INORGANIC

CHEMISTRY II

MOHAMMED SULEIMAN (Author)

A.S.P ICHADO (Co-Author)

i
ISBN: 978-978-50497 – 3 – 2

First print 2013

No part of this publication may be reproduced in any process e.g photocopy,

recording storage in retrieval system or transmitted by any means without prior

permission of the copyright owner.

Published by:

AGUNBAY PUBLISHERS

08030756846

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 DEDICATION

This book is dedicated to the Almighty Allah for his guidance, protection,
sustenance and the wisdom for the compilation of this text

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 ACKNOWLEDGEMENT

First and foremost, we thank God for making this work possible and also for His
immeasurable wisdom given to us.

We are grateful to the earlier author in the subject who has shaped our thought on
various topics.

Our gratitude is also extend to our colleagues, friends as also to our students, for
the invaluable general helpfulness and many constructive suggestions and
contributions in bringing to reality of this book

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 PREFACE

The aim of this book is to present core Inorganic chemistry knowledge that is
desirable for students of higher institutions. Care has been take to make the
treatment of the subject simple and accessible to the average students.

This book is mainly about the chemistry of the element, which is properly regarded
as Inorganic chemistry. The book incorporates information's on the chemistry
element regardless of the sources of that chemistry.

To make the work more comprehensive and informative, the authors have
consulted many authoritative books, we are great full to all those great scholars
whose work are cited or substantially reproduced.

There can be no claim to originality except in the manner of treatment and much of
the information has been obtained from the books.

MOHAMMED SULEIMAN (Author)

A.S.P ICHADO (Co-Author) 2024

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 TABLE OF CONTENTS

Title page - - - - - - - - - - i

Dedication - - - - - - - - - - ii

Acknowledgments - - - - - - - - iii

Preface - - - - - - - - - - iv

Table of contents - - - - - - - - - v

CHAPTER ONE

1.0 INTRODUCTION - - - - - - - - 1

CHAPTER 2

2.0 THE ALKALINE METALS (GROUPIA ELEMENTS) - - 4

2.1 Alkaline Metals - - - - - - - - 4

2.2 Electronic Configuration - - - - - - - 5

2.1 Properties of Group IA element: Soft, Lew Melting point and Low density
- - - - - - - - - -
8

2.2.2 Atomic Properties - - - - - - - - 13

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2.3 Physical Properties - - - - - - - - 15

CHAPTER 3

3.0 THE SIMILARITIES IN THE CHEMICAL PROPERTIES OF ALKALINE

METALS

3.1 Reactivity - - - - - - - - - 16

3.2 General Properties of Group IA Atom and Their Corresponding ions 23

3.2.1 Size of atoms and ions - - - - - - - 24

3.2.2 Ionization energy - - - - - - - - 24

3.2.3 Electronegativity - - - - - - - - 27

3.3 Differences between lithium and other Group IA Anomalous Behavior of

lithium) - - - - - - - - - - 29

CHAPTER 4

4.0 THE ALKALINE EARTH METALS (GROUP IIA ELEMENTS) - 31

4.1 Introduction - - - - - - - - - 31

4.2 Group IIA Elements - - - - - - - - 31

4.3 Electronic configuration - - - - - - - 33

4.3.1 Atomic and Ionic Size - - - - - - - 34

4.3.2 Melting and Boiling Point of Group IIA - - - - 37

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4.3.3 Ionization Energy - - - - - - - - 37

4.3.4 Electronegativity - - - - - - - - 39

4.3.5 Melting and boiling points - - - - - - 40

4.4 The Gradation properties of elements in Group II - - - 42

4.4.1 Atomic Properties - - - - - - - - 42

4.4.2 Physical properties - - - - - - - 42

4.4.3 Chemical properties of Group IIA Metals - - - - 42

4.5 Some Comparism in Chemical properties - - - - 46

4.6 Solubility and Lattice Energy - - - - - - 50

4.7 hydration energy - - - - - - - - 51

4.8 Anomalous Behaviour of Beryllium - - - - - 51

4.9 Resemblance of Lithium with Group IIA - - - - 53

CHAPTER FIVE

EFFECTS OF THE PRESENCEOF GROUPII METALION IN WATER 55

5.1 Hard Water - - - - - - - - - 55

5.1.1Types of Hardness - - - - - - - - 56

5.1.2 Advantages of Hard water - - - - - - 67

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5.1.3 Disadvantage of Hard water - - - - - - 68

CHAPTER 6

GROUP II ELEMENTS (BORON GROUP) - - - - 72

6.1 Introduction - - - - - - - - - 72

6.2 Electronic configuration - - - - - - - 74

6.2.1 Atomic and Ionic size - - - - - - - 75

6.2.2 Melting and Boiling point - - - - - - 76

6.2.3 Electropositive Character - - - - - - - 76

6.2.4 Ionization Energy - - - - - - - - 77

6.4 Graduation in the properties of the Elements of Group III - - 79

6.4.1 Metallic Characteristic - - - - - - - 80

6.4.2 Halides - - - - - - - - - 80

6.4.3 Oxidation states - - - - - - - - 83

6.4.4 Hydrides - - - - - - - - - 84

6.4.5 Oxides - - - - - - - - - 85

6.5 Difference between Boron and other members In the Group - - 86

6.6 Uses of the Elements - - - - - - - - 87

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CHAPTER 7

GROUP IV ELEMENTS (CARBON GROUP) - - - - 94

7.1 Introduction - - - - - - - - - 94

7.2 Electronic Configuration of the Element - - - - - 95

7.3 Physical Characteristics of Group IV Element - - - - 98

7.3.1 Boiling Point - - - - - - - - 98

7.3.2 Densities - - - - - - - - - 99

7.3.3 Atomic Radii - - - - - - - - 99

7.4 Graduation in the Properties of the Elements - - - - 99

7.4.1 Metallic Characteristics - - - - - - - 100

7.4.2 Nature of Bonding in Their Halides - - - - - 100

7.4.3 Relative stability of the oxidation state - - - - - 101

7.4.4 Acidic/ Basic Nature of their Oxides - - - - - 101

7.5 Diagonal relationship between Boron and silicon - - - 110

7.6 Why the properties of the First Element in the Group Differ from those of the
other Element in the Group due to - - - - - - 111

7.7 Uses of Group (IV) Elements - - - - - - 112

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CHAPTER 8

8.0 HALOGENS - - - - - - - - - 114

8.1 Introduction - - - - - - - - - 114

8.2 The Occurrence of Halogens in Nature - - - - - 114

8.3 The Electronic Configuration of the Halogens - - - - 119

8.4 Elemental forms of Group VII Elements - - - - - 121

8.5 Physical Properties - - - - - - - - 121

8.6 Chemical properties - - - - - - - - 122

8.6.1 Oxyacids of Chlorine - - - - - - - 123

8.6.2 Hydrogen Halides - - - - - - - - 126

8.6.3 Metal halides - - - - - - - - 127

8.6.4 Inter-halogen compounds - - - - - - - 128

8.6.5 Organ Halogen Compounds - - - - - - 128

8.6.6 Polyhalogenated compounds - - - - - - 129

8.6.7 Reactions of Halogens with Water - - - - - 129

REFERENCES - - - - - - - - - 134

INDEX - - - - - - - - - - 135

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 CHAPTER ONE

INTRODUCTION

Inorganic chemistry is a branch of chemistry that deal with the properties and
behaviors of inorganic compounds. Inorganic compounds are those that are not
biological and characterized by not containing any hydrogen and carbon bonds. It
is almost easier to discuss this field in terms of what is not organic chemistry.
Organic chemistry is the study of any chemical reaction that involves carbon,
which is the element that all life based on.

The term organic has traditional referred only to animal and plant matter, so there
is common misconception that organic chemistry always refers to life processes or
that inorganic chemistry refers to all those that does not. This assumption is
inaccurate. Many chemical processes veer always from this line of thinking and
there many chemical life processes that depends on inorganic chemical processes.

There are exceptions to every rule, although carbon is the main compound can
contain carbon too. For example, carbon on element in organic chemistry,
inorganic chemical monoxide and carbon dioxide both contain carbon but are
inorganic compounds. Carbon dioxide, in particular, is also very important to
chemical processes necessary for life, especially plants' life. The truth is that the
line between inorganic and organic chemistry are often blurred.

There are many branches of inorganic chemistry available for specialization.

Geochemistry is the study of chemistry of the Earth and other plants and its covers
the chemical composition of rocks and soils. Within the field of geochemistry,

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there are several subfield including isotope geochemistry, Cosmo-chemistry and
biogeochemistry.

Another type is physical chemistry which relates to the concept of physics in

chemical system. This field is also sometimes called physic chemistry. It's used the
principles of thermodynamics, quantum chemistry and kinetics as its basis.

Inorganic chemistry lends itself to many different industries, including education,

environmental science and governmental agencies. A scientist who focuses on this
field may create or improve formulae for household cleansers. He may also work
in any chemical research coming up with new ways to manipulate the properties of
elements into useful functions.

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 CHAPTER TWO

THE ALKALINE METALS (GROUP IA ELEMENTS)

2.1 Alkaline Metals

The alkaline metals are a group in the periodic table consisting of element such as
Lithium (Li), Sodium (Na), Potassium (K), Rubidium (Rb), Caesium (Cs) and
Francium (Fr). They are all metals; therefore they possess all the metallic
properties.

They are found in S-block orbital (i.e they are the first group of element in the
periodic table). They are called alkaline metals because when dissolved in water
they form alkaline solution. They all possess one outermost electron, hence they
are highly reactive. The alkaline metals provide the best example of group trends
in properties in the periodic table with element exhibiting well characterized
homologous behavior.

The alkaline metals have very similar properties: they are all shiny, soft, highly
reactive metal at standard temperature, pressure, and readily lose their outermost
electron to form cations with charge +1. They can all be cut easily with a knife due
to their softness, exposing a shiny surface that tarnishes rapidly in air due to
oxidation. Because of their high reactivity, they are store in oil or kerosene to
prevent reaction with the air. They are found naturally only in salts and never as
free elements. All the discovered alkali metals occur in nature; in order of
abundant, Sodium (Na), is the most abundant, followed by Potassium (K), Lithium
(Li) Rubidium (Rb), Caesium (Cs) and finally Francium (Fr), which is very rare

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due to its extremely highly radioactivity and thus occur only in traces due to its
presence in natural decay chain.

All the alkaline metals react with water with the heavier ones reacting more
vigorously than the lighter ones to form hydrogen gas and a solution of alkali
metal's hydroxides, which in each case is a strong base. These metals also react
vigorously with varieties of other substance, for example, oxygen (in the air) and
halogens (i.e fluorine, chlorine, bromine, e.t.c).

2.2 Electronic Configuration

Electronic configuration of an element is the arrangement of electrons in its atomic

orbital's when it is at ground state and atomic orbital referred to any point or space
where there is a high possibility of finding electron. There are four types of atomic
orbitals, which include s. p. d, and f orbitals. Theses atomic orbitals represent
energy levels in the shell that surrounded the atom.

The first shell which is the closest to the nucleus is known as K-shell and has only
S-orbital. The second (L-shell) has s and p orbitals as its energy level. The third,
fourth, fifth sixth and the seventh shells are M, N, O, P, and Q shells respectively
and may contain S, P, D and F orbitals.

The electron distribution in the atomic orbitals is as shown below:

Atomic orbital Maximum electron distribution

S 2
P 6
D 10
F 14

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Electronic configuration of the alkali metals

Element Symbol Electronic configuration

Lithium 3Li 1s2 2s1

Sodium 11 Na 1s2 2s2 2p6 3s1

Potassium 19 K 1s2 2s2 2p6 3s2 3p6 4s1

Rubidium 37 Rb 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s1

Caesium 55 Cs 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s1

Francium 87 Fr 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f14
5d10 6p6 7s1

Group 1A elements are: lithium (Li). Sodium (Na), Potassium (K), Rubidium (Rb),
Caesium (Cs) and Francium (Fr) and they have the following atomic number of 3,
11, 19, 37, 55 and 87 respectively. They are univalent; hence they exhibit similar
chemical properties.

They ionize easily by the loss of one electron per atom hence powerful reducing
agents. They are good conductor of electricity and are highly electropositive. E.g

Na Na+ + e

K K+ + e

They react with cold water vigorously to liberate hydrogen gas and form alkalis
hence the name. e.g.

2K(S) + 2H2O(L) 2KOH(aq) + H2O(g)

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Their reactions increase down the group as the atomic number increases. They
form strong basic oxides which dissolve in water very strong alkalis.

2Na2O(S) + H2O(L) 2NaOH(aq)

Their trioxocarbonates (IV) with exception of lithium are not decomposed by heat.
Their trioxonitrates (V) are decomposed to give oxygen and dioxonitrate (III) salt.
E.g

2NaNO3(S) NaNO2(S) + O2(g)

2.2.1 Properties of Group IA element: Soft, Low melting point and Low
density

Some of the properties of group IA elements are softness, low density and low
melting point. Unlike most metals, the alkali metals are:

Soft: e.g sodium has the consistency of cold butter and potassium can be squeezed
like clay.

Lower melting and boiling points: the alkali metals also have lower melting and
boiling points than any other group of metals. Except for lithium, they all melt
below 1000C and Caesium melts a few degrees above room temperature. The
melting point of a substance is the point where its change state from solid to liquid
while the boiling point is a substance (in liquid state) is the point where the vapour
pressure of the liquid equals the environmental pressure surrounding the liquid and
the liquid change state to gas. As a metal is heated to its melting point, the metallic
bonds keeping the atoms in place weaken so that the metallic bonds eventually
break complete at the metal's boiling point. Hence, the melting point and the

xvii
boiling point of the alkali metals decrease down the group. The reason for this is
that, the strength of the metallic bonds of the alkali metals decrease down the
group and this is because metal atoms are hold together by the electromagnetic
attraction from the positive ions to the delocalized electron. As the atoms increase
in size going down the group (because their atomic radii increase), the nuclei of the
ions move further far away from the delocalized electron and hence the metallic
and boiling points.

Meanwhile, note that the increase nuclear charge is not a relevant factor due to
shielding effect.

Lower density: the density of a substance is defined as the mass per unit volume
of the substance and has the S.I unit grams per meter cube (g/m 3) or (g/cm3). Alkali
metals have lower density than most metals. Example lithium floats on lightweight
home hold liquid. These properties of alkali metals or unusual physical behavior
can be traced to their atomic size, the largest in their respective periods, and to the
ns' electronic configuration. Because the single valence electron is relatively far
from the nucleus, there is only a weak attraction between the delocalized electrons
and the atom cores. This week metallic bonding means that the alkali metal crystal
structure can easily deformed or broken down, which results in a soft consistency
and low melting point. These elements also have lower molar masses in their
period, so with their large atomic radii they have relatively low density.

