DEPARTMENT OF PURE & INDUSTRIAL CHEMISTRY

BAYERO UNIVERSITY KANO

CHM 1231: INORGANIC CHEMISTRY LECTURE NOTES

Course content: Principles of atomic structure, isotopes, empirical and molecular formulae,
energy levels, quantum numbers and electronic configuration, periodicity and building up of the
periodic table. Chemical reactions, Chemical equations and stoichiometry. Chemical bonding and
valence forces. Extraction of metals. Introduction to transition metals chemistry. Introduction to
nuclear chemistry.

Atomic Theory of Matter

A Greek philosopher in the 5th century B.C, Democritus, expressed the belief that all matter consist
of very small, indivisible particles, which he called “Atomos”, meaning indivisible or incapable of
being cut further. This idea was rejected by some his colleagues e.g. Plato and Aristotle. Later in the
year 1808 an English scientist and school teacher, John Dalton, formulated a precise definition of the
indivisible building blocks of matter that we call atoms.
The hypotheses about the nature of matter which Dalton’s atomic theory is based are as follows:
1. All matter is composed of indivisible atoms. An atom is an extremely small particle of matter
that retains its identity during chemical reactions.
2. An element is a type of matter which is composed of only one kind of atom; each atom is
having the same property. Mass is one such property and atoms of a given element have a
characteristic mass.
3. A compound is a type of matter composed of atoms of two more elements chemically
combined in a fixed proportion. The relative numbers of any two kinds of atoms in a
compound occur in a simple ratio. An example is that CO2 is a compound consisting of
carbon and oxygen in ratio of 1 : 2.
A chemical reaction consists of the rearrangement of the atoms present in the reacting substances.
Thus atoms are neither created nor destroyed in any chemical reaction, as the basis of Dalton’s
atomic theory. “Atom” can be defined as the basic unit of an element that can enter into chemical
combination. Dalton imagined that an atom is extremely small and indivisible. However, in the
1850’s through to the 20th century, a series of investigations were carried out which revealed that
atoms actually possess internal structure. These included the “nucleus’’ (which is the atom’s central

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core and is positively charged and contains most of atom’s mass) and one or more “electrons’’ (very
light in mass, negatively charged) that exist around the atom’s positively charged nucleus.
Discovery of Electron
J.J Thompson conducted a series of experiments that showed atoms were not indivisible; in fact they
contain sub particles. Thompson used an apparatus which contains two electrodes sealed into a glass
tube from which air had been evacuated. The negative and positive electrodes are called cathode and
anode respectively. He observed that when a high-voltage is turned on, the glass tube emits a
greenish light; however, he confirmed that the emission originated from the cathode. He found that
the cathode rays (light) move towards the anode (which is positive) and from this experiment
Thompson concluded that cathode rays consist of a beam of negatively charged particles (electrons)
and that electrons are constituent of all matter.
Protons and Neutrons
In the early 1900s, it became clear that atoms contain electrons and are electrically neutral. For an
atom to be electrically neutral it must contain equal number of positive and negative charges. Based
on this reasoning, Thompson proposed that an atom could be thought of as a uniform, positive
sphere of matter in which electrons are embedded.

J.J. Thomson’s model of the atom

In the year 1910, Ernest Rutherford conducted series of experiments using very thin foils of
gold and other metals as targets for α-particles from radioactive source. He observed that the
majority of particles penetrated the foil either not deflected or with only a slight deflection. In some
instances the α-particle bounced back in the direction from which it had come or is scattered at a
large angle.

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Rutherford explains the result of this α-scattering experiment in terms of new model of the atom.
According to Rutherford, most of the atom must be empty space. This is the reason why majority of
the α-particles passed through the gold foil with little or no deflection. He then proposed that the
atom’s positive charges are concentrated in the “nucleus” which is the dense neutral core within the
atom. The positively charged particles in the nucleus are called “protons”.

Earnest Rutherford discovered protons in

1920 by the Rutherford scattering
experiment.

Rutherfords model of the atom

At this stage of experiment scientists proposed that the atom contains a nucleus which
occupies 1/1013 of the volume of the atom and is the heaviest part of the entire atom.
The molecular dimensions of an atom are expressed in SI units, called picometer (pm), where
Ipm = 1 x 10-12m
Usually an atomic radius is about 100pm whereas the radius of nucleus is only about 5 x 10-3 pm.
The Neutron
Rutherford experiments did not solve one problem, as why the mass of hydrogen atom (simplest
atom) which has one proton is significantly lower than that of Helium atom which contains 2
protons. Literally, since the mass of electrons are negligible, their mass contribution is neglected,
thus the ratio of their masses shall be 1:2 (Hydrogen: Helium). However, the mass ratio was found to
be 1:4 (H:He). This mystery was solved by a scientist called Sir James Chadwick, when he
bombarded a sheet of beryllium with α– particles. He observed a very high-energy radiation similar
Chadwick discovered neutrons in 1932 by the Chadwick 3
Alpha Bombardment Experiment
to γ-ray was emitted by the metal. Later it was confirmed that the energy is emitted by a third type of
sub-atomic particles which he called “neutrons” because they are electrically neutral with mass
slightly greater than that of protons. Chadwick proposed his model thus:

Chadwick’s model of the atom

This experiment explains the mystery of mass ratio between the helium and hydrogen atoms. In the
hydrogen atom, there is only one proton and no neutron while in the helium atom there are 2 protons
and 2 neutrons; as such the mass ratio is 1:4.

Mass and charge of subatomic particles

Particle Mass (g) Charge
Coulomb charge unit
28 19
Electron 9.10939 x 10- -1.6022 x 10- -1
Proton 1.67262 x 10-24 +1.6022 x 10-19 +1
Neutron 1.670493 x 10-24 0 0

Atomic number, Mass number

An atom is regarded as the unit quantity of an element that exists either alone or in chemical
combination with other atoms of the same or different element. An atom contains positively charged
nucleus and negatively charged electrons. Example is hydrogen atom (which has one proton and one
electron). All other elements except hydrogen have protons and neutrons in their nucleus.
Some notations are used in describing an atom of an element. These notations are for
identification of the referred atom. These include atomic number, mass number and the symbol of
the atom. E.g mass number

Z
A
E Where is E = element 23 Na
11

A= mass number

4
 Z = atomic number

It was discovered that each element has a unique charge that is a number multiple of the magnitude
of the electron charge, in other words, this integer is the atomic number. For example, a hydrogen
atom nucleus which has a magnitude of (+1) charge and equals to that of electron (-1), has the
smallest atomic number. In any neutral atom, the number of protons present in that atom equals the
number of electrons present; e.g nitrogen has 7 protons and 7 electrons.
Atomic number = number protons in the nucleus
Mass number: This is the total number of protons and neutrons in the nucleus of an atom.
For example, Sodium (Na) has an atomic number of 11 and 12 number of neutrons.
:. The mass number = Atomic number + number of neutrons

11 + 12 = 23 23 Na
11

Relative atomic mass: The mass of an atom is concentrated in the nucleus of an atom. The actual
masses of protons and neutrons are relatively very small (non-integral) numbers. For convenience
purpose a system of relative atomic mass is used.
The atomic mass unit (a.m.u) has a value of approximately 1.660 x 10-27kg. This value
corresponds closely to the mass of proton or a neutron. As result, the mass of each proton and
neutron as taken to be one atomic mass unit. The scale of relative atomic masses (R.a.m) is based
upon measurement taken for carbon with all atomic masses stated relative to 12C = 12.000

Isotopes: An element is characterized by the number of protons and to keep the atom neutral this
number of protons must be equal to the number of electrons. However, the number of neutrons may
vary e.g.

