solid of an appealing consistency
is obtained. Complete hydrogenation is
avoided because a completely saturated
glyceryl trialkanoate (oil) is very hard
and brittle.
This is the pwass of makig margarine.
When the hardened oils is mixed with
vitamins, various fats, milk and salt,
margarine is produced.
Vegetable oils + H2  Ni catalyst
  margarine

Physical properties of fats and oils
1 Fats have a higher melting point.
2 Oils have a lower melting point.
3 Both fats and oils are insoluble in water.
177
RCO– Na+
+ R’CO–Na+
RCO–Na+
Sodium caroxylates (soap)
4 Both fats and oils decompose at
temperatures below 300°C.
Uses of fats and oils
1 Vegetable oils (palm oil or groundnut
oil) are important parts of our foods.
2 Edible vegetable oils like palm oil and
groundnut oil are hydrogenated to fats
used in making margarine.
3 Linseed oil is used in paints and
varnishes.
4 Cod liver oil is used in making drugs.
5 Fats and oils are used for soap
production.
O
CH2OC (CH)7 CH = CH (CH2)7 CH3
(from oleic acid)
CHOC (CH2)7CH = CHCH2CH=CH (CH2)4 CH3
O (from linoleic acid)
CH2OC(CH2)7CH = CHCH2CH = CH (CH2) 4 CH3 translucent when a drop of fat is placed
on it.
• Fats and oils are used in soap production
O and in making drugs. Vegetable oils are
used as food and in making margarine.
CHOC(CH2)16CH3
O
Review questions
CH2OC(CH2)16CH3
Glyceryl tristearate (a solid fat) A Multiple-choice questions
1 Fats and oils are esters of fatty acids
with
Summary A monohydric alcohols.
B 1,2-glycols.
This chapter hastaughtthe following: C glycerol.
• Fats and oils belong to the group of D amines.
organic compounds known as lipids. 2 The hydrolysis of fats and oils, using
• Fats are solid and are mainly found in sodium or potassium hydroxide is
animals while oils are liquid and are known as
mainly of plant origin. A esterification.
• Fats consist of a higher proportion of B hydrogenation.
esters of saturated fatty acids while oils C neutralisation.
consist of a higher proportion of esters D saponification.
of unsaturated fatty acids. 3 Triolein is the triester of glycerol
• Physical properties of fats and oils with oleic acid (octadec-9-enoic acid).
include the following: both fats and oils Ordinarily, triolein can be described as
are insoluble in water; they decompose A a soap.
at temperatures below 300°C; fats have B a fat.
a higher melting point and oils have a C an oil.
lower melting point. D a carbohydrate.
• Chemical properties of fats and oils 4 Fats and oils belong to the group of
include the following: organic compounds known as
Hydrogenation reaction – vegetable A acids.
oils are hydrogenated until a semi-solid B salts.
of an appealing consistency is obtained. C hydrides.
Saponification reaction – this is the D lipids.
alkaline hydrolysis of fats and oils to
produce glycerol and a mixture of salts B Short-structured questions
of long-chain carboxylic acids (soaps). 1 List four physical properties of fats and
• Test for fats. A greasy spot is formed oils.
and filter paper becomes permanently 2 What are lipids? Give two examples of
lipids.

178
3 What is a fatty acid? Are fatty acids
water-soluble?
4 Complete the equation:
Vegetable oil +oil
Vegetable H+ 
2 


C Essay-type questions
1 Explain the meaning of these terms
with the acid of chemical equations:
a) Saponification
b) Hydrogenation of oils
c) Saturated fatty acids
2 Differentiate between fats and oils.
3 State five uses of fats and oils.
4 State the sources of some commercially-
used oils.
5 How do you test for fats?
6 How are phospholipids related to fats?
How are they different? In what ways
do phospholipids resemble simple fatty
acids?

179
 11 Soap and detergents

Introduction 5 describe the mode of action of

detergents; and
Soaps are the sodium (RCOO- 6 distinguish between soap and
N a +) o r p o t a s s i u m ( R C O O -K +) o r detergents.
triethanolammonium (RN+ (CH2CH2OH)3
salts of long-chain organic acids. The
organic chain is the hydrophobic end of Soaps
the molecule while the carboxylate end
(–COO–) of sodium and potassium soaps is Soaps are the salts of long-chain carboxylic
the hydrophilic end. Other common metal acids. They are the sodium or potassium
salts of long-chain organic acids are not as salts of fatty acids.
soluble and therefore are poor surfactants. Historically, natural fats and oils have
The presence of Mg2+Ca2+, and A13+ ions been the source of long-chain carboxylic
in washing water will precipitate the long- acids. Naturally-occurring triglycerides are
chain organic acid anions. This makes the esters of glycerol.
soap less efficient. When these ions occur
naturally in washing water, the water is O
said to be hard. The trietanolammonium 
H2C – OC – (CH2)n(CH3
salts are soluble in organic solvents and can
be used in dry cleaning processes. O

HC – OC – (CH2)nCH3 + 3OH–
Performance objectives
O

At the end of this chapter, you should be H2C – OC – (CH2)n CH3
able to:
1 identify the materials for making soap; (triglyceride
2 prepare soap from local sources;
3 explain the emulsifying action of soap
using relevant equations;
4 define and explain detergents;

180
 H2COH hydroxide until hydrolysis is complete.
O Sodium chloride is then added to the
 mixture. This causes the soap to precipitate
CH – OH + 3CH3 – CH2)n CO–
out (a process called salting out). The
H2C – OH soap separates out and the glycerol, a by-
(glycerol product, is removed by distillation.
Perfumes, dyes and disinfectants are
Acids obtained from fats and oils are shown added (in the case of toilet soaps). Sodium
in Table 11.12. carbonate, sand and other fillers can also
be added before the soap is cut into bars.
(percent carboxylic acid)
Locally, the ashes from dried and burnt
Fat or oil Caprylic Capric Lauric Myristc Palmitic plantain peels is mixed with water to
obtain an alkaline solution which is then
Coconut 8.0 7.0 48.0 17.5 8.2 boiled with palm oil/palm kennel oil
Babassu 6.5 2.7 45.8 19.9 6.9 (PKO) to produce the common local black
Palm Kernel 3.0 3.0 52.0 15.0 7.5 soap.
Palm ... ... ... 1.0 52.5 We shall now produce some soap in the
Olive ... ... ... ... 6.0 laboratory and show some of its properties.
Peanut ... ... ... ... 7.0
Beef tallow ... ... ... 2.0 32.5 Class experiment 11.1 Preparation of soap
Land ... ... ... 1.1 30.4 from animal fat or
vegetable oil
Table 11.2 Acids obtainable from fats ad oils Place 5 cm3 of vegetable oil in a 100 cm3
beaker. If tallow or lard is to be used,
Preparation of soap place 5 g of the solid fat in the beaker and
Traditionally, wood ashes are leached with dissolve with 10 cm3 of 95 per cent ethanol.
water to produce a strongly basic solution. Heat in a water bath as necessary. Add 15
Soap is formed when an oil or fat is heated cm3 of per cent sodium hydroxide solution
with this basic solution. The village soap from a small measuring cylinder. Warm the
maker knows from experience when the mixture as you stir until the oil has reacted
basic solution, often evaporated to dryness fully. The sodium hydroxide is in excess.
first, has taken enough oil to give a good Add another 50 cm3 of water and mix
soap. thoroughly. Ensure that the oil dissolves
The commercial and home processes completely. Now add 50 cm3 of saturated
for making soap are virtually identical, sodium chloride solution chloride, and
except for aspects which relate to scale of wait until the precipitation of the soap is
production and the purity of the alkali used complete. The solid soap rises to the top of
to make the soap. the mixture. Decant the solution and reject
it. Wash the solid twice with a mixture of 20
Preparation cm3 water and 40 cm3 prop none (acetone).
During the process of manufacturing soap, Using the soap so prepared, carry out
fats and oils are boiled in aqueous sodium the following exercise:

181
 O Na+
C Na+ aqueous
O Na+
hydrophobic end hydrophillic Na+
end Na+
Lathering properties of soaps
Try to wash your hand with the solid soap.
Use deionised water for this exercise.
Record your observations.
Structure of soap
When soap dissolves in water, it exists
as micelles. Soap micelles are usually
spherical clusters of carboxylate ions that
are dispersed throughout the aqueous
phase.
The carboxylate ions are packed
together with their negatively charged
(hydrophilic) carboxylate groups at the
surface and their non-polar (hydrophobic)
hydrocarbon chains on the interior, or
pointing inwards. The sodium ions (Na+)
are scattered throughout the water as
individual solvated ions.
The formation of micelles accounts
for the fact that soap dissolves in water.
The non-polar hydrocarbon chain
(hydrophobic) of the soap remains in a
non-polar environment (the interior of the
micelle) while the polar carboxylate groups
points outwards to a polar environment
(the aqueous state). The negatively charged
heads of the micelles keep individual
micelles apart due to repulsion, and thus
they remain dispersed throughout the
aqueous phase.
182
Na+
Na+ phase
Solubility and emulsification of soaps
Put 6 drops of a non-polar oil such as cotton
seed, palm kernel oil or coconut oil into
each of three test tubes. Put 10 drops of
methylene chloride (dichloromethane) into
one tube, 10 drops of water into a second
tube and 10 drops of your soap solution
into a third tube. Stopper the test tubes
with rubber bungs and shake vigorously
for ten seconds. Set the test tubes aside for
a few minutes. Describe the contents of the
three test tubes. What is the effect of soap
on the solubility or miscibility of polar and
non-polar liquids?
Effect of hard water on soaps
Pour 5 cm3 of your soap solution into each
of three test tubes. Add 3 cm3 of 0.l M CaCl2
to one test tube, 3 cm3 of O.lM MgCl2 to the
second test tube, and 3 cm3 of O.lM FeCl3
to the third test tube. Shake each of the test
tubes and record your observations.
Alkalinity of soaps
Use a glass rod to put a drop of your soap
solution on a strip of universal indicator
paper. Compare the colour produced with
the standard colour chart on the paper
container. This will help you to determine
the pH of the solution. Write your own
observed pH.
Acidification of soaps
Add bench hydrochloric acid in drops to
cm3 of soap solution in a test tube until
the soap solution is definitely acid to
litmus. Cool the test tube under tap water.
Filter out the solid which forms and wash
the solid with distilled water. Test the
solubility of a small portion of the solid in
water. Test the resulting saturated solution
for the properties of soap. Record your
observations. What is the precipitate?
Cleansing action of soap
Most dirt particles (on the skin or a grease
coated fabric for example) is surrounded
by a layer of an oil or fat. Water molecules
alone cannot remove such dirt because they
are unable to penetrate the oily layer.
Soap solutions, however, because of
their hydrophobic end (hydrocarbon
chain) are able to dissolve in the oily layer.
Each individual particle develops an outer
layer of carboxylate ions (hydrophilic end)
which dissolves in the water while the
hydrophobic tail dissolves in the oily layer.
The water molecules then attract the polar
end of the soap molecules. This helps to lift
the oily dirt away from the spot.
Theory of detergency
SURFACE
Fig. 11.1 Surface tension in a pure liquid
is a resultant strong pull on the surface
molecules into the liquid. For small
amounts of water, the final effect is that
the water is forced into a spherical shape
which we call a drop of water.
Surface active molecules, which are
called surfactants, are those molecules which
spontaneously gather at liquid surfaces.
Surfactants have a special geometry. Good
surfactants are long organic molecules
which carry polar groups at one end.
When a surfactant dissolves in pure water,
a solution is formed. In this solution, the
polar ends of the surfactant molecules, also
called the hydrophilic or water-loving ends,
become attached to water molecules on
the surface. When this happens, we say
that the polar groups are solvated. The
long, non-polar part of the surfactant also
known as the hydrophobic or water-fearing,

Pure water has a surface tension of 72 × 10-5

SURFACE
Newton. This is due to the unequal forces
acting on water molecules in the surface
compared with the forces in the bulk of
the liquid.
Molecules within the bulk of the liquid
are attracted by forces from all directions.
Since there are fewer molecules of water
above the surface compared to the bulk Fig. 11.2 Surfactant molecules at the surface
of the liquid, the net result is that there of a liquid

183
is repelled by the water molecules. The
surfactant molecules thus reduce the
surface tension of water. This is done by
opposing the attractive forces generated
by water molecules withint the bulk of the
liquid.
The surfactant molecule is what we call
an emulsifier because it is capable of holding
oil and water together in one phase. Recall
that, ordinarily, oil and water are mutually
immiscible substances. Thus, the emulsifier
is not wholly soluble in either oil or water.
One part of the structure is strongly polar
and usually ionic, whilst the other part of
the structure is non-polar.
polar non-polar
head “tail”
Fig. 9.12 Surfactant molecule
In a mixture of oil and water, an
emulsifier molecule will become oriented
with the ionic end well solvated by water
molecules. The carbons, chain repelled
by water, dissolve in the oil. The ionic
ends of the surfactant molecules arrange
themselves in the oil droplet as shown in
Fig 11.4.
184
The ionic ends of the surfactant
molecule repel one another. In this way,
they maintain the most stable arrangement
of charges around the surface of the oil
droplet. This small oily pocket is known
as a micelle. Micelles carry similar charges
and because of this they repel one another
within the body of the emulsion.
A surfactant dislodges an oily smear on
a cotton fabric. This is achieved by getting
the non-polar ends of the molecules to
dissolve in the oil.
The oil is then broken up as miceiles
form. Many fibres carry polar groups, such
as —OH on cotton fibres and, —NH and
—CO on nylon. These polar groups tends
to encourage water spreading or weeting
along te fibre
Advantages of soap
1 Soap is a good cleansing agent in
water.
2 It is biodegradable (it can be
decomposed by bacterial action).
Disadvantages
1 Soap forms scum (a white oily ring
around buckets when hard water is
used).
2 When dissolved in acidic water, the
hydrogen ions (H+) present react
with the carboxylate ions to form
fatty acids, making the soap less
reactive.
3 Soap causes wastage.
Soapless detergents
Soapless or synthetic detergents do not
form scum with hard water. They are made
from petroleum products (alkene) and not
from vegetable oils. A long-chain alkene
(C12 – C18) is first treated with concentrated
tetraoxosulphate(VI) (sulphonation) to
give a sulphonated alkene.
C12 H24 + H2SO4 → C12 H25HSO3 →
C12 H25HSO3(aq) + NaOH(aq) → C12
H25SO3Na + H2O
Typical synthetic detergents include:
CH3(CH2)10 CH2SO2O– Na+
sodium
alkanesulfonate
CH3(CH2)10 CH2OSO2O– Na+
sodium alkyl sulphate
CH3
CH3CH2(CH2)10 CH O SO2O– Na+
sodium alkylbenzensulfonate
Synthetic (soapless) detergents like
soaps, have long non-polar hydrocarbon
(alkane) chains with polar groups at the
end (that is, hydrophilic).
185
The hydrophilic heads of most
detergents are sodium sulfonates or
sodium sulphates.
Synthetic detergents function well in
‘hard’ water. This is because of the fact
that the calcium and magnesium salts
of alkanesulfonates and alkylhydrogen
sulphates are largely water soluble and
hence, synthetic (soapless) detergents
remain in solution.
Advantages of soapless detergents
1 Soapless detergents are not affected
by hard water.
2 Soapless detergents do not form
scum and thus do not stain cloths.
e
Disadvantages of soapless detergent
1 Soapless detergents are non-
biodegradable and so can result in
water pollution.
Detergents
A detergent is a surfactant or a mixture
of surfactants having cleaning properties
in dilute solutions. Detergents are
alkylbenzenesulphates, a family of organic
compounds similar to soap, but are not
affected by hard water. Detergent, to
most people, commonly refers to laundry
detergent or dish detergent as opposed to
soap or other types of cleansing agents. It the non-polar portion allows it to dissolve
is commonly available in powder form. greasy substances.
Detergents are classified into three
depending on the electrical charge of the Major uses of detergent
surfactants: 1 Laundry detergents: Detergents
arelargely used for cleaning clothing.
Anionic detergents: These are alkylbenzene Laundry detergents contain a
sulfonates. The alkylbenzene portion (that variety of other substances like
is, the hydrocarbon end, the lipophilic and water softeners, bleach, enzymes,
the sulfonate) is hydrophilic. brighteners, fragrances, surfactants
There are two common varieties those and many other agents. Formulations
with straight-chain (linear) alkyl groups, of detergents are affected by the
and those with branched alkyl groups. temperature of the cleaning water
Branched alkylbenzenesulfonates are and they vary from country to
no longer being used in some countries country. Most modern detergents
because it is poorly biodegradable. formu la tio n s con ta in se ve ra l
components. Three main ingredients
Cationic detergents: Cationic detergents are:
are alkylbenzenesolfonates just like a) The surfactants: that is, the
anionic detergents but have a hydrophobic alkylbenzenesulfonates.
component and a quaternary ammonium b) Builders: These are water
as the polar end. The ammonium centre is softeners. Typical builders
positively charged. are sodium carbonate, soap
and zeolites. They function
Ethoxylates: These are compounds that a s p re c i p i t a t i n g a g e n t s ,
have long hydrocarbon chains, but end precipitating calcium or
with (OCH2 CH2)n group. These groups are magnesium ions.
highly hydrophilic due to the presence of c) Bleach: Most kinds of beach
many oxygen centres. The groups are not in laundry detergents are
charged. oxidisers, e.g. sodium
hypochlorite. The main targets
N o n - i o n i c d e t e r g e n t s : T h e s e a re of bleach are substances
characterised by their (net) charged, that are of vegetable
hydrophilic head groups. They are based origin such as chlorophyll,
on polyoxyethylene glycol, glycosides (i.e., tannins, anthocyanin dyes
octyl-thioglucoside), bile acids, lipids, or and carotenoid pigments.
phosphate oxides. Other agents added as
Detetents are ions or molecules ‘bleach activators’ to enhance
that contain both polar and non-polar t h e e ff e c t i v e n e s s o f t h e
components. The polar components allow bleaching agent include
the detergent to dissolve in water, while tetraacetylethylenediamine.

186
 Enzymes are also added.
They help to degrade
recalcitrant stains composed of
proteins, fats or carbohydrates.
Each type of stain requires a
different type of enzymes.
Other additives include,
dye transfer inhibitors, and
antirepleposition agents.
2 As fuel additives: When added to
fuel it helps to prevent damage to
both carburetors and fuel injector
components of auto engines.
Long chain amines and amides
such as polyisobuteneamine and
polyisobuteneamide are used for
such detergents.
3 Detergents are also used as soapless
soap, that i,s a soap-free liquid
cleanser with a slightly acid pH.
Soapless soaps are used in a variety
of products.
Disadvantages of detergents
1 Most branched alkylbenzene-
sulfonates are non-biodegradable.
2 The discharge of soluble phosphates
into natural waters increases the
amount and growth of algae, kill fish
and plants due to the consumption
of muct of the oxygen in the water.
Summary
• Soaps are the salts of long-chain
carboxylic acids.
• During the process of manufacturing
soap, fats and oils are boiled in
aqueous sodium hydroxide until
hydrolysis is complete.
• Some advantages of soap are that it
is a good cleansing agent in water,
187
and is biodegradable.
• Disadvantages of soap include it that
forms scum when used in hard water,
and causes wastage.
• Soapless detergents are synthetic
detergents. They do not form scum
with hard water.
• Soapless detergents have long non-
polar hydrocarbon chains with polar
groups at the end.
• One disadvantage of soapless
detergents is that they are non-
biodegradable.
• Detergents are surfactants or a
mixture of surfactants having
cleaning properties in dilute
solutions.
• Detergents are classified into anionic
detergents, cationic detergents and
non-ionic detergents.
• Uses of detergents include the
following: as fuel additives, as
laundry detergents, and as soapless
soaps.
Review questions
A Multiple choice questions
1 Salts of long-chain carboxylic acids
known as
A fat.
B oil.
C soap.
D detergent.
2 Soaps form scum in
A hard water.
B soft water.
C distil water.
D water vapour.
3 When soap dissolves in water, it exits
as
 A soapless.
B micelles.
C powder.
D foam.
4 Detergents can be classified into the
following except
A cationic detergents.
B anionic detergents.
C cathodic detergents.
D non-ionic detergents.
5 Soapless detergents are not affected
by hard water.
A True
B False
C All of the above
D None of the above

B Short structured questions

1 List the three classes of detergents.
2 Give the structure of soap.
3 a) Write the equation of the
preparation of a soapless
detergent.
b) Give the name of the soapless
detergent prepared above.
4 Give the equation for the preparation
of a named soap.

C Essay-type questions
1 a) State two advantages and two
disadvantages of the following:
i) Soap
ii) Detergents
b) Describe briefly how soap can
be prepared in the laboratory.
2 Write short notes on the following:
a) Soapless detergents
b) Anionic detergents
c) Non-ionic detergents

188
 12 Giant molecules
Introduction
Giant molecules or macromolecules are
widely found in living things where
they play very important structural and
physiological roles. The major giant
molecules include carbohydrates and
proteins.
In this chapter, we shall study some of
the molecules known to function in specific
biological roles. Many of these molecules
are biopolymers. We should answer such
questions as: What kinds of molecules
make up the living systems? How does a
living system produce the energy it needs?
What structures do biopolymers have?
Performance objectives
At the end of this chapter, you should be
able to:
1 explain the importance of sugars,
starches, cellulose and proteins in
living systems;
2 illustrate how living systems utilise
energy stored in carbohydrates; and
3 describe the functions of enzymes.
189
Carbohydrates
This is a group of organic chemicals
composed of carbon, hydrogen and
oxygen; and includes sugars, starches
and celluloses. Naturally-occurring
carbohydrates are photosynthetically
produced by green plants from carbon(IV)
oxide and water, and are used by plants
for growth and other functions. The
carbohydrates are a major class of animal
foods, the others being proteins and fats.
Nomenclature in carbohydrates
Names of the simpler carbohydrates end
in -ose. Carbohydrates with the structure of
alkanals are known as aldoses while those
with the structure of alkanones are known
as ketoses. A carbohydrate which contains
five carbon atoms is called a pentose while
a carbohydrate which contains six carbon
atoms is called a hexose.
Classes of carbohydrates
Carbohydrates are divided into two
main classes: the simple sugars and the
complex sugars. Simple sugars are soluble
crystalline substances with a sweet taste.
There are two major groups of sugars:
the monosaccharides and the disaccharides.
Complex sugars have relative molar mass
far larger than those of simple sugars. The
polysaccharides constitute good examples
of complex sugars. Fig. 12.1 shows the
various classes of carbohydrates.
Carbohydrates

Simple sugars Complex sugars

Monosaccharides Disaccharides Polysaccharides

galactose

glycogen

cellulose
fructose

maltose
glucose

sucrose

lactose

starch
Fig. 12.1 Classes of carbohydrates

Monosaccharides

Monosaccharides are sugars which cannot
be hydrolysed into smaller molecules. They
represent single molecules of the particular
sugar. The most important are the hexoses,
the pentoses and the trioses.
The hexoses constitute the most
important monosaccharide. Hexoses
contain six carbon atoms per molecule.
Examples of hexoses include glucose,
fructose, galactose and mannose. Hexoses
have the same molecular formula, C6H12O6
but possess different spatial arrangements.
Trioses, C 3 H 6 O 6 are those mono-
saccharides with three carbon atoms
per molecule. Examples of trioses
include 2,3-dihydroxypropanal and l,3-
dihydroxypropanone.
Pentoses are those monosaccharides with
five carbon atoms per molecule. Examples
of pentoses include ribose, deoxyribose and
xylose.
Glucose
Glucose is commonly known as grape
sugar and is present in honey, in golden
syrup and in fruits. All sugar and starch in-
gested by animals are first of all converted
to glucose which is then used to provide
energy for animal tissues. Glucose exists
in two forms: in an open chain form and in
a cyclic form.

190
 H O H
1
C H 1C OH
H 2
C OH HO 2
C O
HO 3
C H H
3
C H
H 4
C OH H 4
C OH
H 5
C OH H 5
C OH
6
CH2OH 6
CH2OH

(open chain glucose) (open-chain fructose)

HO6CH2 O
HO6CH2 H
5
C O 5
C 2
C
H H
H 1
CH2OH
4
C 1
C
OH 4
C C
3
OH OH
3
C 2
C OH H
H (cyclic-form of fructose)
(cyclic form of glucose)

Laboratory preparation of glucose Fructose

In the laboratory, glucose can be prepared
via the hydrolysis of starch with a dilute
acid.
(C6H10O5)n + n H2O → nC6H12O6
(starch) (glucose)
Properties of glucose
1 When treated with concentrated
tetraoxosulphate(VI) acid, a black
residue of carbon is formed.
C6H12O6 6C
2 It is a very strong reducing agent.
3 Its solution readily ferments to ethanol
and carbon(IV)oxide in the presence of
the enzyme, zymase.
Fructose is a sweet, optically-active sugar.
It is found especially in fruits and in honey
together with glucose. In many ways,
fructose resembles glucose. Fructose exists
in two forms: in an open chain form and
in a cyclic form.
The chemical reactions of fructose are
essentially similar to those of glucose. The
only noticeable difference is the behaviour
of the two sugars towards oxidising
agents. For instance, on oxidation with
trioxonitrate(V)acid, fructose gives a
mixture of acids, each containing less than
six carbon atoms.

