TABLE OF CONTENTS

CHAPTER 1: ATOMIC STRUCTURE .................................................................................................. 5

1.0. General introduction and definition of an atom ............................................................................ 5
1.1. Particles which constitute an atom ................................................................................................ 5
1.2. Isotopes and relative atomic mass (RAM) .................................................................................... 8
1.3. Description of mass spectrometer ................................................................................................. 9
2.1. The history of the periodic table ................................................................................................. 18
2.2. Classification of elements in the Periodic Table according to Mendeleev and the modern
P.Table................................................................................................................................................ 19
2.3. Variation of physical properties in Groups and Periods ............................................................. 20
2.3.1 Atomic radius ........................................................................................................................ 20
2.3.2 Ionization energy ................................................................................................................... 22
2.3.3. Electron affinity .................................................................................................................... 25
2.3.4. Electronegativity ................................................................................................................... 27
2.3.5. Electrical conductivity ......................................................................................................... 28
CHAPTER III: ELECTRONIC STRUCTURE ..................................................................................... 30
3.1. Bohr’s model of an atom ............................................................................................................. 31
3.2. Atomic spectra............................................................................................................................. 32
3.3. Hydrogen spectra and spectra series ........................................................................................... 32
3.4. Energy levels, sub-energy levels and orbitals ............................................................................. 37
3.4.1. The three quantum numbers ................................................................................................. 37
3.4.2. Representation or shapes of orbitals ..................................................................................... 39
3. 4. 3 Electron spin and the Pauli Exclusion Principle .................................................................. 40
3. 4. 4. The aufbau method and electron configuration .................................................................. 40
3. 4. 4. Interpretation of a graph of ionization potential against the number of electrons. ............. 43
4.1. Ionic bonding............................................................................................................................... 45
4.1.1. Formation.............................................................................................................................. 45
4.1.2. Giant ionic structures ............................................................................................................ 46
4.1.2. Properties of ionic compounds ............................................................................................. 46
4.2. Covalent bonding ........................................................................................................................ 48
4.2.1. Formation.............................................................................................................................. 48

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 4.2.2. Properties of covalent compounds........................................................................................ 49
4.2.3. Covalent network solids ....................................................................................................... 49
4.2.4. Dative and coordinate bond .................................................................................................. 50
4.2.6. Shapes of molecules ............................................................................................................. 53
4.2.7. Polarity of molecules ............................................................................................................ 56
4.3. METALLIC BONDING AND THE PROPERTIES OF METALS ........................................... 57
4.3.1. Formation.............................................................................................................................. 57
4.3.2. Physical Properties of Metals ............................................................................................... 57
4.4. INTERMOLECULAR FORCES ................................................................................................ 59
4.4.1. Types of intermolecular forces ............................................................................................. 59
4.4.2. Effect of Intermolecular forces on melting and boiling points of molecular covalent
substances: ...................................................................................................................................... 61
4.4.3. Effect of Intermolecular Forces on Solubility ...................................................................... 63
5.1. CHEMISTRY OF GROUP I AND II ELEMENTS.................................................................... 64
5.1.1. Introduction .......................................................................................................................... 64
5.1.2. Physical properties of the elements ...................................................................................... 64
5.1.2. Chemical properties and reactions of elements .................................................................... 65
5.2. STUDY OF GROUP III ELEMENTS ........................................................................................ 68
5.2.1 Introduction ........................................................................................................................... 68
5.2.2 Physical properties of boron and aluminium ......................................................................... 68
5.2.3 Reaction of aluminium. ......................................................................................................... 68
5.2.4. Compounds of aluminium .................................................................................................... 69
5.2.5. Uses of some groupIII elements ........................................................................................... 71
5.3. GROUP IV ELEMENTS ............................................................................................................ 72
5.3.1. Comparative study of physical properties of group IV elements ......................................... 72
5.3.2. Allotropes of carbon ............................................................................................................. 72
5.3.3 Uses of group 4 elements....................................................................................................... 74
5.3.4. Reaction of C, Sn, Pb and Si. ............................................................................................... 74
5.3.5. Compounds of group IV elements ........................................................................................ 76
5.3.6. Diagonal relationship of group I, II, III and IV .................................................................... 79
5.4. GROUP V ELEMENTS.............................................................................................................. 81
5.4.1 Physical state and metallic character ..................................................................................... 81
5.4.2 Allotropes of phosphorus....................................................................................................... 81
5.4.3 Chemical properties of nitrogen and phosphorus .................................................................. 82
5.4.4 Preparation of nitrogen .......................................................................................................... 82
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 5.4.6 Chemical, properties of phosphorus compounds. .................................................................. 83
5.5 GROUP VI ELEMENTS ............................................................................................................. 84
5.5.1 Physical properties................................................................................................................. 84
5.5.2 Chemical properties of sulphur.............................................................................................. 84
5.6 GROUP VII ELEMENTS ............................................................................................................ 85
5.6.1 Comparative study of physical properties of halogens .......................................................... 85
5.6.2 Comparative study of chemical properties of halogens......................................................... 85
5.6.3 Uses of halogens .................................................................................................................... 88
5.7 GROUP VIII ELEMENTS........................................................................................................... 89
5.8 PERIOD III ELEMENTS............................................................................................................. 89
CHAPTER VI: CLASSIFICATION OF REACTIONS ...................................................................... 119
6.1. Introduction ............................................................................................................................... 119
6.2. Oxidation number...................................................................................................................... 119
6.3. Reactions in which oxidation state does not change or metathesis reactions ........................... 120
CHAPTER VII. TRANSITIONS ELEMENTS (FIRST SERIES) ...................................................... 125
7.1 General introduction ................................................................................................................... 126
7.2. General characteristics of transition metals .............................................................................. 128
7.3. Naming complex metal ions...................................................................................................... 139
7.4 Complex metal ions - ligand exchange reactions ....................................................................... 141
7.5. Complex ions - The acidity of the hexaaqua ions ..................................................................... 145
7.6. Reactions of hexaaqua metal ions with hydroxide ions ............................................................ 148
7.7. Uses of complex ions ................................................................................................................ 154
7.8. Chemical reactions of Chromium, manganese, cobalt, iron, copper, and zinc with water and
mineral acids( HCl, HNO3, H2SO4) ................................................................................................. 155
CHAPTER VIII: IDENTIFICATION OF IONS/QUALITATIVE ANALYSIS. ............................... 158
8.1 Appearance ................................................................................................................................. 158
8.2 Procedure of carryng out flame tests .......................................................................................... 161
8.3. Confirmatory tests for some gases ............................................................................................ 162
8.4 Some examples of practical work about qualitative analysis ..................................................... 164
REFERENCES .................................................................................................................................... 175

3
GENERAL OBJECTIVES BY THE END OF SENIOR FOUR

By the end of senior four, students should be able to:

1. Describe atomic structure.

2. Explain the concept of isotopes.
3. Explain the variation trends of physical properties in the periodic table.
4. Establish the electronic configuration of elements using s, p, d and f-orbitals.
5. Explain the formation of various types of bonds.
6. Describe the different molecular shapes.
7. Describe the physical and chemical properties of elements in the periodic table.
8. Explain the preparation and uses of some elements and their compounds.
9. Define oxidation and reduction in terms of loss or gain of oxygen or hydrogen and in tems of
loss or gain of electrons.
10. Identify the substances that are oxidized and those that are reduced in a redox reaction.
11. Distinguish between oxidizing agent and reducing agent in a redox reaction.
12. Describe the chemical diversity shown by the transition elements.
13. Explain the properties of some transition element and their compounds.
14. Identify experimentally anions and cations from their various solutions and compounds.