1 2 3
1 1 1
↓ ↓ ↓
Hydrogen Deuterium Tritium
1 proton 1 - proton 1 – proton
No neutron 1 – neutron 2 – neutrons

Atoms whose nuclei have the same atomic number but different mass number are called isotopes.
The difference in mass number arises due to the difference in the number of neutrons present in the

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atoms. Other examples of isotopes include lithium ( 63 Li and 7 35 37
3 Li
) , chlorine ( 17 Cl and 17 Cl )
63 65
and copper ( 29 Cu and 29 Cu ) .

Isobars :These are isotopes of different elements which have the same mass numbers but different
115 115
atomic numbers, eg ( 50 Sn and 49 In)

Isotones : These are atoms, also of different elements, whose nuclei contain the same number of
14
neutrons but have different atomic numbers. Examples include 6C, 157N and 168O
Relative atomic mass:- e.g. calculate the relative atomic mass of naturally occurring magnesium if
26
25
24 10.1%12 Mg and 11.2% Mg
the distribution of isotopes is 78.7% 12 Mg , 12 . The accurate masses of the

isotopes to three significant figures are 24.0, 25.0 and 26.0

Solution
 78.7   10.1   11 .2 
Relative atomic mass =  24.0    25.0    26.00 
 100   100   100 
R.am = 24.3 (to 3 significant figures)
12
Abundances of isotopes: e.g calculate the percentage abundances of C and 13C if the relative
atomic mass of naturally occurring carbon is 12.011, and the accurate masses of the isotopes are
12.00 and 13.003 (to 5 significant figures)

Let the % abundances of the two isotopes be x and (100 – x). The value of R.am is therefore:
 x   100  x 
R.am = 12.011  X 12.000     13.003 
 100   100 

12.011  12.000 x    1300.3  13.003x 

 100   100 
12.011 100 12.000 x  1300.3  13.003x

1201.1 1300.3  1.003x

1300.3  1201.1 99.2

x x = 98.9 (to 3 significant figures)
1.003 1.003
The abundances of the isotopes 12C and 13C are 98.9% and 1.1% respectively.

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 Class work: calculate the relative atomic mass of a sample of naturally occurring boron
which contains 19.9% 105B and 80%115B. Accurate masses of the isotopes to 3 significant figures are
10.0 and 11.0.

The chemical formula is the alphabetical

DETERMINATION OF CHEMICAL FORMULAS representation of chemical expression

Before we go on to the determination of chemical formulas it is important to know the definition of

some terms.
THE MOLE
MOLE (symbol Mol): This is defined as the amount of substance containing the same number or
particles as the number of carbon atoms in exactly 12g of C-12. The particles may be atoms,
molecules, ions or electrons.

Amadeo Avogadro found that one mole contains 6.02 x 10 23 particles. This figure, 6.02 x 1023, is
called the Avogadro constant and is the same for every single mole of an atom, formula unit (eg KBr,
NaCl) or molecule, eg CO2.
Therefore No of moles = No of Particles
Avogadro constant

Molar Mass: This is the mass in grams of one mole of the compound. Another term for it is
molecular weight. It is expressed in gmol-1.
For example, the formula mass of NH3 is 17.0, but the molar mass is 17.0gmol-1

 No of Moles = Mass of a substance

Molar mass of the substance

By extension.
mass
NumberofParticles  xAvogadros ' sNumber
Molarmass
Suppose a sample of vitamin C is known to contain 1.29 x 1024 hydrogen atoms. Express that
number as the number of moles of hydrogen atoms:
1.29 x1024
Number of moles of H atoms = = 2.14 mol
6.022 x10 23

- Molar Mass of an element is the mass of the element per mole of its atoms.
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 - The molar mass of a molecular compound is the mass of the compound per mole of its
molecules.
The mass of a sample = number of moles x molar mass
Number of moles = mass of samples (grams)
molar mass (grams per mole)

The determination of chemical formulas is achieved via two steps: the first is to determine the
empirical formula and the second (if the compound is molecular or contains a polyatomic ion) is to
determine the molecular formula.

EMPIRICAL FORMULA: The empirical formula of a compound is a chemical formula that shows
the relative numbers of atoms of each element. For example, the empirical formula of glucose, which
is CH2O, tells us that carbon, hydrogen and oxygen are present in the ratio of 1:2:1. The elements are
present in these proportions regardless of the size of the sample.

MOLECULAR FORMULA: This refers to the actual number of atoms of each element in a
molecule. The molecular formula for glucose, which is C6H12O6, tells us that each glucose consist of
six carbon atoms, twelve hydrogen atoms and six oxygen atoms.
To determine the empirical formula of a compound, we begin by measuring the mass of each
element present in a sample. This composition is usually reported as the mass percentage
composition, that is, the mass of each element expressed as a percentage of the total mass.
massofelement in sample
Mass of element = x100
totalmassofsample

For example, a sample of Vitamin C of total mass 8.00g was analysed to find which element it
contains and how much of each. The following data were collected: C = 3.27g, Hydrogen = 0.366g
and Oxygen = 4.36g
Mass percentage of carbon in Vitamin C is
Mass percentage of C = Mass of C in Sample x 100%
Total mass of Sample

= 3.27g x 100 = 40.9 %

8.00g

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The same procedure gives the following values for the mass percentage of hydrogen and oxygen:
Hydrogen 4.58% and oxygen 54.5%
The analysis of a sample of eucalyptus of total mass of 3:16g gave its composition as 2.46g of
carbon, 0.373g hydrogen and 0.329g oxygen. Following the same procedure the mass percentage
composition of carbon was determined to be 77.8%

DETERMINING EMPIRICAL FORMULAS

To determine the empirical formula of a compound, we need the relative number of atoms of each
element in the sample or the relative number of moles of each type of atom. We can get this
information by calculating the number of moles of atoms present from the mass percentage
composition. For example, Vitamin C with mass percentage composition of 40.9% C, 4.58% H and
54.5% O, we find the number of moles of each element as follows:

40.9
Number of moles of C atoms = = 3.41mol
12.01

4.58
Number of moles of H atoms = = 4.54mol
1.008

54.5
Number of moles of O atoms = = 3.41mol
16

Divide the number of moles with the smallest value

:. C: H: O = 3.41 : 4.54 : 3.41

3.41 3.41 3.41

= 1: 1:33 :1
One number is still not a whole number; hence we must multiply each number by a factor until all
numbers are whole numbers or can be rounded off to whole number. So, we multiply through by 3 to
obtain 3: 3.99: 3 or approximately 3: 4: 3
So the empirical formula of Vitamin C is C3H4O3

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A sample of magnesium of mass 0.450g burns in nitrogen to form 0.623g of magnesium nitride.
Determine the empirical formula of magnesium nitride.( R.am: Mg = 24.31, N =14.01)
By definition, number of moles = Mass in grams/atomic mass (g/mol)
Number of moles of magnesium = 0.450g/24.31gmol-1 = 0.0185mol
The mass of nitrogen in the compound is
Mass of nitrogen = 0.623g – 0.450g = 0.173g
Hence,
Number of moles of N = 0.173g/14.01gmol-1 = 0.0123
Ratio of Mg: N = 0.0185 : 0.0123 = 1.5:1
0.123 0.123

Multiplying through by 2 gives 3:2. This result suggests that the empirical formula of magnesium
nitride in indeed Mg3N2

Self test 1: A sample of bromine of mass 1.546g reacts with fluorine to form 2.649 of bromine
fluoride. Determine the empirical formula of the compound.(R.am: F = 19, Br=79.9)

Self test 2: The first compound of the noble gases was prepared in 1960s. In one experiment, it was
found that 2.56g of xenon reacted with fluorine to produce 4.04g of xenon fluoride.
What is the empirical formula of this compound? (R.am: Xe =131.30)