191
Galactose Deoxyribose
Galactose is an isomer of glucose. Deoxyribose is also a pentose sugar
Galactose is found in galactans and is also obtained by hydrolysis from certain nucleic
combined with glucose in the disaccharide acids. The structure of deoxyribose is as
lactose. shown:
Galactose may be prepared by
hydrolysing lactose and separating it O
CH2OH OH
from glucose via fractional distillation from
water in which glucose is more soluble than CH HC
galactose. Galactose has a cyclic structure
as shown. H
HO6CH2
C C H
5
C O
OH H
HO
(deoxyribose)
4
C 1
C
OH D-xylose
H
3
C 2
C D-xylose is a wood sugar and has the
formula C5Hl0O5. It melts at 144°C (417 K).
H OH Its structural formula is :
(cyclic structure of galactose)
H
Mannose
Mannose is a sugar obtained by oxidising O
mannitol with trioxonitrate(V)acid. H H H
Mannose is prepared commercially by
hydrolysing seminine with boiling dilute OH
OH H
tetraoxosulphate(VI)acid. Seminine occurs HO
in many plants, particularly in the shell of
the ivory nut.
H OH
Ribose D-xylose is not fermentable, and it
Ribose is a pentose sugar obtained by the behaves chemically as other sugars.
hydrolysis of certain nucleic acids. The
structure of ribose is as shown: Disaccharides
O
CH2OH OH
Disaccharides consist of two
C HOC monosaccharide units which have been
H H joined together by an oxygen atom. All
disaccharides are crystalline solids which
C C are soluble in water.
There are two classes of disaccharides:
(ribose)
OH H the reducing sugars and the non-reducing

192
sugars. A reducing sugar is one which has Maltose is a crystalline, soluble white
an effect on Fehling’s solution. A non- solid with the melting point between 433
reducing sugar is one which has no effect K and 438K (160°C and 165°C). Maltose is
on Fehling’s solution. a reducing sugar. When hydrolysed with
We shall study the disaccharides dilute acids, or by the enzyme maltase,
sucrose, maltose and lactose. maltose yields two molecules of D( +
)-glucose.
Sucrose
Commercially, sucrose is the most
important of all the sugars. It is obtained
from sugarcane and sugar-beet. Sucrose is
a colourless crystalline solid with a very
sweet taste. The ordinary sugar, which we
all know, is indeed sucrose! Sucrose is a
non-reducing sugar because it has no effect
on Fehling’s solution.
When heated above its melting point,
sucrose forms a brown substance known as
caramel. Concentrated tetraoxosulphate(VI) Lactose
acid chars sucrose, the product being Lactose is commonly called milk sugar and
almost pure carbon. On hydrolysis with occurs in the milk of all mammals. A white
dilute acids, or with the enzyme invertase, crystalline solid with a melting point of
sucrose yields an equimolecular mixture 476 K (203°C), lactose is hydrolysed by
of D( + )-glucose and D(-)-fructose. dilute acids or by the enzyme lactase to an
equimolecular mixture of D( + )-glucose
and D(+)-galactose.

Maltose
Maltose, the so-called malt sugar, C12H22O11
does not occur naturally but is produced by
the action of malt on starch. Malt contains Polysaccharides
the enzyme diastase.
n n Polysaccharides are high polymers of
(C 6 H10 O 6 )n + H 2 O diastate
→ C12 O12 monosaccharides with molecular weights
2 2

193
which range from a few thousands to several Glycogen
millions. olysaccharides can be hydrolysed Glycogen, (C6H10O5)n, is present in nearly
to yield the component monosaccharides. all animal cells, particularly in the liver.
Important polysaccharides include starch, Glycogen is the reserve carbohydrate of
glycogen, cellulose and inulin. All these
animals and is often called the animal starch
are polymers of hexoses with the general
although it has now been isolated from
molecular formula of (C6H10O5)n, where n
is a very large number. plant sources.
For our purposes, we shall study A white powder, glycogen is soluble in
the polysaccharides starch, glycogen and water, and on hydrolysis with dilute acid,
cellulose. glycogen gives D(+)-glucose. A highly-
branched chain molecule, the molecular
Starch weight of glycogen ranges between
Starch occurs in all green plants. However, 1 000 000 and 5 000 000. Glycogen resembles
the commercial sources of starch include amylopectin and serves as a rapid access
maize, wheat, barley, potato, sorghum store for glucose and, therefor,e for energy.
and rice. In animals with backbone (vertebrates),
Generally, starch consists of two when muscles are active, glucose is utilised
fractions. One fraction is known as
to supply the necessary energy. When
α-amylose while the other fraction is
the glucose in the muscle is exhausted,
known as β-amylose or, more popularly,
as amylopectin. About 10-20% of starch is glycogen is broken down into glucose
made up of α-amylose with 80-90% of starch which now serves as a replacement.
being made up of amylopectin. When the glycogen in the muscle
The mol ecules wh ich make up becomes fully used up, then glycogen in
α-amylose contain around 1 000 to 4 000 the liver is converted into glucose which
glucose units. is then carried in the bloodstream to the
CH2OH CH2OH CH2OH muscles where it is used.
H O HH O HH O H
H H H
OH H OH H OH
H Cellulose
O O O O
Cellulose, (C6Hl0O5)n, is the main structural
H OH H OH H OH
component of the cellwalls of plants.
(α–amylose)
However, it is now known that cellulose
The molecules which make up amylopectin is available in certain animal tissues. The
contain over 1 000 000 glucose units. main sources of cellulose include cotton
CH2OH
and wood, and it is the most widely
H O H
H distributed organic compound.
OH H
O O A white solid, cellulose is insoluble
H OH in water. Under complete hydrolysis,
CH2OH CH2OH CH2OH cellulose gives only glucose. Under partial
O HH O HH O H hydrolysis, cellulose yields the disaccharide
H
H
OH H
H
OH H
H
OH
H cellobiose. Generally, cellulose molecules
O O O O contain between 20 000 and 500 000 glucose
H OH H OH H OH units.
(amylopectin)

194

H O O
CH2OH
H O O H
CH2OH H
H H
OH
H O O H
CH2OH H H
H OH
H O O
OH
H
H
OH H H OH
O H
H OH
(cellulose)
The enzyme cellulase readily hydrolyses
cellulose. Cellulase is present in the
digestive systems of termites and herbivores
but absent in the digestive system of man,
and, therefore, man cannot digest cellulose.
However, cellulose is important in our diet
because it serves as roughage capable of
promoting bowel movement.
Test for reducing sugars
To 3 cm3 of glucose solution, add 2 cm3
of Fehling’s solution. Boil. A brick-red
precipitate indicates a reducing sugar.
Test for non-reducing sugars
With 5 drops of hydrochloric acid, boil
3 cm3 of sucrose solution for 3 minutes.
With sodium hydroxide, make the solution
alkaline and add, 3 cm 3 of Fehhing’s
solution. Boil. A brick-red precipitate
indicates that the non-reducing sugar has
been hydrolysed to a reducing sugar.
Test for starch
Mix about 0.1 g of starch with 5 cm3 of
water in a test tube. In another test tube,
boil about 5 cm3 of water. Add this boiling
water to the starch suspension. Boil and
cool the mixture. When the mixture is
cool, add 5 drops of iodine solution. A
blue colour indicates that starch is present.
CH2OH
Carbohydrates and energy in living
H
OH H systems
OH
We shall, in this section, be mainly
concerned with the basic outline on how
glucose provides the energy needed by
living systems. As we know, glucose is
the first product of photosynthesis by green
plants.
When animals eat green plants, the
starch in plants is broken down to glucose
units. This is in the digestive system of
the animal. The glucose is then carried by
the bloodstream to the liver. In the liver,
the glucose is recombined into glycogen.
Living organisms use glycogen as a
source of energy to sustain their biological
activities. The question is: how is this
energy obtained?
The energy is obtained via a step-
by-step breakdown of glucose. The entire
process is known as cellular respiration.
The first few steps of cellular respiration
are known as glycolysis. Glycolysis results
in the breakdown of glucose to pyruvic
acid. Glycolysis does not require oxygen.
However, further breakdown of glucose
requires oxygen and the pathway is the
Kreb’s citric acid cycle, popularly called
Kreb’s cycle. For glucose to be broken down
to water, carbon(IV) oxide and energy,
both glycolysis and the Kreb’s cycle are
involved. The process is variously referred
to as oxidative metabolism of glucose, which
can be summarised as follows:
C6H12O6 + 6O2 → 6H2O + 6CO2 +
2 827 kilojules
(potential (oxygen) (water) (carbon (kinetic
energy) and (IV) oxide) heat
energy)
195
The various steps in the breakdown of
glucose involve the release of energy. This
energy is linked with the production of
high-energy adenosine diphosphate (ADP)
and a tetraoxophosphate(IV) group.
It is now known that a total of 38
adenosine triphosphate (ATP) molecules
are released when one molecule of glucose
is completely oxidised. In living cells, ATP
is the most important source of energy.
Energy is released when ATP is hydrolysed
to ADP. Some of the released energy can
be used directly in the cell while the rest is
expended as heat.
ATP + H2O → ADP + H3PO4 + 34 kj
During the breakdown of sugar, many
of the intermediate products are used to
produce other useful substances, such as
fats, oils and proteins.
Proteins
Proteins may be regarded as the products
of successive condensations between the
carboxyl group of one amino acid and the
amino group of another amino acid. A
protein from one biological source will
always have an identical sequence of
amino acids. For example, cytochrome c
has 104 amino acids in many vertebrates.
Thus, proteins are complex combinations
of amino acids which are essentially
constituents of all living cells, being
responsible for growth and the maintenance
of all tissues. Proteins are also the essential
nitrogeneous constituent of the food of
animals. Proteins can be synthesised from
inorganic nitrogeneous materials by plants
but, apparently, not by animals.
When proteins are exposed to drastic
conditions, such as heating, extreme pH,
196
they tend to lose their biological activity
and undergo other changes in properties.
This is because the very delicate structure,
which depends on hydrogen bonding and
other relatively weak forces, is broken and
the molecule loses its shape. In most cases,
denaturation is irreversible.
During starvation, proteins may serve as
a source of energy. The proteins in muscles
are degraded to amino acids which are
then broken further to produce some
intermediates. These intermediates enter the
Kreb’s cycle and lead subsequently to ATP
production.
For now, we can think of two classes
of proteins: the conjugated proteins and the
unconjugated proteins. Conjugated proteins
are chemically bound to other types of
material. Unconjugated proteins consist of
amino acids only.
Test for proteins
Into a test tube, add 3 cm 3 of gelatin
solution followed by 1 cm3 of concentrated
trioxonitrate(V) acid. A yellow colour is
seen. Dilute and cool the solution with
water. Carefully and slowly add excess
concentrated ammonia solution. A change
from yellow colour to orange colour confirms
the presence of protein.
Enzymes
These are a large class of complex
p ro t e i n a c e o u s s u b s t a n c e s o f h i g h
molecular weight formed in and produced
by living matter. Enzymes are responsible
for promoting the chemical reactions
upon which life itself depends. They
accomplish this by acting like catalysts
while themselves undergoing little or no
change. Enzymes act with a high degree
of specificity and efficiency. Their reactions
are reversible and may be dependent upon
temperature, pH and the presence of co-
enzymes and activators.
Enzymes are obtained from plants,
animals and microorganisms by extraction
with a suitable solvent, preferably after
the cell structure has been destroyed by
drying and grinding. They can be purified
by precipitation and re-solution, and by
fractional absorption and elution. Many
enzymes have been obtained in crystalline
form.
Enzymes often need for their activity the
presence of a non-protein portion, which
may be closely combined with the protein,
in which case it is called a prosthetic group,
or more loosely associated, in which case
it is a co-enzyme.
One very outstanding feature of
enzymes is that many of them are highly
specific. Those that act on carbohydrates
are particularly so, the slightest change
in the stereochemical configuration of
the molecule being sufficient to make
a particular enzyme incompatible and
unable to effect hydrolysis.
Enzymes act by lowering the overall
activation energy of a reaction sequence
by involving a series of intermediates,
or a mechanism, quite different from the
spontaneous unanalysed reaction. Most
enzymes work best within a narrow pH
range and are susceptible to a wide variety
of compounds which inhibit or sometimes
promote the activity. The majority of
enzymes work most efficiently at around
313 K (40°C) and, at higher temperatures,
are rapidly destroyed.
Classification of enzymes
Enzymes are classified in terms of the
197
reactions which they catalyse, and the
particular subtrate. On these bases, six
main classes of enzymes an recognised:
hydrolases, isomerases, ligases, glyases,
oxidoreductases and transferases.
Hydrolases
These are enzymes which catalyse the
hydrolytic cleavage of C-O, C-N, and
C-C bonds. Examples include esterases,
peptidases, proteinases, glucosidases and
phospholipases.
Isomerases
These are enzymes which catalyse the
structural or geometric changes within a
molecule. Examples include racemases,
mutases, epimerases and tantomerases.
Ligases
These are enzymes which catalyse the
joining together of two molecules coupled
with the hydrolysis of a pyrophosphate
bond in ADP or a similar triphosphate.
Iigases include some carboxylases and
many enzymes known as synthetases.
Lyases
These are enzymes which cleave C-C,
C-O,C-N and other bonds by elimination,
leaving double bonds or, conversely, add
groups to double bonds. Examples of lyases
include decarboxylases, dehydratases,
hydratases and some carboxylases.
Oxidoreductases
These are enzymes which catalyse redox
reactions. The substrate which is oxidised is
regarded as the hydrogen donor. Examples
of oxidoreductases include oxidases,
dehydrogenases, reductases, hydroxylases
and peroxidases.
Transferases
These are enzymes which transfer a
group, possibly a methyl group or a
glycosyl group, from one compound
to another compound. Examples of
transferases include methyltransferases
and aminotransferases.
How enzymes work
Before an enzyme can act as a catalyst,
it must combine with its substrate. Most
enzymatic reactions involve substrates that
are small compared with the size of the
enzyme molecule. Every enzyme molecule
has only one or at most a few specific sites
suitably molded to receive the substrate.
The lock and key hypothesis is used
to explain the path of enzyme-controlled
reactions. Briefly, the steps involved are as
follows:
1 Substrate molecule attracted to active
site of enzyme.
2 Split in substrate molecule catalysed by
the enzyme.
active site
substrate
enzyme
Fig. 12.2
198
3 The enzyme-product complex splits to
give the enzyme and product.
The unchanged enzyme can be used
again (see Fig. 12.2).
Uses of enzymes
Enzymes are used in wine-making,
in baking, in cheese manufacturing,
in brewing, in distillation, in leather
tanning, in pharmaceuticals, in paper
manufacturing, in adhesives, in sewage
disposal, in detergents and in animal feed.
Nucleic acids
Nucleic acids are essential components
of all living cells because they carry the
necessary hereditary information enabling
highly specific proteins to be constructed.
There are two types of nucleic acids:
deoxyribose nucleic acids (DNA) and
ribose nucleic acids (RNA).
DNA
DNA is found in the nuclei of cells. DNA is
a polynucleotide, built of the nucleotides of
the purine bases: adenine, guanine, cytosine,
thymine and pyrimidine.
The DNA molecule consists of two
helical chains coiled round the same axis.
DNA is considered as a gene and the
chemical structure is characterised by
sequences of four nitrogen bases: adenine,
thymine, guanine and cytosine. These occur
in one of the two nucleic acid chains,
and in a complementary fashion in the
other nucleic acid chain. The sequence
of bases in a gene constitutes a code. This
code determines the nature of the quality
conferred on the organism which is
inheriting that gene.
 A T
T A
AT
G • The major giant molecules include
GC
A T
T A
G C
T
AT
G the complex sugars.
C
T A
AT
T amino acids.
T A
G C
A T
Fig. 12.3 Helical structure of DNA
The two helical structures of DNA are
held together by hydrogen bonds between
the bases. Of the two linked bases, spatial
considerations demand that one of the
bases must be a purine and the other a
pyrimidine. It is also believed that only two
specific pairs of bases can bind: adenine
with thymine and guanine with cytosine.
Thus, if we know the sequence of bases
in one chain, the sequence of bases in the
other chain can be determined.
RNA
RNA is a nucleic acid quite similar to DNA
but has a sugar residue, ribose, instead of
deoxyribose. RNA serves as an intermediary
in protein synthesis. RNA is found mainly
in the cytoplasm.
Different varieties of RNA exist with
widely different molecular weights.
For example, there are messenger RNA
(m-RNA), ribosomal RNA (r-RNA), and
transfer RNA (t-RNA).
199
Summary
This chapter has taught the following:
carbohydrates and proteins.
• Naturally-occurring carbohydrates are
photo-synthetically produced by green
plants.
• T h e re a re t w o m a i n c l a s s e s o f
carbohydrates: the simple sugars and
• A protein from one biological source
will always have the same sequence of
• Proteins can be synthesised by plants
but not by animals.
• There are two classes of proteins:
the conjugated proteins and the
unconjugated proteins.
• Enzymes are responsible for promoting
the chemical reactions upon which life
itself depends.
• Enzymes are highly specific.
• Enzymes are classified in terms of the
reactions which they catalyse.
• There are two types of nucleic acids:
DNA and RNA.
• DNA is found in nuclei of cells.
• RNA is found in the cytoplasm.
Review questions
A Multiple-choice questions
1 All the statements about sucrose are
true except that which says that
A it is a reducing sugar.
B it is a dimer of glucose and fructose.
C neither the ketonic function of
fructose nor the aldehydic function
of glucose is free.
 D It is hydrolysed in the body by the C Adenine
enzyme invertase. D Cytosine
2 Which is the odd compound in the
following? B Short-structured questions
A Starch 1 Name three agents which are capable
B Glycogen of denaturing an enzyme.
C Cellulose 2 Name the three pathways of glucose
D Lactose metabolism.
3 Which is the odd compound in the 3 What nucleotide base is unique to
following? DNA?
A Maltose 4 What nucleotide base is unique to
B Cellobiose RNA?
C Amylase 5 Name four functions of enzymes.
D Sucrose
4 Lipids are those water-insoluble C Essay-type questions
compounds extracted from cells with 1 Draw a structural formula of the
an organic solvent, such as hexane or open-chain version for the fructose
benzene. It includes all the compounds molecule. Explain why fructose cannot
listed below except be oxidised to a six-carbon acid.
A lecithin. 2 Outline the structural relationship
B retinol. between glucose, starch and cellulose.
C ascorbic acid. Describe how you would distinguish
D cholesterol. between the three substances by two
5 All the activities listed below take place chemical tests only.
in the citric acid or Kreb’s cycle except 3 What is a purine base? What is a
A synthesis of ATP. pyrimidine base? Which purines and
B production of carbon(IV)oxide. pyrimidines are used in DNA?
C production of water molecules. 4 Outline the various tests for
D synthesis of FADH2. a) fats.
6 Which of the organic nitrogen bases b) proteins.
listed below does not occur in DNA? c) reducing sugars.
A Uracil d) non-reducing sugars.
B Thymine 5 Give a general classification of enzymes
and describe each class.

200
 13 Nuclear chemistry
Introduction
In your study chemistry, you have learn
about the rearrangement of the outermost
electrons reacting atoms. Two common
reactions which you are already familiar
with are:
a) covalency, in which the atoms combine
by sharing electrons; and
b) electrovalency, which involves
transferring electrons from one atom
to the other.
In these two reactions, the nuclei of the
atoms remain unchanged.
Performance objectives
At the end of this chapter, you should be
able to:
1 enumerate radioactive elements;
2 state the nature of alpha (α) and beta
(β) particles, and gamma( γ ) rays;
3 distinguish between α, β and γ rays;
4 explain half-life as a measure of the
stability of a nucleus;
5 give the two types of radioactivity
and explain each of them;
6 explain nuclear fusion and nuclear
fission and give their applications;
and
201
7 state the important peaceful uses of
radioactivity.
Evidence for the atomic nucleus
In 1886, Crookes discovered the negative
charge while experimenting with discharge
tubes at very low pressure. He found that
the cathode emitted cathode rays which
travelled in straight lines and carried
negative charge of electricity. The same
year, Goldstein discovered positive rays
emitted from the electrode of a discharge
tube on the opposite of the one emitting
cathode rays. A typical discharge tube
consists of a glass tube with two metal
plates or electrodes, sealed at both ends.
The glass tube is connected to a vacuum
pump.
– high voltage +
cathode anode
to vacuum pump
Fig. 13.1 A typical discharge tube
 The electrodes are connected to the
positive and negative ends of a high-
voltage source and are known respectively
as anode and cathode. When the tube is
full of air at normal pressure, nothing is
observed even if 104 volts is applied across
the electrodes. As soon as air gets pumped
out of the tube, electricity starts to flow. The
air remaining in the tube begins to glow.
Compounds, such as zinc sulphide placed
between the electrodes give off an intense
light that can serve as detectors.
Goldstein used a discharge tube in
which the cathode had a hole at the centre
to show that positive ions produced by
collision of gas molecules and electrons
were attracted to the cathode. Some of the
positive ions passed through the hole and
struck the tube. This spot was detected
as a green spot as the end of the tube was
coated with zinc sulphide.
negative positive
+
+ ∝
+ + +
+
+
high voltage
Fig. 13.2 Discharge tube for studying positive
particles
These and similar experiments
demonstrated the existence of positive and
negative particles produced from atoms. To
unravel the complex structure of the atom,
J.J. Thomson in 1899 proposed the ‘plum
pudding’ model of the atom consisting
of rings of negatively-charged electrons
embedded in a sphere of positive charge,
202
so that a neutral atom resulted. The mass
of the atom was considered to be due to the
electrons. This is incredible as the hydrogen
atom would have contained 1 800 electrons.
Rutherford’s classic experiment
In 1911, Professor Rutherford and his
assistants, Geiger and Marsden, performed
the classic experiment which tested the
Thomson model. According to the Thomson
model, a metal is essentially a sea of
positive electricity containing negative
charges. Since alpha particles are very
∝
energetic, they should go right through
metal foils. If the positive charge and the
∝ gold foil
∝
screen
vacuum
Fig. 13.3 Main component of Geiger’s apparatus
mass are evenly distributed throughout
the metal, the alpha particle has little
or no reason to swerve off its original
course.
Rutherford investigated the scattering
of alpha particles by thin sheets of metal.
In his experiment, a narrow beam of
positively-charged helium particles was
projected at right angles to a thin sheet
of gold foil. Most of the particles passed
through the foil and were detected by a
 polonium source of lead plate
alpha particles with hole
Fig. 13.4 Details of Rutherford’s experiment
movable zinc sulphide fluorescent screen.
However, some were deflected at fairly
larger angles. A few of the particles were
deflected back from the foil along their
path.
The Thomson model was unable
to account for such large deflections.
Positively-charged helium particles would
not encounter a large repulsion or major
obstacle anywhere in its path if mass and
positive charges are uniformly spread
through the metal.
According to Rutherford, the only way to
account for the large deflection is to assume
that the positive electricity and mass in
the metal foil are concentrated in a very
small region. Most of the alpha particles
can go through the gold foil without any
deflection, though occasionally one comes
very close to the high concentration of
positive charge. The high concentration
of positive charge coming close together
repel each other and the repulsion may be
great enough to cause the alpha particle to
swerve considerably from its original path.
203
thin foil movable zinc
sulphide detector
Rutherford, therefore, proposed that an
atom has a nucleus, a centre, in which its
positive charge and mass are concentrated.
Radioactivity
After the discovery of the nucleus by
Rutherford, the understanding of its
complex nature rested with the following
earlier discoveries:
1 discovery of X-ray in 1875 by Withelm
Rontgen;
2 discovery of radioactivity in 1896 by
Henri Becquerel.
Withelm Rontgen discovered that
highly penetrating radiation was produced
when cathode rays bombarded metals.
Henri Becquerel discovered radioactivity
accidentally when he observed that a
photographic plate wrapped in black paper
blackened on development when it was
left near uranium salts. Becquerel quickly
deduced that the penetrating radiation
was emitted spontaneously by uranium
minerals. He also made the following
observations:
1 the penetrating radiation was not
affected by:
a) temperature, and
b) the chemical state of the uranium;.
2 the penetrating radiation resembled
X-rays but were of shorter wavelength;
and
3 the penetrating radiation caused
ionisation of gases just like X-rays.
Soon, many other nuclides were found
to possess similar properties. Pierre
and Marie Curie attempted to measure
ionisation of gases by radioactive
sources. In the process, they discovered
two new radioactive elements, polonium
and radium from tons of pitchblend.
Radium is a more powerful
radioactive element than uranium.
Radioactivity can, therefore, be defined
as the spontaneous disintegration of
nuclides resulting in emission of particles
and rays in the process known as radioactive
decay.
Rutherford was the first to make
a systematic study of radioactivity
from radio nuclides or radioisotopes.
The nature of radiation was studied
N
S
uranium
source
magnet
Fig. 13.5(a) Radioactive decay particles in a magnetic field
204
by applying magnetic and electric
fields to the radiation and observing
its deflection in both fields. As shown
in Fig. 13.5(a) and Fig. 13.5(b), positive
and negative particles were deflected
in opposite directions while uncharged
particles go through the magnetic field
undeflected. The paths of the particles
can be detected by photographic film
or zinc sulphide screens. In recent
times, they are detected by a cloud
chamber or a bubble chamber.
In the cloud chamber, the passage
of a particle causes supercooled water
vapour to condense into droplets along the
particle’s trajectory. If, as in Fig. 13.5(a), a
piece of uranium mineral is placed in the
bottom of a hole drilled in a lead block,
a beam of particles emerges and it is
separated by the magnetic field, or electric
field, into three component beams. The
heavy lead absorbs all radiation, except
the narrow beam coming through the
hole. The whole apparatus is housed in a
chamber from which air is evacuated. A
magnetic or electric field is imposed on the
beam and the final result is recorded on a
photographic plate.
T h e re s u l t s s h o w t h re e b e a m s
γ
α
deflection
 photographic plate

