A’LEVEL INORGANIC CHEMISTRTY NOTES

Introduction

Inorganic chemistry is the study of substances other than carbon compounds through a
few of the latter are, conventionally included in inorganic chemistry

Early studies in inorganic chemistry were directed towards solving analytical and
mineralogical problems. There is, too, a mass of relatively factual information concerning
the preparation, manufacture, properties factual and uses of inorganic chemicals

Periodic Table

The original form of the periodic table was first put forward by Mendeleev in 1869 when
he arranged the known elements in the order of their relative atomic masses.

The elements fall into 8 vertical groups numbered from I-VIII and horizontal rows of
elements are known as periods which are 7 numbered 1-7.

Those periods containing 8 elements are known as short periods and the others as long
periods

The elements in any one vertical group have similar chemical and physical properties.
Therefore the properties of elements are periodic function of their atomic number which is
periodic law

1
Electronic configuration

Describes how the electrons of an atom are arranged in the energy levels, sub shells and
orbitals. The term normally applies to an atom in their ground states.

Rules for filling electrons

Rule 1: Aufbau Principle

The electrons in the ground state occupy orbitals in order of the orbital energy. The lowest
energy orbitals are always filled first

E.g. for 3 Li 1S 2S

Rule 2: Pauli Exclusion Principle

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This states that an orbital cannot contain more than two electrons and then only if they
have opposite spins

e.g.3Li

1S 2S

Rule 3: Hund`s Rule

This states that the orbitals of a sub shell must be occupied singly first and with parallel
spins before they can be occupied in pairs

e.g.7N

1S 2S 2P

1S22S22P3

Rule 4:

Electrons in degenerate orbital’s which are singly occupied have parallel spins

The order of filling in the electrons in subshells is summarized in the diagram below.

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Principal quantum number, n where n= 1,2,3,4 etc

This is the main energy level of an atom which determines the energy of an electron.

This denotes the principal quantum energy shell in which the electron in an atom is found.
Within the principal quantum energy shell there are shells but the total number of
electrons that can occupy any principal quantum shell is given by 2n2

The inner most orbital i.e. the one nearest to the nucleus has principal quantum number of
1 and the number of electrons in each energy level is shown as
n 1 2 3 4 5
Max. no. of electrons 2 8 18 32 50

Subsidiary quantum number

Within the principal quantum energy shell there are sub shells which are denoted as s, p, d
and f and the number of electron that an orbital can accommodate is shown as
Orbital s p d f
No. of electron 2 6 10 14

Question

Write the electronic configuration of the following elements with their respective atomic
number

(i) Aluminium (Z=13) (ii) Phosphorous (Z=15) (iii) Calcium (Z=20)(iv) Chlorine
(Z=17)

(v)Vanadium (Z=23) (vi) Selenium (Z=34) (vii) Nickel (Z=28) (viii) Copper
(Z=29) and chromium (24)

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N.B Fully filled and half filled orbital’s are regarded as thermodynamically more stable
therefore the electronic configuration of Chromium (Z=24) and Copper (Z=29) follow
this. 1S22S22P63S23P64S13d5 and 1S22S22P63S23P64S13d10 respectively

Determination of Block of an element

The block to which an element belongs is determined by the orbitals which are in the
process of filling up.

E.g. 11Na −1S22S22P63S1 belongs to the S- block

Selenium 34 with electronic configuration[Ar]4s2 3d104p4 is a p block element

N.B. Electronic configuration can be used to determine the period and group of the
element.

PERIODIC PROPERTIES

1. Atomic radius/ covalent radius

Atomic radius is half the inter-nuclear distance between two atoms of the same element
joined by the singly covalent bond.

The covalent radius depends on:

 Nuclear charge. This is the attraction of the positively charged nucleus for the
outermost electron. Increase in nuclear charge, decrease in atomic radius

 Screening effect/ shielding effect. This is tendency of inner electrons to shield outer
electrons from nuclear attraction. Increase in screening effect results into increase in
atomic radius.

Variation across the period

Atomic radius decreases across the period. This is because the nuclear charge increases
due to the addition of protons to the nucleus. For every proton added, an electron is added
to the same energy level and screening effect almost remains constant. The effective
nuclear charge increases thus the electrons become more strongly attracted and closer to
the nucleus

Example of the period variation is that of period 3

Element Na Mg Al Si P S Cl Ar
Atomic 0.156 0.136 0.125 0.117 0.110 0.104 0.09 0.094
radius(nm)

N.B. In the transition metal series the decrease is gradual

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn

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 At.
Radius 1.44 1.32 1.22 1.17 1.17 1.16 1.16 1.15 1.17 1.25
(oA)
The metallic radius decreases from scandium to nickel and it slightly increases from nickel
to Zinc.

As atomic number increases, the nuclear charge increases. However, the electrons are
being added to inner 3d-subshell therefore these electrons are poorly shielded from the
nuclear charge hence the nuclear attraction for the outer for the most electron increases
resulting into increase in atomic radius/ metallic radius.

The slightly increase from nickel to Copper is because the 3d-subenergy level in copper is
fully filled with electrons and this increases the shielding of the outer electrons from the
nuclear charge hence atomic radius increases.

The decrease in radius coupled with increasing atomic mass causes an increase in the
density and decrease in atomic volume in passing from Scandium to Nickel.

Variation down the group

Atomic radius increases down the group. Both nuclear charge and screening effect
increase. However, the increase in screening effect is more than the increase in nuclear
charge due to addition of extra energy level of electrons thus the effective nuclear charge
decreases such that the outermost electrons are less strongly attracted towards the nucleus.

Example of such variation is in group 1:

Element Li Na K Rb Cs
Atomic Radius (nm) 0.123 0.156 0.203 0.216 0.235

Ionic radius

(a) Positive ions

These are formed by removing one or two electrons from the outer most energy level. The
nuclear attraction for the remaining electrons increases thus the radius of the cation is
smaller than that of the atom from which it is formed.

Examples include
Species Mg Mg2+ Fe Fe2+
Radius 0.136 0.065 0.116 0.076

(b) Negative ions / Anion

Formed by addition of one or more electrons to a neutral gaseous atom. The effective
nuclear charge is reduced and hence the electron cloud expands. Therefore the anions are
larger than corresponding atoms .e.g.
Species Cl Cl- O O2-
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 Radius (nm) 0.09 0.18 0.066 0.140

2. Ionization energy/ Potential

The first ionization energy is minimum amount of energy required to remove one mole of
electrons from one mole of free gaseous atoms to form one mole of unipositively charged
gaseous ions.

Successive ionization energies refer to loss of a second, third……………, nth electron.

Thus the second ionization energy of X is the first ionization energy of X+ and sum of
the first n ionization energies gives the energy change for the formation of the Xn+ ion
The magnitude of ionization energy depends:
 Nuclear Charge; ionization energy increases with increasing nuclear charge.

 Screening effect: increase in screening effect decreases the magnitude of ionization

energy

 Nature of orbital: Electrons being removed from fully filled and half filled energy
levels require more energy because such electronic structures are stable.

 Type of orbital: s, p, d and f orbital have different shapes. In energy level the S-
orbital penetrate closer to the nucleus therefore the penetrating trend is S>P>d>f hence
an orbital of higher penetrating power requires more energy

 Atomic radius: Atoms with small radius the electrons are strongly bound by the
nuclear attraction and thus require more energy to be removed.

Variation across the period

Element Li Be B C N O F Ne

I.E 520 899 801 1086 1403 1310 1681 2080

(KJmol-1)

Across a period, ionization energy increases with increase in atomic number . Electrons
are added to the same main energy level as nuclear charge increases. These electrons
shield each other poorly from the increasing nuclear charge therefore atomic radius
decreases resulting into increase in ionization energy along the period

However, beryllium, neon and nitrogen have abnormally high ionization energy because
the electrons are removed from 2S2, 2P6and 2P3 which are fully filled and half filled
respectively and are regarded as thermodynamically stable.

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Qn:The table below shows the elements in period 3 of the Periodic Table
Element Na Mg Al Si P S Cl Ar
Z 11 12 13 14 15 16 17 18
st
1 I.E 502 745 587 791 1020 1000 1260 1530
(a) Plot a graph of first ionization energy against atomic number

(b) Explain the shape of your graph in (a)

Variation down the group

Ionization energy decreases down the group. Both nuclear charge and screening effect
increase down the group. Due to extra energy level of electrons being added, the increase
in screening effect exceeds the increase in nuclear charge. Effective nuclear charge
decreases such that the outer most electrons become less strongly attracted hence less
energy is required

The values of ionization energy can be used to deduce:

 Atomic number of an element. The number of successive ionization energy indicates

the number of electrons present. E.g. Mg has 12 successive ionization energies.

 Arrangement of electrons and distribution of energy levels

 Metallic character. Elements which easily lose electrons have low values of ionization
energy and are electropositive. The 1st ionization energy is usually below 800KJmol-1

Qn: The data given below are for the elements A, B, C and D which belong to the same
period in the periodic table
Element A B C D
st
1 I.E 495 580 790 1255
Melting point
of oxide ………… 2300 1610 -20

(a) Which ones of the elements A, B, C and D is a metal? Explain your answer

(b) State the type of bonding and structure of the oxides of elements A and D

(c) The 2nd, 3rd, and 4th ionization energy of element B are 1500, 7700 and
10500KJmol-1 respectively. To what group in the periodic table does B belong?
Give reason for your answer

ELECTRON AFFINITY (E.A)

This is the energy released when an electron is gained by one mole of an isolated neutral
gaseous atom to form a uninegatively gaseous ion.

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Electron affinity values are negative i.e. exothermic process even for highly
electropositive elements. The more exothermic the E.A, the easier an atom gains electron
hence the more stable the ion is.

The second E.A is accompanied by absorption of energy i.e. endothermic. This is because
the incoming electron experiences greater repulsion from both outermost electron and the
negative ion. In addition, the increased radius of the ion decreases the nuclear attraction
for the incoming electron.

E.A. Values are not experimental and thus inaccurate. They are determined indirectly from
Born-Haber cycle.

Variation across the period

Across the period, E.A increases. This is due to decrease in atomic radius and increase in
effective nuclear charge which increases the nuclear attraction for the incoming electron
thus more energy is evolved.

N.B. E.A. of Beryllium and Magnesium are less exothermic because the electron is
added to completely filled s-orbital which is stable.

Variation down the group

Down the group, E.A decreases due to decrease in effective nuclear charge caused by
addition of an extra energy level of electrons. The nuclear charge decreases and ability of
the nucleus to attract electrons is reduced hence less energy is given out.

ELECTRONEGATIVITY

This is the tendency of an element to attract bonding electrons towards itself in a covalent
compound.

The magnitude of electronegativity depends on:

 Nuclear charge

 Atomic radius

 Screening effect

Variation across the period

Across the period, electronegativity increases because the atoms become smaller and the
effective nuclear charge increases therefore the electron attractive power increases.

Variation down the group

Down the group, electronegativity decreases due to increasing atomic radius and decrease
in effective nuclear charge.

Example of such variation is;

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 Element F Cl Br I
Electronegativity 4.0 3.0 2.8 2.5

ELECTROPOSITIVITY

This is the ability to lose outermost electrons to form a positively charged ion. This is
basically a property of metallic elements because they have few electrons in the outermost
energy level with low ionization energy.

Down the group, Electropositivity increases because:

 The shielding of outer most electrons from nuclear attraction increases as more
completed energy levels are added.
 Atomic radius increases

The most reactive metals are therefore found at the bottom of the group e.g. Lithium in
group I reacts slowly with cold water due to low Electropositivity value

CHARGE DENSITY

This is the ratio of charge of a given ion to its ionic radius.

According to Fajan, polarization is favoured by:

 High charge. Highly charged positive ions greatly polarize anions with large negative
charge

 Small radius of the Cation

 Large anions. Anions with large radius are more polarizable

Polarization affects both the chemical and physical properties of ionic compounds

Examples include:

The melting point of chlorides of Sodium, Magnesium and Aluminium are shown below
Chloride NaCl MgCl2 AlCl3
Melting point 801 746 Sublimes

DIAGONAL RELATIONSHIP

This is the similarity in chemical properties between elements in period two to their
diagonal neighbors in period three and adjacent groups.

The pairs of elements with similarity in chemical properties include:

• Lithium and Magnesium

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• Beryllium and Aluminium
• Boron and Silicon

The similarity in chemical properties is due to following reasons:

• Similar polarizing power or charge density

• Similar electronegativity
• Similar Electropositivity
• Similar electrode potential
[Link] similarity in Chemical properties between the pairs See S- block elements.

ATOMIC STRUCTURE

Evidence for Sub-atomic particles

See physical chemistry notes

Hydrogen Spectrum

The hydrogen spectrum consists of a series of lines both in the visible and invisible region
of the electromagnetic spectrum i.e. line spectrum.

In each series, the spacing between the adjacent lines decreases towards the continuum i.e.
the energy levels get closer as energy decreases due to decreased nuclear attraction on the
electrons in the energy levels which nearly become constant and converge into continuous
spectrum.

For the visible spectrum, each line has a different color and represents a radiation of
definite wavelength and frequency

I.R U.V

red violet
frequency increases

wavelength increases

Explanation of the line Spectrum

When an electric discharge is passed through hydrogen gas at low pressure the gas
molecules break down to form gaseous atom, the hydrogen atoms absorb energy in
discrete units called quanta.

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The electron in each hydrogen atom becomes excited and gets promoted from levels of
lowest energy (ground state) to higher energy levels far away from the nucleus.

The electron in higher permissible state is unstable and falls back towards the ground state
emitting light/ radiations with definite frequencies.

When the radiations are resolved by the spectrometer, an emission spectrum develops.
n=
n=7
n=6

n=5

n= 4

n=3
paschen series

n=2
balmer series

n=1

lyman series

Each series represent a transition from a higher energy level to a given level of lower
energy.

The wavelength of each line is by;

1 1 1
= RH 2 − 2 Where RH is Rybergs constant = 109678

n1 n2

The energy given out when an electron falls back to lower energy level is given by:

E = hf Where h –Planck’s constant and f-frequency of radiation

c hc
Since f = , the expression can be written as E= where c is speed of light

When an electron is removed fromn , it is removed from the influence of the nucleus .i.e
.ionization
Qn: The diagram below shows some energy levels in the hydrogen atom
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 n
0

-82 n=4

-146 n=3

-329 n=2

-1310 n=1
KJmol-1

(a)If an electron is in ground state, what is the minimum energy for ionization?

(b) What is the significance of the shaded area?

(c) If an electron is in energy level 4 what is the frequency of the lowest energy it can
emit (h=6.63X10-34J s)

Evidence for existence of energy levels

 Hydrogen atoms has one electron but produces a spectrum containing a series of
lines

 The lines in each series have definite frequency and wavelength.

 The spacing between the adjacent lines in each series differs and converges into a
continuum.

 The number of lines in spectra-series increases with an increase in the resolving

power of the spectrometer prism used. hence atom has got an infinite number of
energy levels

Qn:The atomic spectrum of hydrogen can be divided into a number of series

(a) Why does the spectrum consist of lines?

(b) Explain why each series converge

(c) Explain how ionisation energy of an element can be calculated from

spectralmeasurement

(d) Explain the term convergence limit

(e)What is meant by the term principal quantum number?

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(f)State the information that can be obtained from the separate lines about the electronic
structure of hydrogen atom.

BONDING AND STRUCTURE

BONDING

(a) Covalent bond

These are bonds formed by equal sharing of two or more electrons between two atoms in a
molecule.

Each atom contributes equal numbers of electrons so that the atomic orbital overlap. The
shared electrons must be unpaired with opposite spin.

Covalent bonds are usually formed between non-metal atoms due to their high
electronegativity. E.g. Ammonia, Chlorine, carbon dioxide, methane etc

Polar and Non-polar covalent compounds

When a covalent bond is formed between atoms of different electronegativity, the more
electronegative atom attracts bonding electrons towards itself leading to slight charge
separation.

Examples include:

 Carbon dioxide and tetrachloromethane have polar bonds due to difference in

electronegativity but the bond polarity cancels out because the molecule is
symmetrical therefore they are called non-polar covalent compounds.

 Trichloromethane the bonds are polar but the molecule is unsymmetrical therefore it a
polar covalent compound

Properties of covalent compounds

 They contain simple discrete molecules held by weak vanderwaals forces in simple
molecular structure e.g Sulphur, carbondioxide and giant atomic structure e.g. Silicon
(IV)oxide, Diamond

 They are soluble in non-polar solvents e.g. benzene

 They are non-electrolyte in fused state

 They have low melting and boiling point

 They react together slowly especially organic compounds

(b) Co-ordinate/ Dative bond

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This is weak covalent bond formed between an electron rich atom and electron deficient
atom/ion.

The atom with lone pairs of electrons donates an electron pair therefore it is called donor
atom and the atom receiving the electrons is acceptor

Examples include:

Hydroxonium, ammonium and dimerised AlCl3 and BeCl2 i.e in the vapour phase
Aluminium Chloride and Beryllium chloride exist as

Cl Cl Cl
Cl

Al Al Cl Be Be Cl

Cl Cl
Cl
Cl

Qn:A compound contains 79.78% chlorine and rest Aluminium. The vapour of his
compound has a density of 2.28X103 gm-3 at 1427K and 1.013X105Pa

(a) Calculate the molecular formula Q and draw its structure.

(b) State the conditions under which the above structure exists

(c) Ionic bond

Ionic bond is bond formed by electron transfer from electropositive element to another
electronegative atom.

The electropositive atom loses electrons to become positively charged while the
electronegative atom gains the electrons to become negatively charged.

There is a total separation of charges held by strong electrostatic forces of attraction which
constitute a large continuous arrangement of oppositely charged ions resulting into a giant
ionic lattice.

The strength of the ionic bond depends on the magnitude of the forces which depends on:

 Charge of the ion. Electrostatic forces of attraction increases with increase in the
magnitude of the charge on the ions.

 Ionic radius. Electrostatic attraction decreases with increase in ionic radius.

Properties of Electrovalent compounds

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 At ordinary temperatures they are invariably exist as crystalline solids. The crystal
consist of infinite assembly of ions joined together in a regular pattern

 They have high melting and boiling point owing to strong electrostatic force of
attraction between oppositely charged ions.