DETERMINING MOLECULAR FORMULAS

The molecular formula of a compound is found by determining how many empirical formula units
are needed to account for the measured molar mass of the compound. Therefore to determine the
molecular formula for a compound, both its empirical formula and its molecular weight must be
known.
Molecular formula = n (empirical formula)
For example: the molar mass of Vitamin C is found to be 176.14gmol-1 by mass spectrometry,
with an empirical formula of C3H4O3. The molecular formula:
Molecular formula = n (e.f)
To find n we relate the above formula with molar mass.
Molar mass of vitamin C = n (e.f of vitamin)
176.14gmol-1 = n (3 x 12 + 4 x 1.008 + 3 x 16)

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176.14gmol-1 = n 88.06gmol-1
N = 176.14gmol-1/88.06gmol-1 = 2
Molecular formula = n (empirical formula)
= 2 (C3H403)
= C6H8O6

CALCULATIONS WITH CHEMICAL FORMULAS AND EQUATIONS

Example
Given 4.80g of ammonium carbonate find
i) The number of moles of the compound,
ii) The number of moles of ammonium ion
iii) The number of moles of carbonate ions
iv) The number of moles of hydrogen atoms
v) The number of hydrogen atoms
vi) The mass of a molecule of ammonium carbonate
(R.a.m: H = 1.0; C = 12.0; N = 14.0; O = 16.0)

Ans: Ammonium carbonate = (NH4)2CO3

= (14 + 1 x 4)2 + 12 + (16 x 3) = 96.0gmol-1
a) 96g = 1mol
 4.8g = 0.05mol of (NH4)2CO3
ii) For every mole of (NH4)2CO3, there are two moles of NH4+
 0.05 x 2 = 0.10 mole of NH4+
iii) For every mole of (NH4)2 CO3, there is one mole of CO32-
 0.05 x 1 = 0.05 mol of CO32-
iv) For every mole of (NH4)2 CO3, there are 8 moles of H-atoms.
 0.05 x 8 = 0.4mol of H-atoms
v) Every mole of H atoms contain 6.02 x 1023 atoms of Hydrogen.
 0.4 mol of H = 6.02 x 1023 x 0.4 mol = 2.408 x 1023 atoms
vi) 1 mole of (NH4)2 CO3 has mass of 96g and is composed of 6.02 x 1023 particles.
 1 molecule has a mass of 96g = 15.95 x 10-23g
23
6.02 x 10
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CHEMICAL REACTIONS AND CHEMICAL EQUATIONS

New substances are formed when chemicals react with one another. To write down the names of the
reactants and products for every reaction will be untidy and will take too much time and space, so
we summarize everything by use of chemical equations.
A chemical equation is a statement, in formula, which shows the relative numbers of particles
involved in a chemical reaction. Both reactants and products and even their physical states, whether
solid, in aqueous form or gas state are shown.
Mg(s) + 2HCl(aq) MgCl2(aq) + H2(g)
The starting materials are called reactants and the substance(s) formed as a result of the reaction are
called products. Chemical equations help us to describe chemical reactions. Depending on the kind
of information we want to convey for a reaction involving ions, we have a choice of chemical
equations. The reactions can be represented by:
a) A molecular equation :-A form of expressing chemical equations in a molecular pattern
b) A complete ionic equation :-An equation that tells us what is happening in an
Ion state
c) A net ionic equation. :-A complete ionic equation with
canceled spectators ion

A Molecular Equation: is a chemical equation in which the reactants and products are written
as if they were molecular substances, even though they may actually exist in solution as ions. E.g
Ca (OH)2 (aq) + Na2CO3(aq) CaCO3(s) + 2NaOH(aq)
The molecular equation above clearly shows what the reactants and products are, and even their
physical states.

COMPLETE IONIC EQUATION tells as what is happening at the level of ions. Using the same
Ca(OH)2 and Na2CO3 which are all soluble ionic substances and therefore strong electrolytes, we can
see that when they dissolve in water they go into solution as ions. Each formula unit of Ca(OH) 2
forms one Ca2+ and two OH- ions in solution, while a formula unit of Na 2CO3 forms two Na+ ions
and a CO32- ion.
Ca2+(aq)+ 2OH-(aq) + 2Na+(aq) + CO32- (aq) CaCO3(s) + 2Na+(aq) + 2OH (aq)

A complete ionic equation is a chemical equation in which strong electrolytes (such as soluble ionic
compounds) are written as separate ions in the solution. As can be seen above, the Ca 2+ reacts with

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the CO32 to precipitate out as a solid, while the Na+ and OH- ions stay in solution, not taking part on
the reaction. These are called spectator ions since they do not take part in the reaction.

A NET IONIC EQUATION is an ionic equation from which the spectator ions have been
cancelled. In the example given above, it shows that the reaction that actually occurs at the ionic
level is between Ca2+ ions and CO32- ion to form solid calcium sulphate.
The net ionic equations is
Ca2+ (aq) + CO32- (aq) CaCO3(s)

When writing chemical equations, we must learn to balance them. In this case, we must know how
many moles of the reactants combine to give a definite number of moles of products.
STOICHIOMETRY refers to the relative number of moles of substances involved in a chemical
reaction. The numbers appearing before the chemical formula in any equations are called
stoichiometric co-efficients. A balanced chemical equation gives us all the information about a
chemical reaction. We can always deduce the number of products formed if the quantities of the
reactants are known, and vice versa. To be valid, a chemical equation must satisfy three conditions:
1. It must be consistent with experimental facts, i.e, it must state what chemical species
disappear and appear.
2. It must be consistent with the conservation of mass, i.e, every atom must be accounted for.
3. The chemical equation must be consistent with the conservation of electric charge.
A balanced equation contains the same number of atoms of the different kind on the left and
right hand sides; furthermore, the net charge is the same on both sides. An equation can be
balanced by inspecting both the left and right sides to determine whether the right side equals
the left. The examples below are balanced.

2K2Cr2O7(s) + 2H2O(l) + 3S(g) 3SO2(g) + 4KOH(aq) + 2Cr2O3(s)

3NiCl2(aq) + 2Na3PO4(aq) Ni3(PO4)2(s) + 6NaCl(aq)

H2SO4(aq) + 2NaHCO3(aq) Na2SO4(aq) + 2H2O(l) + 2CO2(g)

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TYPES OF CHEMICAL REACTIONS
We can classify the millions of possible chemical reactions into one of three types:
1. Precipitation Reactions: In this type of reaction, two solutions of ionic substances are mixed
and a solid ionic substance is precipitated.
NaCl(aq) + AgNO3 (aq) NaNO3(aq) + AgCl(s)

2. Acid – Base reaction: An acid reacts with a base with the involvement of the transfer of
proton between reactants:
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

3. Oxidation. Reduction Reaction: This involves the transfer of electrons between reactants
Fe(s) + CuSO4(aq) FeSO4(aq) + Cu(s)

CALCULATIONS INVOLVING MOLE RATIO OF REACTING MASSES

1. Calculate the mass of copper formed when 12.45g of copper(II) oxide is completely reduced
by hydrogen
(R.a.m : H = 1.0;0=16.0;Cu = 63.5)

Ans: (write down the balanced chemical equation first!)

CuO(s) + H2(g) Cu(s) + H2O(l)

From the above equation, the mole ratio of Cu:CuO is 1:1. The number of moles of copper formed
is the same as the number of moles of CuO reduced. 