The alkali metals all have the same crystal body structure (body center cubic) and
thus the only relevant factors are the number of the atoms that can fit into a certain
volume and the mass of one of the atoms. The first factor depends on the volume
of the atom and thus the atomic radius, which increases going down the group; thus
the volume of alkali atom increases going down the group. The mass of an alkali

xviii
metal atom also increase going down the group. Thus the trending for the densities
of the alkali metal depend on their atomic weight and the atomic radii: therefore,
the resultant trend is that the densities of the alkali metals increase down the group
on the table, with an exception at potassium.

The table below is a summary of the key physical and atomic properties of the
alkali metals.

Element Symbols Density Melting Boiling Atomic Ionic radius

(g/m3) point (0O) point (0O) radius (pm) (pm)
Lithium Li 0.834 180 1336 152 68
Sodium Na 0.968 98 883 186 98
Potassium K 0.890 63.5 759 227 133
Rubidium Rb 1.532 39 700 248 148
Caesium Cs 1.930 28.5 670 265 167
Francium Fr - - - - -

2.2.2 Atomic Properties

Atomic radius: atomic radius of an atom is defined as the distance of the closest
approach atom to another identical atom. The atomic radii of the alkali metals
increase down the groups. Because of the shielding effect when an atom has more
than one electron shell, each electron feels electric repulsion from other electrons
as well as electric attraction from the nucleus. In alkali metals, the outermost
electron only feels a net charge of 1 as the some of the nuclear charges (which is
equal to the atomic number) is cancelled by the inner electrons, the number of the
inner electron of alkali metals are always one less than the nuclear charge.
Therefore, the only factor which affects the atomic radius of the alkali metal is then

xix
number of electron shell. Since this number increase down the group, the atomic
number the alkali metals also increase down the group on the periodic table.

Ionic radius: the ionic radii of alkali metals also increase down the group and
much smaller than their atomic radii. This is because the group and the outermost
electron of the alkali metals is in different shell that the inner electron and thus,
when it is removed the resulting atom has fewer electron shell and it is smaller.
Additionally the effect of effective nuclear charge has increased and thus, the
electron was attracted more strongly to the nucleus and the 1onic radius decreases.

Atomic properties of Alkaline Metals

a. They have group electron configuration to be ns 1 (where n = 1, 2, 3, - - -)

and all members have the +l oxidation state and form an ion m + (where m =
metal).
b. In their respective period, their atoms have the largest size and lowest
ionization energy (IE) and electronegativity (EN).
c. Down the group, atomic and ionic size increases while ionization energy
(IE) and electronegativity (EN) decreases.

2.3 Physical Properties

Metallic bonding is relatively weak because there is only one valence electron.
Therefore, these metals are soft with relatively low melting and boiling points.
These values decreased down the group because larger atom cores attract
delocalized electrons less strongly.

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 CHAPTER THREE

THE SIMILARITIES IN THE CHEMICAL PROPERTIES OF ALKALINE

METALS

3.1 Reactivity

The reactivity of a substance refers to the chemical reaction of the substance singly
or the chemical reaction of two or more substances that interact with each other.

The reactivity of the alkali metals increases down the group. This is the result of
combination of two factors, the ionization energy and the atomi1zation energy of
the alkali metals. Because the ionization energy of the alkali metals decreases
down the group, it is easier for the outermost electron to be removed from the atom
and participate in the chemical reaction thus increasing reactivity down the group.
The atomization energy measures the strength of the metallic bond of the element,
which falls down the group as the atom increases in radius and thus the metallic
bond increases in length, making delocalized electron further away from the
attraction of the nucleus of the heavier alkali metal. Adding the atomization energy
and the ionization energy, gives a quantity closely related to (but not equal to) the
activation energy of the reaction of the alkali metals with another substance. The
quantity decrease going down the group and so does the activation energy; thus
chemical reactions can occurs faster ad reactivity increases down the group. The
alkali metals are extremely reactive elements. They are powerful reducing agents
and, thus always occur in nature as +1 action rather than on free metals (highly
endothermic reaction processes are required to prepare). The free metals
industrially form their molten salt. They form the following reactions:

xxi
 a) They reduce halogen and form ionic solid: in this process large quantity of
heat is released. The alkali metals are among the most electropositive
elements on he periodic table and thus tends to bond ionically to the most
electronegative elements (halogens) on the periodic table and the salt formed
are known as halides. This include sodium chloride (NaCl) salt otherwise
known as common salt. The reaction becomes higher from the lithium to the
caesium and drops form fluorine to iodine. All of the alkali metal halides
have the formula MX where M is an alkali metal and X is a halogen and is
all white ionic crystalline solids.

All alkali metals halides are soluble in water except for lithium fluoride (LiF),
which is insoluble in water due to its very high lattice enthalpy. This is due to
the small size of the lithium and fluorine ions (Li + and F-) causing the
electrostatic interaction between them to be very strong.

2M + X 2MX

Where M represent and alkali metal and X represents a halogen

For example

2Na(s) + Cl2(g) 2NaCl(s)

2M(s) + X2 2MX(s) (X=F, CI, Br, I)

b) All the alkali metals react vigorously or explosively with cold water:
producing an aqueous solution of the strongly base alkali metal hydroxide
and releasing hydrogen gas. I his reaction becomes more vigorously going
down the group: Lithium reacts readily with effervescence but sodium and

xxii
 potassium can ignite and rubidium and caesious sink in water and generate
hydrogen gas so rapidly that shock waves form in the water may shatter the
glass container. When an alkali metals is dropped into water, it produces an
explosion of which there are two separate stages. The metal reacts with
water first, breaking the hydrogen bonds in the water and producing
hydrogen gas; this takes place faster for the more reactive heavier alkali
metals. Second, the heat generated by the first part of the reaction often
ignites the hydrogen gas, causing it to burn explosively into the surrounding
air. This secondary hydrogen gas explosion produces the visible flame above
the bowl of water, lake or other body of water, not the initial reaction of the
metal with the water. The chemical reaction of the alkali metals and water is
as shown below; they react vigorously with water to release hydrogen gas
(Rb and Cs explosively) e.g.

2M(s) + 2H2O(L) 2MOH(aq) + H2

Where M represents an alkali metal

For example,

2Na(s) + 2H2O 2NaOH(aq) + H2(g)

Sodium water sodium hydroxide hydrogen

c) They reduce oxygen in air: so they tarnish rapidly (nut the product depend
on the metals e.g. Li forms oxides, (Li2O) Na forms peroxide Na2O2 while K,
Rb and Cs form superoxide. The alkali metals react vigorously with oxygen
at standard conditions. They form various types of oxides, such as simple
oxides. Their reactivity increases going down the group while lithium

xxiii
 sodium and potassium merely burn in the air, rubidium and caesium are
pyrophoric (spontaneously catch fire in the air):

4Li(s) + O2(g) 2Li2O(s)

K(s) + O2(g) KO2(s)

Note: for this reason Na and K are kept under paraffin oil, and Rb and Cs are
handled with gloves under inert argon atmosphere.

d) They also react with hydrogen to form ionic hydride: However, the ease
with which they do so decrease from lithium to caesium; e.g.

2Li(s) + H2(g) 2Li2H(s)

2Na(s) + H2(g) 2NaH(s)

e) Formation of sulphides: The elements all react with sulphur, forming

sulphide such as Na2S and polysulphides. Na, Sn where n = 2, 3, 4, 5 or 6.
The Polysulphide ions are made form zig-zag chain of sulphur atom. Sodium
sulphide can also be made by heating sodium sulphate with carbon or by
passing H2S into NaOH solution.

NaSO4 + 4C Na2S + 4CO

NaOH + H2S NaHS + H2O

NaOH + NaHS Na2S + H2O

xxiv
Some Important Compounds

1. Lithium chloride and lithium bromide, LiCl and LiBr because the Li' ion is
so small, Li salts have a high affinity for water. Then they are used in air-
cooling units.
2. Lithium carbonate Li2CO3 is used to make porcelain enamels and toughened
glasses and as a drug in the treatment of manic-depressive disorders.
3. Sodium chloride NaCl is used industrially in production of Na, NaOH,
Na2CO3/NaHCO3 and Na2SO4 it is also pin tied as table salt.

1. Na2CO3 and NaHCO3 are used as industrial base and also to make glass.
Hydrogen carbonate, which release CO2 at low temperature (500c to 1000 c)
used in baking powder and in fire extinguishers.
2. NaOH is used to make bleach, sodium phosphates and alcohol.
3. KNO3 powerful oxidizing agents used in gun power and fireworks.

3.2 General Properties of Group A Atom and Their Corresponding Ions

3.2.1 Size of atoms and ions

Group IA atoms are the largest in their horizontal period. When the outer electron
is removed to give a positive 10n the size decreases considerably, the tow reasons
for this;

(a) Because outermost shell of electron has been completely removed.

(b) Because the differences, in the charges now the nuclear charges overcome the
electronic changes. Generally cations are always smaller in size than their
corresponding neutral gaseous atoms.

xxv
Note:

a. Li+ is smaller in size than any member in the group.

b. For this smaller size of Li, mixes with sodium above 380 0 C and with K, Rb and
Cs even in molten.
c. Other metals such as; Na, K, Rb and Cs are miscible with each other in all
proportions.

3.2.2 Ionization energy

The first ionization energy of an element or molecules is the energy required to

remove the most loosely held electron form one mole of gaseous atoms of the
elements or molecules to form one mole of the gaseous ions with electric charge
+1. The factor affecting the first ionization energy are the nuclear charge, the
amount of shielding by the inner electron and the distance of the most loosely held
electron form the nucleus, which is always an outer electron in the main group
elements. The first two factors change the most the effective nuclear charge that
the most loosely held electron feels. Since the outermost electron of the alkali
metal always feel the same effective nuclear charge of +1, the only factor that
affect the first ionization energy of the alkali metals is the distance of the most
loosely held electron to the nucleus. Since the distance increases down the group,
the outermost electron feels less attraction form the nucleus and thus the first
ionization energy decreases. However, this trend broke at francium due to the
relativistic stabilization and contraction of 7s orbital: brining francium valence
electron relativistic calculations. This makes the outermost electron of first
ionization energy slightly beyond that of caesium. Consequently, the second
ionization of the alkali metals is much higher than the first ionization energy as the

xxvi
second most loosely held electron is part of full filled electron shell and thus
difficult to remove.

The first ionization energy of the alkali metals are shows on the table below:

Element Symbol First ionization energy (kj/mol)

Lithium Li 520.2
Sodium Na 495.8
Potassium K 418.8
Rubidium Rb 403.0
Caesium Cs 375.7

Their first ionization energies in this group are appreciably lower than those and
any other group in the periodic table. Due to their large size their outer electrons
are only held weakly by the nucleus, hence the energy required to remove this
outer electron is very small, As you move down the group the size of the atom
increase the outermost electrons become less strongly held. So the ionization
energy decreases. The second ionization energy is extremely high because it
involves removing electron from smaller positive ion and secondly it involves
removing of electron form a closes shell. The second electron is never removed
under normal condition.

3.2.3 Electronegativity

Electronegativity is a chemical property that describes the tendency of an atom or a

functional group to attract electron or electron density towards itself. This property
of an atom is affected both by its atomic number and the distance that its valence
electron resides from the charged nucleus. The higher the associated

xxvii
electronegativity number, the more an element or compound attracts electron
towards itself.

The electronegativity of the alkali metal decreases down the group as the atomic
number and the distance of the valence electrons reside from the nucleus increases.
However, lithium is highly electronegativity because of its less atomic number and
distance of valence form the charged nucleus. For example, if the bund between
sodium and chloride is sodium Chloride (NaCl) were covalent, the pair of shared
electrons would be attracted towards the chlorine because the effective nuclear
charge on the outer electron is +7 in chlorine but only +1 in the sodium. The
electron pair is so attracted so closed to the chlorine atom that they are partially
transferred to the chlorine atom (an ionic bond). However, if the sodium atom was
replaced by the lithium atom, the electron will not be attracted as closed to the
chloride atom as before, because the lithium atom is smaller, making the electron
pair more strongly attracted to closer effective nuclear charged from the lithium
atom.

Note: Because of very high electronegativity of lithium, some of its compounds

have more covalent characters. For example, lithium iodine (LiI) will dissolve in
organic solvents, a common property of most covalent compounds. Lithium
fluoride (LiF) is the only alkali metals halide that is not soluble in water, and

lithium hydroxide (LiOH) is the only alkali metals hydroxide that is not
deliquescent.

The electronegativity values for the elements in this group are very small in fact
the smallest value of any element. Thus then these elements react with other
elements to form a compound, a large electronegatıvity difference between the two
atom is probable and ionic bonds are formed.

xxviii
Example: Sodium electronegativity = 0.9

Chlorine electronegativity = 3.0

Electronegativity difference = 2.1

The table below shows the first and second ionization energy together with the
trend in electronegativity.