 In fused state or molten state they are good conductors of electricity due presence of
free ions which are attracted and discharged at electrodes

 They dissolve readily in water

 When oppositely charged ions react together in aqueous solution they do so almost
instantaneously.

(c) Metallic bond

This is an electrostatic attraction between the delocalized electrons of the metal atoms and
positive nucleus.

The strength of the metallic bond increases with increase in the number of delocalized
electrons

Qn: The melting points of group I metals decreases down the group

Soln: The metallic radius increases therefore the delocalized electrons are held by weak
forces hence decrease in melting point.

Qn: The table below shows the melting points of elements in period 3 of the periodic
table
Element Na Mg Al Si P S Cl
At. no. 11 12 13 14 15 16 17
Melting
point(oC) 98 650 660 1410 44 119 -101
(a) Plot a graph of melting point against atomic number

(b) Explain the shape of graph

(d) Hydrogen bonding

It is a permanent bond formed by dipole-dipole attraction between the hydrogen atom and
a highly electronegative atom in a molecule with at least a lone pair of electron

Compounds of Nitrogen, Oxygen and Fluorine form hydrogen bonds

Effects of hydrogen bonding on the physical properties

1. Solubility in water

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Organic compounds with polar functional groups such as Alcohols, Amines and
Carboxylic acids are soluble due to association of the molecule with water through
hydrogen bond

2. Boiling and Melting points

Hydrogen bonds in molecule elevate the boiling points due to extra energy required to
overcome the bonds before molecule vapourise.

The effects of hydrogen bonding on boiling point depend on:

 Number of hydrogen bond formed

Electronegativity of the atom Examples include:



CH3CH2CH2OH CH3CH2CH2NH2 H2O HF NH3

98 49 100 24 -33
Since oxygen is more electronegative than nitrogen, the b.p .t of CH3CH2CH2OH is
greater than CH3CH2CH2OH.

Water molecule forms more hydrogen bond although the electronegativity of Fluorine is
higher hence a higher b.p.

3. Density and Volume

Hydrogen bonds increase the volume and lowers the density e.g. Ice floats on water

Each oxygen atom is tetrahedrally attached to four hydrogen atoms i.e two are normal
covalent bonds and the other are longer hydrogen bond. This arrangement gives ice a
more open structure hence an increased volume therefore a fixed mass for water, the
density decreases and it freezes.

Qn:

(a) Explain what is meant by the term Melting point

(b) State the factors that affect the melting point of:

(i) Metal

(ii) Molecular substances

(c) Explain the trend in the melting points of the elements in group II and group VII of
the Periodic

Table

(d) Why are transition metals of period 4 having higher melting point than
nontransition metals of the same period.
(e) Explain why

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(i) The melting point of Aluminium chloride is abnormally low compared to that
Aluminium Oxide

(ii) The melting point of Calcium oxide is higher than of Calcium chloride

S-BLOCK ELEMENTS (Group I and II)

The elements in this block have their valence electrons placed in the S-orbital. The outer
most configurations are:

Group I (Alkali metals) -ns1

Group II (Alkaline earth metals)-ns2 where n is principal quantum number.

The physical properties include:

Group I (Table 1)
Element Li Na K Rb Cs
Ist I.E (KJmol-1) 520 500 420 400 380
2nd I.E(KJmol-1) 7300 4600 3100 2700 2400
Atomic radius(nm) 0.15 0.19 0.23 0.25 0.26
Melting point (oC) 180 98 63 39 29
Density(gm-3) 0.53 0.97 0.86 1.53 1.87
Hydration energy(KJmol- -499 -390 -305 -281 -248
1
)
Electrode potential(V) -3.05 -2.71 -2.92 -2.93 -3.02
Group II(Table 2)
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 Element Be Mg Ca Sr Ba
Ist I.E (KJmol-1) 900 740 590 550 500
nd -1
2 I.E(KJmol ) 1800 1460 1150 1060 970
Atomic radius(nm) 0.11 0.16 0.20 0.21 0.22
o
Melting point ( C) 1280 650 838 768 714
-3
Density(gm ) 1.86 1.74 1.55 2.60 3.50
Hydration -2385 -1897 -1561 -1414 -1274
energy(KJmol-1)
Electrode potential(V) -1.85 -2.37 -2.87 -2.89 -2.91
The standard electrode potential for conversion of each metal to its ion is positive
(endothermic) thus S- block elements are reducing agents.

Group I elements are stronger reducing elements than Group II and the tendency increases
as you move down the group.

Qns: (a) State three energy factors which make group I elements stronger reducing
agent than Group II elements.

(b) Explain briefly why Potassium is a stronger reducing agent than Sodium.

CHEMICAL PROPERTIES OF S-BLOCK ELEMENTS

1. HYDROGEN

The hot metals react with dry hydrogen gas to form ionic hydrides i.e.

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

Mg (s) + H2 (g) MgH2 (s)

Since the metals are electropositive, the oxidation state of hydrogen in the hydrides is -1.

2. WATER

All group I elements readily react with cold water to form strong alkaline solution e.g.

2K (s) + 2H2O (l) 2KOH (aq) + H2 (g)

All the group II elements except Beryllium react with water with increasing vigour down
the group to liberate hydrogen gas.

Reactivity of group (II) elements with water increases down the group as atomic radius
increases due to increase of Electropositivity.

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Magnesium reacts slowly with cold water but vigorously with steam

Mg (s) + H2O (g) MgO (s) + H2 (g)

Calcium, Barium Strontium reacts readily with water to form the hydroxide and hydrogen
gas.

M (s) + 2 H2O (l) M(OH)2 (aq) + H2 (g)

Where M= Ca, Ba and Sr.

3. ACIDS

Group I elements react violently with dilute mineral acids to form salt and hydrogen gas.

2M (s) + 2H+ (aq) M+ (aq) + H2 (g)

Group II elements react but the reaction becomes more vigorous down the group except
with dilute sulphuric acid. e.g.

Mg (s) + 2 H+(aq) Mg2+ (aq) + H2 (g)

Calcium, Strontium and Barium react slowly with dilute sulphuric acid due to formation
of sparingly soluble salt which prevent further reaction e.g.

Ba (s) + H2SO4 (aq) BaSO4 (s) + H2 (g)

Magnesium, Calcium and Barium react with very dilute nitric acid to liberate hydrogen
gas e.g.

Mg (s) + 2HNO3 (aq) Mg (NO3)2 (aq) + H2 (g)

Qn: Compare the reaction of beryllium and barium with sulphuric acid

4. OXYGEN

Group II elements form normal oxides .i.e.

2M (s) + O2 (g) 2MO(s)

However barium and Strontium can form peroxides when the normal oxide is heated in
more oxygen .e.g.

2BaO (s) + O2 (g) 2BaO2 (s)

Group I elements burn in excess oxygen to form variable oxides .i.e.

Lithium forms only a normal oxide .i.e.

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

Sodium forms a yellow normal peroxide .i.e.

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2Na (s) + O2 (g) Na2O2 (s)

Potassium, Caesium and Rubidium form super oxides when burnt in excess in oxygen e.g.

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

All the oxides are basic except beryllium oxide which is amphoteric .i.e.

BeO(s) + 2 H+ (aq) Be2+ (aq) + H2O (l)

BeO(s) + 2 OH- (aq) + H2O (l) Be (OH)42-(aq)

The peroxides form hydroxides or/and hydrogen peroxides when dissolved in water

Na2O2(s) + 2 H2O (l) 4NaOH (aq) + O2 (g)

BaO2(s) + 2 H2O (l) Ba(OH)2 (aq) + H2O2 (aq)

The super oxides liberate oxygen gas, hydrogen peroxide and the hydroxide when
dissolved in water.

2KO2 (s) + 2H2O (l) 2KOH (aq) + O2 (g) + H2O2 (aq)

Qn:(a) Be, Mg, Ca and Ba belong to group II of the periodic table. Describe the
reactions of the elements with;

(i) Water

(ii) Air

(b) Explain why Lithium doesn’t form peroxide or superoxide when burn in oxygen.

(c) State what is observed when potassium super oxide is dropped in water. Write the
equation of reaction.

5. CHLORINE (HALOGENS)

The hot metals directly combine with chlorine to form ionic halides except beryllium i.e.

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

Ca (s) + Cl2 (g) CaCl2 (s)

The anhydrous chlorides are ionic except beryllium chloride which is covalent

NOTE: Beryllium behaves differently from the rest of the elements due:

• Small atomic radius

• High charge density
• Low electropositivity

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• High polarizing power

COMPOUNDS OF S-BLOCK ELEMENTS

Group I compounds are more ionic than the corresponding compounds of

group II. This is due to high charge density.
The salts of group II elements are less soluble in water than group I.
Solubility of ionic compounds in water is affected by lattice energy and
hydration energy i.e.
Hs = Hh +U Where Hs is enthalpy of solution

Hh Is hydration energy

U Is lattice energy
Soluble salts have negative enthalpy of solution. The more negative the enthalpy of
solution the more soluble the salt.

Some hydrated salts e.g hydrated copper (II) sulphate crystals dissolve endothermically
while anhydrous salt dissolves exothermically.

This is because for hydrated salt, the ions are already partly hydrated therefore hydration
energy is lost thus when the crystals are dissolved in water this hydration energy is not
enough to outweigh lattice energy. For anhydrous salt, the hydration energy is readily
available and able to outweigh lattice energy.

Qn: Given the following thermo chemical data

Salt Hydration energy (KJmol- Lattice energy (KJmol-1)
1)

AX 880 860
BX 790 800
State which salt is more soluble and explain your answer

1. HYDROXIDES

The hydroxides of Group I elements are all white solids and deliquescent except lithium
hydroxide. They dissolve in water exothermically to form strong alkaline solution.

The hydroxides become more soluble down the group due to increasing ionic radius of the
cation which decreases the lattice energy.

Qn: (a) Describe how sodium hydroxide is prepared on a large scale.

(b) Explain how sodium hydroxide pellets react with air.

Soln:(a) It is prepared by electrolysis of brine using Mercury cathode.

Page 22
At the cathode, Na+ ions are discharged instead of H+ ions because of the high
concentration of the Brine. The sodium thus formed dissolves in the mercury surface to
form Sodium amalgam. The sodium amalgam then flows out and mixes with water to form
a mixture of hydrogen gas, sodium hydroxide and mercury.

2NaHg (l) + 2 H2O (l) 2NaOH (aq) +H2 (g) + 2Hg (l)

The mixture is then heated and sodium hydroxide is then stable at high temperatures
hence it is formed.

(b) It is deliquescent hence absorbs water to form sodium hydroxide solution which reacts
with carbon dioxide to form sodium carbonate and in excess a white crystal of
sodium hydrogen carbonate is formed . I.e.

2NaOH (s) + CO2 (g) Na2CO3 (aq) + H2O (l)

Na2CO3 (aq) + H2O (l) + CO2 (g) 2NaHCO3 (s)

Group II hydroxides are sparingly soluble and are prepared by precipitation method. i.e.

M2+ (aq) + 2OH- (aq) M (OH)2 (s)

They can also be prepared by dissolving a normal oxide of the metal in water. e.g.

CaO (s) + H2O (l) Ca (OH)2 (s)

Qn: Explain why beryllium hydroxide cannot be prepared by precipitation method.

Soln : Because Beryllium hydroxide is amphoteric and therefore it forms complex .

Be(OH)2 (s) + 2OH- (aq) Be(OH)42- (aq)

The table below shows the solubility of the hydroxides of group II elements
Hydroxide Solubility at 25oC

Be(OH)2 0.00
Mg(OH)2 0.01
Ca(OH)2 0.015
Sr(OH)2 0.89
Ba(OH)2 3.32

The solubility generally increases down the group. This is because the radius of the
cations increases while charge remains constant therefore both hydration and lattice
energy decrease. However due to small size of the hydroxide ion, the lattice energy
decreases more rapidly than the hydration energy therefore the enthalpy of solution
becomes more negative.

N.B. The trend is similar for fluoride ions (F-)

Page 23
The table below shows the solubility of sulphates of group II elements
Sulphates Solubility
BeSO4 4095.24
MgSO4 3600
CaSO4 11.0
SrSO4 0.62
BaSO4 0.009

The solubility decreases. Both lattice energy and hydration energy decrease due increase
in ionic radius of the cation. Since the sulphate ion is large, the hydration energy decreases
more rapidly than the lattice energy therefore the enthalpy of solution become less
exothermic.
N B. The trend is similar for CO32-, CrO42-, PO43- , and Cl-

2. CARBONATES AND HYDROGEN CARBONATES

Group I elements form soluble carbonates except lithium carbonate.

The carbonates are prepared by bubbling carbon dioxide through the hydroxide solution to
precipitate the less soluble hydrogen carbonate which on heating decomposes to
anhydrous carbonate.

Qn: Explain why Lithium carbonate is insoluble in water.

Soln: Due to high charge density of lithium ions which greatly polarize the carbonate
ion thus Lithium carbonate is covalent.

Qn: Describe how sodium carbonate is prepared by solvary process on a large scale.

Soln: See A New Certificate of Chemistry, 6thedition (1987), Holderness and Lambert,
page331.

Group II carbonates are insoluble in water and undergo thermo decomposition to form
oxide and carbon dioxide gas.

The carbonates are prepared by addition of sodium carbonate solution to the solution
containing the metal ion I.e. precipitation e.g.

Ba2+ (aq) + CO32- (aq) BaCO3 (aq)

THERMOSTABILITY OF CARBONATES, NITRATES AND HYDROXIDE

The stability of the ionic compound depends on the standard lattice energy.

Lattice energy is affected by:

Page 24
• Ionic charge, the greater the charge on the ion, the stronger the attraction between the
ions thus lattice energy increases with ionic charge.

• Ionic radius, Smaller ions closely approach each other in the lattice thus increasing the
lattice energy.

NITRATES:The nitrates of group I decompose to nitrites and oxygen gas except lithium
nitrate I.e.

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

4LiNO3 (s) 2Li2O (s) + 4NO2 (g) + O2 (g)

Qn : Explain why Sodium nitrite is more stable than Sodium nitrate

Soln: Because in Sodium nitrite, the nitrite ion has a smaller relative to the nitrate thus it
forms a stable lattice.

However, for group II nitrates, the oxide ion is smaller and more highly charged than
nitrites therefore the nitrates of groupie ie elements decompose to metal oxide, nitrogen
dioxide and oxygen gas. e.g.

2Mg (NO3)2 (s) 2MgO (s) + 4NO2 (g) + O2 (g)

CARBONATES

The carbonates of Potassium, Sodium, Rubidium and Caesium are stable and do not
decompose.

Qn: Explain why Lithium carbonate decomposes while other carbonates of group I do
not

Soln: It is because the Lithium ions have a high charge density hence easily polarize the
carbonate ions to form a covalent compound which is held by weak Vander Waals
forces which makes it easily decompose

Qn:

(a) Explain why Sodium carbonate is used as a base in acid-base titration

(b) (i) State and Explain what is observed when sodium carbonate solution is added to
aluminium chloride solution

(ii) Write the equation of reaction in b (i)

The table below shows the decomposition temperatures for group II carbonates
Carbonate BeCO3 MgCO3 CaCO3 SrCO3 BaCO3

Page 25
 Temperature 100 350 900 1290 1350
(oC)
The thermal stability increases due to increasing ionic character i.e. Lattice enthalpy. The
larger the metal ion, the less the polarizing power thus the carbonates become ionic and
the stronger the electrostatic forces of attraction.

Group I metal carbonates are more stable than group II metal carbonates. This is because
M2+ ions have higher charge density than M+ ions therefore they polarize the large
carbonates more than M+

COMPLEX FORMATION

Complex formation is favored by:

• High charge density of the cations I.e. Small and highly charges cations easily attract
the lone pair of electrons in the ligand ( donor atom )

• Presence of suitable vacant orbital to accommodate the lone pairs of electrons from
ligand to form a dative bond

Down the group, the tendency to form complexes decreases due to decrease in charge
density.

The Be2+ion has the highest charge density in the group and thus forms complex ions.

Examples of complexes formed include:

Be (H2O)42+ , Be(H2O)42- , BeF42+ , Al(H2O)63+

HYDROLYSIS OF SALTS

Hydrolysis is the reaction of salts with water molecules which results in change Ph.

The large group I and II metals are hydrated in solution and their salts don’t undergo
hydrolysis.

However the carbonates and hydrogen carbonate of Sodium and potassium undergo
hydrolysis to form alkaline solution.

Qn:Explain why sodium carbonate is used in acid-base titration.

Salts containing cations of high charge density undergo hydrolysis e.g. Soluble beryllium
salt exists as Be(H2O)42+ in aqueous solution which hydrolyses to release a proton which
causes the solution to be acidic.

Be(H2O)42+ (aq) [Be(H2O)3OH]+ (aq) + H + (aq)

Qn :Explain why Magnesium chloride solution has a PH less than seven.

Page 26
 DIAGONAL RELATIONSHIP

This is the similarity in chemical properties between elements in period two to their
diagonal neighbours in period three and adjacent groups.

The pairs of elements with similarity in chemical properties include:

• Lithium and Magnesium

• Beryllium and Aluminium
• Boron and Silicon

The similarity in chemical properties is due to following reasons:

• Similar polarizing power or charge density

• Similar electronegativity
• Similar electropositivity
• Similar electrode potential

Similarities in chemical properties include:

Li and Mg Be and Al B and Si
Both react Oxides and hydroxides Both form acidic oxide as B2O3 and
with are amphoteric. SiO2
nitrogen on

Page 27
Page 28
Halides
(except
fluorides)
and
chlorates
(VII) are
soluble in
organic
solvent.

Qn .State three properties in which:

(a) Lithium differs from the rest of group I elements.

(b) Beryllium differs from the rest of group II elements.

(c) Boron differs from the rest of group III elements.

(d) Beryllium resembles other elements in groupie of the periodic table

QUALITATIVE ANALYSIS OF Ca2+, Mg2+ and Ba2+

Dilute Sodium hydroxide Solution until in excess:

A white precipitate insoluble in excess is observed by Ca2+, Mg2+ and Ba2+

Dilute Ammonia solution until in excess

Mg2+ - White precipitate insoluble in excess.