No of moles of CuO reduced = 12.45 = 0.157 mol

63.5 + 16.0

No of moles of copper formed = 0.157 mol

Since No of moles = mass of Cu = mass of Cu = 0.157 mol,
Molar mass 63.5
Then mass of Cu
= 63.5 x 0.157 = 9.97g

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2. Sodium hydrogen carbonate decomposes according to the following equation:
2NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(1)
In order to obtain 240 cm3 of CO2 at room temperature and pressure, what is the minimum amount of
NaHCO3 required? ( H = 1.0; C = 12.0, 0=16.0, Na = 23.0; Molar volume at R.T.P = 24.0 cm3 mol-1)

Ans: From the equation, ratio of NaHCO3 : CO2 = 2:1

NO of moles of CO2 formed = 240 = 0.01mol
24000

No of moles of NaHCO3 required = 0.01 x 2 = 0.02 mol

Mass of NaHCO3 required = 0.02 moles x molar mass
= 0.0 2 x (23.0 + 1.0 + 12.0 + (16.0x3) )
= 0.02 x 84.0 = 1.68g (minimum mass of NaHCO3 needed)

THE QUANTUM MECHANICAL PICTURE OF THE ATOM

Through the works of Louis de Broglie, Clinton Davisson and Lester Germer, we know that
electrons in atoms can be treated as waves more effectively than as small particles traveling in
circular or elliptical orbits. Large objects such as golf balls and moving automobiles obey the laws of
classical mechanics (Isaac Newton’s law), but very small particles such as electrons, atoms and
molecules do not. A different kind of mechanics called quantum mechanics, which is based on the
wave particles of matter, describes the behavior of very small particles much better. Quantization of
energy is a consequence of these properties.
The Heisenberg Uncertainty Principle states that it is impossible to determine accurately both the
momentum and the position of an electron (or any other very small particles) simultaneously.
Momentum is mass times velocity, mv. Because electrons are so small and move rapidly, their
motion is usually detected by electromagnetic radiation. Photons that interact with electrons have
about the same energies as the electron and severely disturb the motion of the electrons. It is not
possible to determine simultaneously both position and velocity of an electron, so we resort to a
statistical approach and speak of the probability of finding an electron within specified regions in
space. With these in mind, we list some basic ideas of quantum mechanics.
1. Atoms and molecules can exist only in certain energy states with a definite energy. When
an atom or molecule changes its energy state, it must emit or absorb just enough to bring
it to the new energy state (the quantum condition).

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 2. When atoms or molecules emit or absorb radiation (light), they change their energies. The
energy change in the atoms or molecules is related to the frequency or wavelength of the
light emitted or absorbed as seen in the equations overleaf:

∆E = hv or ∆E = hc/λ………

This gives a relationship between the energy change, ∆E, and the wavelength of the radiation
emitted or absorbed. The energy lost (or gained) by atom as it goes from higher to lower (or
lower to higher) energy states is equal to the energy of the photon emitted (or absorbed)
during the transition.
3. The allowed energy states for atoms and molecules can be described by sets of numbers
called quantum numbers

QUANTUM NUMBERS
The solution of the Schrodinger and Dirac equation for hydrogen atom give wave functions, that
describe the various states available to hydrogen’s single electron. Each of these possible states is
described by four quantum numbers. These quantum numbers play important roles in describing the
energy levels of electrons and the shapes of the orbitals that describe distribution of electrons in
space. The interpretation will become clearer when we discuss atomic orbitals later.
Let us define each quantum number and describe the range of values it may take.
1. The Principal quantum number n, determines the size and energy of the orbitals and has
integral values of n = 1, 2, 3, 4 …….It describes the average distance of an electron from
the nucleus, like the innermost electron shell, which has a principal quantum number of
1. An increase in n means higher energy, because the electron is less tightly bound to the
nucleus.

2. The Angular momentum quantum number l, designates the shape of the region in space
that an electron occupies (orbital). The energy of the sub-shell increases as the value of l
increases. This number l, may take the integral values from 0 up to and including (n-1)
for each level of n, and the value of l for a particular orbital is commonly assigned a
letter, ie,

L = 0, 1, 2, 3, 4…… (n-1)
s p d f g
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For each of the principal quantum number n, the angular momentum quantum number will be:

Principal quantum number angular momentum quantum number

n =1 0
n=2 0, 1
n=3 0, 1, 2
n=4 0, 1, 2, 3
In the first shell, the maximum value of l is zero, which tells us that there is only an s sub- shell
and no p sub-shell. In the second shell, the permissible values of l are 0 and 1, which tells us that
there are only s and p sub-shells.

3. The Magnetic quantum number, ml, designates the specific orbital within a sub- shell.
Orbital within a given sub-shell differ in their orientation in space, but not in their
energies. Within each sub-shell, ml may take any integral values from –l through zero to
+l
ml = (-l…0…+l)
The maximum value of ml depends on the value of l. For example when l = 1, which
designates the p sub shell, there are three permissible values of ml: -1, 0 and +1. Thus, three
distinct regions of space, called atomic orbitals are associated with a p sub shell. We refer to
these orbitals as the Px, Py and Pz orbitals.

4. The Spin quantum number, Ms refers to the spin of an electron and the orientation of the
magnetic field produced by this spin. For every set of n, l, ml values, ms can take the
value + ½ or – ½ , ms = + ½

17
 Permissible values of the Quantum Numbers through n=4

n L ml ms Electron Electron capacity

capacity of sub of shell=2n2
shell= 4L + 2
1 0 (1s) 0 +½,-½ 2 2
2 0 (2s) 0 ½,-½ 2 8
1 (2p) -1, 0, +1 + ½ for each ml 6
3 0 (3s) 0 +½,-½ 2 18
1 (3p) -1, 0, +1 +½ for each value of mc 6
2 (3d) -2, -1, 0, +1, +2 + ½ for each value of ml 10

4 0 (4s) 0 +½,- ½ 2 32
1 (4p) -1, 0, +1 + ½ for each value of ml 6
2 (4d) -2, -1, 0, +1, +2 + ½ for each value of ml 10
3 (4f) -3, -2, -1, 0, +1, +2, + ½ for each value of ml 14
+3

ELECTRONIC CONFIGURATIONS
Let us now examine the electronic structures of atoms of different elements. The electronic
configuration that we will describe for each atom is called the ground state electron configuration.
This corresponds to an isolated atom in its lowest energy or unexcited state.
In describing ground state electron configuration, the guiding idea is that the total energy of the atom
is as low as possible. To determine these electron configurations, we use the Aufbau principle as a
guide.
Aufbau principle states that the orbitals of an atom are arranged in an increasing energy order with
orbitals lower in energy being accommodated first before those of higher energy.That is, the energy
of the orbitals increases with the order:1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s,5f,
6d,7p….. . One would not expect students to memorize this order as this sequence can be built by
following this simple guide:

18
The electronic structures of atoms are governed by the Pauli exclusion principle which states that:
No two electrons in an atom may have identical sets of four quantum numbers. For two electrons in
1S2, they have the same, n, l, ml, but different ms values.
3Li 1S2 2S1
4Be 1S2 2S2
5B 1S2 2S2 2P1
6C 1S2 2S2 2Px1 2Py1
8O 1S2 2S2 2Px2 2Py1 2Pz1

We see that some atoms have unpaired electrons in the same set of energetically equivalent or
degenerate orbitals. This leads us to Hund’s rule which states that ‘electrons occupy all the orbitals
of a given sub shell singly before pairing begins’.
These unpaired electrons have parallel spins.

THE ELECTRON CONFIGURATION OF IONS

A neutral atom becomes a cation when it loses one or more electrons and an anion when it gains
electron(s). For example, the electron configuration of a neutral magnesium is 1s2 2s2 2p6 3s2 and that

19
of Mg 2+ is 1s2 2s2 2p6 because two electrons have been lost. Similarly, the electron configuration of a
neutral oxygen atom is 1s2 2s2 2p4 while that of O2- is 1s2 2s2 2p6 having gained two electrons.