γ +

α β

electrically electrically
charged plate charged plate
(–ve) (+ve)
radium

lead block

Fig. 13.5(b) Radioactive decay particles in an electric field

representing a, b and γ-rays. The directions -1 unit. Often, both radiations are emitted
of deflection of the beams indicate that: one after the other. For example, the decay
1 the a-ray is positively-charged; of uranium of mass number 238 occurs as
2 the b-ray is negatively-charged; and follows:
3 the γ-ray has no charge.
Rutherford found the b-radiation more 1 238
92 U → 90TH + 2 He (an α -particle)
234 4

penetrating but less ionising than the 2 Thorium, with an atomic mass of 234,
a-radiation. decays by 234 the loss of a beta-particle
92 U → 90TH + 2 He (an α -particle)
234 4
It was Villand who later discovered the into protactinium, with atomic mass
γ-radiation which is more penetrating than of 234.
0n234→ 1 H + 234−1 e (an electron)
1 1 0
the other two rays, but possesses no charge.
Th → 91 Pa + −1e (an β -particle)
0
The emission of radiation by most 90

radioactive elements is accompanied by Note that 234

the loss 4of a b-particle has
the gradual disintegration of the original
238
U →
given rise to a90new
92 TH +element.
2 He (anThe
α -particle)
ejection
element and the appearance of a new one. of a β- particle from the nucleus of an atom
Thus, atoms of one element spontaneously is due
234 to the conversion
92 U →
of a neutron into
90TH + 2 He (an α -particle)
234 4

change into atoms of the other element. a proton and an electron as shown:
The process is known as transmutation. 1
n → 11 H + 0
e (an electron)
For example, uranium atoms disintegrate 0 −1

to form thorium atoms and alpha particles. The decay of 92238 U into 90234 Th and into
Pa represents the first two steps in
234
238
U → 234
TH + 42 He (an α -particle) 91
92 90
uranium radioactive series, ending in the
During radioactive decay, the atomic production of non-radioactive lead, 82206Pb .
92 U →
emits90TH He α-particle,
(an α -particle)
234 234
nucleus + 42an
either which
has been shown to be a helium nucleus Nuclides and nucleous
of mass 14 units0 and charge + 2 units, or Any nuclear species with a specific atomic
0 n → 1 H + −1 e (an electron)
1

a β-particle, which is equivalent to an number Z and a specific mass number A is

electron of negligible mass and of charge referred to as a nuclide. For example, 126 C is

205
a nuclide. is an isotopic nuclide of 12C;
both have the same atomic number but
different mass numbers.
The particles that make up the nucleus,
the protons and neutrons, are called
nucleons. Hence, the mass number refers
to the total number of nucleons within
the nucleus. When discussing nuclear
phenomena, we usually refer to specific
nuclides, and it is important to give the
atomic number as well as the mass number.
You will note from the Periodic Table
that all nuclides with atomic numbers
greater than 83 (bismuth) are radioactive.
Examples include polonium 84, astatine 85,
radon 86, francium 87, etc.
Properties of radiation
We shall now study the properties of alpha
radiation, beta decay and gamma decay.
Alpha (a) radiation
From the deflection of the alpha particles in
electric and magnetic fields, it is deduced
that alpha rays contain positively-charged
particles. The following are also known
about alpha radiation:
1 The charge to mass ratio (e/m)
for alpha particles was measured
by Rutherford and Robinson. The
modern value for of alpha particle
is 4.82 × 104 coulombs/kilogram.
2 Alpha particles are highly ionising
and are easily stopped by even thin
paper or a piece of cloth.
3 Alpha particles are emitted at high
speeds. For a given radioisotope, the
speed or kinetic energy of emitted
alpha particles is fixed or quantised,
usually between 5 and 9 Mev. An
206
example is , a radium isotope.
An alpha emitter gives alpha particles
with three discrete energies at 4.79,
4.61 and 4.21 Mev respectively (Mev
= 9.648 × 107kJmol-1).
4 The mass of an alpha particle was
determined. To find the mass, it was
necessary to measure the charge.
Rutherford and Geiger succeeded in
measuring the charge.
The charge on one alpha (a) particle was
calculated to be approximately 3.19 × 10-19
coulombs. The calculation was carried out
by using the charge to mass ratio as shown:
Mass = Charge ÷ (Charge/Mass)
3.19 × 10 –19
=
4.82 × 107
Mass = 6.62 x 10-27 kg
This mass is equivalent to the masses
of four hydrogen atoms and also equal
to the mass of one helium nucleus. This
was further confirmed by collecting alpha
particles in a chamber and observing
the emission spectrum of the resulting
gas which was obtained by discharging
electricity through it.
Rutherford and Royds succeeded in
obtaining the emission spectra of helium
by using the apparatus shown in Fig. 13.6.
The apparatus consists of a thin tube A
containing some radon source. The alpha
particles penetrated A into a discharge tube
B. It was observed that the alpha particles
regained electrons from the walls of B and
settled as gas. When a sufficient quantity
had collected, the gas was forced into the
narrow end of B by means of mercury. A
current was then discharged through the
gas.
 Other examples of isotopes that decay
terminals for by loss of alpha particles are radium-226,
discharge plutonium-238 and radon-220. Alpha
decay usually occurs with radioactive
isotopes of elements with atomic number
greater than 82 (lead). It is the alpha decay
thin-walled inner vessel
containing radon process combined with spontaneous fission
that currently limits the ability of chemists
to make new elements in the laboratory.

mercury Beta (b) decay

Fig. 13.6 Rutherford’s apparatus for investigating
the nature of α-particles
The emission spectrum obtained was
analysed and identified to be that of helium.
Alpha decay is, therefore, a radioactive
disintegration in which a nucleus of the
helium atom is ejected. It involves:
1 a reduction of the atomic mass of the
parent nuclide by four;
2 a decrease of the atomic number of the
parent nuclide by two, the daughter
Beta decay is the radioactive transformation
in which beta particles are emitted. The
loss of b-particle results in the formation
of a new element whose atomic number is
one unit greater than that of the decaying
element. The ejection of a particle from the
nucleus of an atom is due to the conversion
of a neutron into a proton and an electron.
1
0 n → 11H (a proton) + 0−1e (an electron)
The decay can be depicted thus:
A
Z X → A
Z+1 X + 0−1e + Q

nuclide resulting from the decay being Examples of b decay include:

a new element, two places to the left of
238 Hg → 238 Tl + 0e
the parent nuclide on the periodic table; 80 81 -1
and
3 a decrease in the number of neutrons 238 238 0
81 Tl → 82 Pb + -1 e
by two.
Alpha decay is summarised below as
238 Pb → 238 Bi + 0e
follows: 82 83 -1

A
Y → A–4
X + 42 He + Q 238 238 0
91 Pa 92 U + -1 e
Z Z−2
→
Q is the kinetic energy of the decay
products. The maximum stability for A = 238 (or
This is depicted pictorially in Fig. 13.7. 238
92 U) is, therefore, reached through this
Examples of alpha decay include: process.
From the deflection of b-rays in a
210
84 Po → 206
82 Pb + 42 He(t 12 = 138 days) magnetic or an electrical field, we can make
the following deductions:
238
92 Po → 234
90 Pb + 42 He(t 12 = 4.5 × 106 years) 1 b-rays are made of negatively-charged

207
 4
2 He
n p
p
P n
n p p p n
n p p
n n p
n n n n n p
p n n
p p

A A–4 alpha
ZY Z–2 X particles

Fig. 13.7 Pictorial representation of alpha decay

particles. Electron capture and positron decay

2 Its charge to mass ratio is exactly the Another form of beta decay is that in which
same as that of an electron. Its charge orbital electrons are captured by the nucleus,
can also be measured in the same resulting in nuclear transformation.
way as for the alpha particles. All the A 0 A
measurements confirm that the beta ZY + -1 e → Z-1 X + V
particle is the same as the electron.
3 Beta rays are not as ionising as alpha The atomic number of the nucleus is
particles but they are more ionising reduced by one and a neutrino is given off
than gamma rays. as shown in the above equation. In most
4 Beta rays are more penetrating than nuclei undergoing electron capture, about
alpha rays. The beta particle is ejected 90% of the electrons are captured from the
from the parent nucleus at a very high K-orbital. This is known as K-capture. Some
speed which approaches the velocity examples of decay by electron capture
of light. include:
5 Unlike alpha particles, beta particles 51 0 51
are ejected with velocities ranging 24 Cr + -1 e → 23
V +V
from zero to a maximum for any given 54 0 54
radioisotope. 25 Mn + -1 e → 24Cr +V
A positive beta is also observed in the
decay of certain radionuclides. It is called A nucleus with a ratio of neutron to
positron and is identical in mass and other proton too low for stability may also decay
physical properties with the electron. The by emitting a positron. In this type of
only difference is its positive charge. If decay, a proton is changed into a neutron,
negative beta is denoted as e–, the positive a positron and a neutrino.
beta is denoted as e+. The electronic configurations of the two
products are, however, quite different. The

208
resulting atom of positron emission has an Other examples of gamma decay
extra electron which gives the atom a -1 include:
charge state. The resulting atom of electron-
12
capture decay is electrically neutral, but 3[42 He]
6
→ C + γ
a vacancy exists in one of its innermost
12 C 4 He 16
electron orbitals. This accounts for the 6
+ 2
→ 8O + γ
X-ray emission that generally accompanies
electron-capture decay. These equations are appropriate for helium
6C
14
burning reactions.
Gamma decay In some nuclear equations, however,
Gamma decaye is usually accompanied by the gamma decay is slowed down because

the emission  of nuclear structure effects. The symbol m
 m  of alpha and beta particles.
This occurs in a nuclear reaction in which (for meta stable) is usually added after the
the nucleus is in an excited state. For the mass number of these nuclear reactions to
e
excited nucleus to go back to the ground indicate this factor. Gamma decay does not
m
state, it releases its excess energy in the involve any changes in the chemical nature
form of gamma rays. For example, the of the parent nucleus; the mass number and
isotope 199
50 Sn ,
when in such an excited state, the atomic number also remain unchanged.
decays with the emission of gamma rays We now have the following information
having energies of 0.065 and 0.024 MeV. about the gamma rays:
1 Gamma rays are electromagnetic
199 199
50
Sn → 50
Sn + γ waves, such as X-rays and light rays.
The wavelength of a gamma ray is
The gamma ray is made up of high
10-12 metres. It is one tenth (10–1) the
energy electromagnetic waves. It is neutral
wavelength of X-rays and about 10–5
as we have demonstrated in Fig. 13.5 and
of the wavelength of visible light.
it has no mass. It is, therefore, the least
2 Gamma rays are not deflected by an
ionising and most penetrating of the three
electric or magnetic field.
types of radiations. Its properties are
3 Gamma rays can penetrate several
similar to those of X-rays, but it is more
centimetres of lead.
energetic.
Table 13.1 Summary of the nature and properties of alpha-particles, beta-particles and gamma rays
Relative effect of Range Relative
Emission Nature magnetic/electric in air penetrating
field power

Alpha particles Helium Small deflection A few 1

nuclei cm
( 42 He
4
2 He )
Beta particle Electrons Large deflection A few 100
( − 00 e ) m
− 1e1

Gramma rays Electro- No deflection A few 10 000

magnetic km
waves

209
4 Gamma rays are diffracted by a crystal Nuclear force and binding energy
lattice. There is a measure of stability for any
The nature and properties of alpha nuclide. By the rule of electrostatic
particles, beta particles and γ-rays are repulsive force, particles with a similar
summarised in Table 13.1. charge repel each other. Within the nucleus,
protons, separated from one another by
Note a very small distance, repel each other.
Changes in the nucleus itself, as shown However, these protons remain together
by radioactive emission and release of because there exists a nuclear force which
enormous quantities of energy, still pose counteracts the electrostatic repulsive
a major unsolved problem for chemists. force.
In 1905, Albert Einstein showed that
Nuclear equations energy and mass are related by the equation
In a nuclear equation, both mass number
E = mc2
and atomic number must balance. Notice
where E is the energy, m the mass and
also that both mass and charge are
c the velocity of light. A stable nucleus
conserved in both alpha and beta decay.
has less energy than the particles which
238U 234
constitute its nucleons. The difference in
→ Th + 4 He
92 90 2 energy between the stable nucleus and
14 0 the constituents of its nucleon is called
14 C
6
→ 7N + -1
e
mass defect.
0 Mass defect can be calculated, and
1
n → 11p + -1 e
0
converted to binding energy in the nucleus.
Binding energy may be regarded as the
amount of energy needed to separate the
Nuclear stability nucleus into its component nucleons. It is
also the energy released when a nucleus is
So far, we have learnt of naturally-occurring
formed from the particles which compose
radioactive isotopes and their mode of
it. The larger the mass defect, the larger the
disintegration, types of radioactive changes
binding energy and, therefore, the more
and the products of decay. As scientists,
stable the nucleus.
we are also concerned with the rate of
disintegration and the relative stability of
Stability and the ratio of neutrons and
the different radioactive isotopes.
protons
You will recall that Henri Becquerel,
The stability of the nucleus is also
who discovered radioactivity, observed
determined by its number of protons
that natural decay of radioactive isotopes
and neutrons. Elements with low atomic
was neither retarded nor accelerated
numbers (up to Z = 20) are most stable
by physical or chemical processes. For
when the number of protons p in the
example, pressure or temperature had no
nucleus equals the number of neutrons
effect on the rate of decay of radioactive n
n, such that the ratio =1. Nuclei with a
isotopes. p

210
greater number of neutrons than protons
have lower binding energies and are,
therefore, less stable.
For elements with higher atomic
number, as the force between the protons
n
increases, the ratio also increases
p
progressively up to 1.6. Above this value,
the nuclei become so large and, therefore,
begin to fission. Fission is the process in
which a very heavy nucleus splits and
forms intermediate-mass nuclei.
In summary, the shorter the half-life,
the faster the isotope decays and the more
unstable it is. On the other hand, the longer
the half-life, the slower the decay process
and the more stable the isotope. The half-
life of a radioactive isotope provides a
quantitative measure of its relative stability.
From Table 13.2, uranium-238 isotope
1
with t = 4.5 × 109 years is almost stable
2 1
while polonium-214, with t = 1.5 × 10-4
2
seconds, is described as unstable.

Half-life as a measure of stability of the Nuclear reactions

nucleus
The degree of stability of the nuclide is also
determined by its half-life for radioactive
decay. Half-life may be defined as the time
taken for half of a sample to decay. This is a
characteristic of the particular isotope.
The half-life remains constant and
unique for each radioactive decay process.
The half-life for 146 C is 5.7 × 103 years. This
means that, starting with a given mass of
carbon-14, for example, it will reduce to
92 U× 10 years. This mass
238
half its mass in 5.7 3
In ordinary chemical reactions, the
outermost orbital electrons of the reacting
atoms are rearranged while the nuclei
remain unaffected in any way. In nuclear
reactions, however, both the electrons and
nuclei of the reacting atoms are involved.
Nuclear reactions are often referred to
as radioactivity. There are two types of
radio activities: natural radioactivity and
artificial radioactivity.

will reduce to a quarter

92 U
238
in another 5.7 × 103 Natural radioactivity
years and to one-eighth
692C
14
238
U in another 5.7 × 103 This is the spontaneous disintegration
years, etc. Table 13.2
238C shows some examples
14 or decay of naturally-occurring unstable
692 U
of half-life. 226
Ra nuclides. Two examples are:
238
14
CU
688
92
226
90
238
14
238CRa
Sr
U
U
210
Po → 206
Pb + 42 He
Table 13.2 688
3892
92
84 82

Sr
90
C
14
Ra
226
U
Radioactice isotope Half life
238
38
688

Co
60
92 238
U12→ 123494 Th32 + 42 1He
Uranium-238 Sr
C
90
14
CU
14Ra
226
238
27
38
6 4.5 × 109 tears
92
S + 0 n →15 P +1 H
688
92
16

Carbon -14 Co
60
C
14
27
38
Ra
226
Sr
90
88 5.7 × 103 years
6

Radium-226 P
32
Sr
Co
90
60
Ra
226
1.6 × 103 years
Ra Artificial radioactivity
226
C
14
15
38
2788
688
Strontium-90 P
32
Sr
Co
90
60
SrRa
226
90
15
38 28 years This is an induced disintegration of a
27
3888
Cobalt-60 PI
131
Co
60
32
5.2 years nuclide caused by the bombardment of
Sr
90
Ra
226
53
27
15
3888
Posphorus-32 I
131
Co
P
60
32
Co
60 14 days the stable nucleus of the atom with a
Sr
90
53
27
15
27
Iodine-131
38
PI
32
Bi
214
131
8.1 days high-speed particle. If the particle has
Co
60
15
5383

Bismuth-214
27
Bi
214
P 19.7 minutes sufficiently large energy, it combines with
PI
32
131
32
Co
60
15
53
15
27
83
the stable nucleus to form a larger unstable
Polonium-214 PIBi 1.5 x 104 seconds
Po
214
131
214
3284
5383
15
214
Po
PIIBi
131
214
131
32883
53 4
53
15
214
Bi
IPo 211
131
883
4
53
214
214
13183
883
4
Bi
IPo
Bi
53
214
214
84 Po
Bi
83
nuclide which then disintegrates. For Using protons and alpha particles
example, as bullets in transmutation has a major
disadvantage. Since protons and alpha
32
S + 01 n → 32
P + 11 H
16 15
particles are both positively-charged, they
Recall the agony of the alchemists of the are repelled by the positive nucleus of any
sixteenth and seventeenth centuries in target atom they approach, no matter how
their futile attempt to convert lead to gold. fast they are.
They were the first scientists to attempt the Fortunately, E. Fermi in 1934 discovered
transmutation of elements. that neutron bombardment can be used
In 1919, Rutherford succeeded in for nuclear transmutation. The neutron
disintegrating an atomic nucleus. He is not charged and, therefore, it is not
bombarded nitrogen gas with fast-moving repelled by the positive nucleus. Neutron
alpha particles and discovered that protons was, therefore, successfully used to
were ejected. bombard some elements. For example,
Blackett later showed that a new 1
n + 27 Al → 24
Na + 42 He
0 13 11
element, oxygen-17 isotope was formed in
the process. The sodium-24 produced in the above
transmutation is a radioactive beta-
He ++ 1777N
44 He
N→→ 178 O + 11 H
4 emitter with a half-life of 15 hours. Other
22
examples of transmutations by neutron
Within a few years, Rutherford, Chadwick bombardment are:
and others, accomplished the following
11
nn +
+ 3115 P → SS +
+ 001ee
31 32
15 P →
32
successful transmutations, using alpha- 00 15
15 1

particles as ‘bullet’:
11
nn +
+ 14147N
N→ C+ H
+ 111H
14
→ 14
C
F → Ne 00 7 77 1

Na → Mg Artificial radioactivity, as we have seen,

Al → Si
Crockroft and Walton, working under
Rutherford, developed a machine for
bombarding atoms with protons instead
of alpha particles. They ionised hydrogen
gas to obtain electrons and protons.
The protons were accelerated to a very
high speed by attracting them through
a potential of 300kV. In 1932, both men
successfully bombarded lithium atoms
with protons to obtain helium.
1
1
H + 73 Li → 42 He + 42 He
requires the use of machines. These
machines energise the bullets to a definite
level before they are allowed to strike
the target nucleus. One of such machines
which is of interest to us is the cyclotron.
The cyclotron
This machine was invented by E.O.
Lawrence (1901-1958) of the University of
California. It is made up of an evacuated
cylindrical box placed between two poles of
a huge electromagnet (Fig. 13.9(a)). Inside
the box are located two hollow, D-shaped
metal electrodes know as the dees. The dees
are connected to a source of high voltage
through an oscillator. The bullets, used for

212
 To AC
N pole of electromagnet voltage
source
dee 2 dee 2
dee 1
vacuum filament deflector
chamber dee 1
S pole of electromagnet

target
(a) Cyclotron

Fig. 13.9 (b) Bullets in a cyclotron moving in a spiral course

bombarding nuclei, are injected into the synthesise new elements. In 1940, McMillan
box through its centre. carried out artificial transmutation of
When the cyclotron is at work, the uranium-238 by bombarding it with
oscillator reverses the electric charge on neutrons. He produced uranium-239, a
the dees within seconds. The effects of the radioactive beta-emitter, as shown in the
electromagnetic field and the high-voltage equation:
alternating potential combine to make the
bullets inside move in a spiral course (Fig. 1
0
n + 238
92
U→ 239
92
U
13.9).
As they move near the outside, the The uranium-239
93 Np →
239
disintegrates as shown
94 Pu + −1 e (Pu = plutonium)
239 0

bullets accelerate, gaining more energy in the equations:

until they reach the rim of the box where 239
U → 239
Np + 01 e (Np = neptuium)
92 93
they are deflected towards the target atom.
The energy involved in accelerating a
239
93 Np → 239
94 Pu + 0
−1 e (Pu = plutonium)
particle in a very simple cyclotron is about
15 Mev. This amount of energy is what an By 1955,239 Seaborg and his colleagues
92 U → 93 Np + 1 e (Np = neptuium)
239 0

electron would need to accelerate across synthesised seven additional elements

a potential difference of 1.5 × 107 volts.
Note that 1 Mev (million electron volts) is
equivalent to 9.648 × 107 kJmol-1.
Other machines used in artificial
radioactivity are synchrotrons, betatrons
and cosmotrons. We shall not study these
machines.
The search for new elements
After the development of machines for
artificial radioactivity, scientists began to
with atomic numbers from 95 to 101. The
next four elements with atomic numbers
from 102 to 105 were synthesised by 1975.
Element 103 was named Lawrencium after
E.O. Lawrence who built the first cyclotron.
Element 106 has also been synthesised. Both
American and Soviet scientists are claiming
credit for this feat. No name has been given
to this element yet. Although element 106
is stable enough to enable its momentary
existence be observed, it is too unstable