3.3 Differences between lithium and other Group IA (Anomalous Behavior of

lithium)

Although, they have the same oxidation state but lithium and its compound differ
from the rest of the group. Some of the differences are listed below:

1. It has high melting and boiling point than those in the group.
2. It is harder than the rest of the group.
3. Its reaction with oxygen is least readily forming the normal oxide, it forms
peroxide only with great difficulty.
4. Lithium hydroxide is less basic than the other hydroxide in the group, and
therefore many of its salts are less stable, Li 2CO3, LiNO3 and LiOH all form
oxide on gentle heating.
5. Lithium forms nitride Li3N (group II also form thing).
6. React with carbon directly (also group II do the same thing).
7. Lithium has greater tendency to form complexes e.g (Li (NH 3)4) which exist
as solid.
8. Li2, CO3, Li3, PO4 and LiF are all insoluble in water (also the Corresponding
magnesium compound are insoluble in water) etc.

xxix
 CHAPTER FOUR

THE ALKALINE EARTH METAL (GROUP IIA ELEMENTS)

4.1 Introduction
The alkaline earth metals are all silvery-colour, soft, and have relatively low
density, melting points and boiling points. In chemical terms, all the alkaline earth
metal halides all of which ionic crystalline compounds (except for beryllium
chloride which is covalent). All the alkaline earth metals except beryllium react
with water to form strongly alkaline earth metal hydroxides and thus should be
handled with care. The heavier alkaline earth metals react vigorously than the
lighter ones. Therefore, reactivity increases down the group of the alkaline earth
metals.
4.2 Group IIA Elements
The alkaline earth metals (elements) are metallic elements found in the second
group (Group II) of the periodic table. All alkaline earth metals have an oxidation
state of +2, making them very reactive. Because of their reactivity, the alkaline
earth metals are not found freely in nature.
The alkaline earth metals include; beryllium (Be), Magnesium (Mg), Calcium (Ca),
Strontium (Sr), Barium (Ba), and Radium (Rd). The alkaline earth metals are all
shiny, silvery-white, somewhat reactive at standard temperature and pressure and
readily lose their two outermost electrons to form cations with charge +2. Alkaline
earth metals (group II) lies in the s-block of the periodic table as they all have their
outermost electrons in an s-orbital.
They show the same trends in properties as were observed with group IA.
However, beryllium stands apart from the rest of the group and differs much more
from them than the num goes from the rest of group IA. Because the beryllium
atom and beryllium ion are both extremely small, and the relative increase in size

xxx
from beryllium ion (Be+) to magnesium ion (Mg2+) is four time greater than the
increase between Li and Na+. These metals are also highly reactive but less reactive
that group IA. They are typically divalent and generally form colourless ionic
compounds. The oxides and hydroxides are less baric than group IA. While these
oxo-salt (carbonate Sulphates, nitrates) are less stable to heat. The members of this
group are Beryllium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium
(Ba) and Radon (Ra).
4.3 Electronic Configuration
The alkaline earth metals are s-block elements. They all have their outermost
electron on the s=block orbital. All alkaline earth metals have two electrons on
their valence shell, so the energetically preferred state of achieving a filled electron
shell is to lose two electrons to a filled electron shell is to two electrons to form
doubly charged ions (+2). Like other groups, alkaline earth metals show a pattern
in its electronic configuration, especially the outermost shell, resulting to trends in
their chemical behaviours.
Element Symbol Electronic configuration
Beryllium 4Be 1s2 2s2
Magnesium 12 Mg 1s2 2s2 2p6 3s2

Calcium 20 Ca 1s2 2s2 2p6 3s2 3p6 4s2

Strontium 38 Sr 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2

Barium 56 Ba 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2

Radon 88 Ra 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f14
5d10 6p6 7s2

xxxi
Or simply written as;

Element Symbol Electronic configuration

Beryllium 4Be [He] 2s2

Magnesium 12 Mg [Ne] 3s2

Calcium 20 Ca [Ar] 4s2

Strontium 38 Sr [Kr] 5s2

Barium 56 Ba [Xe] 6s2

Radon 88 Ra [Rn] 7s2

i.e all have ns2 outer electronic configuration outside the noble gas kernel.

4.3.1 Atomic and Ionic Size

The atomic and the ionic radii of the alkaline earth metals are smaller than that of
the corresponding members of the alkali metals. This due to the fact that the
alkaline earth metals having a higher number of charges allow electrons to be
attracted more towards their nucleus. This reduces the size of the atomic and the
ionic radii of the alkaline earth metals.

On moving down the groups, the atomic and the ionic radii of the alkaline earth
metals increase due to gradual increase in the number of the shells and the
screening effect.

The atomic and the 1onic radii of the alkaline earth metals are give bellow

xxxii
Group IIA atoms are large, but are smaller than the corresponding group IA
elements as the extra charges on the nucleus draws the orbital electrons; similarly
their ions are of two orbitals electrons increases the effective nuclear charge even
further. Thus, elements have higher densities than group IA metals.

Property Beryllium Magnesium Calcium Strontium Barium Radium

(Be) (Mg) (Ca) (Sr) (Ba) (R)
Atomc 112 160 197 215 222 -
radius (pm)
Ionic radius 27 72 100 110 135 140
(pm)

Table showing size and density:

Element Metallic Radius (A0) Ionic Radius (A0) Density g/cm3

Be 1.12 0.13 1.85
Mg 1.60 0.71 1.74
Ca 1.97 1.00 1.55
Sr 2.15 1.18 2.63
Ba 2.22 1.35 3.62
Ra - 1.48 5.5
Consequently alkaline earth metals are harder. have higher cohesive energy and
have much higher melting and boiling point than the alkali metals but the metals
are relatively soft. The melting point does not vary regularly. The table below
shows the melting and boiling point.

xxxiii
4.3.2 Melting and Boiling Point of Group II A

Element Melting point (0C) Boiling point (0C)

Be 1287 2500
Mg 649 1105
Ca 839 1494
Sr 768 1381
Ba 727 1850
Ra 700 1700

4.3.3 Ionization Energy

Ionization energy is the energy required to remove completely one ole of electrons
from one mole of calcium atom or ion. Since the atoms are smaller than those in
group I. the electrons are tightly held so that the energy needed to remove the first
electron (first ionization energy) is greater than for group I. once one electron has
been removed, the ratio of changes on the nucleus to orbital electrons is increased,
so that the remaining electrons are more tightly held. Hence, the energy needed to
remove a second electro nearly double that require for the first. The first plus
second ionization energy of Group II is four times greater than first ionization
energy of the groups I.

The alkaline earth metals have the second lowers first ionization energies in their
respective period on the periodic table because of their somehow low effective
nuclear charges and the ability to attain a full outer shell configuration by loosing
just two electrons.

The second ionization energies of the alkaline earth metals are also somewhat low
down the group, he ionization energy decreases as their atomic size increase. This

xxxiv
is due to new shells being added and increases in the magnitude of the shielding
effect of the inner shell electron.

Member of the group II (the alkaline earth metals) have higher ionization energies
values as compared to the group I (the alkali metals) because of their smaller size,
with their electrons been more atom.

Correspondently, they are less electropositive than the alkali metals.

Although, the first ionization energy values of the alkaline earth metals are higher
than that of the alkali metals, the second ionization energy values of the alkaline
earth metals are smaller than those of alkali metals. This occurs because in alkali
metals the second electron is to be removing form a cations, which has already
acquired a noble gas configuration. In the case of the alkaline earth metals, the
second electron is to be removed nonviolent cations which still have one electron
in the outermost shell. Thus, the second electron can be removed more easily in the
case of group II elements that alkaline earth metal than in eh group I elements
(alkaline metals).

4.3.4 Electronegativity

Electronegativity is the relative ability of bounded atoms attract shared electrons.

The electronegativity of values of group II is low, but is higher than that of group I.
when Mg, Ca, Sr and Ba react with elements such as halogens and oxygen, the
electronegativity is large and the compounds are ionic.

The value for Be is higher than for other. BeF 2 has the biggest electronegativity
difference for a compound of Be and so is the most likely compound of Be to be
ionic. BeF2 has very low conductivity when fused; hence it is regarded as covalent.

xxxv
Table showing 1st and 2nd ionization energies and electronegativity

Elements 1st Ionization energy 2nd Ionization energy Electronegativity

value
Be 899 1757 1.5
Mg 737 1450 1.2
Ca 590 1145 1.0
Sr 549 1064 1.0
Ba 503 965 0.9
Ra 509 979 -

4.3.5 Melting and boiling points

The melting and the boiling points of the alkaline earth metals are
characteristically low and do not show regular trends down the group. However
these points are higher than the corresponded alkali metals in the period as atoms
of the alkaline earth metals have smaller size compare to the alkali metals. This
causes them to be more closely packed together in their crystal lattices. They also
have two electrons per metal atom in their valence shell (as compared to one for
the alkali metals) forming strong boding for binding the atoms in the crystal lattice
of the metals. Hence, they have higher melting and boiling point than the alkali
metals.

Note:

Beryllium is an exceptional in the alkaline earth metals. It does not react with
water and steam, and it halides are covalent. If beryllium form compound with a
ionization state of +2, it would polarize electron clouds that are near it very
strongly and would cause extensive orbital overlap since beryllium has a high large

xxxvi
charge density. All compounds that include beryllium have covalent bond. Even
the compound beryllium fluoride (BeF2), which most ionic beryllium compound,
has a low melting point and a low electrical conductivity when melt.

4.4 The Gradation properties of elements in Group II

4.4.1 Atomic Properties

They all have outer electron configuration of ns 2, hence all members have the +2
oxidation state. Therefore they form ion as M 2w+ Atomic and ionic size increases
down the group but smaller than the corresponding group IA/k the ionization
energy and electronegativity decrease down the group but higher than the
corresponding group IA.

4.4.2 Physical properties

Metallic bonding involves two valence electrons. These metals are relatively soft,
but are much harder than group I metals because two electrons are involved in the
metallic bonding. Melting and boiling points generally decrease and densities
hardly increase down the group. These values are much higher than the
corresponding group IA.

4.4.3 Chemical properties of Group IIA Metals

(a) Reaction with water: the reduction potential of beryllium is much less than
those for the rest of the group. Infact beryllium is much less electro positive, less
metallic than the others, it does not react with water but Ca, Sr and Ba have
reduction potential similar to those of the corresponding Group IA metal and are
quite high in the electron-chemical series.

xxxvii
IA metal and are quite high in the electron-chemical series. They react with cold
water quite readily liberating hydrogen and forming metal hydroxide e.g

Ca + 2H2O Ca (OH)2 + H2

In summary:

S/N Reaction Comment

1 M + H2O M(OH)2 + H2 Be probably react with hot water an Ca. Sr and Ba
react rapidly with cold water.
2 M + 2HCl MCl2 + H2 All metals react with acid liberating hydrogen gas
3 Be + NaOH Na(OH)4 + H2 Be is amphoteric
4 a). 2M + O2 2MO Normal Oxides are formed by all members.
b). Ba + O2 BaO2 Excess Be also form peroxides.
oxygen
5 M + H2 MH2 Ca, Sr & Ba form ionic "Salt-like" hydrides at high
temperature
6 3M + H2 M2N2 All metals form Amides at high temperature
7 3M + 2P M2P2 All form phosphides at high temperature
8 M+S MS All metals form sulphides
9 M + X2 MX2 (x= halogens) They form fluorides, chlorides, bromides and iodides
10 1M + 2NH3 2M (NH3)2 All metals form amides at high temperature

Some important of compounds

1. Beryl: this is the industrial source of beryllium (Be). It occurs as a gemstone

with a variety of colours.
2. Magnesium Oxide (MgO): this has a high melting point (285 0C) hence it is
used as refractory material for furnace brick and wire insulator.

xxxviii
3. Alkyl magnesium halides, Rmgx (R = hydrocarbon, X = halogen): these
compounds called Grignard reaction are used to synthesize many organic
compounds (organometallic).
1. Calcium carbonate (CaCO3): occurs as enormous natural deposits of
limestone marble, chalk and coral. Use as a building materials to make lime and
in high purity as a tooth-paste abrasive and an antacid.

Some comparism in physical properties of group IA metal and group IIA

metals

These differences and similarities in physical properties of these two groups can be
summaries as follows:

i. Most of the difference occurs as the result in the outer electrons

configuration is ns1 and ns2.
ii. One electron is involved in the metallic bonding of group IA while two
electrons are involves in metallic bonding in group IIA.
iii. As a result of this differences in number or outer electron(s), the nuclear
charges in group II are greater as much more greater attraction of the
decolonized electron by nucleus hence the boiling and melting point of
group II are much higher than group IA.
iv. They are both soft and have high weight, but group II metals are much
harder, soft and more dense than alkali metals.

4.5 Some Comparism in Chemical properties

i. Group II metal have smaller atomic radii hence they have higher ionization
energy than group I.
ii. Despite the high ionization energy all group II metal form ionic compound
(except Be) be compound re-polar covalent.
xxxix
iii. Like alkali metals, alkaline earth metals are strong reducing agent e.g the
elements reduce O2 in air to form oxide except for Be, an Mg which form
adherent oxide coating.
i. They reduce water (H2O) at room temperature to form hydrogen gas.
ii. Except Be they reduce halogens, N2 and H3 to form ionic compounds.
iii. Their oxide (except BeO = amphoteric) are strongly basic, and react with
acidic oxides to form salts such as sulphite and carbonates e.g
SrO(s) + CO2(g) SrCO3(s)
iv. Alkaline earth metals re-reactive because the high lattice energies of their
compounds more than compensate for the large total ionization energy need
to form +2 cation.
i. Group IIA salts have much higher lattice energies than those of Group IA,
because the group II cations are smaller and doubly charge.
ii. Group II salt has lower solubility in water than group I salts because their
1ons are smaller and highly charged than group I ions, resulting in much
higher charge densities.

Even though this increases heat of hydration, it increases lattice energies even
more, hence most group IIA fluorides, Carbonates, Phosphates and sulphates are
considered insoluble.

Conclusion

There are no much change from group IA to group IIA and the elements behaved
as metals both physically and chemically, with smaller atomic a size and stronger
metallic bonding group IIA are harder, higher melting point and denser than those
in lattice energies and hence less solubility of their salts.

xl
4.6 Solubility and Lattice Energy

The solubility of most salts decreases with increased atomic weight, though
weight, though the usual trend is reversed with the fluorides and hydroxides in this
group. Solubility depends on the lattice energy of the solid, and the hydration
energy of the ions. Consider some lattice energy values for group II compound
below.

The lattice energies are much higher than group IA compounds, because of the
effect of the increased charge on the ions.

Lattice Energies of some Compounds (kjmol-1)

MO MCO3 MF3 MI2

Mg -3923 -3178 -2906 -2292
Ca -3517 -2986 -2610 -2058
Sr -3312 -2718 -2459 -
Ba -3120 -2614 -2369 -

4.7 hydration energy

The hydration energy also decreases as the metal ions become large. For substance
to dissolve, the hydration energy must exceed the lattice energy. Examples are
group of compounds such as the chlorides or all group II metals. On descending
the group, the metals ions become larger an so both the lattice energy and the
hydration energy decrease. A decrease in lattice energy favour increased solubility,
but a decrease in hydration energy favours decreased solubility.

Enthalpy of Hydration
xli
Elements H(Kjmol-1)
Be2+ -2494
Mg2+ -1921
Ca2+ -1577
Sr2+ -1443
Ba2+ -1305
4.8 Anomalous Behaviour of Beryllium

Beryllium differs from the other members of the group due to the following reason;

1. It is extremely small, and Fajan's rules state that small highly charged ions tend
to form covalent compounds.
2. Be has a comparatively high electronegativity. When it reacts with another
atom, the difference in electronegativity is large, favour the formation of
covalent compound e.g. BeF2 and BeO have electronegativity of 2.5 mad 2.0
respectively. This show an evidence of covalent character.
3. Be hydride is electron deficient and polymeric with multicentre bonding like
aluminium hydride.
4. Be form many complexes
5. Be is amphoteric, liberating H2 with NaOH and forming beryllates, Al forms
Aluminate.
6. Be (OH2) like Al (OH)3 is amphoteric.
7. Be like Al rendered passive by nitric acid.
8. Be salts are extensively hydrolyzed.
9. Be salts are among the most soluble salts know
10.Be forms unusual carbide Be2C which like Al2C3 yield methane on hydrolysis.

xlii
Note: there is a diagonal similarity between beryllium in group II and Aluminium
in group III just as was the case with lithium and magnesium, the similarly in
atomic and ionic sizes is the main factor underlying this relationship.