4
CHAPTER 1: ATOMIC STRUCTURE

GENERAL OBJECTIVES

By the end of this chapter, students should be able to:

a) Describe atomic structure.

b) Explain the concept of isotopes

SPECIFIC OBJECTIVES

 Define an atom
 Describe the structure of an atom.
 Distinguish between relative atomic mass and isotopic mass of an atom.
 Calculate the relative atomic mass using isotopic masses and relative abundance.
 State the functional of each part of mass spectrometer.
 Explain how the mass spectra are obtained
 Interpret a mass spectrum.

CONTENTS

1.0. General introduction and definition of an atom

Chemistry is defined as a study of matter and how matter behaves .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 that 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. Each element is made of tiny particles called atoms.

2. The atoms of a given element are identical; the atoms of different elements are different in
some fundamental way or ways

3. Chemical compounds are formed when atoms combine with each other. A given compound
always has the same relative numbers and types of atoms.

4. Chemical reactions involve reorganization of the atoms-changes in the way they are bound
together. The atoms themselves are not changed in a chemical reaction.

1.1. PARTICLES WHICH CONSTITUTE AN ATOM

PROTON (p)
5
It is an atomic nucleus constitutive particle

Properties

 It has got a positive charge (+1) equal to 1.6*10-19C (coulomb)

 It has got a mass of 1.672*10-24 g which is almost 1 amu (atomic mass unit).

NEUTRON (n)

It is an atomic nucleus constitutive particle

Properties

 It has got no charge

 It has got a mass of 1.674*10-24 g which is almost 1 amu (atomic mass unit).

ELECTRON (e-)

It is a particle moving around the nucleus at a distance that is large relative to the nuclear radius.

Properties

 It has got a negative charge (-1) equaling to 1.6*10-19C

 It has got a mass of 9.1*10-28 g, they are 1840 times less light than a hydrogen atom

Electrons have no detectable shape or structure and are a universal constituent of any element.

An important question to consider at this point is, “if all atoms are composed of these same
components, why do different atoms have different chemical properties?”

The answer to this question lies in the number and the arrangement of the electrons.

The electrons comprise most of the atomic volume and thus are the parts that “intermingle” when
atoms combine to form molecules. Therefore, the number of electrons possessed by a given atom
greatly affects its ability to interact with other atoms. As a result, the atoms of different elements,
which have different numbers of protons and electrons, show different behavior.

Note.

 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, or, alternatively, the mass number (A)

 Electrons, neutrons, and protons are elementary particles—that is, they are among the smallest
parts of matter that scientists can isolate.

 Since the absolute value of the charge of a proton is the same as that of an electron, the atom is
electically neutral because the number of protons an atom has got equals that of electons
surrounding its nucleus.

 As the mass of electron is negligeable, the mas of an atomis concentrated in its nucleus.

6
Table 1.1: The mass and charge of sub-atomic particles

Particle Charge/C Relative charge Mass/Kg Mass/u

Proton +1.6022×10-19 +1 1.6726×10-27 1.0073
Neutron 0 0 1.6750×10-27 1.0087
Electron -1.6022×10-19 -1 9.1095×10-31 5.4858×10-4

Assignment: Read and write a summary about discovery of atomic particles.

ATOMIC PARTICLES DISCOVERY

PROTON DISCOVERY

The proton has been discovered by Ernest Rutherford noticed that, when he shot alpha particles into
nitrogen gas, being knocked off by the impact of the alpha particle, producing 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.

Discovery that a proton is present in all other nuclei as an elementary particle led Rutherford to give it
a special name as a particle, the proton, after the neuter singular of the Greek word for "first", πρῶτον.

NEUTRON DISCOVERY

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 indeed
fundamental parts of every atom.

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ATOMIC NUMBER AND ATOMIC MASS

a. Atomic number, Z

It shows:

 the number of electrons 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 20 th place in the periodic table.

b. Atomic mass, 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 occupythe same place on the periodic table since they have
the same number of protons and electrons.

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.

An other notation is AZX where A is the atomic mass, Z atomic number and X is the element symbol.

8
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 M 1,
M2, M3,…, Mn, the relative atomic mass(RAM) is given by the following equation:

Worked example:

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 37 Li and 7.42% for 36 Li . Determine
the relative mean mass of lithium?

1.3. Description of mass spectrometer

Mass spectrometer is an instrument that separates atoms and molecoles according to their mass 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 which occurs in magnetic field.

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 although electrically neutral ones aren't.

9
The sequence is:

Stage 1: Ionization

The atom is ionized by knocking 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.

Stage 2: Acceleration

The ions are accelerated so that they all have the same kinetic energy.

Stage 3: Deflection

The ions are then deflected by a magnetic field according to their masses. The lighter they are, the
more they are deflected.

The amount of deflection also depends on the number of positive charges on the ion - in other words,
on how many electrons were knocked off in the first stage. The more the ion is charged, the more it
gets deflected.

Stage 4: Detection

The beam of ions passing through the machine is detected electrically.

A full diagram of a mass spectrometer

ACCELERATION
IONIZATION
electromagnet

to vacuum pump
vaporized sample

DEFLECTION

DETECTION amplifier

chart
recorder

10
Understanding what's 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.

Ionization

electron trap

ion repeller electrons

vaporised
sample
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 to make 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.

Acceleration

final plate at 0 volts

intermediate plate

ionization chamber
at + 10,000 volts

ion beam

11
The positive ions are repelled away from the very positive ionization chamber and pass through three
slits, the final one of which is at 0 volts. The middle slit carries some intermediate voltage. All the ions
are accelerated into a finely focused beam.

Deflection

electromagnet

mixed ion ion stream C

stream

ion stream B
ion stream A

Different ions are deflected by the magnetic field by different amounts. The amount of deflection
depends on:

 The mass of the ion. Lighter ions are deflected more than heavier ones.
 the charge on the ion. Ions with 2 (or more) positive charges are deflected more than 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 talking about will have a charge of 1+.

Assuming 1+ ions, stream A has the lightest ions, stream B the next lightest and stream C the heaviest.
Lighter ions are going to be more deflected than heavy ones.

12
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 up electrons 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 on to
the ion (right hand diagram). That 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

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 on to 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 heavier 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 what called
mass spectrum.

13
Uses of mass spectrometry

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. Multiply 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

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.

