INORGANIC CHEMISTRY

STPM

2011

CONTENT
CHAPTER 1
THE PERIODIC TABLE AND PERIODICITY
1 26
CHAPTER 2
S BLOCK AND GROUP 2
27 37
CHAPTER 3
GROUP 13
ALUMINIUM
38 49
CHAPTER 4
GROUP 14
50 - 66
CHAPTER 5
GROUP 15 NITROGEN AND COMPOUNDS
67 80
CHAPTER 6
GROUP 17 HALOGEN AND COMPOUNDS
81 - 93
CHAPTER 7
INTRODUCTION TO TRANSITION ELEMENTS AND
COMPLEX
94 -114

CHAPTER 1
THE PERIODIC TABLE AND PERIODICITY
1. The forms of a periodic table.
There are two forms of the periodic table.
1 The wide form.
2 The spiral form.
2. Structure of a periodic table.
The vertical columns or sets of elements are known as groups.
The horizontal rows or set of elements are known as periods.
In the periodic table, elements are arranged in the increasing order of proton number
from the left to the right across a period. The element at the right always has its proton
number one unit higher the element at its left. As the proton number of the elements
increases, the electronic structures of its atoms are building up in according to the Aufbau
principle. Thus, the arrangement of elements in the periodic table is closely related to the
electronic configuration of its atoms, especially their valence electrons. The valence electrons
in turn determine the chemical properties of the element and its compounds.
All elements in a period have similar core of electrons (fully filled shells), which is same to
the noble gas at the end of the previous period.
Example: Electronic configuration of chlorine (Period 3) is: 2.8.7
2.8 is the core, which is the same as the electronic configuration of Neon, 2.8 of
period 2.
All elements in a group have similar characteristic valence electronic configuration (eg:
Elements of group 1 have nS1 as their valence electron), which responsible to the similarity
of chemical properties among the member elements of the same group (eg: Elements of
group 1 forms M+ ions).
Base on their electronic configurations of the orbital in the valence shell, elements are
grouped into different blocks.
p-block
Noble
H
gas
s-block
Lanthanide f-block
Actinide f-block

Transition elements
d-block

Element
s
s-block
p-block

d-block
f-block

Valence electron

Valence electronic
configuration
Electrons are being filled
into the s orbital.
Electrons are being filled
into the p orbitals

Group 1: ns1 (Alkaline metals)

Group 2: ns2 (Alkaline earth metals)
Group 13: ns2np1
Group 14: ns2np2
group 15: ns2np3
Group 16: ns2np4
Group 17: ns2np5 (Halogen)
Group 18: ns2np6 (Noble gas)
Period 4,5 and 6: nd(1-10) (Transition metals)

Electrons are being filled

into the d orbitals
Electrons are being filled
into the f orbitals.

Period 5 and 6: nf (1-14) . (Known as inner transition

metals or lanthanides and actinides)

3. Periodicity of physical properties

The physical properties of elements are a function of the proton numbers.
In this chapter we study certain physical properties of the elements and to examine the
pattern or the trend of these physical properties varies across the 2nd or the 3rd period and
descending a group.
There are two main types of physical properties.
i. The atomic properties
ii. The bulk properties
3.1. The atomic properties
They are physical properties that directly related to the atomic structure of the element.
3.1a. Atomic radius
3.1a.i. The atomic radius decreases across a period from the left to the right
Across the 3rd period, atom of all elements has the same number of electron filled shell. The
nucleus charge of atom increases while electrons are being filled into the same valence shell.
As a result, the valence electrons are attracted increasingly stronger toward the nucleus.
Thus, the valence shell becomes closer to the nucleus and the atomic radius decreases.
3.1a. ii. The atomic radius increases as descending a group
Descending a group, the number of electron filled shells in atom of elements increases. The
valence electrons of atom are shielded from the attractive force of nucleus by the inner full
shells (or the cores of electrons) and at the same time, the screening effect.
(the core pushes the electrons of the valence shell further away from the nucleus)gets
stronger. As a result, the valence electrons are attracted weaker by the nucleus and the
valence shell drifts further from the nucleus. Thus, the atomic radius increases.
atomic radius (nm)

Na Mg Al Si P S Cl Ar 3rd period

atomic radius (nm)

Li

Na

Rb

Rb Group 1

3.1. b. The ionic radius

Isoelectronic means same electronic configuration. Two ions are isoelectronic if both have the
same electronic configuration.
Cation in a period is isoelectronic with the noble gas before the period.
Example: Ions Na+, Mg2+, Al3+ and Si4+ of 3rd period are isoelectronic 2.8 and isoelectronic
with noen.
Anion in a period is isoelectronic with the noble gas at the end of the same period.
Example: Ions P3-, S2- and Cl- of the 3rd period are isoelectronic 2.8.8 and isoelectronic with
argon.
The cations of a period are isoelectronic to the anions of the previous period.
Examples: Na+, Mg2+, Al3+, Si4+ (ions of the 3rd period), N3-, O2- and F- (ions of the 2nd period)
are isoelectronic and isoelectronic with neon.
radius (nm)
atom
cation

Na+ Mg2+ Al3+ Si4+

Radius(nm)

Atom forms cation when loses its valence electrons. Thus, cation
has one shell less than its atom. Thus, cation is smaller than its
atom.
Across the 3rd period from Na+, Mg2+, Al3+ to Si4+, the nucleus
charge increases (11 to 14) while the number of electrons in the
core of electron remains unchanged(or these ions are
isoelectronic 2.8). Thus, the electrons are held increasingly
stronger by the nucleus. The cationic radius decreases across the
period from Na+ > Mg2+ > Al3+ > Si4+.
To form anion, atom accepts electrons and completing the octet of
its valence shell. Thus, anion has stronger screening effect and is
bigger than its atom.
Across the period from P3-, S2- to Cl-1 ions, The nucleus charge
increases (15 to 17),while the number of electron remains
unchanged (isoelectronic 2.8.8). Thus, the electrons are attracted
stronger by the nucleus. anionic radius is gets smaller, P3- > S2- >
Cl-1.

anion
atom

P3
S2
Cl
The changes of the atomic radii and the ionic radii of elements in the 3rd period are shown as
in the graphs below. It is important to note that, in the same period, the cation is always
smaller than its atom, whereas the anion is always larger than its atom.
radius(nm)

radius(nm)

radius(nm)

anion
atom
cation
across a period

Li Na K Rb Cs
Group 1

F Cl Br I
Group 17

Descending a group, radii of cation and anion increase. This is due to the increase in the
number of completely filled electron shells and the increase of the screening effect. Thus, the
electrons are held increasingly weaker by the nucleus. Consequently, the cationic and the
anionic radii increase descending a group.
Isoelectronic and ionic radii of two neighbouring period.
Ionic radii of anions of 2nd and the cations of 3rd periods decreases as N3- > O2- > F- > Ne > Na+
> Mg2+ > Al3+. Ions are isoelectronic 2.8 and the nucleus charge increases from 7 to 13.
Electrons are attracted increasingly stronger. Ionic radii decrease.e ionic radii decrease form
radius(nm)

N3- O2- F-Ne Na+ Mg2+ Al3+

3.1c. The ionization energy.
The first ionization energy refers to the minimum energy requires to eliminate one mole of
valence electron from one mole of gaseous atom, against the attractive force of its nucleus.
M(g) M+(g) + e
Hence, if the valence electron is held stronger by the positively charge nucleus, higher energy
is required to eliminate the electron.
Across a period, the ionization energy increases across a period in a zig-zag pattern.
As crossing a period, atomic radii decrease and electron in the valence shell are held stronger
by the nucleus.
Ionization energy, kJ/mol

Na Mg Al Si P S Cl Ar

Ionization energy, kJ/mol

3rd period

Li Na K Rb Cs Group 1

The ionization energies of magnesium, phosphorus and argon are distinctively higher due to
their more stable electronic configurations of the valence shell.(Mg: fully fill;
P: halh filled 3p and Ar: Octet (3s23px23py23pz2))
The ionization energy of magnesium atom is higher than aluminium atom. The 3s orbital of
magnesium atom is fully filled (3s2) and has higher stability than the electronic configuration
of aluminum.

The ionization energy of phosphorus atom is higher than that of sulfur atom.The 3p of
phosphorus atom is half filled( 3s23px13py13pz1). This electronic configuration has higher
stability than that of sulfur.
The ionization energy of argon atom is highest. The valence electronic configuration of argon
atom is 3s2 3p6, the 3rd shell is fully filled (or acquired octet) and most stable.
The ionization energy generally decreases as descending group.
Descending a group, atomic radii increase. Thus, Valence electrons are held increasingly less
strongly by the nucleus. Consequently, the ionization energy decreases.
.
3.1 d. Electron affinity and electronegativity
Electron affinity is defined as the energy change when one mole of gaseous atom receives
one mole of electrons in order to produce one mole of gaseous anions.
X(g) + e X-(g)
It measures the readiness of an atom to capture a free electron to form an anion.
Electronegativity is defined as the tendency of an atom to attract bonding electron toward
the atom in a covalent bond.
Electron affinity and electronegativity of an element increases across a period.
Across a period, the atomic radius decreases. The force of attraction of the nucleus becomes
stronger across the period. Thus, atom becomes increasing easy to capture free electron or
attract bonding electrons in a covalent bond.
Electron affinity and electronegativity of an element decreases as going down a group.
Descending a group, the atomic radius increases. As a result, the force of attraction of the
nucleus becomes weaker. Thus, atom becomes increasingly less ready to capture free electron
or attract bonding electrons in a covalent bond.
electronegativity
electronegativity

Na Mg Al Si P S Cl 3rd period

Cl

Br

Group 17

In the periodic table, elements at the right top most of the table always have the highest
electronegative. Examples: nitrogen, oxygen and fluorine (non metals of the 2nd period). On
the contrary, elements at the left bottom most of the table have the lowest electronegativity.
Examples: cesium and francium (metals of group 1).
3.2. The bulk properties.
Bulk properties are physical properties that depend on the atomic structure and the types of
crystal lattice of the element or compounds.
Across the 3rd period, the metallic property changes form metal, metalloid and non metal.
This lead to the crystal lattice structures of elements change.
Element

Na

Mg

Al

Si

Cl
7

Metallic
properties

Metal

Metalloid

Non-metal

Crystal lattice

Giant metallic

Giant covalent
molecule

Discrete covalent
molecule

Bonding and
particles

Metallic bonding
between positive
metal ions and
electron cloud.

Covalent bond
between atoms

van der Waals forces

between molecules.

Breaking of
bond/ forces
between
particles

Strong metallic
bond between metal
ions and electrons
Cloud

Strong covalent bond

between atoms

Weak van der Waals

forces between discrete
molecules

3.2a. The melting point, boiling point, heat of fusion and heat of evaporation.
Across the 3rd period, the melting point, the boiling point, the heat of fusion and the heat of
evaporation increase from sodium to silicon. Then, they drop sharply from silicon to
phosphorus and remain low from phosphorus to chlorine.
Temperature, oC.
Energy, kJ/mol
heat of
evaporation
Boiling point
heat of fusion
Melting point

Na Mg Al Si

Cl

Na Mg Al

Si

Cl

Fusion, evaporation and boiling involved the change of states of mater and required energy.
Energy is used for breaking the bond or van der Waals forces (depend on the type of
substance) during change of state of the substance.
Energy is used to break the metallic bonds in the metallic crystal lattice, or the covalent
bond in the giant covalent molecular crystal lattice or the van der waals forces in the
discrete covalent molecule crystal lattice.
Since the metallic bond and the covalent bond are much stronger than the van der Waals
forces, more energy is required to break these bonds. Thus, the melting point and the boiling
point of Na, Mg, Al and Si are high. However, the van der waals forces are much weaker than
those bonds. Thus, the melting point and the boiling of P, S and Cl are low.
The melting point, the boiling point, the heat of fusion and the heat of evaporation increase
from sodium < magnesium < aluminium.
The electronic configurations of these elements are: Na (2.8.1), Mg (2.8.2) and Al (2.8.3).
The number of valence electrons available for formation of metallic bond increase from 1 in
each sodium atom to 3 in each aluminium atom. While the ionic charge of metal ion increases
from 1+ in sodium ion to 3+ in aluminium ion. As a result, the metallic bonds formed in these
8

metals become increasingly stronger. Thus, require increasingly more heat to break these
bonds.
Silicon has extremely high melting point and boiling point. Silicon has giant covalent
molecular lattice. In the lattice, each silicon atom is bonded covalently with 4 other Si atoms
with strong and stable Si-Si bonds. Thus, it requires very high energy to break these bonds.
Phosphorus, sulfur and chlorine form P4, S8 and Cl2 molecules respectively. They have
discrete covalent molecular structure. In between these molecules, there are weak van der
waals forces. Since the van der waals forces are much weaker than the metallic bond and the
covalent bond, hence, energy requires to break the van der waals forces is lesser.
Consequently, their melting point and the boiling point are low.
However, the strength of van der waals forces decreases as S8 > P4 > Cl2 due to the molecule
sizes decrease as S8 > P4 > Cl2. Thus, the melting and the boiling point decreases as S8 > P4 >
Cl2.
3.2b. The electrical conductivity.
Sodium, magnesium and aluminium are metal and
Conductivity
thus are good conductors of electricity. Silicon is
metalloid and a semiconductor. Phosphorus, sulfur
and chlorine are non-metals. They are non-conductors
of electricity.
When metal atoms are arranged closely in the crystals
lattice positions, the atomic orbital of the valence shell
of these atoms overlapped each other adjacently through
out the crystal lattice to form enormously large number
of bonding orbital with very close energy level. They can
be group into two groups called bands. They are the
conduction band, which is higher energy level and
Na Mg Al Si P S Cl
the valence band, which is lower energy level.
The valence band is filled with the valence electrons whereas the conduction band is empty.
energy
Conduction band
Conduction band
Conduction
band
Small energy gap

big energy gap

overlap
Valence band
Conductor

Valence band
semiconductor

Valence band
non-conductor /
insulator

In metals, the valence band and the conduction band overlap each other. Electrons in the
valence band are easily promoted into the conductive band and become mobile. Thus, these
mobile electrons can be transported when a different of potential is applied on a piece of
metal. Metal conducts electricity.

The conductivity of electricity reduces as the temperature increase. Metal ions and the mobile
electrons vibrated faster at higher temperature. As a result, it disrupts the smooth flowing of
mobile electrons.
The conductivity of electricity increases from sodium to aluminium. This is due to the
number of valence electrons that can be contributed into the valence band increase from one
in each sodium atom to three in each aluminium atom. Thus, more valence electrons can be
promoted into the conduction band of aluminium than sodium. Consequently, the conduction
band of aluminium has more mobile electrons than that of sodium.
In a semiconductor such as the silicon, the valence band is separated from the conduction
band by a small energy gap. At room temperature only limited electrons from the valance
band can be promoted into the conduction band. Thus, semiconductor is a weak conductor of
electricity at room temperature.
As the temperature increase, more electrons from the valance band are being promoted into
the conduction band. Thus, the conductivity of a semiconductor increases as the temperature
increases.
Non conductor such as the phosphorus, sulfur and chlorine, have bigger energy gap between
the two bands than that in the semiconductor. Therefore, no electron can be promoted into the
conduction band. Thus, they do not conduct electricity.
4. Periodicity of physical properties of d-block elements.
Elemen
Sc
t
Valence 3d14s
electron 2
s
Atomic 160
radius
(pm)
1stH ion 631
kJ/ mol
nd

2 H

Ti

Cr

Mn

Fe

Co

Ni

Cu

Zn

3d24s

3d34s

3d54s

3d54s

3d64s

3d74s

3d84s

3d104s

3d104s

146

131

125

129

126

125

124

128

133

658

650

650

717

759

758

737

746

906

1235

1310

1414

1592

1509

1561

1646

1753

1958

1732

2.99

4.50

5.96

7.20

7.20

7.80

8.90

8.90

8.92

7.14

1541

1680

1900

1890

1240

1540

1500

1450

1080

----

ion kJ/ mol

Density
g/cm3
Melting
point
o
C

4.1. The atomic properties.

4.1a. the atomic radius.
The d-block elements have relatively smaller atomic radius than the s-block and the p-block
elements of the same period.
Among the members of the d-block elements of the same period, their atomic radius are
almost similar.
10

Across the period from scandium to zinc, the additional of electrons are being filled into the
3d orbital of the second last shell instead of the 4p orbital of the outer shell. At the same time
the nucleus charge increases as the proton number increase. As a result, the increase in
attractive force of the nucleus is cancelled off by the increasing of the screening effect. Thus,
causes slight change in atomic radius of these elements across the period from Scandium to
zinc.
4.1b. the ionization energy.
During the ionization, electrons are being eliminated first from the 4s orbital of the valence
shell then followed by the 3d electrons in further ionizations.
The ionization energies are depending on the atomic radius and the electronic configuration
of atoms.
The first ionization energies are relatively low and increase slightly across the period from
scandium to zinc. This is due to the slight change in atomic radius of these elements across
the period from Scandium to zinc.
The first ionization energy of Zinc is highest because 3d and 4s orbital are fully filled.
The subsequent ionization energies are higher due to smaller ionic radius and the stability of
electronic configuration of the metallic ions.
Second ionization involves removing an electron from an M+ ion.
The second ionization energy of chromium and copper are higher than expected. This is due
to both of the Cr+ ion [(Ar) 3d5, 3d orbital are half filled] and the Cu+ ion [(Ar) 3d10, 3d orbital
are fully filled] have more stable electronic configurations.
The third ionization involves removing an electron from an M2+ ion.
The third ionization energy of chromium and copper are higher than expected. This is due to
both of the Mn2+ ion [(Ar) 3d5, 3d orbital are half filled] and the Zn2+ ion [(Ar) 3d10, 3d orbital
are fully filled] have higher electronic configurations.
Ionization energy kJ/mol.
Sc3+: (Ar)
Fe3+: 3d5
4th ( M3+ M4+ + e )
Mn2+: 3d5

Zn2+: 3d10
3rd ( M2+ M3+ + e )
Cu+: 3d10

Cr +: 3d5

Sc

Ti

Cr

2nd ( M+ M2+ + e )
Zn: 3d104s2
1st( M M+ + e )
Mn

Fe

Co

Ni

Cu

Zn

4.2 The bulk properties.

4.2a. the density of element.
11

d-block elements have much higher densities than the s-block and the p-block elements
because the metal atoms in the d-block elements are packed closer in their crystal lattices,
have higher atomic mass and smaller atomic radius.
The densities of d-block elements increase across the period from scandium to zinc. This is
due to the increase of atomic mass across the period while the atomic radius remains almost
unchanged.
4.2b. the melting point.
Elements of d-block exhibit high melting point as well as the boiling point and the heat of
fusion and evaporation. This is due to the combination of factors like small atomic radius,
high ionic charge, the giant metallic crystal structure and the electronic configuration of
metals ions.
Atoms of d-bock elements have many valence electrons from their valence 3d and 4s orbitals
that can be donated into the sea of electron during the formation of metallic bond. As a result,
the sea of electrons is expected to have high number of delocalized electrons. On top of that,
the metal ions have high ionic charge and small ionic radius. Thus, strong metallic bond is
formed. In addition to this, d-block elements have giant metallic crystal structure.
Consequently, the melting points of d-block elements are high.
The melting point of manganese and zinc are lower as the atoms of these elements have more
stable electronic configuration. The atoms of manganese and zinc use only 4s electrons to
form metallic bond and keep all electrons in the 3d orbitals to make up half filled 3d5 (in
Mn2+) and 3d10 (in Zn2+) respectively. Consequently, less bonding electron is found in the sea
of electron, the metallic bond formed is weaker.
The melting points of Sc, Ti, V and Cr are higher than Fe, Co and Ni. The former group of
metal have their 3d orbital filled with single electrons while later group of metal have their 3d
orbitals filled with pairs of electrons. As the number of pairing electron increases, the
electronic configuration becomes more stable. Thus, the melting point becomes lower.
Melting point /oC

3d5, half filled

Number of electron pair
In 3d orbital increases

Number of single
un-pair electron
In 3d orbital increases

Sc Ti

Cr

3d10 fully filled.

Mn Fe

Co

Ni

Cu

5. The periodicity of chemical properties of elements in period three.

Elements
Electronic
configuratio

Na
2.8.1

Mg
2.8.2

Al
2.8.3

Si
2.8.4

P
2.8.5

S
2.8.6

Cl
2.8.7

Ar
2.8.8

12

n
Metallic
properties

metallic

metalloi
d

non-metal

5.1. Chemical properties of elements.

Sodium, magnesium and aluminium are metal. They are strong reducing agents. The
chemical reactivity and the strength of reducing agent decrease from Na > Mg > Al.
5.1a. Reaction with water.
Sodium reacts vigorously with water to form hydrogen and an alkali solution. The reaction is
usually characterized by explosion, burning into flame and extremely exothermic.
2Na +
2H2O 2NaOH + H2
Magnesium reacts aggressively with steam to form magnesium oxide and hydrogen.
Mg + H2O
MgO + H2
Aluminium reacts slowly with steam to form aluminium oxide and hydrogen.
4Al + 3H2O 2Al2O3 + H2
Silicon reacts very slowly with steam at high temperature.
Si + H2O SiO2 + H2
Phosphorus and sulfur do not react with water whereas chlorine reacts with water to produce
acidic solution
Cl2 + H2O
HCl + HOCl
5.1b. Reaction with oxygen.
They react vigorously with oxygen and the reactions are usually characterized by explosion,
burning into flame and extremely exothermic. Stable ionic oxides are formed.
4Na + O2 2Na2O
2Mg + O2 2MgO
4Al + 3O2 2Al2O3
Magnesium and aluminium usually turns passive when exposed to oxygen due to the thin
layer of oxide formed at its surface of the metals, preventing them from contact with oxygen.
Thus, stop the further reaction.
Silicon reacts with oxygen when it is heated.
Si + O2 SiO2
Phosphorus reacts with oxygen to form P4O10 and sulfur reacts with oxygen to form SO2
when heated. However, chlorine does not react with oxygen.
P4 + 5O2 P4O10
S8 + 8O2 8SO2

13

5.2. Physical and chemical properties of oxides.

Element
Formula
Melting point,
o
C
Structure and
bonding

Na
Na2O
1275

Mg
MgO
2852

Al
Al2O3
2027

Si
SiO2
1610

Giant ionic crystal lattice

Particles / force

Ionis of opposite charge/

ionic bond

Acidity

Base

P
P4O10
24

Giant
covalent
molecule
Atoms/
covalent
bond

S
SO3
17

Cl
Cl2O7
-92

Discrete covalent molecular

structure
Discrete molecules/ van der
Waals forces

amphoteri
c

acidic

i. melting point
temperature, oC

Na2O MgO Al2O3 SiO2 P4O10 SO3 Cl2O7 oxides

Na2O, MgO and Al2O3 have giant ionic structure and strong ionic bond. Thus, they have very
high melting point. The melting point of oxides of metals increases as Na2O < Al2O3 < MgO.
Metal ionic radius decreases as Na+ > Mg2+ > Al3+ and the ionic charge increases from 1+ to
3+. As a result the charge density increases as Na+ < Mg2+ < Al3+.
Due to charge density of Al3+ ion is extremely high, the ionic bond of Al2O3 becomes highly
in covalent characteristic. Consequently, the ionic bond of Al2O3 becomes weaker than MgO.
So Al2O3 has lower melting point.
SiO2 has giant covalent molecular structure. Atoms of Si and O are bonded with strong
covalent bond. Thus, it has high melting point.
P4O10, SO3 and Cl2O7 have discrete covalent molecular structure. Molecules are held together
by weak van der waals forces. Thus, they have very low melting points.
The strength of van der waals forces decreases as P4O10 > SO3 > Cl2O7. As a result, the
melting point decreases as P4O10 > SO3 > Cl2O7.
P4O10
(solid)

SO3 (solid)
O

P
O

O
O

O P

O
O

O
S
S

O
O

O
14

ii. Acidity of oxide across the third period

Na2O and MgO are basic oxide.
Na2O dissolves in water to form an alkali solution. It reacts with dilute acid to form salt and
water.
Na2O + H2O 2NaOH
Na2O + 2HCl 2NaCl + H2O
MgO is insoluble in water but dissolve in dilute acid.
MgO + 2HCl MgCl2 + H2O
Al2O3 is insoluble in water. However, it is amphoteric and reacts with both hot dilute acid and
alkali solution.
Al2O3 + 6H+ 2Al3+ + 3H2O
Al2O3 + 2OH- + 3H2O 2[Al(OH)4]SiO2, P4 O10, SO3, and Cl2O7 are acidic oxide.
SiO2 is a weak acid. It does not dissolve in water but reacts with hot concentrated alkali
solution.
SiO2 + 2OH- SiO32- + H2O
P4 O10, SO3, and Cl2O7 are stronger acid. They dissolve in water to form acidic solution and
react with alkali solution in neutralization reaction to form salt and water.
P4 O10 + 6H2O 4H3PO4
P4 O10 + 12NaOH 4Na3PO4 + 6H2O
SO3 + H2O H2SO4
SO3 + 2NaOH Na2SO4 + 2H2O
Cl2O7 + H2O 2HClO4
Cl2O7 + 2NaOH- 2NaClO4 + 2H2O

15

PAST YEARS QUESTIONS:

OBJECTIVE
1990/13. Which of the following graphs represent the change of electric conductivity of
elements in period three of the Periodic Table?
A Conductivity
B
Conductivity
Al
Na

Mg

Mg
Na

Si
P

Al

S
Si

Cl
S

Cl

Ar

Ar

Conductiviry

Conductivity

Al
Na
Mg
Mg

Na
Al
Si
Si
P S Cl Ar

P S Cl Ar

E Conductivity
Al
Na
Mg
Si

P S Cl Ar
1990/14. X, Y and Z are elements from the third period of the Periodic Table. The
observations were gathered when the oxides of these elements react with water.
i. Oxide of X is insoluble in water.
ii. Oxide of Y dissolved in water to give a solution of pH 13.
iii. Oxide of Z dissolved in water to give a solution of pH 3.

