TABLE OF CONTENTS

CHAPTER 1: ATOMIC STRUCTURE ................................ 9

1.0. General introduction and definition of an atom ............ 9
1.1. Particles which constitute an atom.............................. 10
1.2. Isotopes and relative atomic mass (RAM) .................. 14
1.3. Description of mass spectrometer ............................... 16
CHAPTER II: PERIODIC TABLE OF CHEMICAL
ELEMENTS......................................................................... 31
2.1. The history of the periodic table ................................. 31
2.2. Classification of elements in the Periodic Table
according to Mendeleev and the modern Periodic Table ... 33
2.3. Variation of physical properties in Groups and Periods
36
2.3.1 Atomic radius ......................................................... 36
2.3.2 Ionization energy .................................................... 40
2.3.3. Electron affinity ..................................................... 47
2.3.4. Electronegativity.................................................... 50
2.3.5. Electrical conductivity .......................................... 52
CHAPTER III: ELECTRONIC STRUCTURE ................... 57
3.1. Bohr’s model of an atom ............................................ 57
3.2. Atomic spectra 60
3.3. Hydrogen spectra and spectra series ........................... 61
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 3.4. Energy levels, sub-energy levels and orbitals ............. 68
3.4.1. The three quantum numbers .................................. 68
3.4.2. Representation or shapes of orbitals ...................... 72
3. 4. 3 Electron spin and the Pauli Exclusion Principle ... 74
3. 4. 4. The aufbau method and electron configuration ... 75
3. 4. 4. Interpretation of a graph of ionization potential
against the number of electrons. ...................................... 80
CHAPTER IV: CHEMICAL BONDING ........................... 83
4.1. Ionic bonding 85
4.1.1. Formation .............................................................. 85
4.1.2. Giant ionic structures ............................................. 86
4.1.2. Properties of ionic compounds .............................. 86

Melting Point ............................................................. 87

Conductivity .............................................................. 88

Brittleness .................................................................. 89
4.2. Covalent bonding 90
4.2.1. Formation .............................................................. 90
4.2.2. Properties of covalent compounds ......................... 91
4.2.3. Covalent network solids ........................................ 91
Case of Carbon .............................................................. 92
4.2.4. Dative and coordinate bond ................................... 94
4.2.6. Shapes of molecules .............................................. 98
4.2.7. Polarity of molecules ........................................... 103
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 4.3. METALLIC BONDING AND THE PROPERTIES OF
METALS 105
4.3.1. Formation. ........................................................... 105
4.3.2. Physical Properties of Metals .............................. 105

Conductivity ............................................................ 106

Melting Points .......................................................... 107

Optical Properties ................................................... 108
4.4. INTERMOLECULAR FORCES .............................. 109
4.4.1. Types of intermolecular forces ............................ 109
a) Dispersion Forces (London Forces or Weak
Intermolecular Forces or van der Waal's Forces) .... 109
b) Dipole-dipole Interactions ...................................... 110
c) Hydrogen bonds ...................................................... 111
4.4.2. Effect of Intermolecular forces on melting and
boiling points of molecular covalent substances: .......... 112
4.4.3. Effect of Intermolecular Forces on Solubility ..... 114
CHAPTER V: COMPARATIVE STUDY OF CHEMICAL
REACTIONS OF ELEMENTS IN THE PERIODIC TABLE
........................................................................................... 117
5.1. CHEMISTRY OF GROUP I AND II ELEMENTS . 118
5.1.1. Introduction ......................................................... 118
5.1.2. Physical properties of the elements ..................... 118
5.1.2. Chemical properties and reactions of elements ... 120

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5.2. STUDY OF GROUP III ELEMENTS ...................... 126
5.2.1 Introduction .......................................................... 126
5.2.2 Physical properties of boron and aluminium ........ 126
5.2.3 Reaction of aluminium. ........................................ 127
5.2.4. Compounds of aluminium ................................... 128
5.2.5. Uses of some groupIII elements .......................... 131
5.3. GROUP IV ELEMENTS .......................................... 132
5.3.1. Comparative study of physical properties of group
IV elements.................................................................... 132
5.3.2. Allotropes of carbon ............................................ 134
5.3.3 Uses of group 4 elements...................................... 136
5.3.4. Reaction of C, Sn, Pb and Si................................ 138
5.3.5. Compounds of group IV elements ....................... 140
5.3.6. Diagonal relationship of group I, II, III and IV ... 146
5.4. GROUP V ELEMENTS ........................................... 150
5.4.1 Physical state and metallic character .................... 150
5.4.2 Allotropes of phosphorus...................................... 151
5.4.3 Chemical properties of nitrogen and phosphorus . 152
5.4.4 Preparation of nitrogen ......................................... 153
5.4.6 Chemical, properties of phosphorus compounds. . 155
5.5 GROUP VI ELEMENTS ........................................... 155
5.5.1 Physical properties................................................ 155
5.5.2 Chemical properties of sulphur ............................. 157
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 5.6 GROUP VII ELEMENTS ......................................... 158
5.6.1 Comparative study of physical properties of halogens
....................................................................................... 158
5.6.2 Comparative study of chemical properties of
halogens ......................................................................... 159
5.6.3 Uses of halogens ................................................... 164
5.7 GROUP VIII ELEMENTS ........................................ 167
5.8 PERIOD III ELEMENTS .......................................... 167
CHAPTER VI: CLASSIFICATION OF REACTIONS .... 221
6.1. Introduction 222
6.2. Oxidation number 222
6.3. Reactions in which oxidation state does not change or
metathesis reactions 223
CHAPTER VII. TRANSITIONS ELEMENTS (FIRST
SERIES) ............................................................................. 235
7.1 General introduction .................................................. 236
7.2. General characteristics of transition metals .............. 239
7.3. Naming complex metal ions ..................................... 257
7.4 Complex metal ions - ligand exchange reactions....... 262
7.5. Complex ions - The acidity of the hexaaqua ions ..... 269
7.6. Reactions of hexaaqua metal ions with hydroxide ions
274
7.7. Uses of complex ions ................................................ 284

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 7.8. Chemical reactions of Chromium, manganese, cobalt,
iron, copper, and zinc with water and mineral acids( HCl,
HNO3, H2SO4) 284
CHAPTER VIII: IDENTIFICATION OF
IONS/QUALITATIVE ANALYSIS.................................. 291
8.1 Appearance 292
8.2 Procedure of carryng out flame tests ......................... 298
8.3. Confirmatory tests for some gases ............................ 300
8.4 Some examples of practical work about qualitative
analysis 307
REFERENCES .................................................................. 331

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METHODOLOGICAL APPROACHES

Understanding chemistry through this textbook is relevant for

students to read and to analyze different concepts even before
explanations from the chemistry teacher. For this, students
should work in groups in order to share each other their
experience. During reading, it is better to check for objectives
written on first’s pages for each chapter. This will help
students to understand themselves different concepts using
their own effort and prerequisites.
Also, in reading they could discover some challenges that
make them to search in other available chemistry books or
internet and to ask questions in case of misunderstanding in
order to avoid misconception.
Hands-on activities using real or concrete materials should be
prepared for learners in order to help them gaining
experience, construct abstract ideas, obtain scientific
findings, build self-confidence, be self-determining and
inculcate the team spirit.
Learning in groups should be emphasized to help learners to
develop social skills, encourage cooperation and build self-
confidence. Environment awareness and conservation skills
should also be developed through the teaching and learning
process in the classroom by using examples, and showing
positive and negative impact of chemicals on the
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environment by using chemical reactions and equations in the
context of modeling.
Various teaching strategies and approaches such as learner-
centered learning and formative evaluation to determine the
effectiveness of teaching and learning process must be taken
into consideration.
Planning and carrying out evaluation or assessment as a part
of the classroom activities would be also more important.
Teacher should organize practical tests to ensure that students
have indeed acquired the basic skills suggested in this
textbook

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CHAPTER 1: ATOMIC STRUCTURE
1.0. General introduction and definition of an atom
Chemistry is defined as a study of composition, structure,
properties of matter and the changes that matter undergoes.
Matter is anything that has mass and occupies space. In
Dalton’s atomic theory, matter is composed of atoms.
Atom is the smallest particle of an element that has the
properties of that element. Atoms combine chemically to
form molecules. An atom consists of a nucleus with electrons
around it.
Atomic structure is the structure of the nucleus and of the
extra nuclear electrons. The extra nuclear electrons are
arranged in atomic shells.
The main points in Dalton’s atomic theory can be
summarized as follows.
1. Matter is composed of tiny particles called atoms, which
can not be created or destroyed or split.
2. All the atoms of a given element are identical: they have
the same mass and the same chemical properties. They
differ from the atoms of all other elements.
3. A chemical reaction consists of rearranging atoms from
one combination into another. The individual atoms
remain intact. No atoms are created, destroyed, or
broken in a chemical reaction.

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 4. Compounds are formed when atoms of different
elements unite in fixed proportion. When elements
combine to form compounds, small whole numbers of
atoms combine to form compound molecules

Chemists today know that there are problems with two of

these points.
First there are differences between atoms in most elements
(isotopes).
Second, some atoms in most elements (of radioactive
elements) do transform themselves into others, and a wide
variety of such changes are possible given enough energy.
1.1. Particles which constitute an atom

ELECTRON (e-): is a subatomic particle with a negative

electric charge. It is the smallest subatomic particle with a
mass of 9.109 x 10-31 kg. Electrons form the outer layer or
layers of an atom. The electron is also one of the few
elementary particles that is stable, meaning it can exist by
itself for a long period of time. Most other elementary
particles can exist independently for only a fraction of a
second.
Electrons have no detectable shape or structure.
PROTON (p): is a subatomic particle with a positive charge.
The charge is equal and opposite to that of an electron. The
mass of a proton is 1840 times that of an electron. The proton

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is one of the few elementary particles that are stable—that is,
it can exist by itself for a long period of time.
NEUTRON (n): is a subatomic particle with a mass almost
equal to the mass of a proton. It has no electric charge. The
neutron is about 10-13 cm in diameter and weighs 1.6749 x
10-27 kg.
Note.

All sub-atomic particles are said to be elementary
particles because they are the smallest parts of matter
that scientists can isolate.

The neutrons and protons make up the nucleus, or core,
of the atom and are both nucleons. The number of
protons and neutrons is called nucleons number, or,
alternatively, the mass number (A)

The number of protons is called the atomic number (Z)
or proton number.

The mathematical relationship between atomic

number(Z), mass number (A)and neutron number(n) is
A=Z+n

The unit used to measure the mass of an atom is called

the atomic mass unit, abbreviated “amu or u” and is
defined as a 1/12 times the mass of an atom of carbon-12
i.e. 1/12×1.992 ×10-23g

1amu=1.66×10-24g or 1.66×10-24g;
1amu=1/6.023×1023
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Table 1.1: The mass and charge of sub-atomic particles
Particle Charge/C Relative Mass/Kg Mass/u
charge
Proton +1.6022×10- +1 1.6726×10- 1.0073
19 27

Neutron 0 0 1.6750×10- 1.0087

27

Electron -1.6022×10- -1 9.1095×10- 5.4858×10-

19 31 4

ATOMIC PARTICLES DISCOVERY

PROTON DISCOVERY
The proton has been discovered by Ernest Rutherford. He
noticed that, when he shot alpha particles into nitrogen gas,
being knocked off by the impact of the alpha particle; it
produces oxygen-17and a particle having a positive charge
with the same absolute value of that of an electron. This was
the first reported nuclear reaction.
14
N + α → 17O + p
The discovery that a proton is present in all other nuclei as an
elementary particle led Rutherford to give it a special name,
the proton!
NEUTRON DISCOVERY

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In 1931, Walther Bothe and Herbert
Becker in Germany found that if the very energetic alpha
particles emitted from polonium fell on certain light
elements, specifically beryllium, boron, or lithium, an
unusually penetrating radiation was produced.
In 1932, James Chadwick performed a series of experiments
at the University of Cambridge, suggesting that the new
radiation consisted of uncharged particles of approximately
the mass of the proton, and he performed a series of
experiments verifying his suggestion. These uncharged
particles were called neutrons, apparently from the Latin root
for neutral and the Greek ending -on (by imitation
of electron and proton).
ELECTRON DISCOVERY
In 1897, the British physicist J.J. Thomson was venturing
into the interior of the atom. At the Cavendish Laboratory at
Cambridge University, Thomson was experimenting with
currents of electricity inside empty glass tubes. He was
investigating a long-standing puzzle known as "cathode
rays." His experiments prompted him to make a bold
proposal: these mysterious rays are streams of particles much
smaller than atoms; they are in fact minuscule pieces of
atoms.
The rays are made up of electrons: very small, negatively
charged particles that are fundamental parts of every atom.

ATOMIC NUMBER AND ATOMIC MASS NUMBER

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 a. Atomic number, Z
It shows:
 the number of protons in the atomic nucleus
 the number of electrons around the atomic nucleus
 the place of an element in the periodic table
e.g: calcium, Z= 20, i.e it has 20 protons, 20 electrons and
occupies the 20th place in the periodic table.
b. Mass number, A
It is the sum of the number of protons and neutrons
A= N+Z
Remember, the number of protons and neutrons is called
nucleons.

1.2. Isotopes and relative atomic mass (RAM)

Isotopes are the atoms of the same element which have

different mass numbers for that element. As all atoms of an
element have the same number of protons, isotopes differ in
having different numbers of neutrons in the nucleus of the
atoms, and occupy the same place on the periodic table since
they have the same number of protons and electrons.

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Example:
There are three isotopes of carbon, one with a mass number
of 12, 13 and 14. All isotopes have six protons in their nuclei
so one isotope has six neutrons, the other seven neutrons and
the last one has got 8 neutrons. Isotopes are shown by writing
the mass number after the element, e.g. carbon-12 is the
isotope of carbon with a mass number of 12.
Another notation is AZX where A is the atomic mass, Z
atomic number and X is the element symbol.

Relative atomic mass (RAM) is the ratio of the mass of one

atom of an element to one-twelfth of the mass of one atom of
carbon-l2. Most elements consist of isotopes of its atoms;
hence the relative atomic mass measures the average mass
per atom of the normal isotopic composition of an element.
Let A1 , A2, A3,…, An be abundance of n isotopes of the same
chemical element with atomic mass M1, M2, M3,…, Mn, the
relative atomic mass(RAM) is given by the following
equation:

Worked example:
012-Page 15
Calculate the relative average mass (RAM) of
chlorine, whose abundance of isotopes Chlorine-35
and chlorine-37 are respectively 75% and 25%.
Method:
Using the expression given bellow, we find that

Testing your knowledge and understanding

1. State the number of protons, neutrons and electrons in
the following atoms:
a)
What is the relationship between the different atoms of
hydrogen?
2. The relative atomic mass of Copper is 63.54 .Given
that copper occurs naturally in terms of 2 isotopes 63Cu
and 65Cu, what is their abundance in percentages?
3. The nature isotopes composition of lithium is 92.58% for
7
3 Li and 7.42% for Li . Determine the relative mean mass of
6
3

lithium?
1.3. Description of mass spectrometer
Mass spectrometer is an instrument that separates positive
gaseous ions according to their mass-to- charge ratios and
that records the resulting mass spectrum. In the mass
spectrometer, atoms and molecules are converted into ions.
The ions are separated as a result of the deflection thanks to a
magnetic field applied to them.
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An outline of what happens in a mass spectrometer
Atoms can be deflected by magnetic fields - provided the
atom is first turned into an ion. Electrically charged particles
are affected by a magnetic field while electrically neutral
ones aren't.
The sequence is:
Stage 1: Ionization
The atom is ionized by knocking its one or more electrons off
to give a positive ion. This is true even for things which you
would normally expect to form negative ions (chlorine, for
example) or never form ions at all (argon, for example). Mass
spectrometers always work with positive ions. Ionisation is
caused by electrons emitted by an electrically heated metal
coil. All this takes place in the ionization chamber.
Stage 2: Acceleration
The ions are accelerated in such a way that they may all have
the same kinetic energy. Accerelation is ensured by an
electric field positioned immediately after the ionizer-the
electrically heated metal coil. The acceleration persuades the
positive ions throughout the slits of 3 metal plates positioned
just after the ionization chamber.
Stage 3: Deflection
The ions are then deflected by a magnetic field according to
their masses (especially). The lighter they are, the more they

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are deflected.The amount of deflection also depends on the
number of positive charges on the ion; that is, on how many
electrons were knocked off in the first stage-in ionization.
The greater the ion charge is, the more it gets deflected. By
combining the two factors, one says: the deflection of any
gaseous ion depends on its mass/charge ratio (mass-to-
charge ratio).
Stage 4: Detection
The beam of ions passing through the machine is detected
electrically by a device known as detector.
A full diagram of a mass spectrometer
A C C E L E R A T IO N
IO N IZ A T IO N
e le c t r o m a g n e t

to v a cu u m p u m p
v a p o r iz e d s a m p le

D E F LE C T IO N

D E T E C T IO N a m p lifie r

ch a r t
re co r d e r

Understanding what is going on

The need for a vacuum

It's important that the ions produced in the ionization
chamber have a free run through the machine without hitting
air molecules.

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Ionization-in the ionization chamber
electron trap

ion repeller electrons

vaporised
sam ple
positive ions

electrically heated

The vaporized sample passes into the ionization chamber

(with positive voltage of about 10,000 volts). The electrically
heated metal coil gives off electrons which are attracted to
the electron trap which is a positively charged plate.
The particles in the sample (atoms or molecules) are
therefore bombarded with a stream of electrons, and some of
the collisions are energetic enough to knock one or more
electrons out of the sample particles thereby forming positive
ions.
Most of the positive ions formed will carry a charge of +1
because it is much more difficult to remove further electrons
from an already positive ion.
These positive ions are persuaded out into the rest of the
machine by the ion repeller which is another metal plate
carrying a slight positive charge as well. Note that some
molecules break into fragments, the largest ion being the
molecular ion.

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Acceleration-by an electric field
final plate at 0 volts
intermediate plate

ionization chamber
at + 10,000 volts

ion beam

At this level, a negative potential (8000V) is applied and the

positive ions are repelled away from the very positive
ionization chamber and pass through three slits of three metal
plates, the final one of which is at 0 volt.

The middle slit carries some intermediate voltage. All the

ions are accelerated into a finely focused beam.
Deflection-by a magnetic field
electromagnet

mixed ion ion stream C

stream

ion stream B
ion stream A

Different ions are deflected by the magnetic field by different

amounts-of deflection indeed. The amount of deflection
depends on:

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 • The mass of the ion: Lighter ions are deflected more
than heavier ones.
• The charge of the ion: Ions with 2 (or more) positive
charges are deflected more than the ones with only 1
positive charge.
These two factors are combined into the mass/charge ratio.
Mass/charge ratio is given the symbol m/z (or sometimes
m/e).
For example, if an ion had a mass of 28 and a charge of 1+,
its mass/charge ratio would be 28. An ion with a mass of 56
and a charge of 2+ would also have a mass/charge ratio of 28.
In the last diagram, ion stream A is most deflected - it will
contain ions with the smallest mass/charge ratio. Ion stream
C is the least deflected - it contains ions with the greatest
mass/charge ratio.
It makes it simpler to talk about this if we assume that the
charge on all the ions is 1+. Most of the ions passing through
the mass spectrometer will have a charge of 1+ so that the
mass/charge ratio will be the same as the mass of the ion.
Note: You must be aware of the possibility of 2+ (etc) ions,
but the vast majority of A'level questions will give you mass
spectra which only involve 1+ ions. Unless there is some hint
in the question, you can reasonably assume that the ions you
are working with will have a charge of 1+.
Assuming 1+ ion, stream A has the lightest ions, stream B
the heavier and stream C the heaviest. Lighter ions are going
to be more deflected than heavier ones.
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Detection
Only ion stream B makes it right through the machine to the
ion detector. The other ions collide with the walls where they
will pick electrons up and be neutralized.
Eventually, they get removed from the mass spectrometer by
the vacuum pump.
ion steram B
positive ion

metal box electrons

wire to amplifier

When an ion hits the metal box, its charge is neutralized by

an electron jumping from the metal onto the ion (right hand
diagram). This leaves a space amongst the electrons in the
metal, and the electrons in the wire shuffle along to fill it.
A flow of electrons in the wire is detected as an electric
current which can be amplified and recorded. The more ions
arriving, the greater the current

Detecting the other ions

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How might the other ions be detected - those in streams A
and C which have been lost in the machine?
Remember that stream A was most deflected - it has the
smallest value of m/z (the lightest ions if the charge is 1+).
To bring them onto the detector, you would need to deflect
them less - by using a smaller magnetic field (a smaller
sideways force).
To bring those with a larger m/z value (the heaviest ions if
the charge is +1) on to the detector you would have to deflect
them more by using a larger magnetic field.
If you vary the magnetic field, you can bring each ion stream
in turn on to the detector to produce a current which is
proportional to the number of ions arriving. The mass of each
ion being detected is related to the size of the magnetic field
used to bring it on to the detector. The machine can be
calibrated to record current (which is a measure of the
number of ions) against m/z directly. The mass is measured
on the 12C scale.
Note: The 12C scale is a scale on which the 12C isotope
weighs exactly 12 units.

Recorder
The electric current operates a pen which traces a peak on a
recording. These peaks make the object of what is called
mass spectrum.
Uses of mass spectrometry

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 1. Determination of the relative atomic mass of an element
Consider the mass spectrum of neon

114

Height of peak

11.2

0.2

20 21 22
m/z

The average atomic mass of neon is calculated as follows:

Multiplying the relative abundance (the height of peak) by
the mass number to find the total mass of each isotope
present:
Mass of 22Ne =11.2×22.0 = 246.4 u
Mass of 21Ne = 0.2×21.0 = 4.2 u
Mass of 20Ne= 114×20.0 = 2280.0 u
Total=125.4 = 2530.6 u
Average mass of neon (Ne)=2530.6/125.4 u
=20.18 u
The average atomic mass of neon is 20.2 u, and the relative
atomic mass is 20.2.
2. Determination of the relative molecular mass of a
compound

012-Page 24
The ion with the highest value of m/z is the molecular ion,
and its mass gives the molecular mass of the compound. If
isotopes are present, the average molecular and the relative
molecular mass are found as in the neon example. Some large
molecules (e.g. polymers) are fragmented, and do not give
molecular ions.
3. Identification of compounds
A mass spectrum is obtained, and information about the peak
heights and m/z values is fed into a computer. The computer
compares the spectrum of the unknown compound with those
in its data bank, and thus identifies the compound.
Calculation related to the mass spectrometer
a) Calculation of the number of peaks
Example
There exists 3 isotopes of oxygen that occur naturally
with atomic mass 16, 17 and 18 with abundance 99.1% ;
0.89% and 0.01% respectively. Given that oxygen occurs
naturally as a diatomic molecule, predict the number of
peaks that will be observed on the screen of mass
spectrometer.
From the number of isotopes, the combination of one by
one show that only 5 peaks will be recorded as follows:
16-16
O2+ at 32 16-17
O2+ at 33

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 16-18
O2+ overlaps with 17-17O2+ at 34
17-18
O2+ at 35 18-18
O2+ at 36
b)Determination of the height of peaks
Considering the above example, we have that
Oxygen- 16 has the percentage abundance of 99.1%,
Oxygen-17 has the percentage abundance of 0.89%, and
Oxygen- 18 with the percentage abundance of 0.01%
To determine the height of peaks, the following chart/table is
drawn.

16 17 18
O with O with O with 0.01%
99.1% 0.89%
16
O with P1= P 2= P3= =0.01
99.1%
17
O with P3’= P4= 0.0001
0.89%
18
O with P5=
0.01%

Therefore the height of 1st peak (p1 in 32) is 98.20

The height of 2nd peak (p2 in 33) is 0.88
The height of 3rd peak (p3 and p3’ in 34) is 0.01+0.008=0.02
The height of 4th peak (p4 in 35) is 0.0001
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The height of 5th peak (p5 in 36) is 0.000001
Note: The sum of peaks’ height must, in general, be 100%.
Testing your knowledge and understanding
1. Bromine consists of two isotopes, 79Br (relative
abundance 50.5%) and 81Br (relative abundance 49.5 %).
a) How many peaks will have Br2+ through a mass
spectrometer?
b) Draw those peaks with their heights.

2. The figure below shows the mass spectrum of lead.

The heights of the peaks and the mass numbers of the
isotopes are shown on the figure. Calculate the average
atomic mass of lead.
52.3

Height of peak
23.6
E 22.6
X
1.5
E
R
204 206 207 208
C Mass number
I
S
E When, H2, is analyzed in the mass spectrometer, three
S
peaks are observed in the molecular ion region. Knowing
that hydrogen has two isotopes, 1H with 99.985% as
percentage and 2H with 0.015%, explain the observation
realized.
012-Page 27
1. (a) A proton, a neutron and an electron all travelling at
the same velocity enter a magnet field. State which
particle is deflected the most and explain your answer.
(b) Give two reasons why particles must be ionized
before being analyzed in a mass spectrometer.
(c) A sample of boron with a relative atomic mass of
10.8 gives a mass spectrum with two peaks, one at
m/z=10 and other at m/z=11. Calculate the ratio of the
heights of the two peaks.
2. Bromine consists of two isotopes 79Br (relative
abundance 50.5%) and 81Br (relative abundance 49.5%)
a) calculate the relative atomic mass of bromine
b) Copy the figure shown below and sketch on it the
peaks you would expect in the mass spectrum of
bromine vapor.

Relative abundance

158 159 160 161 162 m/z

3. (a) State the meaning of the term mass number of an

isotope
(b) Define the term relative atomic mass of an element

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 (c) A mass spectrometer measures the relative
abundance of ions with different values of m/z. Explain
the meaning of the symbols m and z
(d) A sample of nickel was analyzed in a mass
spectrometer. Three peaks were observed with the
properties shown in the following table
Relative 69 27 4
abundance/%
m/z 58 60 62
i) Give the symbol, including the mass number and the
atomic number for the ion which was responsible
for the peak with m/z=58
ii)Calculate the relative atomic mass of this sample of
nickel.
4. (a) State the meaning of the term ”atomic number”
(b) What is the function of electron gun and the magnet
in the mass spectrometer?
(c) The mass spectrum of a pure sample of a noble gas
has peaks at the following m/z values
m/z 10 11 20 22
Relative 2.0 0.2 17.8 1.7
intensity
i) Give the complete symbol, including mass number
and atomic number for one isotope of this noble gas.
ii)Give the species which is responsible for the peak at
m/z=11

012-Page 29
iii) Use appropriate values from the data above to
calculate the relative atomic mass of this sample of
noble gas.

012-Page 30
CHAPTER II: PERIODIC TABLE OF CHEMICAL
ELEMENTS
GENERAL OBJECTIVE
By the end of this chapter, student should be able to:
Explain the variation trends of physical properties in the
periodic table.
SPECIFIC OBJECTIVES
− Explain the arrangement of elements in a periodic table
according to their atomic number.
− Explain the variation in conductivity, melting and
boiling point, atomic radius, electronegativity,
electropositivity, ionization energy and metallic
character down each group and across each period in the
periodic table.
2.1. The history of the periodic table
There are over 70 metallic elements, and over 20 non-
metallic elements, as you know, elements are classified as
metallic and non-metallic elements.
Table 2.1: properties of metallic and non-metallic elements
Metallic elements Non-metallic elements
Solids( except mercury, a Solids or gases (except
liquid) bromine, a liquid).
A fresh surface is shiny, Have no one characteristic
corrosion can occur. appearance.
012-Page 31
Malleable (can be Shatter when attempts are
hammered) and ductile( made to change the shape.
can be drawn into wire).
Conduct heat and Are poor thermal
electricity. conductors and electrical
conductors, with
exceptions?
The oxides are basic. The oxides are acid or
neutral.

For a long time, chemist look at a ways of dividing up the

two groups, metallic and non-metallic elements, into smaller
sub-groups. They drew up groups of similar elements, such
as the very reactive metals lithium, sodium and potassium.
They grouped together a set of slightly less reactive metals,
Calcium, strontium, strontium and barium. Another such
group was the very reactive non-metals, Chlorine, bromine
and iodine. Some elements were discovered which had
properties in between metallic and non-metallic. These
elements, e.g. silicon, were described as metalloids.
In 1866, a British chemist called John Newlands had the idea
of arranging the elements in order of their relative atomic
masses:
H Li Be B C N O F Na Mg Al Si P S Cl K Ca

012-Page 32
Newlands noticed that similar elements appeared at regular
intervals in the list. He arranged the elements in columns as
shown below.
H Li Be B C N O
F Na Mg Al Si P S
Cl K Ca Cr Ti Mn Fe
In the 1st column were hydrogen and the very reactive non-
metallic elements fluorine and chlorine. In the second column
were the very reactive metals sodium, lithium, and
potassium. Carbon and silicon both fell into the fifth column,
and oxygen and sulphur both fell into the sixth column.
Newlands compared his chemical ‘octaves’ with musical
octaves, and called the resemblance the Law of Octaves. The
comparison was unfortunate: people poured scorn on his
ideas.
2.2. Classification of elements in the Periodic Table
according to Mendeleev and the modern Periodic Table

It was a Russian chemist, Dimitri Mendeleev, who developed

Newlands’ idea and persuaded chemists to use it. In 1869,
Mendeleev summarized his periodic law in the statement:
The properties of chemical elements are not arbitrary, but
vary with their relative atomic masses in a systematic way.
He arranged the elements in order of increasing relative

012-Page 33
atomic mass. A modern version of his classification is called
Periodic Table. You will notice that Mendeleev’s periodic
table lacks the noble gases (helium, neon, argon, etc. in group
0) because they had not yet been discovered! A vertical row
of element is called a group and a horizontal row is called a
period.
The periodic table helped chemists in their search for the
elements which were still to be discovered.
For example, Mendeleev predicted that an element would be
discovered to fill the space under silicon and above tin. His
predictions for the element which he called ekasilicon (below
silicon) were fulfilled the properties of the element
germanium, which was discovered in 1886 by Winkler.
Similar agreement was found between the predicted
properties of eka- aluminium and gallium, which was
discovered in 1875 and between ekaboron and scandium,
discovered in 1879.
The noble gases had not been discovered when the Periodic
Table was drawn up. As they were discovered one by one,
they were found to fit in between the halogens in group 7 and
the alkali metals in group 1. A separate group 0 was added to
the right-hand side of the table. Argon, however, has a higher
relative atomic mass than potassium. It made more sense
chemically to put potassium with the alkali metals, rather
than keep to the order of relative atomic masses. Another
example of this kind was the positions of tellurium and
012-Page 34
iodine. Relative atomic masses placed tellurium under
bromine, and iodine under sulphur and selenium; chemical
properties placed them in the reverse order.
Moseley’s work on X-rays in 1914 solved this problem. He
showed that atomic numbers (proton numbers) of elements
are more significant than their atomic masses. This discovery
is the final step in the validation of the Periodic Table. In the
modern Periodic Table, elements are arranged in order of
proton number (atomic number).
Features of the Periodic Table
What patterns can be seen in the arrangement of the elements
in the Periodic Table? First, note the positions occupied by
metallic and non-metallic elements. The reactive metals are
at the left-hand side of the table, less reactive metallic
elements in the middle block and non-metallic elements at
the right-hand side.
The metals in Groups 1 and 2 are described as s-block
elements because their outer electron subshells contain s
electrons. The metals in the block between Group 2 and
Group 3 are called transition metals. They are described as
d-block elements because they have incomplete d subshells.
Group 3 to 7 form the p-block of the Periodic Table, because
their outer electrons are p electrons.

012-Page 35
2.3. Variation of physical properties in Groups and
Periods
2.3.1 Atomic radius
Atomic radius may be defined as one-half the distance
between the two nuclei of identical atoms that are bonded
together
Example: in chlorine molecule as shown below.

Factors which affect atomic radius

i) Nuclear charge.
The greater the nuclear charge, the more strongly
are outermost electrons attracted and the close they
are to the nucleus and hence the smaller the atomic
radius.
The smaller the nucleus charge the less closely are
the outermost electrons attracted to the nucleus.
ii)Screening effect or Shielding effect
Screening effect is the repulsion of the outermost
electron by those in the innermost shells. The
greater the screening effect, the less closely are the
outermost electrons attracted and further are they

012-Page 36
 from the nucleus and hence the greater the atomic
radius. For small screening effect the outermost
electrons are closely attracted by nucleus and the
smaller the atomic radius.
a) Variation of atomic radius across period
E.g. Period II
Element Li Be B C O F
Radius 0.123 0.089 0.082 0.07 0.066 0.064
(in nm

Note: The size of an atom is determined by

i) The attraction of the positively charged nucleus for
electrons which tends to decrease the size of the
atom.
ii) Screening of outermost electrons from the nucleus
by the inner most electrons.
Trend across period
Atomic radius decreases from left to right across a period.
Explanation
In moving from one element to the next across a period, an
electron is added to the same shell and a proton added to the
nucleus. Therefore, across a period nuclear charge increases
while screening effect does not almost change so that
effective nuclear charge (….) increases such that electrons
012-Page 37
are pulled closer to the nucleus. The size of the atoms
therefore decreases.
b)Variation of atomic radius down the group
Group I Elements Radius ( in oA)
Li 1.23
Na 1.57
K 2.03
Rb 2.16
Cs 2.35

Trend
Atomic radii of the main-goup element increases down group
in the periodic table
Explanation
Down the group both nuclear charge and the number of
electrons are increasing.
The increase in number of electrons as a result of extra shells
of electrons being added causes the increase in screening
effect to outweigh the increase in nuclear-charge. Therefore,
effective nuclear charge decreases such that electrons are less
attracted by the nucleus resulting in the increase of the size of
atoms.
Variation among transition elements
Elemen Sc Ti V Cr Mn Fe Ca Ni Cu Zn
012-Page 38
t

Radius 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
in nm 6 5 4 3 4 3 3 3 3 3
Trend
Among the transition elements, the atomic radius remains
almost the same.

Explanation
This is because the effect of the increased nucleus charge is
roughly balanced by the greater screening effect produced by
adding an extra electron to the penultimate shell.
Ions:
A positive ion is formed by the removal of one or more
electrons from an atom. A cation is smaller that the atom
from which it is formed. This is because after the removal of
the electrons the nuclear attraction of the remaining few
electrons increases so that the electrons are now more
strongly attracted thus reducing the size.
e.g.: atoms/ions Radius
Fe (atom) 1.17oA
Fe2+ 0.76oA
F3+ 0.64oA

012-Page 39
A negative ion (anion) is formed by addition of one or more
electrons to a neutral atom. Addition of electrons increases
the number of electrons and thus reduces the effective pull on
the electrons by the nucleus so that electrons by the nucleus
so that electrons are now weakly held. Therefore, anions are
bigger in size than the corresponding atom.
e.g. Atomic radius of chlorine (Cl) is 1.40oA and that of
chloride (Cl- ) is 1.81oA
2.3.2 Ionization energy
Ionization energy is defined as the minimum energy required
for removing an electron from a gaseous atom or ion against
the attractive forces of the nucleus to form a positively
charged ion.
The first ionization energy is the minimum energy required
to remove one mole of electrons from one mole of a gaseous
atom to produce one mole of gaseous with one positive
charge.
For sodium atom the first ionization is represented as
Ionization energy increases as electrons are removed e.g. for
beryllium.
1st I.E./kJ 2nd I.E. 3rd I.E. 4th I.E.
900 1758 14905 21060

012-Page 40
Ionization energy increases from 1st to the 4th electron.
Normally,The first electron is easily removed.than the second
and so on.
NOTE:
1) The 2nd I.E. is greater than 1st I.E. because after the
removal of the first electron, the proton-electron ratio
increases so that the nuclear attraction for the remaining
few electrons increases. Since the remaining electrons
are now strongly attracted, to remove the next electron
requires more energy.
2) The energy to remove the 2nd electron is about twice the
first the first one and to remove the 3rd electron requires
about 8 times more energy than to remove the 2nd
electron.
3) The energy to remove the 4th electron is about 1.5 times
than of the 3rd.
Therefore in beryllium atom, there are four electrons, two of
which are very easy to remove and two which are difficult to
remove.
Since to remove the 3rd electron there is a very big rise in
energy, therefore the 3rd electron comes from a different shell
of electrons. The electronic configuration of beryllium is
presented as 2:2 or 1s22s2. Therefore beryllium has two
electrons in its lower level which are very near to the nucleus

012-Page 41
and difficult to remove and two others in the higher energy
level which are easy to remove.
Factors affecting the magnitude of ionization energy
Atomic size
In small atoms electrons are held tightly and are difficult to
remove while in large ones, they are less tightly held since
they are far away from the nucleus and are easy to remove.
Nuclear charge
The greater the nuclear charge, the more tightly held is an
electron and the more difficult is to remove it.
Screening effect
Ionization energy decreases with increase in screening effect.
a) Variation of 1st I.E. across period
e.g. Period II
Element Li Be B C N O F Ne
st
1 520 899 801 1086 1403 1310 1981 2080
I.E./kJmol-
1

Period III
Element Na Mg Al Si P S Cl Ar
1st 496 737 577 786 1012 999 1255 1521
-
I.E./kJmol
1

012-Page 42
Trend
Generally, the 1st I.E. increases across a period with
abnormal behavior shown by Mg and P for period III while
Be and N for period II.
Explanation
Moving left to right from one element to the next across the
periodic table, an electron is added to the same shell and a
proton is added to the nucleus. The nucleus charge therefore
increases while the screening effect decreases. Therefore
effective nuclear charge increases and the electrons are now
more tightly held in moving from left to right across period.
Then 1st I.E. of beryllium and magnesium unexpectedly
higher because the single electron is being removed from full
2S and 3S sub shell respectively which is thermodynamically
very stable and thus required more energy.
Be: 1S22S2
Mg: 1S2 2S2 2P6 3S2
Similarly, N and P have unexpected high 1st I.E. because
their electrons are being removed for half full 2P sub shell
respectively. Any half-full shell is thermodynamically stable
and hence, requires more energy.
N: 1S2 2S2 2P3
P: 1S2 2S2 2P6 3S2 2P3

012-Page 43
 b)Variation down a group
Element 1st
I.E./kJmol-
1

Be 899
Mg 737
Ca 590
Sr 549
Ba 503
Trend
Generally, 1st I.E. decreases down the group.
Explanation
On descending a group both the nuclear charge and screening
effect increase but the increase in screening effect as a result
of an extra shell of electrons added outweighs that of the
nuclear charge. Therefore, effective nuclear charge decreases
so that electrons are less strongly held down the group and is
easy to remove.
Importance of ionization in the determination of the
chemistry of an element
Ionization energy provides a basis understanding the
chemistry of an element. The following information is
provided.
i) Atomic number

012-Page 44
The number of successive ionization energies indicates the
number of electrons present in an atom. Sodium has 11
successive ionization energies indicating that the atomic
number of sodium is 11.
ii)Determination of metallic or non- metallic character.
The magnitude of I.E. is used as a measure of the metallic
character of an element. The first ionization energies of
metals are all nearly below 800kJ mol-1 whiles those of non-
metals are all nearly above 800 kJ mol-1.
Down the group ionization energies decrease so that the
elements became more metallic. In groups (IV), (V) there is
change from non metallic to metallic character. Across a
period 1st I.E. increases in moving across a period. The
elements become less metallic but non- metallic.