14
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
diatomic molecular, 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 follow:
16-16
O2+ at 32 16-17
O2+ at 33
16-18
O2+ overlaps with 17-17
O2+ 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 99.1% O with 0.89% O with 0.01%
16
O with 99.1% P1= P2= P3= =0.01
17
O with 0.89% P3’= P4= 0.0001
18
O with 0.01% P5=
st
Therefore the height of 1 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

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

15
 Testing your knowledge and understanding

1. Bromine consists of two isotopes, 79Br (relative abundance 50.5%) and 81

Br (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 p eak
23.6

22.6

1.5

204 206 207 208

M ass number

3. When, H2, is analyzed in the mass spectrometer, three 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.

E
X
E
R
C
I
S
E 1. (a) A proton, a neutron and an electron all travelling at the same velocity enter a magnet field.
S 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

16
 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
(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 abundance/% 69 27 4
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 intensity 2.0 0.2 17.8 1.7
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
iii) use appropriate values from the data above to calculate the relative atomic mass of this
sample of noble gas.

17
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.

CONTENTS

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 liquid)
A fresh surface is shiny, corrosion can
occur.
Malleable (can be hammered) and ductile(
can be drawn into wire).
Conduct heat and electricity.
The oxides are basic.
Solids or gases (except bromine, a liquid).
Have no one characteristic appearance.
Shatter when attempts are made to change the
shape.
Are poor thermal conductors and electrical
conductors, with exceptions?
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

18
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 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 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).
19
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.

2.3. Variation of physical properties in Groups and Periods

2.3.1 Atomic radius

The radius of atom is defined as the distance of closest approach to another nucleus. Atomic radius is
equal to half the distance between the two nuclei in a bonded iodine atoms 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 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 (in nm 0.123 0.089 0.082 0.07 0.066 0.064

20
 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 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 radius increases on descending any 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

Element Sc Ti V Cr Mn Fe Ca Ni Cu Zn

Radius in 0.16 0.15 0.14 0.13 0.14 0.13 0.13 0.13 0.13 0.13
nm
Trend

Among the transition elements, the atomic radius remains almost the same.

21
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. Radius

Fe (atom) 1.17oA

Fe2+ 0.76oA

F3+ 0.64oA

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 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
st th
Ionization energy increases from 1 to the 4 electron. The first two electrons are easily removed.

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 2 nd electron.
3) The energy to remove the 4th electron is about 1.5 times than of the 3rd.

22
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 3 rd electron comes from
a different shell of electrons. The electronic configuration of beryllium is presented as 2:2 or 1s 22s2.
Therefore beryllium has two electrons in its lower level which are very near to the nucleus 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
1st I.E./kJmol-1 520 899 801 1086 1403 1310 1981 2080

Period III

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

23
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

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

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.

24
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
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 3 rd
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 2 nd 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 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 charge 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 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 2 nd electron affinity is

25
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.

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.

a. Variation of electron affinity across a period

e.g. Period II

Element Na Mg Al Si P S Cl
Electron affinity in -20 +67 -30 -135 -60 -200 -346
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.

26
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-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.

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.

27
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 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.

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
28
 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 Point Boiling Point

(K) (K)
Lithium 453 1615
Sodium 370 1156
Potassium 336 1032
Rubidium 312 961
Caesium 301 944
Francium 295 950
E
X
E
R
C
I
S
E 1. The following table shows the ionization energies( in kJ mol-1) of five elements lettered A, B,
S C, D and E
Element 1st I.E 2nd I.E 3rd I.E 4th I.E
A 500 4600 6900 9500
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 I.E 2nd I.E 3rd I.E 4th I.E 5th I.E 6th I.E 7th 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.
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:
29
 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 number 11 12 13 14 15 16 17 18
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
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
30
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

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.
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

31
 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.

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

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 E f, the
light absorbed must have a frequency given by Planck’s equation

hν  Ef  Ei  ΔE whereν isa frequencyin Hz or s-1

h isa Planck's cons tant(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 
Beca us eE  h , we ha ve
 1 1 
E  h  R H  2  2 
n 
 i nf 

In this expression, ni and nf represent the quantum numbers for the initial and final states, respectively.

32
Note

 When the final state quantum number (n f) is larger than the initial state quantum number (n i)
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 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

33
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

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

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.

34
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

 1 1 
1
 RH   where1 a nd2 a repos i ti vei ntegerss howi ngenergyl evel s
λ  n2 n2 
 i f 
λ , i sa wa vel ength, nd
RH i sa Rydberg's cons ta nt(1.097  107 m1
Lyma ns eri es
 1 1 
 RH    , where nf  2,3,4,...
1
λ  12 n2 
 f 
Ba l mers eri es
 1 1 
1
 RH   , where nf  3,4,5,...
λ  22 n2 
 f 
Pa s chens eri es
 
the 1  R  1  1  , where n  4,5,6,...
H 2
λ
3 n2f  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.
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  h But ν   En  En1  and En and En1 are two s ucces i veenergyl evel s
λ λ
c i sa cel eri tyc  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

35
  1 1  R  1 1 
Subs ti tuting ni = 4 a nd nf = 2 i n E  R H  2  2     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  can be used to calculate the wavelength of the radiation ()
C 3.00  10 8 m/s
λ 
ν 6.17  1014 /s
 4.86  10 7 m  486nm

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 , Thisi s jus tequalto RH , 2.18  10 -8 J
It i softenus efulto expres sthisenergyon a molarbas i sTo
. thiswe s i mplymultipl yby 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)

36
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 are whole numbers which theorically can vary from 1 to (1, 2, 3, …)

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

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
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 orbitals in

designation subshell
1 0 1s 0 1

37
2 0 2s 0 1
1 2p 1, 0, -1 3

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

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

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 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

38
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.

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

39
Note that the f orbitals are difficult to represent in three-dimensional contour diagrams.

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 m s). 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.

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
40
 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.

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
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
[He]2s1 [He]2s2 [He]2s22p1 [He]2s22p2 [He]2s22p3 [He]2s22p4 [He]2s22p5 [He]2s22p6

11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
[Ne]3s1 [Ne]3s2 [Ne]3s23p1 [Ne]3s23p2 [Ne]3s23p3 [Ne]3s23p4 [Ne]3s23p5 [Ne]3s23p6

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.

41
 3. The diagram below remembering the order of filling of orbitals to build up the electronic
configuration of any atom.

1s
Any time you have to write an electronic
structure of any element; please remember
2s 2p this diagram!!!

3s 3p 3d

4p 4d 4f
4s

5s 5p 5d 5f Notice that the energy levels are not exactly

in numerical order. For example the 4s
subshell is at a lower energy level tan the 3d
6s 6p 6d 6f subshell.

7s 7p 7d 7f

The ground state electron structures of the first 36 elements in the periodic table

Z Symbo 1s 2s 2p 3s 3p 3d 4s 4p
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
10 Ne 2 2 6
11 Na 2 2 6 1
12 Mg 2 2 6 2
13 Al 2 2 6 2 1
14 Si 2 2 6 2 2
15 P 2 2 6 2 3
16 S 2 2 6 2 4
17 Cl 2 2 6 2 5
18 Ar 2 2 6 2 6
19 K 2 2 6 2 6 1
42
20 Ca 2 2 6 2 6 2
21 Sc 2 2 6 2 6 1 2
22 Ti 2 2 6 2 6 2 2
23 V 2 2 6 2 6 3 2
24 Cr 2 2 6 2 6 5 1
25 Mn 2 2 6 2 6 5 2
26 Fe 2 2 6 2 6 6 2
27 Co 2 2 6 2 6 7 2
28 Ni 2 2 6 2 6 8 2
29 Cu 2 2 6 2 6 10 1
30 Zn 2 2 6 2 6 10 2
31 Ga 2 2 6 2 6 10 2 1
32 Ge 2 2 6 2 6 10 2 2
33 As 2 2 6 2 6 10 2 3
34 E 2 2 6 2 6 10 2 4
35 Br 2 2 6 2 6 10 2 5
36 Kr 2 2 6 2 6 10 2 6

3. 4. 4. Interpretation of a graph of ionization potential against the number of electrons.