16

Which of the following series shows the correct arrangement of these elements from the left
to the right in the third period of the Periodic Table?
A X, Y, Z
B X, Z, Y
C Y, X, Z
D Y, Z, X
E
Z, X, Y
1991/13. The properties of hydrides of X, Y and Z in the third period of the Periodic Table
are shown in the following table.
Element

Properties
Neutral
Acidic
Reacts with water to form H2

X
Y
Z

Which of the following series shows the correct arrangement of these elements in the order of
increasing in proton number?
A X, Y, Z
B X, Z, Y
C Y, X, Z
D Z, Y, X
E Z, X, Y
1992/13. The graph below shows the changes of first ionization energy against proton
number of elements in the Periodic Table.
First ionization energy

x Y

Proton number
Y could be
A Magnesium

B Nitrogen

C Sulphur

D Chlorine

E Argon

1992/14. The properties of oxides of elements R, S and T from the third period of the
Periodic Table are shown as the following.
i
Oxide of R dissolves in water to give a solution of pH 3.
ii
Oxide of S dissolves sparingly in water but is fully soluble in dilute HCl.
iii
Oxide of T is not soluble in water but soluble in dilute aqueous solution of HCl
and NaOH.
Which of the following arrangement is the correct order of acidity of oxides in descending
order?
A R, S, T
B R, T, S
C S, R, T
D T, R, S
E T, S, R
1992/31. The boiling point and the heat of evaporation increase in the following order.
Hydrogen, Nitrogen, Hydrogen chloride, Chlorine
This is because
1 the covalent radius increases.
2. the number of electrons increases.
3. the inter-molecular attraction force becomes stronger.
1993/13. If 0.10 mol of this oxide is dissolved in 1.0 dm-3 of water, which of the following
oxides would produce an aqueous solution with lowest pH?
A SO3
B Na2O
C Cl2O
D Al2O3
E P4O10
17

1993/38. Which of the following molecule is planar?

1. CH4
2. C2H4
3. C6H6
1994/3. Which of the following equation represent the first ionization energy of beryllium?
A Be(g) Be+(g) + e
B Be(g) Be2+(g) + 2e
C Be(p) Be+(g) + e
D Be(p) Be2+(g) + 2e
+
2+
E Be (g) Be (g) + e
1994/5. Which of the following pairs of element in the following periodic table form ionic
bond?
P
S
Q

A R and S; R and T
D P and S; P and T

B P and Q; Q and T
E Q and S; Q and T

C P and S; R and T

1994/13. Which of the graphs correctly shows the change of melting point across the second
period of the periodic table?
Melting point
Ne

Melting point

Melting point

Li

Melting point

Melting point

C
Li

Ne
Be

Ne

N
O
C
Be

F
Be
B
C

O
Be

B N

N
B

Li

Li
F

Be B
N

Ne

O F Ne

C
Li

1995/13. Which of the following statements explain the reduction in the strength as a
reducing agent for the elements in the third period of the Periodic Table from sodium to
chlorine?
A. Covalent radius of element increases.
B. Reduce in the standard potential of element.
C. Increase in the oxidation number of element.
D. Increase in the electronegativity of element.
E. Reduce in the ionization energy of element.
1995/14. X, Y and Z are the elements of the third period in the Periodic Table. Chlorides of
these elements have the following chemical properties.
i. Chloride of X dissolves in water and hydrolyzed to produce white fume.
ii. Chloride of Y dissolves in water to form an aqueous solution with pH 6.
iii. Chloride of Z dissolves in water without being hydrolyzed.
18

Arrange X, Y and Z in the ascending order of their proton numbers.

A. X, Y, Z
B. Y, X, Z
C. Y, Z, X
D. Z, X,Y

E Z, Y, X

1996/7. Which of the following graph represents the change of ionic radii of nitrogen,
oxygen, fluorine, sodium, magnesium and aluminum?
A. ionic radius

B. ionic radius

N3- O2- F- Na+ Mg2+ Al3+

C. ionic radius

N3- O2- F- Na+ Mg2+ Al3+

D. ionic radius

N3- O2- F- Na+ Mg2+ Al3+

E ionic radius

N3- O2- F- Na+ Mg2+ Al3+

N3-O2- F- Na+ Mg2+Al3+

1996/23. W, X, Y and Z are elements of the third period of the Periodic Table. The oxides of
these elements have the following properties.
i. Oxide of W is insoluble in water and acid, but is soluble in hot and concentrated
NaOH solution.
ii. Oxide of X is soluble in both aqueous KOH and aqueous HCl.
iii. Y forms two stable oxides.
iv. Oxide pf Z is sparingly soluble in water and it reacts with aqueous H2SO4.
Arrange these elements in the ascending order of their proton numbers.
A. Y,X,W,Z
B. Y,W,Z,X
C. Z,W,X,Y D. Z,X,W,Y
E. W, X, Y, Z
1996/49. Which of the following statement correctly explain the formation of metallic bond
in a metal?
1 Only positive ions present in the metallic crystal lattice.
2 Valence orbitals of metal atoms overlap to form the negatively charge sea of electrons.
3 Metallic bond strength reduces as the electrons involve in the bonding increases.

19

1997/30. The following table shows the observations obtained when elements of the third
period of the Period Table reacts with oxygen.
Element
Observations
Na
Very aggressive
Mg
Slightly aggressive
Al
Aggressive
Si
Slow
P
Slow
S
Slow
Cl
No reaction
Ar
No reaction
These observations show that, across the third period from sodium to argon,
A. Element becomes increasingly more inert.
B. Element becomes increasingly more difficult to donate electron.
C. Strength as oxidizing agent.
D. The reaction between the elements with oxygen becomes increasingly more
exothermic.
E. Bond strength in oxides of the elements becomes increasingly weaker.
1997/49. Which of the following molecule is linear?
1. CS2
2. SCl2
3. SO2
1998/4. Which of the following statement explains the decrease in ionic radius across the
period three from Na+ to Al3+?
A. The sum of electron and the sum of proton in the nucleus increases.
B. The sum of electron and the sum of proton in the nucleus decreases.
C. The sum of electron and the sum of proton in the nucleus remains unchanged.
D. The sum of electron remains unchanged but the sum of proton in the nucleus
increases.
E. The sum of electron increases but the sum of proton in the nucleus remains
unchanged.
1998/23. Which of the following statement is true about the oxides of elements in the third
period of the Periodic Table?
A. Acidity of oxide decreases from sodium to chlorine.
B. None of the oxide is emphotheric.
C. Silicon forms oxide with the highest oxidation state than other oxides.
D. Oxides of phosphorus do not dissolve in water.
E. Chlorine forms more than two oxides.
1998/49. The structural formulae of water and hydrogen sulphide are shown as the following.
O
S
H x H
H y H
Which of the following statement is true for both molecules?
1 Bond angle x is bigger than bond angle y.
2 Both sulphur and oxygen atoms have two non-bonding pairs of electron.
3. The oxygen atom in water molecule is less electropositive than sulphur atom in
20

the hydrogen sulphide molecule.

1999/4. Which of the following pair of elements has the biggest different in boiling point?
A. Silicon and argon.
B. Sodium and argon.
C. Sodium and silicon.
D. Aluminium and chlorine.
E. Aluminium and phosphorus.
2000/4. The following is the successive ionization energy of an element, X.
940, 2080, 3090, 4140, 7030, 7870, 16000, 19500
X is possibly an element of
A. Group 13
B Group 14
C Group 15
D Group 16
E. Group 17
2000/5. Which of the following correctly match the physical properties of a transition
element?
Melting point, oC Boiling point, oC
Density, g cm-3 Electric conductivity
A.
327
1750
11.3
good
B.
650
1150
1.7
good
C.
1539
2800
7.9
good
D.
1410
2500
2.3
weak
E.
3500
3900
2.3
weak
2000/20. Which of the following is correct regarding to the oxides of the elements of the third
period of the Periodic Table?
A. Sodium oxide is basic because sodium is the most electropositive element in period-3.
B. Oxide changes from basic to acidic from sodium to chlorine because bond formed
between the element and oxygen becomes stronger.
C. Aluminum oxide is amphoteric.
D. Phosphorus oxide is the strongest acid because it is most soluble in water.
E. Silicon oxide does not react with sodium hydroxide because the oxide is neutral.
2000/47. Which of the following is only explained by the force of inter-molecular attraction?
1 Complex ion V(H2O)62+ is purple, while complex ion V(H2O)63+ is green.
2 CO2is gas, while SiO2 is solid.
3 The boiling point of sulphur is higher than the boiling point of phosphorus.
2001/4. Mendeleev arranged the elements in the Periodic Table according to
A. the ascending order of proton numbers.
B. the ascending order of relative atomic mass.
C. the ascending order of molar volume of element.
D. the ascending order of atomic size.
2001/5. Across the third period of the Periodic Table from sodium to chlorine,
A. electronegativity of element decreases.
B. ionization energy of element decreases.
C. standard electrode potential of element increases.
D. strength as a reducing agent of element increases.
2001/6. Which of the following elements form ionic hydride?
A sodium B silicon
C Sulphur
D Chlorine
21

2001/20. Which of the following element form oxide with the highest oxidation number?
A. Silicon
B. Phosphorus
C. Sulphur
D. Chlorine
2001/48. Which of the following organic compounds form hydrogen bond with its own
molecules and also with water molecules?
1. HCHO
2. C2H5OH
3. C2H5NH2
2002/2. The proton numbers of four elements are given as below.
Element
P
Q
R
S
Proton number
24
25
26
29
Which of the following is the correct arrangement of the second ionization energy for these
elements in the ascending order?
A. P, Q, R, S
B. P, Q, S, R
C. Q, R, P, S
D. Q, P, R, S
2002/3. The proton number of elements X, Y and Z are 14, 19 and 26. Which of the following
statements is true for X, Y and Z?
A X is d-block element.
B Y is strong oxidizing agent.
C Z has only one oxidation state in its compounds.
D Oxide of X with this formula (XO3)2- , exist as a polymer.
2002/4. Which of the following statements is true for elements in the Periodic Table?
A Reactivity of elements increases descending a group.
B Atomic size increases when nucleon number increases.
C The metallic property of elements increases descending a group.
D The number of metal is more than the number of non metal.
2003/5. The energy band diagram for a substance is shown as follows.
Conduction band

energy

narrow energy gap

Valance band

Which statement about the substance is true?

A The substance is a metalloid.
B Its electrical conductivity decreases with temperature.
C The electrons flow from the valence band to the conduction band at high pressure.
D The valence band comes into contact with the conduction band at high temperature.
2003/7 The table below shows the proton number of four elements represented by letter
which are not the usual symbol for the elements concerned.
Element
Proton number
Which element has the strongest metallic bond?
A P
B Q
C R

P
3

Q
11

R
13

S
19

D S

22

2003/10 The first four ionization energies of some elements are given below.
Elements
Ionization energy / kJ mol-1
1st
2nd
3rd
W
736
1450
7740
X
653
1590
2990
Y
900
1760
14800
Z
577
1820
2740
The element which is located in the d-block of the Periodic Table is
A W
B X
C Y
D Z

4th
10500
4770
21000
11600

2003/12 Which sequence of isoelectronic ions shows that the ionic radius increases
continuously?
A Ca2+ < K+ < Cl- < S2- < P3B Ca2+ < K+ < P3- < S2- < ClC K+ < Ca2+ < Cl- < S2- < P3D P3- < S2- < Cl- < K+ < Ca2+
2003/17 The diagram below shows a sketch of the Periodic Table which some elements
being represented by letters which are not the usual symbol for the elements concerned.

S T
P R
Q

If the ionic compounds PT, QU and RS formed have the same lattice structure, which
sequence of ionic compounds shows the increase in the magnitude of lattice energy?
A RS < QU < PT
B RS < PT < QU
C PT < QU < RS
D QU < PT < RS
2004/6 Elements X and Y form ionic compound XY. Which of the following pairs of
electronic configuration is correct of X and Y ?
X
Y
1
A 1s
1s22s22p63s23p5
2
5
B 1s 2s2p
1s22s22p63s23p5
C 1s22s22p63s1
1s22s22p4
2
2
6
2
D 1s 2s 2p 3s
1s22s22p4
2005/2 The energy gap between valence band and conduction band of element P is bigger
than element Q. For element Q, its valence band and conduction band are overlap.
What are the valence electronic configuration of elements P, Q and S ?
P
Q
S
A 2s22p2
6s26p2
3s2
B 4s24p2
5s25p2
3s23p1
C 3s23p3
2s22p2
3d64s2
2
4
2
2
D 3s 3p
3s 3p
3s2

23

2005/17 The following graph shows the variation of physical property of Period 3 elements
in the Periodic Table.

Na Mg Al
What is the physical property?
A Electronegativity
C First ionization energy

Si

Cl

Ar

B Electrical conductivity
D Enthalpy of vaporization

STRUCTURED
1991/4. a. Define the first ionization energy of an atom. [4]
b. The diagram below shows the changes in the fist ionization for elements in the
Third Period of the Periodic Table.
Ionization energy kJ/mol

Na Mg Al Si P S Cl Ar
i.
ii.
iii.

Explain why the first ionization energy of aluminium is lower than the first
ionization energy of magnesium. [2]
Sketch a graph to show the subsequent ionization energies for aluminium.
The proton number of aluminium is 13. [1]
State two factors that causes the third ionization energy of magnesium is
higher than it second ionization energy. [2]

(c) i.

Arrange the following elements: Ca, Cl, F, Mg and P in the order of

increasingly more electronegative. [1]
ii. Which of these compounds, CaF2 or PF5, has higher covalent characteristic?
Explain your answer. [2]

24

1994/1. The graph below shows the subsequent ionization energies of an atom X.
Ionization energy kJ/mol

i
ii
iii
iv
v
vi

10

11

12

Determine the number of proton in an atom X. [1]

Write the electronic configuration of atom X. [1]
If atom forms a cation, predict the most possible charge of the cation. Explain
your answer. [3]
X reacts with oxygen to form an oxide with the following formula, XO. State the
thermal stability of this oxide compares to the other oxides of the elements below
X. [1]
State an industrial usage of XO and explain your answer. [2]
What would you observe if the nitrate of X is strongly heated? Write a balance
chemical equation to show the reaction that occurs. [2]

1999/1. (a) Lithium, beryllium, boron, carbon, nitrogen, fluorine and neon are elements
from the Period 2 of the Periodic Table.
i. State the change in atomic radii of these elements across the period. [1]
ii. State two factors the affect the change in atomic radii of these elements across
the period. [2]
iii. Among these elements, which of these elements has the highest melting point?
[1]
2002/2a. (a) Arrange the elements in
i. Period 3 of the Periodic Table in the descending order of atomic radius.
ii. Group 17 of the Periodic Table in the ascending order of ionization energy.
[2]
ESSAY
1991/3(b)

why copper is a conductor of electricity? Explain.

[4]

1991/4.(a) What do you understand by the terms

(i) atomic radius,
(ii) affinity of electron and
(iii) ionization energy ?
Explain these terms by referring to the factors that influent them.
[12]
1992/4. (c) Write the electronic configuration for magnesium atom and iron atom. Explain
why magnesium has only one oxidation state whereas iron has more than one oxidation states
in their compound respectively.
[6]
1994/4. a. Explain; how the following properties change across the Third Period of the
periodic table from sodium to sulfur. Write all chemical reaction involved.
i
The reactivity of these elements as they react with chlorine.
25

ii

Bonding and electric conductivity of molten or aqueous solution of the

chloride for these elements. [10]
(b) State the change in acidity of oxide for the elements in the Third Period of the
periodic table ( sodium to chlorine). For each group of these oxides, write an equation to
represent their acidity as mentioned above. [6]
(c) Compare and explain the acidity of aqueous solution for HCl and H2S. [4]
1997/4. (a) Explain what it means by the term the second ionization energy.
[2]
(b) Plot a graph to show the changes of second ionization energies against the
proton number of the elements in the third period (Na to Ar) of the periodic table.
[5]
(c) Explain the periodicity of the following physical properties across the third
period of the periodic table.
i
Atomic radius.
(ii) Melting point.
(iii) Conductivity of electricity.
[13]
2001/7. (a) A scientist has recently discovered a new element with its proton number is 119
and the electronic configuration of the valence shell of this atom is 8s1. Predict the location of
this element in the periodic table. State three physical properties and one chemical property
of the element.
[5]
(b) Cesium, Cs, an element that was used in a photoelectric cell because its atom can
produce free electron by absorbing light. Explain why a cesium atom behaves as such.
[4]
2001/8. (b) Aluminum, silicon, phosphorus and sulfur are elements from the third period of
the periodic table. The melting points of these elements are show as the following table.
Element
Aluminum
Silicon
Phosphorus
Sulfur

Melting point, oC
660
1410
44
119

Explain the changes of the melting points of these elements by referring to their bonding and
structure.
[8]
A
1 only

B
1 and 2

C
2 and 3

D
1,2 and 3

ANSWERS
1990: 13D, 14C / 1991: 13E / 1992: 13D, 14B, 31D / 1993: 13A, 38C / 1994: 3A, 5E, 13C
1995: 13D, 14E / 1996: 7A, 23D, 49B / 1997: 30B, 49A / 1998: 4D, 23E, 49D / 1999: 4A
2000: 4D, 5C, 20A, 47C / 2001: 4B, 5C, 6A, 20D, 48C / 2003: 5A, 7C, 10B, 12C, 17D
2004: 6D / 2005: 2D, 17D

26

CHAPTER 2
THE S-BLOCK ELEMENTS.
1. Introduction.
The elements of group 1 and group 2 of the periodic table are known as the s-block elements
because their valence electrons are found in the s orbital.
Atoms of group 1 Elements have their valence shells electronic configuration as ns1, whereas
the group 2 elements have their valence shell electronic configuration as ns2. Group 1
elements are known as the alkali metals because they react with water to produce alkali
solution. Elements of group 2 are called the alkali earth metals.
2. The periodicity of physical properties of group 1 and group 2 elements.
Elements of:
Group 1

Li
1s 2s1

Na
(Ne)3s1

K
Rb
Cs
1
1
(Ar)4s (Kr)5s (xe)6S1

Be
1s22s2

Mg
(Ne)3s2

Ca
Sr
Ba
(Ar)4s2 (Kr)5s2 (xe)6S2

Group 2

Descending these groups, the number of electron filled shell increase.

The atomic sizes increase.
As the results:
1. The ionization energy decreases.
2. The electronegativity decreases.
3. The metallic bond strength the melting point and the hardness of the metal decreases
so also with.
4. Metal of group 1 has body centered cubic crystal structure. Thus, they have low
density.
The density of element increases descending these groups due to the increase of
atomic mass.
Do you know?
When metals or salts of group 1 and 2 are burned in the flame of a Bunsen burner, they produce
different colored flame.
Metal of group 1: Lithium
Sodium
Potassium Rubidium Cesium.
Color: Carmine Red Yellow golden
Lilac
Red
Blue
Metal of group 2: Magnesium
Calcium
Barium
Color: Silver bright
Maroon Red
Apple green
This is called the flame test, where an element can be identified by the color of it flame when burned.

27

3. The periodicity of chemical properties for elements in group 1 and group 2

Generally, elements of group 1 and group 2 have low ionization energies.
As the results, they are very reactive elements. They are good electrons donors. They donate
valence electrons easily during chemical reactions and act as strong reducing agents.
Therefore, chemical reactions which they involved normally are characterized by high
reaction rate and very exothermic (explosive and burning with fire).
As going down the group (respectively), the ionization energy decreases due to the increase
of the atomic radius. Thus, the chemical reactivity of group 1 and group 2 elements
increases as going down these groups. Finally, the strength as a reducing agent increases as
going down the groups.
However, the ionization energies of group 1 elements are lower than that of the elements of
group 2. This is due to their atomic radiuses (of group 1 elements) are larger. Thus, elements
of group 1 are more reactive than act as stronger reducing agent than the elements of group
2.
3.1. Elements of Group 1 and group 2 react with oxygen in different degree of reactivity
to form stable oxides.
Elements of group 1 and group 2 react aggressively with oxygen and the reaction is usually
explosive and bust into colored flame producing white oxides. The reactivity increases as
going down the group.
Group 1: 4 M + O2
Example: 4 Na + O2
Group 2: 2 M + O2
Example: 2 Mg + O2

2 M2O
2 Na2O
2 MO
2 MgO

In these reactions, the metals act as reducing agents. They are oxidized to become M+ and
M2+ ions. Whereas the oxygen acts as oxidizing agent and being reduce to O2- ion.
The oxides of group 1 are highly ionic. They have high melting points.
However, oxides of group 2 are ionic with partially covalent characteristic. Example: BeO is
covalent. The covalent characteristic decreases as going down the group. This is due to the
ionic radius of M2+ ion become bigger and the charge density of the ion decreases as going
down the group.
Due to its high charge density, M2+ ion form stronger ionic bond with O2- ion than the M+ ion.
Thus, Oxides of group 2 have higher melting point than oxides of group 1.
MgO is used as refractory material due to it high melting point. A refractory agent
is material of high melting point used to make lining of furnaces.

Oxides of group 1 are soluble in water and form alkali solution.

Group 1: M2O + H2O
2MOH
Example: Na2O + H2O
2NaOH
28

Comparatively to the oxides of group 1, oxides of group 2 are less soluble in water. Their
solubility increases as going down the group. BeO and MgO are not soluble. However, CaO
is partially soluble and SrO and BaO are soluble. The solution is alkaline.
Group 2: MO + 2H2O
Example: BaO + 2H2O

2 M(OH)2
2 Ba(OH)2

Oxides of group 1 and 2 are basic. They react with acidic to form salt and water. However,
beryllium oxide, BeO is amphoteric. It reacts with both acids and alkalis solution.
Group 1: M2O + 2H+
Example: Na2O + 2H+
Group 2: MO + 2H+
Example: BaO + 2H+

2M+ + H2O
2Na+ + H2O
M2+ + H2O
Ba2+ + H2O

Amphoteric BeO : BeO + 2H+

Be2+ + H2O
BeO + 2OH + H2O
[Be(OH)4]23.2. Elements of Group 1 and group 2 react with water in different degree of reactivity
to form hydroxides.
Elements of group 1 react aggressively with cold water and usually explosive and bust into
colored flame on top of the water surface, producing alkaline hydroxide solution.
The reactivity increases as going down the group.
Group 1: 2M + 2H2O
Example: 2Na + 2H2O

2 M(OH) + H2
2 Na(OH) + H2

Elements of group 2 react less aggressively with water. The reactivity increases as going
down the group. Beryllium reacts very slowly with steam, magnesium react readily with
steam and calcium, strontium and barium react with cold water with increasingly
aggressiveness.
Group 2: M + 2H2O
Example: Ba + 2H2O

M(OH)2 + H2
Ba(OH)2 + H2

4. Thermal stability and solubility of salts.

4.1. Thermal stability of salts of group1 and group 2 increases as going down the group.
Thermal stability depends on two main factors.
i. Going down the groups, the cationic size increases but the cationic charge remains the
same. Thus the charge density of cations and the polarizing power decreases.
ii. Compare to a smaller anion, bigger anion has bigger electron cloud that is easier to be
distorted by the cation. As a result, there is a tendency of overlapping of the
cationic orbital and the anionic orbital. Thus, forms covalent characteristic in the ionic
29

bond. The present of covalent characteristic in the ionic bond will weaken the bond
and further causes the salts to be thermally unstable, making it easier to decompose by
mean of heating. In this thermal decomposition, bigger anions are usually broken
down to form smaller anions, such as the oxide anion.
As a salt becomes thermally more stable, higher temperature of decomposition is needed for
cause the decomposition.
4.2. Thermal decomposition of carbonates, nitrates, sulfates and hydroxides of group 1.
Among the cations of group 1, Li+ ion has the highest charge density. As a result, carbonate,
nitrate, sulfate and hydroxide of lithium have very high covalent characteristic. Consequently,
these salts are thermally unstable. They decompose easily into lithium oxide when heated in
ordinary Bunsen flame.
Li2CO3
Li2SO4
2LiNO3
2LiOH

Li2O + CO2
Li2O + SO3
2Li2O + NO2 +
Li2O + H2O

O2

Nitrate of sodium decomposes when heated at high temperature.

2NaNO3
2NaNO2 + O2
Other salts of group 1 are thermally stable.
4.3. Thermal decomposition of carbonates, nitrates, sulfates and hydroxides of group 2.
The thermal stability of salts for group 2 is relatively lower than the salts of group 1.
This is due to:
1. the cations in group 2 have smaller cationic radius and higher ionic charge (2+).
2. the charge density of cation of group 2 is higher.
3. the polarizing power of cation of group 2 is higher.
The cationic radius increases as going down group 2, while the ionic charge remains as 2+.
Thus, the charge density of cation and its polarizing power decreases as going down the
group. Consequently, the thermal stability of salts of group 2 increases as going down the
group.
Carbonates, sulfates, nitrates and hydroxides of beryllium, magnesium and calcium
decompose to form oxides.
MCO3
MO + CO2
MSO4
MO + SO3
2M(NO3)2
2MO + 4NO2 + O2
M(OH)2
MO + H2O
[ M = Be, Mg and Ca]
Carbonates, sulfates, nitrates and hydroxides of Strontium and barium are thermally stable.