PERIODIC TABLE
Periodicity and building up of the periodic table
The modern periodic table consists of seven horizontal periods whose complexity increases
with increasing atomic number. There is a very close correlation between the numbers of periods
and the electronic structures of the elements. The chemical properties of an element are largely
governed by the number of electrons in the outer shell, and their arrangement. If the elements are
arranged in groups which have the same outer electronic arrangement then elements within a group
should show similarities in chemical properties. One great advantage of this is that initially it is only
necessary to learn the properties of each individual element rather than the properties of each group.
Elements which have their outer electrons in the s-orbital are called the s-block elements. Of
these, those that have one s electron in their outer shell are called Group I (the alkali metals) and
elements with two s electrons in their outer shell are called the Group II (the alkaline earth metals).
These groups are generally called the s-block elements because their properties results from the
presence of s-electrons.
Elements with three electrons in their outermost shell (i.e. two in the S and one p electron)
are called Group III. Similarly Group IV elements have four electrons in their outer most shell and
Group five, six and seven have five, six and seven electrons in their outer most shells respectively.
Group VIII or Group 0 have a full outer shell of electrons so that the next shell is empty; hence
groups III, IV, V, VI, VII and 0 all have p orbitals partially or complete filled and their properties are
dependent on the presence of p-electons. The elements in these groups (III – VIII) are jointly called
the p-block elements. Similarly in elements where d-orbitals are being filled, the elements are called
the d-block or the transition elements. In these, d-electrons are being added to the penultimate shell.
Finally, elements where f-orbitals are filling are called the f-block elements.
The horizontal rows of elements, called periods, are numbered from 1 to 7. In any given
period all the elements have the same number of electron shells; e.g elements of period 3 have 3
electron shells. The elements are arranged in order of increasing atomic number, that is in order of
increasing nuclear charge or increasing number of orbital electrons. Thus each element contains one
more orbital electron than the preceding element. This leads to a parallel progression of properties
for elements in each period. For example, the metallic properties tend to decrease across each period

20
while the non-metallic properties tend to increase, so that the first three elements of each period i.e.
those of groups 1 to 3, are metallic while those of groups 4 to 7 and group 0 are more non-metallic in
character.
In summary, the group and period of any given element in any given block can be determined
as follows.

S-block
Elements in this block have the general outer electron configuration ns2, where n is the
outermost shell and therefore represents the period, while ns1 represents group IA and ns2 represents
group IIA.

P-block
The period is determined by finding the outer electron configuration which for p-block is
ns2npm, where m=1,2,3,…6.
Therefore n represents the period while the group is determined by adding 2 to m i.e. (2 + m)
e.g Al has 3s2 3p1 this means that is belongs to period 3 and group (2+1) = 3

d-block: The period can be determined as described above and the group is obtained from the
general outer electron configuration ndm(n+1)s2, where m = 1,2, ….. 10
i) for m= 1 to 5 the group is (m+2) B
ii) for m = 6 to 8 the group is VIII B
iii) for m = 9 the stable outer electron configuration
nd10 (n+1)S1 the group IB
iv) for m = 10 i.e nd10 (n+1)S2 the group is IIB

The progression of properties for elements in the same period can be illustrated using properties like
effective nuclear charge:- This is the net charge experienced by a particular electron in a
multi-electron atom resulting from the nucleus and the other electrons. The closer the electron is to
the nucleus the higher the charge it experiences. Thus, the effective nuclear charge experienced by
electrons in a multi-electron atom is in the order ns > np > nd > nf. In a given period the effective
nuclear charge increases across the period due to an increase in the number of positive protons in the
nucleus.

21
1.ATOMIC RADII
The radius of an atom r, is defined as half the distance between the nuclei in a molecule consisting of
identical atoms. The atomic radii decrease in going from left to right across a period. This decrease
can be explained in terms of the increasing affective nuclear charge (decreasing shielding) in going
from left to right. This means that the valence electrons are drawn closer to the nucleus, decreasing
the size of the atom. Atomic radius increases down a group because of the increase in the orbital
sizes in the successive principal quantum levels.

2. IONIC RADII
The ionic radius is the effective radius of an ion within a series of ionic crystals in which the ion is a
part. Just as in atomic radii, ionic radii increases down the group due to increase in orbital sizes in
successive principal quantum levels, in spite of the increase in nuclear change whose effect is less
than the increase in additional orbital.
Another variation is due to the type of ion, whether it is a cation or anion. When a cation is
formed from a neutral atom, the effective nuclear charge felt by the outer electron is increased,
thereby pulling the shells more to the nucleus and reducing the size. That is why the cation is smaller
than the neutral atom.
When an anion is formed from a neutral atom, electrons are added to the outer shell, which increases
electron-electron repulsion. This repulsion causes the electrons to spread out, thereby causing the
size of the outer shell to increase, so the negative ion is larger than the neutral atom.

3. IONIZATION ENERGY
This is defined as the amount of energy required to remove one mole of electrons from one
mole of its atoms or ions in the gas phase. Simply put, it can also be defined as the energy
required to remove an electron from its atom (or ions) in the gas phase. Ionization energy is
expressed in KJ mol-1
Four main factors affect the ionization energy of an atom:
a) The electronic configuration of the atom: atoms with completely filled sub-orbitals which
give extra stability to the electron to be removed have higher ionization energies. This is why
noble gases have the highest ionization energies.

b) The positive nuclear charge: Across a period, the atomic numbers increase (i.e. increase in
protons), thereby resulting in greater attraction between the nucleus and the electrons. This

22
 factor is responsible for making it more difficult to ionize atoms (i.e. remove electrons) with
larger atomic numbers. In effect, the larger the atom the larger the ionization energy.
c) The screening effect: Since electrons are negatively charged and so repelling themselves,
atoms having many obitals with many electrons will have lower ionizations energies since
the outer electrons will be more shielded by the many inner electrons. The more the orbitals
and the electrons in them, the more the shielding and so the less the ionization energies.

d) The Atomic Radius: if the outermost shell electrons are further away from the nucleus, then
the less is the attraction by the nucleus, hence the lower the ionization energy.
Using the above reasoning, if we go down the groups, the shielding of the outermost
electrons by the innermost electrons overcomes the effect or influence of increasing nuclear
charge. Therefore, the outer electron is progressively easier to remove as we go down the
group, meaning the ionization energy decreases down the group. However, across the period,
the increase in nuclear charge has a greater role than shielding; as such it will be more
difficult to lose an electron. This means that ionization energy increases across a period.

DENSITY
Density is defined as mass per unit volume. For the non gaseous metals, we can use the atomic radii
in computing the various densities. Across the period, there is a general increase in atomic weight
but a decrease in atomic volume or radii. This means there is an increase in density across the
groups.
However, down the groups, there is an increase in size due to increase in number of orbitals, and
this is greater than the small increase in atomic weight. This means the density decreases down the
group.

ELECTRON AFFINITY
Electron affinity is the energy released when an electron is added to an isolated neutral atom.
The electron affinity in important for determining chemical properties since it says something about
the tendency of an atom to pick up additional electrons. When a neutral atom picks up an electron
from some source, it becomes a negative ion, as indicated below:
X + e- X-
The amount of energy released in this process is the electron affinity. Thus the electron affinity
measures the tightness of binding of an additional electron to an atom. In each period, electron

23
affinity increases from left to right, since the size gets smaller and the effective nuclear charge gets
greater. There is also a decrease in electron affinity down the group since atomic sizes are bigger and
effective nuclear charge in smaller.
ELECTRONEGATIVITY in electro negativity, increase across the period, decrease down the group

Electronegativity is a measure of the tendency of an element to attract electrons to itself. Across a

period, there is progressive increase in the electronegativity of elements. Here, increasing the nuclear
charge has greater effect than the shielding on the outermost electrons. Electrons are pulled more
towards the nucleus and so are less easily lost. Down the group, however, shielding of the outer
electrons by the inner electrons overcomes the influence of increasing nuclear charges, so there is a
decrease of electronegativity. Fluorine has the highest electronegativity and cesium the least
amongst the tested elements.
TYPES OF BONDING

Generally speaking only the inert gas atoms have free existence, but all other atoms of non-unit
gases combine together to form molecules or compounds. The presence of eight electrons in the
outermost shell of their atoms is responsible for stability of the noble gases; therefore, atoms of all
elements tend to acquire eight electrons in their outermost shells by losing, gaining or sharing
electrons with other atom(s). This is the cause of the chemical combinations of the non-inert
elements. The principle of attaining maximum of eight (ns 2np6) electrons in the valence shell of
atoms is called the octet rule.
Chemical Bonding is the union of two or more atoms involving transfer or sharing of electrons
between themselves so that all of them acquire the stable noble gas configuration. The bonding is
ionic if the union is by transfer of electrons from one atom to the other and covalent if the union is
established by the mutual sharing of electrons between the atoms.
Other types of bonds are also formed between molecules: these include van der Waals forces and
hydrogen bonding.