The use of I.E. to predict the properties of elements

Example: The first three ionization energies for elements A,
B, C, and D are given in the table below

Element Ionization
energies
First Second Third
A 780 1500 7730
B 500 4560 6900
C 580 1815 4620
012-Page 45
 D 1310 3460 5300

a) From the 1st I.E. of the elements it can be deduced that

elements B and C have typical metallic properties since
their 1st ionization energies are well be low 800kJmol-1.
b) Element A with 1st I.E. near 800kJ also would show
some metallic properties.
c) i) Moving from 2nd to 3rd I.E. for A there is an increase
of about 5 times. This means the 3rd electron of A comes
from a different shell hence A has 2 electrons on its
outermost shell. A is therefore a group 2 element with
charge of +2
ii) For element B, there is an increase of about 9 times
from 1st to 2nd and an increase of about
times from 2nd to 3rd . Therefore element B has one
electron on its outermost shell and thus is a group 1
element and would have a charge of +1.
iii) In element C, from 1st to 2nd i.e. increase is about 3
times and from 2nd to 3rd by about
Therefore there is similar rise in ionization energy. This
implies that the 3 electrons in C are from the same shell

012-Page 46
 and C therefore would from three positive charges and
hence belongs to group 3.
d) Element D with its 1st I.E. well over 800kJmol-1 is a non
metal. The following compounds therefore would be
formed between.
− A and D = AxD2
− B and D = BxD
− C and D = CxD3
2.3.3. Electron affinity
Electron affinity is the reverse of ionization energy. Electron
affinity is defined as energy change that occurs when one
mole of electrons combine with one mole of gaseous atom to
form one mole of gaseous negatively charged ion.
OR
Is the energy released when atom of an element gains an
electron to form a negatively charged ion.
X(g) + e- X-(g) , A.E = -ve

The negative ion produced by addition of electron now repels

further electron to be added so that to add a second electron
is resisted and energy must be applied to affect it. The 2nd
electron affinity is therefore positive (i.e. an endothermic
process). Electron affinity is estimated by an indirect method
based on Born Haber cycle_ see senior five: Chemical
thermodynamics.

012-Page 47
NOTE

The more exothermic (more negative) the electron
affinity, the more stable is the anion formed. Therefore,
among the halogens below, Cl- is the most stable ion
while I- is the least stable.
Formation of divalent ion is endothermic which shows
that a univalent ion is more stable than a divalent one.
Factors affecting electron affinity
Atomic radius
The smaller the atomic radius the more strongly attracted is
the electron and the greater the electron affinity. For larger
atomic radius nuclear attraction for incoming electron is low
reading to small electron affinity.
Nuclear charge
The greater the nuclear charge the more strongly is the
incoming electron attracted, and the greater the electron
affinity. The smaller the nuclear charge the less strongly is
the electron added attracted and the lower the electron
affinity.
Screening effect
The greater the screening effect the less strongly is the
electron added attracted and the lower the electron affinity.
The smaller the screening, the more strongly attracted is the
incoming electron and the greater the electron affinity.
012-Page 48
 a. Variation of electron affinity across a period
e.g. Period II

Element Na Mg Al Si P S Cl
Electron - +67 - - - - -346
affinity in 20 30 135 60 200
kJmol-1
Trend
Generally, electron affinities across a period increase.
Explanation
Effective nuclear charge increases across a period so that the
nuclear attraction for the incoming electron increases.
The electron affinity of Mg is more positive than expected
because in Mg, the electron is being added to full 3S
(1s22s22p63s2) sub-shell which is thermodynamically stable
and resists the addition hence energy should be put in to
effect.
Similarly, the electron affinity of P is less negative than
expected because in P, the electron is being added to a half
full 3p (1s22s22p63s23p3) sub-shell which is also stable and
resists the addition hence less energy is released.
a. Variation of electron affinity down a group
e.g. Group VII
Element Electron
affinity/kJmol-
012-Page 49
 1

F -323
Cl -364
Br -324
I -295
Trend
Electron affinity generally decreases down the group.
Explanation
Down the group because of an extra shell of electron added,
the increase in screening effect outweighs that of the nuclear
so that of the nuclear charges so that effective nuclear charge
decreases. There is therefore decreasing ability to attract
electrons hence, decrease in electron affinity.
2.3.4. Electronegativity
Electronegativity is the tendency of an atom to attract
electrons toward itself. Elements with high electronegativities
are called electronegative elements and those with low
electronegativities are called electropositive elements.
Factors affecting electronegativity
a. Nuclear charge
The greater the nuclear charge the more strongly are the
bonding electrons attracted and the greater the
electronegativity. For small nuclear charge the bonding
electrons less strongly attracted and the smaller the
electronegativity.
012-Page 50
 b. Screening effect
For low screening effect the bonding electrons have high
nuclear attraction leading to high electronegativity. The
greater the screening effect the less attracted are the bonding
electrons and the lower the electronegativity.
c. Atomic radius
The smaller the atomic radius the more strongly are the
bonding electrons attracted and the greater the
electronegativity. For large atomic radius, the bonding
electrons attracted by the nucleus leading to low
electronegativity.

Variation of electronegativities across a period

e.g. Period 3
Element Na Mg Al Si P S Cl
Electronegativity 0.9 1.2 1.5 1.8 2.1 2.5 3.0

Trend
Electronegativity increases across a period
Explanation
In moving from left to right across a period, from one
element to the next, the nuclear charge increases by one unit
012-Page 51
and an electron is added to the outer shell. As the nuclear
charge increases across, the atoms have an increasing
electron attracting power and therefore an increase in
electronegativity.
Variation of electronegativity down the group
e.g.GroupVII
Element Electronegativity
F 4.0
Cl 3.0
Br 2.8
I 2.5

Trend: Electronegativity decreases down a group.

Explanation
Down the group as a result of an extra shell of electrons
added, the increase in screening effect outweighs that of the
nuclear charge. Therefore, effective nuclear charge decreases
and hence the atoms develop a decreasing power to attract
electrons.

2.3.5. Electrical conductivity

This is the tendency of an element to allow electric current to
pass through it. Metals are good conductors because of the
free electrons which are moving from one point to another.
Metallic character decreases across the period and hence
electrical conductivity decreases from left to right.
012-Page 52
 Similarly, on descending a group, the metallic character
increases consequently electrical conductivity increases as
we move down a group.
2.3.6. Boiling points and melting points
Boiling is the process by which a liquid changes to a gaseous
state. The boiling point is the temperature at which boiling
takes place. Melting is the process by which a solid changes
to a liquid state. Across the period atomic size decreases and
the smaller atoms are compactly together. The greater the
forces of attraction and hence the boiling point (melting
point) increases from left to right of a periodic table. It
decreases down the group due the increase in atomic size
which decreases close packing points also follow the same
trend.
e.g. Variation in group I.
Element Melting Boiling
Point Point
(K) (K)
Lithium 453 1615
Sodium 370 1156
Potassium 336 1032
E
Rubidium 312 961
X Caesium 301 944
E
Francium 295 950
R
C 1. The following table shows the ionization energies( in kJ
I
S mol-1) of five elements lettered A, B, C, D and E
E
S
Element 1st I.E 2nd I.E 3rd I.E 4th I.E
A 500 4600 6900 9500
012-Page 53
B 740 1500 7700 10500
C 630 1600 3000 4800
D 900 1800 14800 210000
E 580 1800 2700 11600
a) Which of these elements is most likely to form an ion
whith a charge of +1? Give reasons for your answer.
b) Which two of the elements are in the same group of the
periodic table? Which group do they belong to?
c) In which group of the periodic table is element E likely
to occur? Give reasons for your answer
d) Which element would require the least energy to convert
one mole of gaseous atoms into ions carrying two
positive charges?

2. a) The first seven ionization energies of an element W

are shown below
1st 2nd 3rd 4th 5th I.E 6th I.E 7th I.E
I.E I.E I.E I.E
785 1581 3231 4361 16002 20001 23602
i) Explain what is meant by the term first
ionization energy
ii) What factors determine the magnitude of the
first ionization energy?
iii) State the group in theperiodic table to which
element w belongs. Give a reason for your answer.

012-Page 54
 b) Explain what is meant by the term electronegativity?
What factors determine the magnitude of
electronegativity of an element?
c) Explain how the following factors affects affect the
magnitude of electronegativity of an element:
i) nuclear charge
ii) atomic radius
iii) the screening effect of the inner electrons.
d) What is the difference between electron affinity and
electronegativity?
3. The first ionization energies of elements in period III of
the periodic table and their atomic numbers are given in
the table below.

Element Na Mg Al Si P S Cl Ar
I.E(kJmol-1 494 742 561 791 1062 1000 1256 1522
Atomic 11 12 13 14 15 16 17 18
number
Plot a graph of ionization energy against atomic number
and explain the shape of the graph
4. The table below shows the first three ionization energies
in kJmol-1 of the elements X, Y, Z, and K
Element 1st I.E 2nd I.E 3rd I.E
X 760 1502 7730
Y 494 4562 6901
Z 577 1816 2745
K 1311 3460 5302

012-Page 55
 a) Which one of the elements belongs to group 1 of the
periodic table? Give the reason for your answer.
b) Which one of the elements forms a cation with three
positive charges?
c) Write the formula of the compound formed by the
elements X and K.

5. Discus the following diagram.

(a) State the element which has the highest first

ionization energy
(b) State the most electronegative elements
(c) The strongest element in metallic character
(d) A gas that has the lowest ionization energy
(e) Compare the first ionization energy of Be and B.
(f) Explain why Rb is the biggest among the elements

012-Page 56
CHAPTER III: ELECTRONIC STRUCTURE
GENERAL OBJECTIVE
By the end of this chapter students should be able t establish
the electronic configuration of elements using s, p, d and f
orbitals
SPECIFIC OBJECTIVES
− Explain Boh’r model of an atom
− Interpret atomic spectra
− Explain hydrogen spectrum and spectral series
− state the rules that govern electronic configuration
− Write electronic configuration of elements
− Interpret a graph of ionization potential against the
number of electrons.
CONTENTS
3.1. Bohr’s model of an atom
Danish physist Niels Bohr develops a theory of the atom in
which he assumes that electrons are arranged in definite
shells, or quantum levels, at a considerable distance from the
nucleus.
Bohr suggested

012-Page 57
 i) An electron moving in an orbit can have only certain
amounts of energy, not an infinite number of values: its
energy is quantized.
ii)The energy that an electron needs in order to remove in a
particular orbit depends on the radius of the orbit. An
electron in an orbit distant from the nucleus requires
higher energy than an electron in an orbit near the
nucleus. Each orbit was assigned an integer, n, known as
the principal quantum number, which may have values
from 1 to infinity.
Thus the larger the value of n, the further the electron
from the nucleus. The energy of the electron depends on
the orbit it occupies.
1  z2   z2 
En = −RH  2  for hydrogenatom and En = −RH  2  = −(1312kJ/mol 2 
n  n  n 
for many - electronatoms

Where RH is the Rydberg constant; its value is 2.18×10-18J or

1.097×107m-1
Note
The negative sign in the equation above denotes stability
relative to some reference state. In other words, the more
negative the value for energy, the more stable the system is.
iii) If the energy of the electron is quantized, the radius
of the orbit also must be quantized. There are a restricted
number of orbits with certain radii, not an infinite
number of orbits.
012-Page 58
 Radius = n 2 (5.30×10−11 m)

iv) An electron moving in one of these orbits does not

emit energy. In order to move to an orbit farther away
from the nucleus, the electron must absorb energy to do
work against the attraction of the nucleus.If an atom
absorbs a photon (a quantum of light energy), it can
promote an electron from an inner orbit to an outer orbit
Notice: Other scientists developed also atomic models
a)Thomson atomic model
Thomson posulated that an atom consists of a diffuse cloud
of positive charge uniformly distributed in a sphere with
negative electrons embedded randomly in it

b) Rutherford model
According to him, an atom consist of a tiny much more
positively centre called nucleus,with electrons moving
around the nucleus at a distance that is very large relatively
to the nucleus radius.

012-Page 59
3.2. Atomic spectra
3.2.1 Continuous spectrum
If sunlight or light from an electric light bulb is formed into
a beam by slit and passed through a prism onto a screen, a
rainbow of separated colours is observed. This spectrum of
colours composed of visible light of all wavelengths is called
a continuous spectrum.
3.2.2 Absorption spectrum
When white light is passed through a substance, black lines
or dark bands appear in the spectrum where light of some
wavelengths has been absorbed by the substance. Hence, the
pattern of wavelengths absorbed by a substance is called its
absorption spectrum.
Note
• All atoms and molecules absorb light of certain
wavelengths
• Atomic absorption spectrometers are instruments used
for viewing absorption spectra.

3.2.3 Emission spectrum

012-Page 60
 If atoms and molecules are heated to sufficiently high
temperatures, they emit light of certain wavelengths. The
observed spectrum consists of a number of coloured lines on
a black background. This is an emission spectrum (or line
spectrum).
3.3. Hydrogen spectra and spectra series
According to Niels Bohr, for an electron to move from an
orbit of energy Ei to one of energy Ef, the light absorbed must
have a frequency given by Planck’s equation
hν = Ef − Ei = ΔE where ν is a frequency in Hz or s-1

h is a Planck' s constant (h = 6.63 × 10-34 Js)

The emission spectrum arises when electrons which have

been excided (raised to orbits of high energy) drop back to
orbits of lower energy. They emit energy as light with a
frequency given by Planck’s equation above. Substituting the
expression for the energy of the electron in Planck’s
equation, we find
−R  −R   1 1 
∆E =  2 H  −  2H  = RH  2 − 2 
 n  n 
 f   ni   i nf 
Because ∆E = hν , we have
 1 1 
∆ E = hν = R H  2 − 2 
n 
 i nf 

In this expression, ni and nf represent the quantum numbers

for the initial and final states, respectively.

Note
012-Page 61
 • When the final state quantum number (nf) is larger than
the initial state quantum number (ni) the term in
parentheses is positive, and ∆E is positive.This means
that the system has absorbed a photon and thus increased
in energy( an endothermic process ).
• When ni is larger than nf, as happens in emission, energy
is given off, ∆E is negative.
• Complete removal of the electron from a hydrogen atom,
corresponding to a transition from n=1(ground state) to
the n=∞ state, is known as ionization. This is represented
as
H(g) H+(g) + e-

The energy required for ionization from the ground state

is called ionization energy.

Figure: The origin of spectral lines

Bohr assigned quantum numbers to the orbits. He gave the
orbit of lowest energy (nearest to the nucleus) the quantum
number 1 with n=1 is known as the ground state and electron
is in its ground state. When the electron is in a higher energy

012-Page 62
orbit, that is, n=2 or higher, the atom is said to be in an
electronically excited state.
If the electron receives enough energy to remove it from the
attraction of the nucleus completely, the atom is ionized.

Energy n= infinity , at this level electron has enough

energy to escape : the atom is ionized
n=6
n=5
n=4

n=3

n=2

n=1 Ground state

Figure : The energy levels at various values of the quantum number, n

When light coming from a discharge tube containing

hydrogen gas is passed through a prism, a series of lines is
observed in the visible part of the spectrum: this is termed
Balmer series. Some are found in the IR( Infra Red) and
UV(ultraviolet) regions.
Those lines detected in the UV are known as Lyman series
and those detected in the IR were discovered by Paschen,
Brackett, and Pfund. The corresponding ranges of energy
levels of these radiations can simply be represented in the
figure below

012-Page 63
Lyman Balmer Paschen
Brackett Pfund

UV Visible part
IR
Figure: Lines in hydrogen emission spectrum
Alternatively,
Infinite

n=7
n=6
n=5

n=4
Brackett series
n=3
Paschen series
IONIZATION
(IR- radiations) ENERGY
n=2

Balmer series

(visible light)

n=1
Lyman series ( UV-radiations)

Figure: Energy transitions in the hydrogen atom

012-Page 64
The Lyman series in the emission spectrum arise when the
electron moves to the n = 1 orbit ( the ground state) from any
of the other orbits.
The Balmer series arises from transitions to the n =2 orbit, n
= 3, n = 4, etc. orbits.
The paschen, bracket and Pfund series arise from transition to
the n =3, n = 4, and n = 5 orbits from higher orbits.
The series of lines are seen to obey the
 1 1 
1
= RH  − where 1 and 2 are positive integers showing energy levels
λ  n2 n2 
 i f 
λ , is a wavelength, nd
RH is a Rydberg' s constant (1.097 × 107 m−1
Lyman series
 1 1 
= RH  −  , where nf = 2,3,4,...
1
λ  12 n2 
 f 
Balmer series
 1 1 
= RH  −  , where nf = 3,4,5,...
1
λ  22 n2 
 f 
Paschen series
 1 1 
1
= RH  − , where nf = 4,5,6,...
λ  32 n2 
 f 

In order to explain this, Bohr made the following

assumptions
i) The atom consists of stationary orbital. In this orbital,
electrons do not emit radiations.

012-Page 65
 ii)An electron may suddenly jump from one of its specified
non- radiating orbits to higher energy level. radiation is
emitted when an electron jumps from a higher energy
level to a lower energy level so that
c hc
En − En−1 = hν But ν = ⇒ En − En−1 = and En and En−1 are two succesive energy levels
λ λ
c is a celerity c = 3 × 10 8 ms −1

Worked examples
01. Calculate the frequency of the hydrogen line
that corresponds to the transition of the electron
from the n = 4 to the n = 2 states.
Method
 1 1  R  1 1 
Substituting ni = 4 and nf = 2 in ∆E = R H  2 − 2  ⇒ ν = H  2 − 2 
n  h  ni n f 
 i nf 
2.18 × 10-18 J  1 1
= −34  2 − 2
6.63 × 10 Js  4 2 
2.18 × 10-18 J  1 1 
=  − 
6.63 × 10 −34 Js  16 4 
2.18 × 10-18 J  3 
= − 
6.63 × 10 −34 Js  16 
= - 6.17 × 1014 s −1

The negative frequency or wavelength is physically

meaningless, so the sign is ignored.
This value for ν can be used to calculate the wavelength
of the radiation (λ)
C 3.00 × 10 8 m/s
λ= =
ν 6.17 × 1014 /s
= 4.86 × 10 −7 m = 486nm

012-Page 66
 02. Calculate the energy required for ionization of
an electron from the ground state of the hydrogen
atom.
Method
The iomization energy may be written as the difference
between the final and initial state energies. we have nf = ∞, ni
=1
1 1 
ΔE = Ef − Ei = RH  2 − 2 
1 ∞ 
= RH (1 − 0 ), This is just equal to RH , 2.18 × 10 -8 J
It is often useful to express this energy on a molar basis. To this we simply multiply by Avogadro' s number :
 J  23 atoms   1kJ 
 2.18 × 10   6.02 × 10 ×  = 1.31 × 10 kJ/mol
-18 3

 atom  mol   1000J 

Testing your knowledge and understanding

− An electromagnetic radiation was emitted in the
Balmer’s series as a result of electron transitions
betweens n =2 and n =5. Calculate the
i) Energy of the radiation in kJmol-1
ii)Frequency of the radiation in hertz
iii) Wavelength of the radiation in metres.
− Calculate the wavelength of a line in the Balmer series
that is associated with energy transition.
E4 to E2 (E4 = -1.362×10-19 J, E2=-5.448×10-19J)

012-Page 67
Assignment: Determine the wavelength and the color of the
light emitted when there is ionization of sodium. Atomic
number of Na is 11.
3.4. Energy levels, sub-energy levels and orbitals
3.4.1. The three quantum numbers
a) The principal quantum number (n)
The principal quantum number designates, in general, the
effective volume of the space in which the electron moves.
An increase in the value of n indicates an increase in energy
associated with the electron energy level or major shell, and
an increase in the average distance of the electron from the
nucleus. The value of n is whole numbers which theorically
can vary from 1 to∞ (1, 2, 3 …)

Value of n 1 2 3 4 5 6 7
Shell or K L M N O P Q
Energy level

b) The Azimuthal quantum number (l)

The secondary quantum number designates the shape of the
region which the electron occupies or orbital. Values of l are
whole numbers which can vary from 0 to n-1.

N l
1 0
012-Page 68
 2 0, 1
3 0, 1, 2
4 0, 1, 2, 3

Designation of orbitals corresponding to the value of l

Value of l 0 1 2 3
Letter used s p d f

c) The magnetic quantum number (m l )

This quantum number describes the orientation of the orbital
in space. It can have integral values between l and – l,
including zero. A collection of orbitals with the same value
of n is called an electron shell. For example, all the orbitals
with n = 3 are said to be in third shell. One or more orbitals
with the same set of n and l values is called a sub-shell. Each
sub-shell is designated by a number (the value of n) and a
letter(s, p, d, f corresponding to the value of l).
Relationship among values of n, l, and ml through n = 4
n l Subshell ml Number of
designation orbitals in
1 0 1s 0 subshell
1

2 0 2s 0 1

012-Page 69
 1 2p 1, 0, -1 3

3 0 3s 0 1
1 3p 1, 0, -1 3
2 3d 2, 1, 0, -1, 5
-2

4 0 4s 0 1
1 4p 1, 0, -1 3
2 4d 2, 1, 0, -1, 5
3 4f -2 6
3,2,1,0,-1, -2,
-3

Note
i) Each shell is divided into the number of sub shells equal
to the principal quantum number, n, for that shell. Thus
− the 1st shell consists of two sub shells, 2s and 2p.
− the 3rd shell consists of three sub shells 3s, 3p, and 3d
Thus every shell has an s sub shell every shell beginning
with the second has a p subshell, every shell beginning
with the third has a d sub shell, and so forth.
ii)Each sub shell is divided into orbitals. Each s sub shell
consists of one orbital; each p sub shell consists of three
012-Page 70
 orbitals; each d sub shell consists of seven orbitals notice
that these are the odd numbers 1, 3, 5, 7)

iii) A p-orbital, for example, has a secondary quantum

number of 1 (l = 1), so the magnetic quantum number
has three possible values: +1, 0, and -1. This means the
p-orbital has three possible orientations in space.
An s-orbital has a secondary quantum number of 0 (l =
0), so the magnetic quantum number has only one
possibility: 0. this orbital is a sphere, and a sphere can
only have one orientation in space. For a d-orbital, the
secondary quantum number is 2 (l = 2), so the magnetic
quantum number has five possible values: -2, -1, 0, +1,
and +2. A d-orbital has four possible orientations in
space.
Note that all orbitals with the same value for the principal
quantum number, n, have the same energy. This is true
only in one-electron systems such as hydrogen.
For other elements, we have the following diagram

012-Page 71
3.4.2. Representation or shapes of orbitals
Electrons occupy a region of space, called an orbital, around
the nucleus of an atom. In the three examples of orbitals
shown here, the atom's nucleus is located at the intersection
of the x, y, and z axes. Each orbital can contain two
electrons. Electrons that have close to the same energy
occupy a set of orbitals called a shell.
s-ORBITAL: Each shell in an atom contains an s orbital. The
s orbital holds the shell's two lowest-energy electrons. The
lowest-energy shell in an atom consists of just one s orbital.
This shell is the smallest one in the atom and the closest to
the nucleus. Higher energy shells contain a larger s orbital as
well as other orbitals.
The shape of s-orbital is spherically symmetrical about the
nucleus. The orbital has no preferred direction. The
probability of finding an electron at a distance from the
nucleus is the same in all direction.
p-ORBITAL: The three p orbitals in a shell hold electrons
that have slightly more energy than those in the shell's s
orbital. The p orbitals are all shaped alike, but they differ in
their orientation in space. The shell with the second lowest
energy in an atom consists of an s orbital and three p orbitals.
Higher energy shells contain larger versions of these orbitals
and also other orbitals.

012-Page 72
A p-orbital is not symmetrical: it is concentrated in certain
directions. The electron density is shaped like an hourglass or
dumbbell.
d-ORBITAL: The five d orbitals hold electrons that have
more energy than those in the p orbitals. Four of the d
orbitals are shaped alike but differ in their orientation in
space. The fifth d orbital differs in shape from the others. The
shell with the third lowest energy in an atom consists of an s
orbital, three p orbitals, and five d orbitals. Higher energy
shells contain larger versions of these orbitals as well as
additional orbitals.
The five different types of d orbitals are called dxy, dyz, dxz,
dz2 and dx2-y2

Note that the f orbitals are difficult to represent in three-

dimensional contour diagrams.

012-Page 73
3. 4. 3 Electron spin and the Pauli Exclusion Principle
The concept of electron spin was developed to describe that
the electron behaves as though it were spinning (to turn
round and round rapidly) on its own axis and to account for
certain features of the line spectra of atoms. Thus, electrons
have another property, called spin that differentiates the two
electrons in each orbital. An electron’s spin has two possible
values: +1/2 (called spin-up) or -1/2 (called spin-down).
These two possible values mean that two electrons can
occupy the same orbital, as long as their spins are different
(electron can spin in one of two opposite directions.
Physicists call spins the fourth quantum number of an
electron orbital (abbreviated ms). Spin, in addition to the
other three quantum numbers, uniquely describes a particular
electron’s orbital.
The Pauli Exclusion Principle states that “two or more
identical electrons cannot occupy the same orbital in an atom
as long as they have four different quantum number that is
they have opposite spin.”
It is convenient to draw an electron in boxes diagram to show
that arrangement of electrons in orbitals
one orbital

ms= +1/2 electron with ms=-1/2

An s subshell consists of one box, a p subshell of three boxes,

a d subshell of five boxes and an f subshell of seven boxes.
012-Page 74
3. 4. 4. The aufbau method and electron configuration
The German word “ aufbau” means “ building up” and
describes how electron structures are built up by applying a
set of three rules below
Rule 1: Electrons go into orbitals with the lowest energy.
Rule 2: The Pauli exclusion principale ( two versions).
(a) It is impossible for two electrons with the same
spin quantum number to be in the same orbital
(b) An orbital can contain a maximum of two
electrons.
Rule 3: Hund’s rule: Electrons will fill a set of degenerate
orbitals by keeping their spins parallel.

Generally, it takes more energy to occupy orbitals with

higher quantum numbers. It takes the same energy to occupy
all the orbitals in a sub shell. The lowest energy orbital is the
one closest to the nucleus. It has a principal quantum number
of 1, a secondary (azimuthal) quantum number of 0, and a
magnetic quantum number of 0. The first two electrons with
opposite spins occupy this orbital.
If an atom has more than two electrons, the electrons begin
filling orbitals in the next sub shell with one electron each
until all the orbitals in the sub shell have one electron. The
electrons that are left then go back and fill each orbital in the
sub shell with a second electron with opposite spin.

012-Page 75
 They follow this order because it takes less energy to add an
electron to an empty orbital than to complete a pair of
electrons in an orbital.
The electrons fill all the sub shell in a shell, then go on to the
next shell. As the sub shell and shells increase, the order of
energy for orbitals becomes more complicated. For example,
it takes slightly less energy to occupy the s-sub shell in the
fourth shell than it does to occupy the d-sub shell in the third
shell. Electrons will therefore fill the orbitals in the 4s sub
shell before they fill the orbitals in the 3d sub shell, even
though the 3d sub shell is in a lower shell.
Notice :
(i) When the orbitals have the same energy level, the more
stable is the one whose sum <<n+l>> is low that it will be
firstly occupied by electrons before.
(ii) The number of electrons in the valence-shell of an atom is
equal to the group number for the representative (A group)
element and predict the Lewis symbol
This can be summarized as following using simple overview
of the periodic table.

Ia IIa IIIa IVa Va VIa VIIa VIIIa

1 2
H He
1s1 1s2
012-Page 76
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
[He]2 [He] [He]2s2 [He]2s2 [He]2s2 [He]2s [He]2s [He]2s2
s1 2s2 2p1 2p2 2p3 2
2p4 2
2p5 2p6
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
[Ne]3 [Ne] [Ne]3s2 [Ne]3s2 [Ne]3s2 [Ne]3s [Ne]3s [Ne]3s2
s1 3s2 3p1 3p2 3p3 2
3p4 2
3p5 3p6

The “aufbau” method in action- conventions

1. Write down the labels of the orbitals and show how
many electrons it contains by writing the number of
electron as a superscript.
2. When an orbital contains only one electron, then we
write down the orbital label with or without a
superscript.
3. The diagram below remembering the order of filling of
orbitals to build up the electronic configuration of any
atom. Any time you have to write an electronic
structure of any element; please remember
this diagram!!!

Notice that the energy levels are not exactly

012-Page 77
 1s

2s 2p

3s 3p 3d

4p 4d 4f
4s

5s 5p 5d 5f

6s 6p 6d 6f

7s 7p 7d 7f

The ground state electron structures of the first 36

elements in the periodic table
Z Sy 1 2 2 3 3 3 4 4
mbo s s p s p d s p
l
1 H 1
2 He 2
3 Li 2 1
4 Be 2 2
5 B 2 2 1
6 C 2 2 2
7 N 2 2 3
8 O 2 2 4
9 F 2 2 5
1 Ne 2 2 6
012-Page 78
0
1 Na 2 2 6 1
1
1 Mg 2 2 6 2
2
1 Al 2 2 6 2 1
3
1 Si 2 2 6 2 2
4
1 P 2 2 6 2 3
5
1 S 2 2 6 2 4
6
1 Cl 2 2 6 2 5
7
1 Ar 2 2 6 2 6
8
1 K 2 2 6 2 6 1
9
2 Ca 2 2 6 2 6 2
0
2 Sc 2 2 6 2 6 1 2
1
2 Ti 2 2 6 2 6 2 2
2
2 V 2 2 6 2 6 3 2
3
2 Cr 2 2 6 2 6 5 1
4
2 Mn 2 2 6 2 6 5 2

012-Page 79
5
2 Fe 2 2 6 2 6 6 2
6
2 Co 2 2 6 2 6 7 2
7
2 Ni 2 2 6 2 6 8 2
8
2 Cu 2 2 6 2 6 1 1
9 0
3 Zn 2 2 6 2 6 1 2
0 0
3 Ga 2 2 6 2 6 1 2 1
1 0
3 Ge 2 2 6 2 6 1 2 2
2 0
3 As 2 2 6 2 6 1 2 3
3 0 3. 4. 4. Interpretation of
3 E 2 2 6 2 6 1 2 4 a graph of ionization
4 0 potential against the
3 Br 2 2 6 2 6 1 2 5 number of electrons.
5 0
3 Kr 2 2 6 2 6 1 2 6
6 0

012-Page 80
Electrons in atoms can only have certain amounts of energy,
groups of electrons can exist with roughly the same amount
of energy, and these positions of roughly similar amounts of
energy are called energy levels.
Size of ionization energy (IE) depends on (Nuclear charge,
Atomic radius, and Electron shielding, energy level)
Successive IE’s increase because electrons are being
removed from increasingly positive ions and so the attractive
forces are greater
Large jumps in IE’s arise from a large increase in attraction,
corresponding to an electron being removed from a new
energy level significantly closer to the nucleus (proving that
electrons are arranged in shells)
IE’s increase across periods (left to right)
• Number of protons increasing, meaning stronger nuclear
attraction
• Extra electrons are at roughly the same energy level, even if
the outer electrons are in different orbital types
• Little extra shielding effect, little extra distance to lessen
the attraction from the nucleus
IEs decrease down groups
• Each element down a group has an extra electron shell

012-Page 81
 • Extra inner shells means extra distance of outer electrons
from the nucleus, and greater shielding from the attraction of
the nucleus, overall reducing nuclear attraction
E
X
E
R
C
I
S 1. Consider elements A and B with the electron
E
S
configuration 1s22s22p63s23p64s23d5 and [Xe]6s1
respectively. In what period and group is each of the
elements A and B belong?
2. Write the electronic configuration of the elements or ions
below
K+ , He, P, N3-, Si and Pb2+
3. In a tabular form specify all the four quantum numbers
for each electron in a atom whose n value is 2. Given all
the orbitals are full of electrons.
4. Give the values of the quantum numbers n, l, and m for
the electron with the highest energy in sodium atom in
the ground state.

012-Page 82
 CHAPTER IV: CHEMICAL BONDING

GENERAL OBJECTIVES
By the end of this chapter students should be able to
a) Explain the formation of various types of bonds
b) Describe the different molecular shapes
SPECIFIC OBJECTIVES
− Describe the formation of ionic bonds
− State the properties of ionic compounds
− Describe the formation of covalent bonds
− State the properties of covalent compounds
− Interpret hybridization of hybrid orbitals
− Explain the formation of sigma and pi bonds in the
single, double and triple bonds

012-Page 83
 − Explain the shapes of molecules basing on VSEPR
theory and and the existence of different bond angles.
− Describe the formation of metallic bond
− State the physical properties of metals and metallic
compounds
− Describe the formation of inter- and intermolecular
forces.
CONTENTS
Introduction
A chemical bond is a force that holds together two or more
atoms forming molecules, ions or combinations of those.
Now, why do atoms form bonds?
They form bonds in order to become more stable. This means
that elements which already have a stable configuration, such
as noble gases, will not readily form bonds but, however,
elements with unstable configuration, such as Li, Na, Mg, O,
F, etc. form bonds.

Elements that do not have a noble-gas configuration (a stable

configuration) try to attain such a configuration by entering
into chemical reactions. Stable molecules are formed when
atoms combine so as to have outer shells holding eight
electrons.

012-Page 84
4.1. Ionic bonding
4.1.1. Formation
An ionic bonding also called electrovalent bonding is formed
when an atom of a metallic element gives an electron(s) to an
atom of a non-metallic element. The ions formed are held
together by an electrostatic attraction.
Typical ionic compounds are formed when metals in group I
or group II react with non-metals in group VI or groupVII.
When the reaction occurs, electrons are transferred from the
metal to the non-metal until the outer electron shells of the
resulting ions are identical to those of a noble gas.
Example: Electron transfers during the formation of sodium
chloride and magnesium fluoride
_
xx xx
+ x x
Na . + x Cl xx Na Cl
. x
(2, 8, 1) xx
xx
(2, 8)
(2, 8, 7)
(2, 8, 8)
sodium atom chlorine atom
sodium ion chloride ion

-
xx 2+ xx
x x
x x Mg F x
Mg : + 2 F x .
xx
xx 2
(2, 8, 2) (2, 8)
(2, 7) (2, 8)
magnesium atom 2 fluorine atoms magnesium ion 2 fluoride ions

Note:
When writing “dot/cross “diagrams, the dots and crosses are
simply a means of counting electrons. They cannot show the
012-Page 85
precise location of electrons within the atom since electrons
are distributed in space as diffuse negative charge clouds.
4.1.2. Giant ionic structures
Ionic structures are formed when atoms with large
differences in electronegativity form compounds. Electrons
are transferred from atoms of low electronegativity to those
of high electronegativity. The oppositely charged ions which
result are held together by strong electrostatic forces of
attraction. The electrochemical force binding the ions
together is described as an ionic or electrovalent bond.
Example: The sodium chloride lattice

Figure: The structure of sodium chloride.

The small circles in figure above represent the centers of Na+
and Cl- ions respectively. While the solid lines in the diagram
show the cubic geometry of the lattice.
4.1.2. Properties of ionic compounds
− Ionic compounds have high melting temperatures and
boiling temperatures. This is because of strong
electrostatic attraction between ions and opposite charge

012-Page 86
 make it difficult to separate the ion and break the cristal
structures thus high melting and boiling temperatures
− Ionic compounds are electrolytes:

Solid doesn’t conduct electricity as no charge carriers
available to move

Molten does conduct electricity as mobile ions can move
− Many ionic compounds dissolve in water. They are
insoluble in organic compounds.

 Melting Point
Ionic compounds have high melting points.
The electrostatic attraction (ionic bond) between cations and
anions is strong. It takes a lot of energy to overcome this
attraction in order to allow the ions to move more freely and
form a liquid.
The factors which affect the melting point of an ionic
compound are:
• The charge on the ions.
In general, the greater the charge, the greater the
electrostatic attraction, the stronger the ionic bond, the
higher the melting point.
The table below compares the melting point and ion
charges for sodium chloride and magnesium oxide.
Ionic Melting Cation Anion
Compound Point Charge Charge
(oC)

012-Page 87
NaCl 801 +1 -1
MgO 2800 +2 -2

MgO has a higher melting point than NaCl because 2

electrons are transferred from magnesium to oxygen to form
MgO while only 1 electron is transferred from sodium to
chlorine to form NaCl.
• The size of the ions.
Smaller ions can pack closer together than larger ions so
the electrostatic attraction is greater, the ionic bond is
stronger, the melting point is higher.
The melting point of Group IA (alkali) metal fluorides is
compared to the ionic radius of the cation in the table
below.
Ionic Melting Cation
Compound Point (oC) Radius
(pm)
NaF 992 99
KF 857 136
RbF 775 148
CsF 683 169

As the radius of the cations increases down Group I from

Na+ to Cs+, the melting points of the fluorides decrease.
 Conductivity

012-Page 88
In order for a substance to conduct electricity it must contain
mobile particles capable of carrying charge.