213
for large amounts of it to accumulate in a From calculations, it was estimated that
nuclear particle accelerator. one gram of natural uranium was capable
More recently, in 1983, West German of producing as much energy as 10 000
scientists synthesised element 109 by grams of coal. The total mass of the fission
bombarding 20983
Bi with 58
26
Fe . products is slightly less than the total mass
of the starting reactants. The difference in
mass corresponds to the energy released. In
Nuclear fission and atomic energy the fissiono of 235
92U, over 40 different pairs
of nuclei may be formed. For example
So far in this chapter, we have been
dealing with nuclear reactions in which
141
56
Ba + 92
36
Kr + 2 01 n ( )
relatively small particles are removed
from a nucleus. In 1939, two German 1
0
n + 235
92
U  236
92
U  90
38
Sr + 143
54 ( )
Xe + 3 01 n
scientists, Hann and Strassman, discovered
that isotopes of intermediate mass were Observe that fission is accompanied
liberated when uranium was bombarded with neutron emission. The fission of
with neutrons. Here, uranium had split uranium-235 can be summarised thus:
into two fragments. This type of splitting 235
U + 01 n → 2 fission fragments + 2 or 3 neutrons
during radioactive decay differs from
92

our earlier examples in which one large You will have observed that for each
fragment was produced. Nuclear fission or neutron used up in the reaction, two or
atomic fission is the term used to describe more new neutrons are formed. Recall that
the disintegration of an atom into two natural uranium possesses two isotopes:
large fragments and it is one of the largest
238
92
U and the much rarer 23592
U. Scientists
sources of energy discovered by man. have discovered that the rarer isotope of
In fission, a heavy nucleus is split mass number 235 is responsible for the
by being bombarded with high-energy enormous release of energy during fission.
neutrons. This is possible because a We have seen that when natural uranium
neutron has no electrical charge. is bombarded by neutrons, the 235 92
U
If the nuclei of heavier elements, such isotopes absorb neutrons and then split
as uranium and plutonium, are split into up violently, releasing two smaller nuclei,
two smaller fragments, the binding energy two or three neutrons and a large quantity
per nucleon is greater in the lighter nuclei. of energy. Plutonium-239 is formed when
Since the products are more stable than uranium-238 is bombarded with neutron.
the reactants, energy is evolved. Nuclear Fission is observed as shown in the
fission is, therefore an, exothermic reaction. following equations:
You will recall that in an exothermic
1 238 239
reaction, the energy content of the system 0n + 92U → 92U + gamma rays....(i)
decreases and, therefore, the energy 239 239 0e
content of products is usually less than that 92U → 92Np + -1
................. (ii)
of the reactants. 239 239 0
93Np → 94Pu + -1e ................. .(iii)

214
Nuclear chain reactions
If the neutrons produced by the initial
fission of uranium attack other uranium
atoms, more neutrons are released which
attack more uranium atoms and so on. In
this way, a large number of fissions will
occur. This is known as a chain reaction. A
chain reaction is self-propagating. This is
what happens in the atomic bomb, where
the reaction results in an explosive release
of energy. Examine Fig. 13.10 carefully.
It demonstrates how a chain reaction
n + 235U
n + 235U
n + 235U
n + 235U n + 235U
n + 235U
n + 235U n + 235U
n + 235U n + 235U
+ energy
n + 235U
n + 235U
n + 235U
+ energy
Fig. 13.10 Highly simplified exploding chain
reaction during uranium fission
can occur during uranium fission. You
will observe that one reaction releases 3
neutrons; 3 neutrons release 9; then 27,
81,243, 729, etc. As long as the chain can be
built up rapidly and completely, there is an
enormous release of energy leading to an
explosion, as in the atomic bomb.
215
Problems associated with nuclear chain
reactions
In a chain reaction, if the neutron moves
too fast, a nucleus cannot be broken. The
neutron will simply pass by the nucleus
and escape. In order to overcome this
problem, two options are available. One
option is to slow down the neutrons after
they have been created and the second
option is to provide enough nuclei to stop
neutrons from escaping.
Neutrons can be slowed down, using
pieces of nuclear fuel (e.g. U-235) which
are placed in a material called a moderator.
The neutrons, after being created by the
fuel, hit the atoms of the moderator. The
neutrons lose speed until they go slowly
enough to break up more nuclei of the fuel.
Graphite and heavy water (D2O) are good
moderators.
A chain reaction can only continue if
each neutron has a good chance of hitting
a fuel nucleus (e.g. U-235). This will only
occur if the sample of the fuel, U-235,
is large enough. If it is too small, the
secondary neutrons will escape from the
sample before they cause further fissions,
and the chain reactions will be broken.
The necessary conditions to bring about
the chain reaction are, therefore, that a
certain amount of fuel, known as the
critical size, is brought together in one place.
Though a small piece of U-235 is quite safe,
a larger piece, within which the secondary
neutrons can cause further fissions before
escaping, may explode. There is, therefore,
a critical size below which U-235 is safe but
above which it may explode (Fig. 13.11(a)
and 13.11(b)).
 generator which produces nuclear energy.
n A nuclear reactor is made up of the
following parts:
n 1 a core which contains the nuclear fuel;
and
n
2 a moderator material.
The nuclear fuel may be U-235 or Pu-239.
The moderator material contains control
n rods made up of materials capable of
absorbing such neutrons as boron and
Fig. 13.11(a) A small piece of U-235
cadmium. The reaction can be started by
partly withdrawing the rods.
n n A mechanism is used to collect the
n nuclear energy that is produced in the core.
n
n This energy appears as heat energy. The
n n
heat generated can boil water and produce
n steam to drive an electrical generator. The
radiations emanating from fission are
n n usually radioactive and very dangerous.
n They gradually accumulate inside the
n reactor. A shield is, therefore, built to
protect people from the radiations.
Fig. 13.11(b) A large piece of U-235

Atomic bomb Radioactive waste

In an atomic bomb, two pieces of pure
uranium-235 or plutonium-239, each below
the critical size, are brought together to
form one piece larger than the critical size.
What follows is the fission of uranium-235
or plutonium-239, and this proceeds in
an uncontrollable manner resulting in a
nuclear explosion.
Nuclear reactors
Scientists have developed a mechanism
for harnessing nuclear chain reactions.
The device is known as a nuclear reactor
in which the controlled fission of the
radioactive material is made to produce
new radioactive substances and energy.
The nuclear reactor can be regarded as a
As nuclear reactors generate energy, they
produce radioactive waste in the form of
spent fuel, waste heat and radioactive efflueats.
Radioactive waste is lethal. Scientists and
members of the Environmental Protection
Agency (EPA) are concerned about dangers
of radioactive waste. They warn that
between its production and final disposal,
radioactive waste must be managed
effectively to avoid accidental releases.
It is the duty of every citizen to see that
our environment is kept safe. Many years
in Nigeria, a foreign country dumped toxic
waste suspected to be radioactive in Koko
Port of Delta State. Nigerians protested and
the waste was evacuated to the country
where it originated.

216
Problems of radioactive waste
We shall study problems of radioactive
waste under the following headings:
1 thermal pollution,
2 radioactive pollution, and
3 management and disposal of radio-
active waste
Thermal pollution
Nuclear reactors and radioactive spent fuel
produce a lot of heat which causes thermal
pollution. The heat from spent fuel results
from activities of the fission products
which include caesium-137, strontium-90
and iodine-129. Water, as a coolant, is used
to remove the waste heat.
Two methods are used to supply cooling
water to the reactor. The first method, called
once-through method, involves circulating
water from a river through the reactor and
back to the river. The second method, the
re-circulating evaporative method, transfers
the heat of the water to the atmosphere by
means of cooling towers. The water is then
recycled into the reactor or discharged into
its source.
Thermal pollution can change the
temperature of our environment and affect
water-based ecosystems.
Radioactive pollution
Nuclear reactors release radioactive
effluents and specks into the environment.
The effluents ionise the atmosphere and
this could bring about a change in the
climatic conditions of a place. Some of the
isotopes released as effluents or specks
include carbon-14, krypton-85, tritium
and plutonium. A speck of plutonium dust
could cause cancer if inhaled or swallowed.
217
Management and disposal of radioactive
waste
Management and removal of radioactive
waste presents a great problem with
more reactors being built in many parts
of the world. Spent fuel, which is a major
radioactive waste, is usually processed
and packaged appropriately for easy
management and disposal.
P re s e n t l y, t w o t r a d i t i o n a l a n d
temporary disposal methods are used:
1 shallow land burial; and
2 storage in waste-filled pools inside
sealed buildings.
These methods are inadequate and unsafe
because the container in which the waste
is buried underground often cracks due
to radioactive heat. When the container
cracks, the waste materials leak into the
ground and contaminate drinking water in
wells located up to half a kilometre away
from the disposal site. Also radioactive
waste materials may be released from the
soil into the atmosphere.
Permanent disposal of radioactive waste
Experts in radioactive waste disposal
have suggested the following permanent
methods of waste disposal:
Seabed and ocean disposal
This involves:
1 deep ocean dumping of the waste;
2 seabed disposal on stable ocean floor;
and
3 ocean trench disposal.
Geological formation disposal on land
This involves:
1 burial in deep geological formations;
2 liquid injection into hydro-fractured
rocks; and
3 disposal in deep holes.
Nuclear fusion
This is another way of obtaining energy
from the nuclei of atoms. Instead of
breaking down the unstable nuclei of
heavy atoms, we can also obtain energy by
joining together two or more light nuclei to
obtain a new and heavier nucleus. In the
process, an enormous amount of energy
is released.
In fusion, a nucleus is built up by
making two fast-moving smaller nuclei hit
each other and fuse. This cannot happen
unless the electrons are removed from the
atoms to expose the nuclei. Once this is
done, the nuclei are then brought together
to interact. Nuclear fusion reaction can only
take place at very high temperatures of at
least 15 million degrees. This is because
very large energies have to be given to the
positively-charged nuclei to overcome the
strong repulsion between them. The high
temperature required is obtained by the
explosion of a fission (atomic) bomb.
In hydrogen fusion, uranium-235 or
plutonium-239 fission bomb is used to
generate the high temperature needed to
start the reaction.
Hydrogen has three isotopes:
1 ordinary hydrogen as found in water;
2 heavy hydrogen, deuterium, 21 H
(which can be obtained in nature, e.g.
from seawater); and
3 tritium, 31 H (made from lithium metal
by a nuclear process).
When a mixture of two heavy isotopes
218
of hydrogen, deuterium (D) and tritium
(T), is exposed to heat generated from
uranium or plutonium bomb, an explosion
combination occurs as follows:
2
D + 31T → 42 He + 01 n + energy
1
The reaction takes place with a mass
loss of 0.0182 atomic mass unit (amu) and
an enormous amount of energy is released
(1 amu = 8.982 x 10–10 kJmol–1). Once the
process has begun, it produces enough
energy to sustain itself, while producing
heat energy.
Using Einstein’s mass-energy
conservation equation, we can calculate
the amount of energy equivalent to 0.0182
amu.
E = mc2 [where E = Energy (j)]
m = mass (kg) and c = speed of light,
(m/s)]
Therefore, E = 0.0182 × 1.6 × 1027 ×
(3 × 108)2J
= 0.0182 × 1.6 × 10-27 × 9 × 1016 J
= 2.6208 × 10-10 J
= 2.621 × 10-10 J
deuterium
nucleus neutron
tritium
nucleus helium nucleus
Fig. 13.12 A nuclear fusion reaction
This type of reaction is the basis of the
hydrogen bomb, which is the most lethal
weapon invented by man. The difficulties
of controlling fusion to generate usable
power have not yet been overcome.
Presently, scientists are investigating
the possibility of using the combination of
heavy hydrogen, 21 H nuclei to provide a
controlled source of energy. If this venture
succeeds, a vast source of very cheap
energy will be available for many millions
of years and this will enhance the well-
being of mankind.
Peaceful uses of radioactivity
Radioactivity is now being put into a
number of peaceful uses. We shall discuss
a few of these uses.
As source of heat energy
Controlled nuclear fission is used to
generate electricity and heat energy.
60
27
In medicine
1 The DNA structure of the genes of
animals and plants can be changed
by radiation to produce desirable
qualities in the animals or plants.
2 Cancerous cells are susceptible
to destruction by radiation. For
example, the gamma rays of Co,
an ionising radiation which destroys
cancerous tissues, are used in the
treatment of cancer.
3 ( )
Radioactive iodine-131 131
53
I is used
to treat thyroid disease.
In chemistry and biochemistry
In biochemistry, tracers are used for
studying metabolic pathways. Radio-
isotopes can be used as tracers to monitor
the uptake and metabolism of various
elements by animals and plants. For
example, the uptake of phosphate(V) and
the metabolism of phosphorus by plants
can be studied, using a fertiliser containing
phosphorus 32, (1532 P) . Also radioactive
219
tracer studies, using carbon 14, 146 C , have
helped in the elucidation of complex
processes of photosynthesis and protein
synthesis.
In chemistry, radio-isotopes provide the
means for studying a variety of reactions,
such as chemical equilibrium, reaction
kinetics and mechanisms, solubility and
structure determination. This application
depends on the fact that a radioactive
element which has been added to the same
stable element will remain in a definite
ratio irrespective of the state in which the
element may be.
In industry
1 Luminescent signs and atomic
batteries are produced, taking
advantage of the ionising effects of
alpha particles.
2 Beta-rays and gamma-rays sources,
with a long half-life, can be used
to control the thickness of paper
or plastic sheets. Recall that the
radiation passing through a material
decreases as the material gets thicker.
Hence, the amount of penetrating
beta or gamma radiation can be used
to estimate the thickness of various
materials-such as paper, metal or
plastic.
Using radiation for measuring
the thickness of materials has an
obvious advantage as the possibility
of touching, marking or tearing the
material concerned is eliminated.
Radiation- thickness gauges can also
be used to control the thickness of
the sheets emerging from high-speed
rolling mills. Beta-rays can be used
for material thickness up to about
 0.2 cm of steel while gamma-rays can
be used with steel up to 10 cm thick.
In geology and archaeology
From radioactive dating, the age of the
earth been estimated to be about 4.5 × 109
years . The half-life of uranium-238 238 (
92
U )
is 4.5 × 10 as well. The decay of U-238
9
suggests the possibility of dating rocks and
minerals. If we assume that the mineral
originally contained uranium, then the
present ratio of uranium-238 to lead-206
in the mineral can be used to calculate the
time when the mineral was formed. This
process is called radiodating.
Carbon dating
Carbon-14, ( 146 - C), a radio-isotope of
carbon-12 is being constantly formed from
nitrogen in the upper atmosphere. The
reaction can be expressed as:
14
7
N + 61 n → 146 C + 11 H
As a result of this transmutation, carbonoxide
is formed from both carbon isotopes i.e.,
carbon -12, ( 126 C), and carbon-14 ( 146 C).
This carbon dioxide is absorbed in plants
during photosynthesis. When the plant
dies, no more carbon(IV) oxide is absorbed
and decaying of radioactive carbon-14,
( )
14
6
C , starts. By comparing the relative
composition of carbon-14 in the remains
of the decaying plant with the composition
in a similar living plant, the age of the
decaying plant could be calculated.
The half-life of carbon-14 ( 146 C) is 5.7 ×
103 years. By determining the amount of
radioactive carbon remaining in an object,
scientists are able to calculate the age of
an object. This method of determining
age is known as carbon dating. It is by
carbon dating that scientists are able to
220
determine the age of objects excavated by
archaeologists.
In agriculture
The control or eradication of insect pests in
agriculture is fundamental to the success
of any agricultural enterprise. Fortunately,
radiation has been successfully employed
in controlling the spread of some insects
that are pests to crops or animals. One of
the methods is to breed the harmful insects
and sterilise them with radiation when
they reach adulthood. Large numbers of
the sterilised insects are then released in
the infested area and allowed to mate with
the normal insects. This mating leads to the
production of a high percentage of sterile
eggs, thus controlling the next generation
of the harmful insects. Also harmful or
destructive insects like the locust can be
labelled in order to trace their life cycles,
gain a better insight into their migration
pattern as well as know their natural
predators. The natural predators can then
be used as biological control agents.
In animal nutrition, tracers have been
successfully used to determine the most
economic feed that produces the best
nutritious meat. They have also been used
to test the effect of growth-stimulating
hormones given to cattle. The tracer
technique makes it possible to examine
the meat processed from such cattle to
ensure that the drug does not appear as a
contaminant.
Radioactivity and biological systems
Mankind and other biological systems
have always been exposed to one form
of radiation or the other. The natural
radiation under which we live is usually
referred to as background radiation. This
background radiation comes from:
1 outer space, that is, cosmic radiation
and
2 radioactivity of some radioactive,
nuclides with long half-life.
The other type of radiation to which
we are exposed is the radiation due to
radioactivity. Both the natural radiation
and the radiation due to radioactivity
are absorbed by the tissues of biological
systems. The amount of natural radiation
which is absorbed by the tissue is measured
in rad units. One rad is defined as the amount
of radiation which deposits 1.0 x 10-7J of energy
per gram of tissue. A different unit, the rem,
is used for radiations due to radioactivity.
One rem is the equivalent dose of ionising
radiation which gives the same biological effect
as the quantity of X-ray or gamma radiation
that liberates by ionisation 8.38 x 10-3 joules
of energy per kilogram of dry air at S.T.P. The
rem is used to set radiation protection
standards. A rad of alpha-particle is
equivalent to 20 rem.
Effects of radioactivity on biological
systems
Excessive exposure to radiation has
dangerous health implications, such
as susceptibility to genetic diseases,
leukemia and other forms of cancerous
diseases. When absorbed into the skin,
radioactive radiations penetrate the tissue,
destroying cells and making some cells
cancerous. Therefore, people who work
with radiations must strictly observe all
safety precautions. The safety limits for
radiation doses are usually defined.
It has been established that if a dose
of 500 rems of radiation is received by
a population sample in a few hours,
about 50 per cent of those exposed can be
expected to die as a direct consequence of
the exposure. However, this dose is 100
times the maximum annual safety limit
established for people who work with
radiation. This same amount is about 3,000
times the annual background exposure.
Currently, the determination of the maximum
safe exposure to radiation is the subject of
extensive research.
Comparing physical, chemical and
nuclear reactions
Table 13.3 compares the changes during
physical, chemical and nuclear reactions
while Table 13.4 compares the heat evolved
during such reactions.

Table 13.3

Physical change Chemical change Nuclear change

No new substance is New substances are Elements are converted

formed formed; valence electrons to different elements by
take part in these nuclear fission or fusion.
reactions. The nucleus
remains unchanged.

221
Table 13.4
Activity Type of change
1 Condensation of Physical
steam at 373 K
2 Burning of carbon Chemical
(graphite)
3 Fission of uranium - Nuclear (Fission)
235
4 Combination of Nuclear (Fusion)
hydrogen nuclei
Summary
This chapter has taught the foowing:
• Radioactivity is defined as the
spontaneous breakdown of unstable
atomic nucleus with the release of
ionising particles. The isotopes which
decay in this way are said to be
radioactive.
• The emission coming from radioactive
elements are made up of alpha-particles,
beta-particles and gamma-rays.
• Gamma-radiation is the most penetrating
of the three forms of radiation. It
can penetrate thick metal sheets
and is responsible for much of the
damage caused by the disintegration of
radioactive substance.
• The half-life period of a radioactive
isotope is the time it takes for one-half
of the atoms in a given sample to decay.
This rate is fixed for each kind of radio-
isotope. Nothing can change this rate.
The half-life period is used as a measure
of relative stability of radio-isotopes.
222
Amount of heat produced
in joules per gram of
substance
2.268 × 103 joules
3.289 × 104 joules
8.4 × 1010 joules
6.3 × 1011 joules
• Nuclear fission is the disintegration of
an isotope into two large fragments. It
is accompanied by enormous release
of heat energy and neutron emission.
• Nuclear fusion is the combination
of the nuclei of lighter elements, e.g.
hydrogen, to form a heavier nuclei.
This takes place at temperatures of
several millions of degrees. A vast
amount of energy is released. The
energy-releasing reaction in the sun is
an example of nuclear fusion.
• In chemical reaction, only electrons
on the outermost orbitals of the atoms
are involved. In nuclear reactions,
protons and neutrons in the nucleus
are involved.
Review questions
A Multiple-choice questions
1 The nuclear process responsible for
limiting the build-up of heavy elements
in both stars and the laboratory is
A positron decay.
 238 234
B gamma decay. A 92 U 90 Th + 2 He
4
→
C electron capture. 239 239 0
D nuclear fission. B 93 Np → 94 Pu + -1 e

2 An important medical use for radiation 137

C 56Ba → Ba + γ
is
14
A activation analysis. D 7N + He → O +
1
1 H
B nuclear power.
8 Which of the following equations
C radiotherapy.
D all of the above. represents alpha decay?
3 The nuclide 252 Cf has 252 106 252
+ 4( 0n
1
98
A 98 Cf → 42Mc + 98 Ba
A 98 nucleons.
B 154 electrons. B 252
U → 106
Th + 42 He
98 42
C 154 neutrons.
D 252 protons. C 239
93 Np → 239
94 Pu + 10e
4 A certain radioactive nuclide has a
D 56 Bo → 94 Ba + X
137 137

half-life of 100 minutes. If a sample

9 Which of the following equations
containing 1 600 atoms is allowed to
represents gamma decay?
decay for 300 minutes, how many
atoms of the radioactive nuclide will A
238
92 U → 234
90 Th + 42 He
remain? 239
Np → 239
Pu + 10e
A 100 atoms B 93 94

B 200 atoms 137m

Ba → 137
Ba + X
C 400 atoms C 56 56

D 800 atoms 4
He + 74 He →17
08 O + 1 H
1
D 2
5 The two most abundant elements in our
10 I n the nuclear reaction,
solar system are 4
He + He → O + X,
4 17

A hydrogen and nitrogen. 2 7 08

the letter X represents

B hydrogen and oxygen. 3
C oxygen and helium. A 2 He1
3
D hydrogen and helium. B 1H1
2
6 Which of the following equations C 2 H1
represents spontaneous fission? 1
D 1H1
252 106 142
A 98 Cf → 42 Mo + 56 Ba +
B Short structured questions
238 252
B 92 U → 98 Th + 42 He 1 a) What are the relative masses
239 239 0 and charges of alpha- and beta-
C 93U → 94 Th + -1 e particles?
14
D 7 N + 2 He → 8 O +1 H
4 17 1 b) What is the nature of gamma-
7 Which of the following equations radiation?
represents Beta decay? c) What evidence can you provide
to support your statements

