1

INORGANIC CHEMISTRY
Introduction
Inorganic chemistry is the study of trends (patterns) in physical and chemical properties of elements and
compounds they form i.e. oxides, chloride and hydrides etc. Carbon and its Compounds are not
considered except the chemistry of the oxides of carbon: the carbonates and hydrogen carbonates.
The behaviour of chemicals can entirely be explained in terms of modern theoretical concepts about the
atom, molecular structure and bonding with the realization that there exists definite relationships and
patterns leading to the periodic classification of the elements.
Similarities and differences in observed involved trends and attempt to explain in terms of
electronegativity, atomic radius, structure and bonding and writing equations.
Main emphasis will be on
 Group (I) and (II)
 Period 3

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  first series of transition elements
 Group (V) and (VII)
 Extraction of metals Aluminium, iron, copper and zinc
Our environment is full of inorganic materials, for example water, minerals, air, light and therefore a
clear knowledge of inorganic chemistry is very important for our logical thinking.
The physical and chemical properties depend on the atomic structure.

Evidence of atomic structure can be obtained from

1. Radio activity
2. Ruther ford’s scattering experiment
3. Hydrogen spectrum
4. Successive ionization energy
5. Melting and boiling points
6. Structure and bonding

RADIO ACTIVITY
Is the spontaneous decay/disintegration of an atom with a emission of at least alpha (α), Beta(β) or
gamma (8) rays

A summary of the properties of radio active particles.

Name (symbol) Identity Change Mass Penetration and defection

4 +
Alpha α 2He 2 4 Low and deflected in away that

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 show it is (+) charged.
0 -
Beta β -1e 1 0 High and deflected in away
that show it is (-) charged.
Gamma Rays - - Not deflected.
Very high penetration
1
Neutron ∩ 0n 0 1 Not deflected

NOTE:
1) During β – decay there is no change in the mass number, but atomic number increases by one.
Therefore decay by β -particles moves the resulting element one place to the right of the periodic
table.
2) All disintegration by loss of a alpha particle result in decrease in the mass number by 4 and
decrease in atomic number by 2. Disintegration by α –particle movesthe resulting element two
places to the left of the periodic table.
3) Emission by gamma rays (radiation) neither affects the relative atomic mass nor the atomic
number and has excess energy which is released in form of gamma rays.

Radioactive equations
There are two
1. Parent daughter equation
2. Integrated rate equation
Parent daughter equation
1. Identify X in the following nuclear reaction
107 1
a) 47Ag + 0n X +0-1e
Total mass number on the left = Total mass number on the right.
That is 107 + 1 = X +0
108 =x
Mass number of X = 108
Total atomic number on the left = Total atomic number on the right
47 + 0 = X + -1
X = 48.

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 Atomic number of X = 48
Then 10848X and from the periodic table X is Cd.
286 92 141
b) 92U + 36Kr X + 56 Ba

X is 310n
2. Insert the missing data in the following decay chain
232 228
90Th X +------- 89Ac + -------- b +………..
Solution
232 Th
90 x+22888Ra 228
89Ac + 0-1e b + 22890Th
NB: Both values of atomic number and mass number must be correct and the symbol should be correct.
Self check:
1. Identify element X in the following equations
235
a) 92U + 10n 160
62 Sn + 410n + X
234 4
b) X 90Th + 2He
4 14 1
c) 2He + 7N 1H +X
214
d) 83Bi 3β + 2α + X

Differences between radio activity and ordinary chemical reactions.

Radio activity Normal chemical equation

 Numberof neutrons and protons change  Only number of electrons change.
 React to form new elements  React to form a compound
 A small mass of the reactants  Energy released or absorbed depends
transformed into energy. on how much energy is contained in
 Mass of reactants is not equal to that of reactants.
products  Mass of reactants is equal to that of the
products.

The integrated rate equation

Radio activity is a first order reaction
Equation[ No]of first order is

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 [N1]
2.303 log10 = Kt
Where [N)0 = initial concentration at time t = 0
[N]t = concentration after time t of the decay
K = rate constant
t is time of decay

Half life (t ½ )
Is the time taken for the concentration of a radio – active material to fall to half of its initial
concentration. Or the time taken for half the atoms to disintegrate
Now. 2.303log [N]0 = Kt ½
At t = t ½ Nt = No
2

2.303log [N]0/[N]0/2 = Kt ½
2.303log2 = Kt ½
And t ½ = 2.303log2
K
t½= 0.693
K

Application of radio activity reactions

 In treatment of cancer
 In radio graphy to detect faults in pipes and welded metals
 In preservation of food (tinned food)
 In carbon 14 dating

Lt us revise
90
1. 38Sr is a fo-emitter with half life of 27 years. Determine the time taken for the activity to reduce
by 90% of its initial concentration.

Solution
t ½ = 0.693
K

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 K = 0.693 = 0.693 (years)-1
t½27

And from 2.303log(100/100-90) = Kt

2.303log10 = 0.693 /27 t
And t = 27x2.303/0.693
= 89.7 years.

2. If the activity of 23490Th is reduced to 25% in 48 days. What is the half life of 23490Th.
Solution:

From 2.303log100/25 = 48K

K=2.303log104
48
But t ½= 0.693
K

= 0.693 X 48
2.303log104
= 23.99days
= 24 days

Self check:
1. The half life of bismuth is 19.7 minutes. Determine the time taken for 43% by mass of bismuthto
decay.
2. (a)Describe the expression for half life for a first order reaction 2.303log (a0) Kt where ao is the
a0-x
initial concentration of the reactant and (a0-x) is the concentration at time t.
b) the half life of a first order reaction is 100s.
i) calculate the rate constant
ii)Determine the percentage of the reactant that reacted after 250s.

(Ans b(i) 6.93 x10-3 S-1 (ii) 82.3%)

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 3. A sample of a radio active element contains 10,000 atoms if the half life of this element is 1.2
minutes , find the number of atoms left after 4.8 minutes (Ans = 625.7)

The structure of the atom and Ruttherfold’s scattering experiment.

When heavy alpha particles were directed at a thin piece of gold foil as shown below.

Observation:
Most of them travel in straight lines (passed straight through the foil) and very few were deflected.

Deduction / explanation
The atom is mostly an empty space with a minute central core that is positively charged.

Hydrogen spectrum or atomic spectrum.

When hydrogen in an enclosed glass tube at low pressure is heated by an electric discharge. The
molecules splint into atoms which absorb energy.
The excited atom then emit a radiation. If the radiation is passed through shits and a prism an emission
spectrum consisting of several lines is obtained.

Information that can be obtained from the hydrogen spectrum:

 There are several lines and therefore many energy levels in an atom.

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 The spaces separating the lines decrease with increases in frequency.
 The lines are at a definite frequency
 The lines converge into a continum.

Interpretation of the hydrogen spectrum:

 There are several energy levels in an atom and when an electron returns to the lowest energy level, a
radiation is emitted and ΔE= hv where ΔE is energy change, h = 6.22x10-34 Js-1 is plack’s constant v
= frequency.
 Energy emitted or absorbed by an electron is in whole number package called quanta.
 The continum corresponds to complete removal of an electron from the atom (ionization)
 Each element has a characteristic spectrum.

Let us revise
1 a) Describe the spectrum of hydrogen
c) Explain how the spectrum of a hydrogen atom
i) Is formed
ii) Provides evidence for existence of energy levels.
d) Frequency of hydrogen at a point of ionization is 32.8x1014HZ. Calculate the ionization
energy (plank’s constant = 6.6x10-34 s-1

Solution:
a) It has series each made of groups of lines. It has both visible and invisible parts. In each series the
spacing between adjacent lines decreases and converge into a continuum. That is

b) i) Absorption spectrum is formed when light is shone through hydrogen atoms in an enclosed
glass tube at low pressure. Electrons jump from ground state to higher energy levels after

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 absorbing energy of definite amount forming an absorption spectrum recorded on a photographic
paper.
c)
(ii) there are series of lines. That is the layman, Balmer, Paschen, Bracket and P- fund series
which indicate that electrons fall on different energy levels.
 Hydrogen has one electron yet it produces a spectrum containing many lines, separated
from one another indicating that there is sub energy level in an energy level.
 The spacing between adjuscent lines in each series differs indicating movement of
electrons from different energy levels.
 There is a continuum in each series of lines, which shows movement of electrons with
different frequencies.
 The lines have different wave length.

C) using
ΔE = hv
= 6.6x10-34 x 32.8x1014
= 2.1648x10-18 joules / atom

Self check
1. Calculate the energy required to ionize 1mole of hydrogen atoms given that the frequency of the
convergence limit of the lines of atomic hydrogen is 3.28x1015Hz. Avayodro’s constant is
6.02x1023 mol-1 and Plank’s constant h= 6.62x110-34Js
(Ans 130.72x104Jmol-1)

2. When alpha particles are directed at a thin gold foil most of them passed through undeflected.
Explain the observation.

Quantum Numbers:
The energy of an electron in an atom can be described completely by stating four quantum numbers.

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 1. The principal quantum number denoted n, 12, -,-,- represents the energy and size of the energy
level.
2. The subsidiary quantum number denoteded (represented by S,P,d,f
3. The magnetic quantum number
4. The spin quantum number.

Rules on electron filling in orbitals, denotes

1. Each orbital may hold up to two election. And no two electrons in one atom can have all four
quantum numbers thatare the same.(Pauli’s exclusion principle). Therefore the number of
electrons possible in each energy level (shell) is 2n2

Shell number Maximum number of electrons accommodated

1 1S2 = 2
2 2522P6 = 8
3 3523P63d 10 = 18
4 4524P64d104f14 =32

2. Electrons enter the lowest energy level available (Aulban principle)

3. Orbitals of same energy are occupied singhly before paring occurs (Hand;s rule). Therefore the
relative order of energy levels can be generated as follows:-

That is, 1s2s2p3s3p4s3d4p5s

Example

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11Na = 2:8:1 1S22S22P63s1
19K = 2:8:9 1S22S22P63s23P64s1
Note: the O-Level approach is now omitted

Check:
18 Ar = Is22s22p63s23p6 it is full (stable)
Then 19K = Is22s22p63s23p64s1
= [Ar]4s1
21 Sc = Is22s22p63s23p63d14s2
= [Ar]3d1452

Self check:
Write the electronic configuration of the following elements:
a) Manganese
b) Nickel
c) Zinc
d) Strontium
e) Tin
f) Iron
Special features relating to electronic configuration:
1. Elements in the same group have similar outer most electronic configuration example.
Group I has ns1 valency + 1
Group II has ns2 valency +2
Group IV has ns2np2 valency +2 and +4
2 5
Group VII has ns np valency -1,0,+1,+2,+3, +4, +5, +6, +7

Also, the outermost electronic configuration shows the block to which the element belongs.
The first series of transition elements are an example because (n-1)d and ns electrons are involved in
bonding.
Example 22Ti Is22s22p63s23p63d24s2
So Ti can show a valency of +2, +3, and +4

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Self check:
1.State the valencies of the following elements that can be used in bonding
a) Iron
b) Copper
c) Chromium
d) Manganese
e) Cobalt
f) Nickel

2. Chronium and copper

The two have a unique electronic structure because of half filled and fully filled sub shells
respectively are favoured in their formation.
There fore Cr is 3d5451 and not 3d4452X
And Cu is 3d10451 and not 3d9452X
2.The atomic number of element A IS 33.
i) Write the electronic configuration of A.
ii) Write the formula of oxide of A.

Physical properties of elements and compounds:

a) Atomic radius
b) Ionization energy
c) Electron affinity and electronegativity
d) Melting and boiling points
e) Electrical conductivity
f) Structure and bonding

The first three properties (a) to (c) are known as atomic properties because a single atom is involved and
these properties are related to the rest of the properties (d) to (f) which take place in bulk.
Ionization energy ΔHoIE:
Is the enthalpy required to remove one mole of electrons from one mole of gaseous atoms or ions at 25oc
and one atmosphere to form gaseous ions.

Example Mg(g) Mg+(g) +e ΔHoIE__________1

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 Mg+(g) Mg2+(g) +e ΔHoIE __________2

Equation (1) shows the first ionization energy of magnesium and equation 2) the second ionization
energy of Magnesium.

First ionization Energy:

Is the energy required to remove one mole of electron from one mole of gaseous atoms at 25oc and one
atmosphere to form gaseous ions.
Example Na(g) Na+(g) +e

Successive ionization energy

Is the removal of all electrons from a gaseous atom to form a gaseous ion at standard conditions.
Example: sodium 11Na has 11 electrons,Therefore the successive ionization energy of sodium is when all
the 11 electrons have been removed.
NOTE:
The pattern of the values to the principal energy levels should be related to:-
i) The period and group the element belongs in the periodic table
ii) The valency or oxidation number of the atom.

a) Trend in first ionization energy across a period:

i) Elements of the third short period of the periodic table.

Element Na Mg Al Si P S Cl Ar

1st J.E (KJmol-1) 500 730 590 860 1260 1000 1260 1330

Explanation:
There is a general increase in ionization energy from Na to Ar with two unexpected decrease at
aluminium and sulphur.

Across the period 3, the nuclear charge increases as atomic radius decreases, this is because each
successive electron added enters an already existingshell and such electrons shield each after poorly from
the increasing effective nuclear change, there fore atomic radius decreases.

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 The increase at Magnesium and phosphorous is because of the electronic configuration 12Mg is
Is 2s 2p63s2 has a full 352 sub shell while 15P is 1s22s22p63s13p3 has exactly a half filled 3p sub shell.
2 2

These require more energy to remove one electron because of their special stability. The unexpected
decrease of aluminium and sulphur are due to their electronic structure with 3p sub shell which is under
half filled13Al22522P63523P1, 16S1522522P63523P4 and requires less energy to be disrupted.
ii) Trend in first ionization energy across the first series of d- block elements.

Element Sc T V Cr Mn Fe Co Ni Cr Zn
1st I.E(KJmol-1) 630 661 648 653 716 762 513 736 715 90

Explanation:
1st I.E increases as nuclear charge increases from Sc to Zn. This is because effective nuclear attraction
increases only slightly. This is because the electrons added to each successive element enter an inner 3d
sub shell and screening effect also increases, but shielding effect is not feasible especially when the d-
shell is completely filled. As a result there is a small increase in the atomic radius for copper atom and a
larger one for Zinc.

b) Trend in first ionization energy down a group:

Group II Be Mg Ca Sr Ba

1st J.E (KJmol-1) 900 76 590 548 502

Group VII F C1 Br I

1stI.E (KJmol-1) 1680 1260 1140 1010

Explanation:
First ionization energy decreases down the group. This is because both nuclear charge and shielding
effect increases but increase in shielding effect over takes the increase in nuclear attraction due to anextra
shell added, as a result atomic radius increases and ionization energy reduces.

NOTE: Effective nuclear charge is the net positive charge which the outer most electron feels through
attraction.

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NOTE: The first ionization energy is less than the second and the second is less than the third and so on.
This is because there is a number of protons in the nucleaus therefore nucleaus has a constant charge.
Nuclear attraction on the remaining electron therefore increases as some electrons are removed.

Let us revise
1. The diagram below shows successive ionization energies for an element X, showing removal of
all electrons.

a) Giving reasons state

i) The group of element X
Group 2 because contains two electrons in the outer most shell i.e two electrons were
removed from the outer most shell.
ii) The period of element X
Period 3, because the outermost electrons in quantum shell is three:
iii) Identify element X
Magnesium because it has 12 successive ionization energy
b) Explain the sudden increase in the energy required to remove electron E
Electrons are being removed from a new shell which is closer to the nuclear (inner shell)
c) Explain how the size of X will change as electrons are removed.
The size decreases because the nuclear change remains the same and the remaining electrons
are strongly attracted to the nucleous and are drown closer.
d) i) Explain what would be the sign of energy change if an electron was added to X to give X-.
Negative

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 iii) How would you expect it to affect the size of X?
The size would increase because the attraction by the nucleus on each electron is reduced.
e) Explain giving reasons whether you would predict X to form compounds in the +1 Oxidation
state.
It will not form compounds of oxidation state (+1) because they would be unstable.

Factors affecting ionization energy:

1. Atomic radius or ionic radius
The smaller the atom, the higher the charge density and the more strongly the electrons are
attracted by the nucleus increasing the ionization energy.
2. Type of election configuration
Full and exactly half – filled are more stable than the underfull and therefore require more
ionization energy to remove an electron.

Let us revise
The graph below shows the variation of first ionization energy with the atomic number across period 3
elements in the periodic Table.

Explain why
i) The first ionization energy increases over all, across the period
Across the period, there is a decrease in atomic radius and increase in nuclear charge. Both factors
hence increases on attraction for the outer most electron.

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 ii) The first ionization energy of aluminium is less than that of magnesium.
2
13 Al2s 2p 3s23p1,12Mg Is22s22p63s2
6

Magnesium has a full 35-subshell which is stable therefore a lot of energy is required to remove an
electron.
Aluminium has one electron in the 3P sub shell which is unstable hence little energy is required to an
electron.
iii) The first ionization energy of sulphur is less than that of phosphorus
2
15PIs 2s 2p63s23p3, 16S1s22s22p63s23p4
2

Phosphoros has half filled 3P sub shell therefore it is stable sulphur has four electrons in the 3P sub shell
therefore it is unstable.
iv) The first ionization energy of magnesium is very high.
12 Mg 1s22s22p63s2This is because the 3s sub shell is full and therefore stable.
3. Screening or shielding effect
The repulsion between the outer most electrons by the inner electrons results into an increase in
atomic radius, and therefore decreases ionization energy.
The penetrating power of valency electrons in a given shell, n, decreases in the order S>P>d>f.
NOTE: Screening / shielding effect is the reduced attraction by the protons for the outer most electrons,
caused by the core electrons.
Let us revise
The table below show the ionization energies inKjmol-I of five elements lettered A,B,C,
D and E.
Element 1st I.E 2nd I.E 3rd I.E 4th I.E
A 500 4600 6900 9500
B 740 1500 7700 10500
C 630 1600 3000 4800
D 900 1800 14800 21000
E 580 1800 2700 11600

a) Which one of these elements is most likely to form an ion with a charge of +1? Give a reason for
your answer.
A, The difference between the first and second ionization energies is very high compared to the
difference between the second and third ionization energies.

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NOTE: take all the differences between 1st and 2nd, 2nd and 3rd and between 3rd and 4th then compare,
very high difference indicates change of energy levels.
b) State i) two elements which belong to the same group in the periodic table
B and D (note)
i) The group to which the element you have stated in b(i) belong
Group (II)
c) i) Write the formula of the chloride of element E
EC13
ii) write equation for the reactions between the chloride of element E and water
EC13(s) + 3H2O(l) E(OH)3(aq) + 3HC1(aq)
Self check:
1. The first four ionization energies of some elements are shown in the table below.

Element Ionization energies

1st 2nd 3rd 4th

A 500 4600 6900 9500

B 740 1500 7700 10500

C 630 1600 3000 4800

D 900 1800 14800 2100

E 580 1800 2700 11600

1) State the element that is most likely to form an ion with a unit positive change. Give a reason for your
answer.

2) a) Write the electronic configuration for the following species Mg, Mg+, Mg2+, Mg3+
b) Which species will have the highest ionization energy and why?

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Atomic and ionic radius for cations and anions
Atomic radius: is half the distance between the nuclei of any two closet atoms in a substance.

a) Cations have smaller radii than the corresponding atoms

Example Na+ 0.018nm Na 0.157nm
This is because, the nuclear charge out weighs the electronic charge and the remaining electrons
arte more strongly attracted to the nucleus.

b) Anions have a larger radii than their atoms

This is because the number of electrons exceed the number of protons, and nuclear attraction
decreases on the electrons.

Trend of atomic radii of elements down the group:

ExampleGroup (II) in the periodic table

Element Be Mg Ca Sr Ba
Atomic radius (nm) 0.112 0.160 0.197 0.215 0.221

Atomic radius increases down the group

Explanation:
Down the group, nuclear charge increases as protons are added to the nuclear. The screening effect /
shielding effect also increases due to extra shell of electrons added, increase in screening effect out
weighs increase in nuclear charge, therefore the effective nuclear charge decreases hence attraction for
the outer most electrons by the nucleus decreases resulting into increase in atomic radius.

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Trend of atomic radius of elements in a period
Example: Period 3
Element Na Mg A1 Si P S C1 Ar
Atomic radius(nm) 0.154 0.145 0.130 0.118 0.110 0.102 0.099 0.190

Explanation:
Across the same period, outer electrons are filled into the same shells. Therefore an increase in effective
nuclear charge increases attraction for the outer most electrons henceout weighing the screening effect
caused by the same core electrons. Therefore as the atomic number increases the atomic radii decreases
in the same period.

Let us revise
The ionic radii of Na+, Mg2+ and A13+are given in the table below
Ion Na+ Mg2+ A13+
Ionic radius /nm 0.095 0.065 0.050

a) Briefly explain the variation in trend of ionic radii of the ions.

Solution:
As the atomic number increases, the greater the number of electrons lost from an atom, the less are the
number of outer electrons to be attracted by the same number of protons, The outer most electrons are
more strongly attracted and therefore, pulled nearer to the nucleus. This results in a smaller ionic radius.
b) Calculate the charge / radius ratio for
i) Na+
Charge ratio / radius = +1
0.095
= 10.526nm-1
ii) Mg2+
Charge / radius ratio = +2

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 0.065
= 30.770nm-1
iii) A13+
Charge / radius ratio = +3
0.050
= 60.0nm-1
Self check:
1. The atomic numbers and the atomic radii of some transition metals are given in the table below.
Element Si Ti V Cr Mn Fe Co Ni Cu Zn
Atomic 21 22 23 24 25 26 27 28 29 30
number
Atomic 1.44 1.32 1.22 1.17 1.17 1.16 1.66 1.15 1.17 1.25
radii(A0)

i) Plot a graph of atomic number versus atomic radii

ii) Explain the shape of your graph
2. The respective atomic sizes of
a) The sodium atom (Na) and the sodium ion (Na+) are 0.154 and 0.095nm.
b) The chlorine atom (C1) and the chloride ion (C1-) are 0.099 and 0.181nm.
Give reasons for the differences in the sizes of the atoms and ions in each case.
c) Explain why the ratio of radii Fe2+ is greater than 1.
Fe3+
Electronegativity / electropostivity
ElectronegativityIs the ability of an atom to attract electrons to itself when it is in a molecule.
Electronegativity is not an energy term and can not be measured directly.
An atom of a molecule which tends to attract more electrons to itself is described as a more
electronegative atom.

 NOTE: The main factor that influences the value of electronegativity is the atomic radius of the
atom. Usually the smaller the atomic radius the higher the electronegativity. Other factors
includes, shielding effect, electronic configuration and charge on the atom.
 Electronegativitiy has no units.
Trends of electronegativity across a period

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Example Period 2

Element Li Be B C N O F Ne
Electronegativity 1.0 1.5 2.0 2.5 3.0 3.5 4.0 0

Electronegativity across a period increases

Explanation:
Across a period the atomic radius decreases, as the atomic number increases, the effective nuclear charge
increases. When atoms are bonded to other atoms, their nuclei are nearer the electrons to attract them.
Thus with a smaller atomic radius the attraction is greater giving the atom a higher electronegativity.