IONIC OR ELETROVALENT BOND

Ionic bonds are the strong non-directional electrostatic forces of attraction between oppositely
charged ions.
In this type of chemical bond, electrons are completely transferred from one atom to another. The
formation of an ionic bond is favoured in the reaction of an atom of low ionization potential with an
atom of high electron affinity. For example, sodium atom has a low ionization potential, i.e. not

24
much energy is required to pull off the outer electron, while chlorine atom has a high electron
affinity, i.e. considerable energy is released when an electron is added to its outer shell.
Taking a closer look, the electronic configuration of sodium, 1s 22s22P63s1 is one electron higher than
its noble gas neighbor, Neon, 1s22s22p6. Sodium has, therefore, a tendency to lose the uttermost
electron to acquire the stable configuration of Neon. For chlorine,1s 22s22P63s23p5, it needs to acquire
one electron to reach the stable octet structure of its neighbor, argon, which is 1s 22s22P63s23p6.
Accordingly, one atom of sodium combines with one atom of chlorine to form sodium chloride,
NaCl.

The electron transferred is equivalent to the valency involved. Similarly, the electron accepted by the
chlorine atom (or any that accepts electrons) is also equivalent to its valency.
The valency is equal to the number of outermost electrons if it is not greater than four. If it is more
than four, then the valency is equal to the number of electrons required to complete the outermost
electron shell of 8, e.g.:
11 Na = 2,8,1; Valency = 1 17 Cl=2,8,7 Valency =1 (8-7)
12 Mg = 2,8,2; Valency = 2 8O = 2,6 Valency = 2 (8-6)
13 Al = 2,8,3; Valency = 3 7 N= 2,5 Valency = 3 (8-5)
14 Si = 2,8,4; Valency = 4 10 Ne = 2,8 complete octet

PROPERTIES OF IONIC COMPOUNDS

1. They from crystals in the solid state.
2. They are solids at room temperature
3. They melt at relatively high temperatures, and also have high boiling points.
4. They do not conduct electricity in solid form, only when molten or in the aqueous state.

25
5. They are soluble in polar solvents (e.g. water) but are insoluble in non-polar solvents (e.g.
benzene, CCl4).
6. In the solid state, they are brittle.
7. They give ionic reactions, which are very fast, e.g.
Ag+ + Cl- AgCl(ppt)

COVALENT BONDING
A covalent bond is a type of chemical bonding in which a pair of electrons is shared by two atoms,
thereby giving each atom the noble gas electronic configuration.
Covalent bonds are formed between non-metals, or between non-metals and metals of groups other
than those of groups IA and IIA. Each atom contributes equal number of electrons (equivalent to its
valency) to the bond. The shared electrons are known as bond pair electrons. A single shared pair of
electrons gives rise to a single bond, while a double shared pair of electrons gives rise to a double
bond. Three shared pair of electrons gives a triple bond. Triple bonds are more stable than double
bonds, which in turn are more stable than single bond.

One can notice that the octet structure has been satisfied.
Note that in ammonia, the structure is satisfied by sharing three electrons. The other two electrons
are not involved in the bonding and are called Lone Pair electrons.

PROPERTIES OF COVALENT BONDS IN COMPOUNDS

1. Covalent compounds exist as molecules
2. The compounds are usually gases (Cl2), Liquids (H2O) or volatile solids (like I2)
3. They have low boiling points and melting points compared to ionic compounds.
4. They do not conduct electricity in any form, be it liquid or in solution.
5. They are soluble in non-polar solvents like benzene but insoluble in polar solvents like water.
6. The covalent bond is rigid and directional.

26
COORDINATE (OR DATIVE COVALENT) BONDS
This is a different type of covalent linkage that can by formed when both electrons for sharing
between the two atoms are contributed by one atom only. This type of linkage is known as
coordinate bond. In a water molecule, for example, the oxygen atom has two pairs of electrons not
yet shared with any atoms. In the formation of hydrogen peroxide (H 2O2), the oxygen atom in water
contributes the unbonded pair of electrons it has to the new oxygen atom.
Another example is the combination of ammonia molecular with hydrogen ion in the formation of a
dative bond as shown below:

PROPERTIES OF COORDINATE COMPOUNDS

The properties of coordinator compounds are similar to those of covalent compounds in many
respects.
- The nuclei in coordinate compounds are held firmly by the electrons and therefore, they do
not form ions in water.
- Coordinate compounds are sparingly soluble in water. A number of them are largely soluble
in organic solvents.
- The coordinate bond is also rigid and directional.
- Since a coordinate linkage results in semi-polarity in the molecule, coordinate compounds lie
in-between electrovalent and covalent compounds in their volatility.

METALLIC BOND
Metals have special physical properties which arise from the unique bonding found in them. They
are shiny, ductile, malleable, and good conductors of electricity and heat in the solid state.
Unlike covalently bonded non-metals, the outer electrons in the metal atoms do not form pairs.
They are not localized between specific nuclei but are free to move around the whole structure.

27
These free electrons are said to be delocalized. Structurally, metals are said to consist of a giant
structure of cationic lattice (regularly arranged and closely packed cations) immersed in a sea of
mobile valence electrons, as shown overleaf:

The force that binds a metal atom to a number of electrons within its sphere of influence is known as
a metallic bond. We can also say that metallic bonding is the attraction between the delocalized
valence electrons and metal cation.
There is considerable force of attraction between the nuclei of atoms and the valence electrons which
leads to a compact solid structure for metals unlike that in liquids and gases. In metallic bonding, the
electrons are free to move from one atom to the next and since electric current is nothing but the
movement of electrons, metals are good conductors of electricity. Furthermore, since rise in
temperature means increase in kinetic energy, the electrons can absorb energy and while moving
freely, pass it on to neighbouring atoms. The result is that metals are good conductors of heat.
The metallic bond strength increases with:
a) decreasing size of the metal atom (i.e. metallic radius)
b) increasing number of valence (outermost shell) electrons of the metal atoms.
From the above, if we take group 1A elements (Lithium to francium),we find that the
metallic radius increases down the group, and so therefore, the bond strength and by
extension, the meeting point, decreases down the group.
The bond strength increases as the number of valence electrons increases across a period (remember,
there is increase in effective nuclear charge). Al 3+ has higher bond strength than Mg2+, which in turn
is higher than Na+. This is why the melting points are arranged in the order Al>Mg>Na.

INTERMOLECULAR FORCES
There are two types of intermolecular forces: Hydrogen bonding and van der Waals forces. Before
going into them, we have to understand what bond polarization and dipole moments are, first.