Ca2+ and Ba2+ - No observable change

Dilute Sulphuric acid / Sodium Sulphate solution

Mg2+ - No observable change

Ca2+ and Ba2+ - White precipitate

Potassium Chromate solution

Ba2+ - Yellow precipitate insoluble in Ethanoic acid

Ca2+ - Yellow precipitate soluble in Ethanoic acid

Ammonium Oxalate followed by Ammonia Solution

Page 29
 Ca2+- white precipitate. Mg2+
- No observable change
Ba2+???
Disodium Hydrogen Phosphate

Mg2+ - A white precipitate insoluble in excess Ammonia solution

Ca2+ and Ba2+ - A white precipitate soluble in acid.

Qn: Name the reagent that can be used to distinguish between the following pairs of ion/
salt. In each case state what would be observed if the reagent is treated with each ion/ salt

(a) MgSO4 and CaSO4

(b) PbSO4 and PbCl2

(c) Zn2+ and Ca2+

GROUP VII ELEMENTS (HALOGENS)

Elements formul Nature Boiling Bond Electron Electro Electrode
a point energy Affinity negativity potential
Fluorine F2 Gas ( -188 37 -322.6 4.0 +2.87
Yellow)

Page 30
Chlorine Cl2 Gas(GreenishYellow) -34 57.2 -364 3.0 +1.39

Bromine Br2 Liquid 58 45.4 -342 2.8 +1.07

(Red-brown)
Iodine I2 Solid (Purple) 183 35.6 -295.4 2.5 +0.54
Astatine RADIOACTIVE ELEMENT

1. The diatomic molecules have simple molecular structure with molecules held by
weak van der waals forces whose magnitude depends on molecular mass of the
molecule.

2. Boiling point / melting point.

Boiling point increases down the group. This is because the simple molecules are held by
weak van der waals forces whose magnitude increases with increase in magnitude
molecular mass.

3. Bond Energy

The bond energy decreases from Chlorine down the group. This is due to increase in
atomic radius which decreases the nuclear attraction for the bond pair electrons thus
increasing the bond length.

However, the bond energy of fluorine is lower than expected due to small radius which
makes the lone pairs of electrons easily approach other thus the further repulsion.

4. Electron affinity

Down the group, electron affinity decreases from chlorine to iodine due to the reduction in
nuclear attraction for the incoming electron caused by the addition of extra energy levels
of electrons therefore the incoming electron experiences greater repulsion hence less
energy is evolved. However, the electron affinity of fluorine is lower than expected due
to small atomic radius which gives a higher electron density hence extra repulsion of the
incoming electron.

5. Electrode Potential

The reduction potential becomes less positive down the group therefore fluorine is the
most powerful oxidizing agent. The most negative electrode potential represents the
strongest reducing agent and the most positive electrode represents the strongest oxidizing
agent.

Page 31
The high oxidizing strength of fluorine is favoured by:

• Low bond dissociation energy

• High enthalpy of hydration

• Absence of enthalpy of fusion and vaporization or enthalpy of atomization

Fluorine behaves differently from the rest of the members due:

• High electronegativity
• Small atomic radius
• Low bond energy

• High electrode potential

Special properties of fluorine which indicate how it behaves differently:

• It combines directly with carbon at room temperature to form carbon tetra fluoride.
• Hydrogen fluoride has a very high boiling point due to formation hydrogen bonding.
• Hydrofluoric acid is the weakest acid compared to other halogen acid.
• Silver fluoride is soluble in water while the chloride, bromide and iodide of silver are
insoluble in water. This is because the small fluoride ions have high hydration energy
which exceeds lattice energy hence the enthalpy of solution is negative.

• Fluorine has only one oxidation state.

• Fluorine does not form oxo-acids.
• Calcium fluoride is insoluble in water while the other halides are soluble in water.

Qn: Describe briefly how fluorine, Bromine and chlorine can be prepared in the
laboratory.

REACTIONS OF HALOGENS

(a) Water

Fluorine oxidizes water vigorously to oxygen and itself reduced to Hydrofluoric acid.

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

Chlorine and bromine reacts with water to form a mixture of halic (I) acid and hydrohalic
acid

Page 32
Cl2 (g) + H2O (l) HCl (aq) + HOCl (aq) Br2
(l) + H2O (l) HBr (aq) + HOBr (aq)
Iodine is sparingly soluble in water but highly soluble in potassium iodide solution due
formation of potassium tri-iodide which is a complex salt I.e.

I2 (s) + I- (aq) I3- (aq)

N.B. In the presence of Sunlight, the halic (I) acid decompose to oxygen.

2HOCl (aq) 2HCl (aq) + O2 (g)

(b) Alkalis

(i) Cold dilute Alkalis:

Fluorine forms oxygen difluoride, fluoride and water

2F2 (g) + 2OH- (aq) OF2 (g) + 2F- (aq) + H2O (l) Chlorine,
Bromine and Iodine form the halide, halite (I) and water.
Cl2 (g) + 2 OH- (aq) Cl- (aq) + OCl- (aq) + H2O (l)

Br2 (l) + 2OH- (aq) Br- (aq) + OBr- (aq) + H2O (l)

I2 (s ) + 2 OH – (aq) I- (aq) + OI- (aq) + H2O (l)

2OCl- (aq) O2 (g) + 2Cl-

(ii) Hot concentrated Alkali:

Fluorine reacts to form oxygen, fluoride and water.

2F2 (g) + 4OH- (aq) O2 (g) + 4F- (aq) + 2 H2O (l)

Chlorine, Bromine and Iodine forms the Halide, halate (V) and water.

3X2 + 6OH- (aq) X- (aq) + XO3- (aq) + 3 H2O (l), X= Cl, Br

and I

(c) Hydrogen

Fluorine explodes in dry hydrogen even in the dark to form hydrogen fluoride.

F2 (g) + H2 (g) 2HF (g)

Chlorine reacts vigorously with hydrogen in presence of sunlight or ultraviolet light to

form hydrogen chlorine.

Cl2 (g) + H2 (g) 2HCl (g)

Page 33
Bromine reacts with hydrogen gas at 200oC in presence of platinum catalyst.

Br2 (l) + H2(g) 2HBr (g)

Iodine reacts with hydrogen at 400oC to hydrogen iodide and the reaction is reversible.

Pt/ 400oC
I2 (s) + H2 (g) 2HI (g)

(d) Oxidation reactions

Chlorine, Bromine and Iodine Oxidize:

(i) Tin (II) to Tin (IV)

Sn2+ (aq) + Cl2 (g) Sn4+ (aq) + 2 Cl- (aq)

(ii) Hydrogen sulphide to Sulphur

I2 (s) + H2S (g) 2HI (g) + S (s) Br2

(l) + H2S (g) 2HBr (g) + S (s)
(iii) Thiosulphate ions to different products:

2S2O32- (aq) + I2 (aq) S4O62- (aq) + 2I- (aq)

S2O32- (aq)+ Cl2 (g) + H2O (l) SO42- (aq) + S (s) + 2 Cl –(aq) + 2 H+ (aq)

S2O32- (aq) + 4Cl2 (g) + 5H2O (l) 2SO42- (aq) + 10H+ (aq) + 8 Cl- (aq)

In excess Cl2)

Similar reactions occur for bromine.

Qn:(a) State what is observed when chlorine gas is bubbled through a solution of sodium
thiosulphate solution. Write the equation of reaction.

(b) State what would be observed when chlorine gas is bubbled through a solution of
Iron (II) chloride solution hence write the equation of reaction.

(c) State what is observed when chlorine gas is bubbled through a solution of potassium
iodide hence write the equation of reaction

COMPOUNDS OF HALOGENS

(a) Hydrides/ Halogen acids

HF HCl HBr HI

Page 34
 Bond Energy (KJmol-1) 556 431 336 229
B.p.t (oC) +19.9 -85 -66.7 -35.4
Ka 5.6×10-4 1.0×107 1.0×109 1.0×1011
1. Boiling point

The boiling point increases from HCl to HI. This is because they are simple molecules
held by van der -waals whose magnitude increases with molecular mass.

However, HF has extremely high boiling point because the molecules associate by
hydrogen bonding due small ionic radius of the fluoride ions.

2. Bond energy

It decreases from HF to HI due to:

• Increased atomic radius which increases the bond length

• Decrease in electronegativity down the group thus the bonds become less polar.

3. Acidic Strength

The acid strength depends on the degree of dissociation of the acid thus the concentration
of the hydrogen ion in aqueous solution.

Since electronegativity decreases down the group due to increase in atomic radius
therefore the bond strength is in the order HF> HCl> HBr> HI thus HF is H-F bond is not
easily broken hence it does not easily release a proton in aqueous solution thus it’s a
weakest acid. The H-I bond is the weakest bond therefore in aqueous solution it easily
releases a proton.

HF slightly ionizes in dilute solution as:

+
HF (aq) H+ (aq) F- (aq)

N.B. When concentrated, HF is a stronger acid than in dilute solution . Hydroflouric acid
dissociates as follows

+
HF (aq) H+ (aq) F- (aq)

The fluoride ions formed associate with more hydrogen fluoride forming hydrogen
difluoride ion

2HF (aq) H+ (aq) + HF2- (aq)

Page 35
More HF molecules dissociate to restored the used fluoride ions leading to release more
protons which make the solution more acid

Qn: Describe how the hydrides of group (VII) elements are prepared in the Laboratory.

REACTIONS OF HALOGEN ACIDS

1. In aqueous solutions, they behave as strong acids except HF .e.g. .e. Liberates
hydrogen gas when reacted with electropositive metals.

2HBr (aq) + Mg (s) MgBr2 (aq) + H2 (g)

2. HF and HCl don’t react with concentrated sulphuric acid. HBr and HI are strong
reducing agents therefore are oxidized to bromine and iodine by conc. Sulphuric
acid. I.e.

2HBr (aq) + H2SO4 (aq) Br2 (l) + SO2 (g) + 2H2O (l)

However, Conc. Hydrochloric acid can be oxidized by the stronger oxidizing agents such
as MnO2 , PbO2 and KMnO4

MnO2 (s) + 4HCl (aq) Cl2 (g) + 2H2O (l) + MnCl2 (aq)

PbO2 (s) + 4HCl (aq) Cl2 (g) + 2H2O (l) + PbCl2 (aq)

2MnO4- (aq) +10 Cl- (aq) + 16H+ (aq) 5Cl2 (g) +8H2O (l) +2Mn2+ (aq)

N.B. Hydroiodic acid (acidified Potassium Iodide) is the strongest reducing agent thus it is
easily oxidized.

Hydrofluoric acid reacts with silicon (IV) Oxide to form Hexafluoro silicic acid

6HF (aq) + SiO2 (s) H2SiF6 (aq) + 2H2O (l) Qn:

Explain the following observations:
(a) When hydroiodic acid is exposed in air, it turns brown.

(b) A colourless solution of acidified hydrogen peroxide turns brown on addition of

acidified potassium iodide.

(b) Oxo- acids / ions

All halogens except fluorine form oxo-ions and oxo-acids e.g. HOCl, HClO2 , HClO3 and
HClO4

Qn: Draw and name the structures of the above oxo- acids.

1. Acid Strength

Page 36
The acidic strength depends on the number of oxygen atoms in the acid molecule. Since
oxygen is more electronegative than chlorine, it pulls the bonding electrons towards itself
and this negative inductive effect is transmitted to the O-H bond weakening it thus
hydrogen ions are released in solution. The greater the number of the oxygen atom, the
greater the effect and the weaker the O-H bond. Thus the strength of the acid is HClO4>
HClO3> HClO2> HClO.

2. Chloric (I) acid is obtained by when chlorine is bubbled through water.

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

Chlorate (I) salts are obtained when chlorine gas is bubbled through cold dilute
alkali solution.

Cl2 (g) + 2OH- (aq) OCl- (aq) + Cl- (aq) + H2O (l)

Aqueous solutions of Chlorate (I) disproportionate at about 75oC to form Chlorate (V) and
Chloride

3OCl- (aq) ClO3- (aq) + 2Cl- (aq)

They decompose in presence of sunlight to form oxygen and a chloride

2OCl- (aq) O2 (g) + 2Cl- (aq)

However, in presence of an acid chlorate (I) ions act as oxidizing agent e.g. it oxidizes
iodide ions to iodine

2H+ (aq) + I- (aq) + OCl- (aq) I2 (aq) + Cl- (aq) + H2O(l)

With concentrated Hydrochloric acid, Chlorate (I) ions liberate chlorine gas

ClO- (aq) + 2H+ (aq) + Cl- (aq) Cl2 (g) + H2O (l)

N.B. The reaction above is used to determine the percentage of chlorine in bleaching
agent.

Qn: (a) 0.6cm3 of jik was dissolved in water and solution made in 250cm3 volumetric
flask. 25cm3of this solution was acidified and 10cm3 of 0.2M potassium iodide
solution added. The iodine liberated required 5.0cm3 of 0.2M Sodium thiosulphate
solution for complete reaction. Calculate the percentage of Chlorine in Jik

(b) Describe an experiment to determine the concentration of Sodium Hypochlorite using

Volumetric analysis.

3. Chloric (V) acid

This is a powerful oxidizing agent that only occurs in aqueous solution. Its salts are
more stable and can be obtained by passing chlorine gas through hot Conc. Alkali. 3Cl2
(g) + 6 OH- (aq) ClO3- (aq) + 5Cl- (aq) + 3H2O (l) The
Chlorate(V) and Chloride are separated by fractional crystallization.
Page 37
In Acidic medium, Chlorate (V) ions are strong Oxidizing Agents and the reduction half
cell equation

ClO3- (aq) + 6H+ (aq) + 6e Cl- (aq) + 3H2O (l)

It oxidizes Iron (II) to Iron (III), Sulphite ions to Sulphate ions and Iodide ions to Iodine.

6Fe2+ (aq) + 6H+ (aq) + ClO3- (aq) 6 Fe3+ (aq) + Cl- (aq) + 3H2O (l)

ClO3- (aq) + 3SO32- (aq) 3SO42- (aq) + Cl- (aq)

ClO3- (aq) + 6H+ (aq) + 6I- (aq) 3I2 (aq) + 3H2O (l) + Cl- (aq)

Qn :(a) A solution of halate (V) ion YO3- contains 2.94g/l. 25cm3 of this solution was
added to an equal volume acidified potassium iodide solution. The iodine
liberated required 25.2cm3 of 24.8g/l Na2S2O3.5H2O. Calculate the relative
atomic mass of Y hence identify Y.

(b) Give the I.U.P.A.C name for the following oxide and calculate the oxidation number of
the halogen in :

(i) ClO2 (ii) BrO3

(iii) I2O5 (iv) Cl2O7

(c) Explain the following observations:

(i) The oxidation states of halogen in Oxides are positive.

(ii) Chlorine dioxide is a mixed acid anhydride.

(c) Interhalogen compounds

These are compounds formed between halogens with the molecular formula AB, AB3,
AB5 and AB7where A- is a less electronegative atom with a vacant orbital and a higher
oxidation state while B- is more electronegative.

Examples include: ICl -Iodine monochloride, ClF3- Chlorine trifluoride, Iodine

pentafluoride IF5

Qn: Draw the shapes of the following interhalogen compounds:

(i) Iodine pentafluoride.

(ii) Chlorine trifluoride

QUALITATIVE ANALYSIS OF Cl-, Br- and I-

1. Silver nitrate solution;

Procedure

Page 38
Add a few drops of silver nitrate solution to the test solution

Observation

Cl- White precipitate

Br- Pale yellow precipitate

I- Yellow precipitate

2. Lead (II) Nitrate solution or lead Acetate solution.

Procedure

Add a few drops of lead(II) nitrate solution to the test solution

Observation

Cl- white precipitate

Br- pale yellow precipitate

I- yellow precipitate

The precipitate dissolves on heating and recrystallizes on cooling.

Qn : Describe an experiment how the concentration of chloride ions can be determined

by Volumetric analysis

GROUP IV ELEMENTS

The outer most electronic configuration is ns2np2where n is the principal quantum number.
Elements Melting point (oC) Density Electronic cofiguration

Carbon 4000 2.25(graphite), 1s2 2s22p2

3.5(Diamond)
Silicon 1680 2.33 1s2 2s22p23s2 3s23p2
Germanium 1210 5.35 1s2 2s22p23s23s23p23d104s24p2
Tin 505 7.28(white), 1s2
5.75(grey) 2s22p23s23s23p23d104s24p24s24p2
Lead 600 11.3 1s2 2s22p23s23s23p24s24p2

1. Existence

Carbon exists as graphite, diamond and amorphous carbon. Silicon occurs as Silica (SiO2).
Tin exist as grey tin and white tin. Lead occurs as an ore in form of galena (PbS)

Page 39
2. Melting point.

The melting points of groupIV elements depend on the structure. Carbon and Silicon have
giant atomic structures which require a lot of energy to break. However the melting point
of silicon is lower than that of carbon since the covalent bonds in silicon atoms are longer
thus weaker.

Germanium is a Metalloid with an intermediate giant atomic structure.

Tin and Lead are weak metals with a metallic structure however lead is more metallic than
tin hence has a higher melting point.

3. Electropositivity

Increases down the group thus metallic character also increases.

4. Electronegativity

Decreases down the group

5. Oxidation states

The elements exhibit both +2 and +4 oxidation states. The +4 oxidation state is attained by
promoting one s- electron to an empty p orbital to avail four electrons.
Down the group, the nS2 electrons become more reluctant to participitate in bonding. This
is called inert pair effect. Therefore the stability of +2 oxidation state increases while that
of +4 decreases.

Qn: Explain the cause of inert pair effect

Soln: As the radius of the atoms increase down the group there is increasing tendency for
the two bonding electrons in the S- Sub energy level to resist taking part in
bonding.

Examples of inert pair effect include:

Carbon forms carbon tetrachloride while lead (IV) chloride readily decomposes to form
Lead (II) chloride and Chlorine

PbCl 4 (l) PbCl2 (s) + Cl2 (g)

Carbon monoxide is readily oxidized to carbon dioxide by air

2CO (g) + O2 (g) 2CO2 (g)

Lead (IV) oxide decomposes on heating to form lead (II) oxide and Oxygen

2PbO2 (s) 2PbO (s) + O2 (g)

Carbon behaves differently from the rest of the group members due:

Page 40
• Small Atomic radius
• High electronegativity

• Lack of vacant orbital

Some of the properties in which Carbon differs from the rest of the members include:

• It forms a stable multiple bonds with itself and with other non-metals.
• Carbon can form a number of hydrocarbons because it can catenate. Catenation is the
ability of the element to form long chains or between atoms of the same element. • It
forms gaseous oxides unlike other members
• The halides are stable to hydrolysis.