4.9 Resemblance of Lithium with Group IIA

The similarity between lithium (the 1st member of group II) and magnesium (2nd
member of group II) is called a diagonal relationship. Diagonal relationship also
exists between other pair of element example Be and Al. B and Si as shown below:

I II III IV

2nd Li Be B C

Period

3rd Na Mg Al Si

The diagonal relationship arises because of the effects of both size and charge. On
descending a group, the atom and ions increase in size. While on moving from left
to right in the periodic table the size decreases. Thus, on moving diagonally, the
size remains nearly the same. It is sometimes suggested that the diagonal
relationship arises because of a diagonal similarities in electro-negativities.

xliii
 CHAPTER FIVE

EFFECTS OF THE PRESENCE OF GROUP II METAL ION IN WATER

5.1 Hard Water

Hard water is one which contains dissolve salts of magnesium or calcium in form
of carbonates, bicarbonates or sulphates. It is difficult to produce lather with soap
instead an insoluble scum is formed. The metal ion Ca 2+ or Mg2+ react with the
stearate ion from the soap, forming and insoluble scum of calcium or magnesium
stearate before any lather is produced. Hard water also produces scale (insoluble
deposits) in water pipes, boilers and kettle.

Hard water is water that has high mineral content (in contrast with soft water".
Hard drinking water is generally not harmful to one’s health, but can pose serious
problems in industrial settings, where water hardness is monitored to avoid costly
breakdowns in boilers, cooling towers and other equipment that handless water. In
domestic settings hard water is often indicated by a lack of suds formation when
soap is agitated in water. Wherever water hardness is a concern, water softening is
commonly used to reduce hard water's adverse effect.

Water's hardness is determined by the concentration of multivalent cations in the

water. Multivalent cations are cations (positively charged metal complexes) with a
charge greater than +1. Usually, the cations have the charge of +2. Common
cations found in hard water include Ca 2+ and Mg2+. These ions enter a water supply
by leaching from mineral within an aquifer. Common calcium containing mineral
are calcite and gypsum. A common magnesium mineral is dolomites (which also
contains calcium). Rainwater and distilled water are soft, because they also contain
few ions.

xliv
The following equilibrium reaction describes the dissolving and formation of
calcium carbonate scales;

CaCO3 +CO2 + H2O Ca2+ +2HCO3

5.1.1 Types of Hardness

1. Temporary: temporary hardness is a type of water hardness caused by the

presence of dissolved bicarbonate minerals (calcium bicarbonate and magnesium
bicarbonate). When dissolved these minerals yield calcium and magnesium cations
Ca2+ and Mg2+) and carbonate and bicarbonate (CO32+, HCO3-) the presence of the
metal cations makes the water hard. However, unlike the permanent hardness
caused by sulphate and chloride compounds, this 'temporary' hardness can be
reduced either by boiling the water, or by the addition of lime calcium hydroxide)
through the softening process of lime softening. Boiling promotes the formation of
carbonate from the bicarbonate and precipitates calcium carbonate out of solution,
leaving water that is softer upon cooling.

Temporary harness is due to the presence of Mg (HCO 3)2) and Ca (HCO3)2). This
type of hardness is called "Temporary’’ cause it can be removed by boiling.

Removal of Temporary hardness or (Softening)

1) Boiling: this decomposes the soluble hydrogen carbonate to form insoluble

carbonate, which can be filtered off Heat

heat

a. Mg (HCO3)2)(aq) MgCO3(aq) + CO2(g) + H2O(l)

Soluble Insoluble

xlv
 heat

b. Ca (HCO3)2)(aq) CaCO3(s) + CO2(g) + H2O(l)

Soluble Insoluble

Or in general

2HCO3- CO32- + CO2(g) + H2O(l)

2). Addition of slake lime: this also known "Lime softening" and by operating at
pH of 10.5, temporary hardness due to HCO 3- can be almost removed by
converting bicarbonate into insolute carbonate.

a. Mg (HCO3)2)(aq) Ca(OH)2(aq) + 2CaCO3(g) + 2H2O(l)

b. Ca (HCO3)2)(aq) Ca(OH)2(aq) + 2CaCO3(g) + 2H2O(l)

2. Permanent Hardness

This type of hardness is caused by dissolved sulphates and chlorides of calcium

and magnesium which become more insoluble as the temperature increases. This
type of hardness is called permanent because it cannot be removed by boiling.
Removed using a water softener or ion exchange column.

Removal of Permanent Hardness

In this method of removing hardness from water, chemicals (softeners) such as

slaked lime [Ca(OH)], washing soda [Na2CO3] or calgon [(NaPO3)6] can be used to

xlvi
soften hard water. Depend on the softener used; each of this method is named
Clark's process Addition of washing soda Calgon process respectively.

i) Addition slake lime (Clark's Process): in clark's process, slaked lime,

Ca(OH)2 is added to temporary hard water. Insoluble calcium carbonate
precipitates out and no longer produces hard complex salt.
Colgon process: calgon is a trade name of, sodium hexametaphosphate
(NaPO3)6. It is used for softening hard water. Calgon ionizes to give a
complex anion: The Addition of calgon to water causes the calcium and
magnesium ions of hard water to displace sodium ions from the anion of
calgon.

Ca2+ + Na4P6O182- 2Na+ + CaNa2P6O182-

From hard water anion of calgon goes into solution

This result in the removal of calcium and magnesium ions from hard water
in the form of a complex with calgon. The water is softened\and sodium ions
are released into water.

ii. Addition of washing soda (Na2CO3.10H2O): washing soda remove the

calcium or magnesium ions as insoluble calcium or magnesium
trioxocarbonate, which can be settle down or filtered off. Calcium and
magnesium ions present in hard water react with sodium carbonate to
produce insoluble carbonate. The water now contain soluble and harmless
sodium salt.

The equations are:

a. MgSO4(aq) + Na2CO3 MgCO3(s) + Na2SO4(aq)

xlvii
 b. CaCl2(aq) + Na2CO3 CaCO3(s) + 2NaCl (aq)

MgCl2(aq) + Na2CO3 MgCO3(s) + 2Na2Cl (aq)

Cause of permanent hardness insoluble

iii. Addition of Caustic Soda: Caustic soda (NaOH) remove calcium or

magnesium or calcium hydroxide.
a. CaSO4(aq) + 2NaOH(aq) Ca(OH)a(aq) + Na2SO4(aq)

b. MgSO4(aq) + 2NaOH(aq) Mg(OH)a(aq) + NaCl (aq)

3. Permutit (ions – exchange) Method

Permutit or sodium aluminium silicate is a complex chemical compound, which

occur as a natural mineral called zeolite.

Permuit or zeolite are insoluble in water and have the property of exchanging ions
present in them with the ions present in the solution.
Permutit or zeolites are packed in a suitable container and a slow stream of hard
water is passed through this material. As a result, calcium and magnesium ions
present in hard water are exchanged with sodium ions in the permutit (Na +Al –
Silicate).
The outgoing water contains sodium salt, which do not cause hardness.
CaCl2 + 2Na + (Al – silicate) Ca(Al – silicate)2 + 2Nacl
In hard water permutit
MgSO4 + 2Na+ (Al – silicate) Mg(Al – silicate)2 + 2Na2SO4

In hard water permutit

xlviii
Moreover, giant organic molecules having acidic or basic group are known as ion-
exchange resins. Acid resins contain the acid group (-COOH).

Acid resin exchange their H+ ions with other cations such as Ca 2+, Mg2+, etc.
present in hard water. Acid resins are therefore known as base-exchanges resins.

2RCOOH+ + Ca2+ (RCOO)2Ca + 2H+

Base exchange from hard water
Resin or acid resin

RCOOH+ + Na+ RCOONa + H+

Acid resin from water

Basic resins exchanges their OH - ions with the other anions Such as HCO 3, CI, and
SO42- present in hard water. Basic resins, therefore, are also known as acid
exchange resins.

RNH3+OH+ + Cl- RNH3Cl + H+

Base resin or from water
Acid exchange resin
2RNH3+OH- + SO42- (RNH3)2SO4 + 2OH-
Base resin from water

xlix
Fig. 1: (Ion-exchange process for water softening)

In the ion exchange process, hard water is passed though two tanks 'A and 'B'.
Tank A contains acid resin and tank B is filled with basic resin. All the cation
present in hard water (except H+) are removed by the acid resin present in Tank A,
and the basic resin present in Tank B removes all the anions (except OH -) present
in hard water. Water obtained after passage through both the tanks is free from all
the cations and anions that make it hard. The water obtained after passing through
the ion exchangers is called deionized water or demineralized water. This is as
good as distilled water. The water becomes soft after this process.

Measurement of Hardness

Hardness can be quantified by instrumental analysis. The total water hardness is

the sum of the molar concentrations of Ca 2+ and Mg2+ in mol/L or Mmol/L units.
Although water hardness usually measure only the total concentration of calcium
l
and magnesium (the two most prevalent divalent metal ions) iron, aluminium and
manganese can also be iron characteristically confers a brownish (rust-like) colour
to the calcification, instead of white (the colour most of the other compound).

This is an ion-exchange technique in which calcium ion (Ca 2+) and Magnesium ion
(Mg2+) are exchanges with sodium ion (2Na+) when hard water run through a
complex substance called zeolite.

a. CaSO4(aq) + Na2Y CaY + Na2SO4(aq)

Sodium calcium

Zeolite zeolite

Or

Permutit

b. MgSO4(aq) + Na2Y MgY + Na2SO4(aq)

Where Y = Al2, Si2O3. XH2O

Note: both temporary and permanent hardness can be removed by;

a. Distillation

b. Addition of washing soda

5.1.2 Advantages of Hard water

1. Because of the dissolved mineral hard water has good taste

li
2. It helps to build strong bones and teeth of animals and also shell of snail and
crabs
3. does not cause lead poisoning (when lead pipes are used)

5.1.2 Disadvantage of Hard water

1. Soap scum: this refers to the effect of hard water on soap, With hard water, soap
solutions form a white precipitate (soap scum) instead of producing lather. This
causes wastage of sap in laundry where water is used as solvent.

This effect arises because the 2+ ions destroy the surfactant properties of the soap
by forming a solid precipitate (the Soap scum). A major component of such scum
is calcium stearate, which arises from sodium state, the main components of soap.

2C17H35COO- + Ca2+ (C17H35COO)2Ca

However, synthetic detergents do not form such scum.

1. Clog plumbing: hard water also forms deposits that clog plumbing. These
deposits called 'Scale', are composed mainly of calcium carbonate (CaCO 3),
magnesium hydroxide Mg(OH)2 and calcium sulphate (CaSO4). Calcium and
magnesium carbonates tend to be deposited as off-white solid on the surface
of pipes and the surfaces of heat exchangers. Deposit of calcium and
magnesium in kettles and boilers, causes power and fuel wastage. This
precipitation (formation of an insoluble solid) is principally caused by
thermal decomposition of bi-carbonate ions but also happens to some extent
even in the absence of such ions. The resulting build-up of Scale restricts the

lii
 flow of water in pipes. In boilers, the deposits impair the flow of heat into
water reducing the heating efficiency and allowing the metal boiler
components to overheat. In a pressurized system, this overheating can lead
to failure of the boiler. The damage caused by calcium carbonate deposits
varies depending on the crystalline form, for example calcite or aragonite.
2. Galvanic corrosion: the presence of ions in an electrolyte, in hard water,
leads to galvanic corrosion, in which one metal will preferentially corrode
when in contact with another types of metal, when both are in contact with
an electrolyte. The softening of hard water by ion exchanger does increase
its corrosives.
3. Turbid or cloudy milky formation: In swimming pools, hard water is
manifested by a turbid or cloudy (milky), appearance to the water. Calcium
and magnesium hydroxide are both soluble in water. The solubility of the
hydroxide of the alkaline earth metals, to which calcium and magnesium
belong (group 2 of the periodic table) increase moving down the column.
Aqueous solution of this metal hydroxide absorbs carbon dioxide from the
air, forming the insoluble carbonates, giving rise to the turbidity. This often
result from the alkalinity (the hydroxide concentration) being excessively
high (pH > 7.6).

From the reasons discussed above, it is often desirable to soften hard water. Most
detergents contain ingredients that counteract the effect of hard water on the
surfactants. For this reason, water softening is often unnecessary. There softening
is practiced, it is often recommended to soften only the water sent to domestic hot
water system so as to prevent or delay inefficiencies an damage due to scale
formation in water heaters.

liii
 CHAPTER SIX

GROUP III ELEMENTS (BORON GROUP)

6.1 Introduction

The third family of the main group elements contains some members and some
familiar ones, some exotic bonding, and some strange physical properties. Boron
(B) heads the family, but its properties certainly do not represent the other
members. Metallic Aluminunm (A) has properties that are more typical of the
group, but its great abundance and importance contrast with the rareness of gallium
(Ga) indium (In) and thallium (TI).

The group III elements also known as boron group is the series of elements in
group 3 of the periodic table comprising Boron(B), aluminium (Al), Gallium (Ga),
Indium (In), Thallium (Ti) and untrium (Unt). The element in the boron group are
characterized by having three electron in their outer energy levels (valence
electron). Boron is classified as a metalloid while the rest, with the possible
exception of untrium, are considered poor metals. Untrium has not yet been
confirmed to be a poor metal and due to relativistic effect might not turn out to be
one. Boron occurs sparsely.

Probably because bombardment by the subatomic particles produce from natural

radioactivity disrupts its Nuclie. Aluminum occurs widely on earth, and indeed is
the third most abundant element in the earth crust (8.36). Gallium is found in the
earth with an abundant element in the earth's crust, and thallium is found in
moderate amounts throughout the planet. Untrium is never found in nature and
therefore is termed a synthetic element.

liv
Several group 3 elements have biological roles in the ecosystem Boron is a trace
element in humans and is essential for some plants. Lack of boron can lead to
stunted plant growth, while excess can also cause harm by inhibiting growth.
Aluminium has either a biological role nor significant toxicity and is considered
safe. Indium and gallium can stimulate metabolism; gallium is credited with the
ability to bind itself to iron proteins. Thallium is highly toxic, interfering with the
function of numerous vital enzymes, and has seen use as a pesticide.

6.2 Electronic configuration

Element Symbol Element configuration

Boron 5B [He] 2s2 2p3

Aluminium 13 Al [Ne] 3s2 3p1

Gallium 31 Ga [Ar] 3d10 4s2 4p1

Indium 49 In [Kr] 4d10 5s2 5p1

Thallium 81 TI [Xe] 4f14 5d10 6s2 6p1

Except boron (metalloid) all the elements in this group are metals and they have
most stable oxidation state of (+3) except thallium with most stable oxidation state
of (+1). They belong to P block in the periodic table. The four elements, Al, Ga, In
and TI and form trivalent compounds. Their compounds are on the borderline
between ionic and covalent. Many of their Compounds are covalent when
anhydrous, but they form ions in solutions.