Ionic Ionic Aqueous

Solid Liquid Solution
Mobility of very good good
Ions poor
Electrical very good good
Conductivity poor
Solid ionic compounds do not conduct electricity because the
ions (charged particles) are locked into a rigid lattice or array.
The ions cannot move out of the lattice, so the solid cannot
conduct electricity.
When molten, the ions are free to move out of the lattice
structure.
• Cations (positive ions) move towards the negative
electrode (cathode)
M+ + e → M
• Anions (negative ions) move towards the positive
electrode (anode)
X- → X + e
When an ionic solid is dissolved in water to form an aqueous
solution, the ions are released from the lattice structure and
are free to move so the solution conducts electricity just like
the molten (liquid) ionic compound.
 Brittleness
012-Page 89
Ionic solids are brittle.
When a stress is applied to the ionic
lattice, the layers shift slightly.
The layers are arranged so that each
cation is surrounded by anions in the lattice. If the layers shift
then ions of the same charge will be brought closer together.
Ions of the same charge will repel each other, so the lattice
structure breaks down into smaller pieces.
4.2. Covalent bonding
4.2.1. Formation
Covalent bond is formed when two atomic orbitals overlap
by sharing a pair of electrons. In the single covalent bond,
two atoms share one pair of electrons. By sharing, the bonded
atoms both gain a full outer shell of electrons. A double bond
is formed when two atoms share two pairs of electrons.
Covalent bonding can be used to explain the structures and
formulas of non-metals (e.g.Cl2, P4, S8) and also of non-
metal/ non-metal compounds (e.g. CH4, HCl, CO2…)
In these substances, each atom usually gains a noble gas
electron structure as a result of electron sharing.
Example: Case of HCl and H2O

012-Page 90
Note
Covalent bonds are divided into two types:
01)Polar covalent where the bonding pair of electrons is
nearer to one atom which is more electronegative.
02)Pure covalent where the bonding pair of electrons is
shared equally. Pure covalent is non-polar covalent.
03)Covalently bonded substances can be either:

i. molecular substances
ii. three dimensional covalent networks
A molecular substance contains discrete molecules with
weaker intermolecular forces attracting one molecule to
another.
A network covalent substance contains only strong covalent
bonds between atoms.
4.2.2. Properties of covalent compounds
− Most covalent compounds are held together by weak
forces of attraction and thus have low boiling points (e.g.
ethanol and iodine). Molecular solids have much lower
melting points than covalent network solids.
− Covalent substances are non-electrolytes
Covalent compounds are often insoluble in water. Many
dissolve in organic solvents such as ethanol or propanone.
4.2.3. Covalent network solids

012-Page 91
The elements carbon, silicon and boron form covalent
networks instead of covalent molecules.
Silicon dioxide, SiO2, also exists as a covalent network and is
known as quartz. Its structure is similar to diamond.

Case of Carbon
Carbon forms 2 naturally occurring covalent network solids:
graphite and diamond

graphite diamond
structure

bonding each carbon each carbon

atom makes 3 atom makes 4
covalent covalent
bonds bonds
structure carbon atoms carbon atoms
in a hexagonal in a
arrangement tetrahedral
forming arrangement
012-Page 92
 layers

melting very high very high

point (sublimes at (~4000K) due
~3500K) due to the large
to the large amount of
amount of energy
energy required to
required to break strong
break strong covalent
covalent bonds
bonds
electrical good insulator due
conductivity conductor to no
between the delocalised
carbon layers electrons (all
due to electrons are
delocalised used in
electrons covalent
between the bonding)
carbon layers
hardness soft because hardest
the carbon known natural
layers can mineral
slide over
each other
colour black colourless
uses lubricant due abrasive due
to its softness to its hardness

012-Page 93
4.2.4. Dative and coordinate bond
A coordinate bond is a covalent bond in which the shared
pair of electrons is provided by only one of the bonded atoms
(one of the overlapping orbitals contained two electrons and
the other none).One atom is the donor and the other is
acceptor. Coordinate bond is sometimes called the dative
covalent bond.
Examples:
− Bond formed between ammonia and hydrogen in the
formation of an ammonium ion.
(the lone pair of the nitrogen atom coordinates into the
valence shell of hydrogen ion)
− Bond formed between water and hydrogen in the
formation of hydroxonium ion.

The symbol is used for a coordinate bond, an arrow from

the donor to the acceptor.
4.2.5. Hybridization of atomic orbitals and formation of
sigma (σ) and Pi (π)-bonds
012-Page 94
Hybridization of atomic orbitals is theoretical mixing up of
atomic orbitals having different shapes, names, energies and
orientation to form hybrid orbitals of exactly similar
properties and improved ability to form chemical bond.
Examples
(1) Covalent bonding in methane
Consider electronic configuration at the ground state of
carbon atom
1s 2s 2p

px py pz
At excited state, it becomes
1s 2s 2p

i.e. one 2s electron promoted to 2p orbital.

px py pz

The four orbitals (2s, 2px, 2py and 2pz) have different names
shapes and energy thus they hybridize and form the
following: For each of the 4sp3 hybrid orbitals has the shape

sp3 sp3 sp3 sp3

Such shape has very strong bond forming power and each of
4sp3 orbitals has one unpaired electron such that they repel
each other to the maximum angle of 109.5o

012-Page 95
Note
The hybridization sp3 means the hybrid orbital has one part s-
property and three parties’ p-properties. When the 4sp3
hybrid orbitals overlap with the s-orbital of hydrogen,
methane with regular tetrahedron geometry is formed.

(2) Covalent bonding in ethene

The structure of ethene is explained by hybridization of only
3 orbitals of the excited carbon atom i.e.hybridisation of 2s,
2px and 2py without involving 2pz orbital
Ethene, only 3 orbitals hybridised rather than all 4, one 2s
electron, two 2p electrons, other 2p electron unchanged (sp2
hybrid orbitals)
- Two Carbon atoms linked by overlap of sp2 hybrid orbitals,
making a σ- bond and a pi-bond formed by sideways overlap
of the non-hybridised p atomic orbitals. Remaining two sp2
orbitals form σ- bond with the s-orbital of hydrogen.

012-Page 96
 H 120o H

C C
H ethene H

- Pi- bond: sideways overlap of two p-orbital to give a two

part orbit above and below a
bond
(3) Covalent bonding in acetylene
Also, structure of acetylene is explained by hybridation of
only one 2s orbital and and one 2p orbital, other two 2p
electrons unchanged (sp hybrid orbitals)

180o

H C C H

Note
1. All double bonds will consist of a pi bond and a σ bond,
while all triple bonds consist of two pi bonds and a
sigma bond.
2. Hybridized orbitals are olways equivalent in names,
energy and shape.
3. The geometry shape of the hybrid orbitals determine also
the geometry of the molecule it will form.
4. The sigma bond is a result of the:
− Overlap of two s-orbitals
012-Page 97
 − Overlap of s-orbital and p-orbital
− Overlap (head on ) of two p-orbitals
The pi bond is a result of the overlap side by side of two
p-orbitals
Overlap head on (sigma) and
Overlap sideway (pi)

pi
sigma

4.2.6. Shapes of molecules

Valence Shell Electron Pair Repulsion (VSEPR)

The shape of a molecule is a description of the way the atoms

in the molecule occupy space. 'Electron Cloud' Repulsion
Theory (Valence Shell Electron Pair Repulsion, VSEPR) is
used to predict shapes and bond angles of simple molecules.
1. In order to determine the shape of molecule, the Lewis
diagram must be drawn first.
2. Lone pairs of electrons (or non-bonding pair of
electrons) occupy more space than bonding electrons
3. Double bonds occupy more space than single bonds
4. Multiple bonds are considered as ingle bond
5. Lone pair-bonding pair repulsion is greater than bonding
pair-bonding pair repulsion
6. Lone pair-lone pair repulsion > lone pair-bonding pair
repulsion > bonding pair-bonding pair repulsion

012-Page 98
Case I: All molecules with the central atom surrounded by 3
bonding pairs have a TETRAHEDRAL shape and the angle
between each is 109.5o
e.g:CCl4, CH4, SiF4,…
Case II: All molecules with the central atom surrounded by 3
bonding pairs and one non bonding pair have a
TRIANGULAR (OR TRIGONAL) PYRAMIDAL shape.
Due to the repulsion, a non bonding electron pair requires
more space than a bonding pair, the angles in these molecules
are 107o not 109.5o as in tetrahedral molecules. e.g. NH3,
PCl3,…
Case III: All molecules with the central atom surrounded by
two bonding pairs and two non bonding pairs have the BENT
OR V-SHAPE. The repulsion between the non bonding pairs
with result in a bond angle of 104.5o.e.g: H2O, H2S, SCl2,…
Remark:
The repulsion involves that for each pair of non bonding
electrons, the bond angle decreases 2.5o
Case IV: All molecules with the central atom surrounded by
5 pairs of bonding pairs have a TRIGONAL
BIPYRAMIDAL shape which consists of two pyramids
sharing the same base.
e.g: PCl5, PF5

012-Page 99
Case V: Molecules with the central atom with an incomplete
octet.
i) Molecules that only have 2 bonding pairs on the central
atom will have a LINEAR shape with a bond angle of
180o. e.g: BeCl2, BeH2,…
ii)Molecules that only have 2 bonding pairs on the central
atom will have a TRIANGULAR PLANAR shape with
a bond angle of 120o. e.g: BCl3, AlCl3,…

The "AXE method" of electron counting is commonly

used when applying the VSEPR theory. The A represents
the central atom and always has an implied subscript
one.
• The X represents the number of sigma bonds
between the central atoms and outside atoms.
Multiple covalent bonds (double, triple, etc) count
as one X.
• The E represents the number of lone electron pairs
surrounding the central atom. The sum of X and E,
known as the steric number, is also associated with
the total number of hybridized orbitals used by
valence bond theory.
• Based on the steric number and distribution of X's
and E's, VSEPR theory makes the predictions in the
following tables.
• Note that the geometries are named according to the
atomic positions only and not the electron
arrangement. For example the description of AX2E1
as bent means that AX2 is a bent molecule without
012-Page 100
 reference to the lone pair, although the lone pair
helps to determine the geometry.

Molecul Shape Electron Geometry Example

e Type arrangement ‡ s
†

AX1En Diatomic HF, O2

AX2E0 Linear BeCl2,
HgCl2,
CO2
AX2E1 Bent NO2−,
SO2, O3
AX2E2 Bent H2O, OF2

AX2E3 Linear XeF2, I3−

AX3E0 Trigonal BF3,

planar CO32−,
NO3−,

012-Page 101
 SO3
AX3E1 Trigonal NH3,
pyramidal PCl3

AX3E2 T-shaped ClF3,

BrF3

AX4E0 Tetrahedral CH4,

PO43−,
SO42−,
ClO4−
AX4E1 Seesaw SF4

AX4E2 Square XeF4

planar
AX5E0 Trigonal PCl5
bipyramida
l

AX5E1 Square ClF5,

pyramidal BrF5

AX6E0 Octahedral SF6

† Electron arrangement including lone pairs.

‡ Observed geometry (excluding lone pairs)

012-Page 102
When the substituent (X) atoms are not all the same, the
geometry is still approximately valid, but the bond angles
may be slightly different from the ones where all the outside
atoms are the same. For example, the double-bond carbons in
alkenes like C2H4 are AX3E0, but the bond angles are not all
exactly 120°. Similarly, SOCl2 is AX3E1, but because the X
substituents are not identical, the XAX angles are not all
equal.
4.2.7. Polarity of molecules
A non-polar molecule has no net dipole. This can be achieved
by the molecule having:
1. only non-polar bonds
2. polar bonds arranged symmetrically so that the dipoles
cancel out
A polar molecule has a net dipole. This is achieved in the
molecule by the molecule being made up of polar bonds
arranged asymmetrically so that the dipoles do not cancel
out.
Examples
Non-polar Molecules
Case I: Only non-polar bonds present
H-H is non-polar since both hydrogen atoms making up the
molecule have equal electronegativity so there is no net
dipole.

012-Page 103
 NCl3 is non-polar since the nitrogen atom and the chlorine
atoms making up the molecule have the same
electronegativity so there is no net dipole.
Case II: Polar bonds arranged symmetrically
CO2 is non-polar. Each C - O bond is polar since oxygen is
more electronegative than carbon, however, these bonds are
arranged symmetrically (all angles are 180o) so that the two
dipoles cancel out resulting in no net dipole for the molecule.
AlCl3 is non-polar. Each Al-Cl bond is polar since chlorine is
much more electronegative than aluminium, however, each
Al-Cl bond in AlCl3 is arranged symmetrically (all angles are
120o) so that the dipoles cancel out resulting in no net dipole
for the molecule.
CH4 is non-polar. Each C-H bond is polar since carbon is
more electronegative than hydrogen, however, each C-H
bond in CH4 is arranged symmetrically (all angles are 109.5o)
so that the dipoles cancel out resulting in no net dipole for the
molecule.
Polar Molecules
Polar bonds arranged asymmetrically
HCN is polar. Both the C-H and the C-N bonds are polar.
Nitrogen is more electronegative than carbon which is more
electronegative than hydrogen. So that the hydrogen takes on
a partial positive charge and the nitrogen takes on a partial

012-Page 104
negative charge. This results in an unequal sharing of the
bonding electrons resulting in a net dipole for molecule since
the two dipoles do not cancel out.
4.3. METALLIC BONDING AND THE PROPERTIES
OF METALS
4.3.1. Formation.
A metal is a lattice of positive metal “ions” in a “sea”of
delocalised electrons.
Metallic bonding refers to the interaction between the
delocalised electrons and the metal nuclei. The physical
properties of metals are the result of the delocalisation of the
electrons involved in metallic
bonding.

Figure: sea”of delocalised electrons

4.3.2. Physical Properties of Metals
The physical properties of solid metals are: conduct heat ,
conduct electricity, generally high melting and boiling points
, malleable (can be hammered or pressed out of shape
012-Page 105
without breaking) , ductile (able to be drawn into a wire)
,metallic lustre and opaque (reflect light).

 Conductivity
Solid and liquid metals conduct heat and electricity.
The delocalised electrons are free to move in the solid lattice.
These mobile electrons can act as charge carriers in the
conduction of electricity or as energy conductors in the
conduction of heat.

The table below shows the electrical conductivity (106Ohm-

1
cm-1) of the metals lithium to indium.
Alka
Alka li
Gro
li Eart
Transition Metals up
Met h
III
als met
als
0.10 0.31
8 3
0.21 0.22 0.37
012-Page 106
0 6 7
0.13 0.29 0.0 0.0 0.0 0.0 0.0 0.0 0.1 0.1 0.5 0.1 0.06
9 8 17 23 48 77 06 93 72 43 96 66 7
0.07 0.07 0.0 0.0 0.0 0.1 0.0 0.1 0.2 0.0 0.6 0.1 0.11
7 6 16 23 69 87 67 37 11 95 30 38 6
 Melting Points
In general, metals have high melting and boiling points
because of the strength of the metallic bond.
The strength of the metallic bond depends on the:
• number of electrons in the delocalised 'sea' of electrons
or the ionic size.
(More delocalised electrons results in a stronger bond
and a higher melting point.)
• packing arrangement of the metal atoms.
(The more closely packed the atoms are the stronger the
bond is and the higher the melting point.)
The table below shows the approximate melting points (oC)
of the metals from lithium to indium.
Alk
Alka ali
Gro
li Eart
Transition Metals up
Met h
III
als met
als
180. 1,27
7 8
012-Page 107
98 650 660
63.3 1,5 1,6 1,9 1,8 1,2 1,5 1,4 1,4 1,0 419.
839 30
5 39 60 02 57 46 35 95 53 85 73
39.6 1,5 1,8 2,4 2,6 2,2 2,2 1,9 1,5
769 961 321 157
4 26 52 68 17 00 50 66 52
Group I metals have relatively low melting points compared
to other metals because they:
• only have 1 electron to contribute to the delocalised 'sea'
of electrons
• are not forming as many metallic bonds as other metals
because Group I atoms are inefficiently packed
• have large atomic radii so the delocalised electrons are
further away from the nucleus resulting in a weaker
metallic bond .
 Malleable and Ductile
Metals are malleable and ductile. The delocalised electrons in
the 'sea' of electrons in the metallic bond, enable the metal
atoms to roll over each other when a stress is applied.

 Optical Properties
Metals typically have a shiny, metallic lustre.

012-Page 108
Photons of light do not penetrate very far into the surface of a
metal and are typically reflected, or bounced off, the metallic
surface.
4.4. INTERMOLECULAR FORCES
4.4.1. Types of intermolecular forces
Three types of force can operate between covalent molecules:
• Dispersion Forces also known as London Forces (named
after Fritz London who first described these forces
theoretically 1930) or as Weak Intermolecular Forces or
as van der Waal's Forces (named after the person who
contributed to our understanding of non-ideal gas
behaviour).
• Dipole-dipole interactions
• Hydrogen bonds
Relative strength of Intermolecular Forces:
Intermolecular forces (dispersion forces, dipole-dipole
interactions and hydrogen bonds) are much weaker than
intramolecular forces (covalent bonds, ionic bonds or
metallic bonds)
• dispersion forces are the weakest intermolecular force,
hydrogen bonds are the strongest intermolecular force .
• dispersion forces < dipole-dipole interactions <
hydrogen bonds
a) Dispersion Forces (London Forces or Weak
Intermolecular Forces or van der Waal's Forces)

012-Page 109
These are very weak forces of attraction between molecules
resulting from:
1. momentary dipoles occurring due to uneven/irregular
electron distributions in neighbouring molecules as they
approach one another
2. the weak residual attraction of the nuclei in one molecule
for the electrons in a neighbouring molecule.
− The more electrons that are present in the molecule,
the stronger the dispersion forces will be.
− Dispersion forces are the only type of intermolecular
force operating between non-polar molecules, for
example, dispersion forces operate between
hydrogen (H2) molecules, chlorine (Cl2) molecules,
carbon dioxide (CO2) molecules, dinitrogen
tetroxide (N2O4) molecules and methane (CH4)
molecules.

b)Dipole-dipole Interactions
These are stronger intermolecular forces than Dispersion
forces occur between molecules that have permanent net
dipoles (polar molecules), for example, dipole-dipole
interactions occur between SCl2 molecules, PCl3 molecules
and CH3Cl molecules.
If the permanent net dipole within the polar molecules results
from a covalent bond between a hydrogen atom and either
fluorine, oxygen or nitrogen, the resulting intermolecular
force is referred to as a hydrogen bond (see below).
012-Page 110
The partial positive charge on one molecule is
electrostatically attracted to the partial negative charge on a
neighbouring molecule.
c) Hydrogen bonds
Hydrogen bonds occur between molecules that have a
permanent net dipole resulting from hydrogen being
covalently bonded to fluorine, oxygen or nitrogen. For
example, hydrogen bonds operate between water (H2O)
molecules, ammonia (NH3) molecules, hydrogen fluoride
(HF) molecules, hydrogen peroxide (H2O2) molecules,
alkanols (alcohols) such as methanol (CH3OH) molecules,
and between alkanoic (caboxylic) acids such as ethanoic
(acetic) acid (CH3COOH) and between organic amines such
as methanamine (methyl amine, CH3NH2).
H bond

H 3 atoms are collinear (points that all lie on the same straight line)
H Additional Van der waals forces between molecules
F F F
H
H

H bond

H
O
H H H O
O
H
H

Hydrogen bonds are a stronger intermolecular force than

either Dispersion forces or dipole-dipole interactions since
the hydrogen nucleus is extremely small and positively
charged and fluorine, oxygen and nitrogen being very
electronegative so that the electron on the hydrogen atom is

012-Page 111
strongly attracted to the fluorine, oxygen or nitrogen atom,
leaving a highly localised positive charge on the hydrogen
atom and highly negative localised charge on the fluorine,
oxygen or nitrogen atom. This means the electrostatic
attraction between these molecules will be greater than for
the polar molecules that do not have hydrogen covalently
bonded to fluorine, oxygen or nitrogen.
4.4.2. Effect of Intermolecular forces on melting and
boiling points of molecular covalent substances:
Since melting or boiling result from a progressive weakening
of the attractive forces between the covalent molecules, the
stronger the intermolecular force is, the more energy is
required to melt the solid or boil the liquid.
If only dispersion forces are present, then the more electrons
the molecule has (and consequently the more mass it has) the
stronger the dispersion forces will be, so the higher the
melting and boiling points will be.
Examples
− Consider the hydrides of Group IV, all of which are non-
polar molecules, so only dispersion forces act between
the molecules.
CH4 (molecular mass ~ 16), SiH4 (molecular mass ~ 32),
GeH4 (molecular mass ~ 77) and SnH4 (molecular mass
~ 123) can all be considered non-polar covalent
molecules.
As the mass of the molecules increases, so does the
strength of the dispersion force acting between the
molecules, so more energy is required to weaken the
012-Page 112
 attraction between the molecules resulting in higher
boiling points?

Figure: Boiling Points of Group IV Hydrides

If a covalent molecule has a permanent net dipole then the
force of attraction between these molecules will be stronger
than if only dispersion forces were present between the
molecules. As a consequence, this substance will have a
higher melting or boiling point than similar molecules that
are non-polar in nature.
− Consider the boiling points of the hydrides of Group VII
elements.
All of the molecules HF (molecular mass ~ 20), HCl
(molecular mass ~ 37), HBr (molecular mass ~ 81) and
HI (molecular mass ~ 128) are polar, the hydrogen atom
having a partial positive charge and the halogen atom
having a partial negative charge
As a consequence, the stronger dipole-interactions acting
between the hydride molecules of Group VII elements

012-Page 113
 results in higher boiling points than for the hydrides of
Group IV elements as seen above.
With the exception of HF, as the molecular mass
increases, the boiling point of the hydrides increase.
HF is an exception because of the stronger force of
attraction between HF molecules resulting from
hydrogen bonds acting between the HF molecules.
Weaker dipole-dipole interactions act between the
molecules of HCl, HBr and HI. So HF has a higher
boiling point than the other molecules in this series.

Figure: Boiling Points of Group VII hydrides

4.4.3. Effect of Intermolecular Forces on Solubility
In general like dissolves like:
• Non-polar solutes dissolve in non-polar solvents. For
example paraffin wax (C30H62) is a non-polar solute that
will dissolve in non-polar solvents like oil, hexane
(C6H14) or carbon tetrachloride (CCl4). Paraffin wax will

012-Page 114
 NOT dissolve in polar solvents such as water (H2O) or
ethanol (ethyl alcohol, C2H5OH).
• Polar solutes such as glucose (C6H12O6) will dissolve in
polar solvents such as water (H2O) or ethanol (ethyl
alcohol, C2H5OH) as the partially positively charged
atom of the solute molecule is attracted to the partially
negatively charged atom of the solvent molecule, and the
partially negatively charged atom of the solute molecule
is attracted to the partially positively charged atom of the
solvent molecule.
Glucose will NOT dissolve in non-polar solvents such as
oil, hexane (C6H14) or carbon tetrachloride (CCl4).
• Ionic solutes such as sodium chloride (NaCl) will
generally dissolve in polar solvents but not in non-polar
solvents, since the positive ion is attracted the partially
negatively charged atom in the polar solvent molecule,
and the negative ion of the solute is attracted to the
partially positively charged atom on the solvent
molecule.

E
X
E
R
C
I
S
E
1. (a) Predict whether each of the following molecules
S possesses a net dipole moment
CCl4, NF3, SO3

012-Page 115
 (b) Predict whether the following molecules are
polar or non polar
ICl, SO2, SF6, NF3, BCl3
2. Consider the acetonitrile molecule, CH3CN,
(a) Predict the bond angles around each carbon.
(b) Give the hybridizations on both carbons atoms
(c) Determine the total number of sigma and pi
bonds in the molecule.
3. Draw “dot/cross” electron structures showing
electrons in the outermost shell of each atom in the
following compounds
Cl2, H2O2, O2, C2H5, HCN, LiF, CaCl2, Al2S3,
POCl3, SOCl2

4. X, Y and Z represent element of atomic numbers 9,

19 and 34.
(a) Write the electronic structures for X, y, and z
(b) Predict the type of bonding which you would
expect to occur between
(i) X and Y (ii) X and Z (iii) Y and Z
(c) Draw “dot/cross” diagrams for the compounds
formed, showing only the electrons in the outermost
shell for each atom.
(d) Predict, giving reasons, the relative
(i) electrical conductance and (ii)solubility in
water

012-Page 116
 of the compound formed between X and Z
compared with that formed between X and Z
5. (a) Which of the following molecules would you
expect to have a permanent dipole?
GeH4, ICl, SiF4, CH2Cl2, CO2
(b) Which of the following molecules have no
permanent dipole what is their shape?
BCl3, CS2, C2Cl2, CBr4
(c) In which of the following compounds will
hydrogen bonding occur?
C2H5NH2, CH3OH, CH3I, CF4, H2SO3,
CH3OCH3

CHAPTER V: COMPARATIVE STUDY OF

CHEMICAL REACTIONS OF ELEMENTS IN THE
PERIODIC TABLE
OBJECTIVES
By the end of this chapter students should be able to:
012-Page 117
 a) Describe the physicl and chemical properties of
elements in the periodic table
b) Explain the preparation and uses of some elements
and their compounds.

CONTENTS
5.1. CHEMISTRY OF GROUP I AND II ELEMENTS
5.1.1. Introduction
Elements in group I and II or alkaline metals and alkaline
earth metals are called the s block elements because they
occupy an area of the periodic table following the noble
gases, an area in which the s orbitals are being filled.
Group I elements are lithium(Li), sodium(Na), potassium(K),
rubidium(Rb), Caesium(Cs), and francium(Fr).Group II
elements are beryllium(Be), magnesium(Mg), calcium(Ca),
strontium(Sr), barium(Ba), and radium(Ra).
Note that francium and radium are radioactive elements
which are artificially made, so their chemistry is not more
important.
5.1.2. Physical properties of the elements
Group 1: All are solid metals: their melting temperatures and
hardness decrease down the group, all conduct electricity.
They have low densities (Li, Na, and K are less dense than
water)
012-Page 118
Group 2: All are solid metals, their melting temperatures and
hardness decrease down the group (except magnesium which
has a lower melting temperature than calcium); all conduct
electricity; their melting temperatures are higher than the
group1 element in the same period.
• Colour flame
Both group 1 and 2 compounds show different flame colours.
Examples: Lithium (red), sodium (yellow), potassium (lilac)
Magnesium (brilliant white), calcium (brick red),
strontium (crimson).
These colours are caused because:
− Heat causes the compound to vaporize and produce some
atoms of the metal which electrons in a higher orbital
than the ground state. e.g. in the 4th shell rather than the
normal 3rd shell to sodium.
− The electron falls back to its normal shell and as it does
so, energy in the form of visible light is emitted. The
light that is emitted is of a characteristic frequency, and
hence colour, dependent on the energy level difference
between the two shells.
Briefly, the outer electron or electrons can be excited to a
higher energy level. When they fall to a lower energy level,
energy is emitted.
• Ionization energy
012-Page 119
The value of the 1st ionization energy for group 1 and of the
1st and 2nd ionization energies for group2 decreases down the
group and is low. This is because the s electrons are shielded
from the attraction of the nucleus by the noble gas core and
are easily removed. As the size of the atoms increases down
the groups, the electrons to be removed become more distant
from the nuclear charge, and the ionization energy decreases.
NOTE:
− The small size of Li+ enables it to polarize anions, and
its compounds have some covalent character.
− Be2+ is small and highly charged. It polarizes anions,
and beryllium compound are mainly covalent.
5.1.2. Chemical properties and reactions of elements
a) Reaction with oxygen
Group 1: All burn
Lithium forms an oxide: 4Li(s) + O2 (g) → 2Li2O(s)
Sodium forms peroxide: 2Na(s) + O2 (g) → Na2O2(s)
Potassium and the others form superoxide: K(s) + O2 (g)
→ KO2(s)
Group 2: All burn to form ionic oxides of formula, MO,
except that in excess oxygen barium forms peroxide (BaO2)
Ca(s) + O2(g) → 2CaO(s)
Note that the vigour of the reaction increases down the
group

012-Page 120
 b)Reaction with chlorine
Group 1:
All react vigorously to form ionic chlorides of formula MCl.
These dissolve in water to produce hydrated ions,
e.g : NaCl (s) → Na+(aq) + Cl-(aq)
Group 2:
All react vigorously to produce ionic chlorides of formula
MCl2, except that BeCl2 is covalent when anhydrous. All
group 2 chlorides ions of formula [M(H2O)6]2+ . Beryllium
chloride gives an acidic solution because of deprotonation.
[Be(H2O)6]2++ H2O ↔[Be(H2O)5(OH)]+ + H3O+
c) Reaction with water
Group 1: All react vigorously with cold water to give an
alkaline solution of metal hydroxide and hydrogen gas. e.g:
2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g)
Group 2: Beryllium does no react but magnesium burns in
steam to product an oxide and hydrogen.
Mg(s) + H2O(l) → MgO(s) + H2(g)
The others react rapidly with cold water to form an alkaline
suspension of metal hydroxide and hydrogen gas.
Ca(s) + 2H2O(l) → Ca(OH)2 + H2(g)
Note: The rate of reaction increases down the group.
012-Page 121
 d)Reactions of group 2 oxides with water
− BeO is amphoteric and does not react with water.
BeO(s) + 2H+(aq) → Be2+(aq) + H2O(l)
BeO(s) + OH-(aq) + H2O(aq) → [Be(OH)4]2-(aq)
− MgO is basic reacts slowly with water to form a
hydroxide.
− All the others reat rapidly and exothermically to form
alkaline suspensions of the hydroxide, which have a pH
of about 13.
e.g. CaO(s) + H2O(l) → Ca(OH)2(aq)
e) Reactions with acids
All the members react with acids forming the corresponding
salts and liberating hydrogen. The vigour of reaction
increases down the group.
Mg(s) + 2HNO3(aq) → Mg(NO3)2 + H2(g)
Na(s) + HCl(aq) → NaCl(aq) +1/2H2(g)
f) Reaction wit alkalis
All the elements except beryllium do not react with alkalis.
Beryllium reacts with aqueous alkalis forming complex
called berraylate.
Be(s) + 2OH-(aq) + 2H2O (l) → [Be(OH)4]2+(aq) +
H2(g)
g) Solubility of group 2 sulphates and hydroxides

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 • Sulphates: their solubility decrease down the group.
BeSO4 and MgSO4 are soluble
CaSO4 is slightly soluble
SrSO4 and BaSO4 are insoluble
• Hydroxides: their solubility increase down the group
Be(OH)2 and Mg(OH)2 are insoluble
Ca(OH)2 and Sr(OH)2 are slightly soluble, and Ba(OH)2
is fairly soluble
h) Thermal stability of nitrates and carbonates
Thermal stability increases down both groups:
− Group 2 nitrates all decompose to give a metal oxide,
brown fumes of nitrogen dioxide and oxygen
e.g. 2Ca(NO3)2(s) → 2CaO(s) + 4NO2(g) + O2(g)
− Group 1 nitrates except lithium nitrate, decompose to
give a metal nitrite and oxygen
2NaNO3(s) → 2NaNO2(s) + O2(g)
but 4LiNO3(s) → 2Li2O(s) + 4NO2(g) + O2(g)
− Group 2 carbonates all decompose (except barium
carbonate which is stable to heat) to give a metal oxide
and carbon dioxide.
CaCO3(s) → CaO(s) + CO2(g)
− Group 1 carbonates are stable to heat except for lithium
carbonate.
Li2CO3(s) → Li2O(s) + CO2(g)
Remark:
012-Page 123
− The compound is more likely to be decomposed on
heating if the cation polarizes the anion. Thus group 2
compounds (cation 2+) decompose more readily than
group 1 compounds (cation only 1+)
− Compounds of metals higher in a group (smaller ionic
radius) decompose more easily than compounds of
metals lower in the group.
J) Uses of sodium and magnesium
1. Molten sodium is used as a coolant in some types of
nuclear reactor. Its high thermal conductivity and
low melting temperature and the fact that its boiling
temperature is much higher than that of water make
sodium suitable for this purpose.
2. Sodium wire is used in electrical circuits for special
applications. It is very flexible and has a high
electrical conductivity. The wire is coated with
plastics to exclude moisture.
3. Sodium vapour lamps are used for street lighting.
4. Sodium amalgam and sodium tetrahydridoborate,
NaBH4, are used as reducing agents.
5. Magnesium is alloyed with aluminium to make
Duralumin (alloys of Al/Mg/Cu)
6. Magnesium is used as a sacrificial anode to prevent
iron from rusting.

012-Page 124
 Testing your knowledge and understanding
1. Which group 1 metal has the highest melting
temperature?
2. Barium compounds normally are poisonous, but barium
sulphate is given to people in order to outline their gut in
radiography ( X-ray imaging). Why a barium sulphate
not poisonous?
3. Explain why the 1st I.E of sodium is larger than the 1st
I.E of potassium.
4. Write balanced equations for the reactions for the
reactions of:
a) Calcium with oxygen
b) Calcium with water
c) potassium with water
d) Magnesium with steam
5. State and explain with group 2 element forms the least
thermally stable carbonate
6. Write balanced equations for the thermal decomposition
of the following; but if there is no reaction at laboratory
temperatures, say so:
a) Lithium nitrate, sodium nitrate and magnesium
nitrate
b) sodium carbonate, magnesium carbonate and barium
carbonate
012-Page 125
 7. The elements Be, Mg, Ca, and ba belong to a group (II)
in the periodic table.
a) i) State three chemical properties shown by the
elements. For each property, write an equation to
illustrate your answer.
ii) Give the trend in the in the solubilities of the
hydroxides and sulphates of the elements in water.
b) Be differs in some of its properties from the rest of
the elements in the group.
i) State two properties in which Be shows
different properties differs from the rest of the
elements in the group.
ii)Give reasons why Be shows different properties
from the rest of the elements.
5.2. STUDY OF GROUP III ELEMENTS
5.2.1 Introduction
The elements of group 3 of the periodic table are boron (B),
aluminium (Al), gallium (Ga), indium (In), and thallium (Tl).
This group marks the beginning of the p-block elements.
Aluminium is by far the most important of them.
5.2.2 Physical properties of boron and aluminium
Boron is a non-metal element with high melting point and
low densities.

012-Page 126
Aluminium is a metal element and has a low density, it is a
good conductor of heat and electricity, and it has high
melting point than group 1and 2 metals.
5.2.3 Reaction of aluminium.
− Reaction with oxygen
On exposure to air, the metal develops very thin layer of
aluminium oxide which prevents further reaction.
4Al(s) + 3O2(g) → 2Al2O3(s)
Aluminium oxide is amphoteric dissolving in mineral
acids to form aluminium salts and in caustic alkali to
form aluminate.
Al2O3(s) + 6H+(aq) → 2Al3+(aq) + 3H2O(l)
Al2O3(aq) + 2OH-(aq) + 3H2O(l) → 2[Al(OH)4]-
(aq)

− Reactions with acids

• Whith HCl
Aluminium reacts when warmed with moderately
concentrated hydrochloric acid forming aluminium
chloride and hydrogen gas
2Al(s) + 6HCl(aq) → 2AlCl3(aq) + 3H2(g)
• With H2SO4
Aluminium does not react with dilute sulphuric acid but
reacts with concentrated sulphuric acid forming
aluminium sulphate, sulphur dioxide and water

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 2Al(s) + 6H2SO4(aq) → Al2(SO4)3(aq) + 3SO2(g) +
6 H2O(g)
Note: Aluminium does not react with HNO3 because of
the insoluble layer of Al2O3 formed which prevents
further reaction.
− Reaction with alkalis
Aluminium reacts vigorously with sodium hydroxide
solution forming sodium aluminate and hydrogen gas.
2Al(s) + 2NaOH(aq) + 6H2O(l) → 2NaAl(OH)4 +
3H2(g)
Note that because of this reaction aluminium saucepan and
other cooking utensils are damaged by alkaline solution.
− Reaction with halogens
• Aluminium fluoride is made by direct combination of the
metal with fluorine.
2Al(s) + 3F2(g) → 2AlF3(s)
• Aluminium chloride is made by passing chlorine gas
over heated aluminium metal
2Al(s) + 3Cl2(g) → 2AlCl3(s)
2Al(s) + 6HCl(g) → 2AlCl3(g) + 3H2(g)
5.2.4. Compounds of aluminium
a) Halides( AlF3, AlCl3, AlBr3 , AlI3)
• Bonding:

012-Page 128
Aluminium shows an oxidation state of +3 in most its
compounds.
Because of high charge (large positive) and small ionic
radius, Al3+ exerts polarizing effect on the halide ion in
contact with it. This polarization is greatest as the size of the
halide ion increases. Therefore the iodide (I-) ion with
greatest size is most polarized while the fluorine (F-) ion
experiences negligible polarization. Therefore AlF3 is ionic
while AlCl3 is intermediate between ionic and covalent.
Aluminium chloride exists as dimmer, Al2Cl6 in vapour
phase and on heating sublimes at 180oC.
The structure of chloride in vapour phase
Cl Cl Cl

Al
Al

Cl Cl
Cl

At ordinary conditions, AlCl3 adopts a tigonal plane

structures

Cl

Al

Cl Cl

012-Page 129
Aluminium bromide is typically covalent because of the large
Br- size. Like aluminium chloride, it also exists as dimmer
Al2I6 is covalent and has also similar properties with Al2Br6
• Behaviour in water
Aluminium chloride solution like other compounds of
aluminium contains hydrated aluminium ion
( [Al(H2O)6]3+)
AlCl3(aq) → Al3+(aq) + 3Cl-(aq)
Al3+(aq) + 6H2O(l) → [Al(H2O)6]3+(aq)
Aluminium chloride gives an acidic solution because of
deprotonation(production of
Al3+(aq) + 6H2O(l) → [Al(H2O)33OH](aq) + 3H+(aq)
Note :
Because of the same reason, aqueous solutions of FeCl3
,CuSO4, Cr(NO3)3 and Co(NO3)3 are acidic;
b) Aluminium hydroxide
Aluminium hydroxide shows amphoteric properties .
− It reacts with basic solution
Al(OH)3(s) + HO-(aq) → [Al(OH)4]-(aq)
− It reacts with acidic solution
Al(OH)3(s) + 3H+(aq) → Al3+(aq) + 3H2O(l)
012-Page 130
5.2.5. Uses of some groupIII elements
Aluminium
− is used in making cooking utensils: this is because of its
bright appearance and lightness
− is used as overhead high tension cables for distribution
of electricity: this is because of its low density and very
good electrical conductivity.
− is used in alloys making. e.g manganlium (Al and Mg)

Gallium
− is used as a semiconductor.e.g: with phosphorus and
arsenic in light emitting diodes.
Note that sodium tetrahydridoborate(III), NaBH4, and lithium
tetrahydridoaluminate(III), LiAlH4, are used as reducing
agents in organic chemistry but LiAlH4 is the more vigorous.