REACTIONS OF GROUP(IV) ELEMENTS

1. Water

When heated, coke reacts with steam to form water gas.

H2O (g) + C (s) CO (g) + H2 (g)

Ge and Sn do not react with water.

Hot silicon reacts with steam to form silicon dioxide and hydrogen gas I.e.

Si (s) + 2H2O (g) SiO2 (s) + 2H2 (g)

Lead reacts slowly with soft water in presence of air (oxygen) to form lead (II) hydroxide
2Pb (s) + 2 H2O (l) + O2 (g) 2Pb(OH)2 (s)
2. Air

The elements burn in air to form dioxides except lead which forms lead (II) oxide

C (s) + O2 (g) CO2 (g)

Si (s) + O2 (g) SiO2 (s)

2Pb (s) + O2 (g) 2PbO (s)

However in limited amount of air, Carbon forms carbon monoxide

2C (s) + O2 (g) 2 CO (g)

3. Acids

The elements do not react with dilute acids except tin which reacts with dilute nitric acid
as :
Page 41
NO3 – (aq) + 4 Sn (s) + 10 H+ (aq) 4 Sn2+ (aq) + NH4+ (aq) + 3 H2O (l)

Silicon reacts with only with hydrofluoric acid to form hexafluoro silicic acid and
Hydrogen gas

Si (s) + 6 HF (aq) H2SiF6 (aq) + 2 H2 (g)

Hot nitric acid oxidizes tin, germanium and Carbon to dioxide and itself reduced to oxides
of nitrogen

3Sn (s) + 4HNO3 (aq) 3SnO2 (s) + 4NO (g) + 2H2O (l)

C (s) + 4HNO3 (aq) CO2 (g) + 4NO2 (g) + 2H2O (l)

Lead forms lead (II) nitrate, nitrogen monoxide and water

3Pb (s) + 8HNO3 (aq) 3Pb (NO3)2 (aq) + 2NO (g) + 4H2O (l)

Hot sulphuric acid oxidizes carbon, tin lead and germanium

Sn (s) + 4H2SO4 (aq) Sn(SO4)2 (aq) + 2 SO2 (g) + 4H2O (l)

C (s) + 2H2SO4 (aq) CO2 (g) + 2SO2 (g) + 2H2O (l)

Pb (s) + 2H2SO4 (aq) PbSO4 (s) + SO2 (g) + 2H2O (l)

Lead and tin react with hot conc. Hydrochloric acid to form dichloride and hydrogen gas.

Sn (s) + 2HCl (aq) SnCl2 (aq) + H2 (g)

Pb (s) + 2 HCl (aq) PbCl2 (aq) + H2 (g)

N.B. lead (II) chloride is sparingly soluble in water but highly soluble in Conc. Acid due
formation of a complex. I.e. PbCl42-

4. Alkalis

All the elements except Carbon react with Conc. Alkali to form complex salts and
hydrogen gas.I.e.

Si (s) + 2OH– (aq) + H2O (l) SiO32- (aq) + 2H2 (g)

Ge (s) + 2OH – (aq) + H2O (l) GeO32- (aq) + 2H2 (g)

Sn (s) + 2OH- (aq) + 2 H2O (l) Sn(OH)42- (aq) + 2H2 (g)

Pb(s) + 2OH – (aq) + 2H2O (l) Pb(OH)42- (aq) + 2H2 (g)

5. Non- metals

When heated, the elements react with Sulphur, chlorine, fluorine and hydrogen
chloride.e.g.
Page 42
Sn (s) + 2HCl (g) SnCl2(s) + H2 (g)

Sn (s) + 2Cl2 (g) SnCl4 (l)

Pb (s) + Cl2 (g) PbCl2 (s)

Si (s) + 2Cl2 (g) SiCl4 (g)

COMPOUNDS OF GROUP (IV) ELEMENTS

1. Oxides

(a) Monoxides: CO and SiO are covalent compounds with simple molecular structure.

GeO, SnO and PbO are amphoteric oxides with giant ionic structure Preparation:
Conc.H2SO4
HCOOH (aq) CO (g) + H2O (l)

Conc.H2SO4
+ CO (g) + H2O (l) H2C2O4(aq) CO2 (g)
GeO2 (s) + Ge (s) 2GeO (s)

SiO2 (s) + Si (s) 2SiO (s)

Pb(OH)2 (s) PbO (s) + H2O (g)

SnC2O4 (s) SnO (s) + CO2 (g) + CO (g)

Qn : Explain why Tin (II) Oxalate is used instead of Tin (II) nitrate to prepare Tin (II)
Oxide.

Some of the reactions of the monoxide according to equations include:

With alkaline solution

PbO (s) +2 OH- (aq) + H2O (l) Pb(OH)42- (aq)

SnO (s) + 2OH- (aq) + H2O (l) Sn (OH)4

CO (g) + NaOH (aq) 150oC

HCOONa (aq) 700KPa

With Acids

SnO (s) + 2 H+ (aq) Sn2+ (aq) + H2O (l)

Qn : (a) 1.5g of impure tin (II) Oxide was dissolved in excess dilute hydrochloric acid and
the resultant solution made to 250cm3 with distilled water. 25cm3 of this solution
was titrated with 0.02M potassium permanganate until the colour turned pink.
The volume of Potassium permanganate solution used was 20cm3. Calculate the
percentage impurity of tin (II) oxide (Sn= 119, O=16) Ans =90%
Page 43
(b) Write an ionic equation when tin (II) ions are added to :

(i) Acidified potassium dichromate solution

(ii) Sodium oxalate solution

(iii) Iron (III) chloride solution

(b) Dioxides

Lead (IV) oxide is prepared by reacting dilead (II) lead (IV) oxide with dilute nitric acid.

Pb3O4 (s) + 4HNO3 (aq) 2Pb(NO3)2 (aq) + PbO2 (s) + 2H2O (l)
The rest of the oxides are prepared by heating the metals with oxygen.
The dioxides are more stable than the monoxides except lead (IV) oxide. i.e.

2PbO2 (s) 2PbO (s) + O2 (g)

The table below shows the nature of the dioxides

Oxide Nature Structure
CO2 Acidic Simple molecular
SiO2 Acidic Giant molecular
GeO2 Amphoteric Intermediate
SnO2 Amphoteric Giant ionic and giant
PbO2 Amphoteric Metallic

Lead (IV) oxide oxidizes strong hot concentrated hydrochloric acid to chlorine gas

PbO2 (s) + 4HCl (aq) Cl2 (g) + PbCl2 (s) + 2H2O (l)

When excess concentrated hydrochloric acid is reacted with lead (IV) oxide at 0oC it
forms a complex ion

PbO2 (s) + 4HCl (aq) + 2Cl- (aq) PbCl62- (aq) + 2H2O (l)

Addition of concentrated ammonium chloride to the complex produces a yellow

precipitate. i.e.

PbCl62- (aq) + 2NH4+ (aq) (NH4)2PbCl6 (s)

Qn : Discuss the reactions of Lead(IV) oxide and Pb3O4 with sulphuric acid.

Soln: If heated lead (IV)Oxide reacts with concentrated sulphuric acid to form
lead(II)sulphate, oxygen and water.

2PbO2 (s) + 2H2SO4 (aq) 2PbSO4 (s) + O2 (g) + 2H2O (l)

Page 44
The same reaction occurs with Pb3O4

Qn: (a) A compound Q contains 90.65%by mass of lead and the rest Oxygen. Deduce the
molecular formula of Q if its molar mass is 685g.

(b) State what is observed when Q is reacted with the following and in each case
write the equation of reaction.

(i) Dilute Nitric acid

(ii) Hot concentrated sulphuric acid.

(iii) Hot concentrated hydrochloric acid

2. Hydrides

The elements form covalent tetrahydrides whose thermo-stability decreases down the
group.

• Preparation.

Are prepared by reduction of their tetrachlorides with lithium aluminum tetra hydrides
at 0oC in ether.

SiCl4(l) + LiAlH4(l) SiH4(l) + LiCls) + AlCl3(s)

• Hydrolysis of the hydrides

• Reactions of the hydrides with Alkalis

Qn :(a) Gaseous hydride of silicon diffuses through a narrow hole for 27.8s. The same
volume of carbondioxide under the same temperature and pressure through the
same in 32.6s

Determine the molecular formula of the hydride.

(b) Write the equation of reaction between the hydride of silicon and sodium
hydroxide solution

3. Chlorides

(a) Tetrachlorides

These are covalent liquids with simple molecular structure and become less stable down
the group due to an increase in M-Cl bond length

Read on: Preparation of the tetrachlorides of group (IV) elements.

Page 45
N.B. Lead (IV) chloride readily decomposes to form chlorine and lead (II) chloride

Qn:Explain why Lead (IV) iodide does not exist.

Reactions of tetrachlorides with water

Carbon tetrachloride does not react with water because of lack of vacant d-orbital. Other
chlorides react with water rapidly to liberate hydrogen chloride. For silicon tetrachloride,
the second product depends on the degree of hydration.

SiCl4 (l) + 2H2O (l) SiO2 (s) + 4HCl (g)

SnCl4 (s) + 4H2O (l) SnO2.2H2O (s) + 4HCl (g)

PbCl4 (l) + 2H2O (l) PbO2 (s) + 4HCl (g)

(b) Dichlorides

The stable chlorides in the +2 oxidation state are only formed by tin and lead

Sn (s) + 2HCl (g) SnCl2 (s) + H2 (g)

Pb (s) + Cl2 (g) PbCl2 (s)

Tin (II) chloride reacts with water to form a basic chloride and hydrochloric acid. i.e. it
undergoes hydrolysis

SnCl2 (s) + H2O (l) Sn(OH)Cl (s) + HCl (aq)

However, in excess hot water tin (II) hydroxide is formed.

SnCl2 (s) + 2H2O (l) Sn(OH)2 (s) + 2HCl (aq)

Lead (II) Chloride is sparingly soluble in water and does not undergo hydrolysis. However
it dissolves on heating since solubility increases with temperature.

PbCl2 (s) Pb2+ (aq) + 2Cl- (aq)

N.B. Lead (II) chloride is more soluble in concentrated hydrochloric acid than in water
due to formation of a soluble complex of tetrachloro plumbate (II)

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

Page 46
N.B. A solution containing tin (II) ions and lead (II) ions react with hydrogen sulphide gas
to precipitate the metal sulphide (black)

Sn2+ (aq) + S2- (aq) SnS (s)

Pb2+ (aq) S2- (aq) PbS (s)

Qn : When a yellow solid A is heated with air at 450oC, a red solid B is formed. B
reacts with hot dilute nitric acid to form a dark brown solid C on precipitation
and after filtration and crystallization of the filtrate; a white solid D is obtained.
When C is heated with concentrated hydrochloric acid, a pale green gas was
evolved and when hydrochloric acid is added to aqueous solution of D at room
temperature, a white precipitate E was formed.

(a) Identify the substances A-E inclusive

(b) Account for your answers in (a) above with aid of equations of reactions.

Qn : The standard enthalpy of formation of tin tetrachloride is -508KJmol-1. The

standard enthalpy of atomization of tin and chlorine are +301 and +121KJmol-1
respectively. The average bond energy of Si-Cl bond is +383KJmol-1

(a) Determine the average bond energy of Sn-Cl bond

(b) Comment on the difference between the average bond energies.

(c) State a reagent that can be used to differentiate between the following ions and in
each case state what would be observed when each is treated with the reagent. (i) Pb2+
and Sn2+
(ii) Pb2+and Al3+

(iii) Sn2+ and Zn2+

Page 47
THIRD SHORT PERIOD OF PERIODIC TABLE

The period runs from sodium to Argon. The table below shows some physical parameters
of the elements involved.
Elements Na Mg Al Si P S Cl Ar
Melting point 98 651 660 1410 44 114 -101 -189

Electronegativity 0.9 1.2 1.5 1.8 2.1 2.5 3.0

Ionization 502 745 587 799 1020 1000 1260 1530
energy
Atomic radius 1.57 1.36 1.28 1.17 1.10 1.04 0.99
Electron Affinity -20 +67 -30 -135 -60 -200 -364
Oxidation states +1 +2 +3 +4 +3, +5 2,+4,+ +1,+3,-
6, 1,+5, +7
Structure Close Close Close Giant Discrete molecular structure
packed packe packed molecu
d lar

1. Melting point

This is a constant temperature at which an element in its solid state changes to liquid state
under constant pressure. The abrupt change in melting point is explained as:

• From sodium- aluminium, the strong metallic bonds have to be broken down. The
strength of the metallic bond increases due to increase in the number of electrons used
per atom and also due to decrease to metallic radius.

• From Aluminium- Silicon, the increase is due to the strong covalent bonds that have to
be broken for a giant atomic structure of Silicon where each silicon atom contributes
four electrons towards covalent bonding.

• From Silicon-phosphorous, the decrease is due to change from giant atomic structure
to molecular discrete structure where the molecules are held by weak van der waals
forces of attraction

• From phosphorous-Sulphur, these are discrete molecules which are as P4 and S8 held
by weak Van der waals force whose magnitude increases with increase in molecular
mass. Since the molar mass of S8 is greater than that of P4 therefore an increase in
melting point.

Page 48
• From Sulphur-chlorine, the diatomic molecule has a lower molar mass than sulphur
therefore the magnitude of the van der waals forces are weaker hence low melting
point.
Qn: Explain the trend of the following parameters across period 3 of the periodic table

(a) Ionization energy

(b) Electron affinity

(c) Electronegativity

REACTIONS OF PERIOD 3 ELEMENTS

1. With Chlorine

Sodium and Magnesium when heated react with chlorine to form ionic chlorides

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

Mg (s) + Cl2 (g) MgCl2 (s)

Aluminium forms a covalent chloride which dimerises in the vapour phase

2Al (s) + 3Cl2 (g) 2AlCl3 (s)

Vaour phase
2AlCl3 (s) Al2Cl6 (g)

Qn: Explain why aluminium chloride is covalent.

Soln: This is because the aluminium ions have a high charge density which greatly
polarizes the chloride ions to form a covalent compound hence reducing the charge
separation.

Silicon, phosphorous and Sulphur also react with chlorine to form covalent chlorides with
simple molecular structure.

Si (s) + 2Cl2 (g) SiCl4 (l)

2P (s) + 5Cl2 (g) 2PCl5 (s)

2P (s) + 3Cl2 (g) 2PCl3 (g)

2S (l) + Cl2 (g) S2Cl2 (l)

Page 49
2. Oxygen

All the elements except chlorine react with oxygen to form oxides.

2Na (s) + O2 (g) Na2O2 (s)

2Mg (s) + O2 (g) 2 MgO (s)

4Al (s) + 3O2 (g) 2Al2O3 (s)

Si (s) + O2 (g) SiO2 (s)

P4 (s) + 3O2 (g) P4O6 (s)

P4 (s) + 5O2 (g) P4O10 (s)

S (s) + O2 (g) SO2 (g)

3. Hydrogen

Sodium and Magnesium burn vigorously in hydrogen gas to form ionic hydrides.

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

Mg (s) + H2 (g) MgH2 (s)

Aluminium, Silicon and Phosphorous do not react with hydrogen gas.

Chlorine and Sulphur form the corresponding covalent hydrides. Chlorine reacts in
presence of Sunlight or ultraviolet light.

Cl2 (g) + H2 (g) 2HCl (g)

S (l) + H2 (g) H2S (g)

4. WITH Acids

Sodium, Magnesium and Aluminium react with dilute acids to form salts and hydrogen
gas i.e. hydrochloric acid and sulphuric acid.

Other elements do not react with dilute mineral acids.

Concentrated Nitric acid reacts violently with sodium and magnesium to form the nitrate,
water and nitrogen dioxide

Na (s) + 2HNO3 (aq) NaNO3 (aq) + NO2 (g) + H2O (l)

Page 50
Aluminium forms a layer of the oxide that prevents further reaction

Silicon and Chlorine do not react with concentrated nitric acid

Phosphorous and Sulphur are oxidized to their respective oxides and itself reduced to
nitrogen dioxide.

S (s) + 4HNO3 (aq) SO2 (g) + 4NO2 (g) + 2H2O (l)

P4 (s) + 10HNO3 (aq) + H2O (l) 4H3PO4 (aq) + 5NO2 (g) + 5NO (g)

COMPOUNDS OF PERIOD 3 ELEMENTS

1. Chlorides
Chlorides NaCl MgCl2 AlCl3 SiCl4 PCl3 , S2Cl2, Cl2
PCl5
b.p.t 1465 1418 423 57 74, 164 138 -35
mpt 808 714 192 -68 160 -76 -101
Bond ionic Ionic
Covalent

structure Giant Giant Simple

ionic ionic molecular structure

Reaction of the chlorides with water

Sodium chloride dissociates in water to form neutral aqueous solution.

Aluminium chloride undergoes hydrolysis due to high charge density and aluminium ions
become heavily hydrated in solution as Al (H2O)63+

The hydrated ions undergo hydrolysis to release a proton in solution which causes the
solution to be acidic

Al(H2O)63+ (aq) [Al(H2O)5OH]2+ (aq) + H+ (aq)

The other chlorides react with water to form hydrogen chloride

SiCl4 (l) + 2H2O (l) SiO2 (s) + 4HCl (g)

PCl5 (l) + 4H2O (l) H3PO4 (aq) + 5HCl (g)

Page 51
2S2Cl2 (s) + 2H2O (l) 3S (s) + SO2 (g) + 4HCl (aq)

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

2. Oxides

Reaction with water

Sodium oxide is highly soluble in water

Na2O (s) + H2O (l) 2NaOH (aq)

Magnesium Oxide is slightly soluble in water

MgO (s) + H2O (l) Mg(OH)2 (aq) Silicon

(IV) oxide and aluminium oxide do not react with water.
Oxides of Phosphorous, chlorine and Sulphur are acidic oxide.