223
 concerning the nature of alpha,
beta and gamma-radiations?
2 a) How do the atomic number and the
mass number of an isotope change
when its nucleus loses
i) an alpha-particle?
ii) a beta-particle?
iii) gamma-rays?
iv) a neutron?
b) 23290Th emits a total of six alpha-
particles and four beta-particles in
its natural decay sequence. What is
the atomic number, mass number
and symbol of the final product?
c) Wr i t e n u c l e a r e q u a t i o n s t o
summarise the following changes:
i) When a 73 Li nucleus absorbs a
colliding proton, the product
disintegrates into two exactly
similar fragments.
ii) 323
90
Th atom undergoes alpha-
decay to form radium atoms.
3 Rewrite the following nuclear equations,
substituting symbols and numbers for
the question marks.
a) 14? ?+ ?? He → ?? + 11 ?
b) ?? H + 56? Fe → 57? Co + 01 ?
4 a) How is carbon-14 produced in
nature?
b) Write an equation for the beta-
decay of 146 C .
224
c) How is 146 C used in ‘dating’
archaeological remains?
5 Write balanced equations for the
following reactions:
a) The alpha decay of 235 U.
92
b) The beta decay of 92 U .
239
c) The fusion of four 11 H nuclei to
form 42 He .
C Essay-type questions
1 Explain what is meant by radioactivity
with reference to:
a) Natural radioactivity and
b) artificial radioactivity.
Give examples.
2 a) Define the half-life of a radioactive
isotope
b) What are the properties of the half-
life period?
c) What are the uses of the half-life?
3 Briefly explain nuclear fission
and fusion. How is each applied?
Have fission and fusion any useful
applications? If so, outline them.
4 a) The discovery of radioactivity is a
curse to man. Discuss.
b) The discovery of radioactivity is a
mixed blessing. Discuss.
5 Outline the importance or uses of two
of the following isotopes: 27 60
Co , 32
15
P,
239
94
Pu .
 14 Projects
Introduction
Our projects shall come under two main
subheadings:
1 literature projects
2 experimental projects
Literature projects include the study of the
biographies of past chemists who have
made major contributions to the study of
chemistry. Also, under Literature projects,
we shall study those historical topics which
have helped to create awareness for the
place of chemistry in relation to other
subjects. Experimental projects will include
fresh investigations and applied chemistry,
such as the quantitative and qualitative
analyses of mineral ores and heavy metals
present in the environment.
Most of the projects linked to certain
topics have already been treated in this
book. The fact that these projects have been
specifically recommended does not in any
way exclude the inclusion of any other
projects which may be identified by your
teacher, or by you, in consultation with
your teacher.
Literature projects
Finding out about the biographies and the
work of chemists in the past would help
you to appreciate the methods of science.
225
Hopefully, you will come to realise that the
thinking of scientists is usually affected by
the personalities involved, the environment
and the prevailing intellectual and social
climate in which major discoveries were
made.
For some of you, you may indeed
be able to put yourselves into the minds
of these great people of the past and, in
consequence, come to realise that what you
see may be very much influenced by what
you ‘know’ and ‘feel’.
Organisation of biographies
Biographies can be organised along the
following sub-headings:
Family background
When and where was the chemist born?
Who were the parents? What type of
education did the chemist receive? Can you
place the family into any particular social
class? Did the chemist have any nuclear
family?
Political background of native country
What was the political scene in the chemist’s
native country at the time of birth and
during the chemist’s lifetime?
Working life
Name the institutions where the chemist
did some teaching and research. Preferably,
give dates and some major achievements
in such institutions.
Interaction with other famous scientists
What famous scientists made an impact
on the chemist’s work? Were there some
parallel or similar scientific activities going
on during the life of the chemist?
Conclusion
Outline the lessons to be learnt from
the life and work of the chemist. Do the
achievements of the chemist still hold
sway or have there been new and more
acceptable developments?
Biography of Marie Curie
Marie Curie was born Manya Sklodowska
in Warsaw, Poland in 1867. Her father was
a teacher of science but the laboratory
in which he worked was very poorly
equipped. The college authorities did not
give much thought to science. Marie’s
father had actually to pay for a good deal
of the apparatus and equipment from his
own pocket. This left him so badly off that
he could not afford an assistant. The help
given him by his little girl, Marie, who
insisted on coming in and washing up the
test tubes and tidying up the laboratory
soon resulted in her taking a keen interest
in her father’s work. Even after school
during the day, she always came to the
laboratory in the evenings to help.
At that time, the social and political
climate in Warsaw was one of agitation
against the Russian colonial masters.
There began a movement for Polish
independence. Marie was one of the rebels,
but the movement failed and she was
forced to flee from her home to Paris. She
was only twenty-two, she had no relatives,
226
no friends, no money and only her brains
and industry to help stave off starvation.
She rented accommodation in a poor area,
lived on bread and milk and barely made
a living by giving lessons.
After sometime, she obtained work at
the Sorbonne. It was merely a matter of
washing bottles and preparing furnaces for
chemical experiments. But she did work so
diligently and gave evidence of so much
knowledge that she attracted the notice
of her head of department, one Gabriel
Lippman. The man found out who she
was, and wrote to her father about her. To
her great joy, Marie subsequently became
a student under the gentleman and clever
Pierre Curie. She later in 1895 became
married to Pierre at the age of twenty-eight.
Pierre was thirty-six.
In 1898, Madame Curie, using the
ionisation method, isolated the radioactive
element radium. She suggested that the
radioactivity of radium was due to the
disintegration of its atoms. She identified
two types of radiation. These were called
α-radiation and β-radiation. In 1900, her
husband, Pierre, discovered a third type
of radiation. This was called γ-radiation.
In 1903, she shared the Nobel Prize for
Physics with her husband, Pierre. In 1911,
she received the Nobel Prize in Chemistry
for the isolation of radium. Thus, Marie
remains one of the very individuals ever
to be honoured with two Nobel Prizes.
It must have been to her marvellous
satisfaction that her daughter, Irene Joliot-
Curie, followed in her footsteps, making
one discovery after another which would
render the name Curie imperishable even
if her mother had never been famous.
Madame Curie died from leukemia in
1934 . Her death was undoubtedly caused
by prolonged exposure to radiation. What
can be gleaned from the brief historical
sketch of Madame Curie’s life is that
she worked very hard and possessed an
indomitable spirit.
Brief biography projects
Your teacher will assist you to do some
biography projects on the following:
1 J. J. Thompson
2 Ernest Rutherford
3 Stradonitz Kekule
4 John Dalton
5 Amadeo Avogadro
6 Fritz Haber
Chance discoveries in chemistry
How hard must a present day research
chemist work, particularly in organic
chemistry? Kekule who discovered the
structure of benzene ring (1866) dreamt
about a fish biting its tail and so intuitively
grasped the structure of benzene. The idea
first came to him in a dream. Kekule’s
discovery may, therefore, be said to be by
chance.
Many other discoveries, for example,
vulcanisation of rubber, were by chance.
The Perkin synthesis (by Sir W. H. Perkin)
of the dye aniline mauve in 1856 was also
a chance discovery. At the time, Sir Perkin
was studying phenylamine (also known
as aniline). This was a local derivative.
Hitherto, dyes were extracted from plant
and animal sources.
Dreams do not appear to work
nowadays. Can we, therefore, say that the
era of chance discovery is over? It took
Federick Sanger, born in 1918, almost his
entire working life to unravel the structure
of insulin. The elucidation of the structure
227
of DNA by Francis Crick, James Watson,
Maurice Wilkins and others could not have
been possible without developments
in computer science in 1954. The three
workers mentioned were awarded the
Nobel Prize for Physiology and Medicine in
1962.
The discovery of radioactivity by Henri
Becquerel raised the question of accidental
but delightful discoveries in science.
When a valuable thing is found when the
discoverer is not really looking for it, such
discovery is called serendipity. In science,
therefore, we talk of serendipity and we
talk also of lucky accidents. Are people still
lucky these days?
Scientists argue that for lucky accidents
to occur, the discoverer must be well-
trained and intellectually very alert.
Henri Becquerel possessed the scientific
background to appreciate his observations.
Science historians in fact tell us that the
soap we know of today was discovered
accidentally when tallow fell off a cooking
pot into the hot ashes of the fire. But then
the discoverer must have played with the
reacted product to discover that it had
some cleansing properties.
Literature projects on chance discoveries
Although the encyclopaedia of science and
technology would be useful, your teacher
will also assist you with the following
literature projects on chance discoveries:
1 Kekule and the structure of benzene
2 Sir William Perkin and the synthesis
of the dye mauveine (mauve)
3 Plunkett and the discovery of the
synthetic polymer
4 Teflon in the laboratories of Dupont
5 Karl Ziegler and the ‘Nickel Effect’ in
the polymerisation of ethene in 1953,
 to give but-l-ene
6 William Hume Carothers and the
discovery of the vulcanisation of
rubber
7 William Hume Carothers and Arnold
Collins and the discovery of neoprene
rubber in the laboratories of E. I.
DuPont
Man and his environment
An awareness of the impact of chemistry on
our environment should help us develop
a point of view about the transformation
or interchangeability of materials, and
the problems of waste products and their
disposal (and pollution) which result from
such transformations.
Chemists have developed three classes
of compounds called pesticides (fungicide,
herbicide and insecticide) which can kill
or control the living organisms which
compete with man for food. Little did they
know that, in solving one problem, other
more serious problems could crop up. Some
pesticides like DDT are not easily detoxified,
remaining for up to fifteen years in the soil.
DDT and other persistent pesticides had to
be banned and taken off the market. In their
search for other active compounds, many
polychlorinated biphenyls (PCBs) were
produced. Very soon, it was suspected that
PCBs could be carcinogenic (i.e., they can
cause cancer) and their production had to
be strictly controlled.
Other kinds of insecticide, such as
organic phosphorus insecticide are not as
persistent as DDT. Many of them though
are quite toxic and took a toll on human
lives in the early stages. Parathion, for
example, has caused more deaths than
any other pesticide. In 1937, Shroeder, a
228
German, while carrying out research on
organophosphorus insecticide in Germany,
discovered the nerve gas. The first of these
was called tabun. Every accidental flash,
involving up to 0.2 mg of tabun on the skin
of workers killed the workers.
In the ‘recent̓̓ war between Iran and
Iraq, there were echoes of the use of nerve
gas on Iranians and Kurdish people by the
Iraqis. The Libyans have also been accused
of using nerve gas on Chadian soldiers
during their contentious war over the
Aouzou strip. Thus, like the atomic bomb,
the hydrogen and neutron bombs, chemists
have come up with discoveries that pose
real problems which threaten the existence
of man.
Nuclear hazards and disasters
Arguments against the use of nuclear
energy focus on four main areas:
1 the risk of an accident;
2 the disposal of waste;
3 alternative sources of energy, and
4 unscrupulous attacks by terrorists.
We shall examine three of these
arguments.
Nuclear disaster: Risk of an accident
The worst ever nuclear accident occurred
in Chernobyl, Ukraine, on 26 April 1986. A
series of human errors resulted in the build-
up of a head of steam in the nuclear reactor.
The steam reacted with hot zirconium
in the reactor to produce hydrogen. The
gas pressure inside the core became so
much that the top of the core blew off. On
coming into contact with air, the gaseous
mixture exploded, causing a fire which
crippled a unit of the Chernobyl nuclear
power plant resulting in the release of a
cloud of radioactive material into the air.
The radioactive cloud was estimated to
be 48.3 kilometres (30 miles) across and
161 kilometres (100 miles) long. The cloud
spread across much of Europe, causing
widespread contamination and alarm.
Some experts estimate that between 1 000
and 10 000 people will die from cancer
over the next decade as a result of being
irradiated by the accident.
The worst ever nuclear accident
in the western hemisphere occurred
in a pressurised-water reactor (PWR) in
Pennsylvania, USA on 28 March 1979. A
series of equipment failures and human
mistakes led to a loss of the coolant
and partial meltdown of the core which
contains radioactive material. A series of
protective barriers prevented a serious
release of radioactive particles and no one
was killed as a result of the accident.
Disposal of waste
Other dimensions to nuclear hazards
include problems of storage and disposal
of highly radioactive waste, some of which
need hundreds, if not thousands of years
before becoming inactive. You may or may
not be aware of the dumping of some waste
materials at Koko in Delta State of Nigeria
many years ago. This toxic waste was
alleged to have been shipped into Nigeria
from Italy. Some of us were witnesses to
the tremendous uproar, and consternation
brought about by this irresponsible act.
At present, we have no experience of
containing radioactive materials for such
long periods. It is claimed that even low-
level waste can result in the build-up of
unacceptably high levels of radioactivity
in the local environment or at sites of
radioactive waste dump.
229
Alternative sources of energy
Those who argue against the use of nuclear
energy point to the availability and lower
risks of other sources of energy. Alternative
sources like coal are less hazardous,
economic and sufficient to provide energy
for hundreds of years.
From what we have discussed so far,
it can seen that a balanced view of the
activities of chemists can only be acquired
through a historical review, plus an
awareness of the social import of chemistry,
including some ‘acquaintance’ or ‘contact’
with past and present-day practising
chemists.
Experimental projects
We shall now turn our attention to some
experimental projects. Experimental projects
very often incorporate some literature
project, especially where information is
necessary before experimentation can
commence. Our project is on the rocks and
minerals of Nigeria.
Rocks and minerals of Nigeria
Before we go on to the project proper, we
need to define the terms rock, mineral and
ore.
Rock
A rock is an aggregate of particles composed
of one or more minerals. Rock form, the
major part of the earth’s crust. There are
different types of rock, such as igneous,
metamorphic and sedimentary.
Mineral
A mineral is any of various naturally-
occurring substances of more or less
homogeneous composition, obtained
from the earth for man’s use. Examples of
minerals include ores, petroleum, sand, clay,
natural gas and coal.
Ore
An ore is a naturally-occurring metallic
compound from which the metal can be
extracted.
Geographical distribution of rocks and
minerals in Nigeria
Granite
This is an igneous, intrusive and crystalline
rock. Road construction has exposed
granite in many parts of Oyo, Ondo,
Kwara, Niger, Kaduna and Plateau states
of Nigeria.
Basalt
This is as extrusive igneous rock with small
crystals, now exposed north of River Benue
and the Biu Plateau of Yobe State.
Limestone
This is a sedimentary rock found all over
Nigeria from Sokoto to Calabar and from
Shagamu to Ashaka. All cement factories
depend on limestone as a major raw
material.
Coal
This is a sedimentary rock found mainly in
Enugu and Benue States of Nigeria.
Marble
This is a metamorphic rock found in
Igbetti, Okpela, and Abakaliki.
Haematite
This is a mineral found as hexagonal
crystals. It is the most important ore of
iron. Iron ore deposits are located at Itape.
230
Galena
This is a mineral which occurs as cubic
crystals in some parts of Abia and Enugu
States of Nigeria.
Stibnite
This is a mineral found as orthorhombic
crystals in parts of Abia State of Nigeria.
It is the chief ore of antimony.
Smithsonite
This is a mineral found as hexagonal
crystals in parts of Enugu State.
Dolomite
This is a mineral found in massive
deposits all over Nigeria. Dolomite exists
as hexagonal crystals, closely associated
with limestone.
Cassiterite
This is a mineral which occurs as tetragonal
crystals. It is the chief ore of tin. It is
frequently called tin-stone and occurs
mainly in Jos, Nigeria.
Collection of rocks and minerals
It is important that, as students, you should
become familiar with as many rock types
and minerals as are commonly found in
Nigeria. This involves your ability to apply
a series of observations and tests. The first
observation each you should automatically
make is to note mentally the appearance of
a specimen.
Procedure
This is a project for the whole class. It will
span the holiday period, to enable you to
collect samples from far and near.
You are to collect any specimen that is
of interest to you. It is up to your teacher to
decide whether the specimen is important.
Schools near established universities
are encouraged to take a field trip to the
Geology Department before you go on
holidays. There, you will see rock and
mineral collections. You will also be able
to see colour photographs of specimens of
rock and minerals which are not native to
Nigeria.

Brief literature projects

Write an account of the following:
1 Tin mining and refining in Nigeria
2 Coal mining and utilisation in Nigeria
3 Iron and steel industry in Nigeria
Your account should focus, among other
things, on:
1 short history of development;
2 problems facing the industry ;
3 contribution to the economic and social
well being of the country; and
4 future prospects and recom-
mendations.

Characterisation of particular rocks and

minerals
After you might have brought back your
collection of specimens to the school, your
teacher will select one or two specimens for
chemical study. The specimen should be of
a simple nature, containing captions which
fall within the scope of qualitative analysis
within your competence at this level.

231
 Test paper I

Section A oxygen and the mixture exploded,

Multiple-choice questions
1 Which of the following methods
would you use to obtain litmus from
litmus indicator solution?
A Filtration
B Distillation
C Chromatography
D Fractional distillation
2 Assume that air contains the
following gases with the boiling
points as indicated:
Gas Boiling point (K)
W 87
x 90
Y 80
Z 77
If a sample of this air is liquefied
and then fractionally distilled by
carefully raising the temperature of
the liquid, the gas that will distil first
is
A W.
B X.
C Y.
D Z.
3 If an eudiometre tube was filled with
26 cm3 of hydrogen and 24 cm3 of
there would remain unchanged
A 2 cm3 hydrogen.
B 11 cm3 oxygen.
C 14 cm3 hydrogen.
D 12 cm3 oxygen.
4 When a colourless gas is dissolved
by water and the resulting solution
turns red litmus paper blue, the gas
is
A HCl.
B H2S.
C NH3.
D SO2.
5 If a container is filled with hydrogen
and another container of the same
size is filled with carbon(IV) oxide,
both containers will, under STP,
contain the same
A mass of gas.
B number of neutrons.
C number of atoms.
D number of molecules.
6 A compound which has a high heat
of formation is normally
A easy to form from its elements
and easy to decompose.
B easy to form from its elements
and difficult to decompose.
C difficult to form from its
elements and difficult to
decompose.

232
 D difficult to form from its
elements and easy to
decompose
7 Real gases will approach the
behaviour of an ideal gas at
A low temperatures and high
pressure.
B high temperatures and low
pressure.
C low temperatures and low
pressure.
D high temperatures and high
pressure.
8 In the reaction given in an unbalanced
form below, KClO3 + C12H22O11→ KCl
+ CO2 + H2O the number of moles of
KClO3 needed to react with one mole
of C12H22O11 is
A 2
B 4
C 6
D 8
9 To which of the following can the
relatively great stability of the HCl
molecule be attributed?
A Ability of chlorine to support
combustion
B Ability of hydrogen gas to burn
C Unequal sharing of the electron
pair
D Non-ionic type of bonding
10 The mole fraction of nitrogen in a
mixture containing 70 g of nitrogen,
128 g of oxygen and 44 g of carbon(IV)
oxide is (N = 14; O = 16; C=12)
A 0.29.
B 0.33.
C 0.36.
D 0.50.
11 The oxidation number of uranium in
the formula UO2(NO3)2 is
A +2.
233
B -2.
C +4.
D +6.
12 Sulphur is soluble in ethanol but not
in water while sodium chloride is
soluble in water but not in ethanol.
One way of separating sodium
chloride from a mixture of sulphur
and sodium chloride is
A by sublimation.
B by chromatography.
C by adding water, filtering and
evaporating the filtrate.
D by adding water and distilling.
Instruction for Questions 13-15
For each multiple-choice question, one or
more of the responses given is/are correct.
Decide which of the responses is/are
correct. Then choose
A if only 1, 2 and 3 are correct.
B if only 1 and 3 are correct.
C if only 2 and 4 are correct.
D if only 4 is correct.
13 Hydrogen is oxidised when it reacts
with
1 oxygen to give water.
2 nitrogen to give ammonia.
3 chlorine to give hydrogen
chloride.
4 sodium to give sodium hydrite.
14 Chlorine displaces oxygen from
heated calcium oxide. In this reaction,
1 the solid product is calcium
chloride.
2 calcium ions are reduced.
3 oxide ions are oxidised.
4 each gram-molecule of chloride
displaces one gram-molecule
of oxygen.
15 Which of the following conversions
are reductions?
 1 CrO42- → Cr2O72- B Cu2+ is reduced to Cu
2 CrO42 → Cr3+ C The oxidation number of
3 CrO42 → CrO3 copper does not change.
4 CrO 2–
4 → Cr2O3 D The oxidation number of
16 How many grams of silver are magnesium increases from 0
displaced from aqueous silver to + 2.
trioxonitrate(V) by 4 g of magnesium? 21 Na2S is a salt of
(Mg = 24; Ag = 108) A a weak acid and a weak base.
A 12 B a strong acid and a strong base.
B 18 C a strong acid and a weak base.
C 27 D a weak acid and a strong base.
D 36 22 What will be the effect of using finely
17 A piece of magnesium ribbon was divided platinum as a catalyst in the
heated to red-hot in nitrogen, then, reaction below?
after cooling, a little water was 2SO2 + O2 → 2SO3 (DH is negative)
added. The gas evolved was A The position of equilibrium
A ammonia. shifts to the left.
B excess nitrogen. B An increase in the yield
C oxygen. of sulphur(VI) oxide at
D nitrogen(IV)oxide. equilibrium.
18 When a current of 0.156 ampere is C An increase in the rate of
passed through a solution of lead(II) attainment of equilibrium
trioxonitrate(V) for a certain period but the yield of sulphur(VI)
of time, 1.0 g of lead is deposited at oxide at equilibrium remains
the cathode. The current was passed unaffected.
for D An increase in the rate of
A 60 minutes. attainment of equilibrium
B 80 minutes. as well as an increase in the
C 100 minutes. yield of sulphur(VI) oxide at
D 120 minutes. equilibrium.
19 5.6 g of a pure alkene, having 23 Increasing the pressure on the
one double bond in the molecule, reaction,
decolourised 16.0 g bromine. The N2 + 3H2  2NH3(DH) is negative)
formula of the alkene is will
A C2H4. A only increase the yield of
B C3H6. ammonia at equilibrium.
C C4H8. B only increase the rate of the
D C5H10. reaction.
20 Which of the following statements is C decrease the yield of ammonia
not true for the reaction given below? at equilibrium but increase
Mg + Cu2+ → Mg2+ + Cu the rate of attainment of
A Mg is oxidised to Mg2 + equilibrium.

234
 D increase the yield of ammonia
at equilibrium and also
increase the rate of attainment
at equilibrium.
24 One mole of propane is mixed with
five moles of oxygen. The mixture
was then ignited and the propane
was completely burnt. The volume
of the products at s.t.p. is
(G.M.V. = 22.4 dm3mol-1)
A 44.8 dm3.
B 56.0 dm3.
C 67.2 dm3.
D 112.0 dm3.
25 Which of the following physical
properties decreases across the
Periodic Table?
A Atomic radius
B Electronegativity
C Electron affinity
D Ionisation potential
26 One mole of an alkane required
8 moles of oxygen for complete
combustion. The molecular formula
of the alkane is
A C3H8.
B. C4H10.
C C5H12.
D C6Hl4.
27 One of the temperatures, A-D, is the
true boiling point of 2-methylpentane.
Select the temperature by examining
the list of boiling points.
n-pentane: (309 K)
2,2-dimethylpropane: (282.5 K)
n-hexane: (342 K)
2,2-dimethylbutane: (323 K)
A 348 K
B 333 K
C 317 K
D 295 K
ForQuestions 28-30, one or more of the
responses given is/are correct. Decide
which of the responses is/are correct. Then
choose
A if only 1,2 and 3 are correct.
B if only 1 and 3 are correct.
C if only 2 and 4 are correct.
D if only 4 is correct.
28 Which of these compounds is an
alkane?
A Cl8H12
B C14H10
C C9H12
D C7H16
29 The members of the homologous
series of alkanes
A are all straight-chain
compounds.
B have the general formula
CnH2n+2
C have identical chemical
properties.
D show a regular gradation of
physical properties.
30 Which of these reactions is a
substitution reaction?
A CH4 + Cl2 → CH3Cl + HCl
B C2H2 + Cl2 → C2H2Cl2
C CHCl3 + Cl2 → CCl4 + HCl
D CH4 + 2C12 → C + 4HCl
31 Which of the following reagents
distinguishes ethene from ethyne?
A Aqueous alkaline potassium
tetraoxomanganate(Vll).
B Chlorine dissolved in
tetrachloromethane.
C Ammoniacal copper(I)chloride
D Concentrated tetraoxo-
sulphate(VI)acid
32 Carbon(II)oxide (12 cm3) is sparked
with oxygen (10 cm3). After shaking

235
 with excess aqueous alkali, the B electron affinity.
volume of gas remaining is C first ionisation energy.
A 2 cm3. D atomisation energy.
B 4 cm3. 37 A metallic ion M2+ with an inert gas
C 12 cm3. structure contains 18 electrons. The
D 18 cm3. number of protons in the ion is
33 The equilibrium constant for the A 2.
reaction, B 16.

N 2 + O2   2NO C 18.
is represented by the expression D 20.
38 One of the following physical
A [NO] 2 properties decreases across the
Periodic Table?
[N2] [O2]
A Atomic radius
B [NO] B Electronegativity
[N2] 2 [O] 2
1 1
C Electron affinity
D Ionisation energy
C [N2] [O2]
39 Which of the following statements is
[NO]2 true?
1 1
D [N2] 2 [O2] 2 A The dissolution of KOH (s) in
[NO] water is endothermic .
34 Which of the following will alter the B The heat of solution of KOH(S) is
value of the equilibrium constant for positive.
a reaction between gases? C The heat of solution of KOH(S) is
A Changing the pressure negative.
B Changing the temperature D The KOH(S) gains heat from the
C Changing the concentration of surrounding.
one of the reactants 40 The periodic classification of the
D Adding a catalyst elements is an arrangement of
35 The formula of a compound formed elements in order of their
in a reaction between a trivalent A atomic masses.
metal M and a tetravalent non-metal B densities.
Y is C molar masses.
A MY. D atomic numbers.
B M3Y4. 41 In the Haber process, the synthesis
C M4Y3. of ammonia is accompanied by the
D M3Y2. giving out of much heat, according
36 The energy change that accompanies to the equation
the addition of an electron to a N2 + 3H2  2NH3 (∆H is -ve).
gaseous is called Increasing the temperature of this
A electronegativity. reaction will
A increase the yield of ammonia.