Testing your knowledge and understanding

1. A chloride of aluminium, X, contains 20% aluminium
and 80% chlorine
a) i) Calculate the empirical formula of X
ii) Determine the molecular formula of X (its
molecular weight is 267)

012-Page 131
 iii) Write the structural formula of X
b) Write an equation to show how aluminium
chloride can be prepared from aluminium
c) Aluminium chloride was dissolved in water. Write
the equation for the reaction that took place
d) Sodium carbonate was added to an aqueous
solution of aluminium chloride.
i) State what was observed
ii) Write the equation for reaction that took place.
2. The relative formula mass of aluminium chloride in the
vapour phase is 267.
a) Write the molecular formula of aluminium chloride
in the vapour phase and its structural formula in the
same state.
b) With reference to aluminium oxide, explain the term
amphoteric oxide. Write equations where necessary.
c) Explain with the aid of equations why
i) aqueous solution of simple Al3+ salts are acidic.
ii)aluminium utensils are not washed in strong
alkaline solutions.
5.3. GROUP IV ELEMENTS
5.3.1. Comparative study of physical properties of group
IV elements
− Group 4 elements are carbon(C) and silicon (Si) which
are non-metallic elements, germanium (Ge), which is
012-Page 132
 intermediate in character, a metalloid, tin (Sn) and lead
(Pb) which are metals. Therefore, the elements become
more metallic down the group.
− The group 4 elements have a characteristic covalency of
4. Due to increasing electropositivity down the group, an
electrovalency of 2 becomes more pronounced down the
group. Therefore, the group members exhibit two
oxidation states of +2 and +4. The stability of +2
oxidation state increases down the group thus, Pb is a
strong oxidizing agent.

C, Si, Ge: Covalent compounds, almost exclusively 4-valent

Sn: Covalent (+4) and ionic (+2) states
Pb: mainly ionic (+2) state, also covalent (+4) state.

The increase in stability of +2 oxidation state is due to inert

pair effect. Inert pair effect is the inability of the s-electrons
to participate in bonding i.e. ns2np2.The +4 oxidation state
decrease in stability down the group. Tin(II) compounds are
reducing agents because tin(IV) is the more stable oxidation
state of tin, but lead(IV) compounds are oxidizing agents
because lead(II) is the stable oxidation state for lead.
− All the 5 elements can have their ground state electronic
configuration ns2np2 promoted to ns1np3 and thus they
are able to form 4 covalent bonds with the structure of
their resultant compound being tetrahedral.
012-Page 133
5.3.2. Allotropes of carbon
Allotropy is the existence of an element in two or more
different physical states. Carbon shows allotropy. It exists as
graphite and diamond.
− Diamond has very high refractive index and dispersive
power hence useful as jewellery. besides, it is the hardest
known substance used for cutting or grinding.
− Graphite is a good conductor of electricity because of the
presence of mobile electrons in its layers. So, it is used
for making electrodes and in the construction of nuclear
reactors. Also, it is used as lubricant (because the layers
slide over one another0 and as a mixture with clay in
“lead” pencils.
− Impure forms of carbon include charcoal, coal and coke.

Allotropic Forms of Carbon

Atoms of the element carbon can link together in several ways to form
substances with very different properties. In diamond, the atoms form a
three-dimensional network that extends throughout a crystal and makes
diamond the hardest naturally occurring substance. Graphite is made up of
layers of carbon that can slide over each other easily, making graphite a
useful lubricant.

012-Page 134
Unique properties of carbon

Carbon behaves differently from the rest of the group

members because of its small size, high electronegativity and
non-availability of d-orbital electrons. Some of the properties
in which it differs from the rest of the group members include
1. It is limited to a coordination number of four while the
others can have six.
2. Carbon is the only member of the group which forms Pi
bonds, it can form multiple bonds with itself and other
elements. i.e.C=C, C≡C, C=O, C≡N, …
3. Carbon can catenate. “Catenation is the ability of an
element to form bonds between atoms of the same
element “. So, carbon can form long chains or rings of
itself.
4. Carbon forms gaseous oxides, CO and CO2, in contrast
to the other members. For carbon energy considerations
favour the formation of two double bonds in O=C=O
rather than four C-O bonds

012-Page 135
In silicon, the formation of four Si-O bonds is preferred on
energy grounds and silicon forms polymeric (SiO2)n in giant
molecule.

O Si O Si O

O O

O Si O Si O

O O

O Si O Si O

5.3.3 Uses of group 4 elements

1. Silicon
Silicon occurs naturally as silicon (IV) oxide, silica,
SiO2, in sand and quartz and also as a number of
silicates. The element is extracted by reduction of the
oxide with carbon(coke).
It is used:
− as asemi-conductor in transistors and other
electronic components
− in silicone waxes and polymers
− as silicates, in ceramics and glass industries.
012-Page 136
2. Germanium
It is used as a semi-conductor in transistors
3. Tin
Tin is mined as tinstone, SnO2. The metal is obtained by
reducing the oxide with coke.
It is used :
− to protect/plate iron on steel to prevent it from
rusting
− in alloys such as bronze (Sn- Cu) and solder( Sn-
Pb)

4. Lead
Lead is mined as galena, PbS, the ore is roasted to form
the oxide, PbO, which is reduced to the metal by coke.It
is used:
1. in plumbing, but because it reacts slowly with water to
form poisonous lead compound, today copper pipes and
plastic pipes are used instead.
2. to make solder and lead-aid accumulators.
3. antiknock, tetraethyllead, has been used for many years
to improve petrol, but its use is being phased out because
it leads to pollution of the air with lead compounds.
4. some lead compounds are used as pigments; e.g. lead
chromate(VI), PbCrO4 (yellow), lead carbonate
hydroxide(white) and trilead tetraoxide Pb3O4(orange).

012-Page 137
5.3.4. Reaction of C, Sn, Pb and Si.
a) Reactions with oxygen
All react with oxygen on heating to form dioxides except
lead which forms a monoxide
C(s) + O2(g) → CO2(g)
Si(s) + O2(g) → SiO2(s)
2Pb(s) + O2(g) → 2PbO(s)
b) Reaction with water
− White hot coke (carbon) reacts with steam to give a
mixture of carbon-monoxide and hydrogen
C(s) + 2H2O(l) → CO(g) + H2(g)
− Silicon reacts with boiling water or steam to form
silicon(IV) oxide
Si(s) + 2H2O(g) → SiO2(s) + 2H2(g)
− Lead reacts slowly with soft water
Pb(s) + 2H2O(l) →Pb(OH)2(aq) + H2(g)
Note: Germanium and tin do not react with water in any
form.
c) Reaction with acids
All do not react with dilute mineral acids except tin
which reacts with dilute nitric acid (cold) according to
the equation
4Sn(s) + 10HNO3(aq) → 4Sn(NO3)2(aq) +
NH4NO3(aq) + 3H2O(l)
i) With nitric acids

012-Page 138
Concentrated nitric reacts with all the elements to form
dioxides except lead which forms lead(II) nitrate.
3C(s) + 4HNO3(aq) → 3CO(g) + 4NO(g) + 2H2O(l)
3Sn(s) + 4HNO3(aq) → 3SnO2(s) + 4NO(g) + 2H2O(l)
3Pb(s) + 8HNO3(aq) → 3Pb(NO3)2(aq) + 2NO(g) +
4H2O(l)
ii)with hot concentrated sulphuric acid
C(s) + 2H2SO4(aq) → CO2(g) + 2SO2(g) + 2H2O(l)
Sn(s) + 4H2SO4(aq) → Sn(SO4)2(aq) + 2SO2(g) +
4H2O(l)
Pb(s) + 2H2SO4(aq) → PbSO4(s) + SO2(g) + 2H2O(l)
iii) With hydrochloric acid
Concentrated HCl reacts with tin vigorously to form tin(II)
chloride
Sn(s) + 2HCl(aq) → SnCl2(aq) + H2(g)
Lead reacts with boiling concentrated HCl forming PbCl2
Pb(s) + 2HCl(aq) → PbCl2(aq) + H2(g)
Note that silicon does not react with any mineral acid.
d)Reaction with alkalis

012-Page 139
All the elements except carbon react with alkalis. Silicon
reacts with dilute sodium hydroxide solution to form sodium
silicate.
Si(s) + 2NaOH(aq) + H2O(l) → Na2SiO3(aq) + 2H2(g)
Tin and lead react with hot concentrated solution of NaOH
forming stannate and plumbate salts respectively.
Sn(s) + 2NaOH(aq) + H2O(l) → Na2SnO3(aq) + 2H2(g)
Pb(s) + 2NaOH(aq) + H2O(l) → Na2PbO3(aq) + 2H2(g)
5.3.5. Compounds of group IV elements
Unlike C and Si, the last three elements Ge, Sn, and Pb
exhibit +2 and +4 oxidation states in their compounds. The
+2 oxidation state in Ge and Sn is unstable and revert to +4
state. Lead is predominantly +2 and +4 is very unstable
reverting to +2 state.
a) oxides
The elements form two types of oxides in both oxidation
states
I. Dioxides
Preparations
Dioxides of C, Si, Ge, and Sn are prepared by direct
combination with oxygen on heating.
e.g: C(s) + O2(g) → CO2(g)

012-Page 140
PbO2 is prepared by the reaction
Pb3O4 (s) + 4HNO3(aq) → 2Pb(NO3)2(aq) + PbO2(s) +
2H2O(l)

Structure
CO2 adopts a simple molecular structure, SiO2, has a giant
molecular while GeO2, SnO2 and PbO2 adopt intermediate
molecular and ionic structures.
Thermal stability and acid-base character
All except PbO2 are thermally stable. PbO2 on heating
decomposes.
2PbO2(s) → 2PbO(s) + O2(s)
PbO2 is an oxidizing agent which oxidizes warm HCl to
chlorine gas.
PbO2(s) + 4HCl(aq) → PbCl2(aq) + Cl2(g) + 2H2O(l)
CO2 and SiO2 are acidic
CO2(g) + 2OH-(aq) → CO32-(aq) + H2O(l)
SiO2(s) + 2OH-(aq) → SiO32-(aq) + H2O(l)
GeO2, SnO2 and PbO2 are amphoteric and become more basic
down the group.
SnO2(s) + 2OH-(aq) → SnO32-(aq) + H2O(l)

012-Page 141
SnO2(s) + 4H+ → Sn4+(aq) + 2H2O(l)
PbO2(s) + 2OH-(aq) → PbO32-(aq) + H2O(l)
PbO2(s) + 4H+(aq)(cold) → Pb4+(aq) + 2H2O(l)
II. Monoxides
Preparation
CO is prepared by reducing of CO2 with C
CO2(g) + C(s) → 2CO(g)
GeO is prepared by reducing of geO2 with Ge
GeO2(s) + Ge(s) → 2GeO(s)
SnO and PbO are prepared by action of heat on their
hydroxide or nitrate.
Sn(OH)2(s) → SnO(s) + H2O(l)
2Pb(NO3)2 (s) → 2PbO(s) + 4NO2(g) + O2(g)
Structure and acid-base character
CO and SiO have simple molecule structure and are neutral
oxides
GeO, SnO and PbO have ionic structures and are amphoteric
and become more basic down the group
SnO(s) + OH-(aq)+ H2O(l) → Sn(OH)3-(aq) (stannate(II)
SnO(s) + 2H+(aq) → Sn2+(aq) + H2O(l)

012-Page 142
PbO(s) + OH-(aq) + H2O(l) → Pb(OH)3-(aq)
(plumbate(II)
PbO(s) + 2H+(aq) → Pb2+(aq) + H2O(l)
b)Hydrades
.The hydrides of group 4 elements are characterized by being
covalent. They are prepared by reduction of their
tetrachlorides with lithium aluminium hydride at 0oC in the
presence of ether.
SiCl4 + LiAlH4 → SiH4 + LiCl + AlCl3
SnCl4 + LiAlH4 → SnH4 + LiCl + AlCl3
The hydrides have simple molecular structure and are
tetrahedral in shape.
.The thermal stability decreases down the group because the
change in character with the +2 oxidation state becoming
more stable.
.The hydrolysis of these hydrides is catalysed by a base and
the greater the electronegativity of the element, the less the
hydrolysis.
SiH4 + 2OH- + H2O → SiO32- + 4H2
c) Halides( Chlorides)
The elements form two types of halides (MX4 and MX2)
I. MX4

012-Page 143
Preparation
SCl4, GeCl4 are prepared by direct combination with chlorine
Si(s) + 2Cl2(g) → SiCl4(l)
CCl4 is prepared by action of Cl2 on CS2
CS2 + 3Cl2 → CCl4 + S2Cl2
PbCl4 is prepared by action of concentrated cold HCl on
PbO2
PbO2 + 4HCl → PbCl4 + 2H2O
Note: - PbCl4 is unstable and revert to stable PbCl2
- The halides have simple molecular structure and are
tetrahedral in shape.
Thermal stability and hydrolysis
The thermal stability decreases down the group because as
the size of the elements increases, M-Cl bonds become
longer and weaker. so, CCl4, SiCl4 and GeCl4 are stable but
SnCl4 and PbCl4 are decomposed by heat.
PbCl4 → PbCl2 + Cl2
The halides except CCl4 are hydrolysed to form the acidic
solutions ( white precipitate + white fumes).
CCl4 is not hydrolysed because it lacks the vacant orbital
needed to accommodate lone pair of electron donated by
water molecules and besides, the C-Cl bond is strong.
012-Page 144
SnCl4(l) + 2H2O(l) → SnO2(s) + 4HCl(g)
Note:
The hydrolysis of SiCl4 is so rapid that it even fumes in
damp air
SiCl4(l) + 2H2O(l) → SiO2(s) + 4HCl(g)
II. MX2
Only formed by Ge, Sn, and Pb and those of Ge and Sn are
less stable while PbCl2 is very stable.
Pb(s) + Cl2(g) + heat → PCl2(s)
Sn(s) + 2HCl + heat → SnCl2(s) + H2(g)
SnCl2 is hydrolysed becoming milky with formation of a
basic solid.
SnCl2 + H2O ↔ Sn(OH)Cl(s) + HCl(aq)
PbCl2 is ionic and is less soluble in water but dissolves more
in conc.HCl because of the formation of a soluble complex
[PbCl4]2-
PbCl2 ↔ Pb2+(aq) + 2Cl-(aq)
PbCl2(s) + 2Cl-(aq) (from HCl) → [PbCl4]2-
Note: SiO2 reacts with hydrofluoric acid HF according to the
equation:
SiO2(s) + 6HF(aq) → SiF62-(aq) + 2H+(aq) + 2H2O(l).

012-Page 145
This explains why HF is conserved in plastic bottle not in
glass bottle.
5.3.6. Diagonal relationship of group I, II, III and IV
Diagonal relationship is the similarity in properties between
the first element in a group and the second element of the
adjacent group that are diagonally related in the periodic
table.
e.g: relationship between Li and Mg, Be and Al or B and si.
Diagonal relationship arises because on moving from left to
right across the period the charge of the ions increases and
their size decreases. Thus, their polarizing power/charge
density increases.
Going down the group, the size increases while the charge of
the ions is constant. Thus the polarizing power decreases. On
moving diagonally i.e. to the right and down at the same
time, the two effects roughly cancel each other.
a) Diagonal relationship between lithium and
magnesium
− Both are hard and cannot easily be cut by a knife
− Both react wit oxygen to form monoxides
4Li(s) + O2(g) → 2L2O(s)
− Both react wit nitrogen to form nitrides
3Mg(s) + N2(g) → Mg3N2(s)
− Both form nitrates that decompose to metal oxide,
NO2 and O2 when heated
012-Page 146
 2Mg(NO3)2 → 2MgO(s) + 4NO2(g) + O2(g)

− The hydroxide of both Li and Mg decompose to

metal oxides and water when heated
2LiOH(s) → Li2O(s) + H2O(l)
Mg(OH)2(s) → MgO(s) + H2O(l)
− Many salts of lithium and magnesium are
hygroscopic because of the high polarizing power of
these elements.
− Most of their compounds are insoluble in water or
sparingly soluble. e.g. their hydrxides, carbonates or
phosphates.
− Halides of both lithium and magnesium are soluble
in non-polar organic solvents.
− Both show considerable degree of covalent
character in most of their compounds.
b)Diagonal relationship between beryllium and
aluminium.
− Both beryllium and aluminium do not show
appreciable reaction with oxidizing acids, HNO3 for
example, due to formation of thin layer of the metal
oxide on their surfaces that prevents further
reaction.
− Both can react with alkalis to form beryllates and
aluminates as they are amphoteric elements.
Be(s) + 2NaOH(aq) → Na2BeO2(s) + H2(l)

012-Page 147
 2Al(s) + 2NaOH(aq) + 2H2O(l) → 2NaAlO2(s)
+ 3H2(l)
− Oxides of both Be and Al are amphoteric as they
can react with both acid and alkalis. If they react
with alkalis, they form complex compounds.
BeO(s) + 2OH-(aq) + H2O(l) → [Be(OH)4]2-
(aq)
Al2O3(s) + 2OH-(aq) + 2H2O(l) →
2[Al(OH)4]-(aq)
On the other hand if react with acids they form both
salts and water.
MO + 2HCl → MCl2 + H2O (M= Be or
Al)
− Compounds of both Al and Be are mostly covalent
and are soluble in organic solvents
− Both their carbides are hydrolyzed to methane and
hydroxide.
Be2C + 4H2O → CH4 + 2Be(OH)2
Al4C3 + 12H2O → 3CH4 + 4Al(OH)3
− Both Be and Al do not decompose even at elevated
temperatures. They never impart any colour to the
Bunsen flame.
c) Diagonal relationship between boron and silicon
− Both have high melting point and low density

012-Page 148
 − Both are non-metals although they are hard and also
exhibit both crystalline and amorphous allotropic
forms.
− Both B and Si dissolve in alkalis producing borates
and silicates.
B(s) + 2OH-(aq) + H2O(l) → BO32-(aq) +
2H2(g)
Si(s) + 2OH-(aq) + H2O(l) → SiO32-(aq) +
2H2(g)
− Oxides of both B and Si can be reduced by Mg
element into their elements but these oxides should
be in excess.
− Both B and Si form a large number of covalent
compounds with hydrogen, oxygen and halogens.

Testing your knowledge and understanding.

1. Carbon, silicon, germanium, tin and lead are in group
IV of the periodic table.
a) i) Write the general outermost electronic
configuration of the elements.
ii) State the common oxidation states exhibited by
the elements in their ions or compounds

012-Page 149
 b) State what would be observed and write equation
for the reaction that would take place, if any, when
the following compounds are treated with water
i) CCl4
ii) SiCl4
iii) SnCl4
2. a) Wrrite equation to show how lead(II) chloride
can be prepared in laboratory
b) State the type of bonding in PbCl2 and alsostate the
physical properties which show that PbCl2 exhibits the
type of bonding stated.
c) Explain why the boiling point of hydrides of
group(IV) is in order
CH4 < SiH4 < GeH4 < SnH4.

5.4. GROUP V ELEMENTS

5.4.1 Physical state and metallic character
The elements in group 5 are nitrogen (N), phosphorus(P),
arsenic(As), antimony(Sb), and bismuth(Bi).
• Nitrogen is a colorless gas and is the major component
of air
• Phosphorus is a white waxy very reactive non-metallic
element

012-Page 150
 • Arsenic, antimony (their oxides are amphoteric) and
bismuth( its oxide is basic) are somewhat metallic in
nature.
Therefore the metallic character increases down the group.
5.4.2 Allotropes of phosphorus
Phosphorus exists in three main allotropic (distinctly
different) forms: ordinary (or white) phosphorus, red
phosphorus, and black phosphorus. Of these, only white and
red phosphorus are of commercial importance.
White phosphorus (P4): When freshly prepared, ordinary
phosphorus is white, but it turns light yellow when exposed
to sunlight. It is a crystalline, translucent, waxy solid, which
glows faintly in moist air and is extremely poisonous. It
ignites spontaneously in air at 34°C and must be stored under
water. It is insoluble in water, slightly soluble in organic
solvents, and very soluble in carbon disulfide. White
phosphorus melts at 44.1°C, boils at 280°C. White
phosphorus is prepared commercially by heating calcium
phosphate with sand (silicon dioxide) and coke in an electric
furnace. When heated to between 230° and 300°C in the
absence of air, white phosphorus is converted into the red
form.
P

P P
P
The white phosphorus molecule.
012-Page 151
 Red phosphorus: is a microcrystalline, nonpoisonous
powder. It sublimates (passes from the solid state directly to
the gaseous state) at 416°C.
P P
P
P P P P
P
P
P P
P

The arrangement of natoms in red phosphorus

Black phosphorus: is made by heating white phosphorus at

200°C at very high pressure.
5.4.3 Chemical properties of nitrogen and phosphorus
− Nitrogen combine with many metals to form nitrides
3Mg(s) + N2(g)→ Mg3N2(s)
6Li(s) + N2(g) → 2Li3N(s)
Al(s) + N2(g) → 3AlN(s)
− Nitrogen monoxide is produced when nitrogen combine
with oxygen
N2 (g) + O2(g) → 2NO(g)
Note that N2 has an inertness chemical properties due to the
very high strength of the nitrogen-nitrogen triple bond (N≡N:
bond energy= 942 kJ.mol-1) comparing to the single bond (N-
N: bond energy=247kJ.mol-1)
− Phosphorus combine with Cl2 to produce PCl3
P4(s) + 6Cl2(g) → 4PCl3(l)
− White phosphorus react with oxygen from to form
phosphorus oxide
012-Page 152
 P4(s) + 5O2 (g) → P4O10(s)
5.4.4 Preparation of nitrogen
− The most important gases present in dry air are oxygen,
about 21% by volume and the nitrogen, about 79% by
volume. The first (O2) and other gases can be removed
and the nitrogen is collected.
− Nitrogen can also be prepared by the action of heating a
mixture of sodium nitrite and ammonium chloride.
NaNO2(aq) + NH4Cl(aq) → NaCl(s) + H2O(l) +
N2(g)
5.4.5 Chemical properties of nitrogen compound (NH3
and HNO3)
• Reaction of ammonia with acids (HCl)
NH3(g) + HCl(g) → NH4Cl(s)
• Reaction with oxygen
4NH3(g) + 3O2(g) → 2N2(g) + 6H2O(l)
• Ammonia can be a reducing agent
3CuO(s) + 2NH3(g) → 3Cu(s) + H2O(l) + N2(g)
• The industrial method of method of making nitric acid is
the catalytic oxidation of ammonia(Ostwald process).
The reaction take place are
Pt, Rh
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(l)
900oC/ 1-8 atm
2NO(g) + O2(g) 2NO2(g)

4NO2(g) + O2(g) + 2H2O(l) 4HNO3(l)

• Reaction of HNO3 with metals

012-Page 153
 • Nitric acid reacts with metals(Mg, Zn, Pb) liberating
H2
Zn(s) + HNO3(aq) → Zn(NO3)2(aq) + H2(g)
• Concentrated HNO3 reacts with copper liberating
NO2
Cu(s) + 4H+(aq) + 2NO3-(aq) → Cu2+(aq) +
2NO2(g) + 2H2O(l)
On the other hand, if the concentrated acid is diluted
by about 50%, nitrogen monoxide is released:
3Cu(s) + 8H+(aq) + 2NO3-(aq) →Cu2+(aq) +
2NO(g) +4H2O(l)
or 2Cu(s) + 8HNO3conc. → 3Cu(NO3)2(aq) +
4H2O(l) + 2NO(g)
• Note that nitric acid has no action on metals such as
silver(Ag), gold(Au), platinum(Pt), and
mercury(Hg).
• Reaction of HNO3 with non-metals
Concetrated nitric acid or fuming one gives the most
vigorous reaction giving off brown fumes of nitrogen
dioxide.
Warning! These reactions can be violent, and nitrogen
dioxide is very poisonous
S(s) + 6HNO3(l) → H2SO4(aq) + 6NO2(g) + 2H2O(l)
F2(s) + 10HNO3(l) → 2HIO3(aq) + 10NO2(g) +
4H2O(l)
P(s) + 5HNO3(l) → H3PO4(aq) + 5NO2(g) + H2O(l)
012-Page 154
5.4.6 Chemical, properties of phosphorus compounds.
• Reaction of P2O3 with water
P2O3(s) + 3H2O(l) → 2H3PO3(aq)
• Reaction of P2O5 and P4O10 with water
P4O10(s) + 6H2O(l) → 4H3PO4(aq)
P2O5(s) + 3H2O(l) → 2H3PO4(aq)
• Reaction of PCl3 with water
PCl3(l) + 3H2O(l) → H3PO3(aq) + HCl(aq)
• Reaction of PCl3 with Cl2 and O2
PCl3(l) + 5Cl2(g) → PCl5(s)
PCl3(l) + O2(g) →2POCl3(l)
• Reaction of PCl5 with water
PCl5(l) + 4H2O(l) → H3PO4(aq) + 5HCl(aq)
• Reaction of phosphates with H2SO4
Ca3(PO4)2(s) + 2H2SO4(aq) ↔ Ca(H2PO4)2(s) +
2CaSO4(s)
Note that calcium phosphate is important in the manufacture
of NPK fertilizers.
Nitrogen derivatives such as ammonium salts and nitrates are
used as fertilizers in order to improve crops. But fertilizers
can cause eutrophication which is a kind of water pollution.
5.5 GROUP VI ELEMENTS
5.5.1 Physical properties
The members of group 6 are oxygen (O), sulphur(S),
selenium (Se), tellurium (Te), and polonium (Po).
012-Page 155
• There is a gradual transition down the group from non-
metallic to metallic properties
• Oxygen is a colourless gas
• Sulphur is a white and waxy non-metal solid
• Selenium has acidic oxides only. For this reason, it
is probably safety to classify selenium as a non-
metal element.
• Tellurium has ampoteric oxides, so it is a semi-
metal element.
• Polonium is a silvery metallic solid only oxygen and
sulphur have the most significant chemistry.
• Sulphur occurs in many important metallic sulfides, such
as lead sulfide, or galena, PbS; zinc blende, ZnS; copper
pyrite, (Cu,Fe)S2; cinnabar, HgS; stibnite, Sb2S3; and
iron pyrite FeS2. It is also combined with other elements
in the form of sulfates such as barite, BaSO4; celestite,
SrSO4; and gypsum, CaSO4 · 2H2O; and it is present in
the molecules of many organic substances such as
mustard, eggs, hair, proteins, and oil of garlic.
• The most common naturally occurring allotrope, S8,
cyclo-octasulphur, has a zigzag arrangement of the
atoms around the ring.
S S
S
S S
S
S
S

012-Page 156
All forms of sulfur are insoluble in water, but the crystalline
forms are soluble in carbon disulfide. When ordinary sulfur
melts, it forms a straw-colored liquid that turns darker with
additional heating and then finally boils. When molten sulfur
is slowly cooled, its physical properties change in accordance
with the temperature, pressure, and method of crust
formation.
Sulfur thus exists in a variety of forms called allotropes,
which consist of several solid varieties, of which the most
familiar are rhombic sulfur and monoclinic sulfur.
The most stable variety of the element is rhombic sulfur, a
yellow, crystalline solid with a density of 2.06 g/cm3 at 20°C
.Rhombic sulfur is slightly soluble in alcohol and ether,
moderately soluble in oils and extremely soluble in carbon
disulfide. When kept at temperatures above 94.5°C but below
120°C the rhombic form changes into monoclinic sulfur
consisting of elongated, transparent, needlelike structures
with a density of 1.96 g/cm3.The temperature at which
rhombic and monoclinic sulfur are in equilibrium, 94.5°C, is
known as the transition temperature.
5.5.2 Chemical properties of sulphur
• Reaction between Sulphur and Oxygen
Sulphur reacts with oxygen forming sulphur dioxide
S(s) + O2(g) → SO2(g)

012-Page 157
Note: Sulfur dioxide is released into the atmosphere in the
combustion of fossil fuels, such as gas, petroleum, and coal,
and constitutes one of the most air pollutants.
• Reaction of sulphur with H2 and metals
H2 + S→ H2S
2 Cu + S→ Cu2S
Fe + S → FeS

Note:
H2S is a poisonous colourless gas with a characteristic smell
of rotten eggs and it is more volatile than water.
5.6 GROUP VII ELEMENTS
5.6.1 Comparative study of physical properties of
halogens
• The elements in group 7 are fluorine (F), chlorine (Cl),
bromine (Br), iodine (I) and astatine (At).
• Fluorine is a poisonous pale yellow gas,
• Chlorine is a poisonous dense green gas,
• Bromine is a caustic and toxic brown volatile liquid,
and
• iodine is a shiny black solid which sublimes to form
a violet vapour on gentle heating.
This is because they all form diatomic molecules which have
no overall dipole. Therefore they are held together by
relatively weak instantaneous dipoles. As iodine has more
012-Page 158
electrons than bromine, which has more than chlorine, the
temporary intermolecular attractions arising from these
dipoles are greatest for iodine. This means iodine is the least
volatile.
Astatine is radioactive and does not occur naturally.
• Their volatility decreases down the group (from gases to
solids)
5.6.2 Comparative study of chemical properties of
halogens
• Reactions of the halogens with water
• Fluorine reacts vigorously with water forming HF
and O2
2F2(g) + 2H2O(l) → 4HF(g) + O2(g)
• Chlorine and bromine react forming the halide ion,
hydroxonium ion and hypohalous acid
Cl2(g) + 2H2O(l) → H3O+(aq) + Cl-(aq) +
HOCl(aq)
Br2(g) + 2H2O(l) → H3O+(aq) + Br-(aq)+
HOBr(aq)
Note:
Iodine is very sparingly soluble in water and the reaction is
reversible in which oxygen oxidizes the iodide ion back to
iodine
I2(s) + H2O(l) ↔ 2H+(aq) + 2I-(aq) + 1/2O2(g)

012-Page 159
Iodine is however very soluble in potassium iodide because
of the formation of a soluble and stable tri-idide complex.
KI(aq) + I2(s) ↔ KI3(aq) OR I-(aq) + I2(s) ↔I3-(aq)
• Reactions of the halogens with alkalis
• Chlorine, bromine and iodine react with cold dilute
alkalis forming both hypohalide ion OX- and the
halide, X-.
Cl2(g) + 2OH-(aq) →Cl-(aq) + OCl-(aq) + H2O(l)
Br2(g) + 2OH-(aq) → Br-(aq) + OBr-(aq) + H2O(l)
i.e. Cl2(g) + NaOH(aq) → NaCl(aq) + NaOCl(aq) +
H2O(l)
(sodium hypochloride)
• Chlorine, bromine and iodine react with hot
concentrated alkaline (KOH or NaOH) to form
both halate ion OX3- and the halide ion, X-.
3Cl2(g) + 6OH-(aq) → 5Cl-(aq) + ClO3-(aq) +
3H2O(l)
3Cl2(g) + 6NaOH(aq) → 5NaCl(aq) + NaClO3(aq) +
3H2O(l)
Note:
Fluorine reacts with cold dilute alkali to form oxygen
difluoride
2F2(g) + 2OH-(aq) →F2O(s) + 2F-(aq) + H2O(l)
012-Page 160
Fluorine reacts with warm concentrated solution of alkali
to form oxygen.
2F2(g) + 4OH-(aq) → 4HF(aq) + O2(g) + 2H2O(l)
• Displacement reactions down the group shows the
oxidizing power of halogens
Halogen added
Solution Chlorine Bromine iodine
Chloride, Cl- No reaction No reaction No
(aq) reaction
Bromide, Br- Yellow-orange No reaction No
(aq) Br2 released reaction
Iodide, I-(aq) Black-dark Black-dark No
brown I2 brown I2 reaction
released released

The result shows that:

i) Chlorine displaces bromine and iodine
Cl2(g) + 2Br-(aq)→2Cl-(aq) + Br2(g)
Cl2(g) + 2I-(aq)→2Cl-(aq) + I2(g)
ii)Bromine displaces iodine
Br2(g) + 2I-(aq)→2Br-(aq) + I2(g)
iii) Iodine displaces neither of the other two; it is a
very weak oxidizing agent, i.e. stronger reducing
agent.
• Reaction of the hydrides with concentrated sulphuric
acid
012-Page 161
 Concentrated sulphuric acid has no effect on HF and
HCl because they are not enough reducing agent to
reduce sulphuric acid.
But it oxidizes HBr,which is a strong reducing
agent, to bromine (brown liquid) and is itself
reduced to SO2.
H2SO4(aq) + 2HBr(g) → Br2(g) + SO2(g) +
2H2O(l)
Concentrated sulphuric acid oxidizes HI to brown
solution of iodine.
H2SO4(aq) + 2HI(g) → I2(g) + SO2(g) +
2H2O(l)
This explain why HCl can be prepared by reacting H2SO4
with NaCl But not HBr by reacting H2SO4 with NaBr
Note:
1. The acid strength of hydrides of the halogens (HX)
increases from HF to HI. Because of the very high
electronegativity of F, it form very strong H-F bond and
in water it is therefore slightly dissociated hence few H+
are present in solution. Hence acidic strengths are
affected by
• Bond energy: down the group bond energy
decreases therefore the tendency to form H+
increases.

012-Page 162
 • size of X-: the greater the size of the halogen ion, the
greater the stability of X- formed and the more
acidic.
2. Boiling point generally increases down the group. This is
because the van der waal’s forces increases with size. Hf
has highest boiling point because of strong hydrogen
bond formed due to the high electronegativity of fluorine
atom.
3. The halogens form various oxides, such as F2O2, Cl2O,
BrO3, Cl2O7, I2O5, …Because oxygen is more
electronegative than Cl, Br and I on combination with
oygen, the halogen assumes a positive oxidation state.
e.g: The oxidation state of I in I2O5 is +5 while F being
more electronegative than oxygen, the oxidation state of
f in F2O is -2.
4. The acid strength of the oxo-acids of chlorine increases
with increase in the number of oxygen atoms. i.e. HClO
< HClO2 < HClO3 < HClO4.
This is due to oxygen atom being more electronegative than
chlorine atom and this pulls electrons more strongly away
from the chlorine atom and effect weakens the H-Cl such that
H+ is easily lost to the solution. The greater the number of
oxygen atoms the greater the effect and the greater the
acidity.
• The silver nitrate test for halide ions
Addition of agNO3 Addition of
012-Page 163
 in presence of ammonia solution
nitric acid
Chloride White precipitate Precipitate
of silver chloride is dissolves; clear
observed solution is
Ag+(aq) + Cl-(aq) observed
→ AgCl(s)
Bromide Pale yellow Precipitate partly
precipitate of silver dissolves
bromide is
observed
Ag+(aq) + Br-(aq)
→ AgBr(s)
Iodide Yellow precipitate Precipitate does not
of silver iodide is dissolve
observed
Ag+(aq) + I-(aq)
→ AgI(s)

5.6.3 Uses of halogens

• Fluorine is used in the manufacture of
fluorohydrocarbons the commercial refrigerant gas
Freon contains CCl2F2, CClF3.
• Chlorine is used as domestic bleach, and as a disinfectant
in swimming baths.
Chlorinated organic compounds find many uses.
Solvents such as trichloroethene CHCl=CCl2, are used
for grease removal. Many antiseptics are chloro-
compounds.
012-Page 164
• Bromine compounds, e.g. C2H2Br2 are used as petrol
additives in leaded petrol. They convert lead into volatile
compounds, which are discharged through the vehicle
exhaust into air.

Testing your knowledge and understanding.

1. a) Describe the reactivity of fluorine, chlorine and
bromine with
i) Sodium hydroxide
ii)Water (use equations to illustrate your answer).
b) How would you distinguish between sodium bromide
and sodium iodide given silver nitrate and ammonia
solutions?
c) State and explain
i) the trend in the boiling points of the halogens
down the group.
ii)the trend in the acidity of the hydrides of group
(VII) elements
2. a) Describe and explain the trend in volatility of
halogens descending in the group (from chlorine to
iodine)
b) Describe what would observe when the solution of
silver nitrate is added to:
i) Cl- ions
012-Page 165
 ii)I- ions
For each case write down the ionic equations for
chemical reactions above
c) How the oxidizing power of halogens varies on
descending in group? Predict which one of the reactions
below could probably occur and give products of the
reaction.
Br2 + KCl →
Cl2 + KBr →
Br2 + KI →
3. This question concerns the chemistry of chlorine and
hydrides of group VII elements of periodic table.
a) Chlorine forms several compounds in which it shows
different oxidation states. Write down the formulae of
chlorine compound in chlorine shows its:
i) Lowest oxidation state;
ii)Highest oxidation state of chlorine in each case.
b) Chlorine is used to treat water to make it safe for
drinking. Write a balanced (reversible) equation for the
reaction of chlorine with water
c) Briefly explain the following observations
concerning the hydrides of halogens.