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

43
 • 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

• 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
1. Consider elements A and B with the electron configuration 1s22s22p63s23p64s23d5 and [Xe]6s1
S
respectively. In what period and group is each of the elements A and B belong?
E
2. Write the electronic configuration of the elements or ions below
S
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.

CHAPTER IV: 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

44
  Interpret hybridization of hybrid orbitals
 Explain the formation of sigma and pi bonds in the single, double and triple bonds
 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.

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

45
 -
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 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 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.

46
  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 Point Cation Anion

Compound (oC) Charge Charge
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 Compound Melting Point (oC) Cation 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

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 Ions very poor good good
Electrical very poor good good
Conductivity

47
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

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

Note
48
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

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.

49
Case of Carbon

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

graphite diamond
structure

bonding each carbon atom makes 3 each carbon atom makes 4

covalent bonds covalent bonds
structure carbon atoms in a hexagonal carbon atoms in a
arrangement forming layers tetrahedral arrangement

melting very high (sublimes at very high (~4000K) due to

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

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)

50
  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

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 4sp 3 orbitals has one unpaired electron
such that they repel each other to the maximum angle of 109.5o

51
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.

H 120o H

C C
H ethene H

- Pi- bond: sideways overlap of two p-orbital

(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)

52
 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 always 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
 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 single 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

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,…

53
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 107 o
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 2.5 o

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

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 AX 2E1 as bent means that AX2 is
a bent molecule without reference to the lone pair, although the lone pair helps to
determine the geometry.

54
Molecule Shape Electron Geometry‡ Examples
Type arrangement†
AX1En Diatomic HF, O2

AX2E0 Linear BeCl2, HgCl2, CO2

AX2E1 Bent NO2−, SO2, O3

AX2E2 Bent H2O, OF2

AX2E3 Linear XeF2, I3−

AX3E0 Trigonal planar BF3, CO32−, NO3−,

SO3

AX3E1 Trigonal NH3, PCl3

pyramidal

AX3E2 T-shaped ClF3, BrF3

AX4E0 Tetrahedral CH4, PO43−, SO42−,

ClO4−

AX4E1 Seesaw SF4

AX4E2 Square planar XeF4

55
AX5E0 Trigonal PCl5
bipyramidal

AX5E1 Square pyramidal ClF5, BrF5

AX6E0 Octahedral SF6

† Electron arrangement including lone pairs.

‡ Observed geometry (excluding lone pairs)

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

A. 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.

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.

56
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.

B. 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 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 without breaking) , ductile
(able to be drawn into a wire) ,metallic lustre and opaque (reflect light).

57
  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 (10 6Ohm-1cm-1) of the metals lithium to indium.

Alkali
Alkali Group
Earth Transition Metals
Metals III
metals
0.108 0.313
0.210 0.226 0.377
0.139 0.298 0.017 0.023 0.048 0.077 0.006 0.093 0.172 0.143 0.596 0.166 0.067
0.077 0.076 0.016 0.023 0.069 0.187 0.067 0.137 0.211 0.095 0.630 0.138 0.116

 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.

Alkali
Alkali Group
Earth Transition Metals
Metals III
metals
180.7 1,278
98 650 660
63.35 839 1,539 1,660 1,902 1,857 1,246 1,535 1,495 1,453 1,085 419.73 30
39.64 769 1,526 1,852 2,468 2,617 2,200 2,250 1,966 1,552 961 321 157

58
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.

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

59
 a) Dispersion Forces (London Forces or Weak Intermolecular Forces or van der Waal's
Forces)

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).

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).

60
 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 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 attraction between the
molecules resulting in higher boiling points?

61
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 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

62
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 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
1. (a) Predict whether each of the following molecules possesses a net dipole moment
S
CCl4, NF3, SO3
E
(b) Predict whether the following molecules are polar or non polar
S 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
63
 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

CHAP V: COMPARATIVE STUDY OF CHEMICAL REACTIONS OF ELEMENTS IN THE

PERIODIC TABLE

OBJECTIVES

By the end of this chapter students should be able to:

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)

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.

64
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 4 th 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

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

b) Reaction with chlorine

Group 1:

All react vigorously to form ionic chlorides of formula MCl. These dissolve in water to produce
hydrated ions,
65
e.g : NaCl (s) → Na+(aq) + Cl-(aq)

Group 2:

All react vigorously to produce ionic chlorides of formula MCl 2, 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.

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) + 2OH-(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 with 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)

66
 g) Solubility of group 2 sulphates and hydroxides

 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:

 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.

67
EXERCICES

Which group 1 metal has the highest melting temperature?

1. 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?
2. Explain why the 1st I.E of sodium is larger than the 1st I.E of potassium.
3. 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
4. State and explain with group 2 element forms the least thermally stable carbonate
5. 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
6. 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.

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.

68
 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
2Al(s) + 6H2SO4(aq) → Al2(SO4)3(aq) + 3SO2(g) + 6 H2O(g)

Note: Aluminium does not react with HNO 3 because of the insoluble layer of Al 2O3 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:

Aluminium shows an oxidation state of +3 in most its compounds.

Because of high charge (large positive) and small ionic radius, Al 3+ 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.

69
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

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)

70
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)
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.

71
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 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 ns 2np2 promoted to
ns1np3 and thus they are able to form 4 covalent bonds with the structure of their resultant
compound being tetrahedral.

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.

72
 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.

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

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

73
5.3.3 Uses of group 4 elements
1. Silicon
Silicon occurs naturally as silicon (IV) oxide, silica, SiO 2, 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.
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).

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)

74
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

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 PbCl 2

Pb(s) + 2HCl(aq) → PbCl2(aq) + H2(g)

Note that silicon does not react with any mineral acid.

d) Reaction with alkalis

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)

75
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)

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)

SnO2(s) + 4H+ → Sn4+(aq) + 2H2O(l)

PbO2(s) + 2OH-(aq) → PbO32-(aq) + H2O(l)

PbO2(s) + 4H+(aq)(cold) → Pb4+(aq) + 2H2O(l)

76
 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)

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)

77
 I. MX4

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.

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 PbCl 2 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-
78
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).

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
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)
79
 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
 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
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

80
 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
 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
The white phosphorus molecule.

Red phosphorus: is a microcrystalline, nonpoisonous powder. It sublimates (passes from the solid
state directly to the gaseous state) at 416°C.

81
 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

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

82
 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
 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)

I2(s) + 10HNO3(l) → 2HIO3(aq) + 10NO2(g) + 4H2O(l)

P(s) + 5HNO3(l) → H3PO4(aq) + 5NO2(g) + H2O(l)

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.
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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).