P4O10 (s) + 6H2O (l) 4H3PO4 (aq)

SO2 (g) + H2O (l) H2SO3 (aq)

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

Cl2O7 (l) + H2O (l) 2HClO4 (aq)

Reaction with sodium hydroxide solution

Sodium and Magnesium oxide are basic oxides therefore they do not react with sodium
hydroxide solution

Al2O3 (s) + 2OH- (aq) + 3H2O (l) 2[Al (OH)4]- (aq)

SiO2 (s) + 2OH- (aq) SiO32- (aq) + H2O (l)

Page 52
 SO2 (g) + 2OH- (aq) SO32- (aq) + H2O (l)

Cl2O7 (l) + 2OH- (aq) 2ClO4- (aq) + H2O (l)

3. Hydrides
Hydrides NaH MgH2 AlH3 SiH4 PH3 H2S HCl

Bond
Ionic Covalent
Structure Giant ionic Simple molecular

The ionic hydrides react with water to form hydroxide and hydrogen gas

NaH (s) + H2O (l) NaOH (aq) + H2 (g)

MgH2 (s) + 2H2O (l) Mg(OH)2 (s) + 2H2 (g)

AlH3 (s) + 3H2O (l) Al(OH)3 (s) + 3H2 (g)

Phosphine does not react with water. Hydride of silicon reacts with water in presence of
a strong base. i.e.

SiH4 (g) + 2OH- (aq) + H2O (l) SiO32- (aq) +4H2 (g)

Hydrogen Sulphide and Hydrogen chloride react with water to form acidic solution.

EXTRACTION OF ALUMINIUM

Ore : Bauxite Al2O3. 2H2O

Bauxite is roasted to convert Iron (II) Oxide (impurity) to Iron (III) Oxide and drive off
the water of crystallization.

The roasted ore is Crushed to powder and heated with concentrated sodium hydroxide
solution to remove aluminum oxide from the impurities.

The amphoteric ore and the acidic silicon (IV) Oxide (impurity) dissolve in the alkali to
form complex salts while the Iron (III) oxide remains undissolved.

Al2O3 (s) + 2OH- (aq) + 3H2O (l) 2Al(OH)4- (aq)

SiO2 (s) + 2OH- (aq) SiO32- (aq) + H2O (l)

The mixture is filtered and the filtrate diluted with water. Carbon dioxide gas is passed
through the mixture to precipitate pure aluminium hydroxide.

2Al(OH)4- (aq) + CO2 (g) 2Al(OH)3 (s) + CO32- (aq) + H2O (l)

Or. The solution is seeded by adding a little aluminium hydroxide to the aluminate to
precipitate aluminium hydroxide.

Page 53
Al (OH)4- (aq) Al(OH)3 (s) + OH- (aq)

The insoluble hydroxide is filtered off, washed and dried. Pure aluminium hydroxide is
then heated to form pure aluminium oxide

2Al(OH)3 (s) Al2O3 (s) + 3H2O (g)

The oxide is then dissolved in molten cryolite to increase conductivity. A small amount of
Calcium fluoride is added to lower the melting point of the electrolyte. Also Aluminium
fluoride is added to lower the solubility of the molten aluminium.

The mixture is electrolyzed between the graphite electrodes at 900oC using a low voltage
to avoid the decomposition of Cryolite and high charge density.

Aluminium ions are discharged at the cathode while oxygen is liberated at the anode.
Cathode:

Al3+ (l)+ 3e Al (l)

Anode:

2O2- (l) O2 (g) + 4e

N.B. The disadvantage of using low voltage is that a lot of energy is used and anode is
replaced several time since it burns off in oxygen produced.

Qn: During the extraction of aluminium, the ore is first purified.

(a) (i) Write the name and formula of the ore

(ii) Name two main impurities in the ore.

(b) Describe briefly how purification process is carried.

(c) Write an equation to show how anhydrous aluminium chloride can be obtained from
aluminium.

(c) Explain briefly Aluminium utensils should not be washed using Soap. (d)
State any four uses of aluminium

Page 54
TRANSITION METAL ELEMENTS

Introduction:

Some statistic about types of elements of the periodic table up to atomic number to 103

(a) Non- metals = 19

(b) Metalloid = 3

(c) Metals = 81

Of the metals, the following are the division:

Page 55
(i) Non- metals – 22

(ii) Transition metals – 59

Transition metals are divided into two:

(a) d- block transition elements located in period 4, 5 and 6

(b) f- block transition elements located in period 6 and 7

Electronic Configuration

After the second energy level, an overlap starts occurring between 3d-subshell which is
nearer the nucleus than 4s- subshell but at a higher energy level. Thus after filling 3S and
3P subshells further electrons after the 4S- subshell (2electrons) later 3d- subshell.

From the electronic configuration, a transition metal is defined as that element having a
partially filled 3d-subshell (between 1-9 electrons) therefore Zinc is not regarded as
transition metal.

However, anomalous behavior occurs between Chromium (Z=24) and Copper (Z=29)
because configuration giving half filled d-subshell are thermodynamically more stable.

Transition metals form ions by losing electrons from 4S-subshell rather than the
3dsubshell.

The table below shows the electronic configuration of the short series of the transition
metals
Element Symbol Atomic Configuration
number
Scandium Sc 21 1S22S22P63S23P64S23d1
Titanium Ti 22 [Ar]4S23d2
Vanadium V 23 [Ar]4S23d3
Chromium Cr 24 [Ar]4S13d5
Manganese Mn 25 [Ar]4S23d5
Iron Fe 26 [Ar]4S23d6
Cobalt Co 27 [Ar]4S23d7
Nickel Ni 28 [Ar]4S23d8
Copper Cu 29 [Ar]4S13d10
Zinc Zn 30 [Ar]4S23d10

Qn: (a) Explain why Fe2+ is easily oxidized to Fe3+

(b) Write the electronic configuration of the following ions

(i) Fe2+ (ii) Fe3+ (iii) Cr3+

Page 56
Soln: (a) Because Fe3+ is has 3d5 subshell electrons which is thermodynamically stable
compared to Fe2+ with 3d6 which is unstable.

(b) (i) 1S22S22P63S23P63d6 (ii) 1S22S22P63S23P63d5 (iii) 1S22S22P63S23P63d3

PHYSICAL PROPERTIES OF TRANSITION METALS

The physical properties of transition metals do not vary greatly and many of them show a
regular trend. Some of the properties include:

1. Metallic character.

The transition metals are true metals and many of them are widely used industrially. They
are hard, strong and lustrous and have high melting and boiling point and high enthalpies
of atomization. These properties suggest presence of strong metallic bonding.

The strong metallic bonding is due to availability of d-electrons.e.g Sodium with only
3Selectron available for bonding therefore it has a low melting point compared to iron
with two 4S-electrons and a maximum of six 3d-electrons. 2. Metallic radius,
density and atomic volume
The metallic radius decreases from scandium to nickel and it slightly increases from nickel
to Zinc.

As atomic number increases, the nuclear charge increases. However, the electrons are
being added to inner 3d-subshell therefore these electrons are poorly shielded from the
nuclear charge hence the nuclear attraction for the outer most electron increases resulting
into decrease in atomic radius/ metallic radius.

The slightly increase from nickel to Copper is because the 3d-subenergy level in copper is
fully filled with electrons and this increases the shielding of the outer electrons from the
nuclear charge hence atomic radius increases.

The decrease in radius coupled with increasing atomic mass causes an increase in the
density and decrease in atomic volume in passing from Scandium to Nickel.

3. Ionization energy

There is a fairly general increase in ionization energy in passing from Scandium to nickel
due to increasing nuclear charge holding the electrons more strongly resulting into
decrease in atomic radius.

Qn. The table below shows the electronegativity values for elements in d-block of the
periodic table
Element Sc Ti V Cr Mn Fe Co Cu Zn
At. No. 21 22 23 24 25 26 27 29 30
Electronegativity 1.3 1.5 1.6 1.6 1.5 1.8 1.8 1.9 1.6
(a) Plot a graph of electronegativity against atomic number

(b) Explain the trend of your graph in (a)

Page 57
 GENERAL CHARACTERISTICS OF TRANSITION METALS

1. Variable oxidation states

The elements exist in variable oxidation states in variety of the compounds due to
availability of the 3d-electrons which can participate in bond formation by either ionic or
covalent

The commonest stable oxidation states are in red as shown in the table
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+1
+2 +2 +2 +2 +2 +2 +2 +2 +2
+3 +3 +3 +3 +3 +3 +3 +3
+4 +4 +4 +4
+5 +5 +5
+6 +6
+7
Some of the compounds with the oxidation state include:

Ti V Cr Mn Fe Co Ni Cu
TiO,TiCl2 VCl2, CrCl2, MnO,MnCl2, FeCl2 CoO,CoCl2, NiO CuO
Ti2O3, V2O3, Cr2O3,CrCl3 MnCl3, FeCl3 Co(NH3)63+ Ni2O3.xH2O Cu2O
TiCl3 VO2 CrCl4, MnO2, CuCl
TiO2, V2O5 CrO3, MnO42MnO4- CuCl2
TiCl4 Cr2O72-

The relative stability of these oxidation states is also indicated by the standard reduction
electrode potential.

Since Zinc has one oxidation state, it is regarded non-transition metal.

Qn: (a) Define the following terms;

(i) Oxidation state

(ii) Oxidising agent

(b) Determine the oxidation state of the transition metalin the following complex

(i) K2Cr2O7 (iii) [Co (NH3)5SO4]Br

(ii) MnO42- (iv) [CuCl2(CH3NH2)2]

2. Paramagnetism

Page 58
A substance that can be drawn into a strong magnetic field is known as paramagnetic
substance.

Transition metals are paramagnetic due to the presence of unpaired 3d-electrons. Every
spinning electron acts as a tiny magnet. However, in an orbital with 2 paired electrons, the
magnetic moment of one electron cancels out. Paramagnetism arises due to spinning of
unpaired electrons about their axes which generates electric current

Paramagnetism increases with increase in the number of unpaired 3d-electrons.

3. Formation of Coloured Compounds

The 3d-electrons in isolated metal atom are degenerate.i.e. energetically alike. However,
in presence of ligands, the orbitals overlap differently and split into two levels of different
energy. This excites electrons from a lower to higher level of energy. The frequency of
light absorbed from this energy transition is from the visible region of the spectrum hence
this appears as colour. The remaining visible light which is not absorbed is reflected as
that colour shown by a transition metal/ion.

Examples of hydrated ions include

V(H2O)62+ - Violet Mn(H2O)62+ - pale pink Fe(H2O)62+ - Pale green

Zn(H2O)62+ - Colourless Sc(H2O)62+ - Colourless Cr(H2O)63+ - Blue-green

N.B. Scandium and Zinc form colourless compounds therefore they are regarded as
nontransition metals.

Qn: (a) State two factors that affect the colour of transition metal compounds

Nature of Ligand and Oxidation state of the metal

(b) Explain why compounds of s-block elements don’t form coloured compounds

4. Catalytic activity

Transition elements and their compounds act as catalysts in several chemical processes

Homogeneous catalysis (where the catalyst are in the same phase with the reactants), due
to variable oxidation state transition metals/ ions form with the activated complex thus
providing an alternative reaction path way of lower reaction energy e.g.

S2O82- (aq) + 2I- (aq) Fe2+ (aq) 2SO42- (aq) + I2 (aq)

Heterogeneous catalysis (where the catalyst and reactants are in different phases), finely
divided solid transition metals/ compound provide an active interface for adsorption of the
reactant where they are bound to the surface by van der waals forces.

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Examples include; V2O5- contact process, Iron- Haber process etc

5. Complex formation

Transition metals form complexes due to:

• Small and highly charged ions

• Presence of vacant 3d-orbitals to accommodate lone pairs of electrons from the ligands

A ligand is an ion or molecule with lone pairs of electrons linked to the central metal ion
by a dative bond

Co-ordination number is the number of ligands molecules that form dative bonds with
central metal ion in the complex ion.

A metal complex or co-ordination compound is a chemical system composed of electron

donor and electron acceptor.

Ligands are classified on basing on the number of atoms directly bonded to the central
metal i.e.

(a) Monodentate ligands / Unidentate ligands

These are ligands with one donor atom per ligand molecule.e.g.NH3, H2O, CH3NH2,
Cl-

(b) Polydentate/ Chelating ligands

These are ligands with two or more donor atoms per ligand molecule e.g.

H2NCH2CH2NH2 (Ethane-1,2-diamine) -with two donor atoms therefore it is

called bidentate

H2COOHCH2COOH

NCH2CN H
CH2COOH CH2COOH (EDTA)-Ethylenediamine tetraacetic
acid

Also ligands can be classified based on charges;

• Neutral ligand Anionic ligands Cationic ligand

H2O- aqua Cl- -chloro

NH3-ammine Br- -bromo

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 CO-carbonyl SO42- - Sulphato

NO-nitrosyl OH- -hydroxo

H2NCH2CH2NH2 (en)-ethane-1,2-diamine CN- - cyano

NO2- Nitro

H- -hydrido

Nomenclature of Complexes

(a) Cationic complexes

(i) Name and number of ligands

(ii) Name central atom with its oxidation state

(iii) If different ligands exist, list them in order of anion, neutral and cation. If the
ligands are of the same nature, use the alphabetical order Examples include:

• [Cu(NH3)4]2+Tetraamminecopper(II)ion

• [Cr(H2O)4(NH3)2]3+ diamminetetraaquachromium(III)ion

• [Pt(NH3)2NO2Cl]2+ chloronitrodiammineplatinum(IV) ion

• [Co(NH3)5SO4]Br Sulphatopentaammine cobalt(III)bromide

(b) Anionic complexes

Name of the central atom ends in –ate or-ic for an acid followed by it oxidation state.

Examples include:

[CuCl4]2- tetrachlorocuprate (II)ion

SiF62- Hexafluorosilicate(IV)ion

[Cr(OH)5NH3]3- pentahydroxoamminechromate(II)ion

[CoCl4(H2O)2]-tetrachlorodiaquacobaltate(III)ion

LiAlH4Lithiumtetrahydridoaluminate(III)

(c) Neutral complexes

These are formed between the central metal atom and a neutral ligand e.g.

• Ni(CO)4 Tetracarbonylnickel.

• V(CO)6 hexacarbonylvanadium.
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ISOMERISM

The following are the kinds of isomerism in complexes;

(a) Ionisation isomerism

This occurs when an ion can occupy positions inside and outside complex ion .i.e. acts as
a free ligand

Example

[Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br

Bromopentaamminecobalt(III)sulphate
Sulphatopentaamminecobalt(III)bromide

These isomers can be differentiated by use of acidified barium nitrate solution and the
observations are:

[Co(NH3)5Br]SO4 – white precipitate is formed

[Co(NH3)5SO4]Br - No observable change

The sulphate ions in bromopentaamminecolbalt(III)sulphate are uncomplexed therefore

they are free to react with barium nitrate solution to precipitate the sparingly soluble
barium sulphate i.e.

Ba2+ (aq) + SO42- (aq) BaSO4 (s)

Qn: Hydrated Chromium(III)chloride forms three isomers which form a white

precipitate with silver nitrate solution.

(a) Write the formula and I.U.P.A.C name of each isomer (b)
Describe how the isomer can be distinguished.
Soln:

(a) [Cr(H2O)6]Cl3 Hexaaquachromium(III)chloride -violet

[Cr(H2O)5Cl]Cl2.H2O Chloropentaaquachromium(III)chloride -light green

[Cr(H2O)4Cl2]Cl.2H2O Dichlorotetraaquachromium(III)chloride -dark green

(b) Add excess 1M Silver nitrate solution to equimolar solution of each isomer. The
number of moles of silver chloride precipitated by isomer is in the ratio of [Link].

Or: Conductivity measurements

Conductivity depends on the number of conducting ions present in solution. The isomer
with more ions gives the highest conductivity.

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(b) Geometrical isomerism

The isomers differ in the spatial arrangement of two ligand molecules in square planar or
octahedral complex giving rise to cis and trans isomers.

Read on the structure of complexes:

 Linear structure formed by complexes with coordination number 2

 Tetrahedral/ square planar formed by complexes with co-ordination no. 4

 Octahedral formed by complexes with co-ordination no.6

STABILITY CONSTANT

Consider;

Mn+ (aq) + 6L (aq) [ML6]n+ (aq)

The equilibrium expression is written as:

Keq = where Keq is the stability constant

A ligand with a higher stability constant substitutes/ displaces others from the complex

Qn: To an aqueous solution of copper (II) sulphate, concentrated hydrochloric acid

was added followed by aqueous ammonia solution

(a) State what was observed

(b) Explain your observation in above in (a)

Soln:

(a) A blue solution turns to yellow finally deep blue.

(b) In dilute solution of copper(II) sulphate, the blue colour is due to [Cu(H2O)6]2+ .
On addition of concentrated hydrochloric acid the aqua ligand are displaced to
form a yellow tetrachlorocuprate (II) complex.

[Cu(H2O)6]2+ (aq) + 4Cl- (aq) CuCl42- (aq) + 6H2O (l)

On addition of ammonia molecules with a higher stability constant displaces the chloro
ligands to form tetraamminecopper(II)ions which is deep blue.

CuCl42- (aq) + 4NH3 (aq) [Cu(NH3)4]2+ (aq) + 4Cl- (aq)

COPPER

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Extraction :

Ores:

• Copper Pyrites (CuFeS2)- principal ore

• Copper glance(Cu2S)

• Cuprite(CuO)

• Malachite ([Link](OH)2)

(a) Concentration of the ore (Froth floatation/ selective wetting)

The ore is crushed to powder and mixed with water containing a frothing agent such as
pine oil. Air is blown through the mixture to agitate the ore.
High density impurities become wet and sink to the bottom. Particles of the ore rise to the
surface and adhere to the air bubbles. They float on the surface as a froth which is
skimmed off, filtered and dried.

(b) Roasting

The concentrated ore is roasted in air to convert pyrites into iron(II)oxide,

copper(I)sulphide and sulphur dioxide gas

2CuFeS2 (s) + 4O2 (g) Cu2S (s) + 2FeO (s) + 3SO2 (g)

(c) Smelting

The mixture is heated in furnace with silicon (IV) oxide in absence of air. Iron(II)oxide
reacts to form a slug of Iron(II)silicate

FeO (s) + SiO2 (s) FeSiO3 (l)

The molten slug floats on the molten Copper(I)sulphide and can be trapped off.

(d) Conversion to blister copper

Copper(I)sulphide is heated in air to form copper(I)oxide and sulphur dioxide gas.