236
 B decrease the yield of ammonia.
C not have any effect on the yield
of ammonia.
D decompose the ammonia
completely.
42 Which one of the following decreases
in value when descending Group 1?
A Atomic radius
B Ionic radius
C First ionisation energy
D Electropositivity
43 Where in the Periodic Table would
you place an element whose electronic
configuration is 1s22s22p63s23p1?
A Group 1
B Group 2
C Group 3
D None of the above
44 What is the percentage by mass of
sulphur in sulphur(VI)oxide?
(S = 32; O =16)
A 67.7%
B 60.0%
C 50.0%
D 40.0%
45 Trioxonitrate(V) acid and potassium
hydroxide are examples of
A strong and weak electrolytes
respectively.
B weak and strong electrolytes
respectively.
C strong electrolytes.
D weak electrolytes.
46 The minimum amount of energy
needed for a reaction to take place is
known as
A bond energy.
B activation energy.
C kinetic energy.
D potential energy.
47 Which of the following is the general
molecular formula for the alkynes?
237
A CnH2n–2
B CnH2n
C CnH2n+1
D CnH2n+2
48 2SO2(g) + O2(g) → 2SO3(g)
From the reaction represented in
the equation above, the oxidation
number of sulphur changes from
A +2 to +4.
B +4 to +6.
C +4 to -4.
D +4 to 0.
49 In the manufacture of soap, palm oil
is first heated with
A sodium chloride.
B potassium chloride.
C sodium hydroxide.
D ammonium hydroxide.
50 Which of the following statements
about ethene and ethyne is not
correct?
A They combine with hydrogen
bromide.
B They both form metallic
derivatives.
C They are unsaturated.
D They burn in air to form
carbon(IV)oxide and steam.
SECTION B
Short-structured questions
1 20 cm3 of an acid X was neutralised
by four different solutions of the same
alkali. The volumes of alkali required
were
a) 10 cm3
b) 40 cm3
c) 20 cm3
d) 30 em3
i) Arrange the alkali solutions
 in order of concentration.
ii) Which of the solutions were
• more concentrated than
the acid?
• less concentrated than
the acid?
• of the same concentration
as the acid?
iii) If the original alkali solutions
were added to 20 cm 3 of
an acid which is half the
concentration of X, what
volumes of A,B,C and D
would be required to
neutralise the acid?
2 Tetraoxosulphate(VI)acid can act
a) as a dehydrating agent.
b) as an oxidising agent.
c) as an acid.
State (giving reasons) how
tetraoxosulphate(VI)acid reacts in
the following cases:
i) Copper(II) tetraoxosulphate-
(VI) crystals turn white and
heat is evolved.
ii) Wo o d s h a v i n g s ( w h i c h
contain carbon) turn to
carbon(IV)oxide.
iii) Magnesium dissolves and
hydrogen is evolved while
heat is given out.
iv) Sugar turns to black charcoal
and heat is evolved.
v) Sulphur turns to sulphur(IV)
oxide.
3 In each of the following, which of the
alternatives (i) or (ii) best describes a
metal?
a) i) Conducts electricity
ii) Does not conduct electricity
b) i) Brittle
ii) Malleable
238
c) i) Forms basic oxides
ii) Forms acidic oxides
d) i) Low melting point
ii) High melting point
e) i) High boiling point
ii) Low boiling point
4 Magnesium was heated in a crucible to
form magnesium oxide. The complete
set of results for the experiment are
a) mass of empty crucible = 5.0 g
b) mass of crucible and magnesium
= 7.4 g
c) mass of crucible and magnesium
oxide = 9.0 g
d) mass of crucible and magnesium
oxide after further heating =
9.0 g
i) Why was the mass of crucible
and mag-nesium oxide taken
twice?
ii) What is the mass of magnesium?
iii) What is the mass of oxygen
involved in the reaction?
iv) How many gramme-atoms of
magnesium and oxygen are
involved in the reaction?
v) Suggest a formula for mag-
nesium oxide.
5 Sodium trioxocarbonate(IV) can be
obtained in large crystals as ‘washing
soda’, (Na2CO3.10H2O).
a) How could it be shown that these
crystals contain a large amount
of water of crystallisation?
b) How might it be shown that
the substance loses water of
crystallisation on exposure to
air?
c) What name is given to substances
that lose water of crystallisation
on exposure to air?
d) To what use is washing soda put
 in the treatment of water?
e) What happens when a solution
of sodium trioxocarbonate(IV) is
added to a solution of copper(II)
tetraoxosulphate(VI)?
f) Give an equation for the reaction
in (e).
g) How might copper(II) oxide be
obtained from the result of the
reaction described in (e) above?
h) Write an equation for the reaction
that takes place in (g) above.
the gas at 300 K and 750 mmHg.
(molar volume = 22.4 dm3 at s.t.p.)
5 The same quantity of electricity was
passed through two voltameters. If
6.4 g of copper were deposited in one
cell, what mass of aluminium would
be liberated in the other cell?
(Al = 27.0; Cu = 64.0; 1 mole of electrons
= 1 Faraday.)

Section C

Essay-type questions
1 Describe and explain what you
would observe when sulphur(IV)
oxide is bubbled through a solution
of
a) iron(III)chloride.
b) hydrogen sulphide.
c) potassium tetraoxomanga-
nate(Vll)
2 Determine the molecular formula of
a compound containing 38.75% of
carbon, 16.1% of hydrogen and 45.2%
of nitrogen, given that its molecular
mass is 31 (relative atomic masses of
C = 12; N =14 and H = l).
3 1.6 g of a mixture of potassium
trioxochlorate(V) and potassium
chloride produced, on strong heating,
360 cm3 of oxygen measured at 290 K
and 740 mmHg. What is the percentage
by mass of the potassium chloride
present in the given mixture?
4 A gas diffuses four times as slowly as
hydrogen. Calculate
a) its molecular mass.
b) the volume occupied by 8.0 g of

239
 Test paper II

SECTION A if pressures are measured in atm?

A atm2
Multiple-choice questions B atm-2
1 When descending a group of elements C atm-1
in the Periodic Table, the radius of the D no units
atom 5 Which of the following compounds
A increases. will form a solution if exposed to air
B decreases. for a few days?
B remains approximately the same. A Na2CO3.10H2O
D first increases and then decreases. B Na2SO4.10H2O
2 For the exothermic forward reaction, C CaCl2
N2(g) + 3H2(g)  2NH3(g) D NaNO3
which one of the following will 6 Consider the following equation:
increase the yield of ammonia at H2O + 2Fe2+ + Cl2→ 2Fe3+ + 2Cl- + H2O
equilibrium? The only ion which behaves as an
A Decreasing the concentration of oxidising agent is
hydrogen A Fe2+.
B Increasing the temperature B Fe3+ .
C Increasing the pressure C Cl2.
D Using a positive catalyst D Cl- .
3 In which one of the following reactions 7 In a titration experiment involving
will an increase in total pressure cause sodium hydroxide solution and dilute
an increase in the concentration of the hydrochloric acid, where would you
underlined species? place the base?
A H2(g) + Cl2(g)  2HCl(g) A In the burette
B 2SO2(g) + O2(g)  2SO3(g) B In the beaker
C CaCO3(s)  CaO(s) + CO2(g) C In the measuring cylinder
D N2O4(g)  2NO2(g) D In the conical flask
4 What are the units of Kp for the 8 The oxidation state of chromium in
reaction K2Cr2O7 is
N2(g) + 3H2(g)  2NH3(g) , A + 3.

240
 B + 5. A Calcium
C + 6. B Lithium
D + 7. C Sodium
9 Oxygen and ozone are D Magnesium
A isomers. 15 Which of the following will not
B isotopes. conduct an electric current?
C oxides. A Lead
D allotropes. B Graphite
10 The total number of atoms in the C Molten potassium chloride
formula KAl(SO4)2 is D Solid calcium chloride
A 6. 16 In the equilibrium
B 11. 2CO2(g)  2CO(g) + O2(g) ,
C 12. which one of the following will move
D 14. the position of the equilibrium to the
11 The type of bonding that best explains right?
the relatively high boiling point of A Addition of carbon(II)oxide
water in relation to other substances B Addition of a metallic catalyst
similar to it in molecular make up is C A decrease in pressure
A Van der Waals forces. D An increase in the volume of the
B covalent bonding. container
C coordinate covalent bonding. 17 A compound has the molecular
D hydrogen bonding. formula C4H10O. The compound could,
12 Which of the following is a non- therefore, be an/a
electrolyte? A ether.
A A water solution of ethanoic acid B ester.
B A water solution of ammonia C alkanal.
C A water solution of ethanol D ketone.
D Molten sodium chloride 18 Hexane, C 6H 14, contains the same
13 In a chemical reaction at equilibrium, number of C-H bonds as
which of the following changes A 3-ethyl pentane.
would always increase the molar B 2-methylbutane.
concentration of the product? C 2, 2-dimethyl pentane.
A Increasing the pressure D 2, 3-dimethyl butane.
B Increasing the temperature 19 The major constituents of air are
C Decreasing the temperature A oxygen and water vapour.
D Increasing the molar B nitrogen and water vapour.
concentrations of the reactants C oxygen and nitrogen.
14 1 g of Cl2 is allowed to react completely D oxygen and carbon(IV) oxide.
with each of the following metals. 20 How many moles of potassium
From which of the metals will the chloride are in 200 cm3 of its 0.5 M
greatest mass of chloride be produced? aqueous solution?
(K = 39, Cl = 35.5)

241
 A 0.01 mole 26 The mass of an atom is determined by
B 0.10 mole A its ionisation energy.
C 0.40 mole B the number of neutrons and
D 1.00 mole electrons.
21 0.16 g of methane, when burnt, raises C the number of neutrons and
the temperature of 100 g of water by protons.
313 K. What is the heat of combustion D the number of protons and
of methane if the specific heat capacity electrons .
of water is 4.2 kJ/kgK? (C=12, H = l) 27 When sodium dioxonitrate(III),
A 1 160 kJmol-1. (NaNO 2), dissolves in water, H is
B 1 180 kJmol-1 positive. The process of dissolution is
C 1, 600 kJmol-1 A exothermic.
D 1 680 kJmol-1 B endothermic.
22 0.07 g of a hydride of carbon occupies C deliquescent.
56.0 cm3 at s.t.p. when vaporised and D hygroscopic.
contains 14.29% by mass of hydrogen. 28 30 cm3 of 0.l M Al(NO3)3 solution is
The formula of the hydrocarbon is (C reacted with 100 cm 3 of 0.15 M of
= 12; H = l) NaOH solution. Which reactant is in
A CH4. excess and by how much?
B C2H2. A NaOH solution, by 70 cm3
C C2H4. B NaOH solution, by 60 cm3
D C2H6. C NaOH solution, by 40 cm3
23 An element X has two isotopes, 10 X
20
D Al(NO3)3 solution, by 20 cm3
and 10 X , present in the ratio 1:3. The
22
29 Element X and Y have electronic
relative atomic mass of X would be c o n f i g u r a t i o n 1 s 22 s 22 p 4 a n d
A 22.0. 1s22s23s2s23p1 respectively. When they
B 21.5. combine, the compound formed is
C 21.0. A XY.
D 20.5. B YX.
24 What mass of sodium hydroxide is C X2Y3.
required to prepare 500 cm3 of 0.2 M D Y2X3.
solution? 30 The minimum volume of oxygen
A 4g needed for the complete combustion
B 10 g of a mixture of 10 cm 3 of CO and
C 20 g 15 cm3 of H2 is
D 40 g A 5.0 cm3.
25 The cracking process is very important B 10.0 cm3.
in the petroleum industry because it C 12.5 cm3.
A gives purer products. D 25.0 cm3.
B yields more candle wax. 31 What is the percentage by mass of
C yields more engine fuels. water in
D yields more lubricants. KAl(SO4)2.12H2O? (K = 39; Al = 27;

242
S = 32,; O = 16; H = 1)
A 40.0%
B 45.6%
C 54.2%
D 57.1%
32 The boiling points of ethyl ethanoate
and water are 77°C and 100°C
respectively. A mixture of the two
liquids can be separated by
A distillation.
B filtration.
C fractional distillation.
D fractional crystallisation.
33 The rate of a chemical reaction is
affected by
A the temperature.
B the surface area exposed.
C the concentration of the reactants.
D all of the abov.e
34 A salt derived from a strong base and
a weak acid will undergo hydrolysis
and give a solution which will be
A basic.
B acidic.
C neutral.
D volatile.
35 The emission of a beta particle results
in a new element with the atomic
number
A increased by 1.
B increased by 2.
C decreased by 1.
D decreased by 2.
36 According to the kinetic-molecular
theory, molecules are in random
motion. The motion is greatest when
a substance is
A being warmed as a liquid.
B being warmed as a gas.
C changing from a solid to a liquid.
D changing from a liquid to a gas at
its boiling point.
243
37 All inert gases, except helium, are
characterised by a completion of the
outer
A s orbital.
B p orbital.
C d orbital.
D none of the above.
38 Equilibrium can be expressed as the
point at which
A all the chemicals present stop
reacting
B the chemicals start to react
C the reactants are used up
D the products react together at the
same rate as the reactants
A if only 1,2 and 3 are correct.
B if only 1 and 3 are correct.
C if only 2 and 4 are correct.
D if only 4 is correct.
39 A substance which gives off a small
amount of heat when it is formed from
its constituent elements will
A be difficult to decompose by the
addition of heat.
B be relatively easy to decompose
by the addition of heat.
C be unstable at low temperatures.
D be stable unless heated.
40 When an alpha particle is emitted from
the nucleus of an atom,
A the atomic number increases by 2.
B the atomic number decreases by
4.
C the relative atomic mass decreases
by 2.
D the relative atomic mass decreases
by 4.
41 Which of the following are chemical
properties of an element?
A Conducts electric current
B Attracted by a magnet
 C Soluble in water
D Coats itself with an oxide in air
42 As you proceed across a Periodic Table,
A the atomic number increases.
B the electronegativity increases.
C the non-metallic properties
increase.
D the relative atomic mass decreases.
43 The chemical properties in the
following list
A is a high boiling point.
B a low heat of vaporisation.
C a dark colour.
D reaction with oxygen.
44 The reaction for the burning of
hydrogen in oxygen is given by the
equation
2H2 + O2 → 2H2O; ∆H = 571.2 kJ.
How much heat is liberated if 10 g of
hydrogen is burnt?
A -229.5 kJ
B -1.148 kJ
C -1,313 kJ
D -1,435 kJ
45 Isotopes of an element have
A different numbers of electrons.
B different numbers of protons.
C different numbers of neutrons.
D different chemical properties.
46 How many moles of electrons are
needed to change one mole of Fe3+ to
Fe metal?
A 1
B 2
C 3
D 4
47 The atomic number of caesium is 55
and its atomic mass is 133. The nucleus
of caesium atom, therefore, contains
A 55 protons and 78 electrons.
B 55 protons and 78 neutrons.
C 78 protons and 55 electrons.
D 78 protons and 55 neutrons.
48 The catalyst used in the contact
process for the manufacture of
tetraoxosulphate(VI)acid is
A manganese(IV)oxide.
B iron metal.
C vanadium(V)oxide.
D iron(III)oxide.
49 A white solid suspected to be
lead trioxonitrate(V), calcium
trioxocarbonate(IV) or zinc
trioxocarbonate(IV) was heated
strongly. Its residue which was yellow
when hot and white when cold is
A lead(II)oxide.
B calcium oxide.
C zinc oxide.
D lead(I)dioxonitrate(III).
50 What reaction takes place when palm
oil is added to potash and foam is
observed?
A Neutralisation
B Saponification
C Esterification
D Hydrolysis
Section B
Short-structured questions
1 The following table gives the
electronic structures of elements in
two groups of the Periodic Table:

244
 Group Y
Element Structure Element
A 1s2s2 R 1s2s22p5
B 1s22s22p63s2 S -----------
C ---------
a) In which group of the Periodic
Table do elements in group
i) Y belong?
ii) Z belong?
b) What are the electronic structures
of
i) the next element in group Y,
i.e. element C?
ii) the next element in group Z,
i.e. element S?
c) The principal quantum numbers
of an atom give only a brief
description of the electronic
structure of the atom. How many
principal quantum numbers are
used to describe the electronic
structure in R?
d) The subsidiary quantum
numbers amplify the principal
quantum numbers. What further
two quantum numbers are
required to fully describe an
electron?
e) How many paired electrons are
there in B and R?
f) If A and R are made to react
together,
i) would you expect the
compound to be ionic or
covalent? Give your reasons.
ii) what would be the formula of
a compound formed between
A and R?
245
Group Z
Structure
2 When 240 cm2 of a hydrocarbon was
completely burnt in oxygen, it was
found that 720 cm2 of carbon(IV)
oxide and 0.03 moles of water were
produced (all measurements were
made at room temperature). Relative
atomic masses: H = 1; C = 1; O = 16.
Molar volume of a gas at room
temperature is 24 000 cm3.
a) i) How many moles of the
hydrocarbon and how many
moles of carbon(IV) oxide
were present?
ii) What is the molecular formula
of the hydrocarbon?
iii) Wr i t e a n e q u a t i o n f o r
the combustion of the
hydrocarbon in oxygen.
iv) What volume of oxygen
would be needed to burn the
240 cm2 of hydrocarbon?
v) What mass of water would be
produced?
vi) S u g g e s t t w o p o s s i b l e
structural formulae for the
hydrocarbon.
b) The hydrocarbon reacted with
hydrogen bromide to give a
compound of molecular formula
C 3H 7Br. What is the structural
formula of this compound?
3 Given that the relative atomic masses
of sodium = 23; oxygen = 16; carbon
= 12 and chlorine = 35.5,
 a) what is the relative molar mass of
i) sodium chloride, NaCl?
ii) sodium trioxocarboate(V),
Na2CO3?
b) what is meant by a ‘mole’?
c) how many grammes of sodium
chloride would be needed to
prepare 500 cm3 of a 2M solution?
4 Four metals A, B, C and D are available
as strips of metal. Solutions of the
trioxonitrate(V) salts of the respective
metals are also available. Placing strips
of metal in the solutions, it is found
that C displaces D, B displaces C, B
displaces D and A displaces B.
a) Arrange the metals in their order
of chemical reactivity, the most
reactive first.
b) Which of the metals is most likely
to react with steam?
c) If this metal has two electrons in
its outer shell, suggest the formula
for
i) its oxide.
ii) its chloride.
iii) its ion.
5 a) State any two chemicals which
will react to produce each of the
following gases:
i) carbon(IV)oxide
ii) hydrogen
iii) chlorine
b) Describe one simple test for each
of the gases in (a).
c) Which two of the gases (i), (ii),
and (iii) in (a) would react to
produce a fourth gas? Give the
formula for the molecule of this
gas. Write the equation for the
reaction.
246
Section C
Essay-type questions
1 When 4.6 g of ethanol, C2H5OH, is
burned in a calorimeter containing
1 kg of water, the temperature rises
from 291 K to 316 K. If the specific heat
capacity of water is 4.18 kJ Kg-1K–1, the
water equivalent of the calorimeter
is 1.3 kJ K-l and the relative molar
mass of ethanol is 46 g, calculate the
enthalpy of ethanol combustion.
2 Calculate the mass of copper that
would be deposited on a copper
cathode from an aqueous solution
of copper(II) tetraoxosulphate(VI),
if the same current, passed for the
same time, liberated 0.900 g of silver
from an aqueous solution of silver
trioxonitrate(V).
3 The equation for the reversible
reaction of bismuth(III)chloride with
water is
BiCl3(aq) + H2O  BiOCl(s) + 2H+ + 2Cl–(aq)
(white)
a) When the reaction goes from left
to right, what would you expect
to see?
b) Explain why it is impossible
to prepare a clear solution of
bismuth(III) chloride in water by
adding some solid to pure water.
c) What would be the effect of
adding dilute hydrochloric acid
to the mixture at equilibrium?
d) What would be the effect of
adding solid sodium hydroxide
to the mixture at equilibrium and
stirring so that it dissolves?
4 Chlorine may be generated by gently
warming a mixture of concentrated
 hydrochloric acid and manganese(IV)
oxide.
a) Sketch an apparatus with which
you could carry out this reaction,
dry the gas, and collect samples.
b) How would you identify the
gas?
c) Write an equation for this
reaction.
d) What are the effects of
i) chlorine upon heated iron?
ii) sunlight upon a solution of
chlorine in water?
iii) chlorine upon potassium
bromide solution?
5 Write equations for the reactions (one
only in each case) by which jars of
a) (i) ethane, and (ii) ethyne can be
prepared in the laboratory.
b) Draw a labelled diagram of the
apparatus you would use for the
preparation of one of the gases in
(a) in the laboratory.
c) Write equations for the reaction
of each of the gases in (a) with
oxygen.
d) Which of ethane or ethyne is said
to be unsaturated? Explain the
term unsaturation.
e) Describe a test which would
enable you to demonstrate that a
hydrocarbon is unsaturated.

247
 General test papers
Hints to candidates
1 Timing
Spend a few minutes reading the
exami nation p ap er. Decide on
which questions you think you can
adequately answer. Do not discard a
question simply because it contains a
small part which you cannot answer.
2 Details
Make sure you understand what
the question requires. Misreading
a question could lead to the loss of
valuable marks.
Do not attempt to ‘show off’ by
dragging in matters which have no
bearing on the question. Mere length
is no advantage.
3 Equations
Whenever you discuss a chemical
reaction, it is usually advisable to
write down the equation and to
specify in the equation the states of
the substances involved. Always
ensure that your equations balance
and that in ionic equations the ions are
represented with their correct charges.
248
4 Diagrams
You should illustrate your answers with
diagrams wherever such diagrams
add to the clarity of your answer. It is
advisable to draw your diagrams in
pencil so that, if need be, alterations
can easily be made. Always label the
parts of your diagrams directly. Do not
label with letters which you will need
to explain underneath the diagram.
Place the labels outside the actual
diagram, not in it.
5 Numerical problems
It is possible to score full marks from
a numerical question. This may not
be so for an essay-type question.
Calculations constitute a valuable
source of marks for candidates who
are gifted in chemical arithmetic.
General test papers
1 Define or explain the following terms:
a) Evaporation
b) Decantation
c) Distillation
d) Fractional crystallisation
2 State how each of the following
apparatus is used in the separation of
mixtures:
 a) Funnel 9 a) Why is air described as a mixture
b) Evaporating dish of gases?
c) Leibig condenser b) Name the component of air which
3 The components of chlorophyll, the supports combustion.
green substance in green plants, are c) De s cribe h ow liqu id a ir is
separated by the process known as separated.
chromatography. 10 In what ways do heterogeneous
a) State the different types of mixtures differ from homogeneous
chromatography. mixtures? In what ways are they alike?
b) What solvent is most useful in 11 a) In what ways does a pure substance
the process of chromatography? differ from a homogeneous
Explain why. mixture?
4 a) What do you understand when b) Classify each of the following
you are told that a substance is homogeneous materials as a
impure? solution, an element, or a
b) W h a t p r o p e r t i e s d o p u r e compound: iron; water; carbon(IV)
substances possess? oxide; oxygen; sulphur; glucose;
c) How would you purify an impure blood plasma.
sodium chloride? 12 a) What is a binary compound?
5 The following information was b) Name the following compounds:
obtained about a substance X: AgF
Mass of impure X = 48 g LiH
Mass of impurity in X = 6 g Na2O
Calculate the percentage purity of the Mg3N2
substance. Al4C3
6 With the help of a suitable diagram, 13 a) Describe, giving one example each
show how the local gin can be purified. of the following:
The boiling points of ethyl ethanoate i) an ionic compound
and water are 350 K and 373 K ii) a covalent compound
respectively. How would you separate b) What are the characteristics of two
a mixture of the two liquids? atoms that will form a covalent
7 a) Explain why crude oil (petroleum) bond?
is described as a mixture of 14 Predict which of the following
hydrocarbons. compounds are ionic and which are
b) Draw a suitable diagram for the covalent, based on the location of their
separation of crude oil in the constituent elements in the Periodic
laboratory. Table.
c) Name four components of crude a) SO2 f) PCl3
oil. b) ClF3 g) H2O
8 Describe how a mixture of sand and c) Na2S h) TiO2
rice can be efficiently separated. d) CuCl2 i) CaBr2
e) MgO j) NH3