Trends of electronegativity down the group:

Example Group I
Element H Li Na
Electronegativity 2.1 1.0 0.9

Electronegativity decreases down the group

Explanation:
Down the group protons are added to the nucleus as an extra shell of electrons is also added there by
increasing the atomic radius and the ability to attract bonded electrons is reduced. Electronegativity
therefore decreases down the same group.

Check:
In water, oxygen has a higher electronegativity than hydrogen although it has a larger atomic radius.
Therefore it pulls the electrons in the bond nearer to itself.

NOTE: In simple molecules the atom with a higher electronegativity has a negative oxidation state, and
the less electronegative, a positive oxidation state. Example in carbondioxide Co2, Oxygen is more
electronegative than carbon so oxygen has -2 and carbon +4.
Self check:
1. Predict, with reasons, whether a magnesium atom (Mg) will have a smaller elctronegativity than a
sodium atom (Na).
Electron affinity

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Is the energy lost or gained when one mole of the gaseous atoms add on one mole of electrons to form
one mole of singly charged anion at 250C and 1 atmosphere.

Example; C1 (g) + e C1-(g)

It is measured in units of KJmol-1.
Atoms add on electrons to achieve the stable inert gas configuration. The more negative the electron
affinity the more stable the anion formed. Generally, non-metals have a high negativeelectron affinity
whilst metals have positiveor low negative electron affinity. This indicates that metals can add electrons
to their outer shell only with difficulty.
Normally anions of metals are not formed.

Factors that influences electron affinity:

 Atomic radius
 Stability of electronic configuration
 Charge carried by the anion.
Trends of electron affinity down the group:
Example Group VII
Element F C1 Br I
First electron -333 -348 -325 -297
affinities

Generally electron affinity decreases down the group.

Explanation:
Down a group, atomic radius increases and electron affinity decreases. This is because less energy is
released when an electron is added.

The unexpected lower negative electron affinity of fluorine is caused by its very small size. The very
small size creates a very strong repulsive field for any incoming electron.
The electron has to be forced into the outer shell of the atom against this strong repulsive force. The
energy used for this reduces the energy released when the electron is added to an atom. The extent of
reduction is far greater than for anyof the other group VII elements. The net effect is that it reduces the
energy released to be lower, negative figure of -333KJMol-1 compared with the nearest atom chlorine
with -348KJMo-1.

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Trends of electron affinity across a period
Example: Period 2

Element Li Be B C N O F Ne
Electron affinity -57 +68 -15 -123 -31 -141 -333 +99

Generally electron affinity increases across a period.

Explanation:
Electron affinity increases because effective nuclear charge increases and attraction for the added
electron increases. More energy is released.

The unexpected lower negative electron affinity of Boronand nitrogen values are due to the less stability
of the electronic configurations of Boron and Nitrogen that is,
5B 1s22s22p1 , 7N1s22s22p3
Boron has the other 2P1 which is under half filled and less stable and therefore less energy is released
when an electron is added compared to Nitrogen with 2p which is half filled.

Then unexpected high positive electron affinity of Benglium Neon values are due to more stable electron
configurations of Beryllium and Neon which are fully filled and therefore more energy is released when
an electron is added compared to other elements in the period. That is,
4Be 1s22s2 , 2 2
10 Ne1s 2s 2p
6

NOTE:The first electron affinity formost elements has a negative sign (for electronegative sets) and
therefore it is an exothermic change. This is because more energy is given out than the energy needed to
force an electron to the nucleus of atom.
The second electron affinity has a positive sign and therefore an endothermic change. This is because the
energy used to force an electron to a gaseous ion is more than the energy realized when the nucleus
attracts the electron.

Let us revise
1. The first electron affinities of group III elements are given below:

25
Element 1st I.E (KJMol-1)
F -328
C1 -349
Br -325
I -295

a) state how the first electron affinities of the elements generally vary.
The first electron affinity decrease down the group as the atomic radius increases because less energy is
released when an electron is added.

b) Explain why the first electron affinities of the elements have negative signs.
Because the energy required to force an electron to the atom is smaller than that given out when an
electron is attracted by the atom.
d) Give a reason (s) for the abnormally low value of electron affinity of fluorine.

Because it has a very small size and has a very high charge density.
2. The table below shows the atomic numbers of some elements and their electron affinities.
Atom number 11 12 13 14 15 16 17

Electron affinity9KJMol-1 2.0 -6.7 -3.0 13.5 6.0 20.0 36.4

a) Draw a graph of electron affinity versus atomic number

b) Explain the shape of the graph
Solution:
a) Good student (draw a graph)
b) Explanation:
There is general increase in electron affinity with increase in atomic number. The electron affinities of
elements with atomic numbers 12 and 15 are lower than expected due to their electronic configuration.
That is, element with atomic number 12, electronic configuration 1S22522P6 352hasa full sub energy level
while element with atomic number 15, electronic configuration 1S22522P6 3523P3 has a half filled sub
energy level, thus the two elements therefore resist the addition of an electron hence less energy is
released.

26
Self check: Explain the difference between electronegativity and electronaffinity.

1. The first ionization energies and first electron affinities of group VII elements are given in the
table below.
Element First Ionisation energy (KJmol-1) first electron affinity (KJmol-1)
Fluorine 1681 -328
Chlorine 1250 -349
Bromine 1139 -325
Iodine 1007 -295

a) State how the first electron affinities of the elements generally vary with their first ionization
energies.
b) Explain why the first electron affinities of these elements have negative signs.
Other physical properties:
 Melting point and boiling point
 Solubility in water
 Structure and bonding
 Electrical conductivity

These properties unlike the previous ones (ionization energy, atomic radius, electronegativity,
electroproductivity and electro affinity) do take place in bulk of atoms.
The first two factors can be explained in terms of structure and bonding.

Structure and bonding:

27
BONDING:
Atoms react or combined with one another by either losing, gaining or sharing of pair of electrons to
attain an inert gas structure. Only electrons in the valency energy level are involved in bonding.

TYPES OF BONDING:
1. Ionic bonding or electrovalent bond:
Formed by complete transfer of electron(s) from one atom to another giving rise to positively charged
ions that are held together by electrostatic attraction.
Its formed between atoms of very different electronegativity values. That is, between a metal and a non –
metal.
Example:Ionic bonding in sodium chloride.
\

Other examples
 Magnesium oxide.
 Calcium oxide.
 Calcium chloride.
 Magnesium chloride.

NOTE: They have high lattice energy

Properties:
 They are normally hard solids
 They have high melting and boiling points due to strong electrostatic attraction.
 They are very soluble in polar solvents like water because water molecules are able to bond with
both the positive and negative ions which breaks up the lattice and keeps the ions apart.
 They cannot conduct electricity when solid because the ions are not free to move but they
conduct in molten state or in aqueous solution .

2. Covalent Bonding
Formed by sharing a pair of electrons in a molecular orbital where each atom donates an electron

28
to form a molecule.

Formed between atoms with similar electronegativities hence the shared pair of electrons in the bond is
almost evenly distributed between the two atoms.
Other examples
 Methane.
 Water molecule.
 Carbon dioxide.
 Silcon (IV) oxide.

Properties:
 They are mainly gases, liquids and some times soft solids.
 They have low melting and boiling points because of the weak covalent bonds.
 They consist of individual molecules held together by weak vanderwaals forces.
 They are less soluble in polar solvents but more soluble in non polar solvents.
 They don’t conduct electricity due to absence of free ions.

Classification of structures containing covalent bonds in compounds

a) Simple molecular structures, are simple , they have strong covalent bonds between the
atomswithin a molecule (intramolecular bonds) but have bonds between the molecules
(intermolecular bonds).
Example : Iodine , Methane ,Water , and ethanol.
b) Giant molecular structures ,Contain many hundreds of thousands of atoms joined by strong
covalent bonds.
Examples , Diamond,Graphite,Silcon (IV)oxide ,plastics(polymers such as polythene) etc.
NOTE: In some cases individual covalent bonds of a compound may be polar but overall the compound
is non-polar example carbondioxide CO2and carbon tetrachloride CC14.

29
Explanation:
In CC14, each carbon-chloride bond is polar but because of symmetrical distribution of chlorine atoms
about the carbon atom, there is equal and opposite dipolemoment in all directions so that they cancel and
hence over all CC14 is non polar.
Therefore covanant bond is directional.

Self check.
Boron trichloride BCl3 is a non polar molecule whereas nitrogen trichloride NCl3 is polar.

3. Co-ordinate or dative bond

Formed by sharing a pair of electrons between two atoms where by any one of the bonding atoms donates
the two electrons to be shared. This is possible only if the donor atom has a lone pair of electron and the
recipient has an empty outer orbital. This bonding is shown by an arrow from the donor to the recipient
or by partial charges example in the formation of H3O+ ions, NH4+ ions and other complexes.
That is,

4. Hydrogen bond
This is a permanent dipole-dipole attraction between a hydrogen atom bonded to an electronegative atom
and to a second electronegative atom with a lone pair of electrons.
Hydrogen bonding occurs in alcohols,
R-O-H-….O-R
H
Water H-O----H----O----
H H
This bonding may occur as intermolecular hydrogen bonding when it is formed between two or more
molecules.

30
Example in water, in 4- nitrophenol.
That is

Or as intramolecular hydrogen bonding which occurs with in the same molecule in some compounds
Example in 2 – nintrophenol, in 2- hydroxyl benzoic acid.
That is

Conditions for hydrogen bonding:

 The hydrogen atom must be attracted to a highly electronegative atom which can withdraw the
bonding electrons towards itself, in order for partial charges to be formed that can lead to some
kind of a weak electrostatic attraction.
 The electronegative atom must have alone pair of electrons.

Effects of hydrogen bonding on properties of compounds

Hydrogen bonding only affects the physical properties.
a) Increased boiling and melting point:
b) Hydrogen bonded molecules like NH3, H2O, HF, alcohols, -COOH, amines have abnormally
higher melting and boiling points because extra energy is first needed to break the hydrogen
bonds before individual molecules can vapourise.

Other effects includes:- b) association of molecules

c) Increased viscosity which reduces the volativity and vapour pressure .
d) increased solubility in water

31
 e) Increased volume and decreased density of ice. In the ice crystal each water molecule is bonded
to 4 other water molecules through hydrogen bonds. This gives ice an open structure with a larger
volume but decreases the density of ice so that it floats on water.
5. Vanderwaals forces
These are intermolecular forces which result from
a) An attraction between permanent dipoles in one polar molecule and another permanent dipole in
the other polar molecule.
b) An attraction between a permanent dipole and an induced dipole. This occurs when molecules
with a permanent dipole are brought near a non –polar molecule.
Effects of vanderwaals forces:
1. Responsible for the non-ideal of real gases.
2. Responsible for the spaces between parallel layers and the sliding of these layers of graphite since
it is a fairly weak force.
3. It increases the strength of non-polar polymers like polythene and polypropene.
4. It leads to increase in boiling points of alkanes with increasing molecular masses along the series.

STRUCTURE OF SOLIDS
Summary of the common type of structure and type of bonds adopted by elements and some
compounds.
Type of structure Type of bond example Melting point
Giant metallic Attraction between nucleus and Na, Mg, Al Moderate
valency electrons (metallic bond)
Simple molecular - Convalent bond between atoms Co2, PH3, NO2 Lower
- Vanderwaals forces between I2, HC1, HBr Lower
molecules
- Hydrogen bonds between NH3, H2O, HF, CH3 Lower
molecules CH2OH, 4 - nitrophenol

Giant ionic Electrostatic attraction between ions NaC1, Cuso4, A2O3, High
of opposite charge (ionic bond) A1C13, Compounds
only
Giant covalent Covalent bond between atoms. SiO2& C, Si compounds Very high

32
1. Giant metallic structure:
Each nucleus that is positively charged is (surrounded) attracted by the delocolised valency electrons
hence metallic bond.
That is,

Factors affecting metallic bonds:

There are two factors
a) Number of valency electrons
The more the number of valency electrons, the more attraction between the nucleus and valency
electrons and the stronger the metallic bond formed.
b) Atomic radius;
The smaller the atomic radius, the more attraction between the nucleus and valency electrons and the
stronger the metallic bond.
2. Giant ionic lattice
This consists of a regular arrangement of positive and negative ions held together by strong
electrostatic attractions which are arranged repeatedly in a 3- dimensional lattice.
Example NaC1, where each Na+ is surrounded by 6 equidistant C1- and so is C1- surrounded by 6
equidistant Na+ making a co-ordination number in NaC1 structure to be 6.

33
 Example
Group I halides, however CsC1 structure, the co-ordination number is eight because Cs+ ion is larger
in size than Na+ there can accommodate more C1- ions a unit cell than Na+.

3. Giant atomic (covalent ) lattice

In this structure, the solid is made of atoms that are covalently bonded together.
a) Graphite
It is hexagonal shaped with layers which are held together by weak vanderwaal’s forces and as a
result it is soft and slippery.

The carbon atom in graphite show a valency of 3 and not 4. The forth electron is delocalized and this
explains why graphite is a conductor of electricity in solid state.

b) Diamond
The atoms are in tetrahedral structure and each atom shows a valency of 4, as a result, diamond is the
hardest natural substance known.

34
Other examples are silcon (IV) oxide
4. Molecular structure
In this structure individual molecules are held together by weak vanderwaals forces. However, with in
each molecule the atoms are held together by the fairly strong cavalent bonds. The weak vanderwaals
forces render these covalent molecules to be gases, liquids or just soft solids with low melting points.

Example iodine I2, carbondioxide CO2,

That is I2, I--I-------I--I
I ----- I

Self-check (A).
1 a)Ice has a lower density than than that of water .Explain the characteristics.
(b) Name the type of crystal lattice formed by the following subtances.
i. Iodine
ii. Caesium chloride
iii. Silcon dioxide.
c) Arrange the substances given in (b) in order of increasing melting point.
d) Explain how the bonding in each of the compounds in (b) affect their melting points.

2.Complete the table below about the properties of different types of crystals.

Type of Force holding Melting point,state whether Form in which

crystal the crystal low,moderate, high or very high. electricity is conductrd if
any
Metallic
Ionic
Network
covalent
3.Complete the table below
Element Formula of oxide Oxidation of the Type of bonding Structure of the
element in the oxide in the oxide oxide
Aluminium

35
Silcon

Phosphorus

Magnesium

Chlorine

4.Repeat question 3 above using formular of hydrides.

Shapes of molecules
The shape of a molecule is related to the number of electron pair in the outer most shell of the central
atom.
The electron pairs repel each other so that they are as far apart as possible in order to give a molecule a
very stable shape. This repulsion applies to both the bonded pairs of electrons and the lone pairs of
electrons.

Steps taken:
a) Identify the central atom or ion (more electronegative atom)
b) Write the outer most electronic configuration of central atom.
c) Work out number of bondpairs and lone pairs on central atom or molecule.
d) Use the valency electron repulsion rule where electrons and lone pairs repel each other such that
Lone pair /lone pair repulsion > lone pair / bond pair repulsion > bond pair / bond pair repulsion.

Examples:
1. Linear shaped molecules:
Adopted by molecules without lone pairs of electrons on a central atom. Occurs when the bonding
electron pairs repel each other to attain a maximum bond angle of 1800,
Normally there are two bonding pairs of electrons

Example

36
BeCl2

That is C1 ----Be----C1
- Carbondioxide
- Hydrogen cylinede etc

2. Trigonal planar
Adopted by molecules with 3 bonded pairs of electrons but without alone pair on a central atom.
The 3 bonding pairs of electrons repel one another and attain a stable shape with a bond angle of 1200

Example – Boron trichloride BC13

5B 2s22p1
2s 2p
unexcited state

Excited state

3 bond pairs
0 lone pair
Then

37
  NO3-
7N 2s22p3
2s 2P

unexcited state

unexcited state
Note negative – gain of electron
3 bonded pairs and 0 lone pairs
Then

Other examples
 Boron fluoride
 Aluminium chloride
 SO3
 CO32-
 CHOOH

3. Bent (v) shaped molecules:

This may be adopted by molecules with one or two lone pair and two bonding pairs of electrons

38
Example water H2O
Central atom oxygen
8O 2s22p4
25 2P
unexcited state
excited state

2 bond pairs
2 lone pairs
Then

Other examples –SO2

- SnC12
- H2S
- C12O
- C1O2-
4. Pyramidal shape
This can be described as tetrahedral. It is adopted by molecules with one lone pair and 3 bonding pairs
Example
NH3
7N 2s22p3
2s 2p

unexcited state
excited state

One lone pair

3 bonding pairs

Then

39
Other examples: H3O+
8O 2s22p4
2s 2p
unexcited state

excited state

One lone pair

3 bonding pairs
Then

Others are - SO32-

- PH3

5. Tetrahedral shape

40
Adopted by molecules with 4 bonding pairs of electrons without any lone pair example
SO42-
16 S 3s23p4
3s 3p

Unexcited state

excited state
One lone pair
3 bonding pairs

Then

Other examples –NH4+

- CH4
- PO43-
- SiC14
- C1O4-

6. Trigonal Bi- Pyramidal shape

Adopted by molecules with 5 bonding pairs of electrons or 4 bonding pairs with alone pair of electrons

Example

41
PC15

SF4

IC12-

Effect of electronegativity of the central atom on bond angle:

The bond angle in the hydrides of group V is in order NH3 > PH3 > A5H3
The decrease in bond angle is due to the decreasing electro negativity of the central atom the more
electronegative the central atom is the nearer the bonding electrons are to it, this increases the
concentration of electrons around the central atom and hence increased repulsion.

Self check

42
 1. Sketch the shape of the following molecules and explain why each shape adopts the shape you
have sketched.
a) NH3
b) BF3
c) H2S
2. The bond angle in water molecule is 1040 whereas that one in a molecule of ammonia is 1070.
Explain.
Trends in structure and types of bonds of elements, chlorides and hydrides in group I, II, VII,
periods and first series of transition elements of the periodic Table.
Periodic table
1. Group I Li Na K Rb Cs

Type of structure Giant metallic

Type of bond metallic
Atomic radius increases
Melting points(oc) 180 90 64 39 29

Group I Be Mg Ca Sr Ba
Type of structure Giant metallic
Type of bond metallic
Atomic radius increases
Melting points(oc) 1280 650 850 770 700

Generally melting point decreases down the group of S – block , that is group I and group II,

Explanation:

43
Melting point decreases down group I and II

This is because, the element exist as a giant metallic structure with metallic bond between atoms. The
strength of metallic bond decreases with increase in atomic radius due to an extra shell added.

Group II members have a higher melting point and are harder than their corresponding group (I)
elements, because of
a) They have a smaller atomic radius
b) Have two valency electrons per atom for attraction , with the nucleus lattice for group(I) it has
only one electron for valency. The larger the number of valency electrons the stronger the metallic
bond.
NOTE: Melting point of group (II) are not decreasing smoothly as that of group (I) hence Mg shows
abnormally low melting point.

2. Group (VII) F C1 Br I
Type of structure Simple molecular
Type of bond weak vanedrwaals forces
Boiling points(oc) -188 -34 58 185

The boiling point increases down group (VII)

Explanation:
This is because the elements exists as simple diatomic molecules with weak vander waals forces
between molecules. The strength of vander waals forces increases with increases in molecular mass
down the group.
3. Elements of third short periods

Elements Na Mg Al Si P S C1
Atomic number 11 12 13 14 15 16 17
Melting point(oc) 98 650 660 1410 44 120 -200

Melting point generally increases

44
Explanation:
From Na to Al the elements exists as giant metallic structures with the strength of metallic bond
increasing with
a) Decreasing atomic radius from sodium to aliminium
b) Increase in number of valency electrons from 1 to 3 respectively.

Si exists as a giant atomic structure with many covalent bonds in a tetrahedral shape holding the atoms
together therefore plenty of heat at a high temperature is need to break the covalent bonds.

From phosphorous to chlorine, the elements exists as simple molecules with weak vander waals forces,
the strength of vander waals forces increases with increase in molecular mass.
That is, phosphorous exists as P4 with the structure below while sulphur exists as S8 with the structure
below.

And chlorine exists as a diatomic molecule C12 with simple molecular structure.

4. The first series of transition elements.

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic number 21 22 23 24 25 26 27 28 29 30
Atomic radii 0.144 0.132 0.122 0.117 0.117 0.116 0.116 0.115 0.117 0.125

Melting point (oc) 1600 1680 1917 1890 1247 1535 1490 1452 1083 420

Transition metals have higher melting point than the non transition metals of the same period four, that is
K, Ca, Sc, Ti, and Zn.

Explanation:

45
All period four elements are metals that exist as giant metallic structures with metallic bonds holding
their atoms together but K and Ca have 1 and 2 valency electrons respectively used in the metallic bond
while transition elements have their 3d and 4s electrons used in metallic bond. Also atomic radius
decreases from Ka to Cu therefore as a result metallic bond strength increases with number of valency
electrons and decreases in atomic radius.

NOTE: The melting point of Zn is lower than expected because of the increase in screening effect as the
3d sub shell gets filled and therefore there is an increase in atomic radius of Zn.
Physical properties of some of the compounds of elements in periodic table:
a) Chlorides of third short periods

Formula of compound NaC1 Mg AlC13 SiC14 PC15/PC13

Type of structure Giant ionic simple molecular
Type of bond ionic Predominantly covalent covalent
Boiling point (oc) 1413 1412 180 58 56
The boiling point decreases from sodium chloride to phosphorous pentachloride.

Explanation:
This is because NaC1 and Mgc12 exist as giant ionic structures with strong electrostatic forces between
ions of opposite charge. The magnitude of ionic bond decreases with
a) Decrease in cationic radius
b) Charge on the ions (cation) and therefore an increases in charge density and polarizing power of
the cation from Na+ to A13+

The rest of period 3 chlorides exists as simple molecules with A1C13 existing as a dimer A12C16.
The molecules have weak vander waals forces between them and ionic bond are relatively stronger than
weak vanderwaals forces.

b) Oxides of third short period 3

46
Formula of oxide Na2O MgO Al2O3 SiO2 P2O5 SO3 C12O7
Atomic number 11 12 13 14 15 16 17
Melting point (oc) 1275 2527 2007 1607 560 30 -91
Type of structure Giant Giant Giant Giant Simple molecular covalent between
ionic ionic ionic covalent atoms and weak vander waals
forces between molecules.

The melting point increases from Na2O to MgO then reduces upto chlorine hepta oxide.

Explanation:
From Na2O to Al2O3, they exist as giant ionic structure with ions of opposite charge having ionic bonds.
The melting point increases from Na2O to MgO because of increasing charge density of the cations from
MgO to A12O3, melting point decreases due to high charge density of Aluminium ion which makes
A12O3 partly covalent.
SiO2 has a giant covalent structure with its atoms held by strong covalent bonds in a tetrahedral shape.

The rest of the oxides have simple molecular structures with its molecules held by weak vander waals
forces.
The strength of vander waals forces decreases as molecular mass decreases and polarity of the molecules
increase as a result of decrease in electronegativity difference with bonding atoms from P2O5 to C12O7.