28
POLAR AND NON-POLAR COVALENT BONDS
In covalent molecules like H2 and Cl2, the electron pair shared between the two atoms lie exactly at
the centre of the molecule, that is, the probability of that pair being found near one nucleus is as high
as near the other. Hence, the molecule is neutral as it contains equal number of protons and also the
centre of the positive charge coincides with the centre of the negative charge. As a result, the
molecule is said to be non-polar molecule and the bond is said to be non-polar bond.
H:H (equal sharing so non-polar)
In most cases, however, one of the atoms is more electronegative than the other, i.e., it has greater
tendency to attract the electron pair to itself. As a result, the electron pair does not lie exactly at the
centre of the molecule, i.e. there is a greater electron concentration near one atom than near the other
in the same molecule. For example, in a molecule of HCl, the electron pair lies closer to chlorine
than to hydrogen since chlorine is more electronegative than hydrogen.
Thus, the chlorine end of the molecule appears negative and the hydrogen end positive. This leads to
the formation of a dipole as the molecule may be considered to have two appositely charged poles
separated by a rigid link or bond.

A molecule with a dipole is said to be polar molecule and the bond is said to be a polar covalent
bond. The polarity of a covalent bond depends primarily on the difference in electronegativities of
the two atoms involved in the formation of the bond. The more the difference in the
electronegativities of the two atoms, the more the bond polarity.

BOND ELECTRONEGATIVITY DIFFERENCE TYPE OF BOND

BETWEEN THE TWO BOND ATOMS
Cl-Cl 3.0-3.0 = 0.0 COVALENT
Cl-C 3.0-2.5 = 0.5 POLAR COVALENT
Cl-H 3.0-2.1 = 0.9 POLAR COVALENT
F-Li 4.0-1.0 = 3.0 IONIC

Examples of non-polar molecules include CO 2, Cl2, H2, F2, etc and also some molecules like CO 2,
BF3. The last two have polar bonds which cancel themselves out, resulting in non-polar molecules.

29
CO2 is linear O = C = O (non polar due to net cancellation)
BF3 is trigonal planer

B Non-polar
F F

CCl4, PCl5 and SF6 are also non-polar.

Examples of polar molecules include H20, NH3 and CHCl3
Oδ-

+
δH Hδ+
TYPE OF DIPOLES
There are three types of dipoles: Permanent dipole, induced dipole and instantaneous dipole.
1) PERMANENT DIPOLE: This exist in all polar molecules as a result of the difference in the
electronegativity of the bonded atoms.

2) INSTANTANEOUS DIPOLE: This is a temporary dipole that exist as a result of fluctuation

in the electron cloud.
The fluctuation can also happen in a neutral atom, e.g. that of Helium, resulting in the formation of
an instantaneous dipole.

Fluctuation of electron cloud

3) INDUCED DIPOLE: This is a temporary dipole that is created due to the influence of a
neighboring dipole. This neighboring dipole can be a permanent one or an instantaneous one. For
example, HCl, which has a permanent dipole, can induce a dipole in neutral atom of Helium.

HCl He

30
van der Waal’s Forces
Van der Waals forces are the weak forces of attraction between two non-bonded atoms of all atoms,
molecules or ions when they are close to one another. Van der Waals forces are responsible for the
condensation of chlorine, hydrogen, carbon monoxide and even the inert gases. These forces are of
three types, viz:
i) Dipole – dipole interaction
ii) Dipole – induced dipole interaction
iii) Instantaneous dipole – induced dipole interaction.

a). Dipole-Dipole Interaction: These type of van der Waals forces are found in polar covalent
molecules like HCl, i.e. molecules with a permanent dipole. These molecules tend to
orientate themselves in such a way that the attractive forces between the molecules are
maximized while the repulsive forces are minimized. The attraction between the δ + and δ- of
the permanent dipoles of neighbouring molecule is a type of van der Waals force known as
permanent dipole-permanent dipole interaction (or simply dipole-dipole interaction).

Compared to a covalent bond, this dipole-dipole interaction is very weak. For example, the
covalent bonds between the H and Cl atoms in HCl are 130 times as strong as the
dipole-dipole interaction between HCl molecules. The force of attraction between the HCl
molecules is so small that HCl boils at -850C.
b). DIPOLE-INDUCED DIPOLE INTERACTIONS: When a polar molecule, e.g. HCl, which
has a permanent dipole is approached by a non-polar molecule or atom, e.g. argon, a dipole
will be induced in the non-polar molecule or atom. This induced dipole will be in opposite
orientation to that of the polar molecule. If HCl is mixed with Argon, a small dipole is
induced on the Argon atom by the distortion of electron around it by the polar HCl molecule.
This creates a weak dipole induced dipole force of attraction between the HCl molecule and
the Ar atom. This force is very weak with bond energy of about 1KJ/mole.

31
c) INSTANTANEOUS DIPOLE – INDUCED DIPOLE INTERACTIONS: The liquefaction of
inert gases cannot be explained by either dipole-dipole or induced dipole-dipole interactions.
What happens here is that an occurrence of an instantaneous dipole on the inert atom will
induce a dipole moment (induced dipole moment) in the neighbouring atom by attracting
opposite charges. If the positive end of the dipole is pointing towards a neighbouring atom,
the induced dipole will then have its negative end pointing towards the positive pole of that
dipole. This makes the instantaneous dipole attract the induced dipole. The forces of
attraction between these fluctuating dipoles are often called dispersion forces or london
forces (after fritz London). London forces are much weaker than dipole-dipole interactions.

HYDROGEN BONDING
In compounds of hydrogen with strongly electronegative elements such as fluorine, oxygen
and nitrogen, the electron pair shared between the two atoms lies so far away from the
hydrogen nucleus that the latter becomes highly positive, i.e. it behaves almost as a bare
proton. It can therefore be readily attracted to any other electronegative atom. In the case of
HF, for instance, the hydrogen atom of one molecule tends to attract the strongly
electronegative fluorine atom in a neigbouring molecule and this attractive force gives rise to
a linkage between the hydrogen and fluorine atoms. This kind of linkage is called hydrogen
bond.
Hydrogen bond can therefore be described as the attractive force which binds hydrogen
atom of one molecule with electronegative atom (F,O, or N) of another molecule.In the case
of HF, hydrogen bonding results in the binding of a large number of molecules of HF to give
an associated molecules (HF)n as shown below:
…H-F….H-F….H-F….H-F….

Oxygen is sufficiently electronegative, and the hydrogen bonding in water is like:

H H H

H O………H O……………..H O
Same thing with nitrogen in ammonia molecule.
32
 Two conditions are necessary for the formation of hydrogen bonds:
a) The hydrogen atom must be directly bonded to a highly
electronegative atom like oxygen, nitrogen or fluorine.
b) The electronegative atom has to possess an unshared pair of electrons.
The boiling points of water (H2O), HF and NH3 are higher than would normally be
due to the presence of hydrogen bonds. Water boils at 100 0C while H2S is a gas at
room temperature. Also, due to the formation of hydrogen bonds, some organic
compounds are soluble in water, e.g. Ethanol (CH 3CH2OH), while chloromethane
(CH3CH2Cl) is not.
There are two types of hydrogen bonds, intermolecular hydrogen bonds and
intramolecular hydrogen bonds. The first, like the example of HF, occurs between one
hydrogen atom of one molecule and the fluoride of another different molecule.
The intramolecular H-bond occurs between the hydrogen and the electronegative
atom of the same molecule or compound.

EXTRACTION OF METALS
Most metals are obtained from land – based deposits that are called ores. An ore is a material that
contains a particular constituent in a sufficiently high concentration that its extraction from the ore is
economically feasible. Due to the wide variety of sources of metals the techniques used in their
extraction are determined by their nature. The periodic table should provide a good starting point for
discussing the principles involved.
Metal sources may be classified broadly into five main types or groups.

Group 1:
These include the highly electropositive metals found as soluble salts, e.g. chlorides, sulfates,
carbonates e.t.c. The metals in this group include Li, Na, K, Rb, Cs, Fr and Be and they are largely
extracted by electrolytic techniques.