The boron group is notable for trends in the electron configuration, as shown
above, and in some of its elements characteristic. Boron differs from the other
group members in it hardness, refractivity and reluctance to participate in metallic

lv
bonding. An example of a trend in reactivity is boron's tendency to form reactive
compounds with hydrogen.

6.2.1 Atomic and Ionic size

The metallic radii of the atoms do not increase regularly on descending the group.
However, the values are not strictly comparable. The ionic values are not strictly
comparable. The ionic radii for M 3+ increase down the group, though not in the
regular way observed in group I and II.

Table showing ionic and metallic radii

Element Metallic Radius (A0) Ionic (M3+) Radius (A0 electronegativity value)
B 0.885 0.27 2.0
Al 1.43 0.535 1.5
Ga 1.225 0.620 1.7
In 1.67 0.800 1.7
TI 1.70 0.885 1.8

6.2.2 Melting and Boiling point

The melting point of point of these element not show regular trend as bonding
changes from network covalent in Boron (B) to metallic in the rest of the group.
Thus Boron (B) to metallic in the rest of the group. Thus Boron (B) has a much
higher melting point than others, but there is no overall trend. Boiling point
decreases down the group.

lvi
Element Melting Point (0C) Boiling Point (0C)
B 2180 3650
Al 660 2467
Ga 30 2403
In 157 2080
TI 303 1457

6.2.3 Electropositive Character

The electropositive or metallic nature of these elements increases from boron to

aluminium but then decreases from Aluminium to thallium is the usual trend on
descending Size. However, Gallium (Ga), Indium (In) and thallium (TI) do not
continue the trend. The elements are less likely to lose electron (and are thus less
electropositive).

6.2.4 Ionization Energy

The ionization energy increases as expected (first ionization energy, second

ionization energy and third ionization energy). The sum of the first three ionization
energies for each of the elements is very high.

Thus boron has no tendency to form ions, and always forms covalent bonds.

The ionization energies values do not decrease smoothly down the group. The
decrease from Boron to Aluminium is the usual trend on descending a group
associate with increased size. The poor shielding by d-electrons and the resulting d
block contraction affect the values for the later elements.

Ionization Energy (Kjmol-1)

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ELEMENT 1ST 2ND 3RD SUMMARRY
B 801 2427 3659 6887
Al 577 1816 2744 5137
Ga 579 1979 2962 5529
In 558 1820 2704 5082
TI 589 1971 2877 5437

6.3 Physical properties

It has been noticed that the elements in the boron group have similar physical
properties, although must of boron's are exceptional. For example, all of the
elements in the boron group, except for boron itself, are soft. Moreover, all of the
other elements in group 3 are relatively reactive at moderate temperatures, while
boron's reactivity only becomes comparable at very high temperatures. One
characteristic that all do have in common is having three electrons in their valence
shells. Boron, being a metalloid, is a thermal and electrical insulator at room
temperature, but a good conductor of heat and electricity at high temperature.
Unlike boron, the metals in the group are good conductors under normal
conditions. This is in accordance with the long standing generalization of all
metals.

6.4 Graduation in the properties of the Elements of Group III

Due to the incomplete shielding of the valence shell electrons by the two electrons
in the first (K) shell and the inability of boron to expand its valence shell to more
than an octet, boron stands apart from other members of group IIIA. Aluminium
has an inert gas core of neon below the valence shell whereas other members (Ga,
In, TI) have the 18 electron shell beneath the valence shells. Hence aluminium also

lviii
is expected to be different from the rest of the members of the group. The
characteristic valences state of (II) is shown by all the elements boron can attain
the trivalent state only by electron sharing (after the promotion of ns 2 pair to ns1
np1 state) for other elements also IE (ionization energy) for the removal of three
electrons to give M3+ is very high and discourage the formation of discrete M 3+ ion.
Hydrate ions like (M (H2O)63+ are stable for these elements (except for boron) due
to high hydration energy. However, boron does not form any hydrate cation, but
forms only anions in which it use Sp3 hybrid orbitals for bonding. The higher
charge density on the small B3+ ion polarizes the water molecules so much that
ionization of proton results.

B (H2O)43+ (OH)4¯ + 4H+

6.4.1 Metallic Characteristic

Metallic character and electropositive nature increase down the group. Boron is a
non – metal, Aluminium and Thallium are metallic.

6.4.2 Halides

The elements in group 3 are also capable of forming stable compounds with the
halogens, usually with the formula MX3 (where M is a boron group element and X
is a halogen.) the only exception this is thallium (III) iodide. Fluorine, The first
halogen, is able to form stable compounds with every element that has been tested
(except neon and helium), and the boron group is no exception. It is even
hypothesized that untrium could form a compound with fluorine, Uutf 3 before
spontaneously decaying due to untrium's radioactivity. Chlorine also forms stable
compounds with all of the elements in the boron group, including thallium, and is
hypothesized to react with untrium. All of the elements will react with bromine
under the right conditions, as with the other halogens but less vigorously than
lix
either chlorine or fluorine. Iodine will react with all natural elements in the
periodic table except for the noble gases, and is notable for its explosive reaction
with aluminium to form 2Al3, Astatine, the heaviest halogen, has only formed a
few compounds, due to its radioactivity and short half life, and no reports of a
compound with an At – B, – Al, – Ga – In, TI or Untrium bond have been seen,
although scientists think that it should form salts with metals.

Nature of boning in their chlorides

All the halides corresponding to the MX 3 formulation are known, TI3 is however,
thallium (I) tri-iodide as it is isomorphous with K 13. Boron Tri halides are volatile,
covalent compounds which form M2X3 vapours. The tri fluorides of Al, Ga and In
are ionic; rest are covalent halides and dimeric in vapour state.

The halogen atoms act as bridging ligands (fig. below), so that the terminal (t) M-
X bonds are difference from bridged (b) M – X bonds.

Structure of Al2 X6 O = Al, O= X, In Chloride, Al – Cl is 206 Pm (t) and 221 Pm

(b); in bromide. Al – Br is 221 pm (t) and 233pm (t = terminal, b = bridged).
Different bond length are expected. However, both the types of bonds are shorter
than the calculated single bond lengths (AI – Cl, calculated 224 Pm).

6.4.3 Oxidation states

lx
The inert s-pair effect is significant in the group -3 elements, especially the heavier
ones like thallium. This results in a variety of oxidation states. In the lighter
element, the +3 state is the most stable, but the+1 state becomes more prevalent
with increasing atomic number, and is the most stable for thallium. Boron is
capable of forming compounds with lower oxidization states, of +1 or +2, and
aluminium can do the same. Gallium cannot form compounds with the oxidation
state +2 but can with +1 and +3, Indium is like gallium, but its +1 compounds are
more stable than those of the other elements. The strength of the inert pair effect is
maximal in thallium, which is only stable in the oxidation state of +1, although the
+3 state is seen in some compounds.

Relative Stability of the Oxidation States.

Al, Ga, In and Ti are Larger than boron hence more metallic in character. The
trivalent state is more important in their compounds although as we approach
thallium, the monovalent state is also important. This was known in the past as due
to inert pair effect. The reason is due to bond energy being smaller on going down
the group and hence does not compensate for promotion of electron from S 2 P1 to
S1 P2. Acidic/ basic nature of their oxides. Al the elements form the trioxide M 2O3
and the hydroxide M(OH)3 B2O3 is acidic; Al2O3 and GaO3 are amphoteric, while
In2O3 and TI2O3 are basic oxides.

6.4.4 Hydrides

Most of the elements in the boron group show increasing reactivity as the element
get heavier in atomic mass and higher in atomic number. Boron, the first element

lxi
in the group, is generally un reactive with many elements expect at high
temperature, although it is capable of forming many compounds with hydrogen,
sometimes called boranes. The simplest borane is diborance, or B 2H6. Another
example is B10 H14.

The group 3 elements, aluminium and gallium, form fewer stable hydrides,
although both AlH3 and GaH3 exist. The next element in the group, is not known to
form many hydrides, except complex compounds such as H 3 In P(Cy)3 which is
considered to be a phosphine. No stable compound of thallium and hydrogen has
been synthesized yet.

6.4.5 Oxides

All of the boron group elements are known to form a trivalent oxide, with two
atoms or the element bonded covalentlv with three atoms of oxygen. These
elements show a trend of increasing pH (from acidic to basic). Boron Oxide (B 2O3)
is slightly acidic, aluminium and gallium oxide (Al 2O3 and Ga2O3) is slightly
acidic, aluminium and gallium oxide (Al2O3) and Ga2O3 respectively are
amphoteric, Indium (III) oxide (In2O3) is nearly amphoteric, and thallium (III)
Oxide (TI2O3) is a lewis base because it dissolves in acids to form salts. Each of
these compounds is stable, but thallium oxide decomposes at temperature higher
than 8750c B2O3 is acidic; Al2O3 and Ga2O3 are amphoteric while I2O3 and TI2O3 are
basic oxides.

6.5 Difference between Boron and other members in the Group

Boron being the first member of group III is unique. Main points of difference are
as follows;

lxii
 1. Boron is a non – metal while others are metallic
2. Boron does not displace hydrogen readily from HCI due to the formation of
the complex (AICI4) ions.
3. Boron oxide is an acidic oxide whereas (Al 2O3) is an amphoteric oxide with
more of a basic nature.
4. Boron hydroxide or boric acid is acidic whereas the other hydroxides are
definite compounds, which are amphoteric and show more basic character.
1. The boron halides are monomeric covalent compound, other tri halides are ionic
or dimeric in vapour phase whereas BX 3 are planar, M2X6 have M in tetrahedral
co ordination with M – X – M bridge.
2. Boron forms unique hydride, called borans
3. In the lower II state B2X4 are definite compounds with B – B bonds, other
metals do not form any compound in II state.

6.6 Uses of the Elements

Boron is only second to cadmium as a neutron absorber, so that its carbide is used
for shielding atomic piles, control rods, Screening operators etc. In mobile reactor
units, High purity boron is a semiconductor and can operate at temperature higher
than those for germanium, Ge (370k) and silicon, Si (570K). Powdered aluminium
wires are used for overhead transmission lines. It can take good polish and is used
in making reflectors and roofing materials. Aluminium foils are use for making
wrappers for cigarettes and confectionery items. In metallurgy, Al is used for the
reduction of metal oxides in the aluminium thermitite process. Due to its resistance
to sea ater, it is used for making sea planes. Magnalium (2 – 15% Mg in Al) is a
very strong alloy used for making low cost balances and machinery parts.
Aluminium bronze (10 – 12% Al in Cu) has a golden luster and is low melting. It
is used for making utensils, photo frames, cheap jewelry, decoration articles and

lxiii
coins. Duralumin (0.5% Mg + 0.5% Ni + 4% Cu in Al) is used for making airship.
Alclad (Duralumin with a thin coating of anodized aluminium) is used sea ship.
Though gallium can be suggested as a thermometric liquid (high liquid range) the
metals Ga, In and TI do not have much applications.

Other Applications of these Elements are:

With the exception of synthetic untrium, all the elements in the boron group have
numerous uses and application in the production and content of many items.

Boron

Boron has found many industrial application in recent decade, and new ones are
still being found. A common application is in fiberglass. There has been rapid
expansion in the market for borosilicate glass: most notable among its special
qualities is a much greater resistance to thermal expansion than regular glass.
Another commercially expanding use of boron and its derivatives ins in ceramics.
Several boron compounds, especial the oxides, have unique and valuable
properties that have led to their substitution for other materials that are less useful.
Boron may be found in pots, vases, plates, and ceramic pan handles for its
insulating properties. The compound borax is used in bleaches, for both clothes
and teeth. The hardness of boron and some of its compounds give it a wide array of
additional uses. A small part (5%) of the boron produced finds use in agriculture.

Aluminium

lxiv
Aluminium is a metal with numerous familiar uses in everyday life. It is most often
encountered in construction materials, its electrical devices, especially at the
conductor in cables, and in tools and vessels tor cooking and preserving food.
Aluminium's lack of reactivity with food products makes it particularly useful for
canning. Its high affinity for oxygen makes it a powerful reducing agent. Finely
powdered pure aluminium oxidizes rapidly in air, generating a huge amount of heat
in the process (burning at about 5500 0f or 30270c), leading to applications in
welding and elsewhere that a large amount of heat is needed. Aluminium is a
component of alloys used for making light weight bodies for aircraft. Cars also
sometimes incorporate aluminium in their framework and body, and there are
similar applications in military equipment. Less common uses include components
of decoration and some guitars. The element is also sees use in a diverse range of
electronics.

Gallium

Gallium is one of the chief components of blue LUEDs Gallium and its derivatives
have only found application in recent decades. Gallium arsenide has been used in
semiconductors in amplifiers, in solar cells (for example in satellites) and in tunnel
diodes for FM transmitter circuit. Gallium alloys are used mostly for dental
purposes. Gallium ammonium chloride is used for the leads in transistors. A major
Application of gallium is LED lighting. The pure element has been used as a
dopant in semiconductors, and has additional uses in electronic devices with other
elements. Gallium has the property of being able to wet glass and porcelain and
thus can be used to make mirrors and other highly reflective objects. Gallium can
be added to alloys of other metal to lower their melting points.

lxv
Indium's uses can be divided into four categories: the largest part (70%) of the
production is sued for coatings, usually combined as Indium tin oxide(ITO); a
smaller portion (12%) goes into alloys and solders; a similar amount is used in
electrical components and in semiconductors; and the final 6% goes to minor
applications. Among the items in which indium may be found are; platings,
bearings, display devices, heat reflectors, phosphors, and nuclear control rods.
Indium tin oxide has found a wide range of application, including glass coating,
solar planets, streetlights, electrophorestic displays (EPDs), electroluminescent
displays (ELDs), Plasma display panels (PDP's), electrochemic displays (ECs),
field emission displays (FEDs), Sodium Lamps, windshield glass and cathode ray
tubes, making it the sing most important indium compound.