 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

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)

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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 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)

85
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)

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-(aq) No reaction No reaction No reaction
Bromide, Br-(aq) Yellow-orange Br2 No reaction No reaction
released
Iodide, I-(aq) Black-dark brown I2 Black-dark brown I2 No 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.
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  Reaction of the hydrides with concentrated sulphuric acid
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.
 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 in presence Addition of ammonia solution
of nitric acid
Chloride White precipitate of silver Precipitate dissolves; clear
chloride is observed solution is observed
Ag+(aq) + Cl-(aq) → AgCl(s)
Bromide Pale yellow precipitate of silver Precipitate partly dissolves
bromide is observed
Ag+(aq) + Br-(aq) → AgBr(s)
Iodide Yellow precipitate of silver Precipitate does not dissolve
iodide is observed
Ag+(aq) + I-(aq) → AgI(s)

87
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.
 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
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;
88
 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.

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

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 Cl 2 < 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

89
 Explanation: Melting and boiling points decrease from NaCl through MgCl 2 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
Pol a ri zi ngpowerNa   10.5
0.095
2
Pol a ri zi ngpowerof Mg 2   30.7
0.065
3
Pol a ri zi ngpowerof 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)

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

90
ATOMIC AND PHYSICAL PROPERTIES OF THE PERIOD 3 ELEMENTS

1. ATOMIC PROPERTIES

a) Electronic structures
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.

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;
91
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.

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 3p x2 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

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.

92
 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 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

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.

93
 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.

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.

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.
94
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 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.
95
The sizes of the melting and boiling points are governed entirely by the sizes of the molecules.

 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

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)

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  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

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

 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:

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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

 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

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  Chlorine and argon

Despite having several oxides, chlorine won't react directly with oxygen. Argon doesn't react either.

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 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.

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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.

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.

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.

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  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

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.

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.

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 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 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.

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, O 2-, which
is a very strong base with a high tendency to combine with hydrogen ions.

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 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.

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

 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.

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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

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

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

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 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:

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.

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4NaOH + P4O6 + 2H2O → 4NaH2PO3

P4O6 + 6H2O → 4H3PO3

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.

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.

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  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:

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:

Sulphuric acid is a strong acid, and solutions will typically have pH's of around 0.
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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.

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.

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:

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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

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.

109
 a) The structures

Sodium chloride and magnesium chloride are ionic and consist of giant ionic lattices at room
temperature

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.

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:

110
This is normally drawn in an exploded form as:

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.

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.

111
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.

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 Al 2Cl6 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 AlCl 3 molecules. As the temperature
increases further, the position of equilibrium shifts more and more to the right.

Al2Cl6 2AlCl3

Summary

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  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 AlCl 3 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.

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 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.

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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), PCl 3

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.

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), PCl 5

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 PCl 5.

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 PCl 5
molecules. Because there are 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.

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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, POCl 3, 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.

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.

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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.

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:

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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.
 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.

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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.

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.
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.

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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.
 State common reducing and oxidizing agents and their behavior in half and overall redox
equations.

CONTENTS

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

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.
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 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

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.
or as oxidation with electrons on the right hand side of the equation,
e.g. Fe (aq) → Fe3+(aq) + e-, here iron(II) ions are being oxidized, and thus are acting as a reducing
2+

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-

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  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,
e.g. MnO4 + 5e- → Mn2+, a process in which the element Mn 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

A balanced equation for a reduction-oxidation process has H and O = 0 for the individual half
reactions and e- = 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 4 oxidising oxalic acid to CO2 in an acid medium:

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

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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 O = 0), then adding H+ to
the side deficient in H (so that H = 0). Now H and O = 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).

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 H = 0, O = 0 and e- = 0:

Reduction: 2( MnO 4 + 8H+ + 5e- → Mn2+ + 4H2O)

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

Overall reaction: 2 MnO 4 + 5(COOH)2 + 6H+ 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.

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 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 H 2O). To balance for O add
OH- to the side with a deficit of O (so that O = 0). To balance for H add H2O on the other side (so
that H = 0). We must add sufficient OH- to form H2O from all excess H (i.e. H+ cannot 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-
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;

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 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.
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) c)
H
O
(+2)
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

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 Cr2O72 in acid solution to form a brown-black deposit of I2 in a
green solution.
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 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 4 + ClO2- → MnO2 + ClO4- (neutral medium)
iii) CrO2- + H2O2 → CrO42- + 2H2O (basic medium)
iv) Cu + SO42- → Cu2+ + SO2 (acidic medium)
v) Cl2 → 2 Cl - + 2ClO3- (neutral medium)
vi) SO2 + IO3- → SO42- + I- (basic medium).
E
X
E 1. Showing all steps, balance the following equations by using half equation method
R
C 1. K2Cr2O7 + H2O + S → KOH +Cr2O3 +SO2
I 2. S+HNO3 → SO2 +NO + H2O
S 3. KMnO4 + Na2C2O4 + H2SO4 → K2SO4 + MnSO4 + Na2SO4 + CO2 +H2O
E 4. KMnO4 + SO2 + KOH → K2SO4 + MnO2 + H2O
5. Cu +HNO3 → Cu(NO3)2 + NO + H2O
S
6. K2Cr2O7 + HCl → Cl2 + CrCl3 +KCl +H2O
7. CaC2O4 + KMnO4 +H2SO4 → Ca SO4 +MnSO4 + K2SO4 + H2O + CO2
8. K2Cr2O7 + KBr + HCl → CrCl3 + Br2 + KCl + H2O
9. KMnO4 + HCl → 2 MnCl2 + Cl2 + KCl + 8H2O

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.
 State the applications of complex ions.
 Explain the chemical reactions of transitions elements
 Describe the properties of oxides, hydroxides and oxoanions of transition elements.
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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)

Writing electronic configurations.

In their electronic structure, after the 2nd energy level, an overlap starts occurring between 3 rd 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
sub-shell( has between 1 and 9) electrons in the 3d sub-shell.

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 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:

 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, Fe 2+ and Fe3+ are the following:

127
 3d 4s

Fe(ground state) : [Ar]

Fe2+ [Ar]

Fe3+ [Ar]

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

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.

128
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 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)

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

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 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 state 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.

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.
 Diamagnetic substance is a substance that lacks any unpaired electrons and hence does not
respond to the supplied magnetic field.

130
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 Fe 2+ 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.

Transition metal forms complexes because:

i) of their small and highly charged ions

ii) of the presence of vacant d-orbitals which can accommodate lone pair of electrons.

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 be 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 monodentate or unidentate) 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

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.

131
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 (edta 4- or EDTA4- or Y4-) is an important example of
hexadentate ligand

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.

132
Examples:

 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+, …

CH2 CH2 2+
2+ H2N NH2
H3N Cu
NH3
Cu
H2N NH2
H3N NH3
CH2 CH2

 Most ions have coordination number of 6.

Example: [Cr(H2O)6]3+, [Cr(NH3)6]3+, [Cr(H2O)4Cl2]-, …

 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 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]+,…
H3N 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

133
 In Pt(NH3)2Cl2, the platinum, the two chlorines, and the two nitrogens are all in the same plane

Cl

NH3 Pt Cl

NH3

Pt(NH3)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

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.
134
 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

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.

135
 Cl
NH3

H3N 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.