Self check:
Hydrides of period 3
Formula of NaH MgH2 A1H3 SiH4 PH3 H2S HC1
hydrides
Atomic number 11 12 13 14 15 16 17
Type of structure Ionic - Simple molecular
Melting point (oc) 88 140 188 158

Explain the trend in melting points of the hydrides

Hint - electronegativity of the atom increases

47
- Polarity increases
- Intermolecular vander waals forces increases
- SiH4 is non polar
- A1H3 is polymeric with unknown structure.

Hydrides of group VII, VI and V

Group Formulae
GroupVII HF HC1 HBr Hi
Boiling point 20 -85 -67 -35
GroupVI H2O H2 S A3H3 H2Te
Boiling point _____________increases _________________
GroupV NH3 PH3 A3H3 SbH3
Boiling point _____________________Increases __________________

With exception of hydrogen floride, which has an unexpectedly high boiling point, boiling points of
group VII hydrides increases down the group.
The very high boiling point of HF is because of the relatively strong hydrogen bonding formed between
molecules as a result of fluorine being the most electronegative atom in group VII.
The rest of group VII hydrides have weak vander waals forces between molecules whose strength
increases with increasing molecular mass down the group.

NOTE: Some explanation is correct for group VI and V hydrides.

CHECK:
Compound M2O3 A1C13 CaO CaC12
Melting point 2270 451 2850 1051

Explain:
a) The melting point of AlCl3 is abnormally low compared to Al2O3
b) Themelting point of CaO is much higher than that of CaCl2

Solution:

48
 a) Aluminium ion has a small cationic radius and a charge of +3. Aluminium ion is highly polarizing
and forms predominantly covalent bonds with chlorine atom that is less electronegative than
oxygen. Aluminium chloride exists as a dimer Al2Cl6 bond with weak vander waals forces
between molecules.
Al2O3exists as a giant ionic structure with strong electrostatic attraction between ions of opposite
charge. This is because oxygen is less polarisable than chlorine
b) Oxide of CaO has acharge of -2 and chlorine has that of -1. The high charge of the oxide increases
on the strength of the ionic with Ca2+ hence need for a higher temperature to melt the oxide
compared to the chloride.

Factors that affect melting points of meatls and non-metals.

Metals – Atomic radius
- Number of valency electrons
- Charge density.
Non metal (simple molecules)
- Vander waals force
- Hydrogen bonds
- Molecular mass
Trend in solubility of group (I) and (II) hydroxides and sulphates.
All common salts of group( I) are soluble in water. The solubility of group(I) salts increases down the
group, because the hydration energy and lattice energy decreases down the group but lattice energy
decreases much more than the hydration energy.
Also the slat of group (II) elements are generally less soluble than those of corresponding group(I) salts.
This is because, the group (II) cations have a double charge and a smaller ionic radius than their
corresponding group (I) ions and therefore are more polarizing and with large lattice energy than
hydration energy.
a) Group (II) hydroxides
Be(OH)2 Mg(OH)2 Ca(OH)2 Sr(OH)2 Ba(OH)2
Solubility increases
b) Group sulphates
BeSO4 MgSO4 CaSO4 SiSO4 BaSO4
Solubility increases
Explain the trends in solubility of hydroxides and sulphates of group (II).

49
Explanation
a) Solubility increase from Beryllium hydroxide to Barium hydroxide. This is because both lattice
and hydration energies decrease with increase in cationic radius, but the decrease in lattice energy
is much more than the decrease in hydration energy due to the single charge on hydroxide ion
involved.
b) Solubility decrease from beryllium sulphate to Barium sulphate. This is because both lattice and
hydration energies decreases with increase in cationic radius, but the decrease in hydration energy
is much more than the decrease in lattice energy due to the double charge in sulpahte ion
involved.

Chemical properties of elements, oxides, chlorides and hydrides of :

The third short period:
The reactions to be considered will be with
1. Water
2. Acids
3. Sodium hydroxide solution
Element Na Mg Al Si P S Cl Ar
Atomic number 11 12 13 14 15 16 17 18
Type of structure Giant metallic Giant atomic simple molecular
covalent bond between atoms and
Metallic covalent weak vander waals forces
Type of bond between molecules.

1. With water
a) Sodium reacts vigorously giving sodium hydroxide and hydrogen gas.
2Na(s) + 2H2O(s) 2NaOH(aq) + H2(g)
b) Clean magnesium reacts very slowly with cold water but when heated, it burns in steam with a
white flame to give hydrogen gas.
Mg(s) + 2H2O(i) Mg(OH)2(aq) + H2(g)
Mg(s) + H2O(g) MgO(s) + H2(g)

50
 c) Aluminium doesn’t react with water or steam even when heated. This is because of a thin film
oxide coating formed on its surface.
(a diagonal relationship with Beryllium).
d) For non metals, silicon when strongly heated reacts with steam to form silicon (IV) oxide
Si(s) + 2H2O(g) SiO2(s) + 2H2(g)
(White solid)
e) Phosphorous and sulphur, do not react with water.
f) Chlorine reacts with cold water forming hydrochloric acid and chlorate (I) acid.
Cl2(g) + H2O(l) HCl(aq) + HOCl(aq)
2. With Acids (HCl, H2SO4 and HNO3)
a) The reactions of the elements with dilute acids are the same as with water, except the
reactions are more vigourous.

Example: 2Na(s) + 2HCl(aq) 2NaCl(aq) + H2(g)

Mg(s) + H2SO4(aq) MgSO4(aq) + H2(g)
b) Aluminium when heated reacts with dilute sulphuric acid
2Al(s) + 3H2SO4(aq) Al2(SO4)3(aq) + 3H2(g)

NOTE: Aluminium does not react with HNO3. Aluminium is made passive by nitric acid, a diagonal
relationship with beryllium in group (II).
c) Silicon is not attacked by any acid except hydrofluoric acid to form hexafloric acid and
hydrogen.
Si(s) + 6HF(aq) H2SiF6(l) + 2H2(g)
d) Phosphorous and sulphur and chlorine do not react with dilute acids but concentrated nitric
acid oxidizes phosphorous in presence of water to give orthophosphoric acid, nitrogen
monoxide and dioxide
i) P4(s) + 12HNO3(aq) 4H3PO4(aq) + 4NO(g) + 8NO2(g)
ii) Sulphur gives sulphunic acid, water and Nitrogen dioxide
S(s) + 6HNO3(l) H2SO4(aq) + 2H2O(aq) +6NO2(g)
iii) Concentrated sulphuric acid oxidizes sulphur to sulphur dioxide and itself is reduced to
water.
S(s) + 2H2SO4(l) 3SO2(g) + 2H2O(l)

51
 3. With sodium hydroxide solution NaOH(aq)
a) Na and Mg do not react with sodium hydroxide because they are strongly electropositive.
b) Aluminium is weakly electropositive and reacts with sodium hydroxide and water to give
Aluminate ion and hydrogen gas. (a diagonal relationship with Berryllium)
2Al(s) + 2OH(q) + 6H2O(q) 2Al(OH)4- (aq) + 3H2(g)

For non metals

Silicon and phosphorous also react with sodium hydroxide and water giving SiO2 and hydrogen
phosphate and phosphine gas.
Si(s) + 2OH(aq) +H2O(l) SiO32-(aq) + 2H2(g)
P4(s) + 3OH(aq) + 3H2O(l) 3H2PO2- (aq) + PH3(g)
(White)

Sulphur reacts slowly with hot concentrated sodium hydroxide to give sulphite and sulphide ions and
water.
3S(s) + 6OH(aq) SO32- (aq) + 2S2- (aq) + 3H2O(l)
With chlorine there are two different products formed depending on the concentration and temperature
i) With cold dilute sodium hydroxide, chloride ions, chlorate (I) ions and water are formed.
Cl2(g) + 2OH(aq) Cl-(aq) + ClO - (aq) + H2O(l)
ii) With hot and concentrated alkali, chloride ions, chlorate (V) and water are formed.
3Cl2(q) + 6OH(aq) 5Cl- (aq) + ClO3-(aq) + 3H2O(l)

Oxides of period 3
Only normal oxides will be discussed. These can be divided into four depending on their behavior with
water, acids and bases.
1. Base
2. Amphoteric
3. Acidic
4. Neutral

Earlier we subdivided oxides according to the type of structure and type of bonding when we considered
physical properties.

52
Element Na Mg Al Si P S Cl
Formula Na2O MgO Al2O3 SiO2 P2O5 SO2 Cl2O7
of oxide
Type of Giant ionic Giant ionic Giant Giant Simple molecular
structure covalent
Type of Ionic ionic ionic covalent Covalent bond between atoms
bond covalent and weak van der waal´s between
molecules
Acid base Strongly ionic Amphoteric Weakly Strongly acidic
acid

Reactions with:

1. Water

A reaction of part or all the salt derived from a weak acid or weak base with water to give corresponding

base or acid usually is specifically known as hydrolysis. Hydrolysis will also be considered in physical

chemistry under ionic equilibrium.

a) Na2O gives sodium hydroxide which is alkaline with PH greater than 7.

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

Sodium hydroxide is used so much in qualitative analysis for identification of cations.

b) MgO and Al2O3 do not react with water and are sparingly soluble in water.

c) For non metals SiO2 is insoluble in water and does not react with it.

d) P2O5(P4O10) reacts with a hissing sound on contact with water to give tetra oxophosphoric acid

(ortho phosphoric acid).

P2O5(s) + 3H2O(l) 2H2PO4(aq)

e) SO2 forms sulphorous acid as SO3 forms sulphuric acid.

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

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

53
2. Acids

a) Na2O and MgO react to form corresponding salt and water example

Na2O(s) + 2HCl(aq) 2NaCl(aq) + H2O(l)

MgO(s) + H2SO4(aq) MgSO4(aq) + H2O(l)

b) Al2O3 is amphoteric and gives also a salt and water

Al2O3(s) + 6HCl(aq) 2AlCl3(aq) + 3H2O(l)

Al2O3+3H2SO4(l) Al2(SO4)3(aq) + 3H2O(l)

c) SiO2 is not attacked by any acid (just like) except hydrofluoric acid to form flourosilicic acid

and water.

SiO2(s) + 6HF(l) A2SiF6(aq) + H2O(l)

d) P2O5 is a strong dehydrated agent and dehydrates concentrated sulphuric acid and nitric acid

according to the equation.

2H2SO4(l) + P4O10(s) 2SO3(g) + 4HPO3(aq)

4HNO3(l) + P4O10(s) 2N2O5(s) + 4HPO3(aq)

e) The rest of the oxides SO2, SO3and Cl2O7 become more acidic to react with acids.

3. Sodium hydroxide solution

a) Na2O and MgO do not react because they are strongly basic.

b) Al2O3 reacts together with water giving aluminate ion

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

c) The rest of the non metal oxides react giving the corresponding ion of the salt and water

Example

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

SiO2(s) + 2OH9(aq) + 2H2O(l) Si(OH)62- (aq)

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

P2O5(s) + 4OH(aq) 2HPO42-(aq) + H2O(l)

54
 SO3(g) + 2OH(aq) SO42-(aq) + H2O(l)

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

(Chlorate(VII) ion)

Chlorides of period 3

Element Na Mg Al Si P S Cl

Formula of NaCl MgCl2 AlCl3 SiCl4 PCl5 S2Cl2 Cl2

Chloride

Type of Giant ionic Simple molecular

structure

Type of bond Ionic Covalent bond between atoms and

weak vanderwaals between molecules

Acid base Neutral Increasing acidic character

character

Reactions
1. With water
a) Solution chloride dissolves in water to give solution with PH=7 because the salt is from a strong
base and a strong acid and complete neutralization is reached.
b) Magnesium chloride undergoes a little hydrolysisand the solution formed is slightly acidic and is
unable to turn litmus paper to blue.
c) The rest of the chlorides undergo hydrolysis giving a solution with a PHless than 7.
Example
i) Aluminium ions are highly polarizing because of the small cationic radius and a high charge
of +3 and therefore exists in aqueous solution as [Al(HO)6]3+
That is
[Al(H2O)6]3+(aq) +H2O(l) [Al(H2O)5OH]2+(aq) + H3O+(aq)
[AlCH2O)5OH]2+(aq) + H2O(l) [Al(H2O)4(OH)2]+(aq) +H3O+(aq)
[Al(H2O)4(OH)2]+(aq) + H2O(l) [AlCH2O)3(OH)3](s) + H3O+(aq)

55
Over all:
[Al(H2O)6]3+(aq) + 3H2O(l) [Al(H2O)3 (OH)3](s) + 3H3O+(aq)
Observation:
A white precipitate of aluminium hydroxide[AlCH2O)3(OH)(aq)is formed and because of this hydrolysis
reaction, Aluminium carbonate is never formed in aqueous solution .

NOTE: Other ions that show similar properties with Al3+ are Fe3+ and Cr3+ ions.
Observation:
Fe3+ gives a brown precipitate
Cr3+ gives a green precipitate
ii) SiCl4(l) + 4H2O(l) Si(OH)4(aq) + 4HCl(aq)
iii) PCl3(l) + 3H2O(l) H3PO3(aq) + 3HCl(aq)
iv) Cl2(g) + H2O(l) HOCl(aq) + HCl(aq)
Check:
Explain what would be observed if
a) Sodium carbonate solution was added to concentrated solution of aluminium chloride.
b) Magnesium ribbon is added to concentrated solution of Aluminium chloride.
Solution:
a) [Al(H2O)6]3+(aq) +H2O(l) [Al(H2O)5OH]3+(q) + H3O+(q)
Then 2H3O+(aq) + CO32-(aq) 3H2O(l) + CO2(g)

Observation:
Bubbles of a colourless gas that turns wet blue litmus paper red and lime water milky.
b) Then
Mg(s) + 2H3O+(g) Mg(OH)2(aq) + 2H2(g)
Observation
Bubbles of a colourless gas hat gives a pop sound with a burning splint.

Self check:
State what would be observed and write equation for the reaction when
a) A solution of potassium carbonate is added to aqueous aluminum nitrate.
b) Solid potassium iodide is heated with concentrated sulphuric acid.

56
Period 3 hydrides
Element Na Mg Al Si P S Cl
Formula NaH MgH2 (AlH3)x SiH4 PH3 H2S HCl
Type of
structure Giant ionic Simple molecular

Reactions:
1. With water
a) NaH and MgH2 react with water and resultant solution turns litmus blue.
NaH(s) + 2H2O(l) NaOH(aq) + 2H2(g)
MgH2(s) + 2H2O(l) Mg(OH)2(S) + 2H2(g)
(White)
b) SiH4 and PH3 do not react with water but SiH4 hydrolyses when a little alkali is present
SiH4(s) + 4H2O(l) + 2OH(aq) Si(OH)62-(aq) + 4H2(g)
c) Phosphine PH3 does not react or dissolve in water.
d) The rest of hydrides H2S and HCl dissolve in water to give solution of PH less than 7
H2S(g) + H2O(s) HS-(aq) + H3O+(aq)
HCl(g) + H2O(l) Cl-(q) + H3O+(aq)

S. Block elements and some compounds the elements from:

a) consists of group (I) also known as alkaline metals and group (II) known as alkaline earth metals.
b) the general outer most electron configuration for group (I) is ns1 and for group (II) is ns2.

These elements are in s-block because their outer most electrons are in s-subshell.
Group( I) shows an oxidation state of +1 while group (II) shows +2.
c) All s-block elements are metals with metallic character increasing with increase in atomic radius
down the group. Therefore group (I) elements are more electropositive than the corresponding
group II elements.
d)
Group (I) Li Na K Rb Cs
Group (II) Be Mg Ca Sr Ba
Group (III) B Al Ga In Tl

57
CHAEMICAL PROPERTIES OF S-BLOCK ELEMENTS WITH
a) Water (b) mineral acids (c) sodium hydroxide (d) non metals.
(a) Water
All s-block elements react with water except Berryllium (diagonal relationship of Berryllium and
aluminium).
This is because of a thin film n oxide coating formed on the surface of metal which protect it from
reacting.
The vigour in reaction increases with increase in atomic radius down the group.
i) Lithium reacts with water slowly and vigorously sodium metal and violently with
potassium giving a purple flame.
2Li(s) + 2H2O(l) 2LiOH(aq) +H2(g)
2Na(s) + 2H2O(l) 2NaOH(aq) +H2(g)
2K(s) + 2H2O(l) 2KOH(aq) +H2(aq)

ii) Berryllium does not react with water or steam even when heated, magnesium reacts
slowly with cold water giving Magnesium hydroxide and hydrogen gas. But vigorous with
steam giving Magnesium oxide and water.
Mg(s) + 2H2O(s) Mg(OH)2(s) +H2(g)
Mg(s) + H2O(g) MgO(s) +H2(g)

Calcium reacts steadly with cold water but Barium is the most vigorous of all.
Ca(s) + H2O(l) Ca(OH)2(s) +H2(g)
Ba(s) + H2O(l) Ba(OH)2(aq) +H2(g)

NOTE; that the resultant solution turns litmus paper to blue.

b) With mineral acids (HNO3, HCl, H2SO4)
i) All s-block elements react with dilute mineral acids except beryllium which is rendered
passive by nitric acid. (A diagonal relationship of beryllium and Aluminium).
Beryllium reacts with other mineral acids after warming and the reactions are similar with
those of water except that they are more vigorous

58
 Example:
2Na(s) + 2HCl(aq) 2NaCl(q) +H2(g)
Be(s) + 2HCl(aq) Warm BeCl2(aq) +H2(g)

Mg(s) + HCl(aq) MgCl2(aq) +H2(g)

Be(s) + H2SO4(aq) BeSO4(aq) +H2O(l)
Mg(s) + H2SO4(aq) MgSO4(aq) +H2O(l)
Ca(s) + H2SO4(aq) CaSO4(aq) +H2O(l)

(ii)Barium reacts with dilute sulphuric acid only after warming because solubility of group (II) sulphates
decreases down the group. Ba(s) + H2SO4(q ) warm BaSO4(s) +H2(g).

(iii)With concentrated sulphuric acid and concentrated nitric acid

Berryllium reacts with hot concentrated sulphuric acid giving beryllium sulphate as sulphuric acid is
reduced to water and sulphurdioxide.
Be(s) + 2H2SO4(l) BeSO4(aq) +2H2O(q) + SO2(g)

A similar reaction occurs with magnesium.

Mg(s) + 2H2SO4(l) MgSO4(aq) +2H2O(l) + SO2(g)
Hot concentrated Nitric acid reacts with Magnesium giving magnesium nitrate as nitric acid is reduced to
water and nitrogen monoxide.
3Mg(s), + 8HNO3(l) 3Mg(NO3)2(aq) + 4H2O(l) + 2NO(g)

c) Alkali (sodium hydroxide)

All s-block elements don’t react with sodium hydroxide solution except beryllium because it is
weakly electropositive and reacts in presence of water to give berryllateion and hydrogen gas.
Be(s) + 2OH(aq) + 2H2O(l) Be(OH)42- (aq) + H2(g)

d) With other non-metal elements

i) With oxygen and chlorine, all s-block elements when heated react with oxygen to form
normal ionic oxides except beryllium oxide which is predominantly covalent and an
amphoteric oxide (diagonal relationship of beryllium and aluminium).

59
 4Li(s) + O2(g) 2Li2O(s)
2Na(s) +O2(g) Na2O(s)
2Be(s) +O2(g) 2BeO(s)

NOTE: with chlorine they form the corresponding chlorides.(Write equations for the equation).
i) With Nitrogen
Lithium like magnesium burns in nitrogen to form a nitride.
6Li(s) + N2(g) 2Li3N(s)
On hydrolysis magnesium nitride Mg3N2gives magnesium hydroxide and ammonia.
Mg3N2(s) + 6H2O(l) 3Mg(OH)2(s) +2NH3(g)
Observation
A colorless gas that turns red litmus paper blue and a colourless solution that turns red litmus paper blue

Other group (II) elements don’t react with nitrogen gas even when heated.
ii) With carbon
Group II element when heated react with carbon to form carbides of general formula MC2
example
Calcium carbide CaC2 except beryllium which forms Berryllium carbide of formula Be2C and
on hydrolysis beryllium carbide gives methane ( a diagonal relationship of beryllium and
aluminium).
Other group (II) carbides form ethyne on hydrolysis
That is
Be2C(s) + 4H2O(l) 2Be(OH)2(s) +CH4(g)
And
Al4C3(s) + 12H2O(l) 4Al(OH)3(s) +3CH4(g)

AlsoCaC2(s) + 2H2O(l) Ca(OH)2(s) +C2H2(g)

60
THE DIAGONAL RELATIONSHIP

Group I II III IV
Period 2 Li Be B C
3 Na Mg Al Si
On moving from left to right across the period in the periodic table the electronegativity increases while
on moving down the group the electronegativity decreases. Hence elements in period 3 diagonally to the
right of those in period 2 have similar electronegativity and similar poralising power and they show
similar properties.

A summary of similarity in which

a) Lithium in group (I) resembles Magnesium in group (II) and differences from other group (I)
element.
That is Na, K, Rb, and Cs
Similarities Differences
 Both burn in nitrogen to give nitrides. That No reaction
is 6Li(s) + N2(g) 2Li2N(s)
3Mg(s) + N2(g) Mg3 N2(s)
(White solid)
 Burn in oxygen to form monoxides only. Burn to form peroxide in addition to
2Mg(s) + O2(g) 2MgO(s) monoxide
2Li(s) + O2(g) Li2O(s)
 Their hydrogen carbonate exist in solution Hydrogen carbonates exist in solid state.
 Their carbonates decompose on heating Donot decompose on heating
 Their nitrates decompose when heated to Decompose to give nitrites and oxygen.
give nitrogendioxide NO2 and oxygen O2
 Their halides with exception of fluoride are Corresponding halides are much less soluble.
soluble in ethanol and other organic solvent

61
b) Beryllium in group(II) resemble aluminium in group III and differs from other group II.
Similarities Differences
 Both do not react with water even when heated They react
 Bothe are rendered passive by nitric acid They react
 Bothe react with sodium hydroxide solution in the presence They do not react because they are
of water to give Aluminate and Berryllate. strongly electropositive.
Be(s)+2OH(aq) + 2H2O(s) Be(OH)42-(aq) + 3H2(g)
2Al(s)+2OH(aq) + 6H2O(l) 2A(OH)4-(aq) + 3H2(g)

 The elements form oxides and hydroxides which are Form basic oxides whose basicity
Amphoteric increase with increase in cationic
radius
 Their carbides hydrorise to give methane Their carbides hydrorise to give
ethyne. That is
CaC2(s)+H2O(l) Ca(OH)2(s)+C2H2

 Berryllium carbide and Alminium carbide exists as No dimmers

dimmers. That is;

 Beryllium chloride and Alminium chloride in hydrorise No hydrolysis.

water giving a solution that turns blue litmus paper red.

c) Boron in group (III) resembles silcon in group (IV) and differs from other group (III) elements.

62
Similarities Differences
 Both are non metals and non conductors of They are metals and good conductors
electricity of electricity.
 Their chlorides are soluble in organic solvents and Insoluble
readily hydrorised
 Their hydrides easily catch fire in air at room Are spontaneously inflammable.
temperature
 Their oxides B2O3 (diborontrioxide) and SiO2 are Al2O3 is amphoteric
weakly acid.