249
15 Write the Lewis structure for the
following:
a) O2 d) NH3
b) KBr e) H3COH
c) CO f) HF
What do you understand by the octet
rule?
16 Wr i t e t h e L e w i s s t ru c t u re f o r
tetraoxophosphate(V)acid, H 3PO 4,
which has one oxygen atom and
three -OH groups bonded to the
phosphorus.
17 a) Give three properties of ionic
compounds which distinguish
them from covalent compounds.
b) How is a covalent bond different
from a coordinate covalent bond?
18 a) Describe how hydrogen bonds are
formed in a water molecule.
b) Distinguish between Van der
Waals forces and hydrogen
bonding.
19 a) What is meant by the electro-
negativity of an element?
b) How does the electronegativity
difference of the atoms in a
covalent bond affect the polarity
of the bond?
20 Carefully study the following four
substances: water, ethanol, chlorine
and potassium chloride.
a) I l l u s t r a t e a n e l e c t ro v a l e n t
compound from the list, using
the electron dot.
b) Illustrate a covalent compound
from the list, using the electron
dot.
21 You are told that an element X could be
any of the following: oxygen, sodium,
potassium, chlorine or sulphur.
The following clue is given to enable
you to identify X:
250
X is a univalent element and forms
electrovalent compounds with
metals and covalent compounds with
hydrogen. What is X? Explain your
choice.
22 a) Calculate the percentage by mass
of carbon in carbon(IV) oxide.
b) Critically study this equation:
MgCO3(s) → MgO(s) + CO2(g)
Calculate the mass of magnesium
trioxocarbonate(IV) that would
be required to produce 5.6 dm3 of
carbon(IV)oxide at s.t.p.
23 a) What do you understand by a
standard solution?
b) Describe, giving all necessary
details, how you would prepare
0.1M sodium trioxocarbonate(IV),
Na2CO3 solution.
c) How many moles of sodium chloride
are in 100 cm3 of its 0.5M aqueous
solution?
24 Carbon(IV)oxide was produced by
reacting excess dilute hydrochloric
acid with calcium trioxocarbonate(IV).
a) Write the chemical formula for
(i) calcium trioxocarbonate(IV)
and (ii) carbon(IV) oxide.
b) Write a balanced equation for the
reaction.
c) I f 1 0 g o f c a l c i u m t r i o x o -
carbonate(IV) was used,
i) calculate the number of moles
of calcium trioxocarbonate(IV)
equivalent to the 10 g;
ii) calculate the volume of carbon(IV)
oxide produced at s.t.p. Use the
following relevant information:
(H = l; O = 16; Ca = 40; molar
volume of a gas at s.t.p.
= 22.4 dm3)
25 a) State four assumptions made in
the kinetic molecular theory.
b) Under what conditions is a gas
most likely to behave as if it were
ideal?
c) What mass does a molar volume
of carbon(IV)oxide have at s.t.p.?
26 a) Using the kinetic molecular theory,
briefly explain what happens to
the molecules of a gas when they
are heated.
b) State Graham’s law of gaseous
diffusion.
c) What is the molar mass of an
unknown gas if it diffuses 0.906
times as fast as argon gas?
27 a) How many grams of sodium
tetraoxosulphate(VI), Na2SO4, are
contained in 1.50 dm3 of a 0.25M
solution?
b) Describe how you would prepare
1.50 dm3 of a 0.25M solution.
c) How many grams of ammonium
tetraoxosulphate(VI), (NH4)2SO4,
are required to prepare 3.50 dm3
of a 1.55M solution?
28 a) State Graham’s law of gaseous
d i ff u s i o n , u s i n g i d e n t i f i e d
mathematical symbols.
b) The rate of diffusion of an
unknown gas is four times faster
than oxygen gas. Calculate the
molar mass of the unknown gas.
c) What then is the name of the
unknown gas?
29 Draw the electron dot (Lewis) structure
for the following molecules:
a) CCl4
b) NH3
c) C2H6
d) CO2
e)
251
30 Using the Periodic Table, predict the
shape of the following molecules
(illustrate with suitable diagrams):
a) H2S
b) SiH4
c) InCl3
d) AsH3
31 Which of the properties listed here are
characteristic of an ionic solid?
a) Low melting temperature
b) Conducts electricity as solid
c) Dissolves in water to form a
solution that contains mostly ions
d) Dissolves to form a solution that
contains mostly molecules
e) Conducts electricity when melted
f) Forms solid crystals
32 a) What do you understand by the
term ‘mole’?
b) How many moles are present in
the following:
i) 2 g of NaOH?
ii) 3.65 g of HCl?
iii) 98 g of H2SO4 ?
iv) 212g of Na2CO3?
c) What is the concentration, in
mole dm3, of a solution which
contains 0.20 g of sodium
hydroxide per 50 cm-3 of solution?
33 Solution A contains 18.25 g of
hydrogen chloride dissolved in water
and then made up to 1 dm 3 . On
titration against solution B, sodium
trioxocarbonate(IV), 30.0 cm 3 of
solution A netralised exactly 25.0 cm3
of solution B.
a) Write a balanced equation for the
reaction between solution A and
solution B.
b) Calculate the concentration of
solution B in moles per dm3.
c) What is the mass concentration of
 solution B?
34 The
NO 3–following samples, A, B and C
were labelled as follows:
A = Zn (aq)
2+
B = Al (aq)
3+
C = Fe(aq)
2+
) b) d ro p s o f w a t e r a re a d d e d
a)A few drops of sodium hydroxide
solution were added to each of
the samples and the following
observations were made:
i) A white precipitate was
obtained.
ii) A greenish precipitate was
obtained.
Predict which of the samples will
give the observed results.
b) Excess sodium hydroxide was
added to each of the samples.
Predict which of the samples will
give the observed results:
i) A white precipicate was
formed which did not
dissolve in excess sodium
hydroxide.
ii) A white precipitate was
formed but then dissolved
in the excess sodium
hydroxide.
iii) A greenish precipitate
which did not dissolve in
excess sodum hydroxide.
c) Write balanced chemical
equations for the reactions above.
35 a) In the following reaction, calculate
the oxidation number of nitrogen
in the reactant and in the product
2NO(g) + O2(g)  2NO2(g)
b) What is the oxidation number
of sulphur in copper(II)
tetraoxosulphate(VI), CuSO4.?
252
c) What is the oxidation number of
nitrogen in NO 3– ?
d) What do you understand by
oxidation number?
A = Zn (aq)
2+
36 What do you observe 3when
B = Al (aq)
+
a) SO2 gas is passed into an acidified
C = Fe
solution of KMnO4?
2+
(aq)
to anhydrous copper(II)
tetraoxosulphate(VI), CuSO4?
c) phenolphthalein solution is
dropped into an acid solution?
d) ammonia gas reacts with hydrogen
chloride gas?
37 Dilute hydrochloric acid is added
to each of the solids A,B,C and the
mixture is gently warmed.
A = sodium trixocarbonate(IV)
B = iron(II) sulphide
C = impure zinc
a) Write a balanced equation for
each of the reactions.
b) Name the gas evolved in each
reaction.
c) What reagent would you use to
identify the gas evolved in each
case?
d) What would have happened if
pure zinc was used?
38 Write balanced equations to show
the thermal decomposition of the
following substances:
a) Potassium trioxochlorate(V)
b) Mercury(II)trioxonitrate(V)
c) Sodium trioxonitrate(V)
d) Copper(II)trioxonitrate(V)
39 a) Define the following:
i) ionisation energy
ii) electron affinity
iii) electronegativity
b) The electronic configuration
of the following neutral atoms
 are given for use in answering the residual oxygen occupied 25 cm3.
Questions (i) to (v): What is the hydrocarbon A, assuming
A 1s22s22p6s2 that all measurements were made at
B 1s22s22p63s1 288 K and 760 mm pressure?
C 1s22s22p6 42 a) Explain the evidence that may be
D 1s22s22p5 obtained about electronic energy
E 1s2s22p3 levels from a study of emission
i) Which of these electronic spectra.
configurations given would b) In what two respects do the
you expect to have the lowest orbitals of the following electrons
ionisation energy? differ in a single atom?
ii) Which of these electronic i) 1s and 2s electrons?
configurations given would you ii) 2s and 2p electrons?
expect for a noble gas? In the case of (ii), illustrate your
iii) List the five configurations in answer with diagrams.
predicted order of increasing c) A particular neutral atom has a
ionisation energy (lowest to ground state electronic structure
highest). 1s22s22p63s23p4. Deduce as many
iv) Predict the configuration that of the following as you can from
should have the highest second this information only and state
ionisation energy. with reasons those which cannot
v) Predict the configuration that be deduced:
should have the lowest second i) the atomic number of the
ionisation energy. element
40 a) Use the Periodic Table to predict ii) the relative atomic mass of
which substance in each of these the element
pairs has the smaller radius. iii) the number of unpaired
i) K, Br electrons in the atom
ii) Ne, F- Atom 1 st ionisation Radius E l e c t ro n i c
iii) K+ , Ga3+ energy (kJ mol–1) (nm) configuration
iv) S, Se. 1s2s2px2py2pz
Give your reasons. Li 520 13.3 ⥮ ↿
b) What is a crystal lattice?
Be 900 8.9 ⥮ ⥮
c) Explain how a covalent bond
B 800 8.0 ⥮ ⥮ ↿
forms between two non-metallic
atoms.
43 a) Define first ionisation energy of an
41 30 cm3 of a gaseous hydrocarbon, A,
atom.
was mixed with 100 cm3 of oxygen
b) Consider the following data:
and exploded. After cooling, the
residual gases occupied a volume
i) Explain why the first
of 85 cm3, and after absorption by
ionisation energy for boron is
aqueous potassium hydroxide, KOH,

253
 greater than that for lithium.
ii) In terms of electronic
configuration, suggest an
explanation for the fact that
the first ionisation energy for
beryllium is greater than that
of boron.
iii) Why do the atomic radii
decrease from lithium to
beryllium to boron?
44 A given gaseous system at a
pressure of 750 mm Hg and at a
temperature of 250 K occupies
20.0 dm3.
a) Calculate the volume of the
system at s.t.p.
b) How many moles of gas are
present in the system?
c) W h a t i s t h e n u m b e r o f
molecules in this system?
(G.M.V. = 22. 4 dm3; Avogadro
constant = 6.023 × 1023 mol-1)
45 The two diagrams which follow
present what happens when metals A
and B are each dipped into an aqueous
solution of one of their salts.
a) Explain, in a sentence each, what
process is taking place in each of
the half-cells X and Y.
+ – –+ – + +–
+ – –+ – + +–
+ – –+ – + +–
b) Write ionic half-equations for
each process (assume that three
electrons per atom are involved
in each process).
254
c) The two metals are connected
externally by a wire and the two
solutions are connected by a salt
bridge. What name is given to the
resulting arrangement? Indicate
the direction of flow of electrons
in the wire, and which metal, A or
B, acts as the anode.
46 A divalent ion, X2+, has the following
electronic structure: 1s22s22p63s23p6.
Deduce the following:
a) The ground state electronic
structure of the atom X and its
atomic number
b) The relative atomic mass of
the isotope of X which has 20
neutrons
c) The number of unpaired
electrons in X
d) The number of electrons in the
third quantum shell of X
47 What is meant by ‘the atomic number
of an element’? Discuss the relationship
between the atomic number of an
element and the X- ray line spectra.
48 a) Discuss the relationship between
the electronic structure of an
element and its position in the
periodic classification.
b) The transition elements occupy
ten consecutive groups in the
Periodic Table and show closely-
related properties. Explain this
observation in terms of the
electronic configurations of these
elements.
c) A given quantity of electricity
flows through two separate
electrolytic cells connected in
series, one containing a solution
of copper(II)tetraoxosulphate(VI),
CuSO4, and the other contains
 dilute hydrochloric acid. If
2 400 cm3 of hydrogen at s.t.p. is
evolved at the cathode of the cell
containing dilute hydrochloric
acid, what mass of copper will
be deposited at the cathode of the
other cell?
(relative atomic mass of Cu =
63.54)
49 A current of 0.1 amp is passed through
a silver voltameter for 30 minutes
to liberate 0.2014 g of silver. Given
that the relative atomic mass of silver
is 107.9 and that the charge on the
electron is 1.602 × 10 -19 coulombs,
calculate the Avogadro number, N.
50 Why is it considered correct that
potassium (K = 39.1) should follow
argon (Ar = 39.9) in the Periodic Table?
What factors explain the lower relative
atomic mass of potassium?
51 The similarity between calcium,
strontium and barium was noted by
Dobereiner in 1829, and he called the
three elements a triad.
a) What is the relationship between
the relative atomic masses of the
three elements?
b) What other properties of the
elements have the same numerical
relationship?
c) List some examples of such triads
in Groups I and VII which possess
the same relative atomic mass
relationship as calcium, strontium
and barium.
52 a) Define first ionisation energy.
b) E x p l a i n w h y t h e f i r s t
ionisation energies of the
alkali metals (i.e. Group IA
decrease with increasing
atomic numbers.
255
53 Name three scientists that have
contributed to the development of the
Periodic Table. Discuss in detail the
contribution of any one of them.
54 Mercury is a conductor but not an
electrolyte. However, molten sodium
chloride is a conductor and an
electrolyte.
a) Explain the terms conductor and
electrolyte.
b) Explain the two statements above.
55 What products would you expect at
the cathode and at the anode when
the following are electrolysed, using
platinum electrodes?
a) Molten magnesium chloride
b) Aqueous magnesium chloride
c) Copper(II) trioxonitrate(V)
solution
56 During the electrolysis of an iron salt,
0.10 g iron is deposited on the cathode
when a current of 0.50A is passed
through the electrolyte for 17 minutes.
Calculate
a) the number of coulombs passed
through the electrolyte.
b) the number of coulombs that
would be needed to produce
1 mole of iron atoms (Fe = 56).
c) the charge on the iron ions
(1 faraday = 9.65 × 104 coulombs
mol-1).
d) Write the equation for the reaction
at the cathode.
57 During the electrolysis of a deep
purple solution of copper(II)
tetraoxomanganate(VII), using U-tube,
a blue colour was seen around the
cathode while a lighter purple colour
appeared around the anode.
a) What kind of charge must the
particles which caused the
 purple colour have?
b) What kind of charge must the
particles which caused the light
purple colour have?
c) Name the ions which caused the
blue colour.
d) Name the ions which caused the
light purple colour.
58 For each of the following, determine
the number of atoms represented and
the moles of atoms represented:
a) 28.0 grams of sodium
b) 28.0 grams of iron
c) 130.8 grams of zinc
d) 2.4 grams of calcium
e) 142.0 grams of chlorine
(relative atomic mass Na = 23;
Fe = 56; Zn = 65.5; Ca = 40;
Cl = 35.5)
59 a) Explain what is meant by atomic
radius.
b) Describe and discuss the changes
in radius in the following series:
i) Na, Mg, Al, Si, P, S and Cl
ii) F, Cl, Br and I
iii) Ti, V, Cr, Mn, Fe, Co
60 When copper metal is placed in 1M
hydrochloric acid, HCl, under standard
conditions, there is no observable
reaction. However, when zinc metal
is placed in the same hydrochloric
acid solution, the metal oxidises and
hydrogen gas is produced. Explain
these two phenomena.
61 The illustration which follows shows
a cell consisting of copper and silver
electrodes.
a) What is solution N?
b) Write down
i) the notation for the cell.
ii) the overall equation for the
cell reaction.
256
c) Name a substance that can be
used in the salt-bridge and state
the purpose of a saltbridge.
d) Calculate the overall electrode
potential, E, of the cell,
Cu2+2e- à Cu E0 + 0.35V
Ag+ +e-àAg E0 = 0.81V
62 a) Compound A contains Fe, 28%;
O, 48% and S, 24%. Calculate the
empirical formula of A.
b) If the relative molar mass of A
is 400, determine the molecular
formula of A.
63 Potassium heptaoxodichromate(VI) in
the presence of tetraoxosulphate(VI)
acid is widely used as an oxidising
agent.
a) Write down the half ionic equation
for the reaction between potassium
heptaoxodichromate(VI) and
potassium iodide in an acidic
medium.
b) Wr i t e d o w n t h e o v e r a l l
ionic equation for the
reaction between potassium
heptaoxodichromate(VI) and
potassium iodide in an acidic
solution.
 c) Name one practical
application of potassium
heptaoxodichromate(VI) as an
oxidising agent.
64 From the information given, calculate
the molar mass of each of the following
compounds:
a) 2 moles of compound A has a mass
of 80 grams.
b) 3.01 × 1023 molecules of compound
B have a mass of 9 grams.
c) 1.57 × 1023 molecules of compound
C have a mass of 7.56 grams.
d) 1.35 grams of compound D contain
4.55 × 1022 molecules.
65 Ethyne gas is used for welding. Ethyne
contains 30 grams of carbon for each
2.5 grams of hydrogen. What is the
empirical formula for ethyne?
66 A compound is composed of 19.01
grams of carbon, 18.48 grams of
nitrogen, 25.34 grams of oxygen and
1.58 grams of hydrogen. Calculate the
empirical formula of this compound.
67 The composition of a compound is
as follows: carbon = 7.20 grams;
hydrogen = 1.20 grams; and oxygen
= 9.60 grams. If the molar mass of the
compound is 180 grams, determine the
empirical and molecular formulae of
the compound.
68 Determine the simplest formula for a
compound which contains 63.6% iron
and 36.4% sulphur.
69 Determine the percentage composition
of a compound which contains 10.12
grams of aluminium and 17.93 grams
of sulphur.
70 How many moles of iron(III)chlonde
could be made with 1.81 x 1023 atoms of
chlorine and the appropriate number
of iron atom?
257
71 What is the mass of one mole of each
of the following compounds?
a) MgCrO4
b) K2CrO4
c) Fe(CN)2
d) sodium tetraoxosulphate(VI)
e) potassium trioxochlorate(V)
f) p o t a s s i u m h e p t a o x o -
dichromate(VI)
72 A 0.050M solution of glycerine,
C 3 H 8 O 3 , and a 0.50M solution of
ethanol, C2H6O, are prepared. Which
solution contains the most dissolved
molecules per dm 3? Explain your
answer.
73 H o w m a n y g r a m s o f s o d i u m
tetraoxosulphate(VI), Na 2SO 4, are
contained in 1.50 dm 3 of 0.25M
solution?
74 If 1.00 dm 3 of water is added to
3.00 dm3 of a 6.00M solution of HCl,
what is the new molarity of the acid
solution?
75 Balance the following equations:
a) Ca + H2O → Ca(OH)2 + H2
b) Mg3N2 + H2O → MgO + NH3
c) (NH4)2SO4 + NaOH → Na2SO4 +
NH3+ H2O
d) FeS2 + O2 → Fe2O3 + SO2
e) Mg(ClO3) 2→4 MgCl2 + O2
76 Write and balance the following word
equations:
a) Potassium + water Potassium
hydroxide + hydrogen
b) lithium + water
lithium hydroxide + hydrogen
c) Magnesium + nitrogen
magnesium nitride
d) Ammonium trioxonitratesodium
hydroxide ammonia + water +
sodium trioxonitrate(V)
77 A mass of 46.0 grams of sodium reacts
 with 38.0 grams of fluorine to produce
84.0 grams of sodium fluoride, NaF.
a) Write down a balanced equation
for this reaction.
b) Express this equation in terms of
atoms and molecules.
c) Calculate the number of moles of
each substance.
78 Calculate the number of moles
of oxygen that will be needed to
completely burn 1.06 moles of
methane, CH4, in order to form water
and carbon(IV)oxide.
79 For the reaction
Cu + 2AgNO3 →Cu(NO3)2 + 2Ag
a) How many grams of copper are
required to replace 9.35 grams
of silver in the solution of silver
trioxonitrate(V)?
b) If 5.50 grams of silver are
produced in the above reaction,
how many moles of copper were
reacted?
80 When 7.52 grams of lead(II)
trioxocarbonate(IV), Pb(CO 3), are
reacted with 27.5 cm 3 of 3.00M
trioxonitrate(V)acid, HNO 3, what
mass of lead(II)trioxonitrate(VI),
Pb(NO3)2 will be formed?
81 If 15.50 grams of lead(II)
trioxonitrate(V), Pb(NO3)2 are reacted
with 3.81 grams of sodium chloride,
NaCl, then sodium trioxonitrate(V),
NaNO3, and lead(II)chloride, PbCl2,
are formed.
a) Which reactant will be in excess?
b) Calculate the mass of the excess
reactant.
c) Calculate the mass of lead(II)
chloride produced.
82 Balance the redox equations for these
reactions:
258
a) Cr2O27+ Hg → Cr3 + Hg2+
b) MnO-4 + H2O2 → Mn2+ + O2
c) Zn + NO-3→ NH2+ + Zn2+
d) I- + → Cl2 → Cl- + I2
83 Consider this equation:
Mg + Cu2+ → Mg2+ + Cu
a) Which substance is oxidised?
b) Which substance is reduced?
c) Which substance acts as the
reducing agent?
d) Which substance acts as the
oxidising agent?
84 Equations for the reactions taking
place in an electrochemical cell are:
Cr → Cr3+ + 3e-
Pb2+ + 2e– → Pb
How many grams of lead will be
deposited on the cathode when 1.56
grams of chromium dissolve from
the anode?
85 When zinc metal is placed in a
concentrated tetraoxosulphate(VI)
acid solution, the zinc dissolves and
hydrogen sulphide, H2S, is produced.
Write the balanced redox equation
for this reaction.
86 Write a balanced equation that
describes each of the following
chemical reactions:
a) Ethyne, C 2 H 2 , burns in air,
forming gaseous carbon(IV)
oxide, CO2, and water, H2O.
b) When heated, pure aluminium
reacts with air to form
aluminium(III)oxide, Al2O3
c) Pure iron reacts with dilute
tetraoxosulphate(VI)acid
solution to form solution of
iron(III)tetraoxosulphate(VI),
Fe2(SO4)3 and gaseous hydrogen.
d) Gaseous water and hot carbon
react to form gaseous hydrogen
 and carbon(II) oxide, CO.
87 Balance the following equations:
a) Al + H2SO4 → Al2(SO4)3 + H2
b) Fe + H2O → Fe3O4 + H2
c) NaClO3 → NaCl + O2
d) PCl3 + H2O → POCl3 + HCl
88 How many grams of potassium
chloride, KCl are produced by
decomposing 118 grams of potassium
trioxochlorate(V), KClO3?
89 How many grams of oxygen will be
required to react completely with
14.6 grams of sodium in order to form
disodium oxide, Na2O?
90 How many grams of copper will be
needed to completely displace silver
from 208 cm3 of 0.10M solution of
silver trioxonitrate(V), AgNO3?
91 a) Give three pieces of information
which the following equation
does not give about the reaction
Zn(s) + MgCl2(ag)→ Mg(S) + ZnCl2(ag)
b) If 12.5 grams of copper are reacted
with an excess of chlorine, then
25.4 grams of copper(II)chloride,
CuCl2, are obtained. Calculate
the theoretical yield and the
percentage yield.
92 Iron metal reacts with a copper(II)
tetraoxosulphate(VI), CuSO4 solution
to produce copper metal and iron(II)
tetraoxosulphate(VI), FeSO4.
a) Which is more active: iron or
copper?
b) What will you observe when the
reaction takes place?
c) How many moles of copper will
be produced if 5.45 grams of iron
are placed in 135 cm3 of a 0.65M
solution of CuSO4?
d) How many grams of copper will
be produced?
259
e) How many atoms of copper will
be produced?
93 a) The specific heat of iron is greater
than the specific heat of gold.
What is the meaning of this
statement?
b) At the microscopic level, what
form does the energy take
when we add heat to raise the
temperature of a solid, a liquid,
or a gas?
94 a) I s t h e m e l t i n g o f i c e a n
endothermic change or an
exothermic change?
b) Which requires more energy:
melting a ton of ice or boiling
away a ton of water?
c) What is the term used to describe
the heat produced or absorbed
when a chemical reaction takes
place at a constant pressure?
d) G for a reaction has a positive
value. What does that allow you
to say about the reaction?
e) The value of G for burning any
fuel is negative.
i) What does this tell you
about the spontaneity of the
reaction?
ii) What happens to the entropy
of the universe when this
reaction takes place?
95 Methane gas, CH4, cannot be formed
by the direct reaction of graphite
(the standard state of carbon) and
hydrogen gas. However, use these
heats of reaction to calculate the heat
of formation of methane.
C(s) + O2(g)-→ CO2(ag) ∆H = - 393.5kJ/mol
2H2(g) + O2(g)→ 2H2O(g)
∆H = -571.7kJ/mol
CH4(g) + 2O2(g)→ CO2(g) + 2H2O 99 For the reaction 2HI (g)  H 2(g)
∆ H = -890.3kJ/mol + I 2(g) , calculate the equilibrium
concentration of HI at 698 K (425°C)
96 a)T h e f o l l o w i n g re a c t i o n i s
if the equilibrium concentrations are
spontaneous:
[H2] = 2.90 × 10-3 and [I2] = 1.70 × 10-3.
CaO(s) + SO3(g) → CaSO4(g)
100 The equilibrium concentrations of
Indicate the sign of each value
sulphur (IV) oxide, SO2-, and O2 are
i) ∆G ii) ∆S iii) ∆H
each 0.0500Meq = 85.0 at 25°C for the
b) The heat of formation of sodium
reaction
hydroxide is -427 kJ/mol.
2SO2(g) + O2(g)  2SO3(g)
Calculate the heat of formation
Calculate the equilibrium
(∆Hf) for each of the following:
concentration for sulphur(VI)oxide,
i) 1 . 3 7 m o l e s o f s o d i u m
SO3, at this temperature.
hydroxide
101 Use Le Chatelier ’s principle to
ii) 4 7 . 0 g r a m s o f s o d i u m
predict how the changes listed will
hydroxide
affect the following equilibrium
97 a) State two ways by which the
reaction.
number of effective collisions
2Hl(g)  H2(g) + I2(g) + 25.9kJ
between reactants can be
a) What is the effect on the concen-
increased.
tration of HI if a small amount
b) How does a catalyst increase
of H2 is added?
collision efficiency?
b) What is the effect on the concen-
98 a) For the reaction
tration of HI if the pressure of
2SO 2(g) + O 2(g) → 2SO 3(g) ∆H
the system is increased?
is negative. Explain now the
c) What is the effect on the concen-
following factors will affect the
tration of HI if the temperature
yield of sulphur(Vl)oxide:
of the system is increased?
i) decrease in temperature
d) What is the effect on the concen-
ii) increase in pressure
tration of HI if a catalyst is
iii) addition of catalyst
added?
b) Describe how sulphur(VI)
e) Write down the equilibrium
oxide is converted to
expression for this reaction.
tetraoxosulphate(VI) acid.
f) At 698 K (425°C), the
c) On warming crystals of sodium
equilibrium constant is 1.88 ×
chloride with concentrated
10-2. Does equilibrium favour
tetraoxosulphate(IV) acid, a gas
the formation of the reactant or
was evolved.
the products?
i) Name the gas.
102 Sketch a potential energy curve
ii) List two physical properties
for an endothermic reaction. Label
of the gas.
the parts representing the activated
iii) Write down an equation for
complex, activation energy, and change
the reaction.
in enthalpy.