30

5. The solubility of salts.

When an ionic salt dissolves in water, the ionic lattice breaks apart and the ions become
surrounded by water molecules in a process called solvation.
Solubility of a salt is depending on two factors.
i. The lattice energy required to break apart the ionic lattice so that gaseous ions are
formed.
MX(s)
M+(g) + X-(g) H = + a kJ mol-1
If the charge density of ion is low, lesser energy is required to break up the ionic lattice.
The value of a is small.
ii. Hydration of ion is when an ion in the gaseous state is dissolved in water and become
hydrated.
M+(g)
M+(aq)
H = - b kJ mol-1
X-(g)
X-(aq)
The hydration process produces energy b. More energy will be released if the ion has
higher charge density.
The solvation process of a salt can be described as the following.
Hsol

MX(s)

M+(aq) + X-(aq)

+a

-b

M+(g) + X-(g)
The energy profile of the solvation process is as the following.
energy
M+(g) + X-(g)
+a
MX(s)

-b

Hsol
M+(aq) + X-(aq)

Hsol = -b + (+a)

(or a - b)

If the hydration energy b released is big enough to meet the lattice energy a needed for
breaking apart the ionic lattice, that is b > a, the Hsol will have a negative value, c, or is
said to be exothermic. The salt will dissolve.

31

5.1. the solubility of salts of group 1.

Salts of group 1 are soluble in water except the salts of lithium. The low solubility of lithium
salts is due to the high covalent characteristic in the compound.
5.2. the solubility of salts of group 2.
Salts of group 2 are basically less soluble compare to the salts of group 1.
Nitrates of group 2 are soluble. However, the solubility of other salts of group 2 changes
according to the size of its anion.
The solubility of hydroxide, M(OH)2.
The solubility of hydroxides of group 2 increases as going down the group. Be(OH)2 is not
soluble in water, Mg(OH)2 and Ca(OH)2 are partially soluble, Sr(OH)2 and Ba(OH)2 are
soluble.
As going down the group, charge density of cations decreases. Thus, the lattice energy a and
the hydration energy b decrease. However, the lattice energy a decreases more rapidly than
the hydration energy b.
energy
b
a
Be Mg Ca Sr

Ba

cations of group 2

Since the heat of solubility, Hsol = -b + (+a), (or a - b). Be(OH)2, Mg(OH)2 and Ca(OH)2
have lattice energy a bigger than the hydration energy b. Thus, the Hsol of these
hydroxides become endothermic. Consequent, these salts are insoluble in water.
Sr(OH)2 and Ba(OH)2 have lattice energy a smaller than the hydration energy b. Thus, the
Hsol of these hydroxides become exothermic. Consequent, these salts are soluble in water.
The table below shows the solubility of hydroxides of group 2 in 100g of water.
Elements
Mg
Ca
Sr
Ba

Hydroxides (x 10 -4)
0.2
15
39.7
150

The solubility of sulfates, MSO4 and carbonates, MCO3 of group 2

These salts have bigger anions. The solubility of these salts decreases as going down the
group.

32

The table below shows the solubility of sulfates and carbonates of group 2 in 100g of water.
Elements Sulfates (x 10-4)
Mg
1830
Ca
11
Sr
0.71
Ba
0.009

Carbonates (x 10-4)
1.5
0.13
0.01
0.009

As going down the group, charge density of cations decreases. Thus, the lattice energy a and
the hydration energy b decrease. However, the hydration energy b decreases more rapidly
than the lattice energy a.
energy
a
b
Be Mg Ca Sr

Ba

cations of group 2

Since the heat of solubility, Hsol = -b + (+a), (or a - b). BeSO4 and MgSO4 have lattice
energy a smaller than the hydration energy b. Thus, the Hsol of these sulfates become
exothermic. Consequent, these salts are soluble in water.
CaSO4, SrSO4 and BaSO4 have lattice energy a bigger than the hydration energy b. Thus,
the Hsol of these sulfates become endothermic. Consequent, these salts are insoluble in
water.

33

PAST YEARS QUESTIONS

OBJECTIVE
1990/19. One important use of concentrated sulphuric acid is for manufacturing paint. Paints
contain insoluble inorganic compound like lead(II)sulphate as pigment. Which of the
following compounds can be a substitute for lead(II)sulphate?
A K2SO4
B MgSO4
C BaSO4
D NiSO4
E ZnSO4
1991/14 (and 1995/15). Which of the following statements is correct in regarding to the alkali
earth metals (group 2)?
A They are solf.
B They form colourless cations.
C They form cations with two oxidation states.
D They do not produce characteristic colours in flame test.
E They react actively with water.
1992/15. Three of the group 2 elements react with water according to the following
equations.
I 2Mg + O2 2MgO
II 2Ca + O2 2CaO
III 2Sr + O2 2SrO
Which of the following pair of statement and reason is correctly matched?
Reactivity of reaction
Reason
A Decreases from I to III
Atomic size of metal atom increases.
B Decreases from I to III
Ionic characteristic of compound decreases.
C Same between I, II and III
These metals are equally reactive.
D Increases from I to III
Covalent characteristic of compound increases.
E increases from I to III
Strength as reducing agent increases.
1993/14. Which of the following statement explain the decreasing solubility of sulphates of
group 2 as descending the group?
A Enthalpy change of action decreases as the size of cations increase.
B Lattice energy of action decreases as the size of cations increase.
C The first and second ionization energies increase.
D Ionic characteristic in the sulphates decreases as the electronegativity of element
increase.
E Force of attraction between the action of elements and water molecule decreases in
strength causes the hydrogen bond in water molecule to increase.
1997/28. Which of the group 2 nitrate has highest thermal stability?
A Beryllium nitrate
B Magnesium nitrate
C Calcium nitrate
D Strontium nitrate
E Barium nitrate
1997/29. Which of the following statement is true concerning MgSO4 and SrSO4?
A Ionic radius of Mg2+ is larger than the ionic radius of Sr2+.
34

B
C
D
E

Hydration energy of Mg2+ is lower than the hydration energy of Sr2+.

Lattice energy of MgSO2 is lower than the lattice energy of SrSO4.
MgSO4 is less soluble than SrSO4.
MgSO4 is easier to decompose than SrSO4 when heated.

1998/25. Which of the following equation represent the thermal decomposition of magnesium
nitrate?
A Mg(NO3)2 Mg(NO2)2 + O2
B Mg(NO3)2 MgO2 + 2NO2
C Mg(NO3)2 MgO + N2O + O2
D 2Mg(NO3)2 2MgO + 4NO2 + O2
E 3Mg(NO3)2 Mg3N2 + 4NO2 +5O2
1999/20. Carbonates of group 2 elements decompose according to the following equation.
MCO3(p) MO(p) + CO2(g)
Which of the following is the correct match as descending group 2?
Lattice energy of MCO3
Lattice energy of MO Temperature of decomposition
A
Increase
Increase
Increase
B
Increase
Decrease
Decrease
C
Increase
Decrease
Increase
D
Decrease
Increase
Increase
E
Decrease
Decrease
Increase
2000/7. Which of the following is the characteristic physical property of Group 2 elements?
A They have high density.
B They have high melting point.
C They have low electronegativity.
D They have high solubility in water.
E They are good conductor at solid state.
2002/20. M is an element of Group 2. The following shows the thermal effect of several
compounds of M.
MCO3 MO + CO2
M(OH)2 MO + H2O
2M(NO3)2 2MO + 4NO2 + O2
Which of the following is correct concerning the thermal decomposition of compounds of
Group 2?
A
MSO4 decomposes to MO when heated.
B
All compounds of Group 2 are thermally unstable.
C
Thermal stability of compounds of M decreases descending Group 2.
D
Thermal decomposition happened to CO32, OH and NO3 anions because the
size of the anions is larger than that of the O2 2 ion.
2003/19 A sample of magnesium was contaminated by magnesium oxide reacts completely
with 22.0 cm3 of 2.0 mol/dm3 hydrochloric acid to evolve 448 cm3 of hydrogen gas at stp.
What is the percentage by mass of magnesium oxide in the sample?
[Relative atomic masses: O =16, Mg = 24; 1 mol of gas is 22.4 dm3 at stp]
A
C

14.29%
50.00%

B
D

16.67%
83.33%

2003/21 The solubility of sulphates of two elements of Group 2 are given as follows
Compound
Solubility (g/100 g of water at 20oC)
CaSO4
2.3 x101
35

BaSO4
2.3 x104
Which of the following best explain the data?
A
The size of the Ba2+ cation is larger than that of Ca2+ cation.
B
Barium ha lower ionization energy than calcium.
C
BaSO4 has lower lattice energy than CaSO4.
D
Ba2+ cation has a lower hydration energy than Ca2+ cation.
2005/25 The carbonate of Group 2 elements in the Periodic Table decomposes on heating.
Which of the following explains why the thermal stability of MCO3 increases down the
group?
A
Radius of M2+ ion increases.
B
The lattice energy of MCO3 decreases.
C
The charge density of M2+ ion decreases.
D
the distance between M2+ and CO32 ions increases.
1 only

B
1 and 2

C
2 and 3

D
1,2 and 3

1990/34. Which of the following statements correctly explain the properties of Group 2
elements in the Periodic Table?
1 The standard electrode potential of elements becomes increasingly more negative as
descending the group.
2 The elements are stronger reducing agents than the elements in Group 1 of the Periodic
Table.
3 Elements form compounds with oxidation states of +1 and +2.
1995/36. Elements of Group 2 form compounds with +2 oxidation state. Which of the
following statements explain the statement?
1 The +2 metal ions have acquired octet electronic configuration at the valence shell.
2 The electronic configuration of atoms of metals in Group 2 is ns2.
3 The second ionization energy of elements is lower than its first ionization energy.
1999/52. Which of the following statements correctly explain the increasing thermal stability
of carbonates of Group 2 elements?
1 Ionic radii of action increases as descending the group.
2 Density of charge for O2- ion is higher than the density of charge of CO32- ion.
3. The polarizing power of action increases as descending the group.
2000/48. The following table shows the successive ionization energy of element Y and Z.
element
Y
Z

Ionization energy kJ/mol

First
Second
494
4560
418
3070

Third
6940
4600

Forth
9540
5860

Which of the following statements correctly explain the elements Y and Z?

1 The first two electrons of elements Y and Z are eliminated from the 1s orbital.
2 The atomic size of Y is bigger than the atomic size of Z.
3 Y and Z are elements of Group 1.
36

2004/47 The decomposition temperature of the carbonates of Group 2 elements in the

Periodic Table increases down the group. Which of the following statements explains this
trend?
1 The size of cation increases.
2 The charge density of cation decreases.
3 The polarizing power of the cation toward the carbonate anion increases.
STRUCTURED
1995/3. (a) Explain why the reactivity of Group 2 elements increases as descending the
group.[2]
(b) i. Write a balance equation to show the reaction between hydrated beryllium
ions, [Be(H2O)4]2+ and water. [1]
ii. State the chemical properties that is exhibited by the hydrated beryllium ions
in the reaction. [1]
(c) Explain why beryllium forms covalent compounds while other elements in the same
group do not. [2]
(d) A sample of magnesium sulfate is contaminated with some barium sulfate.
i. State an experimental method where the barium sulfate can be separated from the
magnesium sulfate from the sample. Explain your answer. [2]
ii. State one industrial usage of barium sulfate. [1]
ESSAY
1990/4. (a) i. By using BeCl2, Be(OH)2 and BeO as examples, describe the atypical
properties of these beryllium compounds compare to the similar compounds of other
elements in 2.
ii. Give three properties of beryllium which is similar to the properties of other elements
in the same group.
1992/4. (a) Explain the thermal stability of nitrates, carbonates and hydroxides Group 2
elements in regarding to their position in the group. [5]
(b) State the trend of the solubility of sulfates for Group 2 elements. Explain; why the
solubility of BeSO4 and MgSO4 differs from the solubility of the sulfate of other elements in
this group. [4]
1992/5. (b) Explain the observations you may get from the following experiment and write
the balance equations involved.
Beryllium chloride is let expose to the moist air and then sodium hydroxide solution is added
to it. [6]
2000/6. (a) Explain; how the following properties change as descend Group 2 from
beryllium to barium and write balance equations involved.
i. The first ionization energy
ii. The reactivity of elements in reacting with water.
iii. Thermal stability of nitrates [14]
Answer:
1990:19C, 34A / 1991:14B / 1992:15E / 1993:14A / 1994:13C / 1995:15E, 36B
1997:28E, 29D / 1998:25D / 1999:20E, 52B / 2000:7E, 48C / 2001:6A
37

CHAPTER 3
GROUP 3 ALUMINIUM
1. Physical Data on Aluminium.
1.1a. Atomic and ionic properties:
Symbol:
27
13
Electronic configuration: 1s2, 2s2 2p6, 3s23p1
Atomic radius: 0.125 nm
Cationic radius: 0.050 nm
Charge density of ion Al3+: high charge density.
Ionization energies: 578(1st), 1816(2nd), 2744(3rd).

Al

b. physical properties.
Color: silver white and shining surface.
Density: low, 2.7 g/cm3.
Strength: high, hard malleable and ductile.
Conductivity of heat and electricity: excellent.
1.2. Extraction of aluminium.
Aluminium is found widely in the forms of hydrated aluminum silicates, rocks such as clays,
micas and feldspar and ores such as bauxite which contain hydrated aluminium oxide,
Al2O3.XH2O.
The aluminium is extracted from molten bauxite by electrolysis. The process is carried out in
a Hall-Heroult cell. The diagram of this electrolysis cell is shown as the diagram below.
Cathode (graphite)
anode (graphite)

Aluminum oxide in cryolite

molten aluminium

During electrolysis, Aluminium oxide which has very high melting point (2072oC) is added to
cryolite, Na3AlF6 in a Hall-Heroult cell. Since cryolite has lower melting point (1020oC), the
mixture melts at about 970oC. Thus, the addition of cryolite into the aluminium oxide has
greatly reduced the melting point of aluminium oxide. The molten is then electrolyzed.

38

Liquid of aluminium is formed at the graphite cathode.

1. Al3+(l) + 3e Al(l)
Oxygen is formed at the graphite anode.
2. 2O2-(l) O2(g) + 4e
At the high temperature and with the present of oxygen, the graphite anode burns away,
producing mainly carbon monoxide and some carbon dioxide
3. 2C(s) + O2(g) 2CO(g)
The overall reaction is:
(1)x4 = 4Al3+ + 12e 4Al
(2)x3 = 6O2- 3O2 + 12e
(+) (3)x3 = 6C + 3O2 6CO
4Al3+(l) + 6O2-(l) + 6C(s) 4Al(l) + 6CO(g)
Poisons gasses like carbon monoxide and hydrogen fluoride (HF) are produced during the
process. The highly corrosive gas, HF is formed is due to the decomposition of cryolite. And
carbon monoxide, CO is form by the incomplete burning of graphite during the electrolysis.
The extraction of aluminium consumes large quantity of electricity. To
produce one metric tonne (1000kg) of aluminum, about 1.3 x 104 to 1.7 x 104 kW
is needed.
During this process, a direct current of over 1.0 x 105 A at the potential
different of 5 Volt is used and the graphite anode will burn away within 20 days.
To produce one metric tonne (1000kg) of aluminum, about 1.3 x 104 to 1.7 x 104
kW is needed. These make the extraction of aluminium expensive.
Bauxite is non renewable recourse. The excessive mining of bauxite has
causes soil erosion, land pollution and finally the extinction of bauxite. Thus, the
recycling of aluminium waste such as aluminium articles and container becomes
increasingly more important. The recycling of aluminium helps to reduce the
mining of bauxite and at the same time making aluminuim cheaper. To recycle
one metric tonne of aluminium, it needs only 10% of the energy required
compares to the extraction of the metal through electrolysis of bauxite.
3. Uses of aluminium.
Aluminum forms two main alloys that widely use in the transport, food and construction
industries. These alloys are Duralumin which contains 95%Al and 4%Cu and Magnalium
which contains 83%Al, 15%Mg and 2%Ca.
In the transport industry, they are extensively used in the construction of air crafts, ships,
boats, cars, and bicycles due to aluminum is strong, light, excellent in conducting heat and
resistant to corrosion.
In the food industry, aluminum is widely used for food packaging, soft drink bottles and
making cooking utensils. This is due to its excellent conductor of heat, light, strong and it is
non-toxic.
In the construction industry, aluminium is widely use for making door and window frames
because it strong, light and resistant to corrosion. Aluminium sheet or foil is also used as
reflector of heat or as insulator in buildings due to it highly reflective shiny surface.

39

Other uses are: High voltage cable (light, excellent conductor of electricity), radiator or heat
exchanger (good conductor of heat) and navigation instruments (non-magnetic).
4. Chemical properties of Aluminium.
Aluminium is a strong reducing agent. It is located at a relatively high position in the
electrochemical series.
Al3+ (aq) + 3e Al(s)
Eo = -1.67volt
Reactions of aluminium.
4.1. Aluminium reacts readily with oxygen.
4Al + 3O2 2Al2O3.
This leads to the forming of a thin layer of Al2O3 on the metal. Al2O3 is non porous and
strongly binds at the surface. These make aluminium resistance to further chemical attack.
4.2. Aluminium which is at the higher position in the electrochemical series. This means the
aluminium atom has higher tendency to release or donate electrons. Thus aluminium
displaces ions which are lower position in the series from their solutions. This reaction is
called the displacement reaction.
Example: 3Cu2+ + 2Al

2Al3+ + 3Cu

4.3. Reactions of Aluminium with acid and alkali solutions.

Reaction with hot dilute acid and alkali solutions:
2Al + 6H+
2Al + 2OH + 6H2O

2Al3+ + 3H2.
2[Al(OH)4] + 3H2

The reactions are slow initially because of the thin layer of aluminium oxide. However,
after the layer of oxide has been removed, the reaction becomes increasingly more vigorous.
Since aluminium reacts with acid and alkali, thus, aluminium is amphoteric.
On the other hand, concentrated and dilute nitric acid and concentrated sulfuric acid oxidized
aluminum. As a result, a thin layer of oxide forms at the surface of the metal and thus,
aluminum is rendered passive under such conditions.
4.4. Thermite reaction.
Since aluminium is a strong reducing agent, it has high affinity of oxygen. In the thermite
reaction, a coarse mixture of aluminium powder, iron(III) oxide and barium peroxide is
ignited by burning magnesium ribbon. The reaction that ensues is violently exothermic,
proceeding with a shower of sparks and brilliant white glare. The temperature of the reaction
may reach 3000oC. Molten iron is formed as the aluminium reduces the iron(III) oxide
2Al(s) + Fe2O3(s) 2Fe(l) + Al2O3(s) H = -1676kJ/mol.
To join rails, this mixture is filled into a mould that set at the rails ends. The mixture is then
ignited and the molten iron is produced. The molten iron, which is denser, runs down into a
mould around the rails ends, joining them together.
In these reactions above, we have seen that, Al reacts as a reducing agent and it is oxidized.
Its oxidation number increases from 0 to +3.
40

5. Chemical properties of aluminium compounds.

Aluminium forms both ionic and covalent compounds.
Aluminium forms highly charge and relatively small size Al3+ ion. Thus, this ion has very
high charge density and becomes highly polarizing. This characteristic of aluminum ion is
account for:
i.
High covalent characteristic in aluminium compounds.
ii.
Al3+ ion has very high hydration energy.
iii.
Solution of aluminium salts is acidic.
5.1 Aluminium oxide.
Aluminium oxide is an ionic compound that has high covalent characteristic due to high
charge density of Al3+ ion.
Aluminium oxide is non porous and can bind strongly on the surface of aluminium. It is
insoluble in water. Thus, it serves as a protective layer to the metal.
This layer of oxide can be made thicker by means of anodizing. Anodizing is an electrolysis
process where the electrolysis is carried out on dilute sulfuric acid by using aluminium as the
anode and graphite as the cathode.
G
Anode
Aluminium

cathode
graphite

Dilute sulfuric acid

During the electrolysis, the hydroxide ions are being discharged at anode. As a result, oxygen
is produce. This oxygen immediately oxidized the aluminium that acts as the anode to
produce aluminum oxide.
4OH 2H2O + O2 + 4e
4Al + 3O2 2Al2O3
Anodizing makes aluminium more durable to corrosion and the ability of aluminium oxide to
absorb dyes enable the metal to be dyed with desirable colours.
High charge density of aluminium ion causes aluminium oxide has high covalent
characteristic. Thus, the oxide becomes amphoteric. It reacts with both hot dilute acid and
alkali solution.
Al2O3 + 6H+ 2Al3+ + 3H2O
Al2O3 + 2OH + 3H2O 2[Al(OH)4]
5. 2 Halides of aluminium.
Aluminium reacts with halogen to form aluminium halides. Aluminium fluoride, AlF3, is
ionic. However, AlCl3, AlBr3 and AlI3 are covalent compounds. The Al3+ ion has high charge
density, thus, it polarizes the anions and causes these compound to become covalent.
Solid AlCl3 is consists of dimer molecules, Al2Cl6. These dimers are form by dative bond
between two AlCl3 molecules as shown in the diagram below.
41

Cl

Cl
Al

Cl
Dative bond between two
AlCl3 molecule.

Al

Cl

Cl

Cl

Draw the Lewis structure of Al2Cl6.

In solid, dimer (Al2Cl6 ) molecules are held together by weaker van der waals forces.
When the solid is heated (180oC), it sublimes, forming vapor that contains Al2Cl6 molecules.
Heat energy is used to break up van der waals forces between dimers.
Al2Cl6 (s) Al2Cl6 (g)
If the vapor is heated further, the dimers dissociate at 400oC, forming AlCl3 molecules. Heat
energy is used to break up the dative bonds between AlCl3 molecules.
Al2Cl6 (g)

2AlCl3(g)

Why gas molecule of aluminum chloride at 200oC has relative molecular mass two times
higher than the gas molecule of aluminum chloride at 500oC?
State the shape and draw the structural formula of AlCl3 and Al2Cl6.
If the solid is left expose to moisture, it produces white fumes of hydrochloric acid, HCl due
to hydrolysis
Al2Cl6 (s)

3H2O(l)

Al2O3(s)

6HCl(g)
white fume

5.3 Aluminium hydroxide.

Aluminium hydroxide appears as white gelatin like precipitate. It is insoluble in water.
Aluminium hydroxide is amphoteric. It reacts with both acid and alkali.
Al(OH)3(H2O)3(s) +
Al(OH)3(H2O)3(s) +

H+ (aq) [Al(OH)2(H2O)4] + (aq)

OH(aq)

[Al(OH)4(H2O)2] (aq)

H2O

Explain why white precipitate is form when sodium hydroxide is added to an aqueous
solution contains Al3+ ion. The white precipitate dissolves upon adding dilute HCl and when
excess sodium hydroxide is added.
6. Chemical properties of the solutions of aluminium salts.
6.1. The acidity of aluminum salts solutions.
Solutions of aluminum salts are always acidic.
Al3+ ions have high charge density and become hydrated in its aqueous solution. Hydrated
[Al(H2O)6]3+ ions are formed.
Al3+

6H2O

[Al(H2O)6]3+
42

The coordinated water molecules in the hydrated [Al(H2O)6]3+ ions are highly polarized by
the Al3+ ion. As a result, the O H bonds of these water molecules become extremely
polarized and weaken, making [Al(H2O)6]3+ ions easier to dissociate by donating proton, H+
or the [Al(H2O)6]3+ ions go through hydrolysis in water.
[Al(H2O)6]3+(aq) +

H2O(l)

[Al(OH)(H2O)5]3+(aq)

+ H3O+(aq)

Thus, the hydrated [Al(H2O)6]3+ ions become hydrolyzed. The hydrolysis of [Al(H2O)6]3+ ions
resulting in the forming of additional hydrogen ions, H3O+ in the solution. Consequently, the
concentration of hydrogen ions, H3O+ becomes greater than 1 x 10-7 mol dm-3. Hence, the pH
value of the solution falls below 7.0 or the solution becomes acidic.
6.2. Reactions with acids and alkalis.
Since the aluminium salt solution is acidic, it neutralizes alkali solutions such as dilute
sodium hydroxide and ammonia solution. White gelatin like precipitate aluminium
hydroxide, Al(OH)3(H2O)3 is formed.
[Al(H2O)6]3+(aq) + 3OH(aq) Al(OH)3(H2O)3(s) + 3H2O(aq)
Aluminium hydroxide is amphoteric. It dissolves in excess of aqueous sodium hydroxide or
acid.
Al(OH)3(H2O)3(s) + OH(aq) [Al(OH)4(H2O)2] (aq) +
Al(OH)3(H2O)3(s) + H+ (aq) [Al(OH)2(H2O)4] + (aq)

H2O

[Al(H2O)6]3+ ion is a stronger acid than the carbonic acid, H2CO3. When sodium carbonate
solution, white gelatin like precipitate aluminium hydroxide, Al(OH)3(H2O)3 is formed
instead of aluminium carbonate precipitate.
2[Al(H2O)6]3+(aq) + 3CO32- 2Al(OH)3(H2O)3(s) + 3CO2(g) + 3H2O(l)
7. The alums and its uses.
Alums are double salts with the general formula as M(I)M(III)(SO4)2.12H2O.
Examples: KAl(SO4)2.12H2O is potash alum and KCr(SO4)2.12H2O is called chrome alum.
These salts dissolve in water, they produce simple ions like K+,Al3+, Cr3+and SO42- ions.
Potash alum and aluminium sulfate are widely used as mordant in dyeing cloths.
First, the cloth is soaked with potash alum solution. Secondly, an alkali solution is added into
it. As a result, precipitate of Al(OH)3(H2O)3 is deposited on the fibers and it bites into the
cloth. Lastly, dye is added. The precipitate of Al(OH)3(H2O)3 helps to absorb and bind the dye
molecules strongly into the fibers of the cloth.
Alums are also widely use in treating water in water treatment plant.
Firstly, water is pump into a filter where solid particles are filtered off. Then, water is stored
in a reservoir. Next, some alum is added into the cloudy water and it is allow to stand for
some time. The Al3+ ion has high charge density, attracts colloids particles such as mud
particles in the water to form heavier and insoluble precipitate of aluminium. These heavier
particles then saddle to the bottom of the reservoir, leaving the clear water on top. After that,
clear water is pump into another reservoir where some chlorine is added to kill most of the
living microbes. Lastly, clean water is pumped to houses for consume.
43

8. Uses of aluminium compounds.

Al2O3 also called alumina. It is used as adsorbent in the thin layer and the column
chromatography. It also used as dehydration agent like dehydration of alcohols.
AlCl3 as catalyze in many chemical reactions in organic chemistry.
Al2(SO4)3 and Al(OH)3(H2O)3 are both use as mordant in dyeing industry and in water
treatment.
Alum is used for water treatment.
Al(C2H5)3 is a component of the Ziegler-Natta catalyst.