Some important uses of group (I) hydroxides and sodium thiosulphate (Na2S2O3.2H2O)
a) Sodium hydroxide solution and aqueous Ammonia is used in quantitative analysis to identify the
cations. Each is added to a little of the solution of an unknown until in excess.

TEST OBSERVATION DEDUCTION

1. Add sodium hydroxide a) White precipitate insoluble Mg2+, Ca2+, Ba2+
solution until in excess in excess

b) White precipitate soluble Al3+, Zn2+, Pb2+

in excess giving a
colourless solution

c) White precipitate turns

pink then brown, insoluble
Mn2+
in excess.
d) Dirty green precipitate
Fe2+
insoluble in excess.

Fe3+
e) Brown precipitate
insoluble in excess.
f) Blue precipitate insoluble
Cu2+
in excess

63
 g) Grey green precipitate
insoluble in excess Ni2+

h) Grey green precipitate

soluble in excess giving a
green solution
Cr3+

i) A blue – green precipitate

Co2+
turns pink and then brown,
insoluble in excess.

Add aqueous ammonia (a)White precipitate insoluble in excess Mg2+,Al3+,Pb2+

until in excess
(b)White precipitate soluble in excess Zn2+.
giving a colourless solution
(c)White precipitate turns pink then Mn2+
brown, insoluble in excess.
Fe2+
(d)Dirty green precipitate insoluble in
excess slowly turns brown.
Fe3+
(e)Brown precipitate insoluble in
excess
Cu2+
(f)Blue precipitate soluble in excess
giving a blue solution.

64
 (g)A green precipitate soluble in Ni2+
excess giving a blue solution.

(h)Grey green precipitate soluble in

excess giving a pink solution Cr3+

(i)Blue precipitate soluble in excess Co2+

giving a red solution.

(j)No observable change Ba2+ , Ca2+

NB: The precipitates are formed because of the insoluble hydroxides of the respective metal salts formed
and ones which dissolve in colourless due to complex. These reactions can be used to identify the
cation(s).

Equation of the table involving aqueous Ammonia and sodium hydroxide solution.

Mg2+(aq) + 2OH(aq) Mg(OH)(s)

Ca2+(aq) + 2OH(aq) Ca(OH)2(s)
Ba2+(aq) + 2OH(aq) Ba(OH)2(s) white precipitate
Al3+(aq) + 3OH(aq) Al(OH)3(s)
Pb2+(aq) + 2OH(aq) Pb(OH)2(s)
Zn2+(aq) + 2OH(aq) Zn(OH)2(s)

In sodium hydroxide there is no reaction with,Ba2+and Ca2+ because the concentration of Hydroxide
IonS from Ammonia solution is very low so that it is insufficient fo Ksp for Ba(OH)2 and Ca(OH)2 to be
reduced. But in excess sodium hydroxide solution only.
Al3+, Zn2+ andPb2+hydroxides dissolves to form complexes

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

Al(OH)3(s) + OH(aq) Al(OH)4-(aq) colourless solutions
Pb(OH)2(s) + 2OH(aq) Pb(OH)42-(aq)

However in excess aqueous Ammonia only Zinc hydroxide dissolves.

65
Zn(OH)2(s) + 4NH3(aq) Zn(NH3)42OH(aq) Colouless solution

c) in both sodium hydroxide and Ammonia solution

Mn2+(aq) + 2OH(aq) Mn(OH)2(s)

Turning brown is due to hydrated manganese (IV) oxide formed by oxidation of Mn(OH)2. That is,
2Mn(OH)2(s) + O2(g) 2MnO2H2O(s)
White ( Brown)

In both sodium hydroxide and Ammonia solution

(d) Fe2+(aq) + 2OH(aq) Fe(OH)2(s)
(Dirty green precipitate)
3+
d) In both, Fe (aq) + 3OH(aq) Fe(OH)3(s)
( Brown precipitate)

e) Cu2+(aq) + 2OH(aq) Cu(OH)2(s)

(Blue precipitate)
The blue precipitate on heating forms a black solid of copper(II) oxide, that is,
Cu(OH)2(s) CuO(s) + H2O(l).

However in excess, aqueous Ammonia the blue precipitate dissolves giving a deep blue solution. That is,
Cu(OH)2(s) + 4NH3(aq) Cu(NH3)42+(aq) + 2OH(aq)
(Deep blue solution)

f) Ni2+(aq) + 2OH(aq) Ni(OH)2(s)

(Green precipitate)
However in excess aqueous Ammonia the precipitate dissolves giving a blue solution.
Ni(OH)2(s) + 6NH3(aq) Ni(NH3)62+(aq) + 2OH(aq)
b) Cr3+(aq) + 3OH(aq) Cr(OH)3(s)
(Grey –green precipitate)

c) In excess sodium hydroxide solution the precipitate dissolves giving a green solution.
That is, Cr(OH)3(s) + 3OH(aq) Cr(OH)63-(aq)
Green solution
And in excess aqueous Ammonia the precipitate dissolves giving a pink solution. That is
Cr(OH)3(s) + 6NH3(aq) Cr(NH3)63+(aq) + 3OH(aq)
c) Co2+(aq) + 2OH(aq) Co(OH)2(s)

66
 (blue precipitate)
However in excess aqueous Ammonia the precipitate dissolves giving a red solution on standing.
Co(OH)2(s) + 4NH3(aq) Co(NH3)42+(aq) + 2OH(aq)
(Red solution)
Sodium thiosulphate (Na2S2O3.2H2O)

This us used used in titration involving iodine. The half ionic equations are used to obtain the overall
equation.
S2O32- (aq) S4O62- (aq) + 2e
I2 (g) + 2e 2 I- (aq)

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

A brown solution turns colourless but starch indicator is usually added to a straw yellow solution of the
mixture to give a blue black solution and a few drops of the thiosulphate are then added to obtain the end
point, a colourless solution.

GROUP( IV) ELEMENTS AND SOME OF THE COMPOUNDS FORMED BY GROUP (IV)
ELEMENTS:
This group consists of carbon, silicon, germanium, tin and lead
Elements have four electrons in the outer most shell i.e. nS2nP2 where n=energy level
Symbol of element C Si Ge Sn Pb
Atomic number 6 14 32 50 82
2 2 2 2 2 2 2 2
Outer most electron 2S 2P 3S 2P 45 4P 5S 5P 6S26P2
configuration

Allotropy and structure

Allotropy refers to the existence of an element in two or more structural forms but in the same physical
state. Both carbon and tin show allotropy ie carbon exists as graphite and diamond. Tin exists as grey tin,
white tin and rhombic.
Silicon, germanium and tin have diamond type of structure though tin exists in metallic form. Lead exists
only in metallic form.

67
Unique nature of carbon atom
Carbon is the first element and differs in general from the rest of group members because of its small
atomic size, high electronegativity which results in high ionic size, more covalent and less metallic
character.carbon differs from other members in the following ways;
1. Carbon atom is limited to forming a maximum of four-covalent bonds because only 2S and 2P-orbital
electrons are available for bonding. During formation of four-covalent bonds, an electron is promoted
from 2S-orbital to the vacant 2P-orbital to form SP3 hybrid orbital. The rest of the members have a
maximum covalence of six because they have easily accessible empty d-orbitals or empty d-orbitals
of low energy.
2. Carbon has the ability to form stable compounds containing long chains and rings of carbon atoms Eg
2-napthol benzene

This process is called catenation and enables carbon to form a wide range of compounds. Silicon forms a
few silanes eg SiH4, Si3H8 which are spontaneously flammable in air
3. Carbon forms stable multiple bonds with itself and other elements. E.g.

Other elements don’t form stable multiple bonds because their atomic orbitals are large and diffuse to
obtain effective overlap of the atomic orbitals. However they can use the d-orbital in the multiple
bonding because they are empty and easily accessible
4. Carbon does not show inert pair effect
5. Carbon forms gaseous oxides i.e. CO and CO2, others form oxides which are solid in state
Oxidation states of group (IV) elements (+4 and +2)
They exhibit +2 and +4 oxidation states in their compounds. Stability of +2 oxidation state increases
from carbon to lead while for that of +4 decreases from carbon to lead. This is due to inert pair
effect;refers to the inability for the outermost S-electrons to take part in chemical bonding hence only 2-
outermost P-electrons are used in bonding.
Reason: this is because in large atoms such as tin and lead the d and f electrons do not shield the
outershell electrons effectively and this result in the outer S-orbital electrons to be much strongly
attracted by the nucleus compared to outer empty P-electrons. The outer shell electrons become sucked
into the inner core of electrons and thus become less available for bonding eg CO is readily oxidized to a
more CO2

68
Silicon monoxide is not known; however it exists at very high abnormal temperatures while silica (SiO2)
is widely distributed like in soil. Germanium exists in both oxidation states, +4 being the most stable eg
GeO2 is more stable than GeO. +4 oxidation state in tin is slightly more stable than +2. Consequently Sn
(II) oxide smoulders in air forming Sn (IV) oxide
2SnO (s) + O2 (g) 2SnO2 (s)
+2 oxidation state in lead is more stable than +4. E.g. PbO2 decomposes to PbO
2PbO2 (s) 2PbO (s) + O2 (g)
Why +4 oxidation state stability decreases and +2 oxidation state stability increases down that group
IV?
Explanation: This is because as atomic radius increases with increasing atomic number, there is
reluctance of S - outer most electrons to unpair and take part in bonding (inert pair effect).
Also the p-sub shell electrons in outer most sub shell are greatly screened off by the inner s sub shell
electrons. This causes the two outer most p-sub shell electrons to be lost easily.
The maximum covalence is 4 but for silicon with easily accessible empty d-orbitals, its 6. This means
that Si-comppounds are open to attack than carbon compounds
e.g. SiCl4 is easily hydrolysed by water while CCl4 is not: this is because carbon atom is small, does not
have suitable suitable empty d-orbitals to accommodate lone pairs of electrons form the oxygen atom of
the water molecule. The other elements such as silicon have larger atoms which have empty d-orbitals of
suitable energy to accommodate lone pairs of electrons form the oxygen atom of the water molecule by
expanding its octet

Variation in physical properties

element Atomic radius Melting point Boiling point Metallic character
Carbon 0.077 3730 4830 Non-metallic
Silicon 0.117 1410 2680 Non-metallic
Germanium 0.122 937 2830 Metalloid
Tin 0.142 232 2270 metal
Lead 0.154 327 1730 metal

Electrical conductivity
On descending down the group, atomic radius increases and bonding between atoms become weaker. The
outer shell electrons become increasingly delocalized and electrical conductivity increases. Therefore
elements become more metallic

69
Variation in covalent radii
There is a general increase down the group. The difference between germanium and silicon is less than it
might be expected because Ge has full 3d10 sub-orbital/shell which shields the nuclear charge rather
ineffectively resulting in strong attraction of the outer electrons; therefore it attracts and becomes smaller
In similar way, the small difference in size between lead and tin atoms is because of filling of 4f-subshell
which has a poor shielding effect.
Ionization energy
There is a general decrease in ionization energy down the group but the trend is irregular because of the;
filling of the d and f-subshells which shield the nuclear charge poorly thus outer electrons are strongly
attracted by the nucleus. The amount of energy to form M4+ ion is extremely large and hence ionic
compounds are rare. The only elements which give large enough electronegativity difference to give
ionic character are fluorine-oxygen.

Group trend in hardness

Graphite is soft in contrast to diamond which is hard. Graphite is made up of hexagonal layers held by
weak van der Waals forces. These forces are easily overcome hence graphite id soft. In diamond, each
carbon atom uses its valency electrons to form covalent bonds with other 4 C-atoms . this results into a 3-
dimensional structure (giant molecular structure) which is very hard and has a high melting point form C
to Pb, there is a great but nonuniform decrease in hardness.
Consider

Explanation
Carbon exists as a macromolecular structure composed of atoms due to its ability to catenate. It has
abnormally high melting point because a large number of short and strong C-C bond has to be broken
before it melts.

70
The elements from Si to Sn have a diamond like structure and this accounts for relatively high melting
point in them. On descending the group, the atomic radii increase hence element-element bond become
longer and weaker thus melting point decreases.
NB: graphite is a good conductor of electricity while diamond is not; this is because in diamond all the
valence electrons are utilized in forming covalent bonds, thus there are no free electrons used for
conductivity. In graphite only 3 of the 4-valence electrons are used by each by each carbon atom to form
3-covalent bonds in a hexagonal layer. The fourth electron is delocalized within the layer therefore its
these free and mobile electrons that are responsible for conduction of electricity and heat in graphite.
Chemical properties of Group (IV) elements
a) Reaction with air
Carbon, tin and germanium are not affected by air at ordinary temperatures. Silicon oxidizes superficially
in air at ordinary temperature.
All group members with exception of lead burn in oxygen when heated to give the corresponding
dioxides.
C(s) + O2(g) CO2(g)
Si(s) + O2(g) SiO2(s)
Sn(s) + O2(g) SnO2(s)
Lead quickly tarnishes in air acquiring a thin layer of hydroxide of HCO3. This protects it from
further attack so that the change is superficial. When just heated above its melting point, lead
oxidizes to yellow form of its oxide. At very high temperature, oxide formed reacts with oxygen
to form trilead tetraoxide
2Pb(s) + O2(g) 400 oC 2PbO(s)
6PbO(s) + O2(g) 470 oC 2Pb3O4(s) (red or dark brown chocolate)
Note: red lead Pb3O4 is formed in excess oxygen.

b) Reaction With other non-metal elements

i) With halogens example, chlorine. All elements react with halogens except carbon which does
not react directly with chlorine to give corresponding tetrahedral.
C(s) + 2Cl2(g) u.v light (no reaction )
Instead CH4(g) + 4Cl2(g) CCl4(g) + 4HCl(g)
Other wise Si(s) + 2Cl2(g) SiCl4(s)
Pb(s) + Cl2(g) PbCl2(s)
Also Pb(s) + I2(g) PbI2(s)

71
 ii) With sulphur, all elements of Group (IV) on heating react with sulphur giving the respective
disulphide except lead which give lead(II), Sulphide, PbS
C(s) + 2S(g) CS2(l)
Sn(s) + 2S(s) SnS2(l)
Pb(s) + S(s) PbS(s)

2. Reaction With water

a) C, Si, and Sn are unaffected by cold water except lead which is attacked by ordinary soft water (not
distilled water) containing dissolved oxygen to give lead(ii) hydroxide, Pb(OH)2.
2Pb(s) + 2H2O(l) + O2(g) 2Pb(OH)2(s)
With hard water, white precipitate of lead carbonate and lead sulphate are formed . this protects it from
any further attack
Pb(s) + CO32-/SO42-(aq) PbCO3/PbSO4 (s)
With steam, lead produces hydrogen and lead monoxide
Pb(s) + H2O (g) PbO (s) + H2 (g)
b) Carbon , silcon when strongly heated react with steam.
Hot cork Carbon reacts with steam to give a mixture of carbon monoxide and hydrogen (water gas);
C(s) + H2O(g) CO(g) + H2(g)
While the rest of the elements named above give the respective dioxides and hydrogen.
Si(s) + 2H2O(l) SiO2(s) + 2H2(g)
Germanium has no reaction with cold water or steam.
2. Reaction With acids (HCl, H2SO4 and HNO3)
a) Dilute Acids
For all group IV elements no reaction occurs except with dilute nitric acid and tin.
Tin forms a mixture of tin (II) nitrate and ammonium nitrate solution, with out evolution of a gas.
4Sn(s) + 10HNO3(aq) 4Sn(NO3)2(aq) + NH4NO3(aq) + 3H2O(l).
But no single equation can be written for the reaction of nitric acid and lead.
b) With hot concentrated nitric acid
All group (IV) elements react except silicon the corresponding oxide in +4 oxidation state
nitrogen dioxide and water are formed, while lead forms lead(II) nitrate.
Carbon reacts with hot concentrated HNO3 to liberate CO2, NO2 and H2O

72
 C(s) + 4HNO3(l) CO2(g) + 4NO2(g) +2H2O(l)
Ge is oxidized by ho concentrated HNO3 to Ge (IV) oxide while its reduced to reddish brown fumes and
water.
Ge(s) + 4HNO3(l) GeO2(s) + 4NO2(g) +2H2O(l)
Tin reacts violently giving off reddish fumes and forming white solid
Sn(s) + 4HNO3(l) SnO2(s) + 4NO2(g) +2H2O(l)
Very pure HNO3 (water free) does not attack lead. Any other concentration of acid attacks the metal more
vigorously with increase in temperature to give lead (II) nitrate reddish brown fumes
Pb(s) + 4HNO3(l) Pb(NO3)2(aq) +2NO2(g) +2H2O(l)
Lead is als attacked by organic acid eg ethanoic acid in presence of air (oxygen)
Pb (s) + CH3COOH (aq) + O2 (g) Pb(CH3COO)2(aq) + H2O (l)
c) Silcon is only attacked by hydrofluoric acid to form hexafluorosilicic acid and hydrogen gas
Si(s) + 6HF(aq) H2SiF6(l) + 2H2(g)
d) With hot concentrated sulphuric acid
Si and Ge are not affected by this acid i.e. hot or concentrated.
Carbon is oxidized to carbon dioxide as acid is reduced to sulphur dioxide and water.
Dilute HSO4 acid has little action on tin, hot concentrated oxides tin to tin (IV) sulphate and itself
reduced to water and sulphur dioxide
For lead, lead(II) sulphate is formed in addition to sulphurdioxide and water but hot concentrated acid
attacks lead slowly.
C(s) + 2H2SO4(l) CO2(g) + 2SO2(g) +2H2O(l)
Sn(s) + 4H2SO4(l) Sn(SO4)2(aq) + 2SO2(g) +4H2O(l)
Pb(s) + 2H2SO4(l) PbSO4(s) + SO2(g) +2H2O(l)
Reaction with Hydrochloric acid
Carbon, silicon and germanium are not affected by hydrochloric acid
Hot dilute HCl attacks tin slowly; the reaction is more rapid at higher concentration to liberate Tin (II)
chloride in solution
Sn(s) + 2HCl (aq) SnCl2 (aq) + H2(g)
Dilute HCl has no reaction with lead; hot concentrated HCl dissolves lead slowly forming lead (II)
chloride and hydrogen gas.
Pb (s) + 2HCl (aq) ) PbCl2 (aq) + H2 (g)
Nb (i) if the acid is cold and concentrated the reaction is very slow because of lead (II) chloride formed
(ii) the reaction is faster if lead is powdered form

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3. Reaction with Alkalis
Carbon has no reaction with alkalis; Silicon and germanium dissolve readily in hot caustic alkali
solutions liberating hydrogen gas and forming silicate and germinate respectively in solution.
e.g.
Si(s) + 2OH(aq) + H2O(l) SiO32-(aq) + 2H2(g)
(Silicate ion)
Ge(s) + 2OH(aq) + H2O(l) GeO32-(aq) + 2H2(g)
(Germanate ion)
Tin dissolves slowly in hot concentrated alkalis to liberate hydrogen gas and hexahydroxostannate (IV) in
solution
Sn(s) + 2OH(aq) + 4H2O(l) [Sn(OH)6]2-(aq) + 2H2(g)
(Hexahydroxostannate ion)
Lead dissolves very slowly in hot concentrated to form hexahydroxoplumbate (II) in solution and
hydrogen gas
Pb(s) + 2OH (aq) + 4H2O(l) [Pb (OH)6]2-(aq) + 2H2(g)

Compounds of group (IV) elements

Oxides
They all form oxides of two types ie MO in which they use an oxidation state of +2 and MO2 in which
they use an oxidation state of +4
Monoxide MO Dioxide MO2
CO CO2
SiO SiO2
GeO GeO2
SnO SnO2
PbO PbO2
Nb: monoxides increase down the group
Dioxides decrease down the group
Oxides of carbon are gaseous while the rest are solids. This is because carbon atoms are small; this
allows close overlap of p-orbitals of carbon atom and oxygen atom hence leading to formation of
multiple bonds between the atom of carbon and oxygen linear structure O=C=O;
As a result descrete molecules of carbon dioxide are formed with very weak Van der Waals forces of
attraction that cannot give it a solid state. For others, the element-oxygen bonds are longer and this place

74
atoms far apart; this does not result into close overlap, however they form strong covalent bond with
other oxygen atoms giving rise to 2-dimensional giant lattice structure in solid state.
Monoxides
Trend in basicity of monoxides
The basicity of monoxides increases down the group
Carbon monoxide shows slight acidic properties by reacting with hot concentrated solution of sodium
hydroxide under pressure methanoate
CO (g) + NaOH (aq) HCOONa (aq)
Silicon monoxide is not known. It only exists in vapour state at 23 oC
The monoxides of Ge, Sn and Pb are all amphoteric though predominantly with PbO being most basic.
The form salts with dilute acids and solutions containing complexes; germanate (II), stannate (II) and
plumbate (II) ions respectively with alkalis. Complexes have a general formula [M(OH)6]
SnO (s) + 4OH – (aq) + H2O (l) [Sn(OH)6]4- (aq)
Dioxides
Formula CO2 SiO2 GeO2 SnO2 PbO2
Appearance colourless White solid ,, ,, Dark brown
solid
Mpoc -56 1710 1720 1800 300(decompose)
Structure Simple Giant
molecular molecular Giant molecular / Ionic

Chemical properties:
a) With water
Only carbondioxide reacts with water forming carbonic acid
CO2(g) + H2O(l) H2CO3(aq)
The rest of the oxides do not react or dissolve in water.

b) With acids
Acidic character decreases as basic nature increases down group (IV) oxides, CO2 and SiO2 are
weakly acidic while others are weakly amphoteric.
- Carbondioxide does not react with any acid.
- Silicon dioxide is only attacked by hydrofluoric acid
SiO2(s) + 6HF(aq) H2SiF6(l) + 2H2O(l)

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 The reactions of acids with germanium(IV) oxide and tin(IV) oxide is not so significant.
Lead (IV) oxide is not affected by dilute acids but concentrated hydrochloric acid and sulphuric acid
react.
Cold concentrated hydrochloric acid gives lead(IV) chloride and water while on warming lead(II)
Chloride and a greenish – yellow gas are formed.
PbO2(s) + 4HCl(l) 0 oC PbCl4(l) + 2H2O(l)
Excess Bright yellow oily liquid
PbO2(s) + 4HCl(l) PbCl2(s) + 2H2O(l) + Cl2(g)

With hot concentrated sulphuric acid

Lead (II) Sulphate, water and oxygen are formed
Observations
A white precipitate and bubbles of a colourless gas are formed.
2PbO2(s) + 2H2SO4(l) 2PbSO4(s) + 2H2O(l) + O2(g).
Also bubbling sulphur dioxide through warmed lead (IV) oxides, a white precipitate is observed.
PbO2(s) + SO2(g) PbSO4(s)
(b) With sodium hydroxide
c) All oxides of group(IV) in +4 oxidation state react giving the corresponding oxoanions and water.
The easy of formation of oxoanions decreases down the group as acidic character decreases and
oxides become more basic and amphoteric. Only concentrated aqueous alkali is used.
Example: CO2(g) + 2OH(aq) CO32-(aq) + H2O(l)
SiO2(g) + 2OH(aq) SiO32-(aq) + H2O(l)
PbO2(g) + 2OH(aq) PbO32-(aq) + H2O(l)

Also
PbO2(s) + 2OH(aq) + 2H2O(l) Pb(OH)62-(aq)

Group (IV) Oxides in +2 oxidation state

The most important of the monoxides are those of SnO(s), Tin (II) oxide and lead (II) oxide, PbO(s).
These are all insoluble solids and amphoteric .
Tin (ii) oxide smoulders when exposed to air.
2SnO(s) + O2(g) 2SnO2(s)

76
Also
PbO(s) + O2(g) Pb3O4(s)
With aqueous NaOH
2SnO(s) + 2OH2(aq) SnO32-(q) + H2O(l)
PbO(s) + 2OH2(aq) PbO32-(q) + H2O(l)
OR: also as
SnO(s) + 4OH(aq) + H2O(l) [Sn(OH)6]4-(aq)
And
PbO(s) + 4OH(aq) + H2O(l) [Pb(OH)6]4-(aq)

NOTE:
Tin (II) oxide is a strong reducing agent.
Trilead tetraoxide Pb3O4 (red lead)
Is obtained when lead(ii) oxide is heated in air.
6PbO(s) + O2 (g) Pb3O4(s)
(red)
And it is a mixed oxide containing (PbO2 + 2PbO)
That is, lead(ii) oxide and lead (iv) oxide.