Example 1: The structures of cis and trans isomers of [Co(NH3)4Cl2]

Cl
Cl
NH3
NH3
Cl H3N
Co
Co
H3N NH3
H3N NH3

NH3 Cl

Cis Trans

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 complex
must contain two different ligands, with two of one ligand and two of another.

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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-

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.

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  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 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 properties Uses
composition
Brass Cu 60, Zn 40 Harder than copper
but just as corrosion-
resistant
Bronze Cu 85, Sn 15 As for brass Statues, plaques,
ships’propellers
Cupro-nickel Cu 75, Ni 25 As for brass, looks Silver coins
silverly
Duralumin Al(95), Cu(4), Traces Density just as low as Aircraft construction
of Mn and Mg aluminium or
Magnalium Al(70), Mg(30) magnesium but much
stronger and more
corrosion-resistant
Solder Pb(67), Sn(33) Harder than lead and
has an even lower
melting
Steel Fe(98), C(1), Traces Much stronger than
of other metals iron
Invar steel Fe(63), Ni(36), trace Much lower In thermostats and
of C coefficient of clock pendulums
expansion than iron
Stainless steel Fe(85), Cr(14), Ni(1) Harder than ordinary
steel and much more
corrosion-resistant

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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 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

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.

139
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.

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 Cu 2+ - 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

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.
140
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]+

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

141
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 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

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.
142
  Replacing the water in the hexaaquacopper(II) ion

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:

small amount an excess

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.

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.

143
  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.

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.

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.
144
  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+.

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.

 The general explanation

A closer look at the distribution of charge in the ion

145
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+
H2O

H2O OH2

Fe

H2O OH2
OH2

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+

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:

146
 [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

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 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.

147
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.

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.

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

148
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

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

[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

149
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 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:

150
 [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.

151
 I. 2+ ions
 hexaaquacobalt(II)

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.

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.
152
  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]-

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)

153
  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

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+

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.
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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.
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 Cr 3+ salt.

4Cr2+(aq) + 4H+(aq) + O2(g) → 4Cr3+(aq) + 2H2O(l)

Hot concentrated sulphuric oxidizes the chromium to Cr 2(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)

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)

155
 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.

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)

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)
156
 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)
Zn(s) + H2SO4(aq) → ZnSO4(aq) + H2(aq)
Reaction with conc. H2SO4 or HNO3 produces products which depend on the conditions of
reaction.

EXERCISES

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

(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:

157
 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.
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:

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
Purple colour Permanganate
158
Pink colour Hydrated salts of manganese
Yellow colour Chromate or ferric salt
Green colour Ferrous, copper, nickel or chromic salt
Blue colour Hydrated cupric salts
Brown colour Metal oxide
Smell of ammonia Ammonium salt
Smell of hydrogen sulphide Sulphide
Smell of sulphur dioxide 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 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
sodium
(v) Nitrogen dioxide Nitrate other than that of sodium, potassium.

(vi) Sulphur dioxide Thiosulphate, sulphite or sulphate

(vii) Ammonia Ammonium salts

(viii) Hydrogen chloride Certain hydrated chlorides
(ix) White sublimate Ammonium salts
(xiv) Residue

(a) Yellow hot, white cold Zinc oxide, Zn2+

(b) Brownish/red hot, yellowish brown cold Lead monoxide, Pb2+
(c) Black hot reddish brown cold. Ferric oxide, Fe3+ from Fe2+
(d) Black Copper or Manganese oxide, Cu2+ or Mn4+
(e) Dark green 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 evolved Basic oxide
(ii) Yellow solid dissolves giving orange Chromate
solution
(iii) White precipitate Insoluble chlorides(or sulphates)
(iv) Carbon dioxide Carbonates or bicarbonates
(v) Nitrogen dioxide Nitrates
(vi) Sulphur dioxide Sulphite

159
 3) Barium chloride solution

Observation Deduction
(i) White precipitate Carbonate, Sulphates or Sulphites
(ii) A yellow precipitate 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, Carbonates,
(ii) Red precipitate 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

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 heating
Ba2+ White precipitate Insoluble
Mg2+ White precipitate Insoluble
Ca2+ White Precipitate (from conc. Insoluble
solution.)
Mn2+ White precipitate Insoluble, turns brown on standing
Al3+ White precipitate Soluble
Zn2+ White precipitate Soluble
Pb2+ White precipitate Soluble
Cr3+ Green precipitate Soluble to give green solution
Fe2+ Green precipitate Insoluble, turns brown on standing
Ni2+ Green precipitate Insoluble
Fe3+ Brown precipitate Insoluble
Co2+ Blue precipitate Insoluble turning pink
Ag+ Brown precipitate(Ag2O) Insoluble
Cu2+ Blue precipitate Insoluble, turns black on heating.
Sn2+ White precipitate Soluble

6) Ammonia solution

This reagent precipitates hydroxides. On adding excess some cation form soluble AMMINE
complexes.

160
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 standing
Zn2+ White precipitate Soluble
Fe3+ Brown precipitate Insoluble
Ag+ Brown precipitate(Ag2O) Soluble
Fe2+ Green precipitate Insoluble, turns brown on standing
Ni2+ Green precipitate Soluble , forming blue solution
Cr3+ Grey-green precipitate Slightly soluble forming pink/violet solution
Cu2+ Blue ppt Soluble forming deep blue solution
Co2+ Blue ppt Soluble turning pink
Sn2+ White ppt 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
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( fumes Irritating Red
in moist air)
NO2 Redish- brown Irritating Red
HNO3 Pale Irritating Red
yellow(vapour
fumes) Red
SO3 White fumes Irritating Red, then
SO2 None Rusting sulphur bleached
H2S None Rotten eggs Faint red

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NH3 None Characteristic & Blue
Choking
H2 None None in pure None

O2 None None Faint red

CO2 None None None

N2 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 ion Symbol Action on heat Conc/dilute Diluted HCl Confirmatory Test
H2SO4
Carbonate CO32- Odorless gas which Odorless gas Odorless gas Dilute HCl (as indicated
evolves turns lime turns lime turns lime under dilute HCl) or
water milky and water milky water milky Silver nitrate followed
blue litmus paper ,and blue ,and blue by dil. HCl, a white ppt
red. The gas is CO2 litmus paper litmus paper soluble in acid confirms
turns red turns red a carbonate.
Sulfate SO42- Colorless gas with - - Add BaCl2 solution
pungent smell. followed by HCl, a
Turns dichromate white precipitate
paper from orange insoluble in acid
to green. Gas is SO2 confirms a sulfate.
Sulphite SO32- Colorless gas with - - Add BaCl2 solution
pungent smell. followed by HCl, a
Turns dichromate white precipitate
paper from orange soluble in acid confirms
to green. Gas is SO2 a sulfite.
thiosulphate S2O32- - - - Add iodine solution,
the brown of iodine is
discharged
Mono HCO3- - - - Add MgSO4 solution,
hydrogeno no precipitate formed
carbonate but with CO32- a white
162
 precipitate is formed
immediately.
Nitrates NO3- Brown gas with - - To the solid, add conc.
pungent smell ,turns H2SO4 and warm
blue litmus red gently. Evolution of
whitish brown fumes
which condense into an
oily liquid at the sides
indicates a nitrate.
Chloride Cl- Pungent and Colorless, No Add 2-3 drops of
chocking colorless pungent and observable aqueous silver nitrate
gas fuming in air. chocking in change followed by excess
white fumes with air. white nitric acid; add
NH3 vapour fumes with ammonia, a white
NH3 vapour precipitate which
dissolves in ammonia
solution confirms a
chloride.