PAST YEARS QUESTIONS

OBJECTIVE
1990/16. Which of the following ion is produced when excess sodium hydroxide solution is
added into an aqueous solution that contains Al3+ ion?
A H2O+ B [Al(H2O)5OH]2+ C [Al(H2O)4(OH)2]+ D [Al(H2O)2(OH)4] E
[Al(H2O)3(OH)3]
1991/15. The electrode potential of aluminium is 1.66V. This shows that the element is
reactive in chemical reaction. However, the metal has very high resistance toward corrosion.
Which of the statements correctly explain aluminium has high resistance toward corrosion?
A The Al3+ ion has very high density of charge.
B The aluminum atoms are closely packed in its lattice.
C The metallic bond between aluminum atoms is strong.
D Aluminium forms amphoteric compounds.
E Aluminum forms a layer of oxide on its surface.
1991/36. Which of the following reactions take place at the electrodes during the extraction
of aluminium by electrolysis?
1 2O2- O2 + 4e
2 2C + O2 2CO
3 Al3+ + 3e Al
1992/16. Aluminium is extracted from the molten that is made up of aluminium oxide and
cryolite. Cryolite reacts with aluminium oxide as the following equation.
Na3AlF6 + Al2O3 3Al3+ + 3Na+ + 3O2- + 6FThis shows that
A aluminium oxide acted as a base.
B aluminium oxide acted as an acid.
C the reaction is a redox reaction.
D cryolite prevents the oxidation of aluminium.
E cryolite enables aluminium oxide to form free ions.
1992/35. Anhydrous aluminium chloride dissolves in benzene. Which of the following
statements correctly explain the compound in benzene?
1 The electronic configuration of aluminum atom in aluminum chloride had acquired octet
rule.
2 Aluminum chloride exists as dimer, Al2Cl6.
3 Van de Waals forces exist between AlCl3 molecules.

44

1993/15. Which of the following statement is correct concerning aluminium (III) chloride?
A AlCl3 is a pyramidal shape molecule.
B AlCl3 is ionic compound.
C AlAl bond exist in Al2Cl6 dimer.
D AlCl3 dissolves in water to form an acidic solution
E AlCl3 dissolves in HCl solution to form complex ion, [AlCl3]3-.
1994/16. Copper is commonly used to make wires. However, high voltage cables are made of
aluminium. Which of the following explain the use of aluminum?
A Aluminium is cheaper
B Aluminium is more reactive
C Aluminium is lighter
D Aluminium is more resistible to corrosion
E Aluminium is better conductor of electricity
1995/16. The following diagram shows an electrolytic cell used in the extraction of
aluminium.
p
Q

A
B
C
D
E

P
Graphite as anode
Graphite as anode
Graphite as anode
Platinum as cathode
Graphite as cathode

Q
Graphite as cathode
Platinum as cathode
Platinum as cathode
Graphite as anode
Graphite as anode

R
Molten Al2O3 in Na3AlF6
Molten Al2O3 in Na3AlF6
Molten Al2O3
Molten Al2O3 in Na3AlF6
Molten Al2O3 in Na3AlF6

1996/25. A strip of aluminium plat is dipped into dilute aqueous sulphuric acid solution and
then is connected to the anode of a battery. Then, the aluminium strip is further tested for its
ability against corrosion. Which of the following is the correct match for the ability of
aluminium to withstand corrosion and its reason?
Ability to withstand
corrosion
reason
A
Increase
Aluminium ions were reduced to aluminium atoms at the
surface of the aluminium strip.
B
Increase
Aluminium atoms were oxidized to aluminium oxide at
the surface of the aluminium strip.
C
No change
Aluminium atoms were oxidized to aluminium oxide at
the surface of the aluminium strip.
D
Decrease
Aluminium ions were reduced to aluminium atoms at the
surface of the aluminium strip.
E
Decrease
Aluminium atoms were oxidized to aluminium oxide at
the surface of the aluminium strip.

45

1997/27. Most of the chemical properties of aluminium are due to the high polarizing power
of aluminium ion. Which of the following chemical properties of aluminum is not related the
high polarizing power of aluminium ion?
A Aqueous solution that contains [Al(H2O)6]3+ is acidic.
B High hydration energy for Al3+ ion.
C The ability of Al3+ ion to form complex.
D AlCl bond is highly covalent.
E High lattice energy for AlF3.
1997/55. Aluminum is gradually replacing iron as material used for the construction of engine
block for vehicles. This is because
1 aluminum has high resistance to corrosion.
2 aluminum has strong metallic bond.
3 aluminum has high density.
1998/24. An oxide has the following properties:
i.
Melting point is 2980 oC.
ii.
It dissolves in sodium hydroxide.
iii.
It forms ionic bond with covalent property.
The oxide is
A Al2O3
B P4O10
C SiO2
D ZnO
E Na2O
1998/26. Aluminium oxide is insoluble in water because
A Aluminium oxide has high melting point.
B Aluminium oxide is amphoteric.
C Aluminium oxide has high covalent property.
D Aluminium oxide is not polarized.
E Al3+ has small ionic size and high density of charge.
1998/27. Gas is released when sodium sulphide is added into an aqueous solution of
aluminium chloride. The gas is
A Cl2
B CO2
C SO2
D HCl
E H2S
1998/53. Which of the following is true regarding to the extraction of aluminium in
electrolysis?
1 Carbon monoxide is formed at cathode.
2 The overall reaction is 3C + Al2O3 3CO + 2Al.
3 If the graphite electrode is replaced by platinum rod, carbon monoxide would not have
released.

46

1999/21. A series of test is conducted on a solution that contains ion Mn+. The tests and
observation are given as in the following table.
Test
To some solution of Mn+

Observation

i. Add some aqueous sodium

hydroxide solution and then add
excess of sodium solution
ii. Add some aqueous sodium
sulphide solution. Test the gas release
by placing a strip of wet lead ethanoate
test paper in the test tube.

White precipitate is formed and it dissolved in

Excess of sodium hydroxide.

Which of the ion fits to the observations?

A Al3+
B Ba2+
C Ca2+

Colour gas with pungent smell is released. The

Gas turns lead ethanoate test paper to black.

D Mg2+

E Pb2+

2000/21. Which of the following correctly explain why aluminium oxide does not dissolve in
water but soluble in aqueous solution of an acid and a base?
A Aluminium oxide is amphoteric.
B Aluminium oxide is a stable compound.
C Aluminium oxide has partially covalent bond.
D Aluminium oxide has high lattice energy.
E Aluminium oxide forms complex ion.
2001/17. Metal aluminium is easily oxidized to form a layer of aluminium oxide deposited on
its surface. This deposit can be removed by using aqueous solution of
A Sodium hydroxide B Sodium chloride C Nitric acid
D Zink sulphate
2001/22. An aqueous solution of aluminium chloride has pH less than 7 because
A aluminium ion has high charge.
B aluminium ion becomes hydrolyzed in water.
C aluminium chloride ionized partially in water.
D aluminium chloride is a covalent compound.
2002/46. Aluminium is used in the transportation industry to make air plane because
1 it has low density
2 it resists corrosion
3 it is an excellent heat conductor
2003/20. Which of the following about the property and use of Aliminium is correct?
Property
Use
A
Good heat conductor
Aluminium Paint
B
Good light reflector
Cooking Pot
C
Resistance to corrosion
Electrical cable
D
Low density
Aircraft body
2004/23. Which of the following is not true of aluminium choride?
A
It is an ionic compound
47

B
C
D

Its aqueous solution is acidic

It is a white solid which sublimes when heated
It acts as a Lewis acid catalyst in the Friedel-Craft reaction

2005/24. Aluminium oxide is suitable to be used as an inside coating of high temperature

furnaces. Aluminium oxide is thermally stale because
A
it is an ionic compound
B
it is amphoteric
C
the charge density of Al3+ ion is high
D
its enthalpy of formation is very exothermic
STRUCTURED
1990/2. a. Most of the internal structure of a warship is constructed by using Aluminium. The
warship bursts into flame in just a few minutes when it is struck by a missile. According to
the fire expert, the damage can be reduced if steel is used for the construction of the internal
part of the ship. Give an explanation to the above statement base on the chemical property of
aluminium.[3]
b. Write the schematic reactions to show how Al(NO3)3.9H2O crystal is formed,
starting with an alum solution that contains K2Al2(SO4)4.24H2O. [4]
c. Explain; why Al2(CO3)3 can not be produced by adding Na2CO3 solution to an
aqueous solution of an aluminium salt. Write all chemical reactions involved. [2]
d. Sate one use of the reaction product in part (c). [1]
1996/2. a. When dry chlorine gas is passed on top of hot aluminium, reaction takes place to
form Al2Cl6.
i
Draw the structural formula for Al2Cl6.
ii
Write a balance equation for the reaction above.
iii
Sate one use of aluminium chloride. [3]
(b) If 1.0g of aluminium is used in the reaction above and 2.3g of AlCl3 is produced.
Calculate the percentage of yield. [2]
c Explain; why the solution of AlCl3 is acidic. [2]
ESSAY
1993/5. a. Describe the extraction of aluminum from bauxite. [5]
b. By the properties of aluminium ion, describe the properties of an aluminium salt
solution. [10]
c. Explain; with the help of balance equations
i
the reaction of AlCl3 with water.
ii
Al2(CO3)3 can not be produced by adding Na2CO3 solution to the aqueous
solution of an aluminium salt.
1998/6. a. Aluminium is widely used in the soft drink industry.
i
State three properties of aluminum that explain the use the metal in the
industry.
ii
State; how the recycling of aluminum is carried out. [5]
(b) Explain; why the aqueous solution of an aluminium salt is acidic. Write the
balance chemical equations involved.[4]
2001/8. (a) Aluminium is extracted mainly from Bauxite.
48

i.
ii.

Describe the extraction of aluminum from bauxite.

Explain; why aluminium is widely used in the aerospace industry. [7]

2002/ 8 (a) By referring to the bonding in aluminium oxide and aluminium chloride,
explain
i.
The amphoteric property of aluminium oxide
ii.
The reaction of aluminium chloride with water.
2004/7(b). Explain what would observed when an aqueous solution of potassium carbonate
is added to an aqueous solution contains aluminium ions. Write equation for the reactions that
occur. [6]
ANSWERS
1990: 16D
1991: 15E, 36D
1992: 16E, 35D
1993: 15D
1994: 16C
1995: 16A
1996: 25B
1997: 27C, 55A
1998: 24A, 27E. 53C
1999: 21A
2000: 21C
2001: 17A, 22B
A
1 only

B
1 and 2

C
2 and 3

D
1,2 and 3

49

CHAPTER 4
GROUP 14
1. ELEMENT AND PHYSICAL PROPERTIES
Element
Electronic
configuration
Atomic radius,
nm
First ionization
energy, kJ/mol
Metallic
properties
Conductivity

C
(Carbon)

Si
(Silicon)

1S2,
2S22P2
0.077

(Ne)
3S23P2
0.114

Ge
(Germanium
)
(Ar) 4S24P2

Sn
(Tin)

Pb
(Lead)

(Kr)5S25P

(Xe)6S26P

0.122

0.140

0.154

1090
970
760
710
720
Ionization energy decreases descending group 14 due to the
increase in the atomic ridius.
Non
metal

Metalloid

Metal

conductivity

Cgraphite Si
Crystal lattice
Melting point
(K)

Ge

Sn

Pb

Giant covalent molecular structure (like Giant metallic crystal

diamond)
structure
3800
1683
1211
505
601
Atomic radius increases, weaker bond is formed between atoms.
Melting point derceases as descending group 14.

2. RELATIVE STABILITY OF OXIDATION STATES AND COMPOUNDS

Elements of group 14 exhibite two oxidation states, +2 and +4, in their compounds. For nonmetals, the most common oxidation state is +4 while metals have +2 as the most common
oxidation state +2.
Element:
C
Si
Ge
Sn
Pb
Stability of +2:
oxidation state

INCREASES

Stability of +4:
oxidation state

INCREASES

50

Descending group 14, the metallic properties increases. The atom of element shows an
increasingly higher tendency to keep the nS2 pair of electrons of the valance shell from
involving in bonding. Thus, the stability of +2 oxidation state increases. The tendency of
keeping the nS2 pair of electrons of the valance shell from involving in bonding is called the
inert electrons pair effect.
Lead (Pb), shows strongest inert electrons pair effect. In chemical reactions, Lead atom keeps
6S2 pair of valence electrons and uses only the 6P2 pair of the valence shell for bonding.
Thus, lead forms compounds with oxidation state of +2 rather than +4. Compounds of lead
with oxidation number of +4 are unstable and easily change to compounds with oxidation
state of +2.
Therefore, lead compounds with oxidation state of +4 are strong oxidizing agent and they are
readily reduced to compounds with oxidation state of +2.
Carbon shows lowest inert electrons pair effect. In reaction, the atom does not keep the 2S2
pair of the valence electrons. However, it uses both 2S2 and 2P2 pairs of the valence electrons
in bonding. Thus, carbon forms compounds with oxidation state of +4 rather than +2.
Compounds with oxidation state of +2 are unstable and easily change to compounds with
oxidation state of +4.
Therefore, carbon compounds with oxidation state of +2 are strong reducing agent and they
are readily oxidized to compounds with oxidation state of +4.
3 OXIDES
Elements of group 14 form oxides of MO and MO2.
The following table shows the relative stability of these oxides.
Elem
ent
Oxid
e:
MO

CO
unsta
ble

Si

Ge

stabil
ity

increa
ses

SiO
unsta
ble

GeO
unsta
ble

SiO2
stabl
e

GeO2
stable

Sn

Pb

SnO
unsta
ble

PbO
stabl
e

SnO2
stabl
e

PbO2
unsta
ble

MO2
CO2
stabl
e

stabil
ity

increa
ses

3.1. Thermal stability of oxides

Stability of oxides, MO: Increases descending group 14 according to CO < SiO < GeO <
SnO < PbO.
51

CO, SiO, GeO and SnO are thermally unstable and easily oxidized to CO2, SiO2, GeO2, and
SnO2 respectively when heated. Thus, CO, SiO, GeO and SnO are reducing agent. The
strength as an reducing agent decreases from CO to SnO.
2CO + O2 2CO2
2SnO + O2 2SnO2
In industry, CO is the reducing agent used to reduce Fe2O3 and SnO2 in the extraction of iron
and tin.
3CO + Fe2O3 3CO2 + 2Fe
2CO + SnO2 2CO2 + Sn
Stability of oxides, MO2 : Decreases descending group 14 according to CO2 > SiO2 > GaO2 >
SnO2 > PbO2.
PbO2 is thermally unstable and easily reduced PbO when heated. Thus, PbO2 is a strong
oxidizing agent.
2PbO2 2PbO + O2
3.2. Acidity of oxides
Element
Monoxide:
MO
Bonding and
structure

C
CO

Covalent
Discrete covalent molecular
structure

Acidity:

Dioxide: MO2
Bonding and :

Acidity:

Si
SiO

Neutral

CO2

Ge
GeO

Sn
SnO

Pb
PbO

Ionic
with strong covalent characteristic
Giant ionic structure
Amphoteric
As base: MO + 2H+ M2+ + 2H2O
As acid: MO + 2OH- + H2O M(OH)42-

SiO2

Covalent
Discrete
Giant
Covalent
covalent
molecular
molecular
structure
structure
Acidic
MO2 + 2OH MO32- +
H2O

GeO2

SnO2
PbO2
Ionic
with strong covalent characteristic

Intermediate of giant covalent molecular

and giant ionic.

Amphoteric
As base: MO2 + 4HCl MCl4 + 2H2O
As acid: MO2 + 2OH- + 2H2O M(OH)62-

52

TETRACHLORIDES
Element
Tetrachloride
Bonding, structure
and shape

C
CCl4

Physical state
Boiling point

Si
SiCl4

Ge
Sn
GeCl4
SnCl4
Covalent
Discrete covalent molecule
Weak Van der Waals froces between molecules
Tetrahedron
Volatile liquid, low boiling point.

Temperature

CCl4

Pb
PbCl4

PbCl4
(decomposes before the
GeCl4
boiling point)
SnCl4
SiCl4

Cl
M
Cl
Cl
Cl

Hydrolised by
water

Not hydrolised
No d orbital in
carbon atom

Hydrolised
The metal atom has vacant d orbitals
MCl4 + 2H2O MO2 + 4HCl
White fumes of HCl are produced when the
tetrachloride is exposed to moist air.

The mechanism of hydrolysis of tetrachloride:

Oxygen atom of H2O molecules donate one lone pair each to the
silicon atom of the SiCl4 molecule.
SiCl4 + 2H2O SiCl4(H2O)2
SiCl4(H2O)2

H2O

Cl

Cl
Si

Cl

Cl
H2O

Further hydrolysis eliminates 4HCl molecules as white fumes and

produces SiO2
SiCl4(H2O)2 SiO2 + 4HCl
Overall
SiCl4 + 2H2O SiO2 + 4HCl
53

5 SILICATES
Silicates are minerals that contain silicon. They made up of 75% of the earth crust. Silicates
minerals include asbestos, mica, clay, granite, feldspar and sand.
The basic unit of silicates is SiO44-, which has the shape of tetrahedron.
O
Si

Oxygen
O

O
Stereochemical formula

Silicon
top view

5.1 Classification of silicates

i. Primary structural unit silicates
(a) Silicates with discrete SiO44- ion.
The silicate anion combines with other cations to form simple silicate minerals like Mg2SiO4,
ZrSiO4, Fe3Al2(SiO4)3 and Be2SiO4. They contain discrete SiO44- ions.
Example:
O
Si
2+

O)

( Mg )2( O
O

Top view

(b) Pyrolesilicates
Two silicate ions, SiO44-, combine by the sharing one oxygen atom to form Si2O76- anion.

Examples: Sc2Si2O7 and Na6Si2O7.

O
O
6Si2O7 anion:
Si
Si
O

O
O
O

O
O
O
Top view
O
O
O
(c) Ring silicates
Three silicate
ions, SiO44-, combine by each silicate ion sharing two oxygen atoms to form
O
Si3O96- anion. Si
O

Example: BeTiSi3O9.
Si
Si
O
O
Si3O96- anion:
O
Si
Si

O
Si O
O
O
O
The empirical formula is SiO32-

Top view
54

ii. Chain silicates

(a) Pyroxenes
The silicate ions, SiO44-, combine by the sharing two oxygen atoms to form a single long
chain structure.
Example: MgSiO3 and CaMg(SiO3)2.
The repeating unit is SiO32-.
SiO44- sharing two oxygen atoms
O

Si

Si

O
O

Si
O
O

O
Si
O

The SiO32- repeating unit.

(b) Amphiboles
Double chain silicate is formed as silicate ions, SiO44-, combine by each silicate ion sharing
two or three oxygen atoms alternately. The repeating unit is Si4O116-. Example: Asbestos. It is
brittle, hard and good insulator of heat and electricity.
O

Si
O

Si

O
O

O
Si first chain
O

Si

O
O

Si
O

O
Si
O
Si
O

O
Si

O
The repeating unit

O
O

Si
O

Si

second chain
O

First chain

55

Second chain
iii. Layer / sheet silicates
Sheet silicate is formed as silicate ions, SiO44-, combine by each silicate ion sharing three
oxygen atoms. The repeating unit is Si2O52-. The structure is like amphibole. 3 or more chains
are joined together and the hexagon rings are extended in both directions to form a layer
structure. The layers can glide over each other. Hence they are slippery and soft. Example:
Mica, talcum, kaolinite and montmorillnolite.
Mica
First chain

Second chain

Third Chain

Mica:
O

Si

Si

Si

O
Si

Si
O

O
Si
O
Si
O

O
Si
O

First chain

O
O

O
O

O
O

Si
O

third chain

Si
O

O
Si

The repeating unit

Si

O
O

Si

second chain

Si

O
O

Si

Forth chain
O
56

Si O
O

or
-O

OSi

-O

Si

OSi

-O

OO

Si

Si

-O

O-

-O

O-

Si
-O

O-

iv. Framework silicates

Framework silicate is formed as silicate ions, SiO44-, combine by each silicate ion sharing
four oxygen atoms. The repeating unit is SiO2.
Examaples: quartz, tridymite and cristobalite are crystaline forms of pure SiO2 and sand is
the impure form of SiO2.
Quartz:
O
O

Si

O
O

Si

O
O

Si

O
O
O

Si

O
O

Si

O
Si
O

O
O

Si
O

Si
O

O
O
Three dimensional

6 ALUMINOSILICATES
Aluminosilicate is formed when some Si atoms in the silicate are replaced by aluminium
atoms. Other metal ions like K+, Na+, Mg2+, Ca2+ or Fe3+ are incorporated into it to maintain
electrical neutrality.
Example: Kaolinite, which empirical formula is Al2Si2O5(OH)4.
Aluminosilicate loses water on heating to form an open structure and porous material called
zeolite. Hard water contains a lot of Mg2+, Ca2+ and Fe3+ ions which cause soap ineffective for
washing. Zeolite is used as cation exchanger to remove soluble Mg2+ and Ca2+ ions from hard
water.
57

2NaAlSiO6 + Mg2+ Mg(AlSiO6)2 + 2Na+

Zeolit softens hard water by exchanging its sodium ions with magnesium or calcium in hard
water.
Zeolite also used as molecular sieve, catalyst for cracking and catalyst for hydration of ethene
to produce alcohol.
7 CLAY MATERIALS
Clays are hydrated aluminosilicates. They are also called silicate clays. Clay has layer
structure that consists of a octahedral sheet that made up of AlO4(OH)2 and a tetrahedral sheet
that made up of SiO4.
H2O
H2O

O
Al

Octahedral sheet

octahedral sheet
tetrahedral sheet

O
O

a layer

Si
O

Tetrahedral sheet
O

O
The layer is made up of one octahedral sheet and one tetrahedral sheet or with 1:1 ratio.
Example: Kaolinite Al2Si2O5(OH)4 , is made up of layers of 1:1 ratio. Between these layers
are relatively weak hydrogen bonds. This makes it easily broken up to sheet and brittle.

hydrogen bonds

Kaolinite is used for modeling and making ceramics, as filler for paint, rubber and plastic and
as cation exchanger softening hard water.
Al2Si2O5(OH)4 + Ca2+ Ca Al2Si2O7(OH)2 + 2H+
Ca2+ is capture by kaolinite in ground water became acidic and lack of free mineral ions. This
causes the soil infertile.
O
O
O
Si
tetrahedral sheet
O
H2O

O
Al

H2O

Octahedral sheet

O
Si
O

layer

tetrahedral sheet
Octahedral sheet
tetrahedral sheet

tetrahedral sheet
O
58

O
NO hydrogen bond between layer

Montmorillonite is a 2:1 clay. The layer is made up of 1 octahedral sheet is sandwiched by 2

tetrahedral sheet.
8 SILICONE
Silicone is an organosilicon polymer. The polymer can be of straight chain or of branched
chain structure.
Straight chain
R
R
R
R
Si

Si

O
R

Si

Si
R

Si

R
O

O
O

Si
R

O
R

O
O

Si
O

Branched chain
R
O

Si
O

Si

O
O

Si

Silicones are thermally stable, resist oxidation and attack from most chemical and good water
repellents. They are oily, greasy and rubbery material. Silicones are used as car wax and
shampoo, lubricant oils, hydraulic fluids, insulator, elastomer, paint, grease, and making
water-proof fabrics.
Silicones are made by hydrolysis of alkylderivative of chlorosilanes such as RSiCl3 or
R2SiCl2. The derivatives are produced by reaction of silicon with alkyl halide at the present of
copper as catalyst when heated.
Si + 2C2H5Cl (C2H5)2SiCl2
The derivatives also can be produced by the reaction between the Grignard reagent and
silicon tetrachloride.
C2H5 MgCl + SiCl4 C2H5SiCl3 + MgCl2
Hydrolysis of (C2H5)2SiCl2
(C2H5)2SiCl2 + 2H2O (C2H5)2Si(OH)2 + 2HCl

59

Polymerisation of (C2H5)2Si(OH)2 to form silicone, a condensation polymer.

C2H5
n (C2H5)2Si(OH)2 (

Si
O

nH2O

)n
C2H5

8. COMPOUND OF LEAD
Tetraethyl lead, Pb(C2H5)4 is tetrahedron covalent molecule and volatile liquid. The
compound widely used as petrol additive to increase the octane number of petrol. It is
prepared by reaction between lead tetrachloride and the Grignard reagent.
PbCl4 + 4C2H5MgBr

Pb(C2H5)4 + 4MgClBr.

The use of the compound as petrol additive is greatly reduced due to lead pollution in the air
and the used of catalyst converter in some vehicles.
9. USE OF TIN
Tin is a soft metal with low melting point.
It is widely used for making alloys like pewter (96%Sn, 3%Cu and 1%Sb), solder (70%Pb,
30%Sn) and bronze (70%Cu, 30%Sn).
It is less electropositive than iron. Thus, it is used in the plating of iron cans through
electroplating.
10. Glass.
Various types of glasses, their compositions and their usage; refers briefly to form 4
Chemistry.