Chemical properties of Trilead tetra oxide

a) When warmed with dilute nitric acid, lead (iv) oxide and lead (ii) nitrate and water are formed.
Pb3O4(s) + 4HNO3 (aq) PbO2(s) + 2Pb(NO3)2 (aq) + H2O (l)
(Brown)
Lead (IV) oxide can also be made by heating a solution of lead (II) nitrate with sodium chlorate (I)
solution or with bleaching powder.
Pb(NO3)(s) + ClO- (l) + H2O(l) PbO2(aq) + 2HNO3(aq) + Cl- (aq)
(b)When warmed with concentrated hydrochloric acid, lead (II) chloride, water, and a greenish yellow
gas (chlorine) are formed. It is a powerful oxidizing agent.
Pb3O4 (s) + 4HCl (aq) PbCl2 (aq) + 4H2O (l) + Cl2 (g)

Group (IV) Chlorides

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All the elements form chlorides in +4 oxidation state that are colourless liquids except lead (IV) chloride
which is a yellow liquid.

Formula of tetrachloride CC14 SiCl4 GeCl4 SnCl4 PbCl4

Type of structure simple molecular

Type of bond covalent between atoms and weak

Vanderwaals forces between molecules
B.pt (OC) 76 57 86.5 114 decomposes

Chemical properties
a) With water
Carbontetrachloride CCl4 is not affected by waters
Observation:
Two layers of a colourless liquids with a liquid junction between them.
All the remaining tetrachloride are covalent compounds that fume in moist air because of rapid
hydrolysis to forms white fumes and white solid, silicon(iv) oxide.

SiCl4(l) + 2H2O(l) SnO2(s) + 4HCl(g)

While fumes are due to hydrogen chloride.
b) NOTE: PbBr4 and PbI4 do not exist because bromide Br and Iodide I ions reduce lead(iv) to
lead(ii) ions and the halogen ions get oxidized to Bromine and iodine respectively.

Why is carbontetrachloride CC14 is unaffected by water whereas SiCl4 is hydrolysed?

This is because of two reasons
g) 14Si IS22S22P63S2 3P23do has 3d orbital of lower energy available to accept alone pair of electrons of
oxygen atom in water molecule. Whereas 6C IS22S22P63S2 3P23do carbon has the 3d orbital of high
energy and cannot accept electrons.

ii) Silicon – chloride covalent bond is weaker than carbon –chloride covalent bond because silicon is less
electronegative than carbon atom since down the group(iv) electronegativity decreases. There fore GeCl4
and SnCl4 hydrolse in water in a similar way as SiCl4 to give similar observations and products.
Example:

78
SnCl4(l) + 2H2O(l) SnO2(s) + 4HCl(g)
Observations:
 White fumes and a white solid
 White fumes are due to hydrogen chloride
 White solid is due to tin (IV) oxide, SnO2.
c) Lead(iv) chloride decomposes on warming
At room temperature to form white crystals of lead (II) chloride and a greenish yellow gas,
chlorine.
PbCl4(l) PbCl2(s) + Cl2(g)

Dichlorides
Only Ge, Sn and Pb form stable dichlorides. They are solids at room temperature and exhibit ionic
properties.
Tin (II) chloride and lead (II) chloride are the only important ones. Carbon, silicon and Germanium are
not known to form stable chlorides in +2 oxidation state.
Physical properties of tin (II) chloride and lead (II) chloride
Property Tin (II) Chloride Lead (II) Chloride PbCl2
SnCl2: obtained in solution by heating tin with its prepared by the action of dilute
moderately concentrated HCl and crystallizes as a HCl on lead (II) nitrate
di-hydrate i.e., Pb2+ (aq) + 2Cl- (aq) PbCl2 (s)
+ 2+
Sn (s) + 2H (aq) Sn + H2 (g)
 It’s partly ionic
 Its hydrolyzed readily so that the anhydrous salt
is best obtained by heating tin in a current of
dry HCl gas
Sn (s) + 2HCl (g) SnCl2 (s) + H2 (g)
1. Soluble in water and in organic solvents e.g. PbCl2 is ionic and only sparingly
ethanol because it is predominantly covalent soluble in cold water according to the
Tin (II) chloride dissolves in water to form a cloudy equilibrium reaction below
solution. This is because it’s partially covalent and Its soluble in hot or boiling water
ionic. So its partially hydrolyzed by water to form because its partially hydrolyzed by it
basic tin (II) chloride which is a cloudy solution to form a basic salt
and HCl

79
 SnCl2 (s) + H2O (l) Sn(OH)Cl (s) + HCl (g)
PbCl2 (s) + H2O (l) Pb(OH)Cl (aq)
If its dissolved in hot water and in are excess, it
+ HCl (g)
undergoes complete hydrolysis
SnCl2 (s) + H2O (l) Sn(OH) (s) + 2HCl
(g)
2. Solution does not conduct electricity Solution conducts electricity; therefore
PbCl2 is predominantly an ionic
compound.
3 - Lead (II) chloride is more soluble in
concentrated hydrochloric acid than in
water because of formation of a
complex ion.
PbCl2(s) + 2Cl- (aq) PbCl4(aq)
In water or dilute HCl the
concentration of chloride ions is not
enough to cause complex ion
formation.

Tin (II) chloride as a reducing agent

Tin (II) chloride in a concentrated aqueous hydrochloric acid is a powerful reducing agent and is oxidized
to tin (IV) ions.Sn2+(aq) Sn4+(aq) +2e
Examples:
1. With iron (III ) salts
Observation; Pale yellow (brown) solution turns to pale green
Sn2+ (aq) + 2Fe3+(aq) Sn4+(aq) + 2Fe2+(aq)
2. With iodine
It reduces iodine usually dissolved in potassium iodide solution i.e.,
Observation; Dark brown solution turns colourless.
Sn2+(aq) + I2(aq) Sn4+(aq) + I-(aq)
3. With potassium manganate (VII) solution
Observation; A golden yellow or orange solution turns green
2MnO4-(aq) +5Sn2+(aq) + 16H+(aq) 2Mn2+(aq) + 5Sn4+(g) + 8H2O(l)
4. With potassium dichromate (VI) solution

80
 Observation; Orange solution turns to a green solution
Cr2O72-(aq) +3Sn2+(aq) + 14H+(aq) 2Cr3+(aq) + 3Sn4+(g) + 7H2O(l)
5. With mercury (ii) chloride
The reduction is done in two stages:
i) when little merucury (II) chloride is used, a white precipitate is formed.
2Hg2+(aq) + Sn2+(q) Hg22+(s) + Sn4+(aq)
ii) In excess, the precipitate turns dark green or black liquid.
Hg22+(s) + Sn2+(aq) 2Hg(l) + Sn4+(q)
6. With nitrobenzene: Phenyl amine (aniline) is formed
C6H5NO2(aq) + 3Sn2+(aq) + 6H+(aq) C6H5NH2(l) + 3Sn4+(aq) + 2H2O(l)
Tetrachlorides
All the elements form tetrachloride, MCl4 where M = C, Si, Ge, Sn and Pb.
At room temperature they are all volatile liquid. Their stability decreases down the group. Pb (IV)
chloride decomposes explosively at its boiling point to form Pb (II) chloride and chlorine gas
Preparation of CCl4
It can be prepared by bubbling chlorine gas through carbon disulphide
Cl2 (g) + CS2 (l) CCl4 (l) + S2Cl2 (l)
Also by heating chlorine with methane in presence or ultraviolet light
U.V
Cl2 (g) + CH4 (g) light CCl4 (l) + 4HCl (g)
The tetra chlorides of Si, Ge and Sn can be prepared by heating the elements with a dry stream of
chlorine gas.
Cl2 (g) + M (s) MCl4 (l) (M = Si, Ge, Sn and Pb)
PbCl4 is prepared by reacting PbO2 with excess concentrated HCl in presence of chlorine has at 0 oC
PbO2(s) + 4HCl(l) 0 oC PbCl4(l) + 2H2O(l)
Bight yellow oily liquid
Hydrolysis of tetrachloride
CCl4 is not hydrolyzed by water: carbon is a small atom and cannot expand its octet or size; its covalence
is being limited to a maximum of four and for due to absence of easily accessible empty orbitals
Tetrachlorides of other elements are hydrolyzed by water because atoms of these elements are large and
have easily accessible vacant d-orbitals and therefore can accommodate a lone pair from the oxygen of
the water molecule by expanding the octet i.e., they have a maximum covalency of more than four.
Silicon (IV) chloride is rapidly hydrolyzed by cold water to form silic acid and HCl gas seen as white
fumes

81
SiCl4 (l) + H2O (l) H2SiO3 (aq) + 4HCl (g)
In excess water, silicon (IV) oxide will appear as a white solid
Germanium is hydrolyzed by water to form GeO2 and HCl gas
GeCl4 (l) + 2H2O (l) GeO2 (s) + HCl (g)
SnCl4 is hydrolysed by excess water especially if heated to form stannic hydroxide, a hydrate of tin (IV)
oxide
SnCl4 (l) + 2H2O (l) SnO2.2H2O (s) + 4HCl (g)
PbCl4 is hydrolyzed by water to form Pb (IV) oxide, brown solid and HCl gas
PbCl4 (s) + 2H2O (l) PbO2 (s) + 4HCl (g)
If concentrated HCl is added to PbO2 at 0oC, a yellow solid is formed
PbO2(s) + 4HCl(l) 0 oC PbCl4(s) + 2H2O(l)
With excess concentrated HCl or excess Cl-, Pb reacts to form a soluble complex plumbate (IV) ion
PbCl4(s) + 2Cl- (aq) [PbCl6]2- (aq)
A similar reaction is obtained by passing Cl2 gas in a mixture of PbCl2 and concentrated HCl at 0 oC
PbCl2(s) + 2Cl- (aq) + Cl2 (g) [PbCl6]2- (aq)
When lead (IV) chloride is heated, lead II chloride and chlorine gas are formed
heat
PbCl4(s) PbCl2 (s) + Cl2 (g)

Group (IV) hydrides

CH4 C2H2
SiH4
GeH4
SnH4
PbH4
Methods of preparation
hydride Method of preparation
CH4 Hydrolysis of aluminium or berrylium carbide
Al4C3(s) + 3H2O(l) 4Al(OH)3 (s) + 3CH4 (g)
Be2C(s) + 4H2O(l) 2Be(OH)2 (s) + CH4 (g)
C2H2 Hydrolysis of calcium carbide
CaC2 (s) + H2O(l) Ca(OH)2 (s) + C2H2 (g)
SiH4 SiCl4 (s) + LiAlH4(aq) dryether SiH4(s) + AlCl3(aq) + LiCl (s)
SnH4 SnCl4(s) + LiAlH4(aq) dryether SnH4(s) + AlCl3(aq) + LiCl (s)

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PbH4 PbCl4(s) + LiAlH4(aq) dryether SnH4(s) + AlCl3(aq) + LiCl (s)

Thermo stability of group IV hydrides

hydride Decomposition temperature
CH4 800
SiH4 450
GeH4 285
SnH4 150
PbH4 0.02

Trend
Decomposition temperature decreases from CH4 to PbH4 down the group
Or thermo-stability of group IV hydrides decreases from CH4 to PbH4 down the group
Explanation
Thermo-stability of +4 oxidation state decreases from carbon to lead down the group due to inert pair
effect
As the ato

CHEMICAL PROPERTIES
1. Methane burns in air above 5000c while silane spontaneously catches fire at room temperature.
Explain
CH4(g) + O2(g) CO2(g) + H2O(l)
SiH4(l) + O2(g) SiO2(s) + H2O(l)
Same explanation as far hydrolysis
2. With water
Methane CH4 is unaffected by water whereas silane SiH4 is hydrolysed by water containing a trace
of alkali.
SiH4(l) + H2O(l) + 2OH(aq) SiO32-(aq) + 4H2(g)
Explain:
14Si IS22522P6352 3P23do

83
6C IS22522P2350 3P03do .This is because silicon has 3d empty sub shell of suitable energy that can
accept a lone pair of electrons from oxygen atom in water molecules where as carbon has the 3d
orbital of high energy and cannot accept electrons.
Also the C-H covalen bond is very strong compared to Si-H covalent bond because silicon is less
electronegative than carbon atom.

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GROUP (VII) ELEMENTS:
The halogens include; Fluorine F2, Chlorine Cl2, Bromine Br2 and Iodine I2
The general outer configuration is nS2nP5
The elements in the group are referred to as halogens derived from Greek word salt formers since they
combine with metals to form salts
Introductory remarks
Elements have structures with one electron sort out of the inert gas like structure, as such are very
reactive and highly electronegative. The last element Astatine being radioactive is rare.
Elements form diatomic molecules X2 with two atoms covalently bonded. The forces operating between
molecules are weak van der waal’s forces whose Magnitude increase on descending the group from
fluorine to iodine because the atomic size of the elements increase, also the number of electrons
associated with them. This is why melting points of halogens increase down the group
Fluorine and chlorine are gases, bromine is a liquid and iodine a solid at room temperature thus on
descending down the group, there is change in state through liquid to solid
Gas liquid solid
In iodine the forces of attraction (van der Waal’s forces) are sufficiently strong to bind iodine molecules
into a 3-dimensiona crystalline –molecular lattice
Iodine sublimes on heating indicating the weakness of van der Waal’s forces of attraction.
On descending the group, as atomic radii increase, electro negativity decreases
Consequently the tendency to form covalent bonds with other elements increases; these bonds become
less polar and weaker. E.g. HI dissociates more rapidly into hydrogen while HCl is relatively stable.
Variation in physical properties of the elements
Bond dissociation energy
Element F Cl Br I

BE KJ/Mol 158 242 193 151

Atomic no. 9 17 35 53

Bond energy rises sharply from fluorine to chlorine and from chlorine to iodine. It increases with increase
in atomic number
The abnormal low BE of fluorine han expected id due to the small size of fluorine atom and therefore
small F-F bond distance; hence internuclear repulsion and also a large electron-electron repulsion and

85
between the lone pair of electrons of two fluorine atoms weakens the bond. The low BDE of florine
accounts for a very reactivity of fluorine

Trend in bond strength

The bond strength decreases with increasing atomic number of F-F showing abnormally very low BE.
This is due to the fact that fluorine atoms are small and F-F distance is also short and it brings the lone
pair fluorine close
Electrons in the atoms of fluorine are very closer than in other halogen molecules hence strong repulsion
occurs between the lone pair of electrons thus weakening the bond.

Electron affinity
This refers to the enegy change which occurs when one mole of electrons combine with one mole mole
gaseous atoms to form one mole of gaseous negatively charged ions

Element F Cl Br I
1st E.A/KJMol- -328 -349 -325 -295

The 1st E.A are exothermic because the orbital of an element theoretically extend to infinity and so
nuclear charge is never completely balanced so the electron added experience greater nuclear attraction
than repulsion from the electron already present in the shell.
E.A decreases with increase in atomic radii from F to I because increase in atomic radii increases
shielding effect and so nuclear attraction for incoming electrons decreases.
However E.A of F is less than that of Cl i.e. is less negative due to the small size of F-atom the electron
being added to the outermost shell experiences greater repulsion from the electrons that are already
present in the shell than the case of Cl atom.

Ionization energy
Element F Cl Br I
1st I.E/KJMol- 1581 1256 1143 1069

Increases with increase in atomic number. They have very high 1st IE and this makes them unstable to
form positively charged ion. However 1st IE decreases down the group showing precisely high I.E than
the rest. This is because of small atomic size

86
Melting and boiling points
Element F Cl Br I

Boiling point -187 -37 39 189

Melting point -220 -101 -71 -113

Trend
Increases with increase in atomic number
Reason
They all exist as diatomic molecules held by weak Van der Waal’s forces. Melting point and boiling
point depend on the magnitude of Van der Waal’s forces of attraction. The magnitude depends on the
atomic weight; the higher the atomic weight, the greater the strength of the force moving down the group,
increase in atomic weight increases the size of Van der Waal’s forces of attraction and thus the trend
The abnormal increase in melting point and boiling point from chlorine to bromine to iodine is due to the
fact that chlorine is a gas , bromine is a liquid and iodine a solid; magnitude of Van der Waal’s forces is
in order
Gas >liquid > solid

Common oxidation states

F -1
Cl -1 +1 +3 +4 +6 +7
Br -1 +1 +3 +4 +6 +7
I -1 +1 +3 +5

Oxidation states of +1 and -1 are the most common and depend n whether the element is the most
electronegative or not
Fluorine only exhibit one oxidation state of negative one (-1) since it lacks easily accessible d-orbitals in
is valence shell due to the energy difference and t being a small atom
Other members of the group can exercise higher oxidation state by making use of the easily accessible d-
orbitals in their valence shell
The highest oxidation state of +7 involves the use of all the electrons of the outermost principle quantum
shell

87
Electrode potentials
Standard electrode potential becomes more positive in the order F>Br>Cl>I
This property is dependent on enthalpy of dissociation, E.A, and hydration energy of the halide
In the case of Br and I, it involves an additional term, enthalpy of sublimation and vaporization
Fluorine is a better oxidizing agent than chlorine despite the fact the fact that it has a lower negative
value of electron affinity
This is because of a long value of BDE and a high value of hydration energy of fluoride ion
NB:
Within the group, F and Br exhibit greater similarity
Fluorine is unique in many ways because;
 The atoms are small and it lacks easily accessible d-orbitals which may be used for bonding
 Iodine has distinct properties because it is the only member of the group with slight metallic character
because it’s the largest atom
Chemical properties of group (vii) elements
Fluorine is the most reactive of all elements
It forms compounds under appropriate conditions except any other element
The greatest reactivity of fluorine can be related to its small dissociation energy which leads to low
activation energy
It can be related to its rate of reaction and great strength of bonds fluorine forms with other elements
Both factors in turn can be related to the size of fluorine and much greater enthalpies of fluorination

Perculiatic (unique properties) of flourine

LiF, MgF2, CaF2 are insoluble in water while corresponding chlorides, bromides and iodides are soluble
Reason: fluorine atom is small therefore forms small fluoride ions which forms strong ionic bond with
calcium ions resulting in high lattice energy which cannot be easily be easily offset by small hydration
energy
While chlorides, bromide and iodides are large ions and form calcium salts with relatively low lattice
energy which can be easily compensated by the hydration energy hence they are soluble
Silver fluoride is soluble in water; the chloride, bromide and iodide of silver are insoluble
Reason: Silver fluoride is ionic hence soluble in water which is a polar solvent; while the rest have
partial covalent bonds
Also the enthalpy of the fluoride ion is higher than the rest of the halide ions

88
Potassium permanganate can oxidize HX (X= Cl, Br, I) HF is not
Hydrogen compound of fluoride is associated through hydrogen bonding and is a liquid at room
temperature. It’s a weaker and can form acid salts and normal salts
The hydrides f fluorine, chlorine and bromine are all gaseous at room temperature; strong acids in
aqueous and form normal salts only
They are not associated but exists as discrete molecules held by weak Van Der Waal’s forces.

Fluorine atom is small and highly electronegative; H-F bond is highly polar; this makes the molecule
associate through hydrogen bonding. Other halogen atoms are not sufficiently electronegative hence exist
as discrete molecules held by weak Van derWaal’s forces whose strength is in the order
HI>HBr>HCl>HF
In its reaction with water and alkalis, fluorine forms no oxo-acids and if formed they are unstable ie;
2HOF (l) 2HF (l) + O2 (g)
Reason: this is due to the greater strength H-X bond as compared with the O-X bond for florin than for
the other halogen
It is the most electronegative element and has a fixed oxidation state of -1. It can’t form compounds
where it has a positive oxidation state. Other halogens have oxidation states ranging from +1…..+7
It tends to bring out the maximum covalence in other elements when in combination e.g. PF5, SF6, IF7
etc. existence of only one oxidation explains the inertness of many fluoride compounds
It is the strongest oxidizing agent because it has got a very low F-F bond energy despite of the small size
Form very strong covalent bonds with other non-metals eg H-F because of the small size which allows
effective overlap of the atomic orbital during bonding.

Lab preparation of chloride, bromine and iodine

The three halogen elements are prepared by the same fundamental method, by heating the chlorine,
bromine or iodide with concentrated sulphuric acid and manganese (iv) oxide
General equation
2X- (aq) + 4H+ (aq) + MnO2 (s) Mn2+ (aq) + X2 (g) + H2O (l)
Where X is NaCl, NaBr, NaI
The particle method depends on the physical state of the halogen in the equation in the equation; chlorine
being gaseous, bromine liquid and iodine solid

89
Reaction of halogens
These will be
a) With water and
b) Sodium hydroxide solution only
a) With water
i) Fluorine: fumes in air because it’s a powerful oxidizing agent; forming hydrogen fluoride and oxygen
gas only
2F2(g) + H2O(l) 4HF(g) + O2(g)
ii) Chlorine: forms hydrochloric acid and chloric (i) acid, (Hypochlorous acid)
Cl2 (g) + H2O (l) HCl(aq) + HOCl(aq)

In presence of sunlight, chloric (I) acid decomposes to form hydrochloric acid and oxygen . it can also be
accelerated by heat or cobalt (II) salts
2HOCl (aq) 2HCl(aq) + O2(g)
iii) Bromine: its unstable in air than chlorine; reacts less readily than chlorine; the products being
a mixture of hydrobromic acid and bromic (I) oxide.
Br2(l) + H2O(l) HBr(aq) + HOBr(aq)
The hypo-bromide ion (BrO-) from HOBr undergoes disproportion (self oxidation and
reduction) forming bromide ion and bromate (V) ion
3BrO- (aq) 2Br- (aq) + BrO3- (aq)
Disproportionation reaction is a reaction in which a single chemical species is simultanepously oxidized
and reduced
Iodine is sparingly soluble in water; there is hardly any reaction with water
BrO- (from HBrO) however undergoes rapid disproportion forming bromide and bromate ion BrO3 -
3BrO- (aq) 2Br- (aq) + BrO3- (aq)
NB: in presence of a reducing agent, HClO acts as an oxidising agent
HClO (aq) + H+ (aq) + 2e 2Cl- (aq) + H2O (l)
NOTE: Moist chlorine and bromine, bromic (i) and chloric (i) acid posses bleaching properties
iv) Iodine is sparingly soluble in water but more soluble in aqueous potassium iodide.
Explanation:
This is because of formation of triodide ion complex.
I-(aq) + I2(s) > I3-(aq)

90
NOTE:
Iodine dissolves in organic solvents such as tetrachloromethane, giving a violet solution while in organic
solvents containing oxygen atom(s) example either, ethanol, iodine dissolves to give a – brown solution.
2. the products formed when group(vii) elements react with sodium hydroxide solution depends on both
the concentration of sodium hydroxide and temperature. Again vigor in reaction decreases down the
group(vii).