012-Page 166
 i)The boiling points increase in the order HCl < HBr
< HI
ii)The acidity of aqueous solutions increase I the
order HCl < HBr < HI
5.7 GROUP VIII ELEMENTS
− All the elements in group 8 are colourless, odorless,
monoatomic gases at room temperature. They neither
burn nor support combustion; in fact, they make up the
least reactive group in the periodic table.
− The very low melting and boiling points of the noble
gases indicate that the dispersion forces holding the
atoms together in the solid and liquid phases are very
weak.
− Noble gases are characterized by very high 1st ionization
energy.
− They can be isolated by liquefaction of air followed by
fractional distillation
− Only xenon shows a slight tendency to react with more
electronegative element(F)
e.g : Xe(g) + 2F2(g) → XeF4(s)
Xe(g) + 3F2(g) → XeF6(s)
Xe(g) + F2(g) → XeF2(s)
5.8 PERIOD III ELEMENTS
General properties

012-Page 167
a) Na, Mg, and Al which adopt giant metallic structures.
Silicon is a metalloid with a giant covalent structure.
P, S and Cl are non-metals which adopt simple
molecular structures
b) Na, Mg, and Al adopt metallic bonding these bonding
increases in strength from Na through Mg to Al. This is
because of the increasing number of valence electron lost
to the charge cloud of the metal. The metals conduct
electricity due to the presence of mobile delocalized
electrons in their lattices.
• Si has a giant covalent structure in which strong and
many covalent bonds link one atom to the next
throughout the whole lattice forming a three dimensional
giant structure. Because strong covalent bonds hold the
atoms tightly close to one another, silicon has a very
high melting and boiling point.
• Non-metals P, S and Cl exist as molecules. Strong
covalent bonds hold the atoms within the molecule but
the molecules are held to one another by weak Van der
Waal’s forces. The magnitude of these forces depends on
the size of the molecules and increase with increase in
the size of the molecules ( the forces increase in the
order Cl2 < P4 < S8)
c) NaCl and MgCl2 are giant ionic structures where there is
a strong electrostatic force of attraction between the
oppositely charged ions hence they have high melting
points and boiling points
012-Page 168
 Explanation: Melting and boiling points decrease from
NaCl through MgCl2 to AlCl3. This is because in moving
from Na+ through Mg2+ to Al3+, the size of the cations
decrease.i.e. Na+ = 0.095nm, Mg2+ = 0.065nm, Al3+ =
0.050nm. The charge on the cations increase from +1 in
Na+ to +3 in Al3+ .This result in Al3+ having the greatest
charge /radius ratio(polarizing power)
1
Polarizing power Na+ = = 10.5
0.095
2
Polarizing power of Mg 2+ = = 30.7
0.065
3
Polarizing power of Al3+ = = 60
0.050

Therefore Al3+ greatly polarizes the Cl- ion more than Mg2+
and Na+ and hence AlCl3 is more covalent than MgCl2 and
NaCl.
d) NaH, MgH2 and AlH3 are ionic and react with water
forming an alkaline solution and hydrogen
NaH(s) + H2O(l) → NaOH(aq) + H2(g)
AlH3(s) + 3H2O(l) → Al(OH)3(aq) + 3H2(g) H- are
being removed from solution so that the solution
becomes less basic; hence from NaH to AlH3 the
solution decrease in alkalinity but increase in acidity.
The rest of hydrides except PH3 dissolve to give acidic
solutions.
SiH4(l) + 3H2O(l) → H2SiO3(aq) + H2(g)

012-Page 169
 Note that Phosphine (PH3) is non polar because P and H
are of almost equal electronegative and hence PH3 does
not react with water.
H2S + H2O → HS- + H3O+
HCl + H2O → H3O+ + Cl-
Therefore the nature of hydrides changes from basic to
acidic across the period.
e) The ionic oxides (Na2O, MgO) react vigorously with
water forming alkaline solution
MgO + H2O → Mg2+ + 2OH-
Al2O3 does not react with water, is amphoteric. The rest
of the oxides dissolve in water to form acidic solution
P2O5 + 3H2O → 2H3PO4
SO3 + H2O → H2SO4
Cl2O7 + H2O → 2HClO4
Note that SiO2 does not react with water but reacts with
conc. alkalis to form silicates
SiO2 + 2OH- → SiO32- + H2O

ATOMIC AND PHYSICAL PROPERTIES OF THE

PERIOD 3 ELEMENTS

1. ATOMIC PROPERTIES

a) Electronic structures

012-Page 170
In Period 3 of the Periodic Table, the 3s and 3p orbitals are
filling with electrons. Just as a reminder, the shortened
versions of the electronic structures for the eight elements
are:

Na [Ne] 3s1
Mg [Ne] 3s2
Al [Ne] 3s2 3px1
Si [Ne] 3s2 3px1 3py1
P [Ne] 3s2 3px1 3py1 3pz1
S [Ne] 3s2 3px2 3py1 3pz1
Cl [Ne] 3s2 3px2 3py2 3pz1
Ar [Ne] 3s2 3px2 3py2 3pz2
In each case, [Ne] represents the complete electronic
structure of a neon atom.
b) First ionisation energy
The first ionisation energy is the energy required to remove
the most loosely held electron from one mole of gaseous
atoms to produce 1 mole of gaseous ions each with a charge
of 1+.
X(g) → X+(g) + e-
It is the energy needed to carry out this change per mole of
X.

012-Page 171
The pattern of first ionisation energies across Period 3

Notice that the general trend is upwards, but this is broken by

falls between magnesium and aluminium, and between
phosphorus and sulphur.
Explaining the pattern
First ionisation energy is governed by:
• the charge on the nucleus;
• the distance of the outer electron from the nucleus;
• the amount of screening by inner electrons;
whether the electron is alone in an orbital or one of a pair.
The upward trend
In the whole of period 3, the outer electrons are in 3-level
orbitals. These are all the same sort of distances from the
nucleus, and are screened by the same electrons in the first
and second levels.
The major difference is the increasing number of protons in
the nucleus as you go from sodium across to argon. That
causes greater attraction between the nucleus and the
electrons and so increases the ionisation energies.
012-Page 172
In fact the increasing nuclear charge also drags the outer
electrons in closer to the nucleus. That increases ionisation
energies still more as you go across the period.
The fall at aluminium
You might expect the aluminium value to be more than the
magnesium value because of the extra proton. Offsetting that
is the fact that aluminium's outer electron is in a 3p orbital
rather than a 3s.
The 3p electron is slightly more distant from the nucleus than
the 3s, and partially screened by the 3s electrons as well as
the inner electrons. Both of these factors offset the effect of
the extra proton.
The fall at sulphur
As you go from phosphorus to sulphur, something extra must
be offsetting the effect of the extra proton
The screening is identical in phosphorus and sulphur (from
the inner electrons and, to some extent, from the 3s
electrons), and the electron is being removed from an
identical orbital.
The difference is that in the sulphur case the electron being
removed is one of the 3px2 pair. The repulsion between the
two electrons in the same orbital means that the electron is
easier to remove than it would otherwise be.
c) Atomic radius
The trend

012-Page 173
The diagram shows how the atomic radius changes as you go
across Period 3.

The figures used to construct this diagram are based on:

• metallic radii for Na, Mg and Al;
• covalent radii for Si, P, S and Cl;
• the van der Waals radius for Ar because it doesn't form
any strong bonds.
It is fair to compare metallic and covalent radii because they
are both being measured in tightly bonded circumstances. It
isn't fair to compare these with a van der Waals radius,
though.
The general trend towards smaller atoms across the period is
NOT broken at argon. You aren't comparing like with like.
The only safe thing to do is to ignore argon in the discussion
which follows.

Explaining the trend

A metallic or covalent radius is going to be a measure of the
distance from the nucleus to the bonding pair of electrons. If
you aren't sure about that, go back and follow the last link.
From sodium to chlorine, the bonding electrons are all in the
3-level, being screened by the electrons in the first and
012-Page 174
second levels. The increasing number of protons in the
nucleus as you go across the period pulls the bonding
electrons more tightly to it. The amount of screening is
constant for all of these elements.
d) Electronegativity
Electronegativity is a measure of the tendency of an atom to
attract a bonding pair of electrons.
The Pauling scale is the most commonly used. Fluorine (the
most electronegative element) is assigned a value of 4.0, and
values range down to caesium and francium which are the
least electronegative at 0.7.
The trend
The trend across Period 3 looks like this:

Notice that argon isn't included. Electronegativity is about

the tendency of an atom to attract a bonding pair of electrons.
Since argon doesn't form covalent bonds, you obviously can't
assign it an electronegativity.
Explaining the trend

012-Page 175
The trend is explained in exactly the same way as the trend in
atomic radii.
As you go across the period, the bonding electrons are always
in the same level - the 3-level. They are always being
screened by the same inner electrons.
All that differs is the number of protons in the nucleus. As
you go from sodium to chlorine, the number of protons
steadily increases and so attracts the bonding pair more
closely.
2. PHYSICAL PROPERTIES
This section is going to look at the electrical conductivity and
the melting and boiling points of the elements. To understand
these, you first have to understand the structure of each of the
elements.
a) Structures of the elements
The structures of the elements change as you go across the
period. The first three are metallic, silicon is giant covalent,
and the rest are simple molecules.
− Three metallic structures
Sodium, magnesium and aluminium all have metallic
structures.
In sodium, only one electron per atom is involved in the
metallic bond - the single 3s electron. In magnesium, both of
its outer electrons are involved, and in aluminium all three.

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The other difference you need to be aware of is the way the
atoms are packed in the metal crystal.
Sodium is 8-co-ordinated - each sodium atom is touched by
only 8 other atoms.
Both magnesium and aluminium are 12-co-ordinated
(although in slightly different ways). This is a more efficient
way to pack atoms, leading to less wasted space in the metal
structures and to stronger bonding in the metal.
− A giant covalent structure
Silicon has a giant covalent structure just like diamond. A
tiny part of the structure looks like this:

The structure is held together by strong covalent bonds in all

three dimensions.
b) Electrical conductivity
• Sodium, magnesium and aluminium are all good
conductors of electricity. Conductivity increases as you
go from sodium to magnesium to aluminium.
• Silicon is a semiconductor.
• None of the rest conducts electricity.

012-Page 177
The three metals, of course, conduct electricity because the
delocalised electrons (the "sea of electrons") are free to move
throughout the solid or the liquid metal.
The rest don't conduct electricity because they are simple
molecular substances. There are no electrons free to move
around.

c) Melting and boiling points

The chart shows how the melting and boiling points of the
elements change as you go across the period. The figures are
plotted in kelvin rather than °C to avoid having negative
values.

It is best to think of these changes in terms of the types of

structure that we have talked about further up the page.
− The metallic structures
Melting and boiling points rise across the three metals
because of the increasing strength of the metallic bonds.
The number of electrons which each atom can contribute to
the delocalised "sea of electrons" increases. The atoms also

012-Page 178
get smaller and have more protons as you go from sodium to
magnesium to aluminium.
The attractions and therefore the melting and boiling points
increase because:
• The nuclei of the atoms are getting more positively
charged.
• The "sea" is getting more negatively charged.
The "sea" is getting progressively nearer to the nuclei and so
more strongly attracted.
• Silicon
Silicon has high melting and boiling points because it is a
giant covalent structure. You have to break strong covalent
bonds before it will melt or boil.
Because you are talking about a different type of bond, it isn't
profitable to try to directly compare silicon's melting and
boiling points with aluminium's.
− The four molecular elements
Phosphorus, sulphur, chlorine and argon are simple
molecular substances with only van der Waals attractions
between the molecules. Their melting or boiling points will
be lower than those of the first four members of the period
which have giant structures.
The sizes of the melting and boiling points are governed
entirely by the sizes of the molecules.

012-Page 179
 • Phosphorus
Phosphorus contains P4 molecules. To melt phosphorus you
don't have to break any covalent bonds - just the much
weaker van der Waals forces between the molecules.
• Sulphur
Sulphur consists of S8 rings of atoms. The molecules are
bigger than phosphorus molecules, and so the van der Waals
attractions will be stronger, leading to a higher melting and
boiling point.
• Chlorine
Chlorine, Cl2, is a much smaller molecule with comparatively
weak van der Waals attractions, and so chlorine will have a
lower melting and boiling point than sulphur or phosphorus.
• Argon
Argon molecules are just single argon atoms, Ar. The scope
for van der Waals attractions between these is very limited
and so the melting and boiling points of argon are lower
again.
3. CHEMICAL REACTIONS OF THE PERIOD 3
ELEMENTS

a) Reactions with water

• Sodium

012-Page 180
Sodium has a very exothermic reaction with cold water
producing hydrogen and a colourless solution of sodium
hydroxide.
2Na + 2H2O → 2NaOH + H2
• Magnesium
Magnesium has a very slight reaction with cold water, but
burns in steam.
A very clean coil of magnesium dropped into cold water
eventually gets covered in small bubbles of hydrogen which
float it to the surface. Magnesium hydroxide is formed as a
very thin layer on the magnesium and this tends to stop the
reaction.
Mg + 2H2O →Mg(OH)2 + H2
Magnesium burns in steam with its typical white flame to
produce white magnesium oxide and hydrogen.
Mg(s) + H2O(l) → MgO(s) + H2(g)
• Aluminium
Aluminium powder heated in steam produces hydrogen and
aluminium oxide. The reaction is relatively slow because of
the existing strong aluminium oxide layer on the metal, and
the build-up of even more oxide during the reaction.
2Al(s) + 3H2O(l) → Al2O3(s) + 3H2(g)
• Silicon

012-Page 181
There is a fair amount of disagreement in the books and on
the web about what silicon does with water or steam. The
truth seems to depend on the precise form of silicon you are
using.
The common shiny grey lumps of silicon with a rather metal-
like appearance are fairly unreactive. Most sources suggest
that this form of silicon will react with steam at red heat to
produce silicon dioxide and hydrogen.
Si + 2H2O → SiO2 + 2H2
But it is also possible to make much more reactive forms of
silicon which will react with cold water to give the same
products.
• Phosphorus and sulphur
These have no reaction with water.
• Chlorine
Chlorine dissolves in water to some extent to give a green
solution. A reversible reaction takes place to produce a
mixture of hydrochloric acid and chloric(I) acid
(hypochlorous acid).
Cl2 + H2O HCl + HOCl

In the presence of sunlight, the chloric(I) acid slowly

decomposes to produce more hydrochloric acid, releasing
oxygen gas, and you may come across an equation showing
the overall change:
2Cl2 + 2H2O → 4HCl + O2
012-Page 182
 • Argon
There is no reaction between argon and water.
b) Reactions with oxygen

• Sodium
Sodium burns in oxygen with an orange flame to produce a
white solid mixture of sodium oxide and sodium peroxide.
For the simple oxide:
4Na + O2 → 2Na2O
For the peroxide:
2Na + O2 → Na2O2
• Magnesium
Magnesium burns in oxygen with an intense white flame to
give white solid magnesium oxide.
2Mg + O2 → 2MgO
• Aluminium
Aluminium will burn in oxygen if it is powdered; otherwise
the strong oxide layer on the aluminium tends to inhibit the
reaction. If you sprinkle aluminium powder into a Bunsen
flame, you get white sparkles. White aluminium oxide is
formed.
4Al + 3O2 → 2Al2O3

012-Page 183
 • Silicon
Silicon will burn in oxygen if heated strongly enough. Silicon
dioxide is produced.
Si + O2 → SiO2
• Phosphorus
White phosphorus catches fire spontaneously in air, burning
with a white flame and producing clouds of white smoke - a
mixture of phosphorus (III) oxide and phosphorus (V) oxide.
The proportions of these depend on the amount of oxygen
available. In an excess of oxygen, the product will be almost
entirely phosphorus (V) oxide.
For the phosphorus (III) oxide:
P4 + 3O2 → P4O6
For the phosphorus (V) oxide:
P4 + 5O2 → P4O10
• Sulphur
Sulphur burns in air or oxygen on gentle heating with a pale
blue flame. It produces colourless sulphur dioxide gas.
S + O2 → SO2
• Chlorine and argon
Despite having several oxides, chlorine won't react directly
with oxygen. Argon doesn't react either.
012-Page 184
 c) Reactions with chlorine

• Sodium
Sodium burns in chlorine with a bright orange flame. White
solid sodium chloride is produced.
2Na + Cl2 → 2NaCl
• Magnesium
Magnesium burns with its usual intense white flame to give
white magnesium chloride.
Mg + Cl2 → MgCl2
• Aluminium
Aluminium is often reacted with chlorine by passing dry
chlorine over aluminium foil heated in a long tube. The
aluminium burns in the stream of chlorine to produce very
pale yellow aluminium chloride. This sublimes (turns straight
from solid to vapour and back again) and collects further
down the tube where it is cooler.
2Al + 3Cl2 → 2AlCl3
• Silicon
If chlorine is passed over silicon powder heated in a tube, it
reacts to produce silicon tetrachloride. This is a colourless

012-Page 185
liquid which vaporises and can be condensed further along
the apparatus.
Si + 2Cl2 → SiCl4
• Phosphorus
White phosphorus burns in chlorine to produce a mixture of
two chlorides, phosphorus (III) chloride and phosphorus (V)
chloride (phosphorus trichloride and phosphorus
pentachloride).
Phosphorus (III) chloride is a colourless fuming liquid.
P4 + 6Cl2 → 4PCl3
Phosphorus (V) chloride is an off-white (going towards
yellow) solid.
P4 + 10Cl2 → 4PCl5
• Sulphur
If a stream of chlorine is passed over some heated sulphur, it
reacts to form an orange, evil-smelling liquid, disulphur
dichloride, S2Cl2.
2S + Cl2 → S2Cl2
• Chlorine and argon
It obviously doesn't make sense to talk about chlorine
reacting with itself, and argon doesn't react with chlorine.

012-Page 186
 4. PHYSICAL PROPERTIES OF THE PERIOD 3
OXIDES
A summary of the trends
− The oxides
Na2O MgO Al2O3 SiO2 P4O10 SO3 Cl2O7
P4O6 SO2 Cl2O
Those oxides in the top row are known as the highest oxides
of the various elements. These are the oxides where the
Period 3 elements are in their highest oxidation states. In
these oxides, all the outer electrons in the Period 3 element
are being involved in the bonding - from just the one with
sodium, to all seven of chlorine's outer electrons.
a) The structures
The trend in structure is from the metallic oxides containing
giant structures of ions on the left of the period via a giant
covalent oxide (silicon dioxide) in the middle to molecular
oxides on the right.
b) Melting and boiling points
The giant structures (the metal oxides and silicon dioxide)
will have high melting and boiling points because a lot of
energy is needed to break the strong bonds (ionic or covalent)
operating in three dimensions.
The oxides of phosphorus, sulphur and chlorine consist of
individual molecules - some small and simple; others
polymeric.
012-Page 187
The attractive forces between these molecules will be van der
Waals dispersion and dipole-dipole interactions. These vary
in size depending on the size, shape and polarity of the
various molecules - but will always be much weaker than the
ionic or covalent bonds you need to break in a giant structure.
These oxides tend to be gases, liquids or low melting point
solids.
c) Electrical conductivity
None of these oxides has any free or mobile electrons. That
means that none of them will conduct electricity when they
are solid.
The ionic oxides can, however, undergo electrolysis when
they are molten. They can conduct electricity because of the
movement of the ions towards the electrodes and the
discharge of the ions when they get there.

− The metallic oxides

a) The structures
Sodium, magnesium and aluminium oxides consist of giant
structures containing metal ions and oxide ions.
Magnesium oxide has a structure just like sodium chloride.
The other two have more complicated arrangements of the
ions.

b) Melting and boiling points

012-Page 188
There are strong attractions between the ions in each of these
oxides and these attractions need a lot of heat energy to
break. These oxides therefore have high melting and boiling
points.

c) Electrical conductivity
None of these conducts electricity in the solid state, but
electrolysis is possible if they are molten. They conduct
electricity because of the movement and discharge of the ions
present. The only important example of this is in the
electrolysis of aluminium oxide in the manufacture of
aluminium.
Whether you can electrolyse molten sodium oxide depends,
of course, on whether it actually melts instead of subliming
or decomposing under ordinary circumstances. If it sublimes,
you won't get any liquid to electrolyse!
Magnesium and aluminium oxides have melting points far
too high to be able to electrolyse them in a simple lab.

− Silicon dioxide (silicon(IV) oxide)

a) The structure
The electronegativity of the elements increases as you go
across the period, and by the time you get to silicon, there
isn't enough electronegativity difference between the silicon
and the oxygen to form an ionic bond. Silicon dioxide is a
giant covalent structure.

012-Page 189
There are three different crystal forms of silicon dioxide. The
easiest one to remember and draw is based on the diamond
structure.
Crystalline silicon has the same structure as diamond. To turn
it into silicon dioxide, all you need to do is to modify the
silicon structure by including some oxygen atoms.

Notice that each silicon atom is bridged to its neighbours by

an oxygen atom. Don't forget that this is just a tiny part of a
giant structure extending in all 3 dimensions.

b) Melting and boiling points

Silicon dioxide has a high melting point - varying depending
on what the particular structure is (remember that the
structure given is only one of three possible structures), but
they are all around 1700°C. Very strong silicon-oxygen
covalent bonds have to be broken throughout the structure
before melting occurs. Silicon dioxide boils at 2230°C.
Because you are talking about a different form of bonding, it
doesn't make sense to try to compare these values directly
with the metallic oxides. What you can safely say is that

012-Page 190
because the metallic oxides and silicon dioxide have giant
structures, the melting and boiling points are all high.
c) Electrical conductivity
Silicon dioxide doesn't have any mobile electrons or ions - so
it doesn't conduct electricity either as a solid or a liquid

5. ACID-BASE BEHAVIOUR OF THE PERIOD 3

OXIDES

− The oxides
Na2O MgO Al2O3 SiO2 P4O10 SO3 Cl2O7
P4O6 SO2 Cl2O
The trend in acid-base behaviour
The trend in acid-base behaviour is shown in various
reactions, but as a simple summary:
• The trend is from strongly basic oxides on the left-hand
side to strongly acidic ones on the right, via an
amphoteric oxide (aluminium oxide) in the middle. An
amphoteric oxide is one which shows both acidic and
basic properties.
For this simple trend, you have to be looking only at the
highest oxides of the individual elements. Those are the ones
on the top row above, and are where the element is in its
highest possible oxidation state. The pattern isn't so simple if
you include the other oxides as well.

012-Page 191
For the non-metal oxides, their acidity is usually thought of
in terms of the acidic solutions formed when they react with
water - for example, sulphur trioxide reacting to give
sulphuric acid. They will, however, all react with bases such
as sodium hydroxide to form salts such as sodium sulphate.
− Chemistry of the individual oxides

• Sodium oxide
Sodium oxide is a simple strongly basic oxide. It is basic
because it contains the oxide ion, O2-, which is a very strong
base with a high tendency to combine with hydrogen ions.
a) Reaction with water
Sodium oxide reacts exothermically with cold water to
produce sodium hydroxide solution. Depending on its
concentration, this will have a pH around 14.
Na2O + H2O → 2NaOH
b) Reaction with acids
As a strong base, sodium oxide also reacts with acids. For
example, it would react with dilute hydrochloric acid to
produce sodium chloride solution.
Na2O + 2HCl → 2NaCl + H2O
• Magnesium oxide
Magnesium oxide is again a simple basic oxide, because it
also contains oxide ions. However, it isn't as strongly basic as
sodium oxide because the oxide ions aren't so free.
012-Page 192
In the sodium oxide case, the solid is held together by
attractions between 1+ and 2- ions. In the magnesium oxide
case, the attractions are between 2+ and 2-. It takes more
energy to break these.
Even allowing for other factors (like the energy released
when the positive ions form attractions with water in the
solution formed), the net effect of this is that reactions
involving magnesium oxide will always be less exothermic
than those of sodium oxide.
a) Reaction with water
If you shake some white magnesium oxide powder with
water, nothing seems to happen - it doesn't look as if it reacts.
However, if you test the pH of the liquid, you find that it is
somewhere around pH 9 - showing that it is slightly alkaline.
There must have been some slight reaction with the water to
produce hydroxide ions in solution. Some magnesium
hydroxide is formed in the reaction, but this is almost
insoluble - and so not many hydroxide ions actually get into
solution.
MgO + H2O → Mg(OH)2
b) Reaction with acids
Magnesium oxide reacts with acids as you would expect any
simple metal oxide to react. For example, it reacts with warm
dilute hydrochloric acid to give magnesium chloride solution.
MgO + 2HCl → MgCl2 + H2O

012-Page 193
 • Aluminium oxide
Describing the properties of aluminium oxide can be
confusing because it exists in a number of different forms.
One of those forms is very unreactive. It is known chemically
as alpha-Al2O3 and is produced at high temperatures.
In what follows we are assuming one of the more reactive
forms.
Aluminium oxide is amphoteric. It has reactions as both a
base and an acid.
a) Reaction with water
Aluminium oxide doesn't react in a simple way with water in
the sense that sodium oxide and magnesium oxide do, and
doesn't dissolve in it. Although it still contains oxide ions,
they are held too strongly in the solid lattice to react with the
water.

b) Reaction with acids

Aluminium oxide contains oxide ions and so reacts with
acids in the same way as sodium or magnesium oxides. That
means, for example, that aluminium oxide will react with hot
dilute hydrochloric acid to give aluminium chloride solution.
Al2O3 + 6HCl → 2AlCl3 + 3H2O
In this (and similar reactions with other acids), aluminium
oxide is showing the basic side of its amphoteric nature.
c) Reaction with bases
012-Page 194
Aluminium oxide has also got an acidic side to its nature, and
it shows this by reacting with bases such as sodium
hydroxide solution.
Various aluminates are formed - compounds where the
aluminium is found in the negative ion. This is possible
because aluminium has the ability to form covalent bonds
with oxygen.
In the case of sodium, there is too much electronegativity
difference between sodium and oxygen to form anything
other than an ionic bond. But electronegativity increases as
you go across the period - and the electronegativity
difference between aluminium and oxygen is smaller. That
allows the formation of covalent bonds between the two.
With hot, concentrated sodium hydroxide solution,
aluminium oxide reacts to give a colourless solution of
sodium tetrahydroxoaluminate.

• Silicon dioxide (silicon(IV) oxide)

By the time you get to silicon as you go across the period,
electronegativity has increased so much that there is no
longer enough electronegativity difference between silicon
and oxygen to form ionic bonds.
Silicon dioxide has no basic properties - it doesn't contain
oxide ions and it doesn't react with acids. Instead, it is very
weakly acidic, reacting with strong bases.
a) Reaction with water

012-Page 195
Silicon dioxide doesn't react with water, because of the
difficulty of breaking up the giant covalent structure.
b) Reaction with bases
Silicon dioxide reacts with sodium hydroxide solution, but
only if it is hot and concentrated. A colourless solution of
sodium silicate is formed.
SiO2 + 2NaOH → 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 materials)
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.
• The phosphorus oxides
We are going to be looking at two phosphorus oxides,
phosphorus(III) oxide, P4O6, and phosphorus(V) oxide,
P4O10.
 Phosphorus(III) oxide
Phosphorus (III) oxide reacts with cold water to give a
solution of the weak acid, H3PO3 , known variously as
phosphorous acid, orthophosphorous acid or phosphonic
acid. Its reaction with hot water is much more complicated.

The pure un-ionised acid has the structure:

012-Page 196
The hydrogens aren't released as ions until you add water to
the acid, and even then not many are released because
phosphorous acid is only a weak acid.
Phosphorous acid has a pKa of 2.00 which makes it stronger
than common organic acids like ethanoic acid (pKa = 4.76).

It is pretty unlikely that you would ever react phosphorus(III)

oxide directly with a base, but you might need to know what
happens if you react the phosphorous acid formed with a
base.
In phosphorous acid, the two hydrogen atoms in the -OH
groups are acidic, but the other one isn't. That means that you
can get two possible reactions with, for example, sodium
hydroxide solution depending on the proportions used.
NaOH + H3PO3 → NaH2PO3 + H2O
In the first case, only one of the acidic hydrogens has reacted
with the hydroxide ions from the base. In the second case
(using twice as much sodium hydroxide), both have reacted.
If you have to do reacting phosphorus (III) oxide directly
with sodium hydroxide solution rather than making the acid
first, you would end up with the same possible salts.
4NaOH + P4O6 + 2H2O → 4NaH2PO3
P4O6 + 6H2O → 4H3PO3
012-Page 197
8NaOH + P4O6 → 4Na2HPO3 + 2H2O

 Phosphorus(V) oxide
Phosphorus (V) oxide reacts violently with water to give a
solution containing a mixture of acids, the nature of which
depends on the conditions. We usually just consider one of
these, phosphoric(V) acid, H3PO4 , also known just as
phosphoric acid or as orthophosphoric acid.
P4O10 + 6H2O → 4H3PO4
This time the pure un-ionised acid has the structure:

Phosphoric (V) acid is also a weak acid with a pKa of 2.15.

That makes it fractionally weaker than phosphorous acid.
Solutions of both of these acids of concentrations around 1
mol dm-3 will have a pH of about 1.
Once again, you are unlikely ever to react this oxide with a
base, but you may well be expected to know how phosphoric
(V) acid reacts with something like sodium hydroxide
solution.
If you look back at the structure, you will see that it has three
-OH groups, and each of these has an acidic hydrogen atom.
You can get a reaction with sodium hydroxide in three stages,
with one after another of these hydrogens reacting with the
hydroxide ions.

012-Page 198
NaOH + H3PO4 → NaH2PO4 + H2O
2NaOH + H3PO4 → Na2HPO4 + 2H2O
3NaOH + H3PO4 → Na3PO4 + 3H2O
Again, if you were to do reacting phosphorus (V) oxide
directly with sodium hydroxide solution rather than making
the acid first, you would end up with the same possible salts.
This is getting ridiculous, and so I will only give one
example out of the possible equations:
12NaOH + P4O10 → 4Na3PO4 + 6H2O

• The sulphur oxides

We are going to be looking at sulphur dioxide, SO2, and
sulphur trioxide, SO3.
 Sulphur dioxide
Sulphur dioxide is fairly soluble in water, reacting with it to
give a solution of sulphurous acid (sulphuric (IV) acid),
H2SO3. This only exists in solution, and any attempt to
isolate it just causes sulphur dioxide to be given off again.
SO2 + H2O → H2SO3
The unionized acid has the structure:

012-Page 199
Sulphurous acid is also a weak acid with a pKa of around 1.8
- very slightly stronger than the two phosphorus-containing
acids above. A reasonably concentrated solution of
sulphurous acid will again have a pH of about 1.
Al2O3 + 2NaOH + 3H2O → 2NaAl(OH)4
SiO2 + CaO → CaSiO3

Sulphur dioxide will also react directly with bases such as

sodium hydroxide solution. If sulphur dioxide is bubbled
through sodium hydroxide solution, sodium sulphite solution
is formed first followed by sodium hydrogensulphite solution
when the sulphur dioxide is in excess.
Na2SO3 + H2O + SO2 → 2NaHSO3

Another important reaction of sulphur dioxide is with the

base calcium oxide to form calcium sulphite (calcium
sulphate(IV)). This is at the heart of one of the methods of
removing sulphur dioxide from flue gases in power stations.
CaO + SO2 → CaSO3
 Sulphur trioxide
Sulphur trioxide reacts violently with water to produce a fog
of concentrated sulphuric acid droplets.
SO3 + H2O → H2SO4
Pure un-ionised sulphuric acid has the structure:

012-Page 200
Sulphuric acid is a strong acid, and solutions will typically
have pH's of around 0.
The acid reacts with water to give a hydroxonium ion (a
hydrogen ion in solution, if you like) and a hydrogensulphate
ion. This reaction is virtually 100% complete.
H2SO4(aq) + H2O(l) → H3O+(aq) + HSO4-(aq)
The second hydrogen is more difficult to remove. In fact the
hydrogensulphate ion is a relatively weak acid - similar in
strength to the acids we have already discussed. This time
you get an equilibrium:
HSO4-(aq) + H2O(l) H3O+(aq) + SO42-(aq)

When a hydrogen ion is lost from one of the -OH groups, the
negative charge left on the oxygen is spread out (delocalised)
over the ion by interacting with the doubly-bonded oxygens.
It follows that the more of these you have, the more
delocalisation you can get - and the more delocalisation, the
more stable the ion becomes. The more stable the ion, the
less likely it is to recombine with a hydrogen ion and revert
to the un-ionised acid.
Sulphurous acid only has one doubly-bonded oxygen,
whereas sulphuric acid has two - that makes for a much more
effective delocalisation, a much more stable ion, and so for a
stronger acid.
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Sulphuric acid, of course, has all the reactions of a strong
acid that you are familiar with from introductory chemistry
courses. For example, the normal reaction with sodium
hydroxide solution is to form sodium sulphate solution - in
which both of the acidic hydrogens react with hydroxide
ions.
2NaOH + H2SO4 → Na2SO4 + 2H2O
In principle, you can also get sodium hydrogensulphate
solution by using half as much sodium hydroxide and just
reacting with one of the two acidic hydrogens in the acid.
Sulphur trioxide itself will also react directly with bases to
form sulphates. For example, it will react with calcium oxide
to form calcium sulphate. This is just like the reaction with
sulphur dioxide described above.
CaO + SO3 → CaSO4
• The chlorine oxides
Chlorine forms several oxides, but the only two mentioned in
this chemistry textbook are chlorine(VII) oxide, Cl2O7, and
chlorine(I)oxide, Cl2O. Chlorine(VII) oxide is also known as
dichlorine heptoxide, and chlorine(I) oxide as dichlorine
monoxide.
 Chlorine(VII) oxide
Chlorine(VII) oxide is the highest oxide of chlorine - the
chlorine is in its maximum oxidation state of +7. It continues
the trend of the highest oxides of the Period 3 elements
towards being stronger acids.
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Chlorine(VII) oxide reacts with water to give the very strong
acid, chloric(VII) acid - also known as perchloric acid. The
pH of typical solutions will, like sulphuric acid, be around 0.
Cl2O7 + H2O → 2HClO4
Unionized chloric(VII) acid has the structure:

When the chlorate (VII) ion (perchlorate ion) forms by loss

of a hydrogen ion (when it reacts with water, for example),
the charge can be delocalised over every oxygen atom in the
ion. That makes it very stable, and means that chloric (VII)
acid is very strong.
Chloric (VII) acid reacts with sodium hydroxide solution to
form a solution of sodium chlorate (VII).
NaOH + HClO4 → NaClO4 + H2O
Chlorine (VII) oxide itself also reacts with sodium hydroxide
solution to give the same product.
2NaOH + Cl2O7 → 2NaClO4 + H2O
 Chlorine(I) oxide
Chlorine(I) oxide is far less acidic than chlorine(VII) oxide.
It reacts with water to some extent to give chloric(I) acid,
HOCl - also known as hypochlorous acid.
Cl2O + H2O 2HOCl
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The structure of chloric (I) acid is exactly as shown by its
formula, HOCl. It has no doubly-bonded oxygens, and no
way of delocalising the charge over the negative ion formed
by loss of the hydrogen.
That means that the negative ion formed is not very stable,
and readily reclaims its hydrogen to revert to the acid.
Chloric (I) acid is very weak (pKa = 7.43).
Chloric(I) acid reacts with sodium hydroxide solution to give
a solution of sodium chlorate(I) (sodium hypochlorite).
NaOH + HOCl → NaOCl + H2O
Chlorine(I) oxide also reacts directly with sodium hydroxide
to give the same product.
2NaOH + Cl2O → 2NaOCl + H2O
6. PROPERTIES OF THE PERIOD 3 CHLORIDES
A summary of the trends
− The chlorides
NaCl MgCl2 AlCl3 SiCl4 PCl5 S2Cl2
PCl3
As you have seen previously, aluminium chloride exists in
some circumstances as a dimer, Al2Cl6.
a) The structures
Sodium chloride and magnesium chloride are ionic and
consist of giant ionic lattices at room temperature

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Aluminium chloride and phosphorus (V) chloride are tricky!
They change their structure from ionic to covalent when the
solid turns to a liquid or vapour. There is much more about
this later on this page.
The others are simple covalent molecules.
b)Melting and boiling points
Sodium and magnesium chlorides are solids with high
melting and boiling points because of the large amount of
heat which is needed to break the strong ionic attractions.
The rest are liquids or low melting point solids. Leaving
aside the aluminium chloride and phosphorus(V) chloride
cases where the situation is quite complicated, the attractions
in the others will be much weaker intermolecular forces such
as van der Waals dispersion forces. These vary depending on
the size and shape of the molecule, but will always be far
weaker than ionic bonds.
c) Electrical conductivity
Sodium and magnesium chlorides are ionic and so will
undergo electrolysis when they are molten. Electricity is
carried by the movement of the ions and their discharge at the
electrodes.
In the aluminium chloride and phosphorus(V) chloride cases,
the solid doesn't conduct electricity because the ions aren't
free to move. In the liquid (where it exists - both of these
sublime at ordinary pressures), they have converted into a
covalent form, and so don't conduct either.

012-Page 205
The rest of the chlorides don't conduct electricity either solid
or molten because they don't have any ions or any mobile
electrons.
a) Reactions with water
As an approximation, the simple ionic chlorides (sodium and
magnesium chloride) just dissolve in water.
The other chlorides all react with water in a variety of ways
described below for each individual chloride. The reaction
with water is known as hydrolysis.
The individual chlorides
 Sodium chloride, NaCl
Sodium chloride is a simple ionic compound consisting of a
giant array of sodium and chloride ions.
A small representative bit of a sodium chloride lattice looks
like this:

This is normally drawn in an exploded form as:

012-Page 206
The strong attractions between the positive and negative ions
need a lot of heat energy to break, and so sodium chloride has
high melting and boiling points.
It doesn't conduct electricity in the solid state because it
hasn't any mobile electrons and the ions aren't free to move.
However, when it melts it undergoes electrolysis.
Sodium chloride simply dissolves in water to give a neutral
solution.
 Magnesium chloride, MgCl2
Magnesium chloride is also ionic, but with a more
complicated arrangement of the ions to allow for having
twice as many chloride ions as magnesium ions.
Again, lots of heat energy is needed to overcome the
attractions between the ions, and so the melting and boiling
points are again high.
Solid magnesium chloride is a non-conductor of electricity
because the ions aren't free to move. However, it undergoes
electrolysis when the ions become free on melting.
Magnesium chloride dissolves in water to give a faintly
acidic solution (pH = approximately 6).
When magnesium ions are broken off the solid lattice and go
into solution, there is enough attraction between the 2+ ions
and the water molecules to get co-ordinate (dative covalent)
bonds formed between the magnesium ions and lone pairs on
surrounding water molecules.