60

PAST YEARS QUWSTIONS

OBJECTIVE
1990/17. Which of the following shows the change in acid and base properties of oxides of
elements in Group 14?
A Acid to amphoteric to acid
B Acid to base to neutral
C Acid to neutral to base
D Base to amphoteric to acid
E Base to acid to neutral
1991/4. Below is a table showing the boiling point of hydrides of Group14.
Hydrides
Boiling point / oC
CH4
- 164
SiH4
- 112
GeH4
- 89
SnH4
- 52
Which of the following best explained the increase of boiling point of hydride descending the
group?
A Increase in metallic property of the element
B Increase in strength of covalent bond between molecules
C Increase in strength of hydrogen bond between molecules
D Increase in strength of Van de Waals forces between molecules
E Increase in M Cl bond strength between the element and hydrogen in the hydrides
molecule
1991/16. Graphite has weak Van de Waals forces between layers of carbon atoms. Which of
the following explained the best use of graphite according to this property?
A As electrode
B As lubricating substance
C As conductor of heat
D As ink pigment E As moderator in nuclear reactor
1991/22. The following scheme shows the reactions of solid X
NaOH(aq)
White precipitate
soluble in excess of NaOH
HCl(aq)
Colourless
solution
White
Solid X
K4Fe(CN)6
precipitate
No change
Conc. H2SO4
A Al2O3

B PbO

C ZnO

D PbCl2

E ZnCl2

1991/37. Which of the following properties of oxide of elements in Group 14 increase when
descending the group?
1 Acidity of oxide
2 Covalent property in MO bond in oxide
3 Stability of +2 oxidation state in oxide

61

1992/17. Which of the following statements is true for both carbon and silicon?
A The elements form giant molecular structure
B The elements form hydride of MnXn
C The elements form double bond with oxygen
D Oxides of the elements dissolve in water
E Chloride of the elements hydrolyzed in water
1992/36. Graphite is used as lubricant in heavy industry because
1 it has high melting point
2 it has layer structure
3 it conducts electricity
1993/16. SiCl4 produce white fumes when exposed to moist air, while CCl4 is not
hydrolyzed by water Which of the following best explain the observation?
A CCl4 is inert
B CCl4 only hydrolyzed when heated
C Si Cl bond is weaker than C Cl bond
D Si atom in SiCl4 molecule has vacant d orbital.
E Coordination of water molecule to the carbon atom of CCl4 molecule during
hydrolysis develop strong steric effect in the molecule
1993/35. Compound X liberates chlorine gas when heated and forms acidic solution when
dissolves in water.
X could be
1 SnCl4
2 PbCl4
3 Al2Cl6
1994/17. Electronic configuration of valence shell of X is ns2np2 and the proton number of X
is between 14 to 50. Which of the following statements is true about the oxide of X?
A X form oxide XO, XO2 and X2O3
B XO is acidic
C XO2 is neutral
D XO form giant molecular structure
E XO2 is thermally stable.
1995/17. Which of the following statements is true for the tetrachloride of Group 14?
A Physical state of the chloride changes from liquid to solid descending the group
B Thermal stability decreases descending the group
C All chloride are hydrolyzed by water
D Only CCl4 is tetrahedron molecule
E CCl4 decomposes to CCl2 and Cl2 when heated.
1996/27. Water is added into test tubes X and Y which contain liquid CCl4 and SiCl4
respectively. Which of the following is the best predicted observation may be produced?
Test tube X
Test tube Y
A CCl4 dissolves
SiCl4 dissolves
B CCl4 remains insoluble
SiCl4 reacts with water to produce white fumes
C CCl4 remains insoluble
SiCl4 reacts with water to produce white precipitate
D CCl4 dissolves
SiCl4 reacts with water to produce white fumes
62

E CCl4 remains insoluble

SiCl4 reacts with water to produce white fumes and white

precipitate
1996/51. Which of the following oxides is amphoteric?
1 SiO2
2 GeO2
3 PbO2
1996/60. One way to detect air pollution is to expose a piece of filter paper with lead(II)
nitrate solution to a certain volume of polluted air. Precipitate of lead compound is than wash
with distilled water and the mass of precipitate is determined by weighing.
Which of the following pollutant gases may form the precipitate of lead compound?
1 H2S
2 SO3
3 NO2
1997/25. Which of the following statements is true for elements of Group 14 as descending
the group?
A Increase in stability in the +4 oxidation state
B Increase in the inert pair effect
C Increase in electronegativity
D Oxides become more acidic
E Boiling point tetrachloride decrease
1997/26. Graphite has delocalized electrons between the layers of carbon atoms. Graphite is
used as
A pencil lead
B moderator in nuclear reactor
C electrode
D lubricant substance
E decoluorizing agent
1998/28. Which of the following correctly match the use and the hardness of graphite and
diamond?
Diamond
Graphite
A Glass cutter
Electrode
B Decorating items
Reducing agent
C Pelelas
Moderator
D Insulator
Pencil lead
E Drill beat
Lubricating substance.
1998/29. Which of the following is true for tetrachloride of Group 14 as descending the
group?
A Stability of +4 oxidation state increases
B M Cl bond becomes stronger
C M Cl bond is ionic with high covalent characteristic
D All tetrachloride decompose when heated
E All tetrachloride react with water.
1998/54. The composition and the use of glass X and Y are shown in the following table
Glass
Composition
X
12%Na, 12%CaO, 76%SiO2
Y
5%Na2O, 3%CaO, 16%B2O3, 76%SiO2
The purpose of adding B2O3 in glass Y is to
1 increase the density of the glass
2 increase the melting point of the glass
3 reduce the expending index of thermal of the glass

Use
Glass bottles
Cooking utensils

63

1999/22. Which of the following explain the increase in stability of +2 oxidation state of
elements in Group 14 as descending the group?
A Increasingly more difficult to eliminate the two valence electrons in the s orbital.
B Increasingly more difficult to eliminate the two valence electrons in the p orbital.
C Increasingly more difficult to eliminate the four valence electrons.
D Increasingly stronger shielding effect.
E Increasing in ionization energy.
1999/23. X is an element of Group 14. The tetrachloride of X, XCl4 has the following
properties.
i. Easily hydrolyzed
ii. Thermally unstable
iii. Decomposes at room temperature to produce XCl2 and Cl2
X is
A Germanium
B Carbon
C Lead
D Silicon
E Tin
2000/22. Which of the following is formed when silicon is heated with chlorine?
A Si2+. 2Cl
B Si4+ .4Cl
C Cl Si Cl
D
Cl
Cl Cl
Si
Cl

Cl Si Si Cl
Cl

Cl Cl

Cl
2000/23. Which of the following best explain the thermal stability of chloride and oxide of
elements descending Group 14?
A Increase in bond energy
B Decrease in first and second ionization energies
C Decrease in standard electrode potential
D Increase in inert pair effect
E Increasingly easier to eliminate four valence electrons
2000/24. Which of the following is true for the electric conductivity of graphite?
A Electric conductivity of graphite is higher than that of a metal
B Electric conductivity of graphite is due to the three dimensional structure of graphite
C Electric conductivity of graphite is due to the presence of delocalized electrons
D Electric conductivity of graphite is due to the carbon atoms use sp2 hybrid orbital for
bond formation
E Electric conductivity of graphite is due to the electronic configuration of carbon is
1s2 2s22p2
2001/7. Which of the following is true for graphite, diamond and fullerene?
A Carbon atoms have delocalized electrons
B Existence of Van der Waals forces in the molecule
C Each carbon atom form four bonds with four neighbouring carbon atoms
D Complete combustion of the substance form carbon dioxide and water

64

2001/21. Oxide of X, XO2 has the following molecular structure.

O
X
O

X
O

X
O
X could be
A Carbon

B Silicon

C Tin

D Lead

2001/23. Oxide of Y liberates chlorine gas when it is heated with concentrated hydrochloric
acid. The solution produces white precipitate when dilute sulphuric acid is added. Oxide Y
could be
A SnO
B PbO
C SnO2
D PbO2
2002/21. The diagram below shows a type of silicate.
Oxygen
Silicon
Which of the following statements is true in regard to the silicate above?
A
It represents the structure of asbestos
B
The repeating unit of the structure is SiO42
C
The structure is found in pyroxene.
D
The ratio of Si atom to O atom is 1:4
2002/22. Oxide of a metal M dissolves in aqueous NaOH and HNO3 to form a colourless
solution. When some aqueous NaCl is added into the solution, a white precipitate is formed.
Oxide M could be
A
Al2O3
B
Fe2O3
C
PbO
D
SnO
2003/23 Carbon fibre is one of the components of a composite substance which is used to
make bulletproof jacket. Which of the following is not a property of carbon fibre?
A
Low density
B
Inert toward chemical substance
C
Stable at high temperature
D
Elastic

65

2003/27. Which statement about the oxide of the Group 14 elements (C to Pb) in the Periodic
Table is true?
A
All the oxides possess covalent bond
B
The acidity of the oxide with the +2 oxidation state increases down the group
C
The Oxide with the +4 oxidation state are more stable descending the group
D
The oxides with +4 oxidation state can react with alkalis
2004/20. Which of the following statements is true about the oxides of Group 14 elements (C
to Pb) in the Periodic Table?
A
All the oxides are covalent compounds
B
The general formulae of the oxides are MO and MO2
C
The oxides of silicon and germanium have amphoteric characteristic
D
The oxides with the +4 oxidationstate are more stable than those with tha +2
oxidation state.
2004/24. A few types of glasses can be produced by the addition of metal and (or) non metal
oxides to silicate. Which of the following glasses has the lowest expansion coefficient after
the addition of metal and (or) non metal oxide?
A
Soda glass
B
Borosilicate glass
C
Fused silica glass
D
Lead glass
2005/21. Which of the following oxides of Group 14 elements is the least thermally stable?
A
CO2
B
SiO2
C
SnO2
D
PbO2
2005/27. Which of the following statements is true of glass?
A
It consist of well arranged silicate unit
B
It withstand the action of strong alkalis
C
It softens at wide range of temperature
D
It can be coloured by adding soda lime
2005/43. Which of the following is/are true of carbon dioxide and carbon monoxide
molecules?
1. The molecules are polar
2. Carbon atom undergo sp hybridization
3. There are and bonds between C and O atom
STRUCTURED
1992/2. a. Leaded petrol contains additive tetramethyl lead(IV), Pb(C2H5)4, which can
increase the performance of cars engine. However, lead causes air pollution and poisoning to
human. Thus, leaded petrol is replaced by unleaded petrol that has equivalent efficiency.
i. By assuming petrol contains hydrocarbon of C8H18, write an equation to show the
combustion of the hydrocarbon in the excess of oxygen.
ii. Draw one branched structural isomer of C8H18.
iii. State three pollutant gasses found in the exhaust gas.
iv. Explain how one of the gasses mention causes air pollution.
v. Explain in term of chemistry, how tetramethyl lead(IV), Pb(C2H5)4, can increase the
performance of cars engine.
vi. State one other means, which can increase the performance of car engine. [8]
66

b. i. Why car fitted with catalyst converter must use unleaded petrol?
ii. What is the function of the catalyst converter? [2]
1994/3. a. The following diagrams are two dimensional crystal structures for asbestos and
talcum.
oxygen
silicon
asbestos
talcum
i. Sketch a three dimensional diagram to show the basic structural unit that forms the
silicates.
ii. State the difference that occurs in the arrangement of the basic units of silicates in
asbestos and talcum.
iii. Explain the the differences that occur interm of the sharing of oxygeen atoms between
the basic units of silicates in asbestos and talcum.
iv. Give one physical property of asbestos and one physical property of talcum. [7]
b. i. Carbon dioxide and silicon dioxide have very distinct different physical properties. At
room temperature, carbon dioxide is gas whereas silicon dioxide is hard crystalline solid.
Explain this statement in term of bonding and structure.
ii. Why concentrated alkali solution is not suitable to be kept in glass bottle? [3]
2000/2. a. Tetrachlorides of group 14 are CCl4, SiCl4, GeCl4, SnCl4 and PbCl4 are liquid at
room temperature. All tetrachlorides, except CCl4, are hydrolyzed in water to produce acidic
solution.
i. State the molecular shape of these tetrachlorides.
ii. Which of this tetrachloride has highest boiling point?
iii. Write equation of hydrolysis for SiCl4.
iv. State why CCl4 is not hydrolyzed. [4]
2003/3 (a). Silicon is mainly used as a semiconductor in the electronic industry. For this
purpose, the silicon used has to be of highest purity. The initial step in the purification of
silicon is to convert it into silicon tetrachloride which is volatile, followed by the reaction
with hydrogen.
(i)
Write balance chemical equations for the reaction which accur in the initial
step of the purification of silicon.
(ii)
State why silicon tetrachloride is volatile
(iii)
State two methods which can be used to increase the electrical conductivity of
silicon.
(b). Kaolinite, Al2Si2O5(OH)4, is a hydrated alminosilicate mineral clay which is able
to absorb cations in aqueous solution on its surface according to the following
equilibrium equation.
M+ + Al2Si2O5(OH)3OH Al2Si2O5(OH)3OM + H+
(i)
State the oxidation number of silicon in kaolinite.

67

(ii)

State why basic clay is not suitable for most plant.

(iii)

Suggest a use of kaolinite with reference to the above equilibrium equation.

ESSAY
1990/5. a. Compare the thermal stability and other chemical properties of tin oxide and lead
oxide. In your answer, include the appropriate chemical equations for the reactions. [16]
b. Dilute nitric acid is added to triplumbum tetraoxide, Pb3O4 and followed by bubbling
gaseous sulphur trioxide through the products of the reaction. Explain the observation and
write appropriate chemical equation for the reaction involved. [4]
1994/6. a. Describe the following properties by referring to the elements in group 14 of the
Periodic Table. In your answer, write equation of reactions involved.
i. Reactivity of the elements toward chlorine
ii. Thermal stability of chlorides for the elements [10]
b. Explain the reactivity of carbon tetrachloride and silicon tetrachloride toward water. Write
equation of reactions involved in your answer. [5]
c. Reaction between silicon oxide and molten base would form silicate anion.
i. Draw the structural formulae of SiO44-, Si2O76- and Si3O96- silicate anions.
ii. State one use of silicon and one use of silicate in industry. [5]
1995/4. a. Discuss the structure and bonding in
i. Diamond
ii. graphite
In your answer, relate the structure and bonding of the respective substances with their
physical properties. [10]
b. Write all formulae of oxides for all elements in group 14 of the Periodic Table. Discuss the
following chemical properties of these oxides.
i. acid-base property
ii. redox property.
In your answer, write one chemical equation for each type of the chemical property mention.
[10]
2002/8 (b) Explain the following statements
ii. Carbon dioxide is gas while silicon dioxide is solid at the room temperature and
pressure. [4]
2005/7(b). A scheme of reaction is shown below.
X(l) Y(s) + Cl2(g)

Conc. HCl
Tetrachloroplumbate(II) ion (aq)
(i)
(ii)

Ibentify compound X and discuss its chemical properties.

Compound X is an oily liquid while compound Y is a white solid. Explain the
different physical states of the two compounds. [5]

Answer
68

1990:17D 1991:4D, 16C, 22C, 37E(1,2) 1992:17A, 36B(1,2) 1993:16D, 35B(1,2)

1994:17D 1995:17B 1996:27E, 51A(all), 60B(1,2) 1997:25B, 26C
1998:28E, 29C, 54C(2,3) 1999:22B, 23C 2000:22D, 23D, 24C 2001:7D, 21B, 23D

CHAPTER 5
NITROGEN AND COMPOUNDS OF NITROGEN
1.INTRODUCTION
Nitrogen has electronic configuration as 1s2, 2s2 2p3. The atom has relative small atomic
radius. Nitrogen made up 78% of the air in the atmosphere. In the air, nitrogen exists as
diatomic N2 molecule. In the molecule, nitrogen atoms are bonded together by a strong triple
covalent bond. However, there are extremely weak van der Waals forces between nitrogen
molecules. Thus, nitrogen has very low melting (-210.0oC) and boiling point (-198.5oC).
Since the nitrogen atom has small atomic radius and it is a non-metal, it has high
electronegativity.
2.EXTRACTION OF NITROGEN
Industry process:
Air is compressed to about 250 atm, cooled and allowed to expend rapidly through a small
aperture to further decrease its temperature. The whole process is repeated for a few times
until the temperature is low enough and air condenses to liquid.
Liquefied air is filtered to separate solid carbon dioxide. The liquid consists of a mixture of
noble gases, oxygen and nitrogen is then subject to fractional distillation where nitrogen is
distilled over leaving behind liquid oxygen (-183oC).
Nitrogen obtained through this method contains some noble gases as impurities.
In laboratory, pure nitrogen is obtained by thermal decomposition of solid ammonium
dichromate or a mixture of solid sodium nitrite and ammonium chloride.
(NH4)2Cr2O7(s) Cr2O3(s) + 4H2O(g) + N2(g)
NH4Cl(s) + NaNO2(s) NaCl(s) + 2H2O(g) + N2(g)
3.CHEMICAL PROPERTIES OF NITROGEN
Nitrogen is relatively unreactive due to the strong triple bond between nitrogen atoms in the
molecule. Thus, it has extremely high bond dissociation energy (or atomization energy).
N2(g) 2N(g)
H = +944 kJ/mol
However, at high temperature and the present of suitable catalyst, nitrogen reacts with oxygen
to form nitrogen oxides.
N2(g) + O2(g) 2NO(g)
2NO(g) + O2(g) 2NO2(g)
These oxides also formed during lightning and in the internal combustion engine.
Nitrogen also forms nitrides with reactive metals like K3N, Na3N, Mg3N2 and AlN. Nitrides
are ionic compounds and easilly hodrolised to form alkali solution and ammonia gas is
liberated.
Na3N + 3H2O 3NaOH + NH3

69

4.COMPOUNDS OF NITROGEN
Nitrogen forms many compounds with oxidation state varies from -3 to +5.
Oxidation state
3
2
1
+1
+2
+3
+4
+5

Examples of compound
NH3, Na3N, Mg3N2, AlN
N2H4
NH2OH
N2O
NO
HNO2
NO2, N2O4
HNO3

5.AMMONIA
5.1 In industry, ammonia is made by the Haber process. In the process, a mixture of nitrogen
and hydrogen at the ratio of 1:3 is allowed to pass through a column that contains preheated
catalyst, Fe2O3 at the temperature of 400 500oC and pressure of 400 500 atm.
N2(g) +3H2(g) 2NH3(g) H = 92kJ
The forward recation is an exothermic and accompanied by a decrease in the number of mole
of gas. According to Le Chatelier principle, high yield of ammonia can be obtained by unsing
high pressure and low temperature as this wolud favor the forward reaction.
However, at low temperature, the rate of reaction is low and it takes a long time for the
reaction to acquire equilibrium. To shorten the time needed, high temperature about 400
500 oC is used along with catalyst, Fe2O3.
If a very high pressure is used, it would incur higher cost of production. Thus a pressure
between 400 500 atm is used.
5.2 In the laboratory, ammonia is prepared by the heating of a strong base with an
ammonium salt.
2NH4Cl(s) + Ca(OH)2(s) 2NH3(g) + CaCl2(s) + 2H2O(l)
4NH4Cl(s) + CaO(s) 4NH3(g) + 2CaCl2(s) + 2H2O(l)
5.3 Physical properties of ammonia
Ammonia is a colourless gas with pungent and chocking smell. The gas is extremely soluble
in water due to its abilities to form hydrogen bond with water molecules and further ionizes
in water.
Ammonia is discrete covalent molecule with the shape of trigon pyramid.

70

N
H

H
H

5.4 Chemical properties of ammonia

Ammonia as a weak base
The present of the non-bonding electrons pair at the nitrogen atom of the ammonia molecule
enables the ammonia to accept proton. Thus, ammonia is a Bronsted base.
NH3 (aq) + H+(aq) NH4+(aq)
Ammonia is stronger base than water. It ionized in water to form OH ion.
NH3 (aq) + H2O(l) NH4+(aq) + OH (aq)
Ammonia reacts with acids to form ammonium salt.
NH3 (aq) + HCl(aq) NH4Cl(aq)
Ammonia as a lewis base
The non-bonding electron pair in ammonia molecule can be donated to the Lewis Acid,
which has at least an empty orbital at the valence shell to form adduct.
:NH3 + BF3 H3NBF3
:NH3 + AlCl3 H3NAlCl3
Ammonia as ligand
The non-bonding electron pair in ammonia molecule can be donated to the metal ions of
transition metals, which has empty d orbital at the valence shell to form complex ions.
4:NH3(aq) + Cu2+(aq) [Cu(NH3)4]2+ (a dark blue square planar complex ion.)
4:NH3(aq) + Zn2+(aq) [Zn(NH3)4]2+ (a colourless tetrahedron complex ion.)
6:NH3(aq) + Ni2+(aq) [Ni(NH3)6]2+ (a blue octahedron complex ion.)
Ammonia as reducing agent
Ammonia is oxidised to nitrogen when it is heated in the present of metal oxides.
2NH3(g) + 3CuO(s) N2(g) + 3H2O(g) + 3Cu(s)
Catalytic oxidation of ammonia produces nitrogen nomoxide when ammonia is heated with
oxygen.
Pt/Ph

4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)

5.5 Uses of ammonia
Ammonia is uses for manufacturing of fertilizer like ammonium nitrate, ammonium sulphate,
ammonium phosphate, urea and ammonium carbonate.
Ammonia is used as refrigerant due to high heat of evaporation.
Ammonia is used for synthesis of nitric acid in Oswald process.

71

6.OXIDES OF NITROGEN
Three most important oxides are NO, NO2 and N2O4.
Oxide

NO

NO2

N2O4

Oxidation
state

+2

+4

+4

Physical
properties

Molecular
structure

Colorless and odorless

gas, neutral and
insoluble in water.

Brown gas with

pungent
smell, acidic gas and
soluble
in water.

Clouless solid with

melting point
11oC.

: N :: O :

:O:N : N::O:

::
:O: :O:

:O::N:O:

linear

Bend / V shape

Planar
A dimer of NO2.
o
600 C

Equilibriu
m

2NO(g) + O2(g)
N2O4(s)
cololess
lighter brown

o
150 C

2NO2(g)

brown
colorless

o
21 C

N2O4(g)

o
- 11 C

N2O4(l)

light brown
(light brown is due to the

present of some NO2)

7.NITRIC ACID
7.1 Oswald process
In this process, dried ammonia is oxidized by oxygen to form nitrogen monoxide when
heated (900 1000 oC) and a pressure of 7 8 atm in the present of catalyst alloy Pt-Rh.
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g) H = - 950kJ
Nitrogen monoxide is allowed to cold and more oxygen is added to further oxydise to
nitrogen dioxide.
2NO(g) + O2(g) 2NO2(g) H = - 114kJ
72

Nitrogen dioxide is absorbed with excess of warm water and oxygen to produce nitric acid.
4NO2(g) + O2(g) + 2H2O(l) 4HNO3 (aq)

7.2 Molecular structure

O

N
O

Pure nitric acid is colourless, vicous liquid due to hydrogen bond between the acids
molecules. The boil point is 86 oC. Concentrated nitric acid turns brownish due to
decomposition of the acid to nitrogen dioxide.
4HNO3(aq) 4NO2(g) + O2(g) + 2H2O(l)
7.3 Chemical properties
i. As strong acid when it is dilute
ii. As strong oxidizing agent when it is concentrated or at higher concentration.
iii. As nitrating agent
7.4 Uses of nitric acid
Mainly use for the manufacturing of nitrate fertilizers, organic nitro compounds such as TNT,
glycerin trinitrate that used as dynamite and production of dyes.
8.POLLUTION BY OXIDES OF NITROGEN
Nitrogen monoxide, NO, is produced from the burning of petrol or fossil fuel in the internal
combustion engine. At high temperature, the nitrogen molecule dissociates and combines
with oxygen to form nitrogen monooxide and is released into the air together with other
exhaust gasses. Other exhaust gasses include unburned hydrocarbons, carbon dioxide, carbon
monoxide and water vapor.
Oxides of nitrogen pollute the air in several ways.
i. Nitrogen monoxide, NO, is oxidised further nitrogen dioxide, NO2, once contact with
excess oxygen in
the air. NO2 dissolves in moist air or cloud to form acidic rain clouds.
2NO2(g) + H2O(l) HNO3(aq) + HNO2(aq)
ii. Nitrogen monoxide, NO, combines with unburned hydrocarbons to form photochemical
smog. Smog is
white fumes that hang in the afternoon sky of cities and industry parks.
iii. Nitrogen monoxide, NO, also catalyzed the oxidation of SO2 to SO3. SO3, which is more
soluble in
water dissolves in moist air or cloud and added to the acidic rain.
2NO2(g) + 2SO2(g) 2NO(g) + 2SO3(g)
2NO(g) + O2(g) 2NO2(g)
Overall reaction: 2SO2(g) + O2(g) 2SO3(g)
73

SO3(g) + H2O(l) H2SO4(aq)

Catalyst converter is fitted along the exhaust pipe in-order to reduce the emission of these
pollutants into the air. The converter, which contains platinum (Pt), palladium (Pd) and
rhodium (Rh), catalyses the oxidation of unburned hydrocarbons and carbon monoxide to
form carbon dioxide and water. At the same time, it also reduced oxides of nitrogen to
nitrogen.
CxHy + (x + y/4) O2 xCO2 + y/2 H2O
2NO + 2CO N2 + 2CO2

Catalyst converter contains heterogeneous catalysts.

CxHy and CO
NO

CO2 and H2O

N2

These reactions take place at a temperature of exceeding 400oC.