Thallium

Thallium is used in its elemental form more often than the other boron group
elements. Un compounded thallium is used in low melting glasses photoelectric
cells, switches, mercury alloys for low range glass thermometers, and thallium
salts. It can be found in lamps and electronics, and is also used in myocardial
imaging. The possibility of using thallium n semiconductors has been researched,
and it is a known catalyst in organic synthesis. Thallium hydroxide (TIOH) is used
mainly in the production of other thallium compounds. Thallium sulphate (TI 2SO4)
is an outstanding vermin killer, and it is a principal component in some rat and
mouse poisons. However, the United state and some European countries have
banned the substance because of its high toxicity to humans. In other countries,
though, the market for the substance is growing. TI 2SO4 is used in optical systems.
The carbon group is a periodic table group consisting of carbon (C), silicon (Si)
Germanium (Ge), Tin(Sn), Lead (Pb) and Flerovium (Fi)

lxvi
 CHAPTER SEVEN

GROUP IV ELEMENTS (CARBON GROUP)

7.1 Introduction

The carbon group elements (group IV element) consist of six chemical elements on
the periodic table; carbon (C), silicon (Si). germanium (Ge) tin (sn) lead (Pb) and
flerovium (Fi).

As the group III element, they are also P block element. Except for germanium and
the artificially produced flerovium, all of these elements are familiar in daily life
either as the pure element or in the form of compounds, although, except for
silicon, none is particular plentiful in the earth's crust. Carbon forms an almost
infinite variety of compounds, in both plant and animal kingdoms. Silicon and
silicate minerals are fundamental components of the Earth's crust; silica (Silicon
dioxide) is sand. Tin and lead, with abundances in the crust lower than those of
some so called rare element, are nevertheless common in everyday life. They occur
in highly concentrated mineral deposits, which can be obtained easily in the
metallic state from those minerals, Germanium, on the other hand, forms few
characteristic minerals and is most commonly found only in small concentrations
in association with the mineral zinc blend and in coals. Although germanium is
indeed one recognition of its Properties as a semiconductor (i.e, limited ability to
conduct electricity).

7.2 Electronic Configuration of the Element

Like other groups, the members of this family show patterns in its electron
configuration, especially the outermost shells resulting in trends in chemical
behavior:

lxvii
6CI 1s2 s2 2p2

14 Si 1s2 2s2 2p6 3s2 3p2

35 Ge 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p2

52 Sn 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p2

82 Pb 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f14 5d10 6p2

Each of the elements in this group has four elements in its outer energy level. The
last orbital or all these elements is the p 2 orbital. In most cases, the elements share
their electrons. The tendency to lose electron increases as the size of the atom
increases, as it does with increasing atomic number. Carbon alone forms negative
ions, in the form of carbide (C4) ions. Silicon and germanium, both metalloids,
each can form +4 ions. Tin and lead both are metals while flerovium is a synthetic,
radioactive (its half life is very short), element that may have a few noble gas like
properties, though it is still most likely a post transition metal. Tin and lead are
both capable of forming +2 ions.

Carbon
Carbon forms tetra - halides with all the halogens except astatine. Carbon also
forms three oxides: Carbon monoxide, carbon sub oxide (C,O,), and carbon
dioxide. Carbon forms disulfides and di selenides.
Silicon
Silicon forms two hydrides: SiH4 and Si2H6. Silicon forms tetra – halides with
fluorine, chlorine, and iodine. Silicon also forms a dioxide and a disulfide. Silicon
nitride has the formula Si3N4.

lxviii
Germanium
Germanium forms two hydrides: GeH4 and Ge2H6. Germanium forms tetra halides
with a all halogens except astatin and forms di – halides with all halogens except
bromine and astatine.
Germanium bonds to all natural single chalcogens except polonium, and forms
dioxides. disulfides, and diselenides. Germanium nitride has the formula Ge 3N4.
Tin
Tin forms two hydrides: SnH4 and Sn2H6 Tin forms dihalide and tetra halide with
an halogens except astatine. Tin forms chalcogenides with one of each naturally
occurring chalcogen except polonium, and forms chalcogenides with two of each
naturally occurring chalcogen except polonium and tellurium.

Lead
Lead forms one hydride, which has the formula PbH4. Lead forms di – Halides
with fluorine and chlorine, and forms a tetra bromide and lead diiodide. Lead
forms form oxides, a sulphide, a selnide, and a telluride. These are no known
compounds of flerovium.
7.3 Physical Characteristics of Group IV Element

7.3.1 Boiling Point

The boiling points of the carbon group tend to get lower with the heavier elements.
Carbon, the lightest carbon group element, sublimates at 3825 0 c tins in 26020c and
lead's is 17490C. The melting Points of the carbon group elements have roughly the
same trend as their boiling points. Silicon melts at 1414 0c, germanium melts at
9390c tin melts at 2320c, and lead melts at 3280c

Carbon's crystal structure is hexagonal. Silicon and germanium have face centred
cubic crystal structures. Tin has a tetragonal crystal structure. Lead a face centred

lxix
cubic crystal structure.

7.3.2 Densities

The densities of the carbon group elements tend to increase in increasing atomic
number. Carbon has a density of 2.26 grams per cubic centimeter, silicon has a
density of 2.33 gram per cubic centimeter and germanium has a density of 5.32
grams per centimeter. Tin has a density of 7.26 gram per cubic centimeter, and lead
has a density of 11.3 grams per cubic centimeter.

7.3.3 Atomic Radii

The atomic radii of the carbon group elements tend to increase with increasing
atomic number. Carbon atomic radius is 77 picometers, silicon's is 118 picometers,
germaniums is 123 picometers, tin's is 141 picometers, and lead's is 175
centimeters.
7.4 Graduation in the Properties of the Elements

The element show the group valence of IV. Due in high ionization Energy required
for the formation of M4+ ions, the form covalent compounds. The Sn 4+ and Pb4+
ions, however, exist in the ionic dioxides SnO 2 and PbO2. The difference in the
properties of the elements are due to the presence of 18 electron in (9n-1) th shell of
Ge, Sn and Pb; and in addition, 32 electron in (n-2) th shell of Pb. Carbon has 2
electron in the (n-1)th shell while silicon has eight electrons in the (9n-1) the shell.
7.4.1 Metallic Characteristics
The metalic character increases progressively from C to Pb. Carbon and silicon
form mainly covalent compounds, but lead gives predominantly ionic compounds.
Silicon and Germanium are semiconductors. Diamond and Graphite are allotropes
of carbon. Diamond is a none conductor while graphite is a good conductor.

7.4.2 Nature of Bonding in Their Halides

lxx
The tetra halides MX4 (except PbBr4 and PbI4) and the dihalide of Ge, Sn and Pb
are known. Except for SnF4 and PbF4 which are ionic, the MX4 are volatile
covalent compounds.
4.3 Relative stability of the oxidation state

Inert pair effect begins to show Germanium, is marked for tin and predominate the
chemistry of lead. The stability of the divalent state with ns 2 configuration
increases from Germanium to lead so much that where as Sn (II) is reducing Pb
(IV) is oxidizing Pb2+ is stable in solid PBS and PbF2 but discrete Sn2+ ion does not
exist in any solid component.

7.4.4 Acidic/ Basic Nature of their Oxides

All the members of the group form MO and MO 2 increase from SiO to PbO.
Except for colourless gaseous CO others are solids; brown SiO, yellow or black
GeO, brown SnO and yellow or orange PbO. The acidic nature of the monoxide,
MO decreases from acidic SiO through amphoteric SnO to predominately basic
PbO.

The MO2 are more acidic and oxidizing than MO. They dissolve in alkalis forming
CO32- + HCO3- polymeric silicates, germinate.

The oxides of the elements at the top group 4 are acidic, but acidity of the oxides
falls as you go down the group. Towards the bottom of the group, the oxides
become more basic – although without ever losing their acidic character
completely.

An oxide which can show both acidic and basic properties is said to be amphoteric.

The trend is therefore from acidic oxides at the top of the group towards
amphoteric ones at the bottom.

lxxi
Carbon and silicon oxides

Carbon II oxide is usually treated as if it was a neutral oxide, but in fact it is very,
very slightly acidic. It doesn't react with water, but it will react with hot
concentrated sodium hydroxide solution to give a solution of sodium methanoate.

NaOH + CO HCOONas

The fact that the carbon monoxide reacts with the basic hydroxide ion shows that it
must be acidic

Carbon and silicon dioxides

These are both weakly acidic.

With water: Silicon dioxide doesn't react with water, because of the difficulty of
breaking up the giant covalent structure.

Carbon dioxide does not react with water to a slight extent to produce hydrogen
ions (strictly, hydroxonium ions) and hydrogen carbonate ions.

Overall, this reaction is:

H2O(l) + CO2(aq) H+ + HCO3(aq)

With base: Carbon dioxide reacts with sodium hydroxide solution in the cold to
give either sodium carbonate or sodium hydrogen carbonate solution – depending
on the reacting proportion.

2NaOH + CO2 Na2CO3 + H2O

NaOH + CO2 NaHCO3

lxxii
Silicon dioxide also reacts With Sodium hydroxide solution but only if it is hot and
concentrated. Sodium silicate solution is formed.

2NaOH + SiO2 Na2SiO3 + H2O

You may also be familiar with one of the reactions happening in the Blast furnace
extraction of iron – in which calcium oxide (from the limestone which is one of the
raw material reacts with silicon dioxide to produce a liquid slag, calcium silicate
this is also an example of the acidic silicon dioxide reacting with a base.

CaO(S) + SiO2(S) CaSiO3(L)

Germanium, Tin and Lead Oxides

The (II) oxides: All of these are amphoteric – they show both basic and acidic
properties. The basic nature of the oxides.

These oxides all react with acids to form salts.

For example, they all react with concentrated hydrochloric acid.

This can be summarized as:

XO(s) + 2HCl(aq) XCl2 + H2O(L)

Where X can be Ge and Sn, but unfortunately needs modifying a bit for lead.

Lead (II) Chloride is fairly insoluble in water and, instead of getting a solution, it
would form an insoluble layer over the lead (II) oxide if you were to use dilute
hydrochloric acid stopping the reaction from going on.

PbO(s) + 2HCl(aq) PbCl + H2O(l)

lxxiii
However, in this example we are talking about using concentrated hydrochloric
acid.

The large excess of chloride ions in the concentrated acid reacts with the lead (II)
chloride to produce soluble complexes such as PbCI 42-. These ionic complexes are
soluble in water and so the problem disappears.

PbCl2(s) + 2Cl(aq) PbCl42-

Unfortunately, it means that you have more to remember!

The (IV) oxides or dioxides: These dioxides are again amphoteric – showing both
basic and acidic properties.

The basic nature of the dioxides: The dioxides react with concentrated
hydrochloric acid first to give compounds of the type XCl4:

XO2 + 4HCl XCI4 + 2H2O

These will react with excess chlorides ions in the hydrochloric acid to give
complexes such as XCI62-

XCl4 + 2Cl- XCI62-

In the case of lead (IV) oxide, the reaction has to be done with ice cold
hydrochloric acid. If the reaction is done any warmer, the lead chloride
decomposes to give lead (II) chloride and chloride gas. This I can effect of the
preferred oxidation state of lead being 2+ rather than +4.

The acidic nature of the dioxides

The dioxides will react with hot concentrated sodium hydroxide, solution to give
soluble complexes of the form (X(OH)6)2-

lxxiv
XO2(s) + 2OH(aq) (X(OH)6)2-(aq)

Some sources suggest that the lead (IV) oxide needs molten sodium hydroxide. In
that case, the equation is different.

PbO2(g) + 2NaOH(l) Na2PbO3(s) + H2O(g)

Note

A diagonal relationship is said to exist between certain pairs of diagonally adjacent

elements in the second and third periods of the periodic table. These pairs Lithium
(Li) and Magnesium (Mg), Beryllium (Be) and Aluminium (Al), Boron (B) and
Silicon (Si) etc. Exhibit similar properties; for example, boron and silicon are both
semiconductors, forming halides that are hydrolyzed in water and have acidic
oxides.

Such relationship occurs because crossing and descending the periodic able have
opposite effects. On moving across the period of the periodic table, the size of the
atoms decreases while moving down the group, the size of the atoms increases.
Similarly, on moving across the period, the elements become progressively more
covalent, less basic and more electronegative, whereas on moving down the group
the elements become more 1onic, more basic and less electronegative. Thus, on
both descending a group and crossing the period by one element, the change
"cancel" each other out, and elements with similar properties which have similar
chemistry are often found the atomic size, electronegativity, properties of
compounds (and so forth) of the diagonal member are similar.

It is found that the chemistry of a first row (second period) element often has
similarities to the chemistry of the second row (third period) element being one

lxxv
column to the right of it in the period table. Thus, the chemistry of Li has
similarities to that of Mg. the chemistry of Be has similarities to that of Al, and the
chemistry of B has similarities to that of Si. These are called diagonal relationships
(NB: it is not as noticeable after B and Si). The reasons for why diagonal
relationships exist are not fully understood, but charge density is a factor. For
example, Li is a small cation with a +1 and M 2+ is somewhat larger with a +2
charge, so the charge density on each ion is roughly the same. Using the Li – Mg
pair (under room temperature and pressure).

1. Li and Mg form only formal oxides whereas Na forms peroxide and metals
below Na, in addition, forms superoxide.
2. Li is the only group I element which forms a stable nitride (Li 3N) . Mg as
well as other group 2 elements, also forms nitrides.
3. Lithium carbonate, phosphate and fluoride are sparingly soluble in water, the
corresponding Group 2 salts are insoluble. (think lattice and sol vation
energies). Both Li and Mg form covalent organometallic compounds. LiMe
and MgMe2.
4. Grignard Reagents) are both valuable synthetic reagents. The other group 1
and Group 2 analogues are ionic and extremely reactive (and hence difficult
to manipulate).

7.5 Diagonal relationship between Boron and silicon

Boron resembles silicon as they are diagonally placed in the periodic table. These
are some of the resemblances.

1. Their hydrides are volatile, covalent, reactive and readily hydrolyzed by water
and acids.
2. The halides are covalent and are hydrolyzed rapid in water

lxxvi
3. Boric and silicic are weak acids. Their salts borates and silicates are poly anions
and form solid solutions with one another in almost all proportions.
4. Silicide and borides are similar.
5. The oxides B2O3 nd SiO2 are acidic, polymeric, covalent macromolecules. They
dissolve metal oxides on fusion forming metal borates and silicates, which are
miscible with one another.
6. The two elements are non – metal
7. Non oxidizing acids do not reach with boron or silicon, with nitric acid; the
elements are oxidized to the oxides.

7.6 Why the properties of the First Element in the Group Differ from those of
the other element in the Group due to:

(i) Incomplete shielding of the valence shell electrons by the two electrons in
the K shield, the nucleus has great influence on the valence electron.
(ii) Small size of the element in the group confers it high charge radius which
makes the element high polarizing and
(iii) Absence of any low – energy vacant orbital for the expansion of the valence
shell to beyond octet.