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Hexaaquamagnesium ions are formed, [Mg(H2O)6]2+.
MgCl2(s) + 6H2O(l) → [Mg(H2O)6]2+(aq) + 2Cl-(aq)
Ions of this sort are acidic - the degree of acidity depending
on how much the electrons in the water molecules are pulled
towards the metal at the centre of the ion. The hydrogens are
made rather more positive than they would otherwise be, and
more easily pulled off by a base.
In the magnesium case, the amount of distortion is quite
small, and only a small proportion of the hydrogen atoms are
removed by a base - in this case, by water molecules in the
solution.
[Mg(H2O)6]2+ + H2O [Mg(H2O)5(OH)]+ + H3O+

The presence of the hydroxonium ions in the solution causes

it to be acidic. The fact that there aren't many of them formed
(the position of equilibrium lies well to the left), means that
the solution is only weakly acidic.
You may also find the last equation in a simplified form:
[Mg(H2O)6]2+ (aq) [Mg(H2O)5(OH)]+(aq) + H+(aq)

Hydrogen ions in solution are hydroxonium ions. If you use

this form, it is essential to include the state symbols.
 Aluminium chloride, AlCl3
Electronegativity increases as you go across the period and,
by the time you get to aluminium, there isn't enough
electronegativity difference between aluminium and chlorine
for there to be a simple ionic bond.
012-Page 208
Aluminium chloride is complicated by the way its structure
changes as temperature increases.
At room temperature, the aluminium in aluminium chloride is
6-coordinated. That means that each aluminium is
surrounded by 6 chlorines. The structure is an ionic lattice -
although with a lot of covalent character.
At ordinary atmospheric pressure, aluminium chloride
sublimes (turns straight from solid to vapour) at about 180°C.
If the pressure is raised to just over 2 atmospheres, it melts
instead at a temperature of 192°C.
Both of these temperatures, of course, are completely wrong
for an ionic compound - they are much too low. They suggest
comparatively weak attractions between molecules - not
strong attractions between ions.
The coordination of the aluminium changes at these
temperatures. It becomes 4-coordinated - each aluminium
now being surrounded by 4 chlorines rather than 6.
What happens is that the original lattice has converted into
Al2Cl6 molecules.
This conversion means, of course, that you have completely
lost any ionic character - which is why the aluminium
chloride vaporises or melts (depending on the pressure).
There is an equilibrium between these dimers and simple
AlCl3 molecules. As the temperature increases further, the
position of equilibrium shifts more and more to the right.
Al2Cl6 2AlCl3

012-Page 209
Summary
• At room temperature, solid aluminium chloride has an
ionic lattice with a lot of covalent character.
• At temperatures around 180 - 190°C (depending on the
pressure), aluminium chloride coverts to a molecular
form, Al2Cl6. This causes it to melt or vaporise because
there are now only comparatively weak intermolecular
attractions.
• As the temperature increases a bit more, it increasingly
breaks up into simple AlCl3 molecules.
Solid aluminium chloride doesn't conduct electricity at room
temperature because the ions aren't free to move. Molten
aluminium chloride (only possible at increased pressures)
doesn't conduct electricity because there aren't any ions any
more.
The reaction of aluminium chloride with water is dramatic. If
you drop water onto solid aluminium chloride, you get a
violent reaction producing clouds of steamy fumes of
hydrogen chloride gas.
If you add solid aluminium chloride to an excess of water, it
still splutters, but instead of hydrogen chloride gas being
given off, you get an acidic solution formed. A solution of
aluminium chloride of ordinary concentrations (around 1 mol
dm-3, for example) will have a pH around 2 - 3. More
concentrated solutions will go lower than this.
The aluminium chloride reacts with the water rather than just
dissolving in it. In the first instance, hexaaquaaluminium ions
are formed together with chloride ions.
012-Page 210
AlCl3(s) + 6H2O(l) → [Al(H2O]63+(aq) + 3Cl-(aq)
You will see that this is very similar to the magnesium
chloride equation given above - the only real difference is the
charge on the ion.
That extra charge pulls electrons from the water molecules
quite strongly towards the aluminium. That makes the
hydrogens more positive and so easier to remove from the
ion. In other words, this ion is much more acidic than in the
corresponding magnesium case.
These equilibria (whichever you choose to write) lie further
to the right, and so the solution formed is more acidic - there
are more hydroxonium ions in it.
[Al(H2O)6]3+ + H2O [Al(H2O)5(OH)]2+ + H3O+

We haven't so far accounted for the burst of hydrogen

chloride formed if there isn't much water present.
All that happens is that because of the heat produced in the
reaction and the concentration of the solution formed,
hydrogen ions and chloride ions in the mixture combine
together as hydrogen chloride molecules and are given off as
a gas. With a large excess of water, the temperature never
gets high enough for that to happen - the ions just stay in
solution.
 Silicon tetrachloride, SiCl4
Silicon tetrachloride is a simple no-messing-about covalent
chloride. There isn't enough electronegativity difference

012-Page 211
between the silicon and the chlorine for the two to form ionic
bonds.
Silicon tetrachloride is a colourless liquid at room
temperature which fumes in moist air. The only attractions
between the molecules are van der Waals dispersion forces.
It doesn't conduct electricity because of the lack of ions or
mobile electrons.
It fumes in moist air because it reacts with water in the air to
produce hydrogen chloride. If you add water to silicon
tetrachloride, there is a violent reaction to produce silicon
dioxide and fumes of hydrogen chloride. In a large excess of
water, the hydrogen chloride will, of course, dissolve to give
a strongly acidic solution containing hydrochloric acid.
SiCl4 + 2H2O → SiO2 + 4HCl
 The phosphorus chlorides
There are two phosphorus chlorides - phosphorus(III)
chloride, PCl3, and phosphorus(V) chloride, PCl5.
− Phosphorus(III) chloride (phosphorus trichloride),
PCl3
This is another simple covalent chloride - again a fuming
liquid at room temperature.
It is a liquid because there are only van der Waals dispersion
forces and dipole-dipole attractions between the molecules.
It doesn't conduct electricity because of the lack of ions or
mobile electrons.
012-Page 212
Phosphorus(III) chloride reacts violently with water. You get
phosphorous acid, H3PO3, and fumes of hydrogen chloride
(or a solution containing hydrochloric acid if lots of water is
used).
PCl3 + 3H2O → H3PO3 + 3HCl
Note: Phosphorous acid is also known as orthophosphorous
acid or as phosphonic acid
− Phosphorus(V) chloride (phosphorus pentachloride),
PCl5
Unfortunately, phosphorus (V) chloride is structurally more
complicated.
Phosphorus (V) chloride is a white solid which sublimes at
163°C. The higher the temperature goes above that, the more
the phosphorus (V) chloride dissociates (splits up reversibly)
to give phosphorus(III) chloride and chlorine.
PCl5 PCl3 + Cl2
Solid phosphorus (V) chloride contains ions - which is why it
is a solid at room temperature. The formation of the ions
involves two molecules of PCl5.
A chloride ion transfers from one of the original molecules to
the other, leaving a positive ion, [PCl4]+, and a negative ion,
[PCl6]-.
At 163°C, the phosphorus (V) chloride converts to a simple
molecular form containing PCl5 molecules. Because there are

012-Page 213
only van der Waals dispersion forces between these, it then
vaporises.
Solid phosphorus (V) chloride doesn't conduct electricity
because the ions aren't free to move.
Phosphorus (V) chloride has a violent reaction with water
producing fumes of hydrogen chloride. As with the other
covalent chlorides, if there is enough water present, these will
dissolve to give a solution containing hydrochloric acid.
The reaction happens in two stages. In the first, with cold
water, phosphorus oxychloride, POCl3, is produced along
with HCl.
PCl5 + H2O → POCl3 + 2HCl
If the water is boiling, the phosphorus (V) chloride reacts
further to give phosphoric(V) acid and more HCl.
Phosphoric(V) acid is also known just as phosphoric acid or
as orthophosphoric acid.
POCl3 + 3H2O → H3PO4 + 3HCl
The overall equation in boiling water is just a combination of
these:
PCl5 + 4H2O → H3PO4 + 5HCl
 Disulphur dichloride, S2Cl2
Disulphur dichloride is just one of three sulphur chlorides
which is formed when chlorine reacts with hot sulphur.

012-Page 214
Disulphur dichloride is a simple covalent liquid - orange and
smelly!
The liquid will have van der Waals dispersion forces and
dipole-dipole attractions.
There are no ions in disulphur dichloride and no mobile
electrons - so it never conducts electricity.
Disulphur dichloride reacts slowly with water to produce a
complex mixture of things including hydrochloric acid,
sulphur, hydrogen sulphide and various sulphur-containing
acids and anions (negative ions).
7. PROPERTIES OF THE PERIOD 3
"HYDROXIDES"

a) Sodium and magnesium hydroxides

These contain hydroxide ions, and are simple basic
hydroxides.
b)Aluminium hydroxide
Aluminium hydroxide, like aluminium oxide, is
amphoteric - it has both basic and acidic properties.
c) The other "hydroxides"
In all of these have -OH groups covalently bound to the atom
from period 3. These compounds are all acidic - ranging from
the very weakly acidic silicic acids (one of which is shown
below) to the very strong sulphuric or chloric (VII) acids.

012-Page 215
There are other acids (also containing -OH groups) formed
by these elements, but these are the ones where the Period 3
element is in its highest oxidation state.
Adding some detail
 Sodium and magnesium hydroxides
These are both basic because they contain hydroxide ions - a
strong base.
Both react with acids to form salts. For example, with dilute
hydrochloric acid, you get colourless solutions of sodium
chloride or magnesium chloride.
NaOH + HCl → NaCl + H2O
Mg(OH)2 + 2HCl → MgCl2 + 2H2O
 Aluminium hydroxide
Aluminium hydroxide is amphoteric.

012-Page 216
Like sodium or magnesium hydroxides, it will react with
acids. This is showing the basic side of its nature.
With dilute hydrochloric acid, a colourless solution of
aluminium chloride is formed.
Al(OH)3 + 3HCl → AlCl3 + 3H2O
But aluminium hydroxide also has an acidic side to its nature.
It will react with sodium hydroxide solution to give a
colourless solution of sodium tetrahydroxoaluminate.
Al(OH)3 + NaOH → NaAl(OH)4
 The other "hydroxides"
A quick reminder of what we are talking about here:

But they vary considerably in strength:

• Orthosilicic acid is very weak indeed.
• Phosphoric (V) acid is a weak acid - although somewhat
stronger than simple organic acids like ethanoic acid.

012-Page 217
 • Sulphuric acid and chloric (VII) acids are both very
strong acids.
The main factor in determining the strength of the acid is
how stable the anion (the negative ion) is once the hydrogen
has been removed. This in turn depends on how much the
negative charge can be spread around the rest of the ion.
If the negative charge stays entirely on the oxygen atom left
behind from the -OH group, it will be very attractive to
hydrogen ions. The lost hydrogen ion will be easily
recaptured and the acid will be weak.
On the other hand, if the charge can be spread out
(delocalised) over the whole of the ion, it will be so "dilute"
that it won't attract the hydrogen back very easily. The acid
will then be strong.
Wherever possible, the negative charge is delocalised by
interacting with doubly-bonded oxygens.
For example, in chloric (VII) acid, the ion produced is the
chlorate (VII) ion (also known as the perchlorate ion), ClO4-.
The structure of the ion doesn't stay like this:

Instead, the negative charge is delocalised over the whole

ion, and all four chlorine-oxygen bonds are identical.

012-Page 218
None of these contains hydroxide ions. In each case the -OH
group is covalently bound to the Period 3 element, and in
each case it is possible for the hydrogens on these -OH
groups to be removed by a base. In other words, all of these
compounds are acidic.
When sulphuric acid loses a hydrogen ion to form the
hydrogensulphate ion, HSO4-, the charge can be spread over
three oxygens (the original one with the negative charge, and
the two sulphur-oxygen double bonds. That's still an effective
delocalisation, and sulphuric acid is almost as strong as
chloric(VII) acid.
Note: Sulphuric acid can, of course, lose a second hydrogen
ion as well from the other -OH group and form sulphate ions.
However, that is a bit more difficult. If you lose that second
hydrogen, you can use all four oxygens to delocalise the
charge - but now you have to delocalise two negative charges
rather than just one. The hydrogensulphate ion isn't a strong
acid. It's strength is similar to phosphoric (V) acid.

Phosphoric (V) acid is much weaker than sulphuric acid

because it only has one phosphorus-oxygen double bond
which it can use to help delocalise the charge on the ion
formed by losing one hydrogen ion - so the charge on that ion
is delocalised less effectively.

012-Page 219
In orthosilicic acid, there aren't any silicon-oxygen double
bonds to delocalise the charge. That means the ion formed by
loss of a hydrogen ion isn't at all stable, and easily recovers
its hydrogen.

Testing your knowledge and understanding.

The elements Na, Mg, Al, Si, P, and Cl are members of
the third period of the periodic table.
a) i) Write down the formula of the principal oxides and
chloride of the elements listed above and in each case
indicate the type of bonding.
ii) Explain what happens when each of the above
oxides and chlorides is added to water and indicate
whether the resultant solution will be acidic, basic or
neutral.
b) i) Which of the element listed above form oxide of the
type M2O3
ii) Describe briefly how you would prepare each of
the oxide and give the equations for the reactions
involved.
iii) What would be observed if each of the above
oxides in b) ii) was reacted with sodium hydroxide.
Write equation for the reactions involved in each case.

012-Page 220
 c) The melting points of Mg, Si, and S are 650oC,
1423oC and 120oC respectively. Explain the differences
in the melting points of the elements.
d) Name the type of the bonding that exists in the
hydride of the elements Na, P, and S and write equations
to show the reaction if any of the hydrides with water.

CHAPTER VI: CLASSIFICATION OF REACTIONS

GENERAL OBJECTIVE
By the end of this chapter students should be able to
a) Define oxidation and reduction in terms of loss or gain
of oxygen
or hydrogen and in terms of loss or gain of electrons
b) Identify the substances that are oxidized and
those that are reduced in a redox reaction
c) Distinguish between oxidizing agent and reducing agent
in a redox reaction.
SPECIFIC OBJECTIVES
− Define oxidation number
− Explain how oxidation number is obtained
− Define oxidation and reduction
− Discuss reactions in which oxidation numbers do not
change
− Explain redox reactions.
012-Page 221
 − State common reducing and oxidizing agents and their
behavior in half and overall redox equations.
6.1. Introduction
There are several ways to categorize chemical reactions.
Considering the variation of oxidation state, we distinguish:
REDOX reactions and METATHESIS REACTIONS.
The redox reactions are those which are achieved with
variation of the oxidation state between the reactants and
products.
The metathesis reactions are those which are achieved
without variation of oxidation state.
6.2. Oxidation number
The oxidation number or oxidation state is defined as the
effective charge on an atom in a compound, calculated
according to a prescribed set of rules. An increase in
oxidation number corresponds to oxidation, and a decrease to
reduction.
The oxidation number is the charge on an atom of the
element in a compound calculated assuming that all the
atoms in the compound are simple monatomic ions. The
more electronegative element is given an oxidation number
of -1 per bond. Oxidation state (O.S.) is a means of assigning
a 'formal charge' to an atom so that electron transfers to and
from an element or compound can be accounted

012-Page 222
There are some rules used for calculating oxidation numbers.
They should be applied in the following order:

1. The oxidation number of an uncombined element is zero.

2. A simple monatomic ion has an oxidation number equal
to its charge.
3. The oxidation numbers of Group 1 metals is always +1,
and of Group 2 metals is +2.
4. Fluorine always has an oxidation number of -1,
hydrogen (except in metallic hydrides
5. of +1, and oxygen (except in F2O and peroxides) of -2.
6. The sum of the oxidation numbers in a molecule adds up
to 0, and those in a
polyatomic ions (such SO42-) add up to the charge on
the ion.
When an element is oxidized, its oxidation number
increases: this process is an Oxidation and it corresponds to
the loss of electrons.
When an element is reduced, its oxidation number decreases:
This process is a Reduction and it corresponds to the gain of
electrons.
6.3. Reactions in which oxidation state does not change or
metathesis reactions

− Decomposition reaction

012-Page 223
The decomposition reaction is effected under heat condition
(thermal decomposition) or electricity (electrolysis) and in
most case lead to gas given off and solid (residue) formation.
CaCO3(s) → CaO(s) + CO2(s)
2KNO3(s) → 2KNO2(s) + O2(g)
Note: Inside this class, there are other subclasses such as
volatilization or precipitation reaction if we take into
consideration to physical state change for products.
FeS (aq) + 2HCl(aq) → FeCl2(aq) + H2S(g)
…………volatilization reaction
AgNO3(aq) + KCl(aq) → AgCl(s) + KNO3(aq) ………
precipitation reaction

− Neutralisation reaction
The neutralization reaction occurs between acid and base

NaOH(aq) + HCl(aq) NaCl(aq) + H2O

6.4. Redox reactions

− Half redox equations
These are written:
either as reduction with electrons on the left hand side of
the half equation,
e.g. Cl2(g) + 2e → 2Cl- (aq), here chlorine is being reduced
and so is acting as an oxidizing agent.

012-Page 224
 or as oxidation with electrons on the right hand side of
the equation,
e.g. Fe2+ (aq) → Fe3+(aq) + e-, here iron(II) ions are being
oxidized, and thus are acting as a reducing agent.

Many oxidizing agents only work in acid solution. Their half

equations have H+ ions on the left hand side and H2O on the
right. This is likely with oxidizing agents containing oxygen
(such as MnO4-),
e.g. MnO4-(aq) + 8H+(aq) + 5e- → Mn2+(aq) + 4H2O(l)
If a redox system is in alkaline solution, OH- may need to be
on one side and H2O on the other,
e.g. Cr3+(aq) + 8OH-(aq) → CrO42+ + 4H2O(l) + 3e-

− Reducing and oxidizing agents

Oxidizing agents are substances which accept electrons.
Reducing agents are substances which donate electrons
e.g. Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
Zn(s) is a reducing agent and Cu2+(aq) is an oxidizing
agent

− Balancing redox equations using half equations

A Redox process implies coupled reduction and oxidation

reactions.
A reduction reaction is one in which an element
undergoes a decrease in oxidation state,
012-Page 225
e.g. MnO + 5e- → Mn2+, a process in which the element Mn
−
4

has decreased its oxidation state (O.S.) from Mn(VII) to

Mn(II). This involves the permanganate ion accepting
electrons.
An oxidation reaction is one in which an element
undergoes an increase in oxidation state,
e.g. Fe2+ → Fe3+ + e-, a process in which Fe has increased
its oxidation state from +2 to +3, i.e. Fe(II) to Fe(III). This
involves the loss of an electron.
The reduction and oxidation reactions are always
coupled. They cannot occur in isolation because 'free
electrons' cannot exist in aqueous solution. The electrons
required in the reduction process are supplied directly and
quantitatively by an oxidation reaction which must occur
simultaneously.
The relative number of species undergoing reduction and
oxidation is governed by the requirement that ∆e- = 0. This
quantitative relationship is the basis of volumetric analysis
using redox processes.
In the above example, the number of Fe2+ reacting with 1 MnO−4

= (change in Mn O.S.)/(change in Fe O.S.) = 5/1.

The reaction, balanced for electrons is:
MnO−4 + 5Fe2+ → Mn2+ + 5Fe3+ ∆e- = 0

012-Page 226
A balanced equation for a reduction-oxidation process
has ΣH and ΣO = 0 for the individual half reactions and
Σe- = 0 for the summation over both the reduction and
oxidation processes.
There are a number of methods for writing 'balanced'
equations for redox processes. The best way to become
competent is to use the 'rules' defined by one of these
methods. The method discussed here will use the example of
MnO oxidising oxalic acid to CO2 in an acid medium:
−
4

MnO−4 + H+ + (COOH)2 → Mn2+ + CO2

Rule 1: Identify the species being reduced and its
reduction product, and the species being oxidised and its
oxidation product, and write two unbalanced half
equations:
Reduction: MnO−4 → Mn2+
Oxidation: (COOH)2 → CO2
Rule 2: Identify the atom being reduced or oxidised and
balance the half equations for this:
Reduction: MnO−4 → Mn2+
Oxidation: (COOH)2 → 2CO2
Rule 3: Balance the two half reactions for O and then H.
For a reaction in acid solution this is done by adding H2O
to the side of the reaction with a deficit of O (so that ΣO = 0),
012-Page 227
then adding H+ to the side deficient in H (so that ΣH = 0).
Now ΣH and ΣO = 0:
Reduction: MnO−4 + 8H+ →Mn2+ + 4H2O
Oxidation: (COOH)2 →2CO2 + 2H+
Rule 4: Add electrons to each half reaction to effect
charge balance, i.e. charge on LHS = charge on RHS.
For the reduction process the electrons will be added to the

reactants, for the oxidation they will be added to the

products:

Reduction: MnO−4 + 8H+ + 5e- → Mn2+ + 4H2O

Oxidation: (COOH)2 →2CO2 + 2H+ + 2e-
Rule 5: To check that your half equations are correct,
calculate the changes in O.S. for the elements being
reduced and oxidised.
They should be the same as the number of electrons entered
in the respective equations. If not then there must be a
mistake in the H, O or e- balance. This is a simple but very
effective cross-check:
In our example Mn(VII) → Mn(II), thus ∆(O.S.) = 5; C(III)
→ C(IV), thus ∆(O.S.) = 1 (per C).

012-Page 228
Rule 6: Combine the two half reactions in inverse
proportion to the electron change in each half reaction.
This will give an overall, balanced equation for which ΣH =
0, ΣO = 0 and Σe- = 0:
Reduction: 2( MnO + 8H+ + 5e- → Mn2+ + 4H2O)
−
4

Oxidation: 5((COOH)2 → 2CO2 + 2H+ + 2e-)

Overall reaction: 2 MnO + 5(COOH)2 + 6H+
−
4 2Mn2+ +
10CO2 + 8H2O

Note:
In acid solution the only protic species which may be used
to balance the half reaction are H+ and H2O.
In alkaline solution the only protic species which may be
used to balance the half reaction are OH- and H2O.
Examples of oxidation half reactions in alkaline solution
are:
Sn2+ → Sn(OH)62-, and Cr(OH)3 → CrO42-
The OH- ion is used both to provide O and to consume H
(by forming H2O). To balance for O add OH- to the side
with a deficit of O (so that ΣO = 0). To balance for H add
H2O on the other side (so that ΣH = 0). We must add
sufficient OH- to form H2O from all excess H (i.e. H+ cannot

012-Page 229
appear as one of the reactants or products in an alkaline
solution).
Sn2+ + 6OH- → Sn(OH)62-, and Cr(OH)3 + 5OH- →
CrO42- + 4H2O
Disproportionation

This occurs when an element is simultaneously oxidised and

reduced. It follows that there must be at least two atoms of
that element, with the same oxidation number, on the left of
the equation, and that the element
must be able to exist in at least three different oxidation
states.
Chlorine disproportionates in alkali:
Cl2 + 2OH- → Cl- + OCI- + H2O
(0) (-1) (+1)

As a summary, here are the steps to follow to balance a redox

equation in acidic medium (add the starred step in a basic
medium):

1) Divide the equation into an oxidation half-reaction

and a reduction half-reaction
2) Balance these :
− Balance the elements other than H and O
− Balance the O by adding H2O
− Balance the H by adding H+
− Balance the charge by adding e-
012-Page 230
 3) Multiply each half-reaction by an integer such that
the number of e- lost in one equals the number
gained in the other
4) Combine the half-reactions and cancel
5) Add OH- to each side until all H+ is gone and then
cancel again
1.

CASE OF CHEMICAL EQUATION INVOLVING

ORGANIC COMPOUND

The balancing of a redox molecular equation involving an

organic compound (usually reducing substance) requires
the following rules for the calculation of the oxidation state.
1) The oxidation state of each hydrogen atom attached to a
carbon atom is -1;
2) The oxidation state of each carbon atom is zero;
3) The oxidation state of a heteroatom (atom which
replaces that of hydrogen such as oxygenate, bromine,
chlorine, nitrogen…) is +1 or +2 or +3 if it attaches to the
carbon atom by simple, double or triple bond
respectively.The (+) sign means that heteroatom replaces
the hydrogen atom whose oxidation state -1;
4) The oxidation state of the carbon atom in an organic
compound is obtained by making the sum of all oxidation
state of the atoms which surround it.

012-Page 231
Example: Calculation of oxidation state of all the atoms of
the organic substances whose formulas are as follows:

(-1) (-1)
(-1) (-1) (-1) (-1) (+2)
a) H H H H H H
O
-3 -2 -2 -1 -1 0
H C C C C C C C
(-1)
H H H H H
(-1) (-1) (-1) (-1) (-1)

b) -1
(+1)
H c) (+2)
O
H O H
+1 -1 0 0 -3
-3
Br C C C C N (+3) H C C C H
(0) +2
H H
H H
H (-1 for each H atom)
-1 -1 -1

Example of chemical equation involving organic

substance
+1 Oxidation +2
K2Cr2O7 + CH3CH2OH +H2SO4 → Cr2(SO4)3 +
CH3COH + K2SO4+ H2O
+6 Reduction +3

Reduction : Cr2O72-+14H+ + 6 é → 2 Cr3++ 7 H2O

x1
Oxidation: CH3CH2OH → CH3COH + 2H+ + 2 é
x 3

012-Page 232
Ionic equation: Cr2O72- + 3 CH3CH2OH+ 8H+ → 2
Cr3+ + 3 CH3COH+7H2O

Molecular equation (balanced)

K2Cr2O7 + 3 CH3CH2OH + 4 H2SO4 → Cr2(SO4)3 + 3
CH3COH + K2SO4 + 7 H2O

Testing your knowledge and understanding.

1) Derive balanced equations for the following redox

processes. (Hint : Remember that it is important to note
whether the reaction is in an acidic or alkaline medium
as this will determine the species used to balance the half
reactions for O and H).
i) is oxidised by Cr O in acid solution to form a
2
2−
7

brown-black deposit of I2 in a green solution.

ii)Mn2+ is oxidised by O2 under alkaline
conditions to form MnO2.
2) Balance the following redox ionic equations.
i) Fe2+ + ClO3- → Fe3+ + Cl - (acidic
medium)
ii) MnO + ClO2- → MnO2 + ClO4- (neutral
−
4

medium)

012-Page 233
 iii) CrO2- + H2O2 → CrO42- + 2H2O (basic
medium)
iv) Cu + SO42- → Cu2+ + SO2 (acidic
medium)
v) Cl2 → 2 Cl - + 2ClO3- (neutral medium)
E vi) SO2 + IO3- → SO42- + I- (basic
X medium).
E
R
C
I
S
E
S
1. Showing all steps, balance the following equations by
using half equation method
1.K2Cr2O7 + H2O + S → KOH +Cr2O3 +SO2
2.S+HNO3 → SO2 +NO + H2O
3.KMnO4 + Na2C2O4 + H2SO4 → K2SO4 + MnSO4 +
Na2SO4 + CO2 +H2O
4.KMnO4 + SO2 + KOH → K2SO4 + MnO2 + H2O
5.Cu +HNO3 → Cu(NO3)2 + NO + H2O
6.K2Cr2O7 + HCl → Cl2 + CrCl3 +KCl +H2O
7.CaC2O4 + KMnO4 +H2SO4 → Ca SO4 +MnSO4 +
K2SO4 + H2O + CO2
8.K2Cr2O7 + KBr + HCl → CrCl3 + Br2 + KCl +
H 2O
9.KMnO4 + HCl → 2 MnCl2 + Cl2 + KCl +
8H2O

012-Page 234
2. Copper (I) sulfate is a white solid. When added to water,
the white solid dissolves and a blue solution with some
brown particles in the bottom remains. Explain the redox
processes which occurred during the washing process.
Answer: The copper has changed from a +1 oxidation state
in copper (I) sulfate to Cu2+ ions (which have a +2 oxidation
state) and solid Cu metal (which has a 0 oxidation state).This
process is called disproportionation

CHAPTER VII. TRANSITIONS ELEMENTS (FIRST

SERIES)
GENERAL OBJECTIVES
By the end of this chapter, students should be able to:
a) Describe the chemical diversity shown by the transition
elements.
b) Explain the properties of some transition elements and
their compounds
SPECIFIC OBJECTIVES
− Give simple explanation of the general characteristics of
transition elements.
− Establish the structure, names of complex ions.
012-Page 235
 − State the applications of complex ions.
− Explain the chemical reactions of transitions elements
− Describe the properties of oxides, hydroxides and
oxoanions of transition elements.
CONTENTS
7.1 General introduction
Transition elements are called d-block elements because of
their electronic structure. In the periodic table they are
between the s and p block elements and their properties are
transitional between the highly reactive metallic elements of
the s-block which typically form ionic compounds and the
less reactive elements of the p-block which form covalent
compounds.
Transition elements are scandium(Sc), titanium(Ti),
vanadium(V),chromium(Cr), manganese(Mn), iron(Fe),
cobalt(Co), nickel(Ni), copper(Cu), and zinc(Zn)

012-Page 236
Writing electronic configurations.
In their electronic structure, after the 2nd energy level, an
overlap starts occurring between 3rd and 4th energy levels
such that 3d sub-shell is nearer to the nucleus than the 4s sub-
shell but at a higher energy level. After filling the 3s and 3p
sub-shells, further electrons enter the 4s subshell and after the
4s sub-shell is filled electrons now enter the 3d sub-shells.
From the electronic configuration, a transition element is
defined as that having a partially filled 3d sb-shell( has
between 1 and 9) electrons in the 3d sub-shell.
4f

n=4 4d
4p
3d
n=3 4s
3p
3s
Energy
n=2 2p

2s

n=1
1s

Energy level diagram showing the overlap of the 3d and 4s sub-shells

( The 4s sub-shell fills before the 3d sub-shell.

Note:From scandium to zinc, the 3d orbitals are being filled.

The pattern is regular except for chromium and copper,
which do not follow the Aufbau principle for placing
electrons in orbitals:

012-Page 237
 • Chromium-the 3d and 4s orbitals all contain one electron
with no orbital being completely filled.
1s22s22p63s23p63d54s1 not 1s22s22p63s23p63d44s2
• Copper-the 3d orbitals are full, but there is only one
electron in the 4s orbital.
1s22s22p63s23p63d104s1 not 1s22s22p63s23p63d94s2
In these two elements it is suggested that electron repulsions
between the outer electrons are minimized, resulting in an
increased stability of the chromium and copper atoms.
− In chromium atoms, the 3d orbitals are all half-filled.
− In copper atoms, the 3d orbitals are all filled.
This also explains why Fe2+ with 3d6 is easily oxidized to
Fe3+ with 3d5 and Mn2+ with 3d5 is resistant to oxidation to
Mn3+ with 3d4.
Transition metals form ions first by losing electrons first
from the 4s sub-shell rather than the 3d sub-shell. Hence
electronic configuration of Fe, Fe2+ and Fe3+ are the
following:

3d 4s

Fe(ground state) : [Ar]

Fe2+ [Ar]

Fe3+ [Ar]

012-Page 238
 Testing your knowledge and understanding.
1. What is the difference between a d- block element and a
transition element?
2. Write the electronic configurations of the following
atoms and ions:
a) Cr- b) Mn2+ c) Sc3+
7.2. General characteristics of transition metals
a) Transition elements have variable oxidation states
Oxidation state is defined as the charge left on the central
atom when all the other atoms of the compound have been
removed as ions.
Transitions metals show variable oxidation states because of
the availability of 3d electrons. The commonest oxidation
states being +2 and +3.
The oxidation states shown by the first transition series are:
Scandium +3
Titanium +2 +3 +4
Vanadium +2 +3 +4 +5
Chromium +2 +3 +6
Manganese +2 +3 +4 +6 +7

012-Page 239
Iron +2 +3 +4 +6
Cobalt +2 +3 +4
Nickel +2 +4
Copper +1 +2
Zinc +2
The values written in bold indicate the most stable.
Note:
− Fe3+ is more stable than Fe2+ i.e. Fe2+ easily converted to
Fe3+. Mn2+ is more stable than Mn3+ i.e. Mn3+ is easily
converted to Mn2+. This is because of the electronic
configurations of Fe3+ and Mn2+ in which the 3d sub-
shell is half full and stable.
− The Cu+ ion is expected to be more stable than Cu2+
because of its electronic configuration
Cu+: [Ar]3d10
Cu2+: [Ar]3d9
But Cu2+ is more stable because the heat change for cu+/Cu is
less exothermic than that of Cu2+/Cu.
b)Transition metal ions and their compounds are
coloured
Formation of coloured ions by transition elements is
associated with presence of incompletely filled 3d sub-shell.
When visible light falls on the metal ion, the 3d sub-energy
012-Page 240
level is split into two. The unpaired electrons in the lower
energy level then absorb energy and jump to higher energy
level. In the process of this jumping (transition of electrons)
the remaining part of the visible light which is not absorbed
is then reflected in form of an electromagnetic radiation
whose wavelength corresponds to the colour of the ion.
Examples:
Sc3+(colourless), Ti3+(purple), V3+(green), Cr3+(green), MnO4-
or Mn7+(purple), Fe2+(green), Fe3+(redish
yellow),Ni2+(green), Cu2+(blue), Co2+(pink), Zn2+(colourless).
Scandium and zinc are not regarded as typical transition
metals because:
i) Their penultimate is full for Zn2+: [Ar]3d10 while for
Sc3+ is empty: [Ar]3d0.
ii)Zn2+ and Sc3+ and their compounds are not coloured.
The colour of a particular transition metal ion depends upon
two factors:
− The nature of the ligand
e.g.: the colour of hydrated copper(II) ion [Cu(H2O)4]2+,
is pale blue but on the addition of sufficient amount of
ammonia turns to deep blue
[Cu(H2O)4]2+(aq) + 4NH3(aq) [Cu(NH3)4]2+ (aq) + 4H2O(l)

(pale blue) (deep blue)

012-Page 241
Also the addition of sufficient concentrated hydrochloric acid
the pale blue solution turns to yellowish brown.
[Cu(H2O)4]2+(aq) + 4Cl-(aq) [CuCl4]2-(aq) + 4H2O(l)

(pale blue (yellow brown)

− The oxidation state of the metal ion

Cr2+(aq) is blue but Cr3+(aq) is green
c) Most transition metals and their compounds have
high ability of being catalyst
They are good heterogeneous catalysts because of:
i) the presence of 3d electrons which enables transition
metal ions to form temporary bonds with reactant
molecules at the surface of a catalyst and weakens the
bond in the reactant molecules
ii)their variable oxidation stete which makes it possible for
an alternative reaction pathway with lower activation
energy. During the catalytic activity, transition metal
ions undergo changes in their oxidation states but are
regenerated at the end of the reaction. The following
reactions are catalyzed by the transition metals.

012-Page 242
 V2O5
2SO2(g) + O2(g) 2SO3(g)

Ni
RCH CH2 + H2 RCH2CH3

Cu
CH3CH2OH + O2 CH3CHO
Fe
3H2(g) + N2(g) 2NH3(g)
MnO2
2KClO3(s) 2KCl(s) + 3O2(g)

Example of catalytic activity of V2O5

1o Each V5+ gains an electron from oxygen ion then oxygen is accommodated by SO3
2V5+ + O2- + SO2 2V4+ + SO3
2o V5+ is regenerated from V4+ by oxygen
2V4+ + 1/2O2 2V5+ + O2-
The overall process is the sum of these4+two stages
2V5+ + O2- + SO2 2V + SO3
2V4+ + 1/2O2 2V5+ + O2-

SO2(g) + 1/2O2(g) SO3(g)

Note that the above reaction happen, because vanadium ion

has an ability of accepting and loosing electron easily.
d)Most transition metal ions are paramagnetic
Paramagnetism is the weak attraction of substances in a
magnetic field.
• Paramagnetic substance is a substance with one or few
unpaired electrons that get weakly attracted towards the
supplied magnetic field.
• Ferromagnetic substance is a substance with large
number of unpaired electrons that gets strongly attracted
towards the supplied magnetic field.

012-Page 243
 • Diamagnetic substance is a substance that lacks any
unpaired electrons and hence does not respond to the
supplied magnetic field.
Transition metal ions show paramagnetism because of the
presence of unpaired electrons in their 3d sub-
shells.Paramagnetism arises due to the spinning of unpaired
electrons on their axes which generate electric current.
The magnitude of paramagnetism effect depends on the
number of unpaired electrons on the 3d sub-shell. The greater
the number of unpaired electrons the strong the paramagnetic
effect.
For that reason
− Fe3+ and Mn2+ have the greatest paramagnetic effect
since they have the greatest number of unpaired
electrons
− Sc3+ and Zn2+ have no paramagnetic effect because they
do not have unpaired electrons
− Fe3+ is more paramagnetic than Fe2+ because Fe3+ has
five unpaired electrons while Fe2+ has four unpaired
electrons
e) Formation of complex ions
A complex ion is an ion which contains a central metal ion
bonded to other ion, atoms or molecules through dative
covalent bond or coordinate bond.