However, cars fitted with catalyst converter cannot use leaded petrol because lead compounds
will coat onto the surface of the catalyst and render it useless.
NO also causes the formation of Ozone in the atmosphere.
NO + O2 NO2 + O
O + O2 O3
In the atmosphere, O3 is a poison gas to the living.
PAST YEARS QUESTIONS
OBJECTIVE
1990/18. Which of the following explain the low reactivity of nitrogen gas?
A Nitrogen atom has stable electron configuration
B Nitrogen atom has high electro-negativity
C Nitrogen atom has high first ionization energy
D Nitrogen atom forms weak bond with other atoms
E Nitrogen molecule has high bond dissociation energy
1990/35. Nitric acid reacts with benzene, sulphur and hydrogen chloride according to the
following equation.
HNO3 + C6H6 C6H5NO2 + H2O
6HNO3 + S H2SO4 + 6NO2 + 2H2O
HNO3 + 3HCl Cl2 + NOCl + 2H2O
In the above reaction nitric acid function as
1 acid
2 Nitrationagent
3 Oxidizing agent

74

1991/17. Which of the following explain the low reactivity of nitrogen gas at the room
temperature?
A Nitrogen atom has half filled p orbitals
B Nitrogen atom has stable electron configuration
C Nitrogen atom has high first ionization energy
D Nitrogen molecule has strong covalent bond
E Nitrogen forms biatomic molecule
1992/19. Concentrated sulphuric acid reacts with ethanedioic acid, nitric acid and sulphur
according to the equation below.
H2SO4
I
H2C2O4

CO + CO2 + H2O
II
HNO3 + 2H2SO4 NO2+ + H3O+ + 2HSO4
III
S + 2H2SO4 2H2O + 3SO2
In the reactions above, the sulphuric acid function as
I
II
III
A Dehydration agent
Acid
Oxidizing agent
B Oxidizing agent
Acid
Dehydration agent
C Dehydration agent
Oxidizing agent
Acid
D Oxidizing agent
Oxidizing agent
Oxidizing agent
E Dehydration agent
Oxidizing agent
Oxidizing agent
1992/37. Exhaust gas contains pollutants like hydrocarbons, oxides of carbon and oxides of
nitrogen. Catalyst converter converts these substances to non-pollutant gases. After the
exhaust gas went through the converter,
1 % of carbon dioxide increase.
2 % of nitrogen oxides is lower
3 % of un-combusted hydrocarbon increase.
1993/17. An aqueous solution X has the following properties.
i
Evaporate when heated strongly without leaving behind any solid residue
ii
Liberate colourless and odourless gas when sodium carbonate is added.
iii
Does not form white precipitate when silver nitrate solution is added.
X could be
A HNO3
B HCl
C NaNO3
D NH4Cl
E NH4NO3
1993/18. In which of the following reaction, the sulphuric acid functions as oxidizing agent?
A C + 2H2SO4 CO2 + 2SO2 + 2H2O
B CuO + H2SO4 CuSO4 + H2O
C PCl5 + H2SO4 ClSO3H + HCl + POCl3
D HCOONa + H2SO4 HCOOH + NaHSO4
H2SO4
E C12H22O11 12C + 11H2O
1994/18. Which of the following is true for oxides of nitrogen at the room temperature?
A N2O4 decomposes completely to form NO2
B NO2 decomposes to NO and O2
C A mixture of N2O4, NO and O2
D A mixture of N2O4 and NO2
E A mixture of NO2 and NO
75

1995/18. Which of the following statement is true for concentrated nitric acid?
A Reacts with all metals to produce hydrogen gas.
B Oxidizes chloride ion to chlorine.
C Reduced to NO2 by metals.
D Donates proton, H+, when reacts with concentrated sulphuric acid.
E Render certain metals to un-reactive through forming of oxide on the metals.
1996/26. Nitrogen gas is stable and un-reactive at the room temperature. Which of the
following explain the statement?
A Nitrogen gas has high atomization energy.
B Nitrogen has low boiling point.
C Nitrogen molecules are bonded by strong Van der Waals force.
D Nitrogen atom has half-filled 2p orbital.
E Nitrogen atom has five valence electrons attracted strongly by the nucleus.
1996/28. The manufacturing of nitric acid in industry involves
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g) H = Ve
2NO(g) + O2(g) 2NO2(g)
H = Ve
4NO4(g) + 2H2O(g) 4HNO3(g)
H = Ve
Which of the following statements explain the use of high pressure during the manufacturing
of nitric acid?
A To prevent the formation of N2O4 dimer
B To avoid from using high temperature
C To increase the solubility of NO2 in water
D To obtain oxygen from the compressed air
E Reactions do not take place at low pressure
1997/24. Compound X is oxidized to compound Y, which is used to manufacture fertilizer Z.
X, Y and Z are
X
Y
Z
A NO2 HNO3
NH4NO3
B HNO2 HNO3
KNO3
C NH3
HNO3 Ca(NO3)2
D SO2
H2SO4 BaSO4
E SO2
H2SO4 Na2SO4
1997/52. Thought nitrogen made up of 78% of the air, nitrogen is relatively un-reactive
because
1 strong triple bond between the nitrogen atoms
2 it dilutes the air and reduce the rate of oxidation of oxygen.
3 it is used to prepare an inert atmosphere.
1997/54. The structure of N2O4 molecule is
O
O
O
O
1
NN
2
NN
3
O
O
O
O

O
NN

1998/30. Nitrogen is highly un-reactive at low temperature because

A nitrogen exist as biatomic molecule.
76

B nitrogen atom has stable electronic configuration.

C nitrogen atom has half filled p orbital.
D nitrogen atom has high ionization energy.
E nitrogen atom has high atomization energy.

1998/55. Which of the following statements is correct for the manufacturing of ammonia
through Haber process?
1 Nitrogen used in the process is obtained from fractional distillation of liquefied air.
2 Hydrogen used in the process is obtained from reduction of steam.
3 Fine iron filling is used as catalyst.
1999/24. Which of the following methods is used to extract nitrogen used in industry?
A Decomposition of ammonia
B Thermal decomposition of ammonium dichromate
C Thermal decomposition of ammonium nitrate
D Heating of benzene diazonium chloride
E Fractional distillation of liquefied air
1999/26. Which of the following equations correctly shows the equilibrium of the oxides of
nitrogen at different temperature starting with the lowest temperature?
A 2NO2 2NO + O2 N2O4
B N2O4 2NO2 2NO2 + O2
C N2O4 2NO2 N2 + 2O2
D N2O4 2NO + O2 N2 + 2O2
E N2 + 2O2 2NO2 N2O4
1999/33. The rate of chlorination of methane in the present of sun light at 140oC is reduced
when some NO2 is added. Which of the following statements explain the observation?
A NO2 reduces the amount of chlorine radical.
B NO2 prevents the formation of chlorine radical.
C NO2 prevents the collision between methane molecules and chlorine radicals.
D NO2 absorbs sunlight required for chlorination reaction.
E NO2 breaks the CH bond in the methane molecule.
2000/25. Which of the following statements is true of ammonia?
A Ammonia forms NH4OH when dissolves in water.
B Ammonia is released when ammonium chloride is heated.
C Aqueous ammonia solution reduces copper(II)oxide to copper.
D Ammonia forms nitrogen oxides when heated with oxygen without using a catalyst
E Ammonia function as Lewis acid when react water molecules to form a complex ion.
2001/24. Which if the following is true of N2O4 molecule?
A Polar molecule
B V shape
C It is form from NO2 D Nitrogen atom has a non-pairing electron
2002/23 An oxide of nitrogen, NxOy has it composition by mass 46.7% of nitrogen and
53.5% of oxygen. This oxide is produced from a internal combustion engine and during
lightning. Which of the following statements is not true regarding to the oxide?
77

A
C
D

Its empirical formula is NO

B
Its molecule has a double bond
Its heat of formation is exotermic
It is produce from the direct reaction between nitrogen and oxygen

2002/24 In industry, nitric acid is obtain from ammonia through

A
Hydrolysis
B
Condensation
C
Hydrogenation
D
Catalytic oxidation
2003/25. Oxides of nitrogen are air pollutants which are released from exhausts of vehicles.
These oxides
A
deplete the ozone layer
B
decompose to tixic substances
C
cause cander
D
generate free radicals by photochemical processes
2003/47. In catalyst converter, platinum/palladium/rodium is used to catalyse
1 The oxidation of sulphur dioxide to sulphur trioxide.
2 The oxidation of hydrocarbon to carbon dioxide and water
3 The reduction of the oxides of nitrogen to nitrogen and oxygen
2004/21. Which of the following compounds cannot be produce directly from ammonia?
A
NO
B
CH3CH3NH2
C
[Cr(NH3)6]3+
D
C6H5NO2
2004/22. Nitrogen dioxide is a brown gas at room temperature. Which of the following
statements is true of nitrogen dioxide?
A
Nitrogen dioxide is a linear molecule
B
Nitrogen dioxide dissolves in water to form nitrous and nitric acid
C
Nitrogen achieves octet through the formation of covalent bond with oxygen
D
Nitrogen dioxide dissociates to form oxygen and nitrogen monoxide gases at the room
temperature
2005/23. Nitrogen oxide and dinitrogen tetraoxide exist in equilibrium in gaseous state.
Which of the following statements is true?
A
N2O4 molecule has two dative bonds
B
NO2 molecule has one bond and one bond
C
The bond angle in NO2 molecule is 120o
D
The hybridization of nitrogen atom in N2O4 molecule is sp3
2005/46. A catalyst converter reduces air pollution by
1 oxidizing lead to lead(II)oxide
2 reducing oxides of nitrogen to nitrogen and oxygen
3 oxidising carbon monoxide and hydrocarbon to carbon dioxide and water

78

STRUCTURED
1992/1. a i. In industry, nitrogen is extracted from the air. State the two stages involved in
the extraction of nitrogen.
ii. What physical property that oxygen has, that enables oxygen in the air to be
separated from the nitrogen gas during the extraction? [3]
b i. Complete tha following table.
Oxidation number
+2
+4

Formula for oxide of nitrogen

Colour of oxide of nitrogen

N2O4
ii. Write an equation to show the equilibrium exist between the oxides of nitrogen at room
temperature. [4]
c i. Explain why nitrogen does not form NCl5 but phosphorus forms PCl5.
ii. Which one of ammonia or phosphine, PH3 is a stronger Bronsted Lowry base?
Write an equation to show the basic property for the compound of your choise. [3]
1993/3. b. 1000 cm3 of a gaseous oxide of nitrogen, NxOy , is passed through preheated
copper . The reaction produces 1000 cm3 of nitrogen gas and the mass of copper increses by
0.71 g. All volumes of gasses are measured at the same temperature and pressure.
i. What can you conclude from the observation, that 1000 cm3 gaseous oxide of nitrogen,
NxOy, forms 1000 cm3 of nitrogen gas?
ii. Write a balanced equation for the reaction.
iii. Calculate the mass of the oxide of nitrogen, NxOy, decomposes in the reaction.
iv. Name the dimer of this oxide of nitrogen. [5]
2004/3 (b). Lightning increases the air temperature in its path to about 33000oC. This
temperature is sufficient to cause nitrogen and oxygen gases to react in air.
(i).
State the name of the oxide formed during lightning.
(ii).
Write the equation for the formation of this gas.
(iii). This gas can be obtained from the oxidation of ammonia in air in the presence
of a platinum catalyst. Write an equation for this reaction.
(iv). Write a chemical equation for the formation of the air pollutants from the gas
in (i). [5]
2005/3(b). Ammonia is prepared in industry by using the Haber process and it is used to
manufacture chemical fertilisers.
i
State one physical property of ammonium salt that makes it suitable as a
chemical fertiliser.
ii
In aqueous solution, ammonia acts as a base. Write an equation for the
reaction involved. Give the chemical formula of the conjugate base in this
reaction and state the type of hybridisation of the ammonium ion.
iii
State the contents of a tank of ammonia gas which is left to stand in hot spot
for a few days. Give a reason for your answer. [6]

79

ESSAY
1999/6. a. In industry, ammonia is produce in the Haber process, whereas in the laboratory,
ammonia is prepared from ammonium salt.
i. State the reagent, the conditions of reaction used and the equation of chemical
reaction involved in the synthesis ammonia in Haber process. Explain how the equilibrium
concept and the kinetic factors are taken into the consideration in the process.
ii. State the reagent, the conditions of reaction used and the equation of chemical
reaction involved in the preparation of ammonia in the laboratory. [11]
b. Ammonia is used for synthesis of nitric acid in the Ostwald process. Nitric acid
ionized fully in water to produce hydrated hydrogen ion and nitrate ion.
i. Describe the synthesis of nitric acid in the Ostwald process.
ii. Determine the oxidation state of nitrogen atom in nitric acid.
iii. Draw the Lewis structure and predict the shape of nitrate ion. [14]
2002/8 (b) Explain the following statement.
i
Nitrogen is inert [4]
2003/7 (a). Nitric acid is an important industry chemical. This substance is a strong acid and
also a strong oxidising agent. Explain these two properties of nitric acid. [4]
(b). Regia aqua is a mixture of concentrated nitric acid and hydrochloric acid at the
ratio of 1:3. The mixture is used to dissolve inert metal such as gold. Explain how regia aqua
reacts on gold based on the following equation.
4H+ + 4Cl + NO3 + Au AuCl4 + NO + 2H2O
Answer:
1990:18E, 35C(2,3) 1991:17D 1992:19A, 37B(1,2) 1993:17E, 18A, 1994:18D 1995:18E
1996:26A, 28C 1997:24C, 52D(1), 54A(all) 1998:30E, 55A(all)
1999:24E, 26B, 33A 2000:25B 2001:24C

80

CHAPTER 6
GROUP 17. THE HALOGEN
1. INTRODUCTION

Element

Fluorine (F)

Chlorine (Cl)

Bromine (Br)

Iodine (I)

Electronic configuration

[He]2s22p5

[Ne]3s2 3p5

[Ar]4s24p5

[Kr]5s25p5

Molecule

Color and appearance at

room temperature and
pressure

Discrete biatomic molecule, X2

Colorless,
Gas

Pale yellow,
Gas

Reddish
brown,
liquid

Dark purple
solid
(purple, gas)

atomic radius
Atomic increases from fluorine to
iodine due to the increase in
number of electrons filled shells
and the screening effect.

Atomic radius/
molecular size

Cl Br

Boiling point
Boiling point/melting
point

Boiling point and melting point

increase from fluorine to iodine due to
increasingly larger electron cloud of
molecule and stronger Van der Waals
forces between molecules.

F Cl Br I
electronegativity
Electronegativity

Electronegativity decreases from

fluorine to iodine due to increasingly
larger atomic size and the nucleus has
decreasingly lesser ability to attract
electron in a covalent bond.
81

F Cl Br I
Electron affinity
Electron affinity

X(g) + e X-(g) H = -ve

Electron affinity decreases from fluorine
to iodine due to increasingly larger
atomic size and the nucleus has
decreasingly lesser ability to capture free
electron to form ve ion. The process
becomes less exothermic.

F Cl Br
E
Standard electrode
potential
Bond dissociation
energy

F Cl Br I

F Cl Br I

2X-(aq) X2(aq) E = +ve

E becomes increasingly less positive
shows that the strength as an oxidizing
agent decreases from fluorine to iodine.
This is due to the decrease in atomic
halogen
X2(g) radius
2X of
(g)theH
= +ve atom and the ability
to accept electron decreases from fluorine
H decreases from chlorine to iodine due to
to iodine.
the increase in atomic radius and the XX
bond becomes increasingly weaker when
atomic size increases.
In Fluorine molecule, nucleuses of the
fluorine atoms come too close to each other
when forming FF bond. They repel each
other and the bond becomes weaken. Thus,
has lower bond dissociation energy.

2. REACTIONS OF HALOGENS
Halogens are oxidizing agent.
X2 + 2e 2X
The anions of halogens, X are reducing agent.
2X X2 + 2e
Strong oxidizing agent halogen has weak reducing agent halide as conjugate
Strength as
oxidizing agent of
halogen atom, X
increases

I2 + 2e 2I
Br2 + 2e 2Br
Cl2 + 2e 2Cl
F2 + 2e 2F

Strength as reducing agent

of halogen anion, Xincreases

2.1. Displacement reaction

Halogen, which is a stronger oxidizing agent displaces the halide anion of the halogen, of a
weaker oxidizing agent halogen (its anion is a stronger reducing agent) from its solution.

82

Example: If chlorine gas is bubbled through a solution contains bromide ions, the solution
turns brownish.
Cl2 + 2e 2Cl
2Br Br2 + 2e
Over all: Cl2(g) + 2Br(aq) 2Cl (aq) + Br2(g)
Chlorine gas, a stronger oxidizing agent, displaces bromide ion, which is a stronger reducing
agent from the bromides solution. In the same way, chlorine displaces iodide ions from its
solution producing iodine, yellowish solution.
Bromine displaces only iodide ions from its solution.
2.2. Reaction with thiosulphate ion.
Halogen oxidized thiosulphate ion and it self is reduced to halide ion, causes the
decolourization of the halogen.
5Cl2 + S2O32- + 5H2O 2SO42- + 10H+ + 8Cl5Br2 + S2O32- + 5H2O 2SO42- + 10H+ + 8BrI2 + 2S2O32- S4O62- + 2I2.3. Reaction with hydrogen
Halogen reacts with hydrogen to form hydrogen halide, HX.
H2 + X2 2HX
The reactivity of reaction decreases from fluorine to iodine. A mixture of fluorine and
hydrogen explodes when it is exposed to the sun light.
H2 + F2 2HF
A mixture of hydrogen and iodine need to be hated at a high temperature for reaction and the
reaction is reversible. HI is thermally unstable.
H2 + I2 2HI
2.4. Reaction with water and alkali solution
Halogen dissolves slightly in water to form acidic solution.
H2O + X2 HX + HOX
In this reaction, the halogen is simultaneously oxidized to hypohalate acid, HOX (oxidation
number of X = +1) and reduced to hydrohalide acid, HX (oxidation number of X = 1). This
reaction is called disproportionation reaction. In disproportionation reaction, the same
reagent is simultaneously oxidized and reduced.
Hydrohalide acid, HX, is a strong acid. It changes blue litmus to red, while hypohalate acid,
HOX, is weak acid with bleaching property. The hypohalate anion, XO , decolorizes the red
litmus.
H2O
+
Cl2

HCl
+
HOCl
Hydrochloric acid hypo chlorate acid
Halogen dissolves more readily in sodium hydroxide solution to form sodium halides and
sodium hypohalate (I) through disproportionation reaction as that of halogens react with
water.
2NaOH + X2 NaX + NaOX + H2O
Example: 2NaOH + Cl2 NaCl + NaOCl + H2O
sodium hypochlorate (I)
NaCl is salt of strong acid strong base. Thus, the chloride anion, Cl is neutral. However
NaOCl is a salt of weak acid strong base. Thus, the hypochlorate anion OCl is hydrolyzed
in aqueous solution and causes the solution to be alkaline.
83

ClO + H2O HClO + OH

Besides that, the OX anion also function bleaching agent. Thus the solution has beaching
property.
With warm (70oC) concentrated NaOH, chlorine reacts to form sodium chloride and sodium
chlorate(V).
6NaOH + 3Cl2 5NaCl + NaClO3 + 3H2O
sodium hypochlorate (V)
The halogen is simultaneously oxidized to sodium chlorate (V) (oxidation number of Cl = +5)
and reduced to hydrochloric acid, HCl (oxidation number of Cl = 1). This reaction is called
disproportionation reaction.
Sodium hypochlorate(V), NaClO3 is used as explosive material and a strong oxidizing agent.
Sodium hypochlorate (V) can be produced by thermal decomposition of sodium hypochlorate
(I).
3NaOCl 2NaCl + NaClO3
3. HYDROGEN HALIDES
3.1. Melting point and boiling point
High boiling point due to hydrogen bond
Boiling point / oC
between molecules
HF

HBr

HI
Boiling point increases from HCl to HI as the
molecular size gets bigger and stronger Van der waals
forces between molecules.

HCl
Group 17
3.2. Thermal stability
Thermal stability

HF is thermally stable. Thermal stability

of hydrogen halides decreases from HF to
HI due to bond length increases or bond
strength decreases from HF to HI as the
atomic radius of halogen gets bigger.
2HI(g) H2(g) + I2(g).

HF
HCl
HBr
HI
Group 17

3.3. Acidity
Acidity

Hydrogen halides dissolve in water

forming acidic solutions. HF is a weak
acid. The acidity increases from HF to
HI due to HX bond strength decreases
as the atomic radius of halogen gets
bigger.

84

HI
HBr
HCl
HF
Group 17
4. REACTION OF HALIDE IONS
4.1. Displacement reaction
See reaction of halogens.
4.2. with silver nitrate solution
From sparingly soluble silver halide, AgX, precipitate
Ionic equation: Ag+ (aq) + X (aq) AgX(s)
Example: Ag+ (aq) + Cl (aq) AgCl(s)
Silver nitrate solution is used to differentiate the present of halides ion in solution by the
different of color of the AgX precipitate and their solubility in ammonia solution.
AgX
AgCl
AgBr
AgI

Color
White
Beige
Yellow

Solubility
Soluble in dilute ammonia solution
Soluble in concentrated ammonia solution
Insoluble in concentrated ammonia solution

Solubility of the salt in ammonia solution is through formation of complex ion.

Example:
AgCl(s) + 2NH3(aq) Ag(NH3)2+(aq) + Cl(aq)
4.3 with concentrated sulphuric acid
Salts contain halide anion would liberate white fumes of HX when react with concentrated
sulphuric acid.
Examples:
2NaCl(s) + H2SO4(aq) Na2SO4(aq) + 2HCl(g) (white fumes)
2NaBr(s) + H2SO4(aq) Na2SO4(aq) + 2HBr(g) (white fumes)
2NaI(s) + H2SO4(aq) Na2SO4(aq) + 2HI(g) (white fumes)
However, Br and Iwill be oxidized to bromine (reddish brown) and iodine (violet/light
purple) while Cl is not oxidized to chlorine. This is because chlorine is a stronger oxidizing
agent than concentrated sulphuric acid, but both bromine and iodine are weaker oxidizing
agents than the concentrated sulphuric acid.
I2 + 2e 2I
Br2 + 2e 2Br
85

H2SO4 + 2e + 2H+ SO2 + 2H2O

Cl2 + 2e 2Cl
2HBr(s) + H2SO4(aq) Br2(g) (reddish brown gas) + SO2(g) + 2H2O(l)
2HI(s) + H2SO4(aq) I2(g) (reddish brown gas) + SO2(g) + 2H2O(l)
Thus, HBr and HI can not be prepared by adding the concentrated sulphuric acid to NaBr or
NaI. Instead a non oxidizing acid like the phosphorus acid is used.
Example:
3NaBr(s) + H3PO4(aq) Na3PO4(aq) + 3HBr(g) (white fume)
Chlorine is produced when a strong oxidizing agent, MnO2 is added to NaCl under hot acidic
condition.
4NaCl(s) + MnO2(s) + 4H2SO4(aq) Cl2(g) + MnCl2(aq) + 4NaHSO4(aq) + 2H2O(l)
Or
4HCl (conc) + MnO2(s) Cl2(g) + MnCl2(aq) + 2H2O(l)
5. PRODUCTION OF CHLORINE
Chlorine is extracted by electrolysis of brine (concentrated sodium chloride) using mercury as
cathode and graphite as anode.
Anode (graphite)
Brine
Mercury
Cathode (mercury)
During the electrolysis process,
Anode (graphite) / Oxidation
Cathode (mercury) / reduction
2Cl(aq) Cl2(g) + 2e
2Na+(aq) + 2e 2Na
Na(l) + Hg(l) Na/Hg(l)
Sodium produced at cathode dissolves in mercury to form unreactive amalgam. The amalgam
is directed into another steel tank where it reacts with water to form sodium hydroxide and
hydrogen gas.
2Na/Hg + 2H2O 2NaOH + 2Hg + H2
The mercury is recycled.
The disadvantage of the method is the disposal of used mercury. Improperly handling of
mercury waste leads to mercury poisoning.