2Cu2S (s) + 3O2 (g) 2Cu2O (l) + 2SO2 (g)

The mixture of copper(I)oxide and unchanged copper(I)sulphide is then heated strongly in

absence of air to form blister copper.

2Cu2O (l) + Cu2S (s) 6Cu (l) + SO2 (g) The

molten copper is run off into moulds.
(e) Purification/Refining of blister copper

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Copper (II) sulphate solution is electrolysed using blister copper as the anode and pure
copper as cathode. The pure copper dissolves from the anode into solution and it is
deposited at the cathode

At anode: Cu (s) Cu2+ (aq) + 2e

At cathode: Cu2+(aq) + 2e Cu (s)

The anode loses mass and cathode gains an equal mass of copper.

PROPERTIES OF COPPER

Copper has a low Electropositivity and thus it is an inert and not attacked by dilute
mineral acids and water.

(a) It is oxidized by hot concentrated sulphuric acid to copper (II) sulphate, sulphur
dioxide and water

Cu (s) + 2H2SO4 (aq) CuSO4 (aq) + SO2 (g) + 2H2O (l)

(b) It is oxidized by cold and hot concentrated nitric acid as shown below respectively

3Cu (s) + 8HNO3 (aq) 3Cu(NO3)2 (aq) + 2NO (g) + 4H2O (l)

Cu (s) + 4HNO3 (aq) Cu(NO3)2 (aq) + 2NO2 (g) + 2H2O (l) (c)
When heated, copper reacts with oxygen and dry chlorine as:
300 C
o

2Cu (s) + O2 (g) 2CuO (s)

1000oC
4Cu (s) + O2 (g)2Cu2O (s)

Cu (s) + Cl2 (g) CuCl2 (s)

(d) Hot copper foil glows red in sulphur vapour forming copper(I) sulphide

2Cu(s) + S(g) Cu2S(s)

COMPOUNDS OF COPPER

Common oxidation states are +1 and +2.

Copper (I) is less stable compared to copper(II) despite the stable electronic configuration
of copper (I) ions. With respect to copper, both copper (I) and Copper (II) ions are
unstable i.e.

Cu+ (aq) + e Cu (s) H =−602KJmol−1

Cu2+ (aq) + 2e Cu (s) H =−795KJmol−1

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 The enthalpy of conversion of Cu+ to Cu2+ is -409KJmol-1and this shows that Cu+ ions
are thermodynamically unstable with respect to both Cu and Cu2+

Copper (I) Compounds

They are unstable in aqueous solution and undergo disproportionation

(a) Copper (I) Oxide

It is prepared by reduction of copper (II) sulphate with Aldehydes in the presence of an

alkali

It is a basic oxide and can be reduced to copper by hydrogen and carbon

Cu2O (s) + 2H+ (aq) Cu (s) + H2O (l) + Cu2+ (aq)

Cu2O (s) + C (s) 2 Cu (s) + CO (g)

(b) Copper (I) chloride

It is prepared by boiling copper (II) chloride with copper in presence of concentrated

hydrochloric acid.

CuCl2 (aq) + Cu (s) 2CuCl (s)

It dissolves in excess hydrochloric acid to form a colourless solution

CuCl (s) + Cl- (aq) [CuCl2]- (aq)

It dissolves in excess aqueous ammonia (concentrated) to form complex

CuCl (s) + 2NH3 (aq) [Cu(NH3)2] + (aq) + Cl – (aq)

Qn: 8.0g of a copper ore was leached with dilute sulphuric acid and the resultant
solution diluted to 250cm3. Excess 10% potassium iodide was added to 30cm3 of
the solution. The iodine liberated 23.5cm3 of 0.05M sodium thiosulphate solution
for complete reaction.

(a) Write all the equations of reactions involved.

(b) Calculate the percentage of copper in ore

(c) Describe the application of copper (I) compounds in distinguishing organic

compounds and synthesis

(d) Explain the similarity between silver (I) and copper (I) ions

Qn: A double salt Cu(NH3)xCly.zH2O where x,y and z are whole numbers. The molar
mass of salt is 277.5g. The chloride in 1.388g of the salt is precipitated as silver
chloride. After washing and drying the mass of the precipitate was 2.870g. When
1.388g of the salt is boiled with excess sodium hydroxide solution, the ammonia

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 liberated neutralizes 10cm3 of 1.0M hydrochloric acid. Determine the formula of
the salt.

Copper (II) compounds

(a) Copper(II) oxide

This a black basic oxide obtained by the action of heat on copper (II) nitrate, carbonate,
sulphate or copper (II) hydroxide

CuCO3 (s) CuO (s) + CO2 (g)

It reacts with dilute mineral acids to form copper (II) salts and water

CuO (s) + 2 H+ (aq) Cu2+ (aq) + H2O (l)

It is reduced to copper by carbon, hydrogen, methane and ammonia

3CuO (s) + CH4 (g) 3Cu (s) + 2H2O (l)+ CO

CuO (s) + C (s) Cu (s) + CO (g)

(b) Copper (II) hydroxide

This a pale blue precipitate formed when dilute sodium hydroxide solution is added to a
solution of Copper (II) ions

Cu2+ (aq) + 2OH– (aq) Cu(OH)2(s)

It dissolves in ammonia solution due to formation of a soluble complex. i.e.

Cu (OH)2(s) + 4NH3 (aq) [Cu(NH3)4]2+ (aq) + 2OH- (aq)

(c) Copper (II) chloride

The anhydrous chloride is prepared by reacting dry chlorine gas with heated copper metal

Cu (s) + Cl2 (g) CuCl2 (s)

The chloride dissolves in concentrated hydrochloric acid to form a yellow- green solution
of tetrachloro cuprate(II)

CuCl2 (s) + 2Cl- (aq) [CuCl4]2- (aq)

An aqueous solution of copper (II) salts are slightly acidic because the Cu2+ ions have a
high charge density therefore they are heavily hydrated as [ Cu(H2O)6]2+ and this
undergoes hydrolysis to release hydrogen ions in solution which causes the solution to be
acidic

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

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The copper (II) salt in solution reacts with:

• Potassium ferrocyanide solution to form brown precipitate

• Excess potassium cyanide solution to form a colourless solution

• Potassium iodide solution to form a white precipitate and brown stains

IRON electronic configuration 1S22S22P63S23P64S23d6

Extraction

Ore:

Haematite (Fe2O3)

Spathic (siderite) (FeCO3)

Magnetite(Fe3O4)

Iron pyrites (FeS2)

The mixture of haematite, coke and limestone are fed into the furnace from top. Air
enriched with oxygen is passed into the bottom of the furnace whose temperature varies
from about 2000oC -200oC at the top

Coke is constantly used to generate carbon monoxide gas

C (s) + O2 (g) CO2 (g)

C (s) + CO2 (g) 2CO (g)

The reaction is exothermic and thus increases the temperature of the furnace. Carbon
monoxide reduces iron (III) oxide to iron
Fe2O3 (s) + 3CO (g) 2Fe (l) + 3CO2 (g)

Limestone decomposes to form calcium oxide which removes the major impurity, Silicon
(IV) Oxide as a slag of calcium silicate.

CaCO3 (s) CaO (s) + CO2 (g)

CaO (s) + SiO2 (s) CaSiO3 (l)

The slag is less dense than the molten iron hence it protects it from re-oxidation. The
excess hot gases pass out of the furnace while the iron and slag are periodically tapped off
from the bottom

N.B. The pig iron can be converted to steel by open-hearth process where the carbon is
converted to gaseous oxide by heating and other impurities form oxides which react with
limestone to form slag

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N.B. If Iron (II) carbonate or Sulphide is used; it is concentrated by froth floatation and
roasted in air to convert it to an oxide

2FeCO3 (s) + ½ O2 (g) Fe2O3 (s) + 2 CO2 (g)

PROPERTIES OF IRON

(a) When heated, iron reacts with oxygen to form black solid of triiron tetraoxide

3Fe (s) + 2O2 (g) Fe3O4 (s)

(b) Red hot iron reacts with stream as shown by the equation

3Fe (s) + 4H2O (g) Fe3O4 (s) + 4H2 (g)

Iron slowly reacts with cold water in the presence of oxygen to form hydrated iron (III)
oxide

2Fe (s) + xH2O (l) + O2 (g) Fe2O3.xH2O (l)

(c) When heated iron reacts with sulphur, chlorine, hydrogen chloride, carbon and carbon
monoxide

Fe (s) + S (s) FeS (s)

2Fe (s) + 3 Cl2 (g) 2FeCl3 (s) (d)

It liberate hydrogen gas when reacted with dilute mineral acids Fe (s)
+ 2H+ (aq) Fe2+ (aq) + H2 (g)

Hot concentrated sulphuric acid oxidizes it to iron (III) sulphate and itself reduced to
sulphur dioxide and water

2Fe (s) + 6H2SO4 (l) Fe2(SO4)3 (aq) + 3SO2 (g) + 6H2O (l)

Concentrated nitric acid renders iron passive due to the formation of layer of the oxide.

COMPOUNDS OF IRON

Oxidation states are +2 and +3

The +3 oxidation state is more stable compared to +2 (why?).

Iron (II) compounds

(a) Iron (II) oxide

This a black basic oxide prepared by thermal decomposition of iron (II) oxalate in absence
of air

FeC2O4 (s) FeO (s) + CO2 (g) + CO (g)

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It reacts with dilute mineral acids to form iron (II) salt and water

FeO (s) + 2H+ (aq) Fe2+ (aq) + H2O (l)

The salts solutions are pale green and are readily oxidized by atmospheric oxygen to the
corresponding iron (III) salts. However, they are stable in presence of an acid. It rapidly
turns brown on exposure to air

½O2 (g) + 2FeO (s) Fe2O3 (s)

(b) Iron (II) hydroxide

This a green precipitate formed by action of dilute sodium hydroxide or ammonia solution
on a solution containing Fe2+

On exposure to air, it turns brown due to the formation of Iron (III) hydroxide

2Fe(OH)2 (s) + ½O2 (g) + H2O (l) 2Fe(OH)3 (s)

An aqueous solution of iron (II) salts contains [Fe(H2O)6]2+ and don’t undergo hydrolysis
due to low charge density

(c) Iron (II) sulphate (FeSO4.7H2O)

It is prepared by warming Iron with excess dilute sulphuric acid and evaporate the
resultant solution to crystallize pale green crystal. The crystals are efflorescent and
oxidized on exposure to air with formation of brown patches of iron (III) sulphate

Ammonium ferrous sulphate is normally preferred to standardize potassium permanganate

because it is resistant to atmospheric oxidation, non-efflorescent and has higher relative
molecular mass.

(d) Oxidation reactions

(i) Hot concentrated nitric acid

A green solution turns yellow with effervescence of a colourless gas which forms brown
fumes in air

3Fe2+ (aq) +4H+ (aq) + NO3- (aq) 3Fe3+ (aq) + NO (g) + 2H2O (l) 2NO
(g) + O2 (g) 2NO2 (g)
(ii) Chlorine gas

The green solution turns yellow

2Fe2+ (aq) + Cl2 (g) 2Fe3+ (aq) + 2Cl- (aq)

(iii) Hydrogen peroxide

The green solution turns yellow

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H2O2 (aq) + 2H+ (aq) + 2Fe2+ (aq) 2Fe3+ (aq) + 2H2O (l)

(iv) Potassium dichromate

6Fe2+ (aq) + Cr2O72- (aq) + 14H+ (aq) 6Fe3+ (aq) + 2Cr3+ (aq) + 7H2O (l)

(d) Potassium hexacyanoferrate (III) solution. It forms a dark blue precipitate

Iron (III) compounds

The iron (III) ions have a high charge density and are heavily hydrated therefore in
aqueous solution they exist as [Fe(H2O)6]3+ hence it undergoes hydrolysis to release
protons which cause the solution to be acidic

[Fe(H2O)6]3+ (aq) [Fe(H2O)5OH]2+ (aq) + H+ (aq)

Complete hydrolysis is represented as

[Fe(H2O)6]3+ (aq) [Fe(H2O)3(OH)3] (s) + 3H+ (aq)

(a) Iron (III) oxide

It is prepared by thermal decomposition of iron (II) sulphate or iron (III) hydroxide

2Fe(OH)3 (s) Fe2O3 (s) + 3H2O (g)

2FeSO4 (s) Fe2O3 (s) + SO2 (g) + SO3 (g)

It is basic and dissolves in dilute mineral acids

Fe2O3 (s) + 6HCl (aq) 2FeCl3 (aq) + 3H2O (l)

The oxide can be reduced by hydrogen, carbon and carbon monoxide to form iron

2Fe2O3 (s) + 3C (s) 4Fe (s) + 3CO2 (g)

(b) Iron (III) sulphate

Obtained by oxidation of iron (II) sulphate using concentrated sulphuric acid

2FeSO4 (aq) + 2H2SO4 (aq) Fe2(SO4)3 (aq) + SO2 (g) + 2H2O (l)

Qn: Sodium carbonate solution was added to aqueous solution of iron (III) sulphate.
Bubbles of a colourless gas and a brown precipitate were observed. Explain this
observation

Soln: Due to high charge density, the hydrated ion undergoes hydrolysis to form insoluble
iron (III) hydroxide and hydrogen ions which cause the solution to be acidic i.e.

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[Fe(H2O)6]3+ (aq) [Fe(H2O)3(OH)3] (s) + 3H+ (aq)

The hydrogen ions react with carbonate ions from sodium carbonate to form carbon
dioxide gas which is a colourless gas.

H+ (aq) + CO32- (aq) CO2 (g) + H2O (l)

REDUCTION OF Fe3+ TO Fe2+

(i) Zinc and hydrochloric acid

Zn (s) + 2Fe3+ (aq) 2Fe2+ (aq) + Zn2+ (aq)

(ii) Hydrogen sulphide gas

The brown solution turns pale green and yellow solid is deposited

S2- (aq) + 2 Fe3+ (aq) 2Fe2+ (aq) + S (s)

(iii) Sulphur dioxide

The brown solution turns pale green

SO2 (g) + 2Fe3+ (aq) + 2H2O (l) 2Fe2+ (aq) + SO42- (aq) + 4H+ (aq)

N.B. Fe3+ ions are confirmed by use of potassium hexacyanoferrate (II) solution, a dark
blue precipitate is observed.

ZINC

The following a reasons why zinc is referred to as a non- transition metal

• It forms colourless compounds in aqueous state

• It exhibits only one oxidation state

• It is not paramagnetic

• It does not act as catalyst or has limited catalytic activity However, like
other transition elements, Zinc forms complexes.

Extraction

Ore: - zinc blende (ZnS)

-Zincite(ZnO)
Concentration of ore

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Zinc blende is crushed into powder and mixed with water containing a frothing agent. Air
is bubbled through the mixture. The low density ore floats as a froth which is skimmed
off.

Roasting

The concentrated ore is roasted in air to form the oxide

2ZnS (s) + 3 O2 (g) 2ZnO (s) + 2 SO2 (g)

Zinc oxide is then mixed with coke and limestone in a blast furnace. The oxide is reduced
to zinc metal by carbon monoxide

ZnO (s) + CO (g) Zn (g) + CO2 (g)

The metal distils off with other blast furnace gases. The mixture of gases is allowed to
cool (quenched) to obtain crude zinc which is purified by redistillation.

The major impurities are lead (II) sulphide, Cadmium and iron.

Reactions of Zinc

(a) It burns in oxygen to form zinc oxide and a little nitride

Zn (s) + ½O2 (g) ZnO (s)

3Zn (s) + N2 (g) Zn3N2 (s)

(b) Steam reacts with heated Zinc form Zinc oxide and Hydrogen gas

Zn (s) + H2O (g) ZnO (s) + H2 (g)

(c) Warm dilute mineral acids readily react with Zinc to liberate hydrogen gas

Zn (s) + 2H+ (aq) Zn2+ (aq) + H2 (g)

Hot concentrated sulphuric acid oxidizes zinc to zinc sulphate

Zn (s) + 2H2SO4 (aq) ZnSO4 (aq) + SO2 (g) + 2H2O (l)

(d) It reacts with sodium hydroxide solution in presence of water to form zincate and
hydrogen

Zn (s) + 2H2O (l) + 2OH- (aq) [Zn(OH)4]2- (aq) + H2 (g)

Compound of Zinc

Zinc oxide and zinc hydroxide are amphoteric compounds

ZnO (s) + 2H+ (aq) Zn2+ (aq) + H2O (l)

ZnO (s) + 2OH- (aq) + H2O (l) [Zn (OH)4]2- (aq)

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The hydroxide dissolves in excess ammonia solution to form a complex colourless
solution

Zn(OH)2 (s) + 4 NH3 (aq) [Zn (NH3)4]2+ (aq)

N.B In aqueous solution salts of Zinc are colourless due to [Zn(H2O)4]2+ and are confirm
by use of disodium hydrogen phosphate where they form a white precipitate soluble in
ammonia solution

Question:

(a) Name one ore of zinc and give its formula

(b) (i) Describe briefly how the ore you have named in (a) is concentrated

(ii) What further treatment of the ore is required immediately after concentration?

(c) Outline the process, giving equations for the production of zinc metal from the
treated ore

(d) Zinc belongs to d-block in the periodic table yet it is not a transition metal.
Explain this statement.

(e) A piece of zinc metal was suspended in a solution of copper (II) sulphate in water.
State what was observed and write the equation for the change that took place.

MANGANESE

ORES

• Pyrolusite-MnO2

• Hausmannite-Mn3O4

The extraction is done by reduction of the oxide using aluminium followed by vacuum
distillation

Direct reduction of manganese (IV) oxide is explosive thus the oxide is heated in oxygen
to be converted to trimanganese tetraoxide

CHEMICAL PROPERTIES OF MANGANESE

1. When heated, manganese reacts with non-metals as

3Mn (s) + 2O2 (g) Mn3O4 (s)

3Mn (s) + N2 (g) Mn3N2 (s)

Mn (s) + Cl2 (g) MnCl2 (s)

Mn (s) + S (s) MnS (s)

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2. Manganese reacts with hot water to form sparingly soluble Manganese (II) hydroxide
and hydrogen gas

Mn (s) + H2O (g) Mn (OH)2 (s) + H2 (g)

3. Dilute hydrochloric and sulphuric acid form pink solution of manganese (II) salts and
hydrogen gas.

Qn: 4.0g impure manganese was dissolved in 20cm3 of 0.2M sulphuric acid.