With cold dilute sodium hydroxide solution.

a) Fluorine again liberates oxygen difluoride gas and forms a fluorides and water. Other group (vii)
cannot give a gas.
Ionic equation:
2F2(g) + 2OH(aq) 2F(aq) + OF2(g) + H2O(l)
b) Chlorine gives a chloride, chlorate(l) and water,
Bromine and iodine give similar products.
Cl2(g) + 2OH(aq) Cl(Q) + ClO(q) + H2O(l)
Br2(g) + 2OH(aq) Br(q) + BrO(q) + H2O(l)
I2(g) + 2OH(aq) I(q) + IO(q) + H2O(l)
With hot concentrated sodium hydroxide solution
a) Again fluorine gives out oxygen and the rest of the elements from halide ion, halite (v) ion and
water
2F2(g) + 4OH(aq) 4F(aq) + O2(g) + H2O(l)
3Cl2(g) + 6OH(aq) 5Cl(aq) + ClO3(g) + 3H2O(l)
Chlorate(v)
3Br2(g) + 6OH(aq) 5Br(aq) + BrO3(g) + 3H2O(l)
Bromated(v)
3I2(S) + 6OH(aq) 5I(aq) + IO3(g) + 3H2O(l)
Iodate(v)
Compounds of group (VII)
Hydrides of group (vii) and group(vii) oxyacids only will be considered.
Chemical properties of group (vii) hydrides.
Hydrogen hydrides are unreactive but react with water to give an acidic solution example
HCl(g) + H2O(l) H3O+(aq) + Cr(q)

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Displacement reactions
Stronger reducing agents than hydrogen chloride are easily oxidized by concentrated sulphuric acid
HCl(g) + H2SO4(l) X
2HBr(g) + H2SO4(q) SO2(g) + 2H2O(l) + Br2(aq)
A reddish brown solution is observed.
6HI(g) + H2SO4(q) S(s) + 4H2O(l) + 3I2(aq)
Also 8HI(aq) + H2SO4(q) H2S(G) + 4H2O(l) + 4I2(aq)

NB:HF<HCl<HBr<HI because of the increasing Atomic redius and decreasing electronegativity.

Group (VII) oxyacids
Example HOCl, HCIO2, HClO3, HClO4. These show acid properties which increase with the number of
oxygen atoms in the molecule.

Explain the trend in acidic properties of the oxyacidic

Acidic strength is caused by the more electronegative oxygen atom pulling the bonding electrons towards
its self through chlorine atom and the more the number of oxygen atoms in one molecule the more
tendency (easily) the hydrogen ion is realized.

NOTE: Increasing oxygen content leads to

a) An increase in thermal stability
b) An increase in strength of the acid
c) A decrease in oxidizing power.

1. The boiling points of the hydrides of group (vii) elements are given in the table below
Compound HF HCl HBr HI
B.P (0c) +19.9 -85.0 -66.7 -35.4
a) Explain the trend in the boiling points of the hydrides

92
b) Giving reasons suggest the trend in acid strength of the hydrides.
c) Using equations where possible explain what happens when concentrated sulphuric acid is mixed into
each of the hydrides.
d) i) Arrange the following compounds in order of their increasing acid strength HClO, HClO2, HClO3,
HCIO4.

ii) Explain your answer in d) (i) above.

Self check:

2. a) Describe briefly how chlorine is produced on a large scale.

b) Describe briefly how chlorine can be converted to potassium chlorate(v) crystals in the laboratory.
c) 2.0g of a mixture of potassium chloride and potassium chloride were dissolved in 250cm3 of
water. 10.0cm3 of the solution was mixed with excess potassium iodide. The iodine liberated
required 8.00cm3 of a 0.2m sodium thiosulphate solution for compete reaction. Potassium
chlorate and potassium iodide react according to the equation.
CIO3(aq) + 6H+(aq) + 6I-(q) 3I2(q) +Cl-(q) + 3H2O(l)
Calculate the percentage of potassium chloride in the mixture.
d) Explain why chlorine is more soluble in dilute sodium hydroxide than in water.

3. a) Explain why fluorine shows some differences in its properties from the rest of the elements of
the periodic table in group(ii)
c) state the differences between the chemistry of fluorine and the rest of the elements of groupvii of
the periodic table.

c) write equations to compare the reactions of fluorine and chlorine when they react separately
with
i) water
ii) Cold dilute sodium hydroxide
iii) hot concentrated sodium hydroxides
d) write equation for the reaction between hydrofloirix acid and silicondioxide.

93
 TRANSITION ELEMENTS:
Are metals with a partially filled d-sub shell in atleast one of the ion formed.
Transition elements are sometimes known as the d-block elements because it is the inner d-subshell that
is filling.

Example: 26Fe IS22522P63523P6 366452

The first series of transition elements scadium to Zinc only will be considered.

The characteristics properties of Transition elements.

1. Shows variable oxidation states.
2. Form complex ions
3. Form coloured ions
4. Show catalytic activity
5. Show paramagnetism

Element Scan Titani Vanad Chroni Manga Ion Cobalt Nickel Coppe Zinc
dium um ium um nese r
Symbol Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic no. 21 22 23 24 25 26 27 28 29 30
Outer 3d14 3d2452 3d3452 3d5452 3d5452 3d6452 3d7452 3d8452 3d1045 3d1045
configuration 52 1 2

NOTE:
a) Electronic configuration of chromium and copper for
Cr 3d5451
Cu 3d10451

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 Chromium has its 3d half filled and copper has full 3d sub shell and their formation is therefore
fovoured.

b) Why scandium and Zinc are not regarded astypical transition elements?
1. Both elements show one oxidation state, Scandium Sc3+ and Znc, Zn2+.
2. The 3d sub shell for scandium ion is empty while the 3d sub shell for zinc ion is full.

As a result of these two reasons, compounds formed by scandium and zinc are white.

Typical transition elements form coloured compounds ions.

1. Variable oxidation states
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 +3 +3
- +4 +4 - +4 - +4 - - -
- - +5 - - - - - - -
- - - +6 +6 - - - - -
- - - - +7 - - - - -

 The most common oxidation states of each element is indicated and should be memorized.
 Manganese at the peak and shows maximum number of oxidation state example MnO4 is +7

That is,
MnO4 let the oxidation state of manganese be x
Then x + (-2x4) = -1 (since oxidation state for oxygen -2)
X -8 = -1
X – 8+8 = -1 +8
X=+7
 The metals show highest oxidation states when combined with oxygen or fluorine, the most
electronegative elements.

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  Multiple oxidation states occur because the 3d sub shells are very close in energy to the 45 sub
shell. So it is relatively easy to lose electrons in 3d and 45 sub shells.
 In lower oxidation states, compounds formed are more ionic and form basic oxides, where as at
higher oxidation states covalent and acidic compounds are formed.
Example FeCl2 and FeCl3, iron (ii) chloride, FeCl2 is ionic and basic and iron(ii) chloride FeCl3 is
covalent and acidic.

2. Form coloured ions

The d-orbitals are not all identical in energy and it is possible to promote electrons from one d-level to
another d-level. The light absorbed in these energy transitions is in visible region of the spectrum. The
colour of the ion is complementary to the colour absorbed.

Example
[Cu(H2O4]2+ ion appears blue because red light is absorbed.
Also type of ligard causes different light to be absorbed.
3. Catalytic activity

Transaction metals and some of the compounds they form can be used to alter the rate of a particular
reaction. This is because the transition atoms have different oxidation states, thus providing a path of
lower activation energy.

4. Paramagnetism
This arises because of the unpaired electrons in the partially filled 3d orbitals of the cations. The ions
attract the magnetic lines of force in a magnetic field. The magnetic field is produced by the movement of
an unpaired negatively charged electron.
A substance (example s-block elements and copper) is said to be diamagnetic because it is repelled by the
magnetic field since it contains no unpaired electrons

5. Complex ions
Explanation for formation of complexes

96
 Because d-block elements have
i) small atomic radius
ii) high charge, this causes the ions to have a stronger polarizing power, and attract other species that
are rich in electrons.
 Transition metal atoms have partially filled 3d sub shell of suitable energy. Ligards that are either
anions or neutral molecules with a lone pair of electrons available donate it to 3d sub shell forming
coordinate bonds

Example
Tetra amine copper (ii) ion
[Cu(NH3)4]2+ has the structure

Has coordination number of 4

Nomenclature of complex ions:
Complex ion can be represented as
[MLn]+y
Where M is the central metal ion
L is the ligard, an atom or group of atoms with negative charge or lone pair of electrons that
forms co-ordinate bonds with central ion.
N is co-ordination number, number of ligrds surrounding the central metal ion.
IY is the over all charge on the complex ion.

Rules used:
1. The name begins with a number and name of the ligards. The prefixes di-, tn-, tetra-, penta-, gexa-
, etc are used to indicate number of ligards.

Ligards are of two types:

97
Anionic or negatively charged e.g SO42-, Cl- etc and Nuetral ligards are not charged. E.g NH3, CH3CH2,
NH2CH2CH2NH2etc.

Formula of ligards Name of liquid in complex

H2O Aquo (aqua)
NH3 Ammine
NO2- Nitro
SO42- Sulphate
Cl- Chloro
Br- Bromo
CN- Cyano
NH2CH2CH2NH2 Ethane 1,2 - diamine

Ligards that are negatively charged, their name ending is with the letter “O”
Ligards can also be classified as
i) Mono dentate – make one bond per molecule with the metal central atom.

Example [Cu(NH3)4]2+

ii) Bidentate: ligards make two bonds with the metal central atom.
iii) Example Cu(NH2CH2CH2NH2)

2. The name of the central metal ion and its oxidation state indicated in Roman cameral is given. If
the complex is negatively charged, the suffix –ate is inserted to the name of the central atom.

98
Example: [Cu(NH3)4]2+tetra ammine copper(ii) ion
[Zn(OH)4]2- Tetra hydroxo Zinate (ii) ion
[Fe(CN)6]4- Hexacyno ferrate (ii) ion

Self check
Name the following complex ions
a) [Cr(H2O)42Cl]+
b) [Co(NH3)6]2+
c) [Fe(CN)6]3-
d) [Cu(CN)4]3-
e) [Ni(CN4)]2-

3. If a complex ion has both anionic and neutral, the number and name of anionic ligard is named
first followed by that of the neutral ligard.

Example:[Ni(NH3)5H2O]2+
Penta ammine aqua Nickel(ii) ion.
Self check:
Name the following complex ions
a) [Ni(H2O)2(NH3)4]2+

Shapes of complex ions

There are two main ones
- Octahedral
- Square planar or tetrahedral
The octahedral shape results when there are six bonds to the central metal ion and tretrahedral when there
are four bonds.

Examples:
h)
[Co(NH3)6]2+

99
 Has shape

And it is octahedral
ii) [Cu(NH3)4]2+
Has shape

And it is square planar or Tetrahedral.

Details of the chemistry of some d-block elements

1. Manganese, Mn
Atomic number 25
Electronic structure IS22522P63523P6 3d5452
Manganese can exhibit all oxidation state from +I to +7
Principal oxidation states +2, +3, +4, +6, +7.

Chemical properties:
1. Pure manganese is not attacked by air at room temperature but if finely divided, burns when
heated strongly.
Mn(s) + 2O2(g) Mn3O4(s)
2. With water
Pure manganese does not attack water or steam but when heated, it gives manganese(ii) oxide and
hydrogen gas.

100
 Mn(s) + H2O(l) MnO(s) + H2(g)
3. With dilute acids
Dilute hydrochloric acid and dilute sulphuric acid separately are rapidly attacked by manganese,
forming corresponding manganese (ii) salt and hydrogen gas
Mn(s) + 2H+(aq) Mn2+(aq) + H2(g)

Dilute nitric acid yields oxides of nitrogen.

Concentrated nitric acid gives namely nitrogendioxide.
4. With other non metals
Manganese when strongly heated separately combines directly with nitrogen and chlorine to give
manganese (ii) nitride and manganese (ii) chloride.
3Mn(s) + N2(g) Mn3N2(s)
Mn(s) + Cl2(g) MnCl2(s)
Compound of manganese
a) The most important oxidation state of manganese is +7 in MnO4(aq)
This compound is purple in aqueous solution and it is a very powerful oxidizing agent in acidic
media where it is reduced to manganese(ii) ions.
Writing the half equation:
Step 1. Identify both the reactants and products
That is, MnO4-(aq) Mn2+(q)
(Reactant) (product)
Step2: Balance the number of atoms, oxygen is balanced using water,
MnO4-(s) Mn2+(aq) + 4H2O(l)
Step 3: a hydrogen is balanced using H+ ions or OH
MnO4-(s) + 8H+(q) Mn2+(aq) + 4H2O(l)
Step 4: Obtain a charge balance for half equation by adding electrons to the right – hand side of the
oxidation half – equation or to the left hand side of the reduction half equation.
MnO4-(s) + 8H+(q) + 5e- Mn2+(aq) + 4H2O(l)

NOTE: The number of electrons added is equal to the difference in charges.

That is LHS = -1 ++8 RHS = +2
= +7

101
Differences = +7 - +2
=5 so you add 5 electrons
But in alkaline solution MnO4- is a less effective as an oxidizing agent and the reduction stops at
manganese (iv), MnO2, a brown solid in aqueous solution but a black solid when anhydrous half
equation MnO4-(q) + 2H2O(l) + 3e- MnO2(s) + 4OH(q)

Example:
Write a balanced equation between acidified potassium manganate(m) andiron(ii) ions.
Solution
MnO4-(q) + 5Fe2+(q) + 8H+(q) Mn2+(q) + 5Fe3+(aq) + 4H2O(l)
Self check:
Write equation between acidified potassium permanganate and
(i) otalate ions (C2O42-)
ii) Sulphate ions (SO32-)
iii) Tin(ii) chloride (Sn2+)
iv) Hydrogen peroxide (H2O2)

Similarities between manganese (vii) and chlorine (vii) compounds.

Apart from the fact that manganese (vii) compounds are highly coloured.
 Manganese (vii) oxide Mn2O7 and chlorine heptoxide Cl2O7 are explosive covalent liquids.
 The manganese(vii) ion MnO4- and the chlorate (vii) ion ClO4- are oxidizing agents but MnO4 is
more powerfull than ClO4-
 They are both isomorphous.

Chromium, Cr
Atomic number 24
Electronic structure IS22522P63523P6 3d5451
Chromium can exhibit the following oxidation states +3 the most stable and +6 oxidizing and +2
reducing).
Chemical properties
a) Reaction with air

102
It is resistant to chemical attack at room temperature, however, it combines with non – metals such as
oxygen and chlorine on heating and will decompose steam at red heat
2Cr(s) + 3O2(g) 2CrO3(s) Chromuim (vi) oxide)

NOTE: CrO is not very stable.

b) Reaction with water
It does not attack water but when heated to red heat it reacts with steam.
2Cr(s) + 3H2O(g) Cr2O3(s) + 3H2(g)
(Red-hot)
c) Reaction with Acids
Dilute hydrochloric acid and cold dilute sulphuric acid reacts very slowly forming the corresponding
chromium(ii) salt and hydrogen gas
Cr(s) + 2H+(q) Cr2+(q) + H2(g)
But Cr2+ ions formed are readily oxidized to Cr3+ by atmospheric oxygen.
It is rendered passive by concentrated nitric acid.
Compounds of chromium:

The most important oxidation state of chlomium is +6 is Cr2O72-(q) and CrO2-(aq)

The chromate (vi) ion, CrO42-can only exist in solution under alkaline conditions and it is yellow in
colour.
When acid is added to an aqueous solution of chromate(vi) ions the colour changes from yellow (the
colour of chromate(vi) ions to orange (the colour of the dichloromate (vi) ion,
That is CrO42-(aq) + 2H+(q) < Cr2O72-(q) + H2O(l)
The reaction is easily reversed by adding alkali (OHions)
The dichromate (vi) ions is an oxidizing agent in acidic media where it is reduced to chromium (iii) ions
which is green in colour.
That is
Identify products Cr2O72-(aq) Cr3+(aq)
Balance atoms Cr2O72-(aq) 2Cr3+(aq)
Balance oxygen Cr2O72-(aq) 2Cr3+(aq) + 7H2O(l)

103
Balance Hydrogen Cr2O72-(aq) + 14H+(aq) 2Cr3+(aq) + 7H2O(l)
Balance charges Cr2O72-(aq) + 14H+(aq)+ 6e 2Cr3+(aq) + 7H2O(l)

Self check:
1. a) Determine the oxidation state of chromium in the following
i) K4[Cr(CN)6] ii) [CrCl2(H2O)4]+
b) with the help of balanced chemical equations, compare the reactions of chromium and
magnesium with
i) Dilute hydrochloric acid
ii) distilled water
2. Write equations between dichromate(vi) ions and the following:-
a) Iron (ii) salt
b) Hydrogen sulphide gas
3. i) state two common oxidation states of chromium
ii) Write the electronic configuration of cronium ions in the oxidation state you have stated in (i).
iii) Write the formula of one compound in each case in which chromium shows the ocidation states
you have stated in (i). (your answer should not include chrome alum and potassium
chromate).
b) a dilute solution of chrome alum, K2Cr2(SO4)4. 2H2O was prepared and divided into two portions.
i) the first portion turned blue litmus red. Explain the observation and write equation to illustrate your
answer.
ii) To the second portion was added few drops of sodium carbonate solution state what was observed
and explain your answer.
c) When about 1cm3 of dilute sulphuric acid was added to about 1cm3 of potassium chromate,
an orange solution was observed. Abortion of an excess dilute sodium hydroxide solution to
the mixture gave yellow solution. Write equations for the reactions that took place.
d) Briefly describe a test that can carried out in the laboratory to confirm that potassium
chromate contains chromium ions.

104
Cobalt, Co
Atomic number 27
Electronic structure IS22522P63523P6 3d5452
Cobalt can exhibit the following oxidation state +2 and +3.

Chemical properties
a) Reaction with air
No reaction at room temperature
Co(s) + O2(g) X
b) Reaction with water
No reaction at room temperature
Co(s) + HO2(g) X
c) Reaction with acids
It reacts with dilute hydrochloric acid and dilute sulphuric acid at room temperature to give the
corresponding cobalt(i0 salt and hydrogen gas.
Co(s) + 2H+(aq) Co2+(aq) + H2(g)
Concentrated nitric acid renders it passive.

Compounds of Cobalt
Cobalt(iii) compounds.
Examples, cobalt(iii) fluoride CoF3, that is
2Co(s) + 3F2(g) 2COF3(s)
Cobalt (iii) sulphate CO2(SO4)3.18H2O
Compounds containing cobalt in the +3 oxidation state are more stable (not such powerful oxidizing
agent).
Cobalt (iii) complexes are all octahedral in shape

105
Examples [Co(NH3)6]3+, (Co(CN)6]3-, [Co(NO2)6]3-
Check: Name the complexes above.
Cobalt(ii) Compounds
This is the most stable oxidation state of cobalt in solution and in the absence of strong completing agents
such as NH3 and CN
In solution Cobalt(ii) salts are pink, the colour being due to the presence of Co(H2O)62+(aq), ions.

NOTE: Cobalt(ii) complexes containing NH3 and CN ligads are readily oxidized to cobalt(iii)
complexes.
Self check:
1. Cobalt(ii) oxide can be obtained by heating cobalt(ii) carbonate or cobalt(ii) nitrate in the absence
of air
a) Write equation in each case
b) Explain what would happen if the salts are heated in the presence of air.

Iron, Fe
Atomic number 26
Electronic structure IS22522P63523P6 3d6452
Iron can exhibit the following oxidation state +2(reducing) and +3 (the most stable).
Chemical properties:
a) Reaction with air
Iron burn in oxygen with a shower of bright sparks forming iron(iii) oxide, Fe2O3
4Fe(s) + 3O2(g) 2Fe2O3(s), But in the massive from iron is coated with a layer of magnetic
oxide of iron, Fe3O4.

NOTE: Combined action of air and water results in the formation of rust, hydrated iron(iii) oxide.
Fe2O3XH2O
b) Reaction with water
At red heat iron is attacked by steam forming magnetic oxide of iron and hydrogen.
3Fe(s) + 4H2O(g) , Fe3O4(s) + 4H2(g)
Other non-metals such as halogens, nitrogen, sulphur and carbon combine with iron on heating.
2Fe(s) + 3Cl2(g) 2FeCl3(s)
Fe(s) + S(s) FeS(s)

106
3Fe(s) + C(s) Fe3C(s)

c) Reaction with acids

Dilute hydrochloric acid and sulphine acid reacts with iron to give the corresponding iron(ii) slats and
hydrogen gas.
Fe(s) + 2H+(aq) Fe2+(q) + H2(g)

NOTE: In presence of air the iron(ii) ions are slowly oxidized to iron(ii) ions.
However concentrated sulphuric acid oxidizes iron to iron (iii) salts.
2Fe(s) + 6H+(aq) 2Fe3+(q) + 3H2O(L) + 3SO2(g)
It is also attacked by dilute nitric acid on warming to form iron(iii) ions.
Fe(s) + 6H+(aq) Fe3+(q) + 3H2O(l) + 3NO2(g)
Concentrated nitric acid renders it passive.
Compounds of iron:
Iron forms compounds in +2 and +3 oxidation states

Examples iron (ii) hydroxide, Fe2O3.XH2O, Haematite, Fe2O3, Magnetic, Fe3Op, Iron (ii) Oxalate,
FeC2Op, Iron (ii) sulpahte FeSO4,
Bothe most important is
Ammonium ferrors sulphate, (NH4)2SO4FeSOP.6H2O
Used as a primary volumetric standard, especially for standardizing
Potassium manganate(vii) solution. That is,
MnO4-(aq) + 8H+(aq)+ Fe Mn2+(q) + 4H2O(l)
+ 5Fe2+(q) 5Fe3+(q) + 5e.
MnO4-(aq) + 5Fe2+(aq) + 8H+ Mn2+(q) + 5Fe3+(q) + 4H2O(l)

NOTE: Iron (iii) carbonate does not exist because hydrated iron(iii) ions are more acidic than hydrated
iron(ii) ions. (the smaller iron(iii) ions polarize co-ordinating water molecules to a greater extent than the
larger iron(ii) ion which are also less heavily charged). A strong base such as Co32- abstracts protons
very readily from hydrated iron(iii) ions forming hydrated iron(ii) oxide.
Fe(H2O)63+(q) + 3CO32(q) < Fe(H2O)3(OH)3(s) + 3HCO3-(q)
Then 2Fe(H2O)3(OH)3(s) Fe2O3(s) + 9H2O(l)
For that same reason, Aluminium carbonate does not exist.