260
103 Hydrogen peroxide reacts with
hydrogen ions and iodide ions
according to the following equation:
H+ + I– + H2O2 → H2O + HOI……..(i)
The mechanism often suggested for
this reaction is:
H+ + H2O2 → H3O+2 fast………….(ii)
H3O2+ + I– → H2O + HOI slow…(iii)
a) Show that adding equations (ii)
and (iii) gives equation (i).
b) How would you expect
the rate to be affected if the
concentration of I– is doubled?
c) How would you expect
the rate to be affected if the
concentration of H+ is doubled?
104 Name three types of carbohydrates,
and give an example of each type.
What is the difference between a
saturated and an unsaturated fat?
Draw the general structure of an
amino acid. How is DNA related to
RNA?
105 Discuss the effect of each of the
following on the position of
equilibrium of a reversible reaction,
the rate at which the equilibrium
is attained, and the value of the
equilibrium constant:
a) temperature
b) pressure
c) catalyst
106 Wr i t e a n e x p re s s i o n f o r t h e
equilibrium constant K c or K p as
appropriate for the following reaction
at equilibrium and indicate the units
in each case:
A + B  C + 2D
where under the condition of the
experiment
a) A, B, C and D are all gases.
b) A, B, C and D are all liquids.
261
c) A, B, C are solids and D is a
gas.
107 Ethanol and phenol (hydroxybenzene)
contain a common functional group.
a) i) Name one reagent that can be
used to distinguish between
the two compounds.
ii) S t a t e w h a t w o u l d b e
observed if each of the
compounds is treated with
the reagent you have named.
b) An aqueous solution of phenol
is acidic to litmus whereas that
of ethanol is neutral. Explain the
observation.
c) Phenol and ethanol react with
ethanoyl chloride to give a
similar product.
i) Write an equation for the
reaction and name the
organic product in each
case.
ii) Outline a mechanism for the
reaction between phenol
and ethanoyl chloride.
108 a) Write equations to show how
phenol (hydroxybenzene) can
be prepared from benzene and
chlorine on an industrial scale.
b) Write an equation, state the
condition and indicate a
mechanism for a reaction in
which ethanol reacts differently
from phenol.
109 The halogens, fluorine, chlorine,
bromine and iodine, are in Group
VII of the periodic table. Discuss the
reaction of each of these elements
with
a) water.
b) aqueoussodium hydroxide.
110 a) Explain what is meant by enthalpy water is added to a mixture of
of a reaction. cement and sand.
b) Briefly describe how the standard 113 Using the reaction sequences shown
enthalpy of a reaction which below, answer the questions which
takes place in solution can be follow. These questions concern the
determined in a laboratory. conditions and reactants needed for
c) State two conditions necessary for the various conversions.
the reaction you have described. Which step
111 The standard enthalpy of combustion a) requires the use of a strong acid
of methanol is - 238.9kJ mol-1 and the catalyst?
standard enthalpies of formation b) can be brought about by heating
of carbon(IV) oxide and water are alone?
-393.7kJ mol -1 and -285.9kJ mol -1 c) results in the production of
respectively. hydrogen chloride?
a) Write an equation for the complete d) involves the production of an
combustion of methanol. ionic compound?
b) C a l c u l a t e t h e e n t h a l p y o f 114 A compound X contains 66.7%
formation in methanol. carbon and 11.1% hydrogen, the rest
112 Cement is a mixture of inorganic being oxygen.
compounds and is widely used in a) Determine the empirical formula
the construction industry. of X.
a) i) Name the processes by which b) The vapour density of X is
cement can be manufactured. 36. Determine the molecular
ii) Name the main raw materials formula of X.
used in the manufacture of c) X reacts with 2,4-dinitrophenyl
cement. hydrazine to form a yellow
b) Describe briefly how cement is precipitate. Write the structural
manufactured and explain the formulae and the systematic
main physical and chemical names of all the isomers of X.
changes involved. d) When X is reacted with iodine
c) Describe what happens when in the presence of sodium
hydroxide, a yellow precipitate
A is observed.
CH3COOH CH3COONH4
i) Which one of the structures
you gave in (c) is the structure
E of X?
B ii) Name the yellow precipitate
CH3COCl formed.
C iii) Write the equation for the
reaction.
CH3COOR 115 Give the structural formulae and
CH3CONH2
D systematic names for three different

262
 esters. Write an equation and name
the ester formed when ethanol reacts
with ethanoic acid. What is the
difference between a fat and an oil?
Briefly describe how fats and oils can
be converted into soaps.
116 Describe a chemical test that can be
used to distinguish between starch
and glucose.
a) What are carbohydrates?
b) How would you obtain a
sample of alcohol (ethanol) from
cassava?
c) What is the action of dilute
hydrochloric acid on sucrose?
117 a) Define the term ‘saponification’
and write an equation for
the saponification of
tripalmitylglycerol, the triester of
palmitic acid CH3(CH2)14CO2H.
b) How many grams of invert sugar
can be produced when 1.00 g of
sucrose, C12H22O11, reacts with
water?
118 a) N a m e t h re e m a c ro s c o p i c
properties by which we can
determine the attainment of
chemical equilibrium.
b) In a flask initially containing
colourless molecules of nitrogen
tetraoxide, N 2O 4, the brown
colour characteristic of NO 2,
appears, and then the colour
steadily becomes darker. Is this
system in equilibrium? Explain.
c) In (b), if the brown colour
b e c o m e s d a r k e r, w h a t i s
happening to the concentration
of the NO3e?
What is happening to the
concentration of the
263
nitrogentetraoxide as the colour
deepens?
d) What, specifically, is equal in
a chemical reaction that is in
equilibrium?
119 The chemical formula C2H6O exists
as two structural isomers. Draw each
isomer and identify the functional
group in each case. Predict how the
boiling points and solubilities in
water of the two compounds differ.
Explain the basis of your predictions.
120 a) What features of an organic
molecule influence its chemical
behaviour?
b) What is a ‘functional group’?
c) From the names of compounds
listed, identify the functional
group each molecule contains:
i) propanol
ii) ethylamine
iii) butanone
iv) methoxymethane
v) ethanal
vi) ethylamide
vii) benzene -1,4-dicarboxylic acid
viii) ethylmethanoate
121 a) Name the units that make up the
following large molecules:
i) proteins
ii) carbohydrates
iii) nucleic acids
b) What is an enzyme?
122 Draw the molecular structures of
fructose and glucose. How do they
differ?
123 Explain how it is possible for twenty
amino acids to make the millions
of proteins that exist in living
organisms.
124 Hydrogen iodide decomposes when
heated according to the equation
 2HI(g)→ H2(g) + I2(g) ∆H = + 11.3kJ mol-1
a) Write the expression for the
equilibrium constant Kc for the
reaction.
b) 1.54 g of HI was heated in
600 cm3 bulb at 803 K (530°C).
When equilibrium was attained,
the bulb was rapidly cooled to
room temperature and broken
under potassium iodide solution.
The iodine formed from the
decomposition required 67.0 cm3
of 0.1M sodium trioxosulphate(II),
Na2S2O3, solution for complete
reaction. Calculate
i) the amount in moles of
hydrogen iodide in 1.54 g.
ii) the amount in moles of iodine
formed when hydrogen
iodide was decomposed.
iii) the value of K c at 803 K
(530°C).
c) State what would be the effect on
the value of Kc if
i) the temperature was raised
from 803 K (530°C) to
1 073 K (800°C).
ii) the volume of the bulb was
increased to 1 200 cm3.
125 a) Give the name of an alkanoate
and write the chemical equation
for its formation.
b) i) What is a monomer? State
the monomers of protein.
ii) Write the two functional
groups present in the
monomers of protein.
iii) What is the name given to
the reaction which leads to
the formation of proteins
from their monomers?
264
126 State the type of chemical processes
involved in the manufacture of
a) polythene from ethene.
b) soap from vegetable oils.
c) margarine from vegetable oils.
d) ethene from kerosene fraction of
petroleum.
e) naphthalene from crude oil.
127 Given the compounds A and B as
shown below:
H Cl H H
\ /
\ /
A C = C : C = C B
/ \ / \
Cl HH Cl Cl
a) What can you say about the two
compounds?
b) State the names of A and B.
c) Do you expect the chemical
properties of the two compounds
A and B to be the same? Give
reasons for your answer.
128 State the direction of the equilibrium
shift (i.e. direction of the reaction that
is favoured) in these reactions when
the pressure is increased):
PCl3(g) + Cl2(g) → PCl5(g)
2NO(g) → N2(g) + O2(g)
4NH3(g) + 5O2 4NO(g) + 6H2O(g)
129 Which of the following reactions
would you expect the product to be
increased at higher pressures?
a) N2(g) + O2(g)  2NO(g)
b) H2(g) + I2(g)  2HI(g)
c) N2(g) + 3H2(g)  2NH3(g)
d) 2SO2(g) + O2(g)  2SO3(g)
130 The equilibrium equation for the
formation of ammonia is
N2(g) + 3H2(g)  2NH3(g)
At 473 K (200°C), the concentrations
of nitrogen, hydrogen and ammonia
 at equilibrium are measured and
found to be [N 2 ] = 2.12, [H 2 ] =
1.75 and [NH 3] = 84.3. Calculate
the equilibrium constant at the
temperature given.
131 The equilibrium concentrations of
sulphur(IV)oxide, SO2 and oxygen,
O2 are each 0.500M and Keq= 85.0 at
25°C for the reaction
2SO2(g) + O2(g)  2SO3(g)
Calculate the equilibrium concen-
tration for sulphur(VI)oxide, SO3 at
this temperature.
132 a) In an equilibrium expression for
a reaction, do the concentrations
of the reactants appear in the
numerator or the denominator?
b) i) Does a large equilibrium
constant (Keq) mean that the
products or reactants are
favoured at equilibrium?
State which one.
ii) Does a small equilibrium
constant (K eq) mean that
the products or reactants
are favoured at equilbrium?
State which one.
133 a) A hydrocarbon is known to
contain 7.7% and 92.3% by
mass of hydrogen and carbon
respectively. The relative molar
mass of the compound is 78.
i) Wh at is th e emp iric a l
formula of the compound?
Derive its molecular
formula.
ii) Wr i t e t h e n a m e a n d
structural formula of the
hydrocarbon.
134 Two compounds X and Y, containing
hydrogen and carbon were each
treated with acidified potassium
265
tetraoxomangnanate(VII), KMnO4
solution. It was found that X
decolourised the solution and Y did
not. Which of the two compounds X
Y will undergo
a) polymerisation?
b) s u b s t i t u t i o n a n d a d d i t i o n
reactions?
c) substitution reaction only?
135 The equilibrium constant for the
gaseous reaction
H2 + I2  2HI
is 50.2 at 721 K (448°C). Calculate the
number of grams of HI that are in
equilibrium with 1.25 mol of H2 and
63.5g of iodine at this temperature.
136 H o w w i l l a n i n c re a s e i n ( a )
temperature and (b) pressure affect
the equilibrium of each of the
following:
a) N2(g) + 3H2g  2NH3(g) ∆ H = 92.2kJ
b) H2O(1)  H2O(g) ∆H = 41kJ
c) N2(g) + O2(g)  2NO (g) ∆H = 181k J
d) CaCO3(s)  CaO(s) + CO2(g)
∆H = 176kJ
e) 3O2(g)  2O3(g) ∆H = 285kJ
137 a) Define the terms hydrophilic
and hydrophobic. What factor
or factors determine whether
a compound is hydrophilic or
hydrophobic? Give an example
of each class of compound.
b) What is an enzyme? Define its
role in chemical reactions within
living systerns.
138 a) Define the following: amino acid,
peptide linkage and protein.
b) What is the ordinary meaning
of carbohydrate. How did this
name arise?
c) Write the name and formula
for one example each of a
 monosaccharide, a disaccharide
and a polysaccharide.
139 a) What is the relationship between
nucleic acids, amino acids and
proteins?
b) How do fats and oils differ in
composition?
c) Which carbon atoms in glucose
are asymmetric?
140 a) Using copper or its compounds as
a reference, give three properties
which are characteristic of
transition metals.
b) Explain the following:
i) T h e a d d i t i o n o f
ammonia solution to
an aqueous copper(II)
tetraoxosulphate(VI) gives
a pale blue precipitate
at first and then a deep
blue solution when more
ammonia solution is added.
ii) A q u e o u s c o p p e r ( I I )
tetraoxosulphate(VI) turns
blue litmus paper red.
iii) Copper(I) compounds are
sometimes white and rarely
show catalytic properties,
whereas those of copper(II)
are usually coloured and
can act as catalysts for many
reactions.
141 a) State how each of the following
properties of the elements in
Group II will change with
increasing atomic number:
i) atomic radius
ii) ionisation energy
iii) strength as reducing agents
iv) vigour of reaction with
chlorine
v) electropositivity
266
b) In each case in (a), explain why the
five properties change in the way you
have suggested.
142 The elements in Group 1A are lithium,
sodium, potassium, rubidium and
caesium.
a) The first member of a group often
shows anomalous properties.
Give two instances in which
the behaviour of lithium is
anomalous.
b) Describe briefly five properties
which show a general gradation
as the group is descended from
lithium to caesium.
c) Explain the meaning of the term
ionisation energy.
d) How are ionisation energies
related to the reactivity of these
elements?
e) Why is the ion Na+ formed in
normal chemical reactions rather
than the ion Na2+ ?
143. Draw up a table to compare the
first three elements in Group IIA
of the Periodic Table: beryllium,
magnesium and calcium. Your table
should include:
a) electronic configurations
b) relative values of ionisation
energies
c) methods of extraction of elements
d) action of water, acids and alkalis
on the elements
e) the basic strength of oxides and
hydroxides
144 a) What is the principal ore of tin?
b) Explain briefly, with an equation,
how tin is obtained from its
principal ore.
c) What are the main uses of tin and
its alloy?
 d) What are the relative advantages
and disadvantages of tin plating
and galvanising iron (zinc
plating) in order to prevent
corrosion?
145 a) What do you understand by the
term transition metal?
b) With explanations, state which
of the following are transition
metals: i )
scandium
ii) iron
iii) zinc
c) Although the salts of transition
elements are usually coloured,
there are several copper(I)
compounds which are white.
Suggest an explanation for this.
d) The densities of transition
elements in the same period
gradually increase with relative
atomic mass. Why is this so?
146 a) Most metals occur naturally in
a combined state because they
are too reactive to occur native
(uncombined). However, a few
metals do occur native.
Give examples of
i) two metals which never
occur native.
ii) two metals which occur both
native and combined.
iii) two metals which almost
always occur naturally in
an uncombined form.
b) Before extraction of a metal
can begin, many ores must be
purified and concentrated. State
two different processes by which
this is done.
c) The primary reduction of an ore
does not always produce metal
267
of sufficient purity for the uses
to which it will be put. Outline
two different processes by which
further purification is carried
out.
147 10 g of an impure iron(II) salt were
dissolved in water and made up
of 200 cm 3 of solution. 20cm 3 of
this solution acidified with dilute
tetraoxosulphate(VI)acid required
25 cm3 of 0.03M solution of potassium
tetraoxomanganate(VII) before a
faint pink colour appeared.
a) Write a balanced chemical
equation (or half-equations)
for the reaction of acidified
manganate(VII) ions with
iron(II) ions.
b) How many moles of iron(II) ions
react with 1 mole of MnO 4 ions?
c) H o w m a n y m o l e s o f F e 2 +
react with 25 cm 3 of 0.03M
solution of potassium
tetraoxomanganate(VII)?
d) How many grams of Fe2+ are
there in the 200 cm3 of original
iron(II) solution? (Fe = 56)
e) What is the percentage by weight
of iron in the impure iron(II)
salt?
148 Metals are usually obtained from
their ores by reduction. Describe
briefly and suggest reasons for the
methods of reduction used for the
following metals:
a) Zinc from zinc blende (ZnS)
b) Magnesium from magnesium
chloride extracted from seawater
c) Iron from haematite (Fe2O3)
149 a) D e s c r i b e c a r e f u l l y t h e
production of aluminium from
pure aluminium oxide by an
 electrolytic process (no account
of the purification of crude
bauxite is required).
b) Discuss the reasons why
i) a thermal reduction process
and
ii) electrolysis of the chloride
are not suitable large scale
methods for aluminium.
c) Explain the corrosion resistance
of aluminum to atmospheric
conditions. Mention three uses
of aluminum, stating clearly
in each case, the property
of the metal which makes it
particularly a suitable material
for the construction of the body
of aircraft.
150 Show, by means of equations, how
each of the following compounds can
be prepared in the laboratory:
a) Iron(II)chloride from iron
b) Iron(II)tetraoxosulphate(VI)-7-
water from iron
c) Aluminium hydroxide from
aluminium
d) Tetraamine copper(II)hydroxide
from copper
e) Diiron(III)tetraoxosulphate(VI),
Fe2(SO4)3 from iron
151 a) D e s c r i b e t h e e l e c t ro l y t i c
process for the production of
pure aluminium from pure
aluminium oxide.
b) Write equations showing how
aluminium reacts with the
following reagents:
i) Concentrated aqueous
sodium hydroxide
ii) Concentrated hydro chloric
acid
iii) Iron(III)oxide
268
c) What properties of aluminium
are illustrated by each of these
reactions?
152 a) Give the detailed electronic
configuration of iron (atomic
number 26).
b) Explain the formation of Fe2+
and Fe3+ ion.
c) How would you distinguish
between iron(II) and iron(IIl)
salts in the laboratory?
d) Write a balanced equation for
the reaction between Fe2+ and
Cr 2O 72– in an acidic aqueous
solution.
153 a) Account for the industrial
manufacture of iron.
b) Name the products and write a
balanced equation to illustrate
the reaction between iron and
steam.
c) How is steel produced from pig
iron?
154 a) Group II metals form only
one oxidation state. Show
how the metals achieve this.
Comment on the stability of the
metallic cations as the group is
descended.
b) What are the flame colours of
calcium, barium and strontium?
Why do magnesium compounds
fail to produce any visible flame
colour?
155 Give three different uses of aluminium
which depend on
a) its low density.
b) good electrical conductivity.
c) resistance to atmospheric
corrosion.
156 Give two uses of calcium
t r i o x o c a r b o n a t e ( I V ) , C a C O 3,
 as an important raw material in
chemical industries. Explain the
chemical functions of calcium
trioxocarbonate(IV) in one of such
industrial applications.
157 Calcium and zinc atoms have the
following electronic configurations:
Ca 1s22s22p63s23p64s2
Zn 1s22s22p63s23p64s23d10
a) Which of these elements would
have smaller values for metallic
and ionic radii?
b) Describe two chemical reactions
of calcium or its compounds
and show how these reactions
differ from those of zinc or its
compounds.
158 a) Outline the chemistry involved
in the extraction of iron from a
named oxide.
b) Give and explain two chemical
properties of iron which are
typical of a transition metal.
c) Give an industrial use of iron
which depends on its physical
properties.
159 Write the formula of the complex ion
formed in the following reactions:
i) Iron(II)tetraoxosulphate(VI),
FeSO 4 + excess potassium
cyanide, KCN.
ii) c C o p p e r ( I I )
tetraoxosulphate(VI), CuSO 4
+ excess concentrated
hydrochloric acid, HCl.

269
 Answers

Chapter 2 Chapter 3 Chapter 8

Section A Section A 1 B
1 1 D 2 D
3 A
2 2 E 4 D

3 3 B Chapter 9
Section A
4 4 A 1 8 6 A
2 C 7 B
5 5 C 3 D 8 D
4 B 9 A
Chapter 4 Chapter 5 5 D 10 C
Section A Section A 6 A 11 C
1 A 1 B 7 B 12 C
2 E 2 A 8 D 13 D
3 C 3 C
4 C 4 C
5 B 5 C TEST PAPER I
6 B 1 C 26 C
7 A 2 D 27 B
8 A 3 B 28 D
9 B 4 C 29 C
5 D 30 B
Chapter 6 Chapter 7 6 B 31 C
Section A Section A 7 B 32 B
1 A 1 B 8 D 33 A
2 C 2 C 9 C 34 C
3 B 3 C 10 C 35 C
4 B 4 A 11 D 36 B
5 B 5 E 12 C 37 D

270
13 B 38 A
14 B 39 C Section C
15 C 40 D 2 CH5N
16 D 41 B 3 75%
17 A 42 C 4 a) 32
18 C 43 C b) 6.24 dm3
19 C 44 D 5 1.8 g
20 C 45 C
21 D 46 B Test Paper II
22 C 47 A
23 D 48 B Section A
24 C 49 C 1 A 26 C
25 A 50 B 2 C 27 B
3 B 28 C
CHAPTER 10 CHAPTER 11 4 B 29 D
1 C 1 C 5 C 30 C
2 D 2 A 6 C 31 B
3 C 3 B 7 D 32 C
4 D 4 C 8 C 33 D
5 A 9 D 34 A
10 C 35 A
CHAPTER 12 CHAPTER 13 11 D 36 B
Section Section A 12 C 37 B
1 B 1 D 13 D 38 D
2 A 2 C 14 A 39 C
3 D 3 C 15 C 40 C
4 D 4 B 16 C 41 D
5 C 5 D 17 A 42 A
6 A 6 A 18 D 43 D
7 B 7 B 19 C 44 D
8 D 8 B 20 B 45 C
9 A 9 C 21 D 46 C
10 C 10 D 22 C 47 B
CHAPTER 12 23 B 48 C
Section B 24 A 49 C
3 i) a 25 C 50 B
ii) b
iii) a
iv) b Section B
v) a 2 a) i) 0.01 mol hydrocarbon and
4 ii) 2.4 g 0.03 mol CO2
iii) 1.6 g ii) C3H6

271
 iv) 1080 cm3 O2 b) 18 g/mol B
v) 0.54 g c) 29 g/mol D
3 c) 58.5 g d) 17.9 g/mol D
69 Al = 36.08%
Section C S = 63.92%
1 –1370 kJ mol–1 70 0.100 mol
2 0.267 g Cu 73 53 grams
74 4.50 M
General test papers 79 a) 2.75 g Cu
5 83.3% b) 0.0255 mol Cu
22 a) 27.3% 80 9.32 g Pb(NO3)2
b) 21 g 81 b) 4.70 g Pb(NO3)2
24 c) i) 0.1 c) 9.06 g PbCl2
c) ii) 2.24 dm3 84 9.32 grams
25 c) 44.0 g 88 71. 8 g KCl
26 c) 48.6 g/mol 89 5.08 g O2
27 a) 53.2 g Na2SO4 90 0.660 g Cu
28 a) 2 g/mol 91 b) theoretical yield = 26.4g
31 iii, v, vi d) 5.6 g
32 b) i) 0.05 mole e) 0.087 × 6.0 × 1.023 atoms
0.1 mole 95 C(s) + 2H(g) × CH4(aq) H = - 74.9 kJ
iii) 1 mole HFCH4 = -74.9 kJ/mol
iv) 2 mole 99 [HI] = 1.63 × 10-2 moles per litre
c) 3.3 moles/dm3 100 0.103M SO3
33 b) 353 g/dm3 117 b) 1.05 g of invert sugar
44 a) 22.74dm3 130 Keq = 626
b) 1 mol 131 0.103 M
c) 6.023 × 1023 135 507 g
48 c) 6.81 g
49 6.02 × 1023
56 a) 510 coulombs
b) 2.586 × 105
c) 2.96 3.0
58 a) (7.3 × 1023; 1.2 mol)
b) (3.0 × 1023; 0.50 mol)
c) (1.2 × 1024; 2.0 mol)
d) (3.6 × 1022; 0.6 mol)
e) (2.4 × 1024; 2.0 mol)
61 E° = + 1.27 V
62 a) Fe2 (SO4)3
b) Fe2 (SO4)3
64 a) 40 grams

272