(a) State what was observed

(b) Calculate the percentage purity of manganese in the impure sample

Compounds of Manganese

Oxidation states are +2, +3, +4, +6, and +7 but +2 is the most stable oxidation state due to
thermodynamically stable half filled 3d- orbital

Mn2+

(a) Potassium permanganate

A mixture of potassium hydroxide, potassium chlorate and manganese (IV) oxide is fused.
Hot water is added and carbon dioxide gas passed through the solution until it is purple(
green traces are removed)

6KOH (aq) + KClO3 (aq) + 3MnO2 (s) 3K2MnO4 (aq) + 3H2O (l) +
KCl (aq)
Carbon dioxide turns MnO42- to MnO4- by disproportionation
3MnO42- (aq) + 4H+ (aq) 2MnO4- (aq) + MnO2 (s) +2H2O (l)

In neutral or alkaline solution the manganate (VII) is reduced to manganese (IV) oxide

MnO4- (aq) + 4H+ (aq) + 3e MnO2 (s) + 2H2O (l)

In presence of manganese (IV) oxide, manganate (VII) is reduced to manganate (VI)

2MnO4- (aq) + MnO2 (s) + 4OH- (aq) 3MnO42- (aq) + 2H2O (l)

(b) Manganese (IV) oxide

It is black solid obtained by thermo-decomposition of manganese (II) nitrate

Mn (NO3)2 (s) MnO2 (s) + 2NO2 (g) It

oxidizes :
 Warm concentrated hydrochloric acid to chlorine
Page 75
 MnO2 (s) + 4HCl (aq) MnCl2 (aq) + Cl2 (g) + 2H2O (l)

 Oxalic acid or oxalate ions in presence of an acid to form carbon dioxide

MnO2 (s) + C2O42- (aq) +4H+ (aq) MnO (s) + 2CO2 (g) + 2H2O (l)

 Hot concentrated sulphuric acid to form oxygen, manganese (II) sulphate and
water

2MnO2 (s) + 2H2SO4 (aq) O2 (g) + 2MnSO4 (aq) +2H2O (l)

(c) Manganese (II) oxide

It is prepared by thermo-decomposition of manganese (II) carbonate or Manganese (II)

oxalate

MnCO3 (s) MnO (s) + CO2 (g)

The oxide is basic and reacts with oxygen at high temperatures to form trimanganese
tetraoxide

MnO (s) + H+ (aq) Mn2+ (aq) + H2O (l)

6MnO (s) + O2 (g) 2 Mn3O4 (s)

The mixed oxide reacts with acid to form manganese (II) ions and Manganese (III) salts
which disproportionate to form manganese (II) salts and manganese (IV) oxide

Mn3O4 (s) + 8H+ (aq) Mn2+ (aq) + 2Mn3+ (aq) + 4H2O (l)

2Mn3+ (aq) + 2H2O (l) Mn2+ (aq) + MnO2 (s) + 4H+ (aq)

(d) In an aqueous solution, the salts exist as [ Mn (H2O)6]2+ which is a pale pink solution.
The solution forms a white precipitate on addition of sodium hydroxide which is
immediately turns brown due to aerial oxidation

Mn2+ (aq) + 2OH- (aq) Mn(OH)2 (s)

4Mn(OH)2 (s) + O2 (g) 2Mn2O3.2H2O (s)

When hydrogen sulphide gas is bubbled through a solution of Manganese (II) ions in
presence of Ammonia, a pink precipitate of manganese (II) sulphide is formed.

Manganese (II) ions are oxidized to manganate (VII) by strong oxidizing agent such as
lead (IV) oxide or Sodium bismuthate (V) in presence of concentrated nitric acid

2Mn2+ (aq) + 5BiO3- (aq) + 14H+ (aq) 2MnO4- (aq) + 5Bi3+ (aq)
+ 7H2O(l)
2Mn2+ (aq) + 5PbO2 (s) +2H+ (aq) - 2+
2MnO4 (aq) +5Pb (aq) + 2H2O (l)

Page 76
CHROMIUM

It exists as the chrome iron ore

The following are some of the reactions of chromium:

(a) Non-metal

Chromium reacts with non-metals when heated

4Cr(s) +3O2 (g) 2Cr2O3 (s)

(b) Acids

Dilute mineral acids react to form blue solution of chromium (II) salt which turns green in
air due to oxidation

Cr (s) + 2H+ (aq) Cr2+ (aq) + H2 (g)

2Cr2+ (aq) +2 H+ (aq) + ½ O2 (g) 2Cr3+ (aq) + H2O (l)

Hot concentrated sulphuric acid oxidizes Chromium to Chromium (III) sulphate and itself
reduced to sulphur dioxide gas and water

2Cr (s) + 12H+ (aq) + 3SO42- (aq) 2Cr3+ (aq) + 3SO2 (g) + 6H2O (l)

(c) Sodium hydroxide solution

It reacts with hot sodium hydroxide solution to form a chromite and hydrogen gas 2Cr
(s) + 6OH- (aq) 2CrO33- (aq) + 3H2 (g)
Qn:

(a) Discuss the reaction of chromium with:

(i) Air (ii) Sulphuric acid

(b) Compare the chemistry of Chromium and Aluminium in terms of the following themes

(i) Reaction with sodium hydroxide solution

(ii) Nature of the oxide

(iii) Nature of the chlorides

Compounds of chromium

Oxidation states are +2 , +3 and +6

Chromium (III) compounds

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The compounds exist as [Cr(H2O)6]3+ and due to high charge density the solution are
acidic due to hydrolysis.

[Cr(H2O)6]3+ (aq)
[Cr(H2O)5OH]2+(aq) + H+(aq)
Chromium (III) Oxide

It is prepared by thermo-decomposition of Chromium (III) hydroxide as a green insoluble

solid

2Cr(OH)3 (s) Cr2O3 (s) + 3H2O (l)

The oxide is stable and resistant to reduction by hydrogen and carbon monoxide

It is an amphoteric oxide i.e.

Cr2O3 (s) + 6H+ (aq) 2Cr3+ (aq) + 3H2O (l)

Cr2O3 (s) + 6OH- (aq) 2CrO33- (aq) + 3H2O (l)

Chromium (III) hydroxide

It is precipitated as a green solid on addition of sodium hydroxide solution to a solution

containing Chromium (III) ions

Cr3+ (aq) + 3OH- (aq) Cr(OH)3 (s)

It is an amphoteric hydroxide and thus dissolves in sodium hydroxide solution to form a

green solution

Cr(OH)3 (s) + OH- (aq) Cr(OH)4- (aq)

It is oxidized by hydrogen peroxide in alkaline medium to form a yellow chromate (VI)

solution

2Cr3+ (aq) + 3H2O2 (aq) + 10 OH- (aq) 2CrO42- (aq) + 8H2O (l)

It dissolves in excess ammonia solution to form a violet solution of

hexaamminechromium(III) complex

Cr(OH)3 (s) + NH3 (aq) [Cr(NH3)6]3+ (aq) +3 OH- (aq)

Chromium (VI) oxide

This is a dark red solid precipitated when concentrated sulphuric acid is added to a
saturated solution of potassium dichromate and cooled

Cr2O72- (aq) + 2H+ (aq) 2CrO3 (s) + H2O (l)

It is deliquescent and soluble in water to form chromic (VI) acid

CrO3 (s) + H2O (l) H2CrO4 (aq)

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It is an acidic oxide which dissolves in alkaline solution to form chromate

CrO3 (s) + 2OH- (aq) CrO42-(aq) + H2O (l)

Chromate (VI)

These are yellow salts of Chromic (VI) acids which are isomorphic to sulphate ions

It is prepared by the action of alkaline sodium hydroxide solution on dichromate

Cr2O72- (aq) + 2OH- (aq) 2CrO42- (aq) + H2O (l)

In acidic medium, the orange dichromate is formed

2CrO42- (aq) + 2H+ (aq) Cr2O72- (aq)+ H2O

Qn: (a)A solution of potassium chromate was added to barium chloride solution followed
by dilute nitric acid. State what was observed and write the equation of the
reaction

(b) The Ksp of silver chloride and silver chromate is 1.0X10-12 and 1.0X10-10
respectively.

(i) State which salt is precipitated first if 0.1M KCl and 0.1MK2CrO4 are separately
added to silver nitrate solution

(ii) Explain the trend in the solubility of the chromates of group (II) of the periodic
table.

Dichromate

It is prepared by acidifying a solution of chromate

It can be acidified by dilute sulphuric acid and hydrochloric acid unlike permanganate
which is only acidified by sulphuric acid.

It oxidizes I- , SO32- , Sn2+, NO2- , H2S and Fe2+ in acidic medium

Dichromates in dilute acidified solution react with hydrogen peroxide solution to form a
blue chromium pentaoxide

Cr2O72- (aq) + 2H+ (aq) + 4 H2O2 (aq) 2CrO5 (s) + 5H2O (l)

COBALT

The oxidation states are +2 and +3 but +2 is more stable than +3 due to low ionization
enthalpy

Cobalt is a blue metal and less reactive than Iron

Reactions of Cobalt

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1. When heated slowly reacts with air to form a mixture of oxides

2Co (s) + O2 (g) 2CoO (s)

3Co (s) + 2O2 (g) Co3O4 (s)

2. Liberates hydrogen from dilute hydrochloric acid and Sulphuric acid

Co (s) + 2H+ (aq) Co2+ (aq) + H2 (g)

Dilute nitric acid forms cobalt forms Cobalt (II) nitrate , nitrogen dioxide and water

Co (s) + HNO3 (aq) Co(NO3)2 (aq) + 2NO2 (g) + 2H2O (l)

The metal is rendered passive by concentrated nitric acid due to a layer of Co3O4

When heated under pressure, cobalt reacts with carbon monoxide to form a neutral
carbonyl

2Co (s) + 8CO (g) Co2(CO)8

It does not react with sodium hydroxide, water and halogens.

Compounds of Cobalt

Cobalt (II) Oxide

Green basic oxide obtained by thermal decomposition of nitrate, carbonate, hydroxide in

absence of air

2CoCO3 (s) CoO (s) + CO2 (g)

The green solid dissolves in an acid to a pink solution

CoO (s) + 2H+ (aq) Co2+ (aq) + H2O (l)

Cobalt (II) hydroxide

Blue basic hydroxide obtained by precipitation as

Co2+ (aq) + 2OH- (aq) Co(OH)2 (s)

The blue turns pink then brown in air due to aerial oxidation

It dissolves in excess ammonia solution to form a pale yellow solution which turns pink
due to aerial oxidation

Co (OH)2(s) + 6NH3 (aq) [Co (NH3)6]2+ (aq) + 2OH- (aq)

[Co (NH3)6]2+ (aq) [Co(NH3)6]3+ (aq) + e

Cobalt (II) Chloride

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It is prepared by reacting dilute hydrochloric acid with Cobalt (II) oxide or hydroxide or
carbonate

CoCO3 (s) + 2HCl (aq) CoCl2 (aq) +CO2 (g) + H2O (l)

CoO (s) + 2HCl (aq) CoCl2 (aq) + H2O (l)

The anhydrous salt is blue but in aqueous solution exist as [Co (H2O)6]2+ which is pink.

The aqua ligands in the hydrated complex can be substituted by NH3, CN- and Cl- due to
higher stability constant

[Co(H2O)6]2+ (aq) + 4Cl- (aq) CbolCule42- (aq) + 6H2O (l)

Pink

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

Pale yellow

Co2+ (aq) + 2CN- (aq) Co(CN)2 (s)

Reddish brown

A solution of cobalt (II) ions react with hydrogen peroxide in presence of an acid to form cobalt (III)

2Co2+ (aq) + H2O2 (aq) + 2H+ (aq) 2Co3+ (aq) + 2H2O (l)
Pink Brown

N.B. Cobalt (III) compounds are more stable when complexed.

Qn: An aqueous solution of cobalt (III) salt is CoCl3.6NH3 whose concentration is 1M.
The complex was reacted with 1M silver nitrate solution to precipitate 1M of silver
chloride.

(a)(i) Identify the complex

(ii) Write the structural formulae for the possible isomers and
give their I.U.P.A.C name

(iii) State the type of isomerism indicated (b) Explain:

(i) Why Cu2+ is colourless while Cu(H2O)42+ ion is blue and that of Cu(NH3)42+ is deeper
blue.

(ii) Aluminium hydroxide dissolves in sodium hydroxide solution while Magnesium

hydroxide does not

(iii)Copper (I) chloride and Lead (II) chloride are both insoluble in water but dissolves in
concentrated hydrochloric acid

Page 81
 (iV) A blue solution of Copper (II) chloride turns green on addition of chloride ions

SAMPLE INORGANIC CHEMISTRY PRACTICAL

Sample Practical 1

You are provided with substance X which contains two cations and two anions. You are
required to carry out the following tests on X and to identify the anions and cations in X.
TESTS OBSERVATION(S) DEDUCTION(S)

a) Heat a spatula end ful A colourless liquid Water of crystallization

of X in adry test tube condenses on sides of test Or: Hydrated salt
tube and turns anhydrous
Copper (II) Sulphate from
white to blue. CO2 from CO32-,C2O42-
A colourless gas turns CH3COO-
damp blue litmus red and
lime water milky

White residue Oxide of Ca2+,

Ba2+,Mg2+,Al3+
b) Shake two spatula end
ful of X with about White residue Non- transition metal cation
5cm3 of water and suspected
filter. Keep both the Colourless filtrate Ca2+,Mg2+,Ba2+,Al3+probably
filtrate and residue. present.
Divide the filtrate in six
parts
(i) To the first part of the
filtrate, add dilute White precipitate insoluble Ca2+, Mg2+,Ba2+ suspected
sodium hydroxide drop in excess
wise until in excess.
)(ii)To the second part of
the filtrate, add dilute No observable change Ca2+ , Ba2+ suspected
ammonia solution drop
wise until in excess.
iii) To the third part of
the filtrate, add 2-3 drops White precipitate Ca2+, Ba2+ suspected
of dilute sulphuric acid

Page 82
iv) To the fourth part, add
2-3 drops of Potassium Yellow precipitate Ba2+ confirmed
Chromate (VI) and then
add dilute Sodium
hydroxide solution drop
wise until in excess and
allow the mixture to
stand.
v) To the fifth part, add 2-
3 drops of lead (II) nitrate White precipitate SO42-, Cl-,SO32- suspected
solution.

vi) To the sixth part, carry

a test of your own to
confirm the anion in the
filtrate.
White precipitate Cl- confirmed
To the portion, add silver
nitrate solution

Or:

To the portion, add lead

ethanoate

c) Wash the residue with Effervescence of a Carbondioxide gas from

water, transfer the residue colourless that turns damp CO32-
to the test tube and add blue litmus red and lime
dilute Nitric acid drop water milky. CO32- confirmed
wise to dissolve the
residue. Colourless solution formed. Transition metal ion present.
Divide the resultant
solution into five parts.
i) To the first part, add
dilute Sodium hydroxide White precipitate insoluble Mg2+ , Ca2+, Ba2+ suspected
drop wise until in excess. in excess

ii) To the second part,

add dilute ammonia No observable change Ca2+, Ba2+ suspected
solution drop wise until
in excess.

Page 83
iii) To the third part, add Ba2+, Ca2+ suspected
2-3 drops of dilute White precipitate formed
sulphuric acid.
iv) To the fourth part, add
2-3 drops of Potassium Yellow precipitate soluble Ca2+ confirmed
chromate (VI) solution in Ethanoic acid to form a
and then Ethanoic acid. yellow solution

v) To the fifth part, carry

out a test of your own to
confirm the cation in the
residue. Ca2+ confirmed
White precipitate
To the solution, add
ammonium ethanedioate
solution

d) Identify the;

(i) Cations in X Ca2+ and Ba2+ (ii) Anions in X CO32- and Cl-

Sample Practical 2

You are provided with substance E which contains three cations and one anion.

Carry out the following tests and identify the ions in E.

TEST OBSERVATION(S) DEDUCTION(S)

a) Heat three spatula end A colourless that turns red NH3 gas from NH4+ salt
ful of E strongly until no litmus blue
further change. Leave the
residue to cool. A colourless liquid Water of crystallization
condenses along side test
tube and turns anhydrous
copper (II) sulphate blue.
A black residue Oxide of Cu2+ , Fe2+ , Ni2+

Page 84
b) To the cool residue in White residue Ba2+, Ca2+,Mg2+,Al3+,Pb2+
3
(a), add about 10cm of
water, shake well and filter.
Divide the resultant Yellow solution Fe3+ suspected
solution into six parts.

(i) To the first part, add A brown precipitate Fe3+ suspected

dilute sodium hydroxide insoluble in excess
drop wise until in excess.

(ii) To the second part, add A brown precipitate Fe3+ suspected

ammonia solution followed insoluble in excess
by solid ammonium
chloride then sodium
carbonate.
(iii) To the third part, add A yellow precipitate Fe3+ suspected
Potassium chromate
solution.

(iv) To the fourth part, add A reddish brown solution Fe3+ confirmed
Ethanoic acid

(v) To the fifth part, add A white precipitate SO42-

lead (II) nitrate solution
and heat the mixture.

(vi) To the sixth part, carry

out a test of your own to
confirm the anion in E
No observable change Cl- absent
To the solution, add Silver SO42− confirmed
nitrate solution

c) Wash the residue in (b)

and dissolve in dilute Colourless solution formed Transition metal ion present.
hydrochloric acid. Warm. Mg2+,Ca2+ , Ba2+,Al3+, Pb2+
and divide the resultant suspected
solution in to two parts

(i) To the first part, add White precipitate insoluble Mg2+, Ca2+ ,Ba2+ suspected
ammonia solution drop in excess.
wise until in excess.

Page 85
(ii) To the second part,
carry out a test of your
own to confirm the
Cation in E
White precipitate formed Ca2+ confirmed
To the solution, add
ammonium ethanedioate
solution

Ions are;

NH4+, Ca2+
(i) Cations and Fe3+ SO42(ii) Anion

Sample Practical 3

You are provided with substance X which contains two cations and two anions. You are
required to identify the anions and cations in [Link] your observations and deductions
in the table below.
TEST OBSERVATION(S) DEDUCTION(S)
a) Heat a spatula end- ful A colourless liquid Water of crystallization
of X in a dry test tube condenses a long side a test
tube and turns anhydrous
copper (II) sulphate blue

Colourless gas turns a damp CO2 from CO32-, C2O42- and

blue litmus red CH3COO- suspected

A residue which yellow when Oxide of Pb2+

hot and white when cold
b) Shake two end ful of X
with water and filter. Keep Colourless filtrate Pb2+,Zn2+, Al3+, Ca2+,
2+ 2+
both filtrate and residue. Mg ,Ba suspected
Divide the filtrate in to six White residue
parts.
(i) To the first part, add
dilute sodium hydroxide White precipitate insoluble Ba2+, Ca2+ and Mg2+
drop wise until in excess. in excess suspected
(ii) To the second part, add
ammonia solution drop No observable change Ba2+, Ca2+ suspected
wise until in excess.

Page 86
(iii) To the third part, add
2-3 drops of dilute White precipitate Ba2+, Ca2+ suspected
sulphuric acid.
(iv) To the fourth part, add
2-3 drops of Potassium Yellow precipitate insoluble Ba2+ confirmed
chromate (VI) followed by
dilute sodium hydroxide
drop wise until in excess
and allow the mixture to
stand.
(v) To the fifth part, add 23
drops of lead (II) nitrate White precipitate soluble on Cl- suspected
solution, heat and allow to heating and reappears on
stand. cooling
(vi) To the sixth part, carry
out a test of your own
choice to confirm the anion
in the filtrate.
A white precipitate Cl- confirmed
To the solution, add silver
nitrate solution

c) Wash the residue with Effervescence of a colourless CO2 gas from CO32-
water, transfer to the test gas which turns a damp blue
tube and add dilute nitric litmus red
acid drop wise to dissolve
the residue. A colourless solution Pb2+, Al3+, Zn2+ suspected
Divide the solution into
five parts
(i) To the first part, add A white precipitate soluble to Zn2+,Al3+and Pb2+ suspected
dilute sodium hydroxide form a colourless solution
drop until excess.

(ii) To the second part, add A white precipitate insoluble Pb2+ and Al3+ suspected
dilute ammonia solution in excess
drop wise until.
(iii) To the third part, add A white precipitate formed Pb2+ confirmed
dilute 2-3 drops of dilute
sulphuric acid.

Page 87
(iv) To the fourth part, add A yellow precipitate formed Pb2+
2-3 drops of Potassium
chromate (VI) solution then
sodium hydroxide until in
excess.
(v) To the fifth part, carry
out a test of your own
choice to confirm cation in
X
A yellow precipitate Pb2+ confirmed
To the solution, add
potassium iodide solution

Or: A white precipitate Pb2+ confirmed

To the solution, add dilute
hydrochloric acid

Ba2+ and Pb2+

d) (i) The cations in X are

(ii) The anions in X are Cl- and CO32-

Sample Practical 4

You are provided with substances F, G and H each of which contains a single anion and a
common cation. You are required to identify the cation and the three anions.
TEST OBSERVATION(S) DEDUCTION(S)

a) Heat a small amount of A colourless gas that turns CO2 from CO32-, C2O42-
F until no further change a damp blue litmus red and ,CH3COO- suspected
lime water milky A
colourless liquid condenses
along side a test tube which Water of crystallization
turns white anhydrous
copper (II) sulphate blue

A black residue formed Oxide of Cu2+, Fe2+, Ni2+,

Co2+ suspected

Page 88
b) To a spatula end ful of F
add a little ethanol and few A sweet fruity smell CH3COO- confirmed
drops of concentrated
sulphuric acid.
Warm the mixture.
c) Dissolve a small
amount of F in 5cm3of A blue solution Cu2+ suspected
water. Warm and allow to
stand. Divide the solution
into three parts.
(i) To the first part, add2-3
drops of iron (III) chloride A reddish brown solution CH3COO- confirmed
solution and warm.
(ii) To the second part, add A pale blue precipitate Cu2+
dilute sodium hydroxide insoluble in excess
solution drop wise until in
excess.
(iii) To the third part, add A pale blue precipitate Cu2+ confirmed
aqueous ammonia drop soluble in excess forming a
wise until in excess. deep blue solution

(iv)To the fourth part, add A yellow solution Cu2+ confirmed

concentrated hydrochloric
acid.

d) Dissolve a small amount A pale blue solution Cu2+

3
of G in 5cm of water.
Divide the solution into
two parts;
(i) To the first part, add A white precipitate insoluble SO42- suspected or Cl-
lead (II) nitrate solution on warming absent
and warm.
(ii) To the second part,
carry out a test of your own
choice to the anion in G.

To the solution, add White precipitate insoluble in SO42- confirmed

Barium nitrate solution the acid.
followed by dilute nitric
acid. SO42- confirmed
Or: No observable change
To the solution, add silver
nitrate solution

Page 89
e) Dissolve a small amount
of H in 5cm3 of water and
divide the resultant solution
into two parts. A green solution Transition metal ions
present.
Cu2+, Ni2+, Cr3+ suspected

(i) To the first part, lead

(II) nitrate solution White precipitate soluble on Cl- suspected
followed by dilute nitric heating and reappears on
acid and warm. cooling

(ii) To the second part, add

silver nitrate solution. White precipitate Cl- confirmed

Cu2+
f) Identify (i) the cation in F, G and H

SO42- , Cl- and CH3COO-

(ii) the anions in F, G and H

g) Explain your observation in test e (ii)

The silver ions from silver nitrate solution react with the chloride ions forming Silver
chloride which appears as a white solid

Ag+ (aq) + Cl- (aq) AgCl (s)

Sample Practical 5

You are provided with substance H which contains two cations and two anions. Carry out
the following tests to determine the ions in H.

TEST OBSERVATION(S) DEDUCTION(S)

Page 90
a) Heat a spatula end ful of Substance melt A
H Strongly until no further colourless liquid Water of crystallization
change condenses along side a test
tube which turns a white
anhydrous Copper (II)
sulphate blue
SO2 gas from SO42- and
A colourless gas which turns SO32-
a damp blue litmus red and
acidified potassium
dichromate solution green

A black residue Oxide of Cu2+, Ni2+ , Fe2+

suspected
b) Dissolve two spatula end Colourless filtrate Al3+, Pb2+,Zn2+,Ca2+, Mg2+,
ful of H in 10cm3 of water. Ba2+ suspected
Shake well and filter. Keep
both the filtrate and the Green residue Fe2+,Cu2+, Ni2+,Cr3+
residue. Divide the filtrate suspected
into four parts
(i) To the first part, add A white precipitate soluble in Al3+, Pb2+ and Zn2+
dilute sodium hydroxide excess forming a colourless suspected
drop wise until in excess. solution

(ii) To the second part, add A white precipitate soluble in Zn2+ confirmed
ammonia solution drop wise excess forming a colourless
until in excess solution
(iii)To the fourth part, add A white precipitate persists SO42- suspected
lead (II) nitrate solution and on heating
warm.

(v)To the fifth part, add A white precipitate insoluble SO42- conformed
barium chloride solution in excess
and dilute hydrochloric
acid.
d) To the residue, add Effervescence of a CO2 gas from CO32-
dilute nitric acid to dissolve colourless gas that turns a
the residue. Divide the damp blue litmus red and
resultant solution into three limewater milky Transition metal ion present
parts. Ni2+, Fe2+, Cu2+ , Cr3+
A green solution formed suspected

Page 91
(i) To the first part, add A green precipitate Ni2+ suspected
dilute sodium hydroxide insoluble in excess
solution drop wise until in
excess.

(ii) To the second part, add A green precipitate soluble Ni2+ suspected
ammonia solution drop wise in excess forming a blue
until in excess. solution

(iii) To the third part, carry

out the test of your own
choice to confirm the cation
in the residue
A red precipitate Ni2+ confirmed
To the solution, add
ammonia solution followed
by dimethylglyoxime

e) Identify the ions in H

Ni2+ and Zn2+

(i) Cations

(ii) Anions SO42- and CO32-

Sample Practical 6

You are provided with substance W which contains two cations and two anions. Cary out
the following tests to identify the ions in W and record your observation(s) and
deduction(s) in the table below.
TEST OBSERVATION(S) DEDUCTION(S)
A colourless liquid Water of crystallization
a) Heat a spatula end ful of condenses along side test
W in a dry Pyrex tube until tube and turns white
no further change.

Page 92
 anhydrous copper Oxide of Al3+, Mg2+,
(II) sulphate blue A Ca2+,Ba2+ probably present
white residue
CO2 gas from CO32-, C2O42-,
A colourless gas that turns CH3COO-
blue damp litmus red and
limewater milky.

b) Dissolve two spatula Colourless filtrate

3
end ful of W in about 3cm Mg2+,Ca2+, Al3+,Ba2+
of water. Shake and filter. White residue probably
Keep both the filtrate and
residue. Divide the filtrate
into six parts.

(i) To the first part, add A white precipitate insoluble Probably Mn2+ present
dilute sodium hydroxide in excess and turns brown
solution drop wise until in on standing Mn2+ oxidized to MnO2
excess.

(ii) To the second part, add A white precipitate insoluble Probably Mn2+ present Mn2+
ammonia drop wise until in excess and turns brown oxidized to MnO2
in excess. on standing
(iii) To the third part, add Purple solution Mn2+ confirmed
concentrate nitric acid
followed by lead (IV)
Oxide and boil.
(iv) To the fourth part, add Purple solution Mn2+ confirmed
sodium bismulthate
followed by concentrated
nitric acid and boil.
(v) To the fifth part, add White precipitate disappears Cl- probably present
Lead (II) nitrate solution on warming and reappears
and warm. Allow it to cool on cooling.
down.

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(vi) To the sixth part, carry
out the test of your own
choice to confirm the
anion in the filtrate.
White precipitate Cl- confirmed
To the solution, add silver
nitrate solution

c) Wash the residue and Effervescence of a colourless CO2 from CO32-

add dilute hydrochloric gas which turns
acid to dissolve the residue. blue damp litmus red
Divide the resultant
solution into three parts. Colourless solution remains Probably Al3+, Ca2+, Ba2+,
Mg2+ present

(i)To the first part, add A white precipitate insoluble Probably Ca2+, Ba2+,Mg2+
dilute sodium hydroxide in excess present
solution drop wise until in
excess.
(ii) To the second part, add A white precipitate insoluble Probably Mg2+ present
ammonia solution drop in excess
wise until in excess.
(iii) To the third part, add A white precipitate insoluble Mg2+ confirmed
disodium hydrogen in excess ammonia solution
phosphate followed by
ammonium chloride and
ammonia solution drop
wise until in excess.

d) Identify the ions in W;

(i) Cations Mn2+ and Mg2+ (ii) Anions Cl- and CO32-

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Sample Practical 7

You are provided with substance R which contains two cations and two anions. Carry out
the following tests on R and identify the cations and anions in it. Identify any gases
evolved. Record your observations and deductions in the table.
TEST OBSERVATION(S) DEDUCTION(S)
(a) Heat a small spatula Substance melted
end ful of R in dry Pyrex
tube. Cracking sound produced

A colourless liquid Water of crystallization

condenses along side test
tube and turns white

anhydrous copper (II)

sulphate blue Oxygen is released

A colourless gas burns with a

pop sound NO2 gas released from NO3-

A brown gas turns damp

blue litmus red Oxide of Cu2+, Pb2+
suspected
A green substance turns
yellow/black

(b) To a spatula end ful of Colourless filtrate Al3+, Zn2+ and Pb2+
R in a test tube. Add 5cm3 suspected
of 2M sodium hydroxide
solution. Shake well and Pale- blue residue
filter. Keep both filtrate Probably Cu2+ present
and residue.

(c) Wash the residue with

water and transfer it to a A green/ blue solution Probably Cu2+ present
test tube. Add 2cm3 of
dilute nitric acid and warm
to dissolve. Cool the
solution and divide it into
two portions.

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(i) To the first portion, add Pale blue precipitate Probably Cu2+ present
dilute sodium hydroxide insoluble in excess
solution drop wise until in
excess.

(ii) To the second portion, Pale blue precipitate soluble Cu2+ confirmed
add dilute ammonia in excess forming a deep blue
solution drop wise until in solution
excess.
(d) To the filtrate from (b), Colourless solution Probably Al3+, Zn2+ and
add dilute nitric acid until Pb2+ present
the solution is acidic.
Divide the solution into
three parts.
(i) To the first part, add A white precipitate soluble in Probably Al3+, Zn2+ and
dilute sodium hydroxide excess forming a colourless Pb2+ present
solution drop wise until in solution
excess.
(ii) To the second part, add A white precipitate in Al3+, Pb2+ probably present
ammonia solution drop soluble in excess
wise until in excess.

(iii) To the third part, carry

out a test of your own to
confirm the cation.

To the solution, Add A yellow precipitate Pb2+ confirmed

Potassium iodide solution

Or
To the solution, add dilute A white precipitate Pb2+ confirmed
sulphuric acid

(e) To a spatula end ful of

R, add 2cm3 of dilute nitric
acid. Heat the mixture to A green solution Probably Cu2+ present
dissolve the solid. Cool the
solution and divide it into
two parts.

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(i) To the first part, add No observable change SO42- absent Cl-
barium nitrate solution. present

(ii) To the second part, add White precipitate formed Cl- confirmed
3 drops of silver nitrate
solution.

Cu2+ and Pb2+

(i) The cations in R are

Cl- and NO3-

(ii) The anions in R are

Sample Practical 8

You are provided with substance W which contains three cations and one anion. You are
required to carry out the following tests on W to identify the cations and anion in it.
Identify any gases evolved. Record your observations and deductions in the table below.
TESTS OBSERVATION(S) DEDUCTION(S)
(a) Heat a spatula end ful of Substance melted
W in dry tube until there is A colourless gas that turns a NH3 gas from NH4+
no further change damp red litmus blue
Colourless liquid condenses Water of crystallization
along side test tube and
turns white anhydrous
Copper (II)suphate blue
Oxide of Cu2+, Fe2+, Mn2+,
A black residue Ni2+ suspected
(b) Shake two spatula
endful of W with about A green residue Probably Fe2+ present
3cm3 of water. Add dilute
ammonia solution drop wise
until in excess. Warm and A deep blue solution Probably Cu2+ present
filter. Keep both the filtrate
and residue.

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(c) To the filtrate, add dilute
nitric acid drop wise until A green solution Probably Cu2+ present
the solution is just acidic.
Divide the acidic solution
into six parts.

(i) To the first part, add

dilute sodium hydroxide A pale blue precipitate
solution drop wise until in insoluble in excess and Probably Cu2+ present
excess. Warm the mixture. turns black on heating

A colourless gas that turns NH3 gas NH4+ present

red damp litmus blue

(ii) To the second part, add Pale blue precipitate soluble Cu2+ confirmed
dilute ammonia solution in excess forming a deep
drop wise until in excess. blue solution

(iii) To the third part, add A yellow solution with a Cu2+ confirmed
potassium iodide solution. white precipitate

(iv) To the fourth part, add

2-3 drops of litmus solution A red solution Acidic salt
followed by ammonia Cu2+ present
solution drop wise until in
excess.
(v)To the fifth part, add 3-4 A white precipitate Probably SO32-,SO42-,Cl-
drops of lead (II) ethanoate present
solution

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(vi) Use to the sixth part to
carry out a test of your own
choice to confirm the anion
in W
White precipitate insoluble SO42- confirmed
To the solution, add in excess acid
Barium nitrate solution
followed by dilute nitric
acid
White precipitate insoluble SO42- confirmed
Or in excess acid
To the solution, add barium
chloride solution followed
by dilute hydrochloric acid

(d) Wash the residue with

water and dissolve it in A pale- green solution Probably Fe2+,Ni2+
dilute hydrochloric acid suspected
and divide the solution into
three parts

(i) To the first part, add A green precipitate Fe2+ suspected

sodium hydroxide solution insoluble in excess and turns
drop wise until in excess brown on standing
(ii) To the second part, add A green precipitate Fe2+ suspected
dilute ammonia solution insoluble in excess and turns
drop wise until in excess brown on standing

(ii) To the third part, add 34

drops of potassium A dark blue precipitate Fe2+ confirmed
hexacyanoferrate (III)
solution

SO42(e) (i) The anion in W is

(ii) The cations in W are
N H4+ , Fe2+ and Cu2+

Sample 9

You are provided with substance X which contains one cation and two anions.

Carry out the following tests on X to identify thecation and anions in X.

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Tests Observations Deductions

Heat a spatula end-ful of X Droplets of a colourless Hydrated salt

strongly in a dry test tube liquid turned white
anhydrous copper(II)
sulphate blue.
Sulphurdioxide gas from
Colourless gas turned blue SO42- or SO32-
litmus red and acidified
potassium dichromate
solution green. Non-transition metal ion
present.
White residue

Dissolve three spatula end – White solid dissolves to Non-transition metal ion
ful of X in about 6cm3 of form a colourless solution. present.
water. Divide the solution
into five parts.

i) To the first part of the White precipitate soluble Zn2+, Pb2+ or Al3+
solution, add sodium forming a colourless suspected.
hydroxide solution solution.
dropwise until in excess

ii) To the second part of the White precipitate insoluble Pb2+ or Al3+ suspected
solution, add aqueous in excess
ammonia solution dropwise
until in excess

iii) To the third part of the No observable change. Al3+ confirmed

solution, add 2-3 drops of
potassium iodide solution. Or No yellow precipitate Pb2+ absent
formed
iv) To the fourth part of the White precipitate insoluble Cl-, SO42- suspected.
solution, add 2-3 drops of in acid.
lead(II) Nitrate solution
followed by dilute Nitric
acid

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v) To the fifth part of the White residue SO42- confirmed
solution, add barium Nitrate
solution drop-wise until in Colourless filtrate
excess. Filter and divide the
filtrate into two portions.

(i) To the first portion, add

equal volume of lead (II) White precipitate insoluble Cl- confirmed
Nitrate solution followed by in acid. Dissolves on boiling
2-3 drops of dilute Nitric and reappears on cooling.
acid. Boil and cool using
cold water

(ii) To the second portion, White precipitate insoluble Cl- confirmed

add silver nitrate solution in acid.
followed by dilute nitric
acid.

The cation in X is Al3+ and anions are SO42- and Cl-

YOUNG CHEMIST SUCCESS DEPENDS ON EFFORT USED AND PRAYS

ENJOY PROFESSIONAL SUCH AS

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