B. Cations

Name of Symbol of Sodium Ammonia Dil/conc Diluted Confirmatory Test

ion ion hydroxide solution H2SO4 HCl
solution
Manganese Mn2+ White White - - To test solution adds
precipitate precipitate few drops of
turns turns Conc.HNO3 followed
brown due brown soon by a small quantity of
to aerial brown due solid sodium
oxidation to aerial bismuthate and boil, a
oxidation purple colouration
confirms Mn2+.
Zinc Zn2+ White White - - White precipitate
precipitate precipitate dissolves both in
soluble in soluble in sodium hydroxide
excess excess and ammonia solution
Ammonium NH4+ No - - - Add sodium
observable hydroxide solution
change and warm. A colorless
pungent smelling gas
turns red litmus blue
and gives dense white
fumes with HCl
vapour.
Magnesium Mg2+ White ppt White ppt - - Magnesium reagent.
insoluble in insoluble in (few drops of
excess excess magneson followed by
little NaOH solution),
a blue ppt confirms
Mg2+
Calcium Ca2+ White ppt No Addition of ammonia
163
 insoluble in observable White ptt solution followed by a
excess change with dilute few drops of
surphuric (NH4)2C2O4 a white
acid ppt is formed of
CaC2O4
Barium Ba2+ White ppt No - To the test solution,
insoluble in observable White ptt add potassium
excess change with dilute chromate solution, a
surphuric yellow ppt of
acid BaCrO4is formed
Aluminium Al3+ White ppt White ppt - - Addition of few drops
soluble in insoluble in of KI solution, no
excess excess formation of yellow
ppt or the no
observable change
confirms Al3+
Iron Fe2+ Green ppt Green ppt - - Gives a deep blue ptt
turns turns with potassium
brown in brown in hexacyanoferrate (III)
air air solution
,insoluble ,insoluble
in excess in excess
Fe3+ Brown ppt Brown ppt - - Addition of potassium
insoluble in insoluble in thiocyanate to test
the excess the excess solution, a lood –red
color observable
Chromium Cr3+ Green ppt Green-grey - - To solution add H2O2
soluble in ppt solution adding
excess to insoluble in NaOH. CrO42-is
form a excess formed. Then add
green Pb(NO3)2 solution, a
solution yellow ppt confirms
Cr3+ or adding few
drops of butanol
followed by 3 drops of
dil.H2SO4, formation
of deep blue lake
solution confirms Cr3+
Lead Pb2+ White ppt White ppt White ppt Add KI solution,
soluble in soluble in White ppt White yellow ppt is
excess excess of PbCl2 formed or dil HCl,
white ppt is formed.

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.

164
Tests
1. Heat one spatula end-full of
Q in a dry test tube until there
is no further change
Observations
-Colorless vapor condenses on
cooler part of the test tube
-A colorless gas with pungent
smell ,turns red litmus blue
forms white fumes with HCl
Deductions
-Water vapor from hydrated
salt
- Ammonia gas(NH3) which
probably may come from
ammonium ion NH4+

-colorless gas with pungent

smell turns orange dichromate -sulfur dioxide(SO2) gas
paper green which may come from
sulfite(SO3-) or sulfate(SO42-)

- light green residue turns into

white powder ,then yellow, Fe2+ suspected
then reddish brown

2. Put 2 spatula end-fulls of Q Colorless solution with -Cr3+, Ni2+, Fe2+ are suspected
in a test tube, add about tendance to clear green. to be present.
5cm3of water and shake.
Divide the solution into five
portions