33
Group 2:
This group includes the electropositive alkaline earth metals found principally as insoluble
carbonates and sulfates (NB: MgSO4 is soluble). They are also extracted by electrolysis and mainly
include metals like Mg, Ca, Sr, Ba, Ra, e.t.c.

Group 3:
The main sources of these metals are oxides and mixed oxides and a variety of methods (such as
electrolysis, chemical reduction with C or CO, or reaction with more electropositive metals) are
employed in their extraction. Examples include B, Al, Si, Fe, Sc, Ti, V, Cr, Mn, and others like Y, Zr,
Nb, La, Hf, Ta, W, Ac, Th, Pa, and U

Group 4:
Metals in this group occur principally as sulphides and less frequently as oxides. The sulphides are
almost always converted to oxides, before reduction with carbon, carbon monoxide and in some
instances with hydrogen or sulfates for subsequent electrolytic treatment.
Examples are Ni, Cu, Hg, Co, Zn, Ga, Ge, As, Se, Mo. Tc, Cd, In, Sn, Sb, Te, Re, Tl, Pb, Bi, and Po.

Group 5:
These are the un-reactive metals and occur in the free state, or as easily reducible compounds e.g. Ag
and Au.

Once a metal ore has been obtained from either the earth or the sea, it must undergo a series of
metallurgical processes that ultimately provide the finished material for commercial use. Because of
the wide variety of sources and the varying nature of the metal compounds in the ores, no single
method can apply to the production of all metals. Despite this the metallurgical processes can be
divided into three principal categories.
These are:
1. Concentration of ores
2. Reduction of the metal compounds
3. Refining of the crude or impure metals

34
1. CONCENTRATION OF ORES
Ores that are contained in rocks must often be treated to concentrate the metal-bearing
constituent. Pretreatment of an ore is also carried out to convert some metal compounds into
substances that can be more easily reduced. This can be subdivided into two:
i. Physical methods: In this process the chemical compositions of the constituents are not
altered. This method involves mixing the powdered ore with oil and water. The metal
bearing components become elevated by the oil while the unwanted material is wetted by
the water. A stream of air is the blown through the mixture and the oil-cohered mineral is
carried to the surface while the unwanted impurities will settle at the bottom.
ii. Chemical methods involve leaching the ore with suitable aqueous solution to extract the
metal as a soluble salt. E.g. bauxite can be dissolved in a strong alkali to produce a
soluble aluminate ion. After the solution is removed from the impurities it is neutralized
with an acid. This precipitates Al(OH)3, which yields pure Al2O3 when heated.
Al2O3 + 2NaOH ∆ 2NaAlO2 + H2O
2NaAlO2 + H2O CO2 Al(OH)3

2Al(OH)3(S) 12000C Al2O3 + 3H2O(g)

2. REDUCTION
Most metals, including those of both representative and transition elements, are always
found in nature in the combined state where they exist in positive oxidation state,
therefore recovering them from their compounds involves chemical reduction, and the
nature of the reduction process depends on the ease with which the metal can be reduced.
Some metals are so easily reduced that many of their compounds can be decomposed just
by heating them at relatively low temperatures.
The following reduction methods are generally applied in the extraction of metals.

i) Electrolysis:- This is used to extract metals with negative electrode potentials e.g. Na, K, Ca
e.t.c. Metals with electrode potentials ranging from -1.66v to -3.04v are usually reduced by
electrolysis of their fused salts. In general, electrolytic reduction can be represented as follows:
Mn+ + ne- M
ii) Chemical reduction:- This method is applicable to metals with low negative reduction
electrode potentials. In this method a variety of reducing agents are employed e.g carbon,

35
 carbon monoxide and reactive metals such as Sodium, Aluminum or Magnesium. Sulphide or
Carbonate ores are first converted to the oxide by heating in air and the oxide is reduced by
heating with carbon or carbon monoxide.
Example 1
Heat
FeCO3 FeO + CO2 (g)
Air
or
Heat
FeS FeO + SO2 (g)
Air

2FeO + O2 Fe2O3

Fe2O3 + 3CO 2Fe + 3CO2

Example 2
Heat
PbS PbO + SO2 (g)
Air

2PbO + CO 2Pb + CO2(g)

iii). Thermal reduction:- This method is used to extract metals of low reactivity i.e those
below hydrogen in the electrochemical series. It involves heating the ore of the metal in the
presence of air. In essence the ore is first converted into the oxide of the metal which is then
further heated until it decomposes thermally.
Example
Heat
2HgS + 3O2 2HgO + 2SO2 (g)
Air

2HgO 2Hg + O2(g)

iv) .Displacement by a more reactive metal:- The fourth method of reduction is by displacement
of an element by one which is higher in the electrochemical series. This method is referred to as
a general method since any metal can be reduced by a more reactive one i.e one above it in the

36
 electrochemical series. This method is expensive because it involves the use of an already
purified metal.

Example
TiO2 + 2C + 2Cl2 TiCl4 + 2CO

TiCl4 + 2Mg Ti + 2MgCl2

3. REFINING:
The purpose of refining metals is to make them as pure as necessary for the particular job
they are required to do. Numerous techniques are available. These include

(i) Zone refining: - This method is applied on a very small scale to produce metals in an
extremely high degree of purity. It depends upon the principle that an impure molten
metal will deposit pure crystals on solidifying. Germanium is purified by this method
before being used as a semi conductor.

(ii) Vapor Phase Refining:- In this method a volatile halide is formed by direct action of the
metal and a halogen. The volatile halide is then purified mostly by fractional distillation
and then decomposed to the metal and the halogen.
Example

ZrI4(s) Heat Zr(s) + 2I2(g)

Zr(s) + 2I2

This method is applicable to metals like vanadium, Hafnium, Tungsten, Titanium, silicon
and Beryllium.
Similar principle is used in the Mond’s process where Nickel is purified using CO. Here,
impure Nickel reacts to form Nickel tetracarbonyl vapour that is then condensed to the
pure liquid (b.p 430C) before being heated to 2300C to decompose it to the pure metal.
Ni(s) + 4CO Ni[CO]4 heat Ni + 4CO

37
 (iii) Distillation:- This method is used in purifying volatile metals like Zinc, Cadmium and
Mercury. It involves heating the metals to their boiling points until they vaporize and
later condense in their pure forms.
(iv) Electrolytic refining:- This method is only applicable to weakly electropositive metals
like tin, copper and lead. These set of metals do not react with water and are easily
oxidized and reduced at the anode and cathode respectively.
For example copper is purified electrolytically by making the impure copper the anode of
an electrolytic cell, which contains aqueous solution of copper(II) sulphate as the
electrolyte and a thin strip of pure copper as the cathode. Application of appropriate
voltage results in transfer of pure copper from the anode to the cathode.

INTRODUCTION TO NUCLEAR CHEMISTRY

The nucleus of every atom of all elements, except hydrogen, contains both protons and
neutrons (the word nucleus is a general term also used to describe protons and neutrons). In the
nucleus, the neutrons appear to act as a kind of nuclear glue by overcoming the proton – proton
repulsion which can cause the nucleus to disintegrate.
Mass defect
It has been found that there is a difference between the mass of the nucleus of an element and
the sum of the masses (of proton and neutrons) in the nucleus of an atom.
For example, the mass of 4He nucleus is 4.00150 amu. However, the two protons and two neutrons
combined have a different mass, thus;
Mass of 2 protons = 2×1.00728 amu = 2.01456 amu
Mass of 2 neutrons = 2×1.00867amu = 2.01734 amu
Total mass of nucleus = 4.03190 amu
∆  (4.03190  4.00150) amu = 0.03040 amu
The loss of mass that occurs when protons and neutrons combine to form a nucleus is called
the Mass defect of the nucleus. The lost mass does not simply disappear, it is converted into energy.
It is this energy that holds the nucleus together and gives it the stability so that the nucleus does not
disintegrate. Nuclear binding energy can