6.USES OF HALOGENS AND THEIR COMPOUND

Halogen
Chlorine

Uses of element
1. Extraction of Bromine

Uses of compounds
1. CCl4 and CHCl3 as solvent
86

2. Sterilizing water
3. Bleaching agent in paper and
textile industry

2. CH2CHCl for PVC

3. DDT as insecticide
4. NaCl as edible salt
5. NaClO3 as herbicide
6. NaOCl as bleaching agent
7. Freons as refrigerants and propellants

Bromine

1. Manufacturing dyes and drugs

1. AgBr for manufacturing photographic

film
and Photochromatic lenses
2. BrCH2CH2Br as additive in leaded
petrol

Iodine

1. 50% of Iodine in ethanol is used

as iodine solution

1. AgI for photographic film

2. AgI for cloud seeding

7.BLACK AND WHITE PHOTOGRAFIC FILM AND PHOTOCHROMATIC LENSE

Black and white photographic film:
Silver chloride and silver bromide turn dark grey when exposed to sunlight due to the
following photochemical decomposition. The dark grey color is due to the formation of silver
metal.
AgCl(s) Ag(s) + Cl2(g)
AgBr(s) Ag(s) + Br2(g)
Black and white photographic film is a clear cellulose strip coated with AgBr. AgBr is used
because it has higher sensitivity to sunlight than AgCl.
Photochromatic lenses
Sunglasses that turn dark when exposed to sunlight are called Photochromatic.
Photochromatic lenses rely on a specific chemical reaction to UV radiation.
Photochromatic lenses have million of AgCl or AgBr molecules embedded in it. These
molecules change shape when exposed to sunlight and absorb portion of visible light, causes
the lenses to be darken.
AgBr(s)

AgBr*(s)
Molecular shape A
Molecular shape B
Clear without UV
Darken when under UV
With the absence of sunlight, the reverse reaction take place causes the lenses becomes
transparent again.
Some Photochromatic lenses have AgCl and catalyst, CuCl, embedded in the lenses. The
chemical reactions are redox in nature as shown in the following:
When exposed to the sunlight
Cl Cl + e
Ag+ + e Ag
The presence of Ag precipitate block the transmission of light, causes the lenses to turn
darken.
Without the sunlight
87

Cl + Cu+ Cl + Cu2+
Ag + Cu2+ Ag+ + Cu+
Without the presence of silver precipitate, the lenses become transparent again. The overall
reaction is
AgCl(s)

Ag(s)
+
Cl(g)
Lenses is
lenses is
Transparent
darken
When without UV
when expose to UV
PAST YEARS QUESTIONS
OBJECTIVE
1992/20. In the following reactions, which of the underlined reagents function as oxidizing
agent?
A H2S + Cl2 S + 2HCl
B Cl2 + 2OH Cl + OCl + H2O
C 2NH3 + 3Cl2 N2 + 6HCl
D 3Cu + 8HNO3 3Cu(NO3)2 + 4H2O + 2NO
E 4NH3 + 5O2 4NO + 6H2O
1993/37. Which of the following factors affect the volatility of halogen as descending the
group?
1 Electronegativity
2 Strength of Van der Waals force
3 Size of halogen molecule
1994/19. Concentrated sulphuric acid is used to prepare HCl from NaCl. In this reaction the
sulphuric function as
A Oxidizing agent
B Dehydration agent
C Sulphonation agent
D Proton donor
E Catalyst

1994/20. The schematic diagram for the reaction of Q is given as the following.
Conc. H2SO4
AgNO3
Redish brown
Aqueous of Q
Yellow precipitate
solution
NH3(aq)
White precipitate soluble
in ammonia solution
Q could be
A AlBr3
B ZnBr2

C ZnCl2

D PbCl2

E Pb(NO3)2

1995/20. Reaction between chlorine and cold sodium hydroxide solution is

Cl2(g) + 2NaOH(aq) NaCl(aq) + NaOCl(aq) + H2O(l)
In this reaction chlorine has gone through
A dispropotionation
B substitution
C neutralization
D decomposition
E redox
88

1996/29. Which of the following explain the reducing in volatility of elements of Group 17?
A The number of electrons in molecule increases.
B Heat of evaporation reduces.
C Melting point and boiling point increases
D Inter-molecular forces between molecules get stronger
E Covalent bond in molecule gets stronger
1997/23. Reaction between chlorine and sodium hydroxide solution is
Cl2(g) + 6NaOH(aq) 5NaCl(aq) + NaClO3(aq) + 3H2O(l)
Which of the following is not true of the above equation?
A Dilute NaCl is used in the reaction.
B The reaction takes place when the mixture is heated.
C Chlorine has gone through dispropotionation.
D Chlorine has highest oxidation state in NaClO3.
E NaClO3 can be used as dynamite.
1998/31. Which of the following combinations of colour density, volatility and boiling point
is correct descending Group 17?
Colour density
Volatility
Boiling point
A Increase
Increase
Increase
B
Increase
Decrease
Increase
C
Increase
Increase
Decrease
D
Decrease
Increase
Decrease
E
Decrease
Decrease
Increase
1999/27. The schematic diagram for the reaction of X is given as the following.
Conc. H2SO4
AgNO3
Redish brown
Aqueous of X
Yellow precipitate
solution
Pb(NO3)2(aq)
Yellow precipitate
X could be
A KCl
B KBr

C KI

D PbBr2

E PbI2

2000/27. Which of the following is not the use of halogen or its compounds?
A Detergent
B Photography
C Water treatment
D Propellant in aerosol
E Extraction of bromine from sea water
2000/52. Reaction between chlorine and hot sodium hydroxide produces
1 ClO3
2 Cl
3 H2O
2001/25. The solution resulting from bubbling chlorine gas through sodium hydroxide
solution can be used
A as pesticide
B as bleaching agent
C to treat water
D in bromine extraction
2002 / 25 The following is the reaction scheme of potassium iodide with concentrated
sulphuric acid and aqueous silver nitrate solution and a test on the precipitate Y using
concentrated ammonia solution.
89

Con. H2SO4
Fumes X
Heating
KI(s)
AgNO3(aq)

Precipitate Y
Conc. NH3

Product

Which of the following is correct in regarding to the colour of fumes and precipitate Y and
the solubility of precipitate Y in concentrated ammonia solution?
Colour of fumes X Colour of Precipitate Y Solubility of precipitate Y in NH3
A
Brown
White
Dissolve
B
Purple
Yellow
Dissolve
C
Purple
White
Insoluble
D
Purple
Yellow
Insoluble
2003/26. An aqueous of solution X has the following properties
i. Reacts with aqueous silver nitrate to form a precipitate which dissolves in
aqueous ammonia.
ii. Reacts with aqueous barium hydroxide to form salt and water.
iii. Decomposes in the presence of sunlight to evolve a gas.
X could be
A
B
C
D

HCl and NH4Cl

HCl and HOCl
HBr and HOCl
HBr and NH4Cl

2004/25. A coloured vapour which condenses to liquid is obtained when compound Q is

heated with concentrated sulphuric acid. Q is
A
potassium iodide
B
potassium chloride
C
potassium bromide
D
potassium ethanedioate
2005/22. Which of the following is not a disproportionation reaction?
A
Cl2 + 2NaOH NaOCl + NaCl + H2O
B
3Cl2 + 6NaOH NaClO3 + 5NaCl + 3H2O
C
4HCl + MnO2 Cl2 + MnCl2 + 2H2O
D
3NaOCl NaClO3 + 2NaCl

STRUCTURED
1993/4
a A series of experiment is carried out to investigate the strength of oxidizing agent of
halogens. Aqueous solutions of NaF, NaBr and NaI are placed into three different test tubes,
A, B and C. Chlorine gas is bubbled through the solutions separately followed by adding of
some CCl4 solution.

90

NaF + Cl2

NaBr + Cl2

NaI + Cl2

CCl4

CCl4

CCl4

State the observation in each of the test tube A, B and C and give explanation to your answer.
b Among chlorine, bromine and iodine, state which of these
i. is the weakest oxidizing agent.
ii. has most stable halide.
c i. Name one compound of bromine and state one use of the compound.
ii. Name one compound of iodine and state one use of the compound.
2002/3 (a) A bleaching liquid is prepared from the reaction between chlorine and aqueous
sodium hydroxide solution at the room temperature.
i
Write an ionic equation for the reaction
ii
State the change in oxidation state of chlorine in the reaction
iii
State the active ingredient that gives the bleaching propertiy. [4]
(c) A photochromatic glass is produced based on the black and white film.
i. State the additive in a photochromatic glass.
ii. State what would happen when a photochromatic glass is exposed to the sunlight.
Write an equation to show the reaction that take place. [3]
ESSAY
1992/5. b
Predict and explain what would happened when aqueous solution of sodium
iodide is added into silver nitrate aqueous solution followed by adding of ammonium
solution.
[9]
1993/4.a
17.
b
bond.

Describe the different of color of chlorine, bromine and iodine descending group
[7]
By the enthalpy of electron affinity, explain the ionic characteristic of H X
Element

Halide
Electron affinity, kJ/mol

Cl
Cl
350

Br
Br
325

I
I
295
State also whether the HX bond has more covalent or ionic characteristic. What
information needed to determine the distribution of electrons in HX bond?
[6]
c
The boiling points of hydrides of group 17 are shown in the following table
Compound
HF
HCl
Boiling Point, K
293
188
By this information, explain the structure and bonding of hydrides of group 17.

HBr
2006
[7]

HI
238

91

1994/5.a
Predict the possible reaction occurs in the following mixtures. Give explanation
and write equation involved.
i. Chlorine gas is bubbled through aqueous solution of sodium hydroxide.
ii. Chlorine gas is mixed with hydrogen gas.
iii. Iodine is added into the aqueous solution of sodium thiosulphate.
iv. Iodine is mixed with hydrogen gas.
[10]
b
Compare the bonding and the thermal stability of hydride of chlorine, bromine
and iodine.
[6]
c
Astatine, an element below iodine in group 17. Predict and explain
i. Volatility and solubility in organic solvent.
ii. Reaction of astatine ion with silver ion and the solubility of the compound
formed in ammonia solution. [4]
1998/6. c
By giving correct equation of reaction, explain the following phenomenon
i. Concentrated sulphuric acid and sodium halide can be used to prepare HCl. But it
can not be used to prepare HBr.
ii. Chlorine gives different products of reaction when added to cold sodium
hydroxide aqueous solution and hot sodium hydroxide aqueous solution. [11]
2000/6. b
following.

i.

Melting and boiling points of elements in group 17 is shown as the

Element
Chlorine
Bromine
Iodine

Melting point, oC
101
7
114

Boiling point, oC
35
59
183

Discuss the change of physical properties of halogens according to their bonding and
structure.
ii. State the order of acidity for HCl, HBr and HI in its aqueous solution.
Explain your answer.
[11]
2004/8 (a) A halogen X and hydrogen gas react when heated in the presence of a platinum
catalyst to form HX. When HX is dissolved in water, an aqueous solution is formed. When
the aqueous silver nitrate solution is subsequently added, a precipitate insoluble in aqueous
ammonia is formed.
i
Identify the halogen X and explain your answer.
ii
Halogen X dissolves in aqueous NaX solution and in trichloromethane. State
and explain the observation of the reaction involved. [7]
2005/8(a). A solid halide reacts with concentrated sulphuric acid to form HX gas which is
then oxidised to X2 gas. The solid plays an important role n black-white photography. Identify
the solid halide. Explain your answer. [6]
1992:20C 1993:37C(2,3) 1994:19D, 20B 1995:20A 1996:29D 1997:23A 1998:31B
1999:27C 2000:27D, 52A(all) 2001:25B

92

CHAPTER 7.
CHEMISTRY OF d BLOCK ELEMENTS
1. GENERAL PROPERTIES
1.1 . Physical properties
a. Hard
b. High density
c. High melting point
1.2. Chemical properties
a. Exhibit variable oxidation states in their compounds
93

b. Form complexs
c. From colored compounds
d. Show catalytic properties
2. VARIABLE OXIDATION STATES
The following table shows the relative stability of oxidation state of d - block metal ions.
Sc
[Ar]3d14S2
Ti
[Ar]3d24S2
V
[Ar]3d34S2
Cr
[Ar]3d54S1
Mn
[Ar]3d54S2
Fe
[Ar]3d64S2
Co
[Ar]3d74S2
Ni
[Ar]3d84S2
Cu
[Ar]3d104S1
Zn
[Ar]3d104S2

+2
+2
+2

+1
(Ar)3d10

+2
(Ar)3d5
+2
(Ar)3d6
+2
(Ar)3d7
+2
(Ar)3d8
+2
(Ar)3d9
+2
(Ar)3d10

+3
(Ar)
+3
+3
(Ar)3d2
+3
(Ar)3d3
+3
+3
(Ar)3d5
+3
(Ar)3d6
+3

+4
(Ar)
+4
+4

+5
(Ar)
+5

+4
(Ar)3d3
+4

+5

+6
[Ar]
+6

+5

+6

+4

+5

+7
(Ar)

+4
(Ar)3d6

The number of oxidation state increases from Sc (one oxidation state) to Mn (seven oxidation
states) and then it decreases from Mn (seven oxidation states) to Zn (one oxidation state).
The electrons in 3d and 4s orbitals are valence electrons. The 4s orbital has slightly higher
energy than the 3d orbitals. During ionization, electrons are removed from 4s orbital first
followed by the electrons from 3d orbitals.
Ion with lower oxidation state is formed when electrons are removed from the 4s orbital.
Example:
Fe2+ = [Ar]3d6
Ion with higher oxidation state is form by further removal of electrons from than 3d orbitals.
Example:
Fe3+ = [Ar]3d5
Oxidation states that are more stable are marked bold.
Electronic configuration of ion contributes to the stability of the ion. Usually ion with halffilled 3d orbitals or fully-filled is stable or ion ioelectronics with Argon is stable.
From Sc to Mn:
Ion with higher oxidation state is more stable than ion with lower oxidation states. The
ion with the higher oxidation state is isoelectronic to argon.
Example:
Ti4+ ion is stable due to the ion is isoelectronic with the argon atom.
94

From Mn to Zn:
Ion with lower oxidation state is more stable than ion with higher oxidation states. The ion
with the lower oxidation state is either has its 3d orbital half-filled or retaining then higher
number of electron pair in the 3d orbital.
Examples:
Fe3+ ion is stable due to the 3d orbitals are half-filled.
Zn2+ ion is stable due to the 3d orbitals are fully-filled or maximum number of electron pairs.
Ion with the higher oxidation state usually does not exist in the form of simple ion due to
the high density of charge of the ion. Thus, it forms oxoanions and oxocompounds.
Examples:
Oxoaonios: [Ti(H2O)4O]2+,[V(H2O)4O]3+
Oxo-compounds: TiO2, V2O5, K2CrO4, K2Cr2O7, KMnO4
Ion with the lower oxidation state exists in the form of simple ionic compounds and hydrated
free ion in aqueous solutions.
Examples:
Simple ionic compound: MnCl2, FeCl3, CuSO4, Ni(NO3)2
Hydrated free ion: [Zn((H2O)6]2+ , [Cr((H2O)6]3+
Ion with the higher oxidation state is usually strong oxidizing agent than the ion at the lower
oxidation state. It is easily reduced to the ion at the lower oxidation state.
Examples: MnO4 + 5e + 8H+ Mn2+ + 4H2O
Fe3+ + e Fe2+
3. FORMATION OF COMPLEX
Complex is compound formed when a central atom
or ion (of transition metal) is bonded to several
molecules or ions (ligands) by dative (coordinate)
bond.
Ligands are molecules or ions that have at least
one non-bonding pair of electrons that are readily
to
be donated
atom
/ ion to the metal atom or ion to form a
dative bond. Ligands are Lewis bases.

L
L

L
M = metal
L
L = ligands

3.1 Formation of complex

Atoms or ions of transition metal have exceptionally strong tendency to form complex
because of its atoms or ions have empty d orbitals in their valence shell.
In the formation of complex, metal atom / ion accept the non-bonding electron pairs from
ligands. The electron pairs are filled into the empty d orbitals of the metal atom / ion. Thus,
the metal atom or ion acts a Lewis acid.
3.2 Name and classification of ligand
A ligand is classified according to the number of donor atom per ligand or the number of
dative bond formed per ligand.
95

Monodentate: Form one dative bond per ligand

H2O (aqua), NH3 (ammine), CO (carbonyl)
F (fluoro), Cl (Chloro), Br (Bromo), OH (hydroxo), CN (cyano), NO2 (nitro), SCN
(thiocyanato)
Bidentate: Form two dative bonds per ligand
H2NCH2CH2NH2,
CH3C CCH3,
(ethane-1,2-diamine)
HON NOH
(dimethylglyoxim)

OCCO

O O
(ethanedioate)

Hexadentate: Form six dative bonds per ligand

CH2COO

OOCCH2

:NCH2CH2N:
OOCCH2
CH2COO
(Ethylenediaminetetraacetate or EDTA)

The bidentate and hexadentate ligands are called Polydentate ligands or chelate compound or
chelate.
Chelates form ring structures that encircle and trap the central metal ion.
3.3 The shapes of complexes
2

180o

109.5o

Linear (sp): [Ag(NH3)2]+, [CuCl2]

LML

Tetrahedron (sp3)
[CoCl4], [Ni(CO)4 ], [Zn(NH3)4]2+

L
M
L

L
L

90o

L
M

Square planar (dsp2)

[Cu(NH3)4]2+, [Pt(NH3)2Cl2],
[Pt(NH3)4]2+
[Ni(CH3CNOH)2]2+

L
CH3CNOH

90o

L
[Ni(C2O4)3]

Octahedron (sp3d2 )
[Cu(H2O)6]2+, [Ni(NH3)6]2+,

L
L

M
L
L

[Co(H2NCH2CH2NH2 )2Cl2]+,
[Ni(EDTA)]2
L
[Cr(H2NCH2CH2NH2)3]3+,
[Fe(H2O)5SCN ]2+

Draw the structural formulae for the complexes above.

96

3.4 Names of complex

Naming a complex depends on the types of the complex. There are three types of complex,
namely neutral complex, cationic complex and anionic complex.
The charge of complex can be determined by calculating the total oxidation number of
ligande and the metal ion.
Examples: [Ni(CO)4 ]
CO molecule is neutral charge. Thus the total oxidation number is zero. Therefore, oxidation
number of nickel is zero because the complex is neutral.
[Fe(H2O)5SCN ]2+
H2O molecule is neutral charge. Thus the total oxidation number is zero. SCN has 1 negative
charge. Thus the oxidation number is 1. Therefore, the oxidation number of ferum is +3
because the total charge of complex is 2+.
Example: [Ni(C2O4)3]4
C2O42- has total cahrge 2. Three unit of this ion have a total charge of 6. Therefore, the
oxidation number of nickel is +2 because the total charge of complex is 4.
In naming a complex, ligands are name first according to the alphabetical order. Prefixes like
di, tri and tetra is added to the name of ligand according to the number of same ligand in the
complex. In case where the name of ligand already has prefix like di or tri or tetra, prefixes
like bis, tris and tetrakis are used.
Metal is named last. If:
The complex is neutral, the name of the metal remain unchanged.
The cationic complex, the name of the metal remain unchanged and followed by the
oxidation state is stated.
The anionic complex, the suffix ium in the name of metal is dropped and is added on with
ate.
Examples:
[Ni(CO)4 ]: Tetracarbonylnickel
[Fe(H2O)5SCN ]2+:Pentaaquathiocynatoferum (III) ion
[CuCl4]2 : Tetrachlorocuprate(II) ion [Ni(C2O4)3]4 : tris(ethanedioate)nickelate(II) ion
Name the following complex:
[Ni(H2O)4Cl2] :
[Cu(H2O)6]2+:
[V(H2O)4O2]+ :
[NiEDTA]2 :
[Fe(CN)6]3 :

[Pt(NH3)2Cl2] :
[Cr(NH3)5Cl]2+:
[Co(H2NCH2CH2NH2 )2Cl2]+:
[CuCl2] :
[Co(NO2)4(OH)2]3 :

4. COLOUR OF COMPLEX
Most complexes of transition metals are colored. The
color of a complex is depends on the nature of the central
metal ion, the oxidation state of the metal ion and the type
of ligand.
The white light is made up of three major colours, red,
yellow and blue. When these major colours are mixed,
they produce secondary color like green, orange and
purple.

red
orange

purple
white
yellow green blue

The d orbitals in the metal atom or ion are at the same energy level.
97

3d
y

y
z

z
z

z
x

x
x
x
dxz (xz plane
between x-z)

dyx (xy plane d (x2- y2), on the axis. dz2 on the axes
between x-y) of x and y
of z

dyz (yz plane

between y-z)

However, when ligands approach the central atom during the formation of complex, the
electric fields of the non-bonding electron pair in ligands and the electric fields of the d
orbitals in the metal ion repel against each other. This causes the d orbitals to split into 2
groups of orbitals with different energy. This is called the d-d splitting of d orbitals.
d (x2- y2) and dz2

E = hv

dxz, dyz and dyx

dxz, dyz and dyx

3d

d-d splitting in octahedral complex is due to the

3dligands that approaching the central atom at the
direction along the x, y and the z exes. This pushes d
2 2
2
(x - y ) and dz orbitals to higher energy level and dxz, dyz
and dyx orbitals to lower energy level. These two
groups of d orbitals are separated with a small energy
gap, E that corespone to a discrete wave length, v from
the vivible light region.
When electron from the lower energy level absorbs v
from the visible light, it is excited and moves up the
higher energy level.
The remaining wave lengths pass through and give the
colour to the complex.

d-d splitting in tetrahedron complex is due to the

ligands that approaching the central atom at the
direction between the x, y and the z exes. This pushes

dxz, dyz and dyx orbitals to higher energy level and d (x2d (x2- y2) and dz2
2
2
) and dz orbitals to lower energy level.
If d-d splitting created a bigger energy gap, the ycomplex
will absorb higher frequency from
the visible light. Thus, it gives color that corresponds to the lower frequency.
Metal ion that has higher oxidation state causes bigger energy gap during d-d splitting.
E = hv

Example: [Cu(H2O)6]2+ is blue color.

During the formation of this complex, the 3d orbitals of copper (II) ion under go d-d splitting
into 2 groups of orbitals. Electron form the lower energy level moves to the higher energy
level by absorbing red and yellow frequencies from the visible light. Blue frequency passes
through and gives blue color to the solution.
d (x2- y2) and dz2
Blue frequency
d-d splitting
passes through
3d
absorb red and

and gives blue
color to the
98
solution


yellow frequencies

dxz, dyz and dyx

5. STABILITY OF COMPLEX
Metal ion of transition metal forms hexaaqua complex, [M(H2O)6]n+ and forming an
equilibrium as the following.
Mn+(aq) + 6H2O(l) [M(H2O)6]n+(aq)
At the equilibrium,
Kstability = [M(H2O)6]n+/ [Mn+][H2O]6
Stable complex has bigger value for the stability constant, Kstability. Thus, the equilibrium is
shifted right and favors the formation of the complex ion.
When some solution contains ligand L is added into the equilibrium, the ligand, L may or
may not form complex ion with the metal ion, M by replacing H2O is depends on the relative
value of the stability constant, Kstability, of the two complexes.
If ligand, L, forms more stable complex with metal ion, molecules of ligand, L, would replace
water molecules in the [M(H2O)6]n+ complex ions to form [MLm]n+ complex ion. This would
accompanied by the change of color of the solution from color A to color B.
[M(H2O)6]n+(aq) + mL(l) [M(L)m]n+(aq) + 6H2O(l)
Color A
color B
Example: When some ammonia solution is added into aqueous solution of copper (II)
sulphate, blue precipitate is formed. If excess of ammonia solution is added, the blue
precipitate dissolves to form a dark blue solution. When some EDTA4 solution is added, the
color turns light blue again.
The stability of complex increases according to the following order:
[Cu(H2O)6]2+ < [Cu(H2O)4(OH)2 ] < [Cu(NH3)4]2+ < [CuEDTA]2
Light blue
blue precipitate
dark blue
light bleu
The reactions are:
[Cu(H2O)6]2+(aq) + 2OH (aq) [Cu(OH)2(H2O)4](s) + 2H2O(l)
Light blue
blue precipitate
[Cu(OH)2(H2O)4](s) + 4NH3(aq) [Cu(NH3)4]2+(aq) + 4H2O(l) + 2OH (aq)
Blue precipitate
dark blue
2+
4
[Cu(NH3)4] (aq) + EDTA (aq) [CuEDTA]2 (aq) + 4NH3(aq)
Dark blue
light blue
Some important notes:
Neutral complexs are solid or precipitate.
Chelates usually form more stable complexes than monodentate ligands.
6. ISOMERISM IN COMPLEX IONS
Isomerism means the existence of two or more compounds with different structural formulae
but having the same molecular formula.
6.1. Structural isomerism
Structural isomerism occurs when complexes having the same molecular formula but are
different with respect to the type of ligands that are bonded to the central atom.
Example:
99

This CrCl36H2O compound has 3 structural isomers and their structural formulae are shown
as in the next table.
They are different in term of the number of free Cl- ion and the number of Cl- ligands bonded
to the chromium ion in the complex.
These isomers can be differentiated from one another by adding silver nitrate solution.
Formula of isomer
Isomer I
[CrCl2(H2O)4]+Cl2H2O

Structural formula
Cl
H2O

Number of free Cl ion

1 free Cl- ion

color
Dark
green

The other 2 Cl ions are bonded

to the Cr ion.

OH2
Cl

Cr
H2O

OH2
Cl

Isomer II
[CrCl(H2O)5]2+ 2ClH2O

H2O
H2O

2 free Cl- ions

Light
green

2+

The other one Cl ion is bonded

to the Cr ion.

OH2
2Cl

Cr
H2O

OH2
Cl

Isomer III
[Cr(H2O)6]3+ 3Cl

3 free Cl- ions

Purple
H2O
H2O

3+

No Cl ion is bonded to
the Cr ion.

OH2
Cr

H2O

3Cl

OH2
H2O

Upon adding silver nitrate solution, AgNO3, white precipitate AgCl is formed.
Ag+(aq) + Cl-(aq) AgCl(s)
The amount of white precipitate produced is depends on the number of free Cl- ions presence
in the isomer. Isomer III and isomer II respectively form 3 times and 2 times more precipitate,
AgCl than isomer I.
The Cl- that bonded to the central chromium (III) ion in the complex will not be precipitated.

6.2. Geometrical isomerism

Geometrical isomerism occurs in
a. Square planar complexes with the formula of Ma2b2. (a and b are monodentate ligands)
b. Octahedron complexes with the formula of Ma4b2. (a and b are monodentate ligands)
c. Octahedron complexes with the formula of Ma3b3. (a and b are monodentate ligands)
d. Octahedron complexes with the formula of Ma2b2. (a is bidentate ligand and b is
monodentate ligand)
a

a. Square planar complexes with the formula

of Ma2b2. (a and b are monodentate ligands)

a
M

Trans isomer has the same ligands at 180 to

each other and cis isomer has the same
ligands at 900to each other.

100

Trans isomer
Example:
Cisplatin or Diamminedichloroplatimun(II), Pt(NH3)2Cl2.
Cl

Cl

Cl

Pt

c. Octahedron complexes with the formula of Ma3b3.

(a and b are monodentate ligands)

NH3
Pt

NH3
NH3
Cis isomer

Facial isomer (fac) has all three same ligands located

at the same surface, while meridian (mer) isomer has
all three ligands at the meridian plane.
a
a
b
a
b
b
M
M
b
a
b
a
b
a
fac-isomer
mer-isomer

NH3
Cl
Trans isomer

Other examples: [Pt(NH3)2(OH)2 ]

Example: [Cr(NH3)3Cl3]

b. Octahedron complexes with the formula of Ma4b2.