3. To the first solution add Green ppt insoluble in excess -Fe2+ is suspected
dilute NaOH, drop wise until and turns brown on standing , Ammonia gas , NH4+ is
the excess on heating gas turns red litmus confirmed.
blue and form white fumes
with Conc.HCl .
4.To second, add ammonia Green ppt insoluble in excess Fe2+ is most likely
solution drop wise until in
excess
5.To the 3rd solution add 2-3 A deep blue ppt Fe2+ confirmed
drops of potassium hexacyano
ferrate (III) solution
6. To the 4th add Lead (II) White ppt SO42-, Cl- suspected
nitrate solution followed by
dilute nitric acid
7. To the 5th add Barium White precipitate insoluble in SO42- confirmed.
chloride solution followed by dil.HCl
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 record your
observations and deductions in the table below. Identify any gas evolves.
165
TEST
1. A spatula end-full of D is
heated strongly in a teste tube
until there is no further change
2. A spatula end-full of D is
3
dissolved in about 5 cm and the solution.
resultant solution is divided into
four parts.
a) To the 1st part is added
ammonium hydroxide solution
drop wise until in excess
b) To the second part is added
dilute sodium hydroxide
solution dropwise until in
excess followed by 1cm3 of
10% hydrogen peroxide
solution and the resultant
mixture boiled and later cooled.
the resultant solution is then
divided into three portions
i) To the 1st portion is added
silver nitrate solution dropwise
until no further change takes
place.
ii) To the second portion is
added a drop of barium chloride
solution
iii) To the 3rd portion is added a The yellow solution turns orange
few drops of hydrochloric acid.
c) To the third part of the
solution is added a few drops of
butanol followed by 3 drops of
dilute H2SO4
d) To the fourth part was added A white ppt is formed
a few drops of lead nitrate
solution.
e) To the last part was carried a A white ppt insoluble in nitric
test of one’s own 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-
166
OBSERVATION
- Colourless vapour which
condenses on the cooler part of
the test tube.
- A colourless pungent gas
which turns potassium
dichromate green is formed.
- The residue is a dark green
solid.
D dissolves to give green
A green precipitate which
slightly dissolves to give a violet
solution.
A green ppt soluble in excess
NaOH to form a green solution.
On boiling with H2O2 a yellow
solution is formed with
evolution of a colourless gas
which relights a glowing splint.
A brick red ppt.
A pale yellow ppt.
A deep blue lake is formed
acid is formed
DEDUCTION
- hydrated salt present.
- Gas is SO2 probably SO32- or
SO42- salt present.
- D is a transition compound
probably containing Cr3+ or Ni2+
Probably D contains Cr3+, Ni2+,
Fe2+ or Cu2+.
Probably Cr3+ present
Cr3+ presence confirmed.
H2O2 oxidises Cr3+ in an
alkaline medium to yellow
chromate.
The gas is oxygen.
Silver chromate is formed.
Hence CrO42- compound
formed.
Barium chromate formed.
Hence CrO42- compound formed
A dichromate has been formed
from a chromate
Presence of Cr3+
Probably Cl-, CO32- or SO42-
present
Presence of SO42- confirmed.
 3) Substance K contains one cation and one anion
TEST OBSERVATION DEDUCTION
a) A spatula end-full of K is Colourless vapour condenses to hydrated salt.
strongly heated give a colourless liquid which Gas is hydrogen chloride and
turns anhydrous copper sulphate Cl- is most likely present.
blue and also turns litmus red
and forms white fumes whith
conc. ammonia. Green solid Black solid is CuO, FeO or
give a black solid residue MnO2
b) To a spatula end-full of Effervescence, a colourless gas, Hydrogen chloride gas.
K is added a few drops of turns litmus red and forms white Cl- is most likely present.
concentrated sulphuric fumes whith conc. Ammonia
acid then the mixture
heated
c) About two spatula end- K dissolves to give a green Fe2+, Cr3+, Cu2+ or Ni2+
full of k is dissolved in solution. suspected
about 5 cm3 of H2O.
The solution is then divided
into 3 portions
i) To the 1st portion is A pale blue ppt insoluble in Cu2+ suspected
added dilute sodium excess.
hydroxide dropwise until On heating the blue ppt forms a
in excess and the mixture black solid Black solid is CuO
heated
ii) To the 2nd portion is A red-brown ppt formed Cu2+ confirmed
added a few drops of
potassium
hexacyanoferrate(II)
solution
iii) To the 3rd portion is White ppt which dissolves on Cl- confirmed
added a few drops of heating and reappears on
lead(II) nitrate solution cooling
and the 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 of L is Colourless vapour condenses Water of crystallization; hence
heated gently first and to give liquid which turns hydrated salt.
then more strongly anhydrous copper(II) sulphate
blue.
167
 A white sublimate formed and
colourless gas which turns red Gas is NH3 hence NH4+
litmus blue and later turns the
blue litmus red and acidified Gas is SO2 hence SO42- or
potassium dichromate solution SO32-probably present
orange to green.
Residue is yellow but turns ZnO
white on cooling
b) Two spatula ends-full of White solid dissolves to give a Pb2+, Al3+, Zn2+, Ca2+, Ba2+,
L is dissolved in 5 cm3. colourless solution NH4+, or Mg2+ present
The resultant solution is
then divided into 4 parts.
i) To the 1st part is added White ppt soluble in excess. Zn2+, Pb2+, or Al3+
sodium hydroxide On warming a colourless gas
solution dropwise turns litmus blue Gas is NH3,NH4+ confirmed
solution until in excess
and mixture heated.
ii) To the 2nd part is added a A white ppt Zn2+ confirmed
few drops of potassium
hexacyanoferrate(II)
solution
iii) To the 3rd part is added A white ppt Cl-, SO42- or CO32- present
2-3 drops of lead(II)
nitrate solution and
mixture heated
iv) To the last part is added A white ppt SO42- confirmed
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-full of G Colourless vapour given off Water of crystallization.
is heated strongly until which turns anhydrous CuSO4 Hydrated salt.
no further change takes blue. The gas is NO2 and hence NO3-
place G decomposes to give thick present.
brown gas. The residue is probably CuO or
The residue is a black solid. MnO2
b) Two spatula end-full of The filtrate is a faint pink Filtrate probably contains Ni2+
G is shaken with about 8 solution. or Co2+
cm3 of water.
The mixture was filtered The residue does not contain a
and both the filtrate and The residue is a white solid transition element. Hence Ca2+,
residue kept. Pb2+, Sn2+, Al3+, Ba2+, or Mg2+
probably present.
c) The filtrate was divided
into four parts.
i) To the first part is added A dity white ppt insoluble in Presence of Mn2+ most likely
168
 dilute NaOH dropwise excess which turns brown is
until in excess formed
ii) To the second part is A white ppt insoluble in excess Mn2+ is most likely present
added dilute aqueous is formed. The precipitate turns
ammonia dropwise in brown
excess
iii) To the third part was A purple solution is formed The Mn2+ is oxidized by PbO2
about some lead(VI) in the presence of conc. HNO3
oxide followed by about to purple MnO4-. Hence
0.5 cm3 of conc.HNO3 presence of Mn2+ in the filtrate
and the mixture boiled. is confirmed.
iv) The last part was used
for carrying out a test of
one’s choice to confirm
the anion in the filtrate.
Test: To the last part is A brown ring forms at the
added about 1 cm3 of junction of the liquids NO3- presence is confirmed
iron(II) sulphate solution.
Conc. H2SO4 is then slowly
added down the side of the
test tube.
d) The residue is washed The residue dissolves to give a Probably Pb2+, Zn2+, Al3+, Mg2+,
and dilute HNO3added colourless solution and Ca2+ present
dropwise until no further
change occurs. The
resultant solution is then
divided into 6 parts
i) To the first part is added A white precipitate soluble in Either Pb2+ or Al3+ present
dilute NaOH dropwise excess is formed
until in in excess
ii) To the second part is A white ppt insoluble in excess Either Pb2+ or Al3+ present
added aqueous ammonia is formed
iii) The third part was used
to carry out a test of
one’s choice to confirm
the cation present.
Test: To the third part is A thick yellow precipitate is Presence of Pb2+ confirmed
added a few drops of formed
potassium iodide solution
iv) To the fourth part is A yellow ppt is formed which Probably I- present.
added about 1 cm3 of on warming dissolves to give a
lead ethanoate solution colourless solution
and the mixture warmed.
v) To the fifth part is added A brown colouration is formed The brown colouration is due to
dilute ethanoic acid which gives a violet solution is Iodine liberated; hence I- is
followed by a few drops CCl4 layer present.
of sodium nitrite and
carbon tetrachloride.
vi) To the sixth part is added A yellow ppt insoluble in Presence of I- confirmed
HNO3 followed by a few ammonia
drops of conc. ammonia
solution.
169
 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 end full of A
in a dry test tube, first gently
then strongly till there is no
thurther change
b) To one spatula end fullof A in
a test tube add a few drops of
concentrated sulfuric acid and
warm gently.
c) To one spatula end full of A
in a test tube add about 6cm3 of
water, shake and divide into
three parts
i) To the first part add dilute
sodium hydroxide solution
dropwise till in excess
ii) To the second part add dilute
ammonia solution dropwise till
in excess
iii) To the third part add a few
drops of dilute hydrochloric acid
The Cation in A is Pb2+
Brown gas with pungent smell NO2 evolved
turns blue litmus red
Residue is orange(hot) and NO3- suspected
yellow(cold)
Brown fumes condense into an NO3- confirmed
oily liquid at the side
A is soluble in water and gives a Absence of a typical transition
colourless solution element
White ppt dissolved in excess Zn2+, Pb2+, Al3+, Sn2+ probably
forming a colourless solution present
White ppt insoluble in excess Pb2+, Al3+, Sn2+ most likely
reagent present
White ppt formed Pb2+ confirmed.

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
41
K. Both isotopes are able to form a positive ion with a single charge.
a) Complete the table below.

Number of Number of Number of

Particle
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.
170
 Percentage
Isotope
abundance
39
K 93%
41
K 7%

(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)
3
In an experiment, 0.76 g of lithium was added to 200 cm 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)
(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.

171
 (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.

(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.

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.

172
 (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?

(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.

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.

173
 ii) Explain the trend in solubilities of the hydroxides and sulphates of the elements in
water(hint: the 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
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.
ii) One property that qualifies Zn as a transition element.
b) i) Name one reagent that can be used to distinguish Zn 2+ and Al3+
ii) State what is observed when Zn2+ and Al3+ are treated separately with the reagent. Write
equation for the reaction.

174
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.

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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