107
Self check:
1. a) Explain the meaning of the terms “transition metal” and “complex ion” illustrating your
answers by reference to manganese.
c) Discuss two examples of the use of complex ion formation in qualitative analysis
d) Justify the classificationof manganese as a transition element, illustrating your answer by
reference to suitable compound of manganese.
COPPER, Cu
Atomic number 29
Electronic structure IS22522P63523P6 3d0451
It exhibits +1 and +2 (most stable) oxidation states.
Chemical properties:
Reaction with air:
At about 3000c it is attacked oxygen giving a black coating of copper (ii) oxide on its surface.
2Cu(s) + O2(g) 2CuO(s)
In moist air it gradually becomes coated with CuCO3, CuSO4 and Cu(OH)2.
Reaction with water
No reaction with water or steam
Cu(s) + H2O(l) X
Reaction with Acids
Dilute hydrochloric acid and sulphuric acid does not react with copper. But hot concentrated sulphuric
acid attacks the metal.
Cu(s) + 2H2SO4(l) CuSO4(s) + 2H2O(l) + SO2(g)
Dilute nitric acid attacks copper to give nitrogenmoxide water and the copper(ii) nitrate.
3Cu(s) + 8HNO3(Q) 3Cu(NO3)2(q) + 4H2O(l) + 2NO(g)
But with concentrated nitric acid nitrogen oxide is given off.
Cu(s) + 4HNO3(l) Cu(NO3)2(q) + 2H2O(l) + 2NO2(g)
Reaction with other non metals
i) Sulphur
Copper is attacked by sulphur vapours to give copper(i) sulphide
2Cu(s) + S(s) Cu2S(s)
b) Aalogens (F2, Cl2, Br2 and I2)
When heated copper give copper (ii) halides except iodine which forms copper(i) iodide. That is

108
Cu(s) + Cl2(g) CuCl2(s) and
2Cu(s) + I2(g) 2CuI(s)
Copper compounds
Copper form compounds in +2 and +1 oxidation state.
Most important is copper(ii) sulphate , CuSO4.5H2O which has many industrial uses such as preparation
of Bordeaux mixture a fungicide and preparation of other copper compounds. It is also used in
electroplating solutions, in textile dyeing and as a timber preservative.
Zinc, Zn:
Atomic number 30, electronic structure IS22522P63523P6 3d10452
Zinc forms only +2 oxidation state.
Chemical properties
Reaction with air:
On prolonged exposure zinc gradually becomes coated with layer of zinc oxide and basic zinc carbonate.
Non metals such sulphur and halogens combines directly on heating.
Reaction with water:
No reaction with cold water but
Hot zinc will displace hydrogen from steam.
Zn(s) + H2O(g) ZnO(s) + H2(g)
Reaction with Acids:
Dilute non- oxidizing acids such as hydrochloric and sulphuric acids attacks zinc forming the
corresponding zinc(ii) ions and hydrogen
Zn(s) + 2H+(q) Zn2+(q) + H2(g)
The reaction is very slow due to a protective layer of oxide.
However with hot concentrated sulphuric acid sulphuroxie, water and zinc sulphate are given out.
Zn(s) + 2H2SO3(l) ZnSO4(q) + 2H2O(l) + SO2(g)
Reaction with sodium hydroxide solution.
Zinc reacts slowly with sodium hydroxide solution liberating hydrogen,
Zn(s) + 2OH(aq) + 2H2O(l) Zn(OH)42-(aq) + H2(g)
NOTE: The action of aluminium on alkalis is more violent.
Compounds of Zinc
Forms compounds in +2 oxidation state. The most important is Zinc oxide which dissolves in an aqueous
solution of sodium hydroxide
ZnO(s) + 2OH(aq) + H2O(l) Zn(OH)42-(aq)

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It is used as filler in rubber. It is used as a catalysit in the manufacture of methanol from synthesis gas.

EXTRACTION OF ELEMENTS FROM ORES

An ore is a naturally occurring substance from which an element may be extracted.
A metal: is a substance, obtained by mining.
General procedures for extraction of metals
Are three
1. Concentration of ore (mineral dressing)
2. Reduction (smelting)
3. Purification or refining of the metal.
1. Concentration of the ore
Before proper concentration is done, physical separation of gangue is done to avoid wasteful smelting of
worthless material.
Gangue consists of siliceous matter (crock, clay and earth)
The ore is broker up into humps which are then ground down (pulverized).
There are two general methods of concentrating ores
a) Physical methods
b) Chemical methods
Physical method: make use of differences in density or magnetic properties and are three
1. Washing:
Ores are usually denser than gague which can be washed away in stream of water.
Example a) Galena Pbs, mixed with limestone. The lime stone is washed away.
b) Cassiterite SnO2 mixed with silicates.
The silicates are washed away.
2. Magnetic separation: is used to separate wayramites the principal ore of tongsten, from cassiterite
with which it is found.
The tongsten ore is attracted by a magnet, the cassiterite is not.
3. Froth flotation: This is a widely used and important method for sulphide ores.
The finely powdered ore is moixed with suitable oil and water. The oil wets the sulphide particles and
water wets the gangue.
Compressed air is then blown through, to a gitate the mixture.

110
The minerals are carried up to the surface, leaving the gangue at the bottom. The froth is skimmed off
and the sulphide recovered.

Examples: Galena and Zinc blende, Zns, Galena is first removed in the froth and then Zinc blende is
removed later.

Chemical methods:
Are two:-
a) Heating, roasting
b) Leaching
1. Heating and roasting
Some moist hydrated iron ores are heated to drive off water. Roasting in air is sometimes used to remove
water, carbonaceous matter, and to convert sulphides and carbonates to oxides.
Example with zinc blende and zinc carbonates.
2. Leading with aqueous solvents
a) Zinc ores are leached with dilute sulphuric acid.
b) Reduction:
1. High temperature reduction with carbon or carbonmonoxide example iron and zinc and
2. Electrolysis of mollen compounds of metals or their aqueous solution.
Example Aluminium and zinc
c) Purification (refining)
Can be by electrolysis, distillation or liquation example of copper and zinc.

Self check:
1. a) 8.0g of copper ore was leached with dilute sulphuric acid and the resulting solution diluted to
250cm3. To 30.0cm3 of this solution was added excess 10% potassium iodide solution. The
liberated iodine required 23.5cm3 of 0.05M sodium thiosulphate solution for complete reaction.
Calculate the percentage of copper in the ore. The reactions which take place are.
2Cu2+(q) + 4I-(aq) Cu2I2(s) + I2(s)
I2(s) + 2S2O32-(aq) 2I-(aq) + S4O62-(aq)

111
 QNS
2. a) Explain what is meant by the term ore
c) Describe two ways in which ores can be concentrated by

1. physical method
2. chemical method
(illustrate your answers with suitable examples)
3. a) explainthe following process as used in the extraction of metals.
i) Flotation
ii) Roasting
iv) Smelting
b) Describe briefly how the percentage purify of an iron ore can be determined in the laboratory (hint)

Extraction of Aluminium:
The most important ore of aluminium is bauxite, Al2O3.2H2O
The chief impurities are iron(iii) oxide, titanium(iv) oxide and sodium aluminium silicate.
Bauxite is roasted in air to convert iron(ii) oxide to iron(iii) oxide. The residue is firely powdered, then
digested with concentrated sodium hydroxide solution under pressure.
Aluminium oxide posses into solution as aluminate ion.
Al2O3(s) + 2OH(q) + 3H2O(l) 2Al(OH)4-(aq)
The impurities remain undissolved (iron iii) oxide). The solution is removed, diluted and seeded by
adding crystals of pure aluminium hydroxide or with carbondioxide.
Al(OH)4-(aq) Al(OH)3(s) + OH(aq)
The precipitate is removed, washed and dehydrated by heating strongly, leaving aluminium oxide.
2Al(OH)3(s) Al2OH3(s) + 3H2O(l)
Aluminium oxide is then dissolved in molten cryolite Na3AlF6 nad electrolysed.
Calcium fluoride is added to lower the melting – point.
Aluminium is discharged at cathode which is made of carbon.
Al3+(aq) + 3e Al(s)
And oxygen at the carbon anode

112
2O2-(q) O2(g)) + 4e
The carbon anodes burn to carbondioxide
C(s) + O2(g) CO2(g)
And CO2 is reduced to carbonmonoxide.
The anode has tobe replaced from time to time because it burns to form carbondioxide.

Self check:
1. a) Write the formula of an ore of aluminium
b) During the extraction of aluminium, the ore is first treated with sodium hydroxide, followed by
aluminium hydroxide.
i) state the purpose of adding sodium hydroxide
ii) write equation for the reaction between the ore and sodium hydroxide.
iv) What is the purpose of adding aluminium can be obtained after the ore has been treated as in
(b).
d) Carbondioxide was used instead of aluminum hydroxide in (b) write equation for the reaction that
took place.
2 during the extraction of alminiumfrom baufite the ore is first heated, powdered and then the
powdered material is heated with sodium hydroxide solution and finally filtered.
a) State why the
i) Ore is first heated before changing it to the powder.
ii) Powdered ore is heated with sodium hydroxide solution and then filtered.
b) Write equation for the reaction between the powdered ore and sodium hydroxide solution.
c) Briefly describe how pure aluminium can be obtained from the products from the reaction in (b)
(your answer should include equations).
d) Write equation for the reaction between aluminium and
i)Fe2O3
ii) Mn3O4(s)
iii) Cr2O3(s)
e) Use equation to show how anhydrous aluminium chloride can be prepared.

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Extraction of Copper:
The most important ore of copper is Copper pyrites, CuFeS2.
The chief impurities are silver and sulphur and iron(ii) oxide.
The ore is first concentrated by froth floatation before it is roasted in air. The copper pyrite is mixed with
pine oil to form a froth while ethylxanthale of potassium or sodium as a collector. It makes the surlphide
parties in the ore water repellant and thus increasing its concentration.
The concentrated ore is roasted in air to form copper(i) sulphide and iron(ii) oxide.
2CuFeS2(s) + 4O2(g) Cu2S(s) + 2FeO(s) + 3SO2(g)
The iron II oxide is removed from the mixture by reacting it with Silica.
FeSO(s) + SiO2(s) FeSiO3(s)
This is removed as a slag.
The copper(i) sulphide is reduced to themetal by burning off the sulphur in a controlled supply of air.
Cu2S(s) + O2(g) 2Cu(s) + SO2(g)
The resulting copper is impure and is refined by electrolysis, impure copper is the anode white a strip of
pure copper is the callode in a solution of copper(ii) sulphate as the electrolyte. During electrolysis
copper is transferred from the anode to the cathode. NB: An anode sludge containing silver and gold is
produced during this process, the helping to make the process economically feasible.

Self check:
1. a) Describe how
i) Impure copper can be obtained from copper pyrites )your answer should include equations).
ii) the percentage purity of copper can be determined in the percentage by fitrimetric method.
b) Outline how an impure sample of copper can be purified.
2. a) i) Write the formula and the name of one ore of copper.
ii) Describe how pure copper can be extracted from the ore you have named in (a) (i).
(write equations for all reactions that take place)
b) State the conditions under which copper reacts with the following acids an din each case write an
equation for the reaction.
i) Sulphuric acid ii) Nitric acid

114
 d) State what would be observed and write an equation for the reaction which will take place when
the following reagents are added dropwise to a solution of copper(ii) sulphate until in excess.
i) concentrated hydrochloric acid
ii) sodium hydroxide solution.
Extraction of Zinc
The chief ore is Zinc blende ZnS
The ore is crushed into powder and mixed with water containing a froathing agent (pine oil) in a
concentration tank.
Air is bubbled into the mixture to agitate the ore .
The air bubles adhere to the ore particles and float as a froath while the heavy impurities sink to the
bottom.
The froath is skimmed off (decanted) and dried roast the concentrated ore in air to form Zinc oxide and
sulphurdioxide gas.
2ZnS(s) + 302(g) 2ZnO(s) + 2502(g)
Zinc oxide is leached with dilute sulphuric acid.
ZnO(s) + H2SO4(g) ZnSO4(q) + H2O(g)
The resultant solution is treated with calcium hydroxide solution to precipitate insoluble metal hydroxide.
Acidify the resultant mixture and electrolyse the solution using an Alminium cathode and carbon anode.’
Zinc ions are discharged ( reduced) to pure Zinc metal at the cathode.
Zn2+(aq) + 2e- Zn(s)
Self check:
1. a) i) Write the name and formula of one ore of zinc
ii) Briefly describe how pure zinc can be obtained from the ore you have named in (i)
c) i) Name one reagent that can be used to distinguish between zinc ions and aluminium ions in
solution.
ii) state what would be observed when zinc and aluminium ions are separately treated with the
reagent. Write equations for the reactions.
d) Explain how zinc protects iron from rusting.
2. a) Describe using equations the reactions of zinc with
i) air
ii) water
iv) sodium hroxide
b) i) Explain why zinc is not considered a typical transaction metal.

115
ii) State what is observed when dilute aqueous ammonia is added dropwise to a solution containing zinc
ions.
iii) Write the equations for the reaction that takes place in (c) (i) above,

Extraction of Iron
The most important ores are haematite Fe2O3, and magnetic Fe3O4. Extraction is done in a blast furnace
and it takes place in two stages.
a) Removal of water and other impurities of low melting point.
Here the ore is crushed and heated using hot gases from furnace to remove water and low boiling point
impurities, leaving iron oxides with silicon(iv) oxide and aluminium oxide impurities.
b) Reduction of oxide to iron

Here coke burns in lower part of furnace exothermically forming carbondioxide gas.
C(s) +O2(g) CO2(g) Then,
Carbondioxide is reduced to carbondioxide with more coke as it rises up the furnace
endothermicallyCO(s) +C(s)2CO(g) here
The carbonmonoxide reduces iron ore to iron at temperatures between 600 -7000c.
Fe2O3(s) + 3CO(g) 2Fe(s) + 3CO2(g)
NOTE: Limestone undergoes thermal decomposition to yield calcium oxide which reacts with impurities
to form slag.
CaCO3(s) CaO(s) + CO2(g)
CaO(S) + SiO2(s) CaSiO3(l) and
Al2O3(s) + CaO(s) CaAl2O4(s)
( calcium aluminate – slag)
CHECK: Iron can also be extracted from ores such as carbonate siderite (spathic iron ) FeCO3,
Ironpyriles FeS2 And the process remains the same in the blast furnace.
Self check:
1. a) Outline the reactions that take place in the blast furnace during the extraction of iron from
spathic iron, FeCO3.
b) Briefly describes how iron reacts with the following (your answer should include equations).
i) water
ii) chloride
iv) Dilute sulphuric acid

116
 v) Concentrated sulphuric acid
2. Describe briefly how the percentage purity of an iron ore can be determined in the laboratory .
a) Describe how sulphuric acid can be manufactured from iron(ii) disulphide (iron pyrites)
b) Outline how iron can be extracted from iron(iii) oxide.

LET’S REVISE

1. Explain each of the following observations

a) When lead (ii) oxide is heated with dilute hydrochloric acid the resultant solution cooled, a
white solid is formed. when concentrated hydrochloric acid is used instead of dilute, the solid
is not formed

Solution

Lead (ii) is sparingly soluble at room temperature that is why a white precipitate (solid) is formed
when the solution is cooled.

PbO(s) +2HCL (aq) PbCl2(s) +H20 (l)

(White solid)
But with concentrated hydrochloric acid a soluble complex of tetra chlorophumbate (ii) ion is
formed that is why no solid is formed.

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

117
 b) Phosphorus bu8rns spontaneously in air at room temperature whereas nitrogen is inert at the
same temperature yet both elements are in the same group of the periodic table.
SOLUTION
Phosphorus exists as p4 molecules with the structure below with weak single covalent bonds
which is readily break.
P
P P
P
Nitrogen has triple covalent bonds of high electron density and small atomic radius of
nitrogen
It also has a linear structure at 1800 which is stable
N≡N

C) When beryllium chloride is added methylbenzene, it ready dissolves white barium chloride does not.

SOLUTION

Beryllium chloride is covalent and soluble non-polar solvents due to high charge density of Be2+
polarized Cl-, Barium chloride is ionic and does not dissociate in non ionizing solvents.

d). When silicon tetrachloride is mixed with water, misty fumes are formed however there is no
observable change with carbon dioxide

SOLUTION

Silicon tetrachloride under gaps hydrolysis to give silicon (iv) oxide and hydrogen chloride gas which is
seen as misty fumes

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

Because silicon has a vacant 3d-orbital to accommodate ion pairs and weak silicon –chloride bonds
whereas carbon is small and lacks vacant o-orbital’s therefore it does not under go hydrolysis.

e) A clear solution of solution sulphate turns cloudy when left standing in air.

SOLUTION

Air contains carbon dioxide which dissolves in solution (water) to form weak carbonic acid

118
CO2(g) +H2O (l) 2H+(aq) +CO32-(aq)

Therefore thiosulphate ions react with hydrogen ions from the weak carbonic acid disproportionate into
insoluble sulphur and sulphurdioxide which are seen as cloudy.

S2O32-(aq) +2H+(aq) S(s) + SO2(g) + H2O(l)

2. The first four ionization energies of some element are as shown in the table below.

Element Ionization energies (kjmol-1

1 2 3 4
A 500 4600 6900 9500
B 740 1500 7700 10500
C 630 1600 3000 4800
D 900 1800 14800 21000
E 580 1800 2700 11600

a) What is meant by the term ionization energy?

SOLUTION

This is the quantity of energy of energy required to remove the most loosely held electron from a
gaseous atom to form a unipositively charged gaseous ion.

b) State giving a reason in each case an element that will form.

(i) A unipositively charged ion

Solution

A i.e. The difference between the first and second ionization energies is very high.

(ii) An ion with a charge of +3

SOLUTION:

B and E, group (ii)

c) Explain why ionization energy generally decreases down any group of the periodic table.

119
SOLUTION:

This is because of increased in the screening effect down a group , both nuclear charge and screening
effect increase as the number of shells increase but the increase in the number of shells gets the outermost
electron further away from the nucleus and weakens the nuclear attraction . Both of there conditions lead
to a reduction in the ionization energy.

3a) what is atomic radius?

SOLUTION:

Is the distance between the nucleus of nulcleus of an atom and the electron cloud of the outermost shell
electron?

b). How does atomic radius vary across a period

SOLUTION

The atomic radius reduces across a period because the nuclear charge increases by +1 as the atomic
number increases white the electrons are added to the same, valence shell and there is n corresponding
increase in screening effect. The outer most electron cloud is therefore drawn closer to the nucleus
causing a reduction in atomic radius.

4. Vander Waals forces are intermolecular forces of attraction

(i) What do you understand by Vander Waals forces

SOLUTION:

These are weak forces holding molecules together in a molecular crystal.

(ii) State one evidence for the existence for Vander Waals

SOLUTION

Low melting points of the Nobel gas

iii) State one other intermolecular force of attraction

Solution

Hydrogen bonds

120
 5. The elements tin and lead belong to group iv of the periodic table
a) Write the formula of the oxides of the elements in which the element has a +4 oxidation state.
Solution
PbO2, SnO2
b) Lead (ii) nitrate solution was added to sodium hypochlorite solution and the mixture heated.
(i) State what was observed.

Solution

A dark brown precipitate is formed

(ii) Write equation for the reaction

SOLUTION:

Pb2+(aq) + OCl(aq) + H2O(l) PbO2(s) + Cl-(aq) + 2H+(aq)

c) Concentrated hydrochloric acid was added to solid tritead tetra oxide and the mixture warmed
(i) State what was observed

SOLUTION:

Greenish yellow gas evolved and a white precipitate formed on cooling.

(ii) Write equation for the reaction.

SOLUTION:

Pb3O4(s) +8HCl (aq) 3PbCl2(s) + 4H2O(l) +Cl2(g)

6.a) Scandium and zinc are not typical transition elements. For each element give a reason why this is
so

(i) Scandium

Solution

The stable Sc3+ ion has emputy 3 d-orbital

(ii). Zinc

Solution

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Forms stable Zn2+ ion with a completely filled 3d-orbital

b). Give three properties of transition elements

SOLUTION:

–variable oxidation states

–complex ion formation

–formation of coloured ions or compounds

7. Give reasons for the following procedures used in analytical chemistry . Illustrate your answers with
equation

a). Sodium hydroxide solution should be prepared using freshly boiled distilled water.

SOLUTION:

Freshy boiled water locks dissolved carbon dioxide, dissolve carbon dioxide would react with sodium
hydroxide solution to form sodium carbonate and thus reduce its concentration.

2NaOH (aq) + Co2(g) Na2CO3(aq) +H2O(l).

c). Nitrates involving thiossphate solutions should not be carried out in acid medium.

SOLUTION:

The acid reacts with thiosulphate ions to precipitate sulpher and liberate sulphurdioxide

2H+(aq) + S2O32-(aq) S (s) + SO2 (g) + H2O (l)

The reaction decreases the concentration of the thiosulution.

c). Hydrochloric acid is not used to acidify potassium manganese (vii) solution

SOLUTION

Potassium permanganate oxides hydrochloric acid to chlorine.

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

8. a) (i) Name one ore of iron and write its formula

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SOLUTION

Heamatite Fe2O3

(ii). State the method by which iron is extracted from the ore

SOLUTION:

Reduction by carbon monoxide

(b). Using equations only show how iron is extracted from the above ore.

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

CO2 (g) + FeO3(s) 2CO(g)

3CO (g) + FeO3(s) 2Fe(s) +3CO2(g)

c).(i) State the conditions under which iron reacts with water .

SOLUTION:

-steam

-Heated iron metal

ii) Write equation for the reaction in C (i) above.

SOLUTION

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

9. Explain each of the following observations

a) When hydrogen iodide is treated with concentrated sulphiric acid, iodine is liberated whereas when
hydrogen chloride is similarly treated, chloride is not evolved.

SOLUTION:

Hydrogen iodide is a stronger reducing agent than hydrogen chloride .it is easily oxidized to iodine by
concentrated sulphuric acid.

H2SO4(aq) + 4HI-(aq) 2H2O (l) +2I2(g) +SO2(g).

123
b). An aqueous solution of sodium sulphite has a PH greater than where as that of sodium hydrogen
sulphite is less than 7.

SOLUTION:

Sodium sulphite is a strong electrolyte formed from a weak acid and acid and strong base. In water the
sulphourous ions undergoes hydrolysis

SO32-(aq) + 2H2O(l) H2SO3(aq) + 2OH(aq)

This disturbs the water equilibrium, more water ionizes increasing the hydroxyl ion concentration hence
Ph>7. The dissociation of hydrogen sulphite ion to hydrogen ions makes the sodium hydrogen sulphite
aqueous solution acid (PA>7).

(c) When hydrogen sulphide is bubbled through an aqueous solution of iron (ii) chloride, a yellow
precipitate is observed.