7.7 Uses of Group (IV) Elements

Naturally occurring diamonds are highly priced because of their lustre and
classification as precious stones. Artificial diamonds or synthetic diamonds are
used for making cutting tools like drillers. Coke is used as a fuel for domestic as
well as industrial consumption and for producing heat and fuel gases (producer
gas, water gas, etc).

lxxvii
In metallurgy coke is used for reducing metal oxides; lining cells and making
electrodes. Coke is also used for making lead pencils, polishes, paints etc.
suspensions of graphite in water (aqua dag) and in oil (oil dag) are used as
lubricant at low temperatures.

Norite activated charcoal or animal charcoal is used as adsorbent for decolourizing

sugar and organic compound Silicon and ferrosilicon (Fe + Si) are used for
reducing metal oxides (MgO) and to remove Mn and O 2 from steel. The silicon
bronzes are used for telephone and exchange wires. Tin is a soft, lustrous plastic
and malleable metal with low tensile strength. It is not ductile at all, and is used
mainly for tin plating the iron sheets for making food containers, wrappers for
confectionaries are mainly tin foils. Lead is a heavy metal with low tensile
strength. It is used for sheathing electric cables, plumbering (pipes for water
supply), storage batteries and alloys. It absorbs nuclear radiations and is used for
making nuclear protection covers. Sodium - Lead alloy is used for preparing the
anti knock agent Pbetc (lead tetraethyl).

lxxviii
 CHAPTER EIGHT

HALOGENS

8.1 Introduction

The halogens or halogen element are a group in the periodic table consisting of
five chemically related element, Fluorine (F), Chlorine (CI), Bromine(Br), Iodine
(I), and astatine (At). The artificially created element 117 (unseptium) may also be
a halogen. The group of halogens is the only periodic table group which Contains
elements in all three familiar states of matter at standard temperature and pressure.
They have the electron short of the next noble gas.

8.2 The Occurrence of Halogens in Nature

Fluorine and chlorine are fairly abundantly, bromine and iodine less so. Fluorine is
present mainly in the insoluble fluorides of calcium: Calcium fluoride (fluorspar,
U.S.A); cryolite, NaAIF65 and fluorbapatite, Ca3(PO4)2 . CaF2. Sea water contains
the chlorides, bromides and iodides, of sodium, potassium, magnesium and
calcium but mainly sodium chloride (2.5% by weight). Certain form chlorine life
concentrate iodine in their systems: various seaweeds, for example, contain up to
0.2 percent iodine. In addition. chile salypeter contain up to 0.2 % sodium iodate.

Fluorine: Fluorine (from the Latin Fluere, for "Flow") was isolated by Henri
Moissan in 1886. It is a highly toxic and reactive greenish-yellow gas at room
temperature. Because of its reactivity, elemental fluorine is never found in nature
and no other chemical element can displace fluorine from its compounds.

In the late 1600's mineral which we now know contain fluorine were used in
etching glass. The discovering of the element was prompted by the search for the
chemical substance which was able to attack glass (it is HF, a weak acid). The

lxxix
early history of the isolation and work with fluorine and hydrogen fluoride is filled
with accidents since both are extremely dangerous. Eventually, electrolysis so the
mixture of KF and HF (carefully, ensuring that the resulting hydrogen and fluorine
would not come in contact) in a platinum apparatus yielded the element.

Compounds of fluorine are present in fluoridated toothpaste and in many municipal

water systems where they help to prevent tooth decay. And, of course,
fluorocarbons such as Teflon have made a major impact on life in the 20th century.

Chlorine: Chlorine, which is similar to fluorine but not as reactive, was prepared
by steele in the alte1700's and shown to be an element of Davy in 1810. It is a
greenish yellow gas with a disagreeable odour (you can detect it near poorly
balanced swimming pools). Its name comes from the Greek word chloros, meaning
greenish yellow. In high concentration it is quite toxic and was used in world war l
as a poison gas.

Like fluorine and the other members of the halogen family, chlorine is diatomic in
nature, occurring as Cl2 rather than Cl. It forms –1 ion in ionic compounds with
most metals. Perhaps the best known compound of that type is sodium chloride
common table salt (NaCl).

Small amounts of chlorine can be produced in the lab by oxidizing HCI with
MnO2. On an industrial scale, chlorine is produced by electrolysis or brines or even
sea water, sodium hydroxide (also in high demand) is a byproduct of the process.

In addition to the ionic compounds that chlorine forms with metals, it also forms
molecular compound with non – metals such as sulphur and oxygen. There are four
different oxides of the element. Hydrogen chloride gas (from which we get
hydrochloric acid) is an important industrial product.

lxxx
Bromine: Bromine is a reddish brown fuming liquid at room temperature with
very disagreeable chlorine like smell. In fact its name is derived from the Greek
bromos or "stench". It was first isolated in pure form by Ballard in 1826. It is the
only non – metal that is a liquid at normal room conditions. Bromine on the skin
causes painful burns that heal very slowly. It is an element to be treated with the
utmost respect in the laboratory. Most bromine is produced by displacement from
ordinary sea Water. Chlorine (which is more active) is generally used to dislodge
the bromine from various compounds in the water. Before leaded gasoline s were
removed from the market, bromine was used in an additive to help prevent engine
"knocking". Production now is chiefly devoted to dyes, disinfections and
photographic chemicals.

Iodine: Elemental iodine is a dark grey solid with a faint metallic lustre. When
heated at ordinary air pressures it sublimes to a violent gas. The name 1odine is
taken from the Greek ioeides which means "violent colour". It was discovered in
1811 by courtois.

Commercially iodine is recovered from seaweed and brines. It is an important trace

element in the human diet, required for proper function of the thyroid gland. Thus
iodine is added to table salt ("Iodized") to insure against done deficiencies.
Radioactive isotopes of iodine are used in medical tracer work involving the
thyroid and also to treat diseases of that gland.

Astatine: Astatine is the last of' the known halogens and was synthesized in 19

940 by corson and others at the University of California. It is radioactive and its
name, from Greek astatos, means Unstable". The element can be produced by
bombarding targets made of bismuth - 209 with high energy alpha particles

lxxxi
(helium nuclei). Astatine 211 is the product and has a half – life of 7.2 hours. The
most stable isotope of astatine is 210 which has a half – life of 8.1 hours.

Not much is known about the chemical properties of astatine but it is expected to
react like the other halogens, although much less vigorously, and it should be more
metallic than iodine. There should be tiny quantities of astatine in the earth's crust
as products of other radioactive decays, but their existence would be short lived.

8.3 The Electronic Configuration of the Halogens

Like other groups, the elements of this family show patterns in its electron
configuration, especially the outermost shells resulting in trend in chemical
behavior.

9F 1s2 2s2 2p5

17 CI 1s2 2s2 2p6 3s2 3p5

35 Br 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p5

53 I 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p5

85 As 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f14 5d10 6p5

Halogens are highly reactive, and as such can be harmful or lethal to biological
organisms in sufficient quantities. This high reactivity is due to the atoms being
highly electronegative due to their high effective nuclear charge. They can gain an
electron by reacting with atoms of other elements. Fluorine is one of the most
reactive elements in existence, attacking otherwise inert materials such as glass,
and forming compounds with the heavier noble gases. It is a corrosive and highly
toxic gas. The reactivity of fluorine is such that if used or stored in laboratory
glassware, it can react with glass in the presence of small amounts of water to form

lxxxii
silicon tetrafluride (SiF4). Thus fluorine must be handled with substances such as
Teflon (which is itself an organofluorine compound), extremely dry glass, or
metals such as copper or steel which form a protective layer of fluoride on their
surface.

The high reactivity off fluorine means that once it does react with something, it
bond with it so strongly that the resulting molecule is very inert and non reactive to
anything else. For example, Teflon is fluorine bonded with carbon.

8.4 Elemental forms of Group VII Elements

Fluorine and chlorine are gases bromine is a liquid and iodine a solid at 25 0c
physical and chemical properties of fluorine, chlorine, bromine and iodine.

8.5 Physical Properties

The table below is a summary of the key physical and atomic properties of the
halogens. Data marked with question marks are either uncertain or are estimation
partially based on periodic trends rather than observation.

Element Melting Boiling Density Electronegativity First ionization

point point (g/cm3at) energy covalent radius
Halogen (0C) (0C) 25(0C) (pauling) (kjmol-1) (pm(10))
Fluorine -219.62 -188.12 0.0017 3.98 1681.0 71
Chlorine 101.5 -34.04 0.0032 3.16 1251.2 99
Bromine -7.3 58.8 3.1028 2.96 1139.9 114
Iodine 113.7 184.3 4.933 2.66 1008.4 133
Iodine 113.7 184.3 4.93 2.66 1008.4 133
Astatine 302 337 2.2 2887.7

They are coloured (the depth of colour increasing down the group), volatile
diatomic molecules with typical penetrating odours. Fluorine and chlorine are

lxxxiii
gases bromine is a liquid and iodine is solid, at 25 0c. Astatine exists only as short
lived radioactive isotope and is not found in nature. All the halogens dissolve
slightly in water and colour dissolve slightly in water and colour it but fluorine
reacts to give oxygen and ozone. They have low melting points and boiling points
due to weak vanderwaals forces.

8.6 Chemical Properties

The chemical reactivity of halogen decreases from F2 to I2 Extremely high

reactivity of F2 is due to (i) low dissociation energy (due to repulsion amongst the
non handed electron pairs, (ii) high electronegativity (iii) small size of F and as
well as F- ion (iv) high lattice energy of ionic compound formed and not the
highest but very high electrons affinity the halogens directly combine with other
elements to form halides: F2, oxidizes the elements to the highest oxidation scale.
Thus, Co, S, V and Bi form CoF 3, SF6 VF5 and BiF5 with F2, but give CoC12, SC14,
VCI4 and BiC13 with Cl2. F2 reacts with all the known elements except.

N2He, Ne and Ar. In Cold water, F, evolves O2 while Cl2 and Br2 give clatherates
Cl27H2O and Br2 7H2O and Br2 8H2O as well as hydrate Cl28H20 which can be
crystallized on chilling the solutions. Adducts of halogens with Lewis base are
known: Me2CO: Br2 dioxin: Br2 C4H8S2I2 or Me3 N : I2 Compares of acid strengths
of Fluorine, Chlorine, bromine and iodine. In water, hydrogen fluoride behaves as
a weak acid and others are strong acid. In water the order of decreasing acid
strength is HI>HBr>HCI>> Hf. In solvents which are poorer proton acceptor than
water, such as formic acid, it can be seen that the order of increasing acid strength
is HF <<HCl<HBr< HI

lxxxiv
8.6.1 Oxyacids of Chlorine

Chlorine forms four oxyacids, Viz. hypochlorous acid (HOCI), Chlorous acid
(HCIO2), chloric acid (HCIO2) and perchloric acid (HCIO4) of which only HCIO4
can be isolated in pure state. The stability of the acids, their salts, and the acid
strength increase down the group but the oxidizing power decreases with
increasing oxidation state of chlorine.

Preparations

Hypochlorous Acid: This can be obtained or prepared by bubbling chlorine

through a suspension of mercuric oxide (HgO) in water.

2C12+ HgO HgCl2 + 2HOCl

Properties

Hypochlorous acid is unstable an loses oxygen on standing, HOCl is a weak acid

but a powerful oxidizing agent. It Oxidizes C- CO2+, Mn2+, Cr3+ and Pb2+ to Cl2, Cr3+
Mn2+. Cr6+ and Pb4+ respectively in acids ammonia is oxidized to nitrogen.

Chlorous acid

This is obtained by adding a calculated amount of dilute H 2SO4 to Ba(ClO2)

solution and filtering the BaSO2 precipitate.

Ba (ClO2)2 + dil H2SO4 BaSO4 + 2HCIO2

Properties

Chlorous acid solutions are colourless, but turn yellow on keeping due to the
formation of CIO2.

4HCIO2 CIO2 +CIO3 +CI + 2H +H2O

lxxxv
In alkalis, chlorites disproportionate to OCI– and CIO3

2CIO3 = CIO + CIO3

Chlorous acid is a moderately strong acid

Chloric acid

Chloric acid can be obtained by acidifying Ba (CIO3) with H2SO4.

Evaporation at low temperature gives about 40 percent HCIO3 solution.

Properties

Chloric acid is a strong Oxidizing agent and a strong acid. It oxidizes Cl - to Cl,
SO2, and can be reduced to HCl easily by Zn, SO2 or H2O2

Perchloric acid

Free HCIO4 is obtained by:

(i) Adding NaCIO4 to concentrated HCI in which NaCl is insoluble

(ii) Addition fluoro silicic acid to KCIO 4 and adding calculated amount of Bal 2
to precipitate excess site.

Properties

Anhydrous HCIO4 is colourless mobile liquid (Mp 162k, Bp 363K with explosion)
miscible with water in all proportions. Perchloric acid is the strongest simple acid
known and functions as an acid even in H2SO4 solution.

lxxxvi
8.6.2 Hydrogen Halides

The halogens all form binary compounds with hydrogen known as the hydrogen
halides: Hydrogen fluoride (HF), hydrogen chlorides (HCI), hydrogen bromide
(HBr), hydrogen iodide (HI), and hydrogen astatide (Hat). All of these are strong
chemical acids when dissolved in water, with the exception of HF. However,
hydrofluoric acid does have quite destructive properties towards animal tissues,
including those of human beings. When in aqueous solution, the hydrogen halides
are known as hydrohalic acids. The names of these acids are as follow:
hydrofluoric acid, hydrochloric acid, hydrobromic acid, and hydroiodic acid. All of
the these acids must be handled with great care because they are dangerous. Some
of these acids are also widely used in chemical manufacturing plants.

Hydrogen astatide should also be a strong acid (hydroastatic acid), but it is seldom
included in presentation about hydrohalic acids because of the extreme
radioactivity of astatine (via alpha decay) and the fact that it readily decomposes
into its constituent elements (hydrogen and astatine).

8.6.3 Metal halides

The halogens form many Compounds with metals. These compounds range from
highly ionic compounds like sodium chloride, monomeric covalent compounds
like uranium hexafluoride, and polymeric covalent compounds like palladium
chloride. Metal halides are generally obtained by direct combination, or more
commonly, neutralization of basic metal salt with a hydrohalilc acid. They serve as
useful entry point into inorganic chemistry.

lxxxvii
8.6.4 Inter-halogen compounds

The halogens react with each other to form Interhalogen compounds. Diatomic
interhalogen compound such as BrF, ICI, and CIF bear resemblance to the pure
halogen in some respects. The properties and behavior of a diatomic interhalogen
compound tend to be intermediate between those of its parent halogens. Some
properties, however, are found in neither parent halogen. For example, Cl 2 and I2
are soluble in CCI4 but ICI is not since it is a polar molecule due to the relatively
large electronegativity difference between I and Cl.