012-Page 244
Transition metal form complexes because:
i) of their small size and highly positive charged ions
ii)of the presence of vacant d-orbitals which can
accommodate lone pair of electrons donated by other
groups.
Complex formation is an association of two or more species
each of which is capable of an independent existence. The
species are called ligands and can classified depending on
the number of sites at which one molecule of a ligand is
coordinated to the central metallic atom, the ligands have
been classified as monodentate9or unidenate) and
polydentate(or multidentate) ligands.
1. Monodentate ligands
The ligands which have only one donor atom or are
coordinated through one electron pair are called monodentate
ligands. Such ligands are coordinated to the central metal ion
at one site or by one metal-ligand bond only. These ligands
may be neutral molecules or in anionic form.
Examples: CO (carbonyl), H2O (aquo or aqua), NO
(nitrosyl), NH3 (ammine), F-(fluoro), Cl-(chloro), CN-(cyano:
coordination through C- atom), NO2-(nitro: coordination
through N-atom), NC-(iso-cyano: coordination through N-
atom), NH2-(amido), etc
2. Polydentate ligands

012-Page 245
These may be bidentate, tridentate, tetradentate, pentadentate,
and hexadentate ligands if the number of donor atoms present
in one molecule of the ligand attached with the central
metallic atom is 2, 3, 4, 5, and 6 respectively. Thus one
molecule of these ligands is coordinated to the central
metallic atom at 2,3,4,5, and 6 sites respectively. In other
words, we can say that one molecule of these ligands makes
2, 3, 4, 5, and 6 metal-ligand coordinate bonds respectively.
Examples:
− Bidentate ligands
CH3
H2 O C O
H2N C CH NH2
C NH2 H2N C O C O
H2 H2
ethylene diamine( en) Propylene diamine Oxalato

− Tridentate ligands
NH2

H2C CH

H2N H2C NH2

1,2,3-Triaminopropane

− Hexadentate ligand
Ethylene diamine tetracetate ion (edta4- or EDTA4- or Y4-
) is an important example of hexadentate ligand

012-Page 246
 O O
(5) (3)
O C CH2 CH2 C O
(1) (2)
N CH2CH2 N
CH2 C O
O C CH2 (4)
(6) O
O
EDTA4-

The structure shows that it has two neutral N-

atoms(numbered as 1 and 2) and four negatively charged O-
atoms (numbered as 3, 4, 5, 6) as its donor atoms which can
form coordinate bonds with a transition metal ions.
The structure of a complex metal ion is such that it consists
of a central metal ion surrounded by a cluster of anions or
molecule called ligand which is a molecule or ion which
donates a pair of electrons to the central metal ion to form a
coordinate or dative covalent bond.
[MLn]y
Where M is a central cation, L is a ligand, n is a number of
ligand and y is a charge on complex. These ligands form
coordinate bonds with the central metal ion by donating their
unshared electrons into the vacant d-orbitals of the transition
metal ion. The number of the coordinate bonds bonded to the
central metal ion is called the coordination number of the
central metal ion.
Examples:

012-Page 247
 • Copper (II) ions have a coordination number of four in
most of its complexes.
[Cu (H2O)4]2+, [Cu(NH3)4]2+, [CuCl4]2-, [Cu(NH2-(CH2)-
NH2)2]2+, …

2+
H3N NH3
Cu
H3N NH3

,
CH 2 CH 2 2+
H 2N NH2
Cu

H 2N NH2

CH 2 CH 2

• Most ions have coordination number of 6.

Example: [Cr(H2O)6]3+, [Cr(NH3)6]3+, [Cr(H2O)Cl2]-, …
• Very few ion have a coordination number of 2:
[Ag(NH2]+,…
Note:
− A chelating ligand is a polydentate ligand which is
attached to the same central metal atom by two or more
of its donor atoms resulting in the formation of a
complex having a strain-free ring structure. The complex

012-Page 248
 having the ring structure is called chelate or chelated
complex.
− Or the shape of complexe ions

Complexes with coordination number of 2 adopt a
linear shape. e.g. [Ag(NH2]+,…
H 3N Ag+ NH3

Complexes with coordination number of 4 adopt a

tetrahedral shapes.
e.g.: [Zn (NH3)4]2+, [NiCl4]2-, [CuCl4]2- and some few
others adopt a square planar shapes, e.g: [Cu(NH3)4]2+,
[Cu(H2O)4]2+, …

The copper(II) and cobalt(II) ions have four chloride ions

bonded to them rather than six, because the chloride ions are
too big to fit any more around the central metal ion.
Cl 2- Cl 2-

Cu
Co
Cl
Cl
Cl Cl
Cl
Cl

2-
2-
CuCl4
CoCl4

In Pt(NH3)2Cl2, the platinum, the two chlorines, and the

two nitrogens are all in the same plane

012-Page 249
 Cl

NH 3 Pt Cl

NH 3

Pt(NH 3 )2Cl2
NH3

NH3 NH3
2+
Zn
NH3 Cu2+
NH3
NH3
H3N
NH3
Tetrahedral structure
Square planar structure

Complexes with coordination number of 6 adopt an

octahedral shape. e.g. [Cr(NH3)6]3+. These ions
have. Four of the ligands are in one plane, with the
fifth one above the plane, and the sixth one below
the plane.
H2O 3-
3+ F

H2O F
OH2 F

Fe Al
F
H2O OH2 F

H2O F

3+ 3-
Fe(H2O)6 AlF6

012-Page 250
Note: Remember that the ligands attached
− to a wedge shaped arrow are coming out of the screen
or paper towards you.
− Those attached to a dotted arrow are behind the plane
of the screen or paper.
− The two ligands attached to the ordinary arrows are
above and below the plane of the rest.

NH3

NH3 NH3

Cr3+

NH3
H3 N

NH3
Octahedral structure

− Isomerism among transition metal ion complexes arises

as a result of different arrangements of their constituent
atoms.

Testing your knowledge and understanding.

1. State the formula and charge of each of these complex
ions
012-Page 251
 a) One cobalt(II) ion and four chloride ions;
b) One iron (III) ion, five water molecules and a chloride
ion.
2. In the complex ion [Cu(NH3)4(H2O2]2+, ammonia
molecules and water molecules are both ligands. Why
can water behave as a ligand?
3. Using any stated complex ion, show what is meant by
the term coordination number.

• Geometric isomerism

This is due to arrangements of ligands in space giving rise to

the usual Cis- or Trans-isomers. The terms cis and trans are
used in the same way as they are in organic chemistry. Trans
implies "opposite" - notice that the ammonias are arranged
opposite each other in that version, and so are the chlorines.
Cis implies "on the same side" - in this instance that just
means that the ammonias and the chlorines are next door to
each other.
Cl
NH3

H 3N Pt Cl Cl Pt Cl

NH3 NH3

The " cis" form The" trans" form

The two structures drawn are isomers because there is no

way that you can just twist one to turn it into the other. The
complexes are both locked into their current forms.

012-Page 252
Example 1: The structures of cis and trans isomers of
[Co(NH3)Cl2]

Cl
Cl
NH3
NH3 H 3N
Cl
Co
Co
H 3N NH3
H 3N NH3

NH3 Cl

C is T ra n s

The cis isomer is puple in colour, the two Cl- ligands are at
adjacent corners of the octahedron and are at 90o to one
another.
The trans isomer is green in colour, the two Cl- ligands are at
opposite corners of the octahedron and are at 180o to one
another
Example 2: The structures of the cis and trans isomers of
Cl
NH3 H3N
H3N
Ni
Ni
Cl NH3
Cl Cl

[NiCl2(NH3)2] Cis Trans

Cis-trans isomerism is also possible in some four-coordinate

complexes with a square planar shape. In this shape, the
ligands are arranged at the corners of a square. This structure
is rather like an octahedral complex, but without the ligands
above and below the plane. For cis-trans isomerism, the

012-Page 253
complex must contain two different ligands, with two of one
ligand and two of another.
• Ionization isomerism
This arises when two isomers differ in the distribution of ions
between those which are directly bonded and those not
directly
Example: Co(NH3)5BrSO4has two isomers.
− [Co(NH3)5Br]2+SO42-
NH3 2+

H3N Br
Co3+ SO42-
H3N NH3

NH3

Here the Br- ligand is directly bonded to the cobalt(III) ion

while the SO42- is free. Therefore the addition of barium
chloride solution would give a white precipitate.
Ba2+(aq) + SO42-(aq) → BaSO4(s)
The addition of a solution of silver nitrate does not produce a
yellow precipitate of silver bromide because the Br- unlike
SO42- is not free.
− [Co(NH3)5SO4]+ Br-

012-Page 254
 NH3 +

H3N SO4
Br-
3+
Co
H3N NH3

NH3

In this isomer, the SO42- is now directly bonded to the Co3+

and is not free but the Br- is not bonded and is free. Therefore
the addition of a solution of silver nitrate produces a yellow
precipitate of silver bromide.
Ag+(aq) + Br-(aq) → AgBr(s)
Since the SO42- is not free, the addition of barium chloride
solution does not produce a white precipitate.
− Because of the very high polarizing power accompanied
by ability to form strong bonds with oxygen atom,
aqueous solution of transition metal ions are acidic.
f) Formation of alloys
An alloy is a homogenous mixture or metallic solid
solution composed of two or more elements. Complete
solid solution alloys give single solid phase
microstructure, while partial solutions give two or more
phases that may or may not be homogeneous in
distribution, depending on thermal (heat treatment)
history. Alloys usually have different properties from
those of the component elements, and nowdays scientists
012-Page 255
can make alloys with the properties they wantfor a
particular job.
Generally, alloys are harder than the separate metals and
have lower melting points. They may also be more
resistant to corrosion.
The table below shows the properties and uses of some
common alloys.
Alloy Percentage Important Uses
composition properties
Brass Cu 60, Zn Harder than
40 copper but
just as
corrosion-
resistant
Bronze Cu 85, Sn As for brass Statues,
15 plaques,
ships’propellers
Cupro- Cu 75, Ni As for Silver coins
nickel 25 brass, looks
silverly
Duralumin Al(95), Density just Aircraft
Cu(4), as low as construction
Traces of aluminium
Mn and Mg or
Magnalium Al(70), magnesium
Mg(30) but much
stronger
and more
corrosion-
resistant
012-Page 256
 Solder Pb(67), Harder than
Sn(33) lead and
has an even
lower
melting
Steel Fe(98), Much
C(1), Traces stronger
of other than iron
metals
Invar steel Fe(63), Much lower In thermostats
Ni(36), trace coefficient and clock
of C of pendulums
expansion
than iron
Stainless Fe(85), Harder than
steel Cr(14), ordinary
Ni(1) steel and
much more
corrosion-
resistant

7.3. Naming complex metal ions

How to work out the names of complex ions?

1. Naming the ligands

− Coding for the ligand

The table shows some common ligands and the code for them
in the name of a complex ion. The old names sometimes
012-Page 257
differ by a letter or so, but never enough for it to be
confusing.

ligand coded by (old name)

H2O aqua aquo
NH3 ammine ammino
OH- hydroxo hydroxy
Cl- chloro
F- fluoro
CN- cyano
Take care with the code for ammonia as a ligand - it has 2
"m"s in its name. If you miss one of these out so that you are
left with "amine" or "amino", you are refering to the NH2
group in an organic compound.
This is probably the only point of confusion with these
names.
− Coding for the number of ligands
The normal prefixes apply if there is more than one ligand
no of ligands coded by
2 di
3 tri
4 tetra
5 penta
6 hexa
Putting this together

012-Page 258
For a complex ion containing only one type of ligand, there is
no problem. For example:
[Cu(H2O)6]2+ is called the hexaaquacopper(II) ion.
(Don't worry about the copper(II) bit for the moment.) The
fact that there are two "a"s next to each other in the name is
OK.
With more than one type of ligand in an ion, the ligands are
named in alphabetical order - ignoring the prefixes. For
example:
[Cu(NH3)4(H2O)2]2+ is called the
tetraamminediaquacopper(II) ion.
The "ammine" is named before the "aqua" because "am"
comes before "aq" in the alphabet. The "tetra" and "di" are
ignored.

2. Naming the metal

You might have thought that this was fairly obvious, but it
isn't necessarily. It depends on whether the complex ion ends
up as positively or negatively charged.
− For positively charged complex ions
A positively charged complex ion is called a cationic
complex. A cation is a positively charged ion.
The metal in this is named exactly as you would expect, with
the addition of its oxidation state.

012-Page 259
Going back to a previous example, [Cu(H2O)6]2+ is called the
hexaaquacopper(II) ion because the copper's oxidation state
is +2.
Copper's oxidation is +2 because the original uncomplexed
ion was Cu2+ - NOT because the complex carries 2+ charges.
The oxidation state is frequently left out if a metal only ever
has one oxidation state. For example, in its compounds
aluminium always has an oxidation state of +3. [Al(H2O)6]3+
is usually just called the hexaaquaaluminium ion rather than
the hexaaquaaluminium(III) ion.
− For negatively charged complex ions
A negatively charged complex ion is called an anionic
complex. An anion is a negatively charged ion.
In this case the name of the metal is modified to show that it
has ended up in a negative ion. This is shown by the ending -
ate.
With many metals, the basic name of the metal is changed as
well - sometimes drastically!
Common examples include:
metal changed to
cobalt cobaltate
aluminium aluminate
chromium chromate
vanadium vanadate
copper cuprate
iron ferrate
012-Page 260
So, for example, suppose you bond 4 chloride ions around a
Cu2+ ion to give [CuCl4]2-.
The name shows the 4 (tetra) chlorines (chloro) around a
copper in an overall negative ion (cuprate). The copper has
on oxidation state of +2. This is the tetrachlorocuprate(II)
ion.
Similarly, [Al(H2O)2(OH)4]- is called the
diaquatetrahydroxoaluminate ion. Take the name to pieces so
that you can see exactly what refers to what. Don't forget that
the two different ligands are named in alphabetical order -
aqua before hydroxo - ignoring the prefixes, di and tetra.
The oxidation state of the aluminium could be shown, but
isn't absolutely necessary because aluminium only has the
one oxidation state in its compounds. The full name is the
diaquatetrahydroxoaluminate(III) ion.

Testing your knowledge and understanding.

Give names for the following Complexes
1. [Fe(CN-)6]3+
2. [NiI2(H2O)2]
3. [CoBrNO2(NH3)4]
4. [Ag(CN)2]-
5. [CrCl2(H2O)4]+

012-Page 261
7.4 Complex metal ions - ligand exchange reactions

Examples of ligand exchange reactions

A ligand exchange reaction is exactly what it says - a reaction
in which one ligand in a complex ion is replaced by a
different one.
1. Replacing water with chloride ions

 Replacing the water in the hexaaquacobalt(II) ion

If you add concentrated hydrochloric acid to a solution
containing hexaaquacobalt(II) ions (for example, cobalt(II)
chloride solution), the solution turns from its original pink
colour to a dark rich blue. The six water molecules are
replaced by four chloride ions.

Conc. HCl

[Co(H2O)6]2+ [CoCl4]2-
( pink)
(Dark rich blue)

The reaction taking place is reversible.

[Co(H2O)6]2+ + 4Cl- [CoCl4]2- + 6H2O

Concentrated hydrochloric acid is used as the source of

chloride ions because it provides a very high concentration
compared to what is possible with, say, sodium chloride

012-Page 262
solution. Concentrated hydrochloric acid has a chloride ion
concentration of approximately 10 mol dm-3.
The high chloride ion concentration pushes the position of
the equilibrium to the right according to Le Chatelier's
Principle (see senior 6).

 Replacing the water in the hexaaquacopper(II) ion

In terms of the chemistry, this is exactly the same as the last
example - all that differs are the colours. Unfortunately, these
aren't quite so straightforward. The colour of the
tetrachlorocuprate(II) ion is almost always seen mixed with
that of the original hexaaqua ion.
What you normally see is:

Conc. HCl

[Cu(H2O)6] [CuCl4]2- + [Cu(H2O)6]2+

(blue) (olive-green or yellow)

The reaction taking place is reversible, and you get a mixture

of colours due to both of the complex ions.
[Cu(H2O)6]2+ + 4Cl- [CuCl4]2- + 6H2O

012-Page 263
You may find the colour of the tetrachlorocuprate(II) ion
variously described as olive-green or yellow.

Help! If you dissolve copper(II) oxide in concentrated

hydrochloric acid (to make copper(II) chloride which will
then go on to form the tetrachlorocuprate(II) ion), you get a
dark yellowish brown solution. This probably better reflects
the colour of the ion.
 Replacing water molecules by ammonia
Water molecules and ammonia molecules are very similar in
size, and so there is no change in co-ordination this time.
Unfortunately, the reactions aren't quite so straightforward to
describe.
Ammonia solution can react with hexaaqua metal ions in two
quite distinct ways, because it can act as a base as well as a
ligand.
If you add a small amount of ammonia solution you get
precipitates of the metal hydroxide - the ammonia is acting as
a base. In some cases, these precipitates redissolve when you
add more ammonia to give solutions in which a ligand
exchange reaction has occurred.
In the diagrams below, both steps are shown, but we are only
going to consider the chemistry of the overall ligand
exchange reaction. The precipitates dissolve because of a
complicated series of equilibrium shifts, and we shan't worry
about that for the moment.
 Replacing the water in the hexaaquacopper(II) ion
012-Page 264
This is a slightly untypical case, because only four of the six
water molecules get replaced to give the
tetraamminediaquacopper(II) ion, [Cu(NH3)4(H2O)2]2+.
What you see in a test tube is:

an excess
small amount
of ammonia of ammonia

[Cu(H2O)6]2+ precipitate of [Cu(NH3)4(H2O)2]2+

copper(II) (deep blue)
hydroxide
(blue)

The main equilibrium involved in the ligand exchange

reaction is:
[Cu(H2O)6]2+ + 4NH3 [Cu(NH3)4(H2O)2]2+ + 4H2O

The colour of the deep blue complex is so strong that this

reaction is used as a sensitve test for copper(II) ions in
solution. Even if you try to reverse the change by adding
large amounts of water to the equilibrium, the strength of the
deep blue (even highly diluted) always masks the pale blue of
the aqua ion.
 Replacing the water in the hexaaquacobalt(II) ion
This time, all the water molecules get replaced.

012-Page 265
 an excess
small amount
of ammonia
of ammonia

[Co(H2O)6]2+ [Co(NH3)6]2+
precipitate
(reddish) of cobalt(II)
hydroxide
(green)

[Co(H2O)6]2+ + 6NH3 [Co(NH3)6]2+ + 6H2O

The straw coloured solution formed changes colour very

rapidly on standing to a deep reddish brown. The
hexaamminecobalt(II) ions are oxidised by the air to
hexaamminecobalt(III) ions. However, that is a quite separate
reaction, and isn't a part of the ligand exchange reaction.

 Replacing the water in the

hexaaquachromium(III) ion
Again, all the water molecules get replaced by ammonias.
The difference this time is that the reaction isn't so complete.
The precipitate has to be left to stand in the presence of
excess concentrated ammonia solution for some time in order
to get the ammine complex.
Even so, you still get left with some unreacted precipitate.

012-Page 266
 small amount an excess of
of ammonia ammonia left

to stand

[Cr(H2O)6]3+ precipitate of [Cr(NH3)6]3+

chromium(III) over chromium(III) hydroxide
hydroxide
precipitate

[Cr(H2O)6]3+ + 6NH3 [Cr(NH3)6]3+ + 6H2O

Two more replacements of the water in the

hexaaquachromium (III) ion
The colour of the hexaaquachromium(III) ion has been
shown as a "difficult to describe" violet-blue-grey in all the
diagrams above. In practice, when it is produced during a
reaction in a test tube, it is often green.
A typical example of this is the use of acidified potassium
dichromate(VI) as an oxidising agent. Whenever this is used,
the orange solution turns green and we nearly always
describe the green ion as being Cr3+(aq) implying the
hexaaquachromium(III) ion. That's actually an over-
simplification.
What happens is that one or more of the ligand water
molecules get replaced by a negative ion in the solution -
typically sulphate or chloride.
 Replacement of the water by sulphate ions
You can do this simply by warming some chromium (III)
sulphate solution.
012-Page 267
 warm

[Cr(H2O)6]3+ [Cr(H2O)5(SO4)]+

One of the water molecules is replaced by a sulphate ion.

Notice the change in the charge on the ion. Two of the
positive charges are cancelled by the presence of the two
negative charges on the sulphate ion.
 Replacement of the water by chloride ions
In the presence of chloride ions (for example with
chromium(III) chloride), the most commonly observed colour
is green. This happens when two of the water molecules are
replaced by chloride ions to give the
tetraaquadichlorochromium(III) ion - [Cr(H2O)4Cl2]+.
Once again, notice that replacing water molecules by chloride
ions changes the charge on the ion.
2. A ligand exchange reaction in the test for iron(III)
ions
This provides an extremely sensitive test for iron(III) ions in
solution.
If you add thiocyanate ions, SCN-, (from, say, sodium or
potassium or ammonium thiocyanate solution) to a solution
containing iron(III) ions, you get an intense blood red
solution containing the ion [Fe(SCN)(H2O)5]2+.

012-Page 268
 SCN-(aq)

solution containing [Fe(SCN)(H2O)5]2+

[Fe(H2O)6]3+
Note that the colour of the original solution isn't the colour
of the [Fe(H2O)6]3+ ion. This is actually very pale violet, but
is rarely seen in solution. That complex reacts with water to
some extent to produce other more strongly coloured yellow
and orange complexes. This is explained in more detail on
the page about the acidity of the aqua ions.

Testing your knowledge and understanding

1. What do you understand by the term ligand substitution?
2. A solution of ammonia was slowly added to an aqueous
solution containing copper (II) ions until the ammonia
was in excess. Initially a pale blue precipitate formed,
followed by the formation of a deep blue solution.
a) Identify the pale blue precipitate and write an equation
for its formation.
b) Write the formula of the complex ion in the deep blue
solution.
7.5. Complex ions - The acidity of the hexaaqua ions

This topic explains why complex ions of the type

[M(H2O)6]n+ are acidic.

012-Page 269
 − The general explanation
A closer look at the distribution of charge in the ion
The pH's of solutions containing hexaaqua ions vary a lot
from one metal to another (assuming you are comparing
solutions of equal concentrations). However, the underlying
explanation is the same for all of them.
We'll take the hexaaquairon (III) ion, [Fe(H2O)6]3+ as typical.
The structure of the ion is:
3+
H 2O

H 2O OH 2

Fe

H 2O OH 2
OH 2

Each of the six water molecules are attached to the central

iron(III) ion via a co-ordinate bond using one of the lone
pairs on the oxygen.
− The effect of dissolving this ion in water
o The theory
The hydrogen atoms attached to the water ligands are
sufficiently positive that they can be pulled off in a reaction
involving water molecules in the solution.
The first stage of this process is:
[Fe(H2O)6]3+ + H2O [Fe(H2O)5(OH)]2+ + H3O+

012-Page 270
The complex ion is acting as an acid by donating a hydrogen
ion to water molecules in the solution. The water is, of
course, acting as a base by accepting the hydrogen ion.
Because of the confusing presence of water from two
different sources (the ligands and the solution), it is easier to
simplify this:
[Fe(H2O)6]3+ [Fe(H2O)5(OH)]2+ + H+

However, if you write it like this, remember that the

hydrogen ion isn't just falling off the complex ion. It is being
pulled off by a water molecule in the solution. Whenever you
write "H+(aq)" what you really mean is a hydroxonium ion,
H3O+.
The hexaaquairon(III) ion is quite strongly acidic giving
solutions with pH's around 1.5, depending on concentration.
You can get further loss of hydrogen ions as well, from a
second and a third water molecule.
Losing a second hydrogen ion:
[Fe(H2O)5(OH)]2+(aq) [Fe(H2O)4(OH)]+(aq) + H+(aq)

. . . and a third one:

[Fe(H2O)4(OH)]+(aq) [Fe(H2O)3(OH)](s) + H+(aq)

This time you end up with a complex with no charge on it.

This is described as a neutral complex. Because it has no
charge, it doesn't dissolve in water to any extent, and a
precipitate is formed.
o In practice
012-Page 271
What do you actually get in solution if you dissolve an
iron(III) salt in water? In fact you get a mixture of all the
complexes that you have seen in the equations above. These
reactions are all equilibria, so everything will be present. The
proportions depend on how concentrated the solution is.
The colour of the solution is very variable and depends in
part on the concentration of the solution. Dilute solutions
containing iron(III) ions can be pale yellow. More
concentrated ones are much more orange, and may even
produce some orange precipitate.
None of these colours represents the true colour of the
[Fe(H2O)6]3+ ion - which is a very pale lilac colour! That
colour is only really easy to see in solids containing the ion.
Looking at the equilibrium showing the loss of the first
hydrogen ion:
[Fe(H2O)6]3+ + H2O [Fe(H2O)5(OH)]2+ + H+(aq)
(Pale lilac) (Orange)

The colour of the new complex ion on the right-hand side is

so strong that it completely masks the colour of the hexaaqua
ion.
− Why are 3+ ions more acidic than 2+ ions?

o The effect of charge on the acidity of the

hexaaqua ions
Solutions containing 3+ hexaaqua ions tend to have pH's in
the range from 1 to 3. Solutions containing 2+ ions have

012-Page 272
higher pH's - typically around 5 - 6, although they can go
down to about 3.
Remember that the reason that these ions are acidic is
because of the pull of the electrons towards the positive
central ion. An ion with 3+ charges on it is going to pull the
electrons more strongly than one with only 2+ charges.
In 3+ ions, the electrons in the O-H bonds will be pulled
further away from the hydrogens than in 2+ ions.
That means that the hydrogen atoms in the ligand water
molecules will have a greater positive charge in a 3+ ion, and
so will be more attracted to water molecules in the solution.
If they are more attracted, they will be more readily lost - and
so the 3+ ions are more acidic.

o The effect of ionic radius on acidity

Charge density and acidity
If you have ions of the same charge, it seems reasonable that
the smaller the volume this charge is packed into, the greater
the distorting effect on the electrons in the O-H bonds.
Ions with the same charge but in a smaller volume (a higher
charge density) would be expected to be more acidic.
You would therefore expect to find that the smaller the radius
of the metal ion, the stronger the acid.

012-Page 273
7.6. Reactions of hexaaqua metal ions with hydroxide ions

This topic describes and explains the reactions between

complex ions of the type [M(H2O)6]n+ and hydroxide ions
from, for example, sodium hydroxide solution.
− The general case
Although there are only minor differences, for simplicity we
will look at 2+ ions and 3+ ions separately.
1. Adding hydroxide ions to 2+ hexaaqua ions
These have the form [M(H2O)6]2+. Their acidity is shown in
the reaction of the hexaaqua ions with water molecules from
the solution:
[Fe(H2O)6]2+ + H2O [Fe(H2O)5(OH)]+ + H3O+

They are acting as acids by donating hydrogen ions to water

molecules in the solution.
Because of the confusing presence of water from two
different sources (the ligands and the solution), it is easier to
simplify this:
[Fe(H2O)6]2+(aq) [Fe(H2O)5(OH)]+ (aq) + H+(aq)

o Disturbing this equilibrium by adding hydroxide

ions - stage 1
What happens if you add hydroxide ions to this equilibrium?
There are two possible reactions.

012-Page 274
 i) Reaction of hydroxide ions with the hydroxonium ions
(hydrogen ions)
The addition of hydroxide ion to the system in equiliblia, the
position of equilibrium will move to the right, producing
more of the new complex ion.
Hydroxide ions combine with these,
removing them from the equilibrium.

[M(H2O)6]2+(aq) [M(H2O)5(OH)]+ + H+(aq)

The position of equilibrium moves to the right

ii)Reaction of hydroxide ions with the hexaaqua ion

Statistically, there is far more chance of a hydroxide ion
hitting a hexaaqua metal ion than of hitting a hydrogen ion.
There are far more hexaaqua ions present.
If that happens, you get exactly the same new complex ion
formed as above.
[M(H2O)6]2+ + OH- [M(H2O)5(OH)]+ + H2O

Notice that this isn't a ligand exchange reaction. The

hydroxide ion has removed a hydrogen ion from one of the
ligand water molecules. The reaction has also become
virtually one-way.
o The second stage of the reaction

012-Page 275
Whichever of the above reactions happens, you end up with
[M(H2O)5(OH)]+ ions in solution. These are also acidic, and
can lose hydrogen ions from another of the water ligands.
Taking the easier version of the equilibrium:
[M(H2O)5(OH)]+ (aq) [M(H2O)4(OH)2](s) + H+(aq)

Adding hydroxide ions again tips the equilibrium to the right

- either by reacting with the hydrogen ions, or by reacting
directly with the complex on the left-hand side.
When this happens, the new complex formed no longer has a
charge - we describe it as a "neutral complex". In all the
cases we are looking at, this neutral complex is insoluble in
water - and so a precipitate is formed.
This precipitate is often written without including the
remaining water ligands. In other words we write it as
M(OH)2. A precipitate of the metal hydroxide has been
formed.

Summarising what has happened so far

012-Page 276
 [M(H2O)6]2+(aq)

Removal of first
OH- hydrogen ion

[M(H2O)5(OH)]+(aq)

Removal of a second
OH- hydrogen ion

[M(H2O)4(OH)2](s)
Precipitate formed

Going further
There is no logical reason why the removal of hydrogen ions
from the complex should stop at this point. Further hydrogen
ions can be removed by hydroxide ions to produce anionic
complexes - complexes carrying negative charges.
Whether this actually happens in the test tube to any extent
varies from metal to metal.
[M(H2O)4(OH)2](s)

OH-

[M(H2O)3(OH)3]- (aq)

the precipitate
OH-
has redissolved

[M(H2O)2(OH)4]2-(aq)

In fact, if you do this using sodium hydroxide solution of the

usual concentrations, most of the 2+ ions that you will meet
012-Page 277
at this level don't go beyond the precipitate. The only one you
are likely to come across is the zinc case - and that has a
complication. The final ion is [Zn(OH)4]2- - a tetrahedral ion
which has lost the remaining 2 water ligands.

2. Adding hydroxide ions to 3+ hexaaqua ions

The argument here is exactly as before - the only difference
is the number of hydrogen ions which have to be removed
from the original hexaaqua complex to produce the neutral
complex.
Going beyond the neutal complex is also rather more
common with 3+ than with 2+ ions, and may go as far as
having a hydrogen ion removed from each of the six water
molecules.
This is summarised in the same sort of flow scheme as
before:

012-Page 278
 [M(H2O)6]3+(aq)

Removal of first
OH-
hydrogen ion

[M(H2O)5(OH)]2+(aq)

Removal of a second
OH-
hydrogen ion

[M(H2O)4(OH)2]+(aq)

OH- etc

[M(H2O)3(OH)3](s) precipitate formed

OH- etc

[M(H2O)2(OH)4]-(aq)

OH- etc

[M(H2O)(OH)5]2-(aq) the precipitate

has redissolved
OH- etc

[M(OH)6]3-(aq)

Looking at the ions of specific metals

In each case the formula of the precipitate will be given
as if it were the simple neutral complex. In fact, these
"hydroxide" precipitates sometimes rearrange by losing
water from combinations of the attached OH groups.
This produces oxides closely associated with the lost
water. These changes are beyond the scope of this site.
I. 2+ ions
 hexaaquacobalt(II)
012-Page 279
 NaOH
on standing
solution

(deep blue)
[Co(H2O)6]2+ [Co(H2O)4(OH)2] (light red)
(dark red)
Precipitate changes colour on standing

 hexaaquacopper(II)

NaOH
solution

[Cu(H2O)6]2+ [Cu(H2O)4(OH)2]
(light blue) (blue precipitate)

 hexaaquairon(II)

Iron is very easily oxidised under alkaline conditions.

Oxygen in the air oxidises the iron (II) hydroxide precipitate
to iron (III) hydroxide especially around the top of the tube.
The darkening of the precipitate comes from the same effect.
 hexaaquamanganese(II)

NaOH
on standing
solution

[Mn(H2O)6]2+ [Mn(H2O)4(OH)2]

Precipitate turns to dark

brown around the top.
012-Page 280
I have shown the original solution as very pale pink, but in
fact it is virtually colourless. The pale brown precipitate is
oxidised to darker brown manganese (III) oxide in contact
with oxygen from the air.
 hexaaquanickel(II)

NaOH
solution

[Ni(H2O)6]2+ [Ni(H2O)4(OH)2]
(green) (light green precipitate)

 hexaaquazinc

excess NaOH
NaOH solution
solution

[Zn(H2O)6]2+ [Zn(H2O)4(OH)2] [Zn(OH)4]2-

You start and finish with colourless solutions, producing a

white precipitate on the way.
I. 3+ ions
 hexaaquaaluminium
excess
NaOH NaOH
solution solution

[Al(H2O)6]3+ [Al(H2O)3(OH)3] [Al(H2O)2(OH)4]-

012-Page 281
This looks exactly the same in the test tube as the
corresponding zinc reaction above - but beware the different
formulae of the precipitate and the final solution.

 hexaaquachromium(III)

NaOH excess NaOH

solution solution

[Cr(H2O)6]3+ [Cr(H2O)3(OH)3] [Cr(OH)6]3-

(green solution)

 hexaaquairon(III)

NaOH
solution

[Fe(H2O)6]3+ [Fe(H2O)3(OH)3]

Note: The original colour of the iron (III) ion is very

variable - from a pale yellow to a darkish orange-brown.

1. Reactions of hexaaqua metal ions with ammonia

solution
012-Page 282
This topic describes and explains the reactions between
complex ions of the type [M(H2O)6]n+ and ammonia solution
Reactions of the hexaaqua ions with ammonia solution are
complicated by the fact that the ammonia can have two quite
different functions. It can act as a base (in the Bronsted-
Lowry sense), but it is also a possible ligand which can
replace water molecules around the central metal ion. When
it acts as a ligand, it is acting as a Lewis base.
We need to look at these two functions separately
i) Ammonia acting as a (Bronsted-Lowry) base
The general case
This is what happens when you only add small amounts of
dilute ammonia solution to any of the hexaaqua ions. The
ligand effect only happens with an excess of ammonia or
with concentrated ammonia - and with some metals you don't
even see it then.
We'll talk through what happens if you add a small amount of
dilute ammonia solution to a solution containing a 2+
hexaaqua ion.
These have the formula [M(H2O)6]2+, and they are acidic.
Their acidity is shown in the reaction of the hexaaqua ions
with water molecules from the solution:
[M(H2O)6]2+ + H2O [M(H2O)5(OH)]+ + H3O+

012-Page 283
They are acting as acids by donating hydrogen ions to water
molecules in the solution.
Because of the confusing presence of water from two
different sources (the ligands and the solution), it is easier to
simplify this:
[M(H2O)6]2+ (aq) [M(H2O)5(OH)]+(aq) + H+(aq)

7.7. Uses of complex ions

EDTA is used to bind metal ions and is known as a chelating
agent. This means that EDTA decreases the concentration of
metal ions in solution by binding them into a complex.
Indeed,the ability of EDTA to bind to metals is exploited in
industry, and EDTA is used in many different consumer
products:
• in detergents – it binds to calcium and magnesium ions
to reduce hardness in water.
• in some foods – as a stabilizer to remove metal ions
that might catalyse the oxidation of the product.
• in medical applications – it is added to blood samples to
prevent clotting and used to treat patients suffering from
lead and mercury poisoning.
7.8. Chemical reactions of Chromium, manganese, cobalt,
iron, copper, and zinc with water and mineral acids( HCl,
HNO3, H2SO4)
1. Reaction of chromium
− with water
Chromium is unaffected by cold or hot water but react
with steam at red heat to form chromium(III) oxide.
012-Page 284
 2Cr(s) + 3H2O(g) → Cr2O3(s) + 3H2(g)
− With acids
Chromium reacts with dilute HCl and dilute H2SO4 to
form a blue solution of CrCl2 or CrSO4 respectively.
Cr(s) + 2HCl(aq) → CrCl2(aq) + H2(g)
Cr(s) + H2SO4(aq) → CrSO4(aq) + H2(g)
These Cr2+ salts then undergo immediate oxidation in air
to give corresponding Cr3+ salt.
4Cr2+(aq) + 4H+(aq) + O2(g) → 4Cr3+(aq) + 2H2O(l)
Hot concentrated sulphuric oxidizes the chromium to
Cr2(SO4)3 and forming sulphur dioxide.
2Cr(s) + 6H2SO4(aq) → Cr2(SO4)3(aq) + 6H2O(l) +
3SO2(g)
Chromium does not react with dil. HNO3 but with
conc.HNO3, a thin layer of CrO3 is formed which renders
it inactive.
2. Reactions of manganese
− with water
Impure manganese reacts with hot water forming H2 gas.
Mn(s) + 2H2O(l) → Mn(OH)2(s) + H2(s)
− with acids
Manganese readily reacts with dilute hydrochloric acid
and dilute sulphuric acids to form Mn2+ salts.
Mn(s) + 2HCl(aq) → MnCl2(aq) + H2(g)
012-Page 285
 Mn(s) + HSO4(aq) → MnSO4(aq) + H2(g)
Nitric acid reacts with manganese to give varied
products.
Manganese reacts with hot concentrated H2SO4 to form
manganese (II) sulphate and sulphur dioxide gas.
Mn(s) + 2H2SO4(aq) → MnSO4(aq) + SO2(g) +
2H2O(l)
3. Reaction of iron
− with water
Iron only reacts with steam at red heat in a reversible
reaction forming of triiron tetra oxide and hydrogen.
3Fe(s) + 4H2O(g) → Fe3O4(s) + 4H2(g)
Note:

In the presence of air and water iron forms a brown
coating called rust. Rust is hydrated(III) oxide
represented as Fe2O3.xH2O

Pure iron does not rust.
− with acids
Iron reacts with dilute HCl and H2SO4 to liberate
hyhdrogen gas
Fe(s) + 2HCl(aq) → FeCl2(aq) + H2(g)
Fe(s) + H2SO4(aq) → FeSO4(q) + H2(g)
Dilute nitric acid forms mixed products.