SOLUTION:

Hydrogen sulphide reduces iron (iii) chloride to iron (iii) and itself oxidized to sulphure which appears as
a yellow precipitate.

2Fe3+(aq) H2S(g) 2Fe2+(aq) 2H+(aq) + S(s)

10. (i) state what would be observed and write equation for the reaction that would take place, if any ,
when the following compound are treated with water.

(i) tetrachloromethane.

SOLUTION:

No observable change or (two separate layers)

ii) Silicon (iv) chloride

SOLUTION:

White solid and white fumes

SiCl4(l) + 2H20(l) SiO2(S) + 4HCl(g)

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Give a reason for your observation in a (i) and (ii) above

SOLUTION:

Tetra chloromethane is not hydrolyses by water because of lack of empty 3d-orbitals in carbon silicon(
(iv) chloride is hydrolyzed by water due to presence of 3d –orbital’s in silicon which receive ion pairs of
elements from water.

11. Write equation for the reactions which would take place and in each case, state what would be
observed when.

A) Ammonia solution is added drop wise until in excess to an aqueous solution of nickel (ii) sulphate
observation

SOLUTION:

Green precipitate soluble to give a pale purplish blue solution.

Equation

SOLUTION:

Ni2+(aq) + 2OH(s)

Then Ni(OH) 2(s) + 6NH3 (aq) + Ni(NH3)2+(aq) + 2-OH (aq)

(b). Excess concentrated hydrochloric acid is added to an aqueous solution of cabolt (ii) sulphate.

OBSERVATION:

SOLUTION:

Pink solution turns blue

Equation:

SOLUTION: CO(H2O)2+(aq) + 4CL-(aq) COCL42-(aq) + 6H2O(l)

C) Sodium carbonate is added drop wise until in excess to an aqueous solution of iron (ii) sulphate.
Observation

SOLUTION:

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Brown precipitate and bubbles of a colourless gas equation

SOLUTION:

2Fe3+(aq) + 3CO32-(aq) +3H3O(l) 2Fe(OH)3(S) +3CO2(g)

d) Sodium hydroxide is added to a solution of sodium dichromate

OBSERVATION:

SOLUTION:

CrO72-(aq) + 2-OH(aq) 2CrO42-(aq) +H2O(l)

e) Alkaline hydrogen peroxide is added to a solution of iron (iii) sulphate.

OBSERVATION:

SOLUTION:

Yellow solution turns green and bubbles of a colourless gas that relight a glowing splint.

Equation:

Solution

H2O(aq) +2-OH(aq) + 2Fe3+(aq) 2H2O(l) + 2 Fe2+(aq) + O2(g)

F) Tin (ii) chloride is added to acidified potassium manganate (vii) solution

OBSERVATION:

SOLUTION:

5Sn2+(aq) + 2MnO-4(aq) + 16H+(aq) 2Mn2+(aq) + 8H2O(l) +5Sn4+(aq)

12. a) Carbon and silicon form tetrachloride with a simple molecule structure and the same shape

a) Write the electronic configuration of

(1) Carbon

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 Solution

1S22S22p6

(ii). Silicon

1S2 2 S2 2p6 3S2 2p2

b)(i) Briefly explain why the tetrachloride molecules have the same shape.

SOLUTION:

The central carbon and silicon atoms are each surrounded by four bonds pairs of electrons and no ion
pairs hence there is equal repulsion between the bond pairs hence the tetrachloride adopt atetradral
structures shown below .

Cl Cl

C and Si

Cl Cl Cl Cl Cl Cl

c. Water was added to each of the tetrachlorides of carbon and silicon

i) State what would be observed in each case

Solution

CCl4 –No observable change

SiCl4 - misty (white) fumes and a white solid (precipitate)

(ii) Explain your observation in c(i) above.

Solution

The carbon atom is small and lacks vacant –d-orbital hence carbon tetrachloride does not hydrolyse

Silicon tetrachloride undergoes hydrolysis to form

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Silicon dioxide and hydrogen chloride gas since silcon has accessible vacant -3d-orbitals

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

13. Using equations to illustrate your answer state any three chemical properties to show the

a) Similarity between lead and manganese.

Solution

 They have +2 and +4 variable oxidation state

 The dioxides oxides hot concentrated hydrochloride acid to chlorine
MnO2(s) + 4HCl (aq) MnCl2(aq) + Cl(g) + 2H2O(l)
PbO2(S) + 4HCL (aq) PbCl2(aq) + Cl2(g) + 2H2O(l)
 Their oxides in oxidation state of +2 (monoxides) react with dilute mineral acid to form salts and
water
 MnO(s) +2H+(aq) Mn2+(aq) + H2O(l)
 Pb(s) + 2H+(aq) Pb2+(aq) + H2O(l)

b). Difference between chromium and magnesium

SOLUTION

 Chromium reacts with hot concentrated sodium hydroxide solution to form a complex and
hydrogen gas
 2Cr(s) +OH(aq) + 7H2O(l) 2(Cr(OH)–(aq) + 3H2(g)
Magnesium does not react with sodium hydroxide solution
Heated magnesium reacts with nitrogen to form a nitrate
3Mg(s) + N2(g) Mg3N2(s)
Chromium does not react with nitrogen gas
Chromium does not react with concentrated nitric but magnesium nitrate, nitrogen dioxide and
water
Mg(s) + 4HNO3(aq) Mg (CUO3)2(aq) + NO2(g) + 2H2O(l)
14. Copper (i) oxide, potassium manganese (vi) and chloride disproportionate in some of their
reactions
a) State what would be observed and write an equation that take place during the
disproportionate of (1) copper (ii) oxide in dilute sulphiric acid.

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 Solution blue solution and a reddish brown solid
Cu2O(s) + 2H+(aq) Cu2+(aq) Cu(s) + H2O(l).

(ii). An aqueous of potassium manganate(vi)

SOLUTION:

Green solution turns purple and a black solid

3MnO42-(aq) + 02H2O(l) 2MnO4-(aq) + MnO2(s) + 4O-H(aq)

Chloride gas bubbled through cold dilute sodium hydroxide solution

SOLUTION:

Colourless solution turns pale yellow

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

b). The product in b(iii) was heated to about 700c to form a colourless solution . Explain this observation
with the aid of an equation of reaction.

Solution

The pale yellow solution turns colourless

Chloride (i) ions disproportionate into chloride ions and chlorite ions

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

15(a) Fluorine belongs to group (vii) of the periodic table however its properties differ from the other
elements in the same group.

(i) Briefly explain why fluorine behaves differently

SOLUTION:

Fluorine has very small atomic radius, high electro negativity, low bond dissociation energy, high
positive electrode potential.

(ii). Sate any five chemical properties to show the anomalous behavior of fluorine

SOLUTION:

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Calcium fluoride is sparingly soluble in water white other holides of calciyu7m are soluble.

Fluorine oxidizes water to oxygen

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

Reacts with dilute alkalis to form oxygen diflouride

2F2 (g) + H20(aq) 4HF(aq) + O2(g)

It Does Not Form Oxycacids or Ox Ions

Hydrogen Fluoride Is A weak Acid In Aqueous Solution

b).Describe the reactions of fluorine and chlorine with

(i). carbon

SOLUTION:

Fluorine reacts with powdered charcoal to form carbontetrafloride

C(s) + 2Fe(g) Cf4(g)

Chloride does not react with carbon directly

(ii). Hot concentrated potassium hydroxide solution

SOLUTION

Fluorine reacts with hot concentrated potassium hydroxide to form oxygen gas, potassium fluoride and
water

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

Chlorine Form Potassium Chloride, Potassium Chlorate and Water

3 Cl2 (g) + 6 -OH(aq) 5Cl- (aq) + ClO3- (aq) + 3H2O(l)

Self check

1. Group (vii) elements undergo disapportionate reaction when treated with water of alkalis
a). what is meant by the term disproportionate reaction

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 b). describe the disproportionate reaction of
(i). chlorine with water
(ii) Bromine with hot concentrated sodium hydroxide solution
c). Iodine was added to dilute sodium hydroxide solution and the dilute mixture warmed
(i) Sate what was observed
(ii) Write equation (s) for the reactions

16.a) Group (ii) metals form few complexes. However the tendency to form completes decreases down
the group
(i) What is meant by the term complex?
Solution
Is a cation or anion formed between a central metal atom or ion and molecules or anions with ione pairs
of electrons through dative bonding.
(ii) Why does the tendency to form complexes decrease down the group.
Solution
The radii of cations increase down the group with a constant charge of +2. This reduces the charge
density of group (II) metal ions hence a decrease in the tendency to attract ligands.
b) Explain the following observations.
(i) A clear solution of sodium thiosulphate becomes cloudy when left standing in air
Solution
Atmospheric carbon dioxide dissolves in the aqueous solution to form carbonic acid which partially
ionizes to produce few hydrogen ions
CO2 (g) + H2O (l) CO32-(aq) + 2H+ (aq)
The hydrogen ions react with thiosulphate ions to form insoluble sulphur and sulphurdioxide gas.
S2O32- (aq) + 2H+ (aq) S(s) +SO2 (g) + H2O (l)
(ii) Aluminum forms stable compounds in the +3 oxidation state only.
Solution
Al- IS2 2S2 2P6 3S2 3Pl
The aluminum atoms lose the three electrons readily from the outermost principal quantum shell to form
Al3+ ions which are thermodynamically stable with completely filled 2p-orbitals.

17. Explain the following observations

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a. The boiling point of hydrogen fluoride is higher than that of hydrogen chloride.
Solution
Fluorine is highly electronegative hence hydrogen fluoride associates through strong intermolecular
hydrogen bonds which require a lot of heat energy to break. Hydrogen chloride molecules are held by
weak vander waals forces which easily break.
b. HClO2 is a weaker acid than HClO4
Oxygen is more electronegative than chlorine hence it has a negative inductive effect on the oxygen
hydrogen bonds. The magnitude of the inductive effect in HClO4 is greater than the effect in HClO2 due
to the presence of more oxygen atom since the more number of oxygen atoms in the molecule the more
tendencies (easy) the hydrogen ion is released.
The oxygen-hydrogen bond in HClO4 is weaker hence it breaks readily to release more protons.
c. Copper (ii) chloride is green while copper (ii) chloride is a white solid
Solution
Cu2+ IS2 2S2 2P6 3S2 3P6 3d9
Cu+ IS2 2S2 2P6 3S2 3P6 3d10
The 3d-orbital in Cu2+ ions are partially filled hence the presence of ligards absorb a radiation from
visible light and reflect green light. The fully filled 3d-orbitals of Cu2+ ions do not split on absorption of
radiations.
18(a) Determine the oxidation and coordination number of the central atom in the following complexes
i. [Pd(NH3)4]2+
Solution
Coordination number 4
Oxidation number +2
ii. [Pd Cl4]2-
Solution
Co-ordination number 4
Oxidation number +2
iii. [Fe(CN)6]3-
Solution
Co-ordination number 6
Oxidation number +3
iv. [CrCl(H2O)5]+
Solution

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Co-ordination number 6
Oxidation number +2
b)i. Write the electronic configuration of chromium
Solution
IS2 2S2 2P6 3S2 3P6 4S1 3d5
(ii) Chromium (iii) chloride was dissolved in water and the solution tested with litmus paper. State
what was observed and explain your answer.
Solution
Blue litmus turns red/pink. When dissolved in water chromium (ii) chloride forms hydrated
chromium (iii) ions or which undergo hydrolysis to form hydrogen ions or hydroxionism ions which
make the solution acid
Cr (H2O)6 3+(aq) + H2O(l) [Cr(H2O)5OH]2+ (aq) + H3O+(aq)
c. Ammonia solution was added drop-wise to an aqueous solution of a chromium (iii) salt until in
excess
(i) State what was observed
Solution
Green precipitate, insoluble in excess
(ii) Write equation for the reaction that took place.
Solution
Cr3+(aq) + 3 H(aq) Cr(OH)3(s)
19a. Draw the structure and name the shape of the following oxy anions of nitrogen.
(i) N 2

Solution
Structure Shape
V-shape

ii. NO3 -
Solution
Structure O Shape
Trigonal planar
N

133
b(i) Name the reagent(s) that can be used to distinguish between the oxy anions in (a)

Solution

 Acidified potassium Manganate (VII) solution

Alternatively

1. Acidified potassium dichromate solution

OR

2. Freshly prepared Iron II Sulphate solution followed by concentrated Sulphiric acid

(ii) State what would be observed if a solution of each oxy anion is treated separately with the
reagents you have named in b(i) above

Solution

NO2- ___ Solution turns from purple to colorless

NO3-___Shows no observable change

Alternatively
NO2- ___ Orange solution turns green

NO3-___Shows no observable change

NO2- ___ No observable change

NO3-___Brown ring at liquid junctions

(iii) Write the equation(s) of any reaction(s) that would take place when a solution of each oxy anion is
treated separately with the reagent(s) you have named in (b)(i)
Solution

2MnO4-(aq) + 5NO2-(aq) + 6H+(aq) 2Mn2+(aq) + 5NO3-(aq) + 4H2O(l)

Alternatively

1-2CrO72-(aq) + 3NO2-(aq) + 8H+(aq) 2Cr3+(aq) + 3NO3-(aq) + 4H2O(l)

OR
6Fe2+(aq) + 8H+(aq) + 2NO2-(aq) 6Fe3+(aq) + 4H2O(l) + 5NOaq

Fe(H2O)62+(aq) + NO(aq) [6Fe(H2O)5 NO]2+aq

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20a. Calculate the oxidation state of chlorine in each of the following ions
i. ClO-2
Solution
Let oxidation state of chlorine be x
X+2(-2) = -1
x-4 =-1
x=-1+4
=+3
ii. ClO-4
Solution
Let oxidation state of chlorine be x
X+ (4x-2) = 1
X – 8 =1
X =1+8
= +7
b) The molecular formula of a complex of cobalt is
[Co (NH3)5 (H2O] Cl3
i. Write he name of the complex.
Solution
Penta-ammine mono aquo Cobalt (III) Chloride
OR, penta-ammine mono aqua Cobalt (III) chloride
ii. State the co-ordination number of cobalt in the complex
Solution
c. Excess dilute ammonia solution was added to the complex
i. State what was observed
Solution
Brown solution turns red
ii. Write equation for the reaction that took place

Solution

[Co (NH3)5 H2O]3+(aq) Co(NH3)3+6(aq) + H2O(l)

135
d. To 10cm3 of a 0.5M solution of the complex, was added excess silver nitrate solution.
(i) State what was observed.
Solution
White precipitate
(ii) Write equation for the reaction that took place
Solution
Ag+(aq) + Cl-(aq Agcl(s)
From [Co (NH3)5H2O]Cl3aq + 3AgNO3 (aq) [Co(NH3)5H2O](NO3)3(aq) + 3AgCl(s)
e. The mixture from (d) above was filtered and the reside dried. Calculate the mass of the dried reside.
.
Solution; Moles of complex = 10× = 0.005

Moles of AgCl formed =3× 0.005

=0.015 moles
RFM of AgCl = 143.5× 0.015
= 2.1525g
21a. Polonium 216 Po undergoes radio-active decay to give elements X and Y according to the following
equation
Po X+ Y+
Write
i. Atomic numbers of X and Y
Solution
X-85
Y-83
ii. Mass numbers of X and Y
Solution
X-216
Y-212
b) Calculate the half-life of Y
The decay constant of Y is 6.54× 10
Solution

0.693 0.693
= =
2 6.54 × 10
= 1059.63

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22. Compare the reactivity of lourine and chlorine with the following compunds.
a. Water
Solution
Fluorine reacts with water vigorously to form oxygen and hydro fluoric acid
2F2(g) + 2H2O(l) 4HF(aq) + O2(g)
Chlorine reacts slowly with water to give hypochtorous acid and hydrochloric acid
Cl2(g) + H2O(l) HOCl(aq) +HCl(aq)

b. Concentrated sodium hydroxide solution

Solution
Fluorine reacts with concentrated sodium hydroxide to give oxygen, sodium fluoride and water
2F2(g) + 2NaOH(aq) 4NaF(aq) + O2(g) + 2H2O(l)
Chlorine reacts with concentrated sodium hydroxide to give sodium chloride, sodium chlorate and
water.
6NaOH(aq) + 2Cl2(l) 5NaCl(aq) + NaClO3(aq) + 3H2O (l)
23a.State three properties in which beryllium resemble aluminum
Solution
 Both metals are rendered passive by concentrated nitric acid
 Both metals react with concentrated solutions of acids
 Both metals form some covalent compounds
 The hydroxides and oxides of both metals are amphoteric.
b)i. What is the name given to type of relationship in (a)
Solution
Diagonal relationship
(ii) Name another pair of element that shows the type of relationship in (a)
Solution
Lithium and magnesium
Boron and silicon
24. A crystalline solid Y dissolved in water to give a pink solution. Addition of excess aqueous
sodium hydroxide produced a dirty white precipitate which rapidly turned brown on standing. When
nitric acid was added to the solution of Y followed by sodium bismuthate solution, the solution
changed from pink to purple.
a) Identify the cation in Y

137
 Solution
Hydrated manganese (ii) ion, Mn2+(aq)
b) Write
i. the equation for the reaction that took place when sodium hydroxide was added to the Solution
Mn2+(aq) + 2H (aq) Mn(OH)2(s)
ii) The formula of the species responsible for the purple color
Solution
MnO0(aq)
iii. Equation for the reaction leading to the formation of the brown solid
Solution
2Mn(OH)2(s) + O2(g) 2MnO2.H2O(s)
25a. Name a reagent that can be used to distinguish between the following pairs of ions. In each case
state what is observed if each ion is separately treated with the reagent
(i) Ba2+ and Ca2+
Reagent
Solution
Potassium chromate (vi) solution and ethanoic acid
Observation
Ba2+ _____ Yellow precipitate insoluble in ethanoic acid
Ca2+ ______ Faint yellow precipitate soluble in ethanoic aid

ii. NO2- and NO3 -

Reagent
Solution
Acidified potassium chromate
Observation
Solution
NO2-___Solution forms from orange to green

NO3-___No observable change

b) Write ionic equations for the reaction between sodium hydroxide and
i. BeO
Solution
BeO(s) + 2 H(aq) BeO2-(aq) + H2O(l)

138
 iii. SiO2
Solution
SiO2s) + 2 H(aq) SiO32-(aq) + H2O(l)

26a. A piece of clean magnesium ribbon was added to a solution of Iron (III) chloride solution
(i) State What was observed
Solution
Effervescence of a colorless gas and reddish brown precipitate formed.
ii. Explain your observation in a (i) above
Solution
The hydrated Iron (III) ion [Fe (H2O)6]+3 present in the solution was hydrolyzed by the water to form an
acid solution which reacted with the magnesium to form hydrogen gas
(ii) Write stepwise equations for the reactions that took place.

Solution
[Fe (H2O)6]3+(aq) + H2O(l) [Fe (H2O)5OH]2+(aq) + H3O+(aq)
[Fe (H2O)5 OH]2+(aq) + H2O(l) [Fe (H2O)42OH]2+(aq) + H3O+(aq)
[Fe (H2O)4 2OH]+3(aq) + H2O(l) [Fe (H2O)3(OH)3]2+(aq) + H3O+(aq)
Mg(s) + 2H3O+(aq) Mg2+(aq) + H2(l)+ 2H2O(l)

b) State what would be observed if a few drops of Iron (III) Chloride was added to the solution of the
following

(i) Sodium acetate

Solution

Reddish-brown solution

c. State three factors that affect complex formation in transition metals.

Solution

The size of the cation

The charge of the cation

Valent-d-orbital of appropriate energy

139
 SELF CHECK

1. Group (VII) elements undergo disproportionation reaction when treated with water or alkalis.
a. What is meant by the term disproportionation reaction?
b. Describe the disproportionation reaction of
i. Chlorine with water
ii. Bromine with hot concentrated sodium hydroxide solution
c. Iodine was added to dilute sodium hydroxide solution and the resultant mixture warmed
i. State what was observed
ii. Write equation(s) for the reaction(s)
d. Commercial bleach can be obtained by building chlorine gas into cold dilute sodium hydroxide
solution. 10cm3 of bleach solution was diluted to 250cm3 with distilled water. 20cm3 of this
solution was acidified with dilute hydrochloric acid and excess potassium iodine solution added.
The liberated iodine required 9.0cm3 0f 0.08M sodium thiosulphate solution.
Calculate the mass of chlorine required to produce 1dm3 of the commercial bleach.
2. a. Explain the term “ionization energy”
b. Explain how the following factors affect the magnitude of ionization energy.
i. Shielding effects of electrons
ii. Penetrating power of the valence electrons
iii. Net charge of an atom or ion.
d. The table below shows the first ionization energies, 1st.I.E and atomic numbers and number of
electrons in the third period of the periodic table
Element Na Mg Al Si P S Cl Ar
1st.I.E (KJmol-1 ) 502 745 587 791 1020 1000 1260 1530
No of electrons 11 12 13 14 15 16 17 18

I. Plot a graph of 1st ionization energy against atomic number of the elements of the third
period
II. Explain the shape of the graph.
3. A 0.570g of a sample of hydrated iron (II) sulphate dissolved in water. After acidification with
dilute sulphuric acid, the solution was formed to react with exactly 22.8cm3 of 0.08 Manganate
(VII) solution and the reaction is said to be a Redox reaction.
i. Why was the reaction termed a redox reaction.
ii. Why was the acidification not done using hydrochloric or nitric acid?

140
b(i). Write half equations for the above reaction.

ii. Deduce the overall reaction for the reaction.

C(i) Calculate the number of moles of water of crystallization present in one of molecule of Iron (ii)
Sulphate.

iii. State with reasons how the volume of Potassium Manganate (VII) would have changed if the
solution of Iron II Sulphate had been left for some time before being titrated.
4. a. Write the electronic configuration and the principal oxidation state of chromium

b. State three properties of Chromium that show that show that it is a typical transition element.

c. The molecular formula of Chromium (III) chloride -6-water is CrCl3.6H2O

i. Write the formula of all isomers of this compound.

ii. Describe briefly an experiment that can be carried out to identify the isomers given in (c)(i)

d. State what is observed and write an equation for the reaction which takes place when hydrogen
Sulphide is bubbled into an aqueous solution of acidified potassium dichromate (VI)

e. Aqueous chromium (III) Sulphate was added to a solution of sodium carbonate

i. State hat was observed

ii. Write equations for the reaction which took place.

5. Explain each of the following observations

a. Ammonia forms a white precipitate with aqueous Manganese (II) ions, but in the presence of
ammonium chloride, no precipitate is formed.
b. When Sodium Hydroxide solution is added drop wise to a solution, a green precipitate is formed,
that dissolves to form a deep green solution. On addition of hydrogen peroxides, the solution turns
from green to yellow.
c. The boiling points of the hydrides of group (IV) are in the order
< < < where was the boiling points of the hydrides of group VII are in
the order < < <
d. Atomic radius decreases along the elements Sodium to Chlorine

141
e. Magnesium readily reacts with concentrated nitric acid where as beryllium does not react with
concentrated nitric acid.
f. Aluminum trifluoride is ionic, while aluminum triflouride is covalent.
g. The bond angle in water molecule is 1040 where as that in a molecule of ammonia is 1070.

˜ THE END ˜

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