8.6.5 Organ Halogen Compounds

Many synthetic organic compounds such as plastic polymers and a few natural
ones, contain halogen atoms; these are known as halogenated compounds or
organic halides. Chlorine is by far the most abundant of the halogen, and the only
one needed in relatively large amounts (as chloride ions) by humans. For example,
chloride ions play a key role in brain function by mediating the action of the
inhibitory transmitter GABA and are also used by the body to produce stomach
acid. Iodine is needed in trace amounts for the production of thyroid hormones
such as thyroxine. On the other hand, neither fluorine nor bromine is believed to be
essential for human. Organ halogens are also synthesized through the nucleophilic
abstraction reaction.

8.6.6 Polyhalogenated compounds

Polyhalogenated compound are industrial created compounds substituted with

multiple halogens. Many of them are very toxic and bioaccumulation in human,
and have a very wide application range. They include the much maligned PCBs,
PBDEs and PFCs as well as numerous other compounds.

lxxxviii
8.6.7 Reactions of Halogens with Water

Fluorine: Fluorine reacts vigorously with water to produce Oxygen (O 2) and

hydrogen fluoride (HF);

2F2(g) + 2H2O(l) O2(g) + 4 HF(aq)

Chlorine: Chlorine has maximum solubility of ca. 7.1 g Cl 2 per kg of water at

ambient temperature (210C), dissolved chlorine reacts to form hydrochloric acid
(HCI) and hypochlorous acid, a solution that can be used as a disinfectant or
bleach:

Cl2(g) + H2O(l) HCl(aq) + HCIO(aq)

Bromine: Bromine has a solubility of 3.41 g per 100g of water, but is slowly
reacts to form hydrogen bromide (HBr) and hypobromous acid (HBrO):

Br2(g) + H2O(l) HBr(aq) + HBrO(aq)

Iodine: Iodine, however, is minimally soluble in water (0.03g/100 water at 20 0c)

and does not react with it. However, iodine will form an aqueous solution in the
presence of iodide ion, such as by addition of potassium iodide (K), because the
triiodide ion is formed.

8.6.7 Inter-halogen compounds

The halogens react with each other to form interhalogen compounds. Diatomic
interhalogen compound such as BrF, ICI, and CIF bear resemblance to the pure
halogen in some respects. The properties and behavior of a diatomic interhalogen
compound tend to be intermediate between those of its parent halogens. Some
properties, however, are found in neither parent halogen. For example, Cl 2 and I2

lxxxix
are soluble in CCI4 but ICI is not since it is a polar molecule due to the relatively
large electronegativity difference between I and Cl.

8.6.8 Organ Halogen Compounds

Many synthetic organic compounds such as plastic polymers, and a few natural
ones, contain halogen atoms; these are known as halogenated compounds or
organic halides. Chlorine is by far the most abundant of the halogen , aad the only
one needed in relatively large amounts (as chloride ions) by humans. For example,
chloride ions play a key role in brain function by mediating the action of the
inhibitory transmitter GABA and are also used by the body to produce stomach
acid. Iodine is needed in trace amounts for the production of thyroid hormones
such as thyroxine. On the other hand. neither fluorine nor bromine is believed to be
essential for human. Organ halogens are also synthesized through the nucleophilic
abstraction reaction.

8.6.9 Polyhalogenated compounds

Polyhalogenated compound are industrial created compounds substituted with

multiple halogens. Many of them are very toxic and bioaccumulation in human,
and have a very wide application range. They include the much maligned PCBs,
PBDEs and PFCs as well as numerous other compounds.

8.6.10 Reactions of Halogens with Water

Fluorine: Fluorine reacts vigorously with water to produce oxygen (O 2) and

hydrogen fluoride (HF);

2F2(g) + 2H2O(l) O2(g) + 4HF(aq)

xc
Chlorine: Chlorine has maximum solubility of ca. 7.1 g Cl 2 per kg of water at
ambient temperature (210C), dissolved chlorine reacts to form hydrochloric acid
(HC) and hypochlorous acid, a solution that can be used as a disinfectant or bleach:

Cl2(g) + H2O(l) HCl(aq) + HClO(aq)

Bromine: Bromine has a solubility of 3.41 g per 100g of water, but is slowly
reacts to form hydrogen bromide (HBr) and hypobromous acid (HBrO):

Br2(g) + H2O(l) HBr(aq) + HBrO(aq)

Iodine: Iodine, however, is minimally soluble in water (0.03g/100 water at 20 0c)

and does not react with it. However, iodine will form an aqueous solution in the
presence of iodide ion, such as by addition of potassium iodide (KI), because the
triiodide ion is formed.

xci
QUESTIONS AND ANSWER ON STC 211

1. Explain the term inorganic chemistry

2. Explain the differences between carbon monoxide and carbon dioxide
3. What is geochemistry
4. Explain the alkaline metal and list with atomic number the elements of the
group
5. Write the physical and chemical properties of the group 1A elements.
6. What is the electronic configuration of element
7. What is atomic orbital
8. Write the electronic configuration of alkali metals
9. The group 1A elements react with cold water and liberate hydrogen gas and
form alkalis hence the name. give chemical equations for the above statement.
10.Explain the term reactivity
11.Name some important compounds
12.What is ionization energy
13.Describe the electronegativity of an element.
14.What are the differences between lithium and other group 1A element
15.Describe the group IIA elements and list all the elements of the group.
16.Write the comparism in physical properties of group 1A metal and group IIA
metal
17.Explain the term hard water.
18.List and explain the type of hardness in water
19.Write the methods of removing permanent hardness in water.
20.Describe halogens

xcii
ANSWER

1. Inorganic chemistry is a branch of chemistry that deal with the properties and
behavious of inorganic compounds. Inorganic compounds are those that are not
biological and characterized by not containing any hydrogen and carbon bonds
2. The major difference between carbon dioxide (CO 2) and carbon monoxide (CO)
is in the number of oxygen atoms they carry though both contain carbon and
oxygen atom while both have the same number of carbon atoms i.e one carbon
atom, carbon dioxide has 2 carbon atom and carbon monoxide has one oxygen
atom.
3. Geochemistry is the study of chemistry of the earth and other plants and it
covers the chemical composition of rocks and soil.
4. The alkaline metals are a group in the periodic table consisting of element such
as Lithium (Li), Sodium (Na), Potassium (K), rubidium (Rb), Caesium (Cs) and
Francium (Fr). They are all metals; therefore they possess all the metallic
properties. They are found in s – block orbital (i.e they are the first group of
element in the periodic table). They are called alkaline metals because when
dissolved in water they form alkaline solution. The elements with their atomic
numbers, Lithium (Li) = 3, Sodium (Na) = 11, Potassium (K) = 19, Rubidium
(Rb) = 37, Caesium (Cs) = 55 and Francium (Fr) = 87.
5. The physical properties of alkaline metals
 They are highly reactive
 They all possess one outermost electron
 They all shiny metals
 They are all very soft they readily lose their outermost electron to form
cations with charge +1
 They can all be cut easily with a knife due to their softness

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Chemical properties
 They ionize easily by theloss of one electron per atom hence powerful
reducing agent
 They are good conductor of electricity are highly electropositive
e.g Na Na+ + e
 They react with cold water vigorously to liberate hydrogen gas and form
alkalis hence the name e.g
2K(s) + 2H2O(l) 2KOH + H2
 They form basic oxides which dissolve in water very strong alkalis
2Na2Os) + H2O 2NaOH
6. The electronic configuration could be define as the arrangement of electrons in
its atomic orbitals when it is at ground state.
7. Atomic orbital referred to any point or space where there is a high possibility of
finding electron. There are four types of atomic orbitals which include s, p, d
and f orbitals. These atomic orbitals represent energy levels in the shell that
surrounded the atom.
8. The electronic configurations of the alkaline metals.
Lithium 4Li 1s2 2s2
Sodium Na
12 1s2 2s2 2p6 3s2
Potassium 19K 1s2 2s2 2p6 3s2 3p6 4s2
Rubidium 38Rb 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2
Cesium Cs
56 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2
Francium 88Fr 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f14
5d10 6p6 7s2

9. The chemical equation

2K(S) + H2O(L) 2KOH(aq) + H2(g)

xciv
10.The reactivity of a substance refers to the chemical reaction of the substance
singly or the chemical reaction of two or more substances that interact with
each other.
11.Some important compounds
 Lithium chloride and lithium bromide LiCl and LiBr, because the Li + ion is
so small, Li salts have a high affinity for water, then they are used in air –
cooling unit.
 Lithium carbonate Li2CO3: it is used to make porcelain enamels and
toughened glasses and as drug in the treatment of manic – depressive
disorders.
 Sodium chloride NaCl which is used industrially in the production of Na,
NaOH, Na2CO3 and NaHCO3
12.Ionization energy: the first ionization energy of an element or molecules is the
energy required to remove the most loosely held electron from one mole of
gaseous atoms of the elements or molecules to form one mole of the gaseous
ions with electric charge +1
13.The electronegativity of element is the chemical property that describes the
tendency of an atom or a functional group to attract electron or electron density
towards itself.
14.Difference between lithium and other group 1A
 It has high melting and boiling point than those in the group
 It is harder than the rest of the group
 Its reaction with oxygen is least readily forming the normal oxide. It forms
peroxide only with great difficulty.
 Lithium form nitride Li3N
 It react with carbon directly

xcv
  Lithium has greater tendency to form complexes e.g (Li (NH 3)4) which exist
as solid
15.The group IIA elements: the alkaline earth metals (elements) are metallic
elements found in the second group (Group II) of the periodic table. All alkaline
earth metals have an oxidation state of +2, making them very reactive. Because
of their reactivity, the alkaline earth metals are not found freely in nature. The
elements of the group are;
Beryllium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba)
and Radium (Rd)
16.The comparism in physical properties of group 1A metal and group IIA metals.
 Most of the difference occurs as the result in the outer electrons
configuration is ns1 and ns2
 One electron is involved in the metallic bonding of group 1A while two
electrons are involves in metallic bonding in group IIA.
 As a result of this differences in number of outer electron(s). the nuclear
charges in group II are greater as such more greater attraction of the
decolorize electron by nucleus hence the boiling and boiling and melting
point of group II are much higher than group 1A.
17.Hard water is one which contains dissolved salts of magnesium or calcium in
form of carbonate, bicarboneates or sulphates. It is difficult to produce lather
with soap instead an insoluble scum id form. The metal ion Ca 2+ or Mg2+ react
with the stearate ion from the soap, forming and insoluble scum of calcium or
magnesium stearate before any lather is produced. Hard water also produces
scale (insoluble deposits) in water pipes, boilers and kettle.
18.The type of hardness in water
 Temporary hardness: Is a type of water hardness caused by the presence of
dissolved bicarbonate minerals (calcium bicarboneate and magnesium
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 bicarbonate).
 Permanent hardness: this type of hardness is caused by dissolved sulphates
and chloride of calcium and magnesium which become more insoluble as the
temperature increases.
19.Method of removing permanent hardness
 Addition of slake lime (clark’s process). In this process slake lime Ca(OH) 2
is added to the water
 Addition of washing soda (NaCO3) calgon can be used to soften hard water
 Addition of washing soda (Na2CO3.10H2O): washing soda remove the
calcium or magnesium ions as insoluble calcium or magnesium
trioxocarbonate which can be settle down or filtered off.
 Addition of caustic soda: caustic soda (NaOH) remove calcium or
magnesium or calcium hydroxide.
20. Halogen: the halogens or halogen elements are a group in the periodic talbe
consisting of five chemically related element, fluorine (F) chlorine (Cl),
Bromine (Br), Iodine (I) and Astatine (At). The group of halogens is the only
periodic table group which contains elements in all three familiar states of
matter at standard temperature and pressure.

xcvii
REFERENCES
Damisa, D. (2009). Inorganic chemistry Theory Published by UNESCO – Nigeria
Technical and Vocational Education Revitalization project – Phase II

The Royal society of Chemistry Experiments Published by the Royal Society of

Chemistry (UK) and free on the Internet
http://www.chemoorg/networks/learnnet/classic exp.ht

Lime softening'" http://water .me.vccs. Educ/ concepts/ softeninglime. Retrieved 4

November 2011

Sienko, M.J and plane, R.A (McGraw Hill). Textbook of advance chemistry .

Silberberg. M. S. Published by McGraw Hill. (The molecular nature of matter and

change)

Salters Advance Chemistry Activities and Assessment pack published by

Heinemann.

Stephen Lower (July 2007). Hard water and water softening http://www.chem
l.com/CO/hardwater.html. Retrieved 2007-10-03

xcviii
 INDEX

Advantage of hard water - - - - - - - 67

Alkaline metals - - - - - - - - - 4

Anomalous behavior of beryllium - - - - - - 51

Anomalous behavior of lithium - - - - - - - 29

Astatine - - - - - - - - - - 119

Barium - - - - - - - - - -

Beryl - - - - - - - - - - 45

Beryllium - - - - - - - - - 34

Boron - - - - - - - - - 89

Bromine - - - - - - - - - 117

Carbon - - - - - - - - - 96

Caesium - - - - - - - - - 67

Calcium - - - - - - - - - 67

Calgon process - - - - - - - - 60

Plog plumbing - - - - - - - - 69

xcix
Chlorine - - - - - - - - - 116

Chlorous acid - - - - - - - - 124

Chloric acid - - - - - - - - 125

Disadvantage of hard water - - - - - - - 68

Fajans rule - - - - - - - - - -

Fierovium - - - - - - - - -

Francium - - - - - - - - - 12

Fluorine - - - - - - - - - 115

Gallim - - - - - - - - - 90

Galvanic corrosion - - - - - - - 70

Germanium - - - - - - - - 97

Griguard reagent - - - - - - -

Group IIA element - - - - - - - 31

Hard water - - - - - - - - 55

c
I

Indium - - - - - - - - -

Iodine - - - - - - - - - 118

Lead - - - - - - - - - 97

Lithium - - - - - - - - - 30

Magnesium - - - - - - - - 45

Measurement of hardness - - - - - - 66

Permutit - - - - - - - - - 62

Perchloric acid - - - - - - - - 125

Potassium - - - - - - - - - 12

Ployhalogenated - - - - - - - - 129

Properties of Group IA elements - - - - - 98

Properties of Group IIA elements - - - - - - 79

Radium - - - - - - - - - -

Rubidium - - - - - - - - - 12

ci
S

Slake line - - - - - - - - - -

S-block element - - - - - - - -

Silicon - - - - - - - - - 96

Soap scum - - - - - - - - - 68

Sodium strontium - - - - - - - - 67

Thallium - - - - - - - - - 92

Washing soda - - - - - - - - -

Zeolite - - - - - - - - - - 67

cii