012-Page 286
 4Fe(s) + 10 HNO3(aq) → 4Fe(NO3)2(aq) +
NH4NO3(aq) + 3H2O(l)
Hot conc. H2SO4 oxidizes iron to iron (III) sulphate and
forming sulphur dioxide.
2Fe(s) + 6H2SO4(aq) → Fe2(SO4)3(aq) + 6H2O(l) +
3SO2(g)
4. Reactions of cobalt
− with water
Cobalt does not react with water at ordinary conditions
but when strongly heated it react with steam to form
cobalt(II) oxide and hydrogen.
Co(s) + H2O(g) → CoO(s) + H2(g)
− With acids
Hot dilute acids such as hydrochloric or sulphuric acid
slowly react with the metal forming hydrogen and then
the corresponding cobalt (II) salts.

Co(s) + 2HCl(s) → CoCl2(aq) + H2(g)

Co(s) + H2SO4(aq) → CoSO4(aq) + H2(g)
Dilute nitric acid reacts with cobalt forming cobalt
nitrate and oxides of nitrogen.
Hot conc. H2SO4 oxidizes Cobalt to CoSO4 and SO2
Co(s) + 2H2SO4(s) → CoSO4(aq) + SO2(g) +
2H2O(l)

012-Page 287
5. Reactions of copper
− with acids
Concentrated sulphuric acid reacts with copper forming
sulphur dioxide
Cu(s) + 2H2SO4(aq) → CuSO4(aq) + 2H2O(l) +
SO2(g)
Boiling concentrated hydrochloric acid reacts with
copper forming and a complex of copper(I)
Cu (s) + H+(aq) + 2Cl-(aq) → [CuCl2]- + H2(g)
Nitric acid reacts with copper at all conditions.
Dilute nitric acid reacts with copper forming nitric oxide.
3Cu(s) + 8HNO3(aq) → 2NO(g) + 3Cu(NO3)2(aq) +
4H2O(l)
Concentrated nitric acid reacts with copper forming
nitrogen dioxide gas (brown gas).
Cu(s) + 4HNO3(aq) → Cu(NO3)2(aq) + 2H2O(l) +
2NO2(g)
− Copper does not react with water at any condition.
6. Reactions of zinc
− with water
Zinc reacts with steam at red heat producing Zno and h2
Zn(s) + H2O(g) → ZnO(s) + H2(g)
− with acids
Zinc reacts with hydrochloric acid (both conc. and
dilute) and dilute sulphuric acid producing the
corresponding salt and hydrogen
Zn(s) + 2HCl(aq) → ZnCl2(aq) + H2(g)
012-Page 288
 Zn(s) + H2SO4(aq) → ZnSO4(aq) + H2(aq)
Reaction with conc. H2SO4 or HNO3 produces products
E
X
which depend on the conditions of reaction.
E
R
C
I
S
E
S

1. a) Iron is a typical transition element.

(i) What is meant by the term transition
element?
(ii) Write the electron configuration for a
Fe2+ ion.
(iii) Using iron as your example, state
the typical properties of a transition element.
(iv) Describe what you would see when
Fe3+(aq) ions react with aqueous sodium
hydroxide and write the ionic equation.
b) What is meant by the term bidentate ligand?
c) State the shape of the following complex
ions.
(i) CuCl42–
(ii) Ni(NH3)2Cl2
012-Page 289
 (iii) Fe(H2O)62+
2. a) A student added concentrated hydrochloric acid to a
solution of aqueous cobalt chloride.
(i) Describe what the student would observe.
(ii) Write the equation for the reaction which
occurred and state what type of process happened
during the reaction.
b) Many aqueous transition element ions undergo
reactions with cyanide CN–(aq) ions, according to the
equation shown below:
Fe(H2O)62+(aq) + 6CN–(aq) 
Fe(CN)6y(aq) + 6H2O(l)
Calculate the value of y.
3. Copper ions, Cu2+, take part in a number of different
ligand substitution reactions.
a) What is meant by the terms:
ligand, complex ion, and ligand substitution
b) Copper(II) salts form aqueous solutions
containing [Cu(H2O)6]2+(aq). A ligand
substitution reaction involving [Cu(H2O)6]2+(aq)
is shown below:
reagent Y
[Cu(H2O)6]2+(aq) [Cu(H2O)2(NH3)4]2+(aq)

i) Identify reagent Y.
012-Page 290
 ii) Write a balanced equation for this ligand
substitution.
iii) State the colours of the two complex ions
involved in this ligand substitution.
iv) Draw the shape of the [Cu(H2O)6]2+
complex ion, showing clearly any bond angles.
4. a) Explain what is meant by the term coordination
number in a complex ion.
b) State the formula and shape of the complex
containing:
i) Co(II) and six H2O ligands;
ii) Ni2+ and three (NH2CH2CH2NH2) ligands.
c) Sketch and label the two isomers of:
i) [Cr(H2O)Cl2]+ , ii) [NiCl2(NH3)2]

CHAPTER VIII: IDENTIFICATION OF

IONS/QUALITATIVE ANALYSIS.
GENERAL OBJECTIVES
At the end of this chapter, students should be able to:
012-Page 291
 a) Identify experimentally anions and cations from
their various solutions and compounds.
b) Specify confirmatory tests for each ion.
CONTENTS
8.1 Appearance
Always note the physical properties of the substances:e.g.
appearance, colour, smell and solubility in water. The
deductions below may be a guide as to the substance present
but do not constitute proof (conclusive evidence).
observation Inference/Deduction
Red colour Oxide of metal
Orange-red colour Dichromate
Puple colour Permanganate
Pink colour Hydrated salts of manganese
Yellow colour Chromate or ferric salt
Green colour Ferrous, copper, nickel or
Blue colour chromic salt
Brown colour Hydrated cupric salts
Smell of ammonia Metal oxide
Smell of hydrogen sulphide Ammonium salt
Smell of sulphur dioxide Sulphide
Sulphate

1) Heating in a closed tube

Heat a small quantity of the solid in a dry hard glass test tube
until no further change occurs. Identify any gases by their
smell, colour, action on litmus, action on litmus, action on

012-Page 292
splint and their usual confirmatory tests. Always observe the
residue.

Observation Deduction
(i) Water vapour Hydrated salt
(ii) Carbon dioxide Carbonate and bicarbonate
(iii) Oxygen Chlorate, higher oxide or
nitrate of potassium or
(v) Nitrogen dioxide sodium
Nitrate other than that of
(vi) Sulphur dioxide sodium, potassium.

(vii) Ammonia Thiosulphate, sulphite or

(viii) Hydrogen chloride sulphate
(ix) White sublimate
(xiv) Residue Ammonium salts
Certain hydrated chlorides
012-Page 293
(a) Yellow hot, white cold Ammonium salts
(b) Brownish/red hot,
(c) yellowish brown cold
(d) Black hot reddish brown Zinc oxide, Zn2+
(e) cold. Lead monoxide, Pb2+
Black Ferric oxide, Fe3+ from Fe2+
Dark green Copper or Manganese
oxide, Cu2+ or Mn4+
Chromium or nickel oxide,
Cr3+, Ni2+

2) Dilute Hydrochloric (or sulphuric)

Add dilute acid to the solid. If there is no reaction always
warm gently. Identify any gases evolved. The formation of a
clear solution indicates the ABSENCE of insoluble metal
chlorides (or sulphates).
Observation Deduction
(i) Solids dissolve, no gas Basic oxide
(ii) evolved Chromate
Yellow solid dissolves
(iii) giving orange solution Insoluble chlorides(or
(iv) White precipitate sulphates)
(v) Carbon dioxide Carbonates or bicarbonates
(vi) Nitrogen dioxide Nitrates
Sulphur dioxide Sulphite

012-Page 294
 3) Barium chloride solution
Observation Deduction
(i) White precipitate Carbonate, Sulphates or
(ii) A yellow precipitate Sulphites
Chromate

Note: On the addition of dilute hydrochloric acid and then

heating only Barium sulphate is insoluble.

4) Silver Nitrate solution

This test gives precipitate of insoluble silver salts
Observation Deduction
(i) A white precipitate Chloride, Nitrites, Sulphide,
(ii) Red precipitate Carbonates, Sulphates.
(iii) Creamy precipitate Chromate(or Dichromate)
(iv) Yelow Bromide
Iodide
Note: On the addition of dilute nitric acid, and then heating,
only silver halides are insoluble.
5) Sodium hydroxide solution

012-Page 295
This reagent precipitates insoluble hydroxides. The
amphoteric hydroxides will redissolve in excess of the
reagent.
Cation A few drops Excess
NH4+ No precipitate Ammonia gas on
Ba2+ White precipitate heating
Mg2+ White precipitate Insoluble
Ca2+ White Precipitate Insoluble
(from conc. Insoluble
Mn2+ solution.)
Al3+ White precipitate Insoluble, turns brown
Zn2+ White precipitate on standing
Pb2+ White precipitate Soluble
Cr3+ White precipitate Soluble
Fe2+ Green precipitate Soluble
Ni2+ Green precipitate Soluble to give green
Fe3+ Green precipitate solution
Co2+ Brown precipitate Insoluble, turns brown
Ag+ Blue precipitate on standing
Cu2+ Brown Insoluble
Sn2+ precipitate(Ag2O) Insoluble
Blue precipitate Insoluble turning pink
White precipitate Insoluble
Insoluble, turns black
on heating.
Soluble

012-Page 296
 6) Ammonia solution
This reagent precipitates hydroxides. On adding excess some
cation form soluble AMMINE complexes.

Cation A few drops Excess

NH4+ - -
Ba2+ No precipitate -
Ca2+ No precipitate -
Mg2+ White precipitate Insoluble
Al3+ White precipitate Insoluble
Pb2+ White precipitate Insoluble
Mn2+ White precipitate Insoluble, turns brown on
Zn2+ White precipitate standing
Fe3+ Brown precipitate Soluble
Ag+ Brown Insoluble
Fe2+ precipitate(Ag2O) Soluble
Ni2+ Green precipitate Insoluble, turns brown on
Cr3+ Green precipitate standing
012-Page 297
Cu2+ Grey-green Soluble , forming blue
Co2+ precipitate solution
Sn2+ Blue ppt Slightly soluble forming
Blue ppt pink/violet solution
White ppt Soluble forming deep blue
solution
Soluble turning pink
Insoluble

8.2 Procedure of carryng out flame tests

Some ions impart characteristic colours to flame when their
salts are treated in the following manner.
Clean a nichrome (or platinum) wire by dipping it in conc.
HCl and holding it in the flame of a Bunsen burner until no
additional colour is produced. Then dip the end of the wire
first in conc. HCl, then the solid under test, and then return
the wire to the flame.
RECOGNITION OF GASES
Gases are often off either when a substance is heated or when
a reagent reacts with a substance. FOUR easy tests serve to
identify most of these gases.
a) The colour of the gas
b) The smell of the gas

012-Page 298
 c) The action of the gas on a lighted splint
d) The action of the gas on moist red and blue litmus paper.

Gas Colour Smell Action on

litmus
Cl2 Greenish Characteristic Red, Then
& Irritating bleached
HCl Colourless( Irritating Red
fumes in
NO2 moist air) Irritating Red
HNO3 Redish- Irritating Red
brown
Pale Red
SO3 yellow(vapour Irritating Red, then
SO2 fumes) Rusting bleached
H2S White fumes sulphur Faint red
None Rotten eggs
None
NH3 Blue
Characteristic
H2 None & Choking None
None in pure
None

O2 Faint red
None

012-Page 299
CO2 None None
N2 None None
None None
None

Note: H2S is a very poisonous gas; therefore this test should

be carried out in the fume cupboard
8.3. Confirmatory tests for some gases
HCl Hold the moist stopper of a conc. ammonia a bottle in
the gas forms dense white smoke of ammonium chloride.
SO2 Decolourises dilute KMnO4 or turns green the orange
K2Cr2O7 paper
CO2 White ppt with lime water.
NH3 Turns moist red litmus blue
The following tables summarize tests for common ions
(anions & cations)

A. Anions
Name of Symbol Action on Conc/dilute Diluted Confirm
ion heat H2SO4 HCl Test
012-Page 300
Carbonate CO32- Odorless Odorless Odorless Dilute H
gas which gas turns gas turns (as indi
evolves lime water lime water under d
turns lime milky ,and milky ,and HCl) or
water blue litmus blue Silver n
milky and paper turns litmus followe
blue litmus red paper dil. HC
paper red. turns red white p
The gas is soluble
CO2 acid
confirm
carbona
Sulfate SO42- Colorless - - Add Ba
gas with solution
pungent followe
smell. HCl, a
Turns precipi
dichromate insolub
paper from acid
orange to confirm
green. sulfate.
Gas is SO2
Sulphite SO32- Colorless - - Add Ba
gas with solution
pungent followe
smell. HCl, a
Turns precipi
dichromate soluble
paper from acid
orange to confirm
green. sulfite.
012-Page 301
 Gas is SO2
thiosulphate S2O32- - - - Add
solution
brown
iodine
dischar
Mono HCO3- - - - Add M
hydrogeno solution
carbonate precipi
formed
with CO
white
precipi
formed
immed
Nitrates NO3- Brown gas - - To the
with add con
pungent H2SO4
smell warm g
,turns blue Evoluti
litmus red whitish
brown
which
conden
into an
liquid a
sides
indicate
nitrate.
Chloride Cl- Pungent Colorless, No Add 2-
and pungent observable drops o
012-Page 302
 chocking and change aqueou
colorless chocking silver n
gas fuming in air. followe
in air. white excess
white fumes with acid; ad
fumes with NH3 ammon
NH3 vapour white
vapour precipi
which
dissolv
ammon
solution
confirm
chlorid

B. Cations
Name of Symbol Sodium Ammonia Dil/conc Diluted C
ion of ion hydroxide solution H2SO4 HCl T
solution
Manganese Mn2+ White White - - T
precipitate precipitate a
turns turns o
brown due brown fo
to aerial soon s
oxidation brown due s
012-Page 303
 to aerial b
oxidation b
c
c
Zinc Zn2+ White White - - W
precipitate precipitate p
soluble in soluble in d
excess excess s
h
a
s
Ammonium NH4+ No - - - A
observable h
change s
w
c
p
s
tu
b
d
fu
v
Magnesium Mg2+ White ppt White ppt - - M
insoluble insoluble re
in excess in excess (f
m
fo
li
s
p
012-Page 304
 M
2+
Calcium Ca White ppt No A
insoluble observable White ptt a
in excess change with s
dilute fo
surphuric fe
acid (N
w
fo
C
Barium Ba2+ White ppt No - T
insoluble observable White ptt s
in excess change with p
dilute c
surphuric s
acid y
B
fo
Aluminium Al3+ White ppt White ppt - - A
soluble in insoluble d
excess in excess s
fo
y
n
c
A
Iron Fe2+ Green ppt Green ppt - - G
turns turns b
brown in brown in p
air air h
,insoluble ,insoluble (I
012-Page 305
 in excess in excess
3+
Fe Brown ppt Brown ppt - - A
insoluble insoluble p
in the in the th
excess excess te
lo
o
Chromium Cr3+ Green ppt Green- - - T
soluble in grey ppt H
excess to insoluble a
form a in excess C
green T
solution P
s
y
c
a
d
fo
d
d
fo
d
s
c
Lead Pb2+ White ppt White ppt White A
soluble in soluble in ppt White W
excess excess ppt of p
PbCl2 d
p

012-Page 306
Note: Sulphite and Carbonate ions also give a white
precipitate with barium ions but these precipitates (unlike
that of barium sulphate) are soluble in dilute acids. This is
why you have to add dilute hydrochloric acid as well as
barium chloride solution.
8.4 Some examples of practical work about qualitative
analysis
1) You are provided with substance Q which contains 2
cations and one anion. You are required to identify the
cations and anion in Q Carry out the following tests and
record your observations and deductions in the table
below. Identify any gas evolves.
Tests Observations Deductions
1. Heat one -Colorless vapor -Water vapor
spatula end-full of condenses on from hydrated salt
Q in a dry test cooler part of the
tube until there is test tube - Ammonia
no further change gas(NH3) which
-A colorless gas probably may
with pungent come from
smell ,turns red ammonium ion
litmus blue NH4+
forms white
fumes with HCl
-sulfur
-colorless gas dioxide(SO2) gas
with pungent which may come
smell turns orange from sulfite(SO3-)
012-Page 307
 dichromate paper or sulfate(SO42-)
green

Fe2+ suspected
- light green
residue turns into
white powder
,then yellow, then
reddish brown

2. Put 2 spatula Colorless solution -Cr3+, Ni2+, Fe2+

end-fulls of Q in a with tendance to are suspected to
test tube, add clear green. be present.
about 5cm3of
water and shake.
Divide the
solution into five
portions

3. To the first Green ppt -Fe2+ is suspected

solution add insoluble in Ammonia gas ,
dilute NaOH, excess and turns NH4+ is
drop wise until brown on confirmed.
the excess standing , on
heating gas turns
red litmus blue
and form white
fumes with
Conc.HCl .
4.To second, add Green ppt Fe2+ is most
ammonia solution insoluble in likely
012-Page 308
drop wise until in excess
excess
5.To the 3rd A deep blue ppt Fe2+ confirmed
solution add 2-3
drops of
potassium
hexacyano ferrate
(III) solution
6. To the 4th add White ppt SO42-, Cl-
Lead (II) nitrate suspected
solution followed
by dilute nitric
acid
7. To the 5th add White precipitate SO42- confirmed.
Barium chloride insoluble in
solution followed dil.HCl
by dilute hydrolic
acid (HCl)

Cations are: NH4+ and Fe2+

Anion is : SO42-
The formula for the compound is Fe SO4 (NH4)2SO4 .n
H2O, where n is the crystallization number. If n is 6, we get
the Mohr salt.
2) You are provided with substance D which contains one
cation and one anion. You are required to identify the
cation and anion in D. Carry out the following tests and

012-Page 309
 record your observations and deductions in the table
below. Identify any gas evolves.
TEST OBSERVATION DEDUCTION
1. A spatula end- - Colourless vapour - hydrated salt
full of D is heated which condenses on present.
strongly in a teste the cooler part of
tube until there is the test tube.
no further change - A colourless - Gas is SO2
pungent gas which probably SO32- or
turns potassium SO42- salt present.
dichromate green is
formed. - D is a transition
- The residue is a compound
dark green solid. probably
containing Cr3+ or
Ni2+
2. A spatula end- D dissolves to give Probably D
full of D is green solution. contains Cr3+, Ni2+,
dissolved in about Fe2+ or Cu2+.
5 cm3 and the
resultant solution
is divided into four
parts.
a) To the 1st part is A green precipitate Probably Cr3+
added ammonium which slightly present
hydroxide solution dissolves to give a
drop wise until in violet solution.
excess
b) To the second A green ppt soluble Cr3+ presence
part is added dilute in excess NaOH to confirmed.
012-Page 310
sodium hydroxide form a green
solution dropwise solution.
until in excess On boiling with H2O2 oxidises Cr3+
followed by 1cm3 H2O2 a yellow in an alkaline
of 10% hydrogen solution is formed medium to yellow
peroxide solution with evolution of a chromate.
and the resultant colourless gas The gas is oxygen.
mixture boiled and which relights a
later cooled. the glowing splint.
resultant solution
is then divided
into three portions
i) To the 1st A brick red ppt. Silver chromate is
portion is added formed.
silver nitrate Hence CrO42-
solution dropwise compound formed.
until no further
change takes
place.
ii) To the second A pale yellow ppt. Barium chromate
portion is added a formed.
drop of barium Hence CrO42-
chloride solution compound formed
iii) To the 3rd The yellow solution A dichromate has
portion is added a turns orange been formed from
few drops of a chromate
hydrochloric acid.
c) To the third A deep blue lake is Presence of Cr3+
part of the solution formed
is added a few
drops of butanol
012-Page 311
followed by 3
drops of dilute
H2SO4
d) To the fourth A white ppt is Probably Cl-, CO32-
part was added a formed or SO42- present
few drops of lead
nitrate solution.
e) To the last part A white ppt Presence of SO42-
was carried a test insoluble in nitric confirmed.
of one’s own acid is formed
choice.
Test: To the last
portion is added a
few drops of
barium nitrate
followed by 1 cm3
of dilute nitric
acid.
The cation in D : Cr3+
The anion in D: SO42-
3) Substance K contains one cation and one anion
TEST OBSERVATION DEDUCTION
a) A spatula end-full Colourless vapour hydrated salt.
of K is strongly condenses to give Gas is hydrogen
heated a colourless liquid chloride and Cl-
which turns is most likely
anhydrous copper present.
sulphate blue and
also turns litmus

012-Page 312
 red and forms Black solid is
white fumes whith CuO, FeO or
conc. ammonia. MnO2
Green solid give a
black solid residue
b) To a spatula end- Effervescence, a Hydrogen
full of K is added colourless gas, chloride gas.
a few drops of turns litmus red Cl- is most likely
concentrated and forms white present.
sulphuric acid fumes whith conc.
then the mixture Ammonia
heated
c) About two K dissolves to give Fe2+, Cr3+, Cu2+
spatula end-full a green solution. or Ni2+
of k is dissolved suspected
in about 5 cm3 of
H2O.
The solution is then
divided into 3
portions
i) To the 1st portion A pale blue ppt Cu2+ suspected
is added dilute insoluble in
sodium hydroxide excess.
dropwise until in On heating the Black solid is
excess and the blue ppt forms a CuO
mixture heated black solid
ii)To the 2nd portion A red-brown ppt Cu2+ confirmed
is added a few formed
drops of
potassium
hexacyanoferrate(
012-Page 313
 II) solution
iii) To the 3rd White ppt which Cl- confirmed
portion is added a dissolves on
few drops of heating and
lead(II) nitrate reappears on
solution and the cooling
mixture warmed.
Note:
a) HCl gas is produced by hydrolysis reaction when certain
hydrated chloride are heated e.g. Copper(II) chloride and
Cobalt(II) chloride as in reaction(a).
b) Lead nitrate solution is used as a confirmatory test for
chloride. See test(c) (iii).
Here initially just like with CO32- and SO42- a white ppt
is formed but with Cl- the white ppt dissolves on heating.

4) Substance L contains two cations and one anion

TEST OBSERVATION DEDUCTION
a) A spatula end-full Colourless vapour Water of
of L is heated condenses to give crystallization;
gently first and liquid which turns hence hydrated
then more anhydrous salt.
strongly copper(II)
sulphate blue.
A white sublimate
012-Page 314
 formed and Gas is NH3
colourless gas hence NH4+
which turns red
litmus blue and Gas is SO2 hence
later turns the blue SO42- or SO32-
litmus red and probably present
acidified
potassium ZnO
dichromate
solution orange to
green.
Residue is yellow
but turns white on
cooling
b) Two spatula White solid Pb2+, Al3+, Zn2+,
ends-full of L is dissolves to give a Ca2+, Ba2+, NH4+,
dissolved in 5 colourless or Mg2+ present
cm3. The resultant solution
solution is then
divided into 4
parts.
i) To the 1st part is White ppt soluble Zn2+, Pb2+, or
added sodium in excess. Al3+
hydroxide On warming a
solution dropwise colourless gas Gas is NH3,NH4+
solution until in turns litmus blue confirmed
excess and
mixture heated.
ii)To the 2nd part is A white ppt Zn2+ confirmed
added a few drops
of potassium
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 hexacyanoferrate(
II) solution
iii) To the 3rd A white ppt Cl-, SO42- or
part is added 2-3 CO32- present
drops of lead(II)
nitrate solution
and mixture
heated
iv) To the last A white ppt SO42- confirmed
part is added
about 1 cm3 of
dilute
hydrochloric acid
followed by a few
drops of barium
chloride.

The cations present are NH4+ and Zn2+

The anion present is SO42-
5) G contains two cations and two anions
TEST OBSERVATION DEDUCTION
a) A spatula end- Colourless vapour Water of
full of G is given off which crystallization.
heated turns anhydrous Hydrated salt.
strongly until CuSO4 blue. The gas is NO2 and
no further G decomposes to hence NO3-
change takes give thick brown present.
place gas. The residue is
The residue is a probably CuO or
black solid. MnO2
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b) Two spatula The filtrate is a Filtrate probably
end-full of G faint pink solution. contains Ni2+ or
is shaken with Co2+
about 8 cm3 of
water. The residue is a The residue does
The mixture white solid not contain a
was filtered transition element.
and both the Hence Ca2+, Pb2+,
filtrate and Sn2+, Al3+, Ba2+, or
residue kept. Mg2+ probably
present.
c) The filtrate
was divided
into four parts. A dity white ppt Presence of Mn2+
i) To the first insoluble in excess most likely
part is added which turns brown
dilute NaOH is formed
dropwise until
in excess
ii)To the second A white ppt Mn2+ is most likely
part is added insoluble in excess present
dilute aqueous is formed. The
ammonia precipitate turns
dropwise in brown
excess
iii) To the A purple solution is The Mn2+ is
third part was formed oxidized by PbO2
about some in the presence of
lead(VI) oxide conc. HNO3 to
followed by purple MnO4-.
about 0.5 cm3 Hence presence of
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 of conc.HNO3 Mn2+ in the filtrate
and the is confirmed.
mixture
boiled.
iv) The last
part was used
for carrying
out a test of
one’s choice A brown ring forms
to confirm the at the junction of NO3- presence is
anion in the the liquids confirmed
filtrate.
Test: To the last
part is added
about 1 cm3 of
iron(II) sulphate
solution. Conc.
H2SO4 is then
slowly added
down the side of
the test tube.
d) The residue is The residue Probably Pb2+,
washed and dissolves to give a Zn2+, Al3+, Mg2+,
dilute colourless solution and Ca2+ present
HNO3added
dropwise until
no further
change occurs.
The resultant
solution is
then divided
012-Page 318
 into 6 parts
i) To the first A white precipitate Either Pb2+ or Al3+
part is added soluble in excess is present
dilute NaOH formed
dropwise until
in in excess
ii)To the second A white ppt Either Pb2+ or Al3+
part is added insoluble in excess present
aqueous is formed
ammonia
iii) The third
part was used
to carry out a
test of one’s
choice to A thick yellow Presence of Pb2+
confirm the precipitate is confirmed
cation present. formed
Test: To the
third part is
added a few
drops of
potassium iodide
solution
iv) To the A yellow ppt is Probably I-
fourth part is formed which on present.
added about 1 warming dissolves
cm3 of lead to give a colourless
ethanoate solution
solution and
the mixture
warmed.
012-Page 319
 v) To the fifth A brown The brown
part is added colouration is colouration is due
dilute ethanoic formed which gives to Iodine liberated;
acid followed a violet solution is hence I- is present.
by a few drops CCl4 layer
of sodium
nitrite and
carbon
tetrachloride.
vi) To the A yellow ppt Presence of I-
sixth part is insoluble in confirmed
added HNO3 ammonia
followed by a
few drops of
conc.
ammonia
solution.

The cations in g are Mn2+ and Pb2+

The anions in G are NO3- and I-
6) You are provided with a substance A which contains one
cation and one anion. You are required to identify the cation
and the anion in A. Carry out the following tests on A and
record your observations and deductions in the table below.
Identify any gases evolved.
Tests Observations Deductions
a) Heat one spatula Brown gas with NO2 evolved
end full of A in a pungent smell turns
dry test tube, first blue litmus red NO3- suspected
012-Page 320
gently then Residue is
strongly till there is orange(hot) and
no thurther change yellow(cold)
b) To one spatula Brown fumes NO3- confirmed
end fullof A in a condense into an
test tube add a few oily liquid at the
drops of side
concentrated
sulfuric acid and
warm gently.
c) To one spatula A is soluble in Absence of a
end full of A in a water and gives a typical transition
test tube add about colourless solution element
6cm3 of water,
shake and divide
into three parts
i) To the first part White ppt Zn2+, Pb2+, Al3+,
add dilute sodium dissolved in excess Sn2+ probably
hydroxide solution forming a present
dropwise till in colourless solution
excess
ii) To the second White ppt insoluble Pb2+, Al3+, Sn2+
part add dilute in excess reagent most likely present
ammonia solution
dropwise till in
excess
iii) To the third White ppt formed Pb2+ confirmed.
part add a few
drops of dilute
hydrochloric acid
The Cation in A is Pb2+
012-Page 321
The anion in A is NO3-
SAMPLE QUESTIONS
1) Potassium was first isolated by Sir Humphrey Davy in
1807. It has two main isotopes, 39K and 41K. Both
isotopes are able to form a positive ion with a single
charge.
a) Complete the table below.

Number Number Number

Particle of of of
protons neutrons electrons
39
K
41
K+

b) The two main isotopes, 39K and 41K, are stable and
naturally occur with the following percentage
abundances. This information can be used to calculate
the relative atomic mass of potassium.

Percentage
Isotope
abundance
39
K 93%
41
K 7%

012-Page 322
(i) Define the term relative atomic mass.
(ii) Use the information in the table above to calculate the
relative atomic mass of potassium.
Give your answer to two decimal places (Ans = 39.14)
(c) A compound consisting of nitrogen and hydrogen has a
composition of 87.5% nitrogen and 12.5% hydrogen. The
relative molecular mass is 32. Calculate the empirical
formula and the molecular formula. Ans : E. f. = NH2, N2H4
(d) Lithium reacts with water as shown in the following
equation:
2Li(s) + 2H2O(l) 2LiOH(aq) + H2(g)
In an experiment, 0.76 g of lithium was added to 200 cm3
of distilled water.
(i) How many moles of lithium reacted? (Ans =
0.11 mol)
(ii) The experiment was carried out at room
temperature and pressure. What volume of hydrogen gas was
produced? [1 mol of gas occupies 24.0 dm3 at room
temperature and pressure] (Ans = 1.3 dm3)

(iii) 25.0 cm3 of the lithium hydroxide solution formed was

neutralised by 23.6 cm3 of dilute hydrochloric acid.
Calculate the concentration of the dilute hydrochloric
acid used. Give your answer to an appropriate number
of significant figures.
LiOH(aq) + HCl (aq) LiCl(aq) + H2O(l)
012-Page 323
 (Ans = 0.58 mol dm-3 )
2) (a) Define the term first ionisation energy.
(b) The elements nitrogen, phosphorus and arsenic
are all found in Group 5 of the Periodic Table. State and
explain the trend in first ionisation energies for these
elements. (key factors: distance from nucleus (or shell
number), shielding effects and nuclear charge.)
(c)The elements sodium, silicon and chlorine are all
found in Period 3 of the Periodic Table.
State and explain the trend in first ionisation energies for
these elements.
(key factors: distance from nucleus (or shell number),
shielding effects and nuclear charge.)
3) (a) Describe the shape of an s-orbital.( Hint: Avoid using
descriptions which imply 2D shapes. For example,
circular would be wrong).
(b) Insert the names of the sub-shells and complete the
box notation for the electronic configuration of carbon.

(c)The ions, Na+, Mg2+, Al3+ and O2- have identical

electronic configurations. Write the formula of another ion
which has the same electronic configuration as these four
ions.
012-Page 324
 (Ans: F- ,Other acceptable responses would be N3-, C4-
and Si4+).
(d) Why do Al3+ ion have smaller radius than an
Na+ ion?
(e) Are O2- ions bigger, smaller or the same size as
Mg2+ ions?

4) (a) What is a covalent bond?

(b) Draw ‘dot-and-cross’ diagrams to show the
bonding in the following compounds. Show the outer
electrons only.
(i) Magnesium oxide, MgO.
(ii) Water, H2O
(iii) Carbon dioxide, CO2.
(c) Draw a 3D diagram for an ammonia molecule,
NH3. State both the name of the shape and the bond
angles. Explain why this shape is adopted by the ammonia
molecule.
(d) Explain the trend in melting points for the
following substances.
Magnesium oxide, MgO, melting temperature
2853OC.
Water, H2O, melting temperature 0OC.
012-Page 325
 Argon, Ar, melting temperature -189OC.
5) (a) The melting points of sodium, magnesium and
aluminium are relatively high and show an increase as
atomic number increases. Explain these facts in terms of
bonding and structure.
(b) Describe what you would see if calcium, a grey
metal, was ignited in air. Construct an equation for the
reaction which takes place.
(c) The reaction between barium and air is far more
vigorous than that for calcium and air. Explain why.
(d) This question is about compounds of strontium.
Substance X was formed by adding 0.1 moles of water to
0.1 moles of strontium oxide, SrO.
Excess water was added to substance X to produce
solution Y.
Carbon dioxide gas was bubbled through solution Y. This
formed precipitate Z.
(i) Name substance X and describe its appearance.
(ii) Name solution Y and give its approximate pH.
(iii) Name solid Z.
(iv) How could substance Z be converted to strontium
oxide, SrO?

012-Page 326
(e) Suggest why magnesium hydroxide, Mg(OH)2, is used
in preference to calcium hydroxide, Ca(OH)2, in
indigestion tablets. (Hint: This question asks you to
suggest an answer. Therefore, you have to use your
chemistry knowledge and apply common sense).
6) (a) Describe the physical states of chlorine, bromine and
iodine at room temperature and explain any trend.
(b) The labels of aqueous potassium chloride, aqueous
potassium iodide and aqueous potassium bromide have
become removed from their containers. Ben has access
to samples of chlorine water, bromine water, aqueous
iodine and cyclohexane, an inert organic solvent.
Explain how he could use these reagents to identify the
solutions. Describe any colour changes he might see and
write equations for any reactions which take place.
(Ans: He should place a sample of each unknown
solution into a test tube. Then add chlorine water to
all three solutions. Two will become coloured, one a
pale orange solution and the other a yellowy-brown
solution. The third solution will keep the very pale
green colour of chlorine water.
As chlorine is the most reactive halogen, it wants to
gain electrons most and so will remove electrons
from both Br- and I- ions. So chlorine displaces both
bromine and iodine from their halide solutions.

012-Page 327
 Bromine is orange when aqueous and iodine is
yellowy-brown when aqueous. To confirm which
halogen has been displaced, add cyclohexane and
shake. Any halogen molecules will preferentially go
to the organic solvent and a bright orange colour is
seen if bromine has been formed, and a bright purple
colour if iodine has been formed.
An equation for a displacement reaction is:
Cl2(aq) + 2KBr(aq) 2KCl(aq) + Br2(aq)
(c) Samples of aqueous potassium chloride, aqueous
potassium iodide and aqueous potassium bromide could
be detected by using aqueous silver ions. Describe the
changes you would observe if aqueous silver nitrate was
added to each of these solutions. Include an ionic
equation, with state symbols, for one of these reactions.
(d) Explain what is meant by the phrase, ‘chlorine
undergoes disproportionation’. Write an equation to
show this occurring.
7) The elements Be, Mg, Ca and ba belong to a group (II)
in the periodic table.
(a) i) State three chemical properties shown by the
elements. For each property, write an equation to
illustrate your answer.
ii) Explain the trend in solubilities of the hydroxides
and sulphates of the elements in water(hint: the

012-Page 328
 solubility of ionic salt in water is dependent on both
hydration and lattice energies_ see senior 5).
(b) Be differs in some of its properties from the rest
of the element in the group.
i) State two properties in which Be differs from the
rest of the elements in the groug.
ii) Give reasons why Be shows different properties
from the rest of the elements.
(c) Explain:
i) Why MgCl2 solution has pH less than 7
ii) Why the tendency to form complexes by group
(II) metals decreases down the group
iii) group (II) metals form less ionic compounds
than group (I) metals
(d) State three properties in which Li and Mg
resemble and explain why.
8) a) Describe one general method for preparing the
halogens in the laboratory(excluding fluorine0 and write
the equation for the reation.
b) describe the reactivity of fluorine, chlorine and
bromine with
i) sodium hydroxide
ii) Water ( use equations to illustrate your answer).
c) How would you distinguish between sodium bromide
and sodium iodide given chlorine water and
tetrachloromethane.
d) State and explain
012-Page 329
 i) the trend in boiling points of the halogens down the
group
ii) the trend in the acidity of the hydrides of group (VII)
elements
9) a) A metallic element A has atomic number of 29.
i) Write down the electronic configuration of element
A.
ii) To which of s, p and d-blocks of elements of the
periodic table does A belong?
b) When A was heated with concentrated sulphuric acid,
sulphur dioxide gas was given off and a blue solution
was formed.
i) Name a reagent used to test for the gas
ii) Write an equation
c) A small volume of the blue solution from (b) was
treated with conc. HCl added drop-wise until in excess
and then the acid solution diluted about ten times its own
volume with water. State and explain what was observed
and what species of A were produced.
i)When the acid was added.
ii) When the acid solution in (i) was diluted.
d) Element A exhibits two oxidation states of +1 and +2.
Explain.
10) a) State
i) Two properties that do not qualify Zn as a
transition element.

012-Page 330
 ii) One property that qualifies Zn as a transition
element.
b) i) Name one reagent that can be used to distinguish
Zn2+ and Al3+
ii) State what is observed when Zn2+ and Al3+ are
treated separately with the reagent. Write equation for
the reaction.

REFERENCES
1. Brown and Lemay (1988), Chemistry the central
science, Prentice Hall, 4th edition.
2. Dave Gent and Rob Ritchie (2008), OCR Chemistry
A2, Pearson Education Limited.
3. E.N. Ramsden (2000), A-Level Chemistry, Nelson
Thornes Ltd, Fourth edition.
4. Geoff Rayner-Canham(2006), Descriptive inorganic
chemistry, University of Hull, 4th edition
5. Graham Hill and John Holman (2000), Chemistry in
context, Nelson Thornes Ltd, 5th edition.

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6. Keith Obot (2008), A complete revision notes in
advanced level physical chemistry.
7. M A Atherton and J K Lawrence ( 1978), Chemistry
for today and tomorrow,London W1X 4BD.
8. NCDC(June,2010), Advanced level chemistry
curriculum for science combinations, Kigali
9. Obot Keit (2006), Advanced Level inorganic
chemistry, 4th edition.
10. Peter.W.Atkins (2000) Physical chemistry, sixth
edition; oxford.
11. Philip Matthews (2003), advanced chemistry,
Cambridge University page 200.
12. Satya Prakash,(2009), Advanced inorganic chemistry
Volume II, Allahabad University.
13. Sedrick.C.Magasi & Kira Ernest (2006),
Comprehensive approach to advanced level chemistry,
Nyambari Nyangwine bookshop, Dar es Salaam.

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