(a and b are monodentate ligands)
b

Cl
H3N

H3N

b
trans

+
H3N

NH3

H3N

NH3

Cr
H3N

Cl

H3N

Cl
Cl
mer-isomer

d. Octahedron complexes with the formula of

M(aa)2b2. (a is bidentate ligand and b is
monodentate ligand)
b
b

Cl
NH3

NH3
Cr

Other examples: [Pt(NH3)3Cl3]+, [Cr(H2O)3Cl3]

Example:
Tetraamminedichlorochromium(III) ion, [Cr(NH3)4Cl2]+

H3N

H3N

NH3
fac-isomer

b
Cis

Cl

Cl
Cl

Cr

Cis isomer

Cr

Cl
trans isomer

Cl

NH3
cis isomer

a
Other examples: [Cr(H2O)4Cl2]+, [Pt(NH3)4Cl2]2+
and Pt(NH3)2Cl4.

M
b

Cis isomer

trans isomer

The cis isomer is also an optical isomer.

Example: [Co(H2NCH2CH2NH2 )2Cl2]+

Cl

Cl

Cl

NH2

NH2
CH2

)+ (

Co
CH2
NH2
CH2

NH2

NH2

CH2

CH2
)+

Co
CH2

CH2
NH2

CH2NH2
Cis isomer

NH2
Cl
trans isomer

Other example: [Cr(H2NCH2CH2NH2 )2Cl2]+, [Ni(C2O4)2Cl2]4

6.3. Optical isomerism

101

Occur only among the octahedron complexes, which do not have a plane of symmetry.
Optical isomers rotate plane polarized light at the same degree but at the different directions
(clockwise or anti clockwise). They exist in a pair of enantiomers which are the mirror image
of the other. They are not superimpose-able.
There are three situations where optical isomerism can occur in the octahedron complexes.
a. Octahedron complexes with the formula of M(aa)2b2. (a is bidentate ligand and b is monodentate ligand)
Only the cis isomer is optically active.
b
b
b

M
a

M
a

a
a

Enantiomers
Example: Cis [Co(H2NCH2CH2NH2 )2Cl2]+
mirror
Cl

Cl

H2N
( CH2
CH2

Cl
)+

Co
NH2

Cl

NH2

CH2 )+
CH2

Co

NH2

NH2

CH2
CH2

NH2

CH2
CH2

NH2

NH2

Other examples: The cis isomer of [Cr(H2NCH2CH2NH2 )2Cl2]+ and [Ni(C2O4)2Cl2]4

b. Octahedron complexes with the formula of M(aa)3. (a is bidentate ligand )

a

M
a

M
a

a
a

Enantiomers

102

Example: [Co(C2O4)3]3

mirror
O

OC

CO
C=O

O=CO
(

O=C

O
)3

Co
O=CO

OC=O
)3

Co

O C=O

O= C

OC

CO

O
Enantiomer

Other examples: [Ni(H2NCH2CH2NH2 )3]2+

c. Octahedron EDTA complexes
Example: [NiEDTA]4
O

mirror

CH2CO

OCCH2

O = C O
(

OC=O
)2

Ni
CH2 N

O=CO
(

N CH2

Ni
CH2 N

CH2CH2

O C=O
)2
N CH2

CH2CH2

OCCH2

CH2CO
Enantiomer

O
Other examples: [CrEDTA],[CuEDTA]2.

7. USES OF CHROMIUM, COBALT, MANGANESE AND TITANIUM

Titanium:
It has the same mechanical strength as steel, light and does not corrode.
It is use for making aircraft body, space capsules and nuclear reactors.
Titanium(IV)oxide, TiO2:
Highly stable.
It is use as white pigment in paint, filler for plastics and rubber.
Chromium:
103

It is used to make alloy like steel.

It increases the hardness of steel and enables steel to resist corrosion.
It has shinning surface and able to resist corrosion. Thus, it is used for electroplating.
Cobalt
Alloy of cobalt and samarium is used to make permanent magnets.
Manganese
Alloy of manganese and steel is use to make high speed cutting tools and rial.

PAST YEARS QUESTIONS

OBJECTIVE
1990/20. Which of the following statements is correct for the transition elements (Cr to Cu)
in the Periodic Table?
A They are silver in colour.
B They have low melting point.
C Atom of these elements have 4s orbital fully filled.
D They react with dilute acid to displace hydrogen gas.
E They are used as catalyst.
1990/21. Which of the following reactions is not true for the formation complex by means
ligand exchange?
A 2[Ag(CN)2] + Zn [Zn(CN)4] + 2Ag
B [Cu(H2O)4]2+ + 4NH3 [Cu(NH3)4] 2+ + 4H2O
C [Fe(H2O)6]3+ + SCN [Fe(H2O)5SCN]2+ + H2O
D [Fe(H2O)5SCN]2+ + 6CN [Fe(CN)6]4 + 5H2O + SCN
E [Fe(H2O)6]2+ + 2C2O42 [Fe(C2O4)2(H2O)2]2 + 4H2O
1991/20. Manganese has various oxidation states. Which of the following explain why
manganese does not form simple ion of Mn+7?
A Manganese is highly reactive.
B The highest oxidation sate of manganese is +6.
C Mn2+ ion has stable electronic configuration (Ar) 3d5
D Mn7+ ion has electronic configuration (Ar) 3d0
E Mn7+ ion has high charge density.
1992/21. Below are observation obtained from an experiment.
i. When sodium chloride is added into silver nitrate, white precipitate is formed. The
precipitate dissolve when added ammonia solution.
ii. When sodium bromide is added into the mixture above, yellow precipitate is formed.
The yellow precipitate dissolves when sodium thiosulphate is added.
Arrange the ligands in the descending order according to their relative strength when react
with Ag+ ion.
A NO3, Cl, NH3, Br, S2O32 B S2O32, NH3 , NO3 , Br, Cl
C Cl ,NO3 , NH3, Br, S2O32 D S2O32 , Br, NH3, Cl, H2O
E H2O, Cl , NH3, Br, S2O32
104

1994/21. Which of the following does not related to the properties of transition elements?
A Nickel is used in hydrogenation of vegetable oil to fat.
B Manganese forms oxides of MnO, MnO2 and Mn3O4.
C Iron reacts with acid to displace hydrogen.
D Copper(II) hydroxide dissolves in excess of ammonia solution
E Iron(II) sulphate is green, while iron(III) sulphate is yellowish.
1995/21. The cyanide ligands in [Cu(CN)4]2- complex ion can be replaced by another ligand
to give a dark blue solution that contains complex ion, Z.
Z is
A [Cu(Cl)2] B [Cu(Cl)4]2 C [Cu(H2O)4]2+ D [Cu(H2O)6]2+ E [Cu(NH3)4]2+
1996/30. Which of the following is not the property of transition elements?
A Form colour ions
B Various oxidation state
C High density
Form complex
E Showing catalytic property

1996/53. Which of the following is true for complex [Cu(NH3)4]SO4?

1 The solution is blue
2 One mole of the complex reacts with two moles of silver nitrate
3 One mole of the complex produces two moles of ions
1996/31. The coordination number of complex, [Co(NH3)4Cl2]Cl is
A 2
B 3
C 4
D 6
E 7
1997/22. Which of the following complex ion is formed when potassium cyanide is added
into iron(II) solution?
A [Fe(H2O)6]2+
B [Fe(H2O)6]3+
C [Fe(OH)6]443D [Fe(CN)6]
E [Fe(CN)6]
1998/32. Which of the following explain the heterogeneous catalytic property of transition
elements?
A The ability of the elements to function as reducing agent.
B The ability of the elements to lower the activation energy of a reaction.
C The ability of the elements to form colour complex.
D The ability of the elements to adsorb gas molecules onto the surface of the solid of the
metals
E The metals exhibit magnetism property.
1999/25. When excess of ammonia solution is added into aqueous copper sulphate solution,
a dark blue solution, [Cu(NH3)4]2+ is formed. Which of the following statements is true?
A Ammonia functioned as Lewis base.
B Complex [Cu(NH3)4]2+ is not stable.
C H2O molecule unable to displace ammonia molecules from [Cu(NH3)4]2+ complex ion.
D Copper atom and ammonia molecule each donate an electron in forming CuN bond.
E Further addition of excess of ammonia solution will produce [Cu(NH3)6]2+ complex
ion.
1999/28. Which of the following is true for the transition elements?
A All the elements have oxidation state varies from +1 to +7.
B Stability of certain oxidation state of the elements in its complex ion does not depend
105

on the ligands in the complex ion.

C The oxidation state of chromium and copper in [Cr2O7]2 and [Cu(H2O)4]2+ is +5.
D Cr3+ and Mn2+ ions are stable in its aqueous solution with the presence of oxygen.
E MnO4 ion is stable in alkaline solution.
1999/29. Transition elements have catalytic ability due to
A It forms coloured ions
B It has high density
C It has suitable surface for reaction to take place
D It has various oxidation states
E Atom of the elements has vacant 3d orbital.
1999/30. Which of the following elements has only one oxidation state?
A Titanium
B Vanadium
C Chromium
D Cobalt
E Zinc
2000/26. Blue precipitate of Cu(OH)2 dissolves in excess of ammonia solution to produce a
dark blue solution. Which of the following reaction represent the reaction for the formation of
the dark blue solution?
A Cu(OH)2(s) + 2OH(aq) [Cu(OH)4]2(aq)
B Cu(OH)2(s) + 4OH(aq) [Cu(OH)6]4(aq)
C Cu(OH)2(s) + 2NH3 (aq) [Cu(NH)2]2+(aq) + 2OH (aq)
D Cu(OH)2(s) + 4NH3 (aq) [Cu(NH)4]2+(aq) + 2OH (aq)
E Cu(OH)2(s) + 6NH3 (aq) [Cu(NH)6]2+(aq) + 2OH (aq)
2000/28. In which of the following compounds, the transition element has the highest
oxidation state?
A CrO2Cl2 B NH4VO3
C K3Fe(CN)6
D Co(NH3)3Cl3
E MnC2O4
2000/53. In which of the following reactions, NH3 donate a pair of non-bonding electrons?
1 HCl(g) + NH3(g) NH4Cl(s)
2 Cu2+(aq) + 4NH3(aq) [Cu(NH3)4]2+(aq)
3 HSO4 (aq) + NH3(aq) NH4+(aq) + SO42(aq)

2000/54. Nickel(II) nitrate solution contain [Ni(H2O)6]2+ complex ion that gives green colour
to the solution. When excess of a bidentate ligand ethelenediamine, H2NCH2CH2NH2, is
added to the solution, the colour changes from green to purple. Which of the following
statements is true to the process?
1 Change of colour indicates the ethelenediamine ligand form complex ion with
nickel(II).
2 Ethelenediamine is stronger ligand than water.
3 The purple colour complex is [Ni(H2NCH2CH2NH2)6]2+
2001/26. This reaction takes place when ammonia solution is added into aqueous solution of
nickel(II).
[Ni(H2O)6]2+(aq) + 6NH3 [Ni(NH3)6]2+(aq) + 6H2O(l)
Which of the following statements is true for the reaction?
106

A
B
C
D

The reaction is exothermic

Colour of the solution changes from green to blue
Complex ion [Ni(H2O)2(NH3)4]2+ also present in the solution
NH3 is stronger ligand than H2O

2001/27. Complex ion [CrF6]3 absorb red frequency from the white light. Which of the
following explain the phenomena? [Electronic configuration of Cr is (Ar) 3d54s1]
A
B
Energy
Energy
3d

C
Energy

3d

D
Energy
3d

3d

2002/ 26 Which of the following most accurately explain homogeneous catalysis of a

transition element?
A
It has multiple oxidation state
B
It reduces the heat of reaction
C
It provides energy to increase the rate of effective collision
D
It provides electron to enable chemosorbtion through forming temporary bond.
2002/ 27 The peroxodisulphate ion oxidizes iodide ion to form iodine in the presence of a
catalyst according to the following reaction.
S2O82(aq) +2I (aq) 2SO42(aq) + I2 (aq)
The standard electrode potential, Eo of several electrode systems are given as follows.
Electrode system
Eo / Volt
2
2
S2O8 (aq), 2SO4 (aq)
+2.28

I2 (aq), 2I (aq)
+0.54
MnO4-(aq),Mn2+(aq),H+(aq)
+1.52
Cu2+(aq), Cu(s)
+0.34
Cr3+(aq), Cr(s)
-0.74
3+
V (aq), V(s)
-0.26
Based on the Eo values, which of the following ions can be the catalyst for the reaction?
A
Cr3+
B
Cu2+
C
MnO4-, H+
D
V3+
2002/47 A complex with formula [Ni(NH3)x(H2O)y]Cl2 has composition by mass 13,98% Ni,
13.27% N,3.79% H. Which of the following statements is correct with regard to the complex?
107

1
2
3

The smallest ratio of x : y in the complex is 2:1

The complex is diaquatetraamminonickel(II)chloride
The cis isomer of the complex is optically active

2003/22. Which element forms the complex ion [XCl4]-?

A
Chromium
B
Copper
C
Lead
D
Silicon
2003/46. Which isomerism is shown by the complex ion Co(NH3)3Cl3?
1 Mer fac
2 Optical
3 Cis trans
4
2004/26. Most of the transition elements and their compounds are heterogeneous catalysts
which are useful for various reactions. The transition elements possess this catalytic power
because they
A
can form complexes
B
can act as reducing agent
C
can alter their oxidation state
D
have a good adsorption characteristic
2004/46. Which of the following statements is true of complex ion [Fe(C2O4)3]3- ?
5 An ethanedioste ion is a bidentate ligand
6 This complex is named as trioxalatoferrate(III) ion
7 The oxidation state of ion in this comples ion is +2
2005/20. Which of the following is the most accurate definition of transition elements?
A
Elements with various oxidation states
B
Elements with melting and boiling point
C
Elements with ability to form coloured compounds
D
Elements with partially filled d orbitals at zero or normal oxidation states
2005/26. Chromium(III) ion forms several complexes with different ligands. A 0.5cm3 of 0.1
mol dm-3aqueous solution of chromium(III) ion is mixed with different volume of 0.1 mol
dm-3 aqueous solution of ligand L. A graph of the relative intensity of the colour of the
complex formed against the volume of ligand L is given below.
Relative intensity

0
Ligand L is
A Cl-

5
EDTA4-

10

15
C

20
NH3

30 Volume of ligand L/ cm-3

25
D

H2NCH2CH2NH2
108

STRUCTURED
1990/7.a When copper tuning and aqueous solution are boiled together with blue copper
sulphate solution, a colorless solution is formed.
i) Explain this observation.
ii) Write an ionic equation for the reaction. [3]
b The reaction mixture is filtered then followed by the addition of excess of water into the
aqueous solution. White precipitate is formed.
i) Name the white precipitate.
ii) Explain the formation of the white precipitate. [2]
c The stability constant, , of a few complexes of copper are given as the following
Complex

X: [Cu(NH3)4(H2O)2]2+
5.01 x 1012
Y: [Cu(H2NCH2CH2NH2)2(H2O)2]2+
5.01 x 1019
Z:[Cu(H2NCH2CH2NHCH2CH2NH2)(H2O)3]2+
1.00 x 1016
i) Arrange these complexes in the descending order of their stability.
ii) Draw the structural formula for isomers formed by complexes X and Y.
iii) Explain the effect due to the increase in the number of donor atoms in a ligand to the
stability of these complexes. [6]
1991/7. The aqueous solutions contain vanadium ion in various oxidation states give different
colors.
a When an aqueous solution containing ammonium polyvanadate(v), NH4VO3, is acidified
with dilute sulphuric acid, a yellowish color solution is formed. State the complexes formed
in the solution. [2]
b VO3 ion is reduced by zinc to give a blue solution, while VO3 ion is reduced by copper
to give a green solution.
i) Identify the oxidation state of the blue and the green complexes formed above.
ii) By referring to the Data booklet, write equations for the reactions involved.
iii) With the help from the Data booklet, calculate the e.m.f. for the reaction between the
Br ion and the VO3 ion. Predict whether VO3 is reduced by Br ion. [8]
1992/7. a Draw all possible isomers that can be derived from the complex with the
molecular formula, Co(NH3)4(NO2)Cl2.[4]
b A series of experiments are carried out to investigate how temperature affects the
equilibrium between the reaction of complex ion, [Co(H2O)6]2+ and the hydrochloric acid.
[Co(H2O)6]2+(aq) + 4Cl(aq) [CoCl4]2(aq) + 6H2O(l)

hot water

cold water

CoCl2 + HCl

CoCl2 + HCl

A
B
C
State the observation and the explanation to the observation in A,B and C respectively. [4]
c When a small quantity of iron (II) chloride is dissolved in water and oxygen os bubbled
through the solution, iron (II) ion is oxidized to iorn (III) ion. If the experimen is repeated

109

using cobalt (II) ion, it does not oxidize to cobalt (III) ion. By the information from the data
booklet, explain this observation. [2]
1993/7. a The standard electrode potential, E for electrode Cu2+/Cu+ and electrode Cu+/Cu
is given as the following.
Cu2+ + e Cu+ E = + 0.15V
Cu+ + e Cu
E = + 0.52V
i) Calculate the e.m.f. of the electrochemical cell.
ii) State why compound of copper(I) is prepared from copper (II) even though the
equilibrium constant for the decomposition of copper (I) to copper (II) is 1.20 x 106. [4]
b Predict the effects from the addition of the following reagents into the ammoniacal copper
(II) sulphate solution.
i) Dilute nitric acid.
ii) Dilute sodium hydroxide.
iii) Sodium sulphate solution.[6]
1994/7. a The extraction of titanium from titanium(IV) oxide, TiO2, begins with the
conversion of the oxide to titanium tetrachloride, TiCl4. Titanuim tetrachloride is colorless
liquid with boiling point, 136oC. Titanium tetrachloride is then heated with magnesium to
800oC in the atmosphere of argon. The mixture is treated further with dilute acid to produce
pure titanium.
i) Write a balance equation for the reaction between titanium tetrachloride and magnesium.
ii) Explain how titanium(IV)oxide is converted to titanium tetrachloride. Write an equation
to represent the conversion.
iii) State the type of bonding and structure in titanium tetrachloride.
iv) Why carbon is not used to reduce titanium(IV) oxide to titanium during the extraction of
titanium? [6]
b In industry, white pigment, titanium(IV) oxide is prepared from ilmenite, FeOTiO2, by
treating it with excess sulphuric acid.
i) State the role of sulphuric acid.
ii) Explain how this pigment is obtained from ilmenite.[2]
c Give two physical properties of titanium for it usage in marine engineering. [2]
1995/7. a The ion, X2+ of a transition element form complex ion, [X(NH3)n(H2O)6n]2+ when
reacts with ammonia. In an experiment, ammonia solution of 1.0 mol dm-3 is added to a
solution contains 1.0 mol dm-3 of X2+ ion in various ratio. The precipitate formed is collected,
dried and weight. The following graph shows the result of the experiment.

Mass of precipitate

110

10 9 8 7 6 5 4 3 2 1
0 cm3 1.0 mol dm-3 of X2+ ion
0 1 2 3 4 5 6 7 8 9 10 cm3 1.0 mol dm-3 of ammonia solution
i) Write a balance equation for the reaction between ammonia and X2+ to form the complex.
ii) From the graph, determine the mole ratio of ammonia that reacts with X2+ ion in forming
the complex.
iii) Write a formula for the complex formed according to the mole ratio. Construct the
possible structural formulae of isomers of the complex.
iv) Based on the structural formulae, suggest the possible identity of X. [5]
b Ion X2+ forms [X(H2NCH2CH2NH2)2(H2O)2]2+ complex ion with ethane-1,2-diamine,
H2NCH2CH2NH2. Construct the structural formulae for the geometrical isomers and
differentiate the cis and trans isomers. [3]
c The stability constant, , of complex ion [X(NH3)4(H2O)2]2+ is 5.01 x 1012 and complex ion
[X(H2NCH2CH2NH2)2(H2O)2]2+ is 5.01 x 1019. Which complex ion is more stable? Explain
your answer. [2]
1998/2. c When sodium fluoride is added to aqueous solution of iron (III) chloride,
colorless complex ion is formed.
i) Name the colorless complex.
ii) Draw the geometrical structural formulae of the complex ion.
iii) State two characteristics of iron (III) ion that enables it to form complex ion. [4]
1999. b i) Complete the following table.
Ion
Mn2+
Fe3+
Cu2+
Number of electrons in the
3d orbitals
Color of ion in the
aqueous
solution
ii) Transition metals like nickel, platinum or palladium are catalysts for hydrogenation of
alkenes. State the role of these catalysts in the hydrogenation of alkenes and explain how this
role is fulfilled. [5]
2001/2. a Cisplatin is the cis isomer for complex that has the following formula,
Pt(NH3)2Cl2. The compound is used as anti-tumor agent.
i) State the IUPAC name of cisplatin.
ii) Draw structural formulae of the geometrical isomers of cisplatin. [2]
b Bis(ethane-1,2-diamine)dichloridecobalt(III) is an example of complex ion that forms
stereoisomers.
i) Draw all stereoisomers of Bis(ethane-1,2-diamine)dichloridecobalt(III).
ii) Write the valence electronic configuration of cobalt (III) ion in the complex ion. [4]
c. Aqueous solution of nickel (II) chloride reacts with ammonia to form precipitate X. This
precipitate dissolves in excess of ammonia solution to form solution Y. State the colors and
the formulae of complex X and complex Y.
Complex
X
Y

color

Formula

111

2002/3 (b) Fe2+ and Fe3+ are stable ions in aqueous solutions.
i
Based on the electronic arrangement, which of the two ion is more stable?
Write the electronic arrangement of the valence shell of the ion.
ii
An aqueous solution contains ferum(III) ions is found to be acidic. Write an
equation that explain this acidic property. [3]
2004/1 (b). Compound M2O3 is added to glass to give the glass a blue colour.
(i).
State in which block in the Periodic Table the element M is located.
(ii).
The valence orbital of M3+ ion have six electrons. Write the valence electron
configuration of the M atom.
(iii). Explain why the M3+ ion is blue.
(iv). What colour were absorbed by the M3+ ion?
(v).
Name the element M. [6]
ESSAY
1990/10. a Discuss the characteristics that the transition metal ion and the ligand have that
enable them to form complex ion. [7]
b i) What it meant by the term transition elements?
ii) Draw structural formulae for isomers of complex ion, [Cr(C2O4)3]3 and explain if the
isomers are optically active.[6]
1991/10. a Explain, how ethane1,2diamine, H2NCH2CH2NH2, function as chelate agent.
[4]
b Extraction of copper from copper (II) sulphide, CuS, causes air pollution. Explain this
statement and give suggestions how to overcome the problem. [7]
c Ammonia solution is added drop by drop to the aqueous solution of copper (II) sulphate
until the ammonia is in excess. State all changes and write all equations for the reactions
involved. [9]
1992/10. b Draw all structural formulae of isomers that can be formed by the following
complex.
Classify the isomers according to the types of isomerism.
i) [Cr(NH3)4Cl2]Cl
ii) CrCl3.6H2O
iii) [Cr(H2NCH2CH2NH2)3]3+

c The stability constants, -lg , of complexes of copper are given as the following.
Reaction
Cu2+ + 4Cl [CuCl4]2
Cu2+ + 4NH3 [Cu(NH3)4]2+
Cu2+ + EDTA4 [Cu(EDTA)]2

-lg
5.6
13.1
18.8

With this information, state what will happen in the following experiments and give
explanation to your answer.
i) Aqueous ammonia is added into aqueous solution of copper (II) sulphate and follow by
the addition of aqueous solution of EDTA.
112

ii) Concentrated hydrochloric acid is added into aqueous solution contains [Cu(NH3)4]2+ ion.
[3]
1993/10. a Explain the following observations and identify the structural formulae of all
species involved.
i) Three crystalline compounds, X, Y and Z have same molecular formula CrCl36H2O. X is
purple, Y is light green and Z is dark green. An equal amount of X, Y and Z respective is
added with certain amount of aqueous silver nitrate solution. The mass of white precipitate
produced produce is according to the ratio of 3:2:1.
ii) A yellowish aqueous solution contains ammonium metavanadate, NH4VO3, in dilute
sulphuric turns bluish and then green and finally becomes purple when shaken with zinc. [11]
b Explain the following observations and write balance equations of reactions involved.
i) Aqueous copper (II) chloride in concentrated hydrochloric acid is boiled with excess of
copper metal. The reaction mixture is then poured into oxygen free water and follow by
adding of ammonia solution.
ii) Aqueous potassium iodide solution is added with excess of copper (II) sulphate solution.
[9]
1995/10. a i) Write electronic configuration of calcium and titanium.
ii) By referring to the ionization energy from the data booklet, explain the differences in
oxidation state between calcium and titanium. [8]
c i) What do you understand by the term of complex ion.
ii) Explain, how ethanedioat ion, C2O42-, function as ligand when reacts with
chromium(III) ion. [4]
1996/6. a i) What it meant by the term transition elements.
ii) Explain, how transition elements form complex. [6]
b Draw structural formulae for isomers of the following complexes and classified them
according to the type of isomerism.
i) [Cr(NH3)4Cl2]+
ii) [Cr(C2O4)3]3
[6]

c When some aqueous solution contains cyanide ion, CN , is added into aqueous iron (III)
solution, white precipitate is formed. The precipitate becomes soluble when excess of cyanide
solution is added to form a yellowish solution. Explain these observation and write equations
for the reactions involved. [4]
2005/8(b). A coordination compound triamminetrichlorococalt(III) exist as two isomers.
i
What is the chemical formula for triamminetrichlorococalt(III)?
ii
Draw the structural formulae of the isomers and name them. [4]
(c). Explain the observations when an aqueous solution of silver nitrate is added to
(i)
triamminetrichlorococalt(III)
(ii)
tetraamminetrichlorococalt(II) chloride. [5]
Answer:
1990:20E, 21A 1991:20E 1992:21E 1994:21C 1995:21E 1996:30C, 53A(all), 31D
1997:22D 1998:32D 1999:25C, 28D, 29E, 30E 2000:26D, 28A, 53A(all), 54B(1,2)
2001:26E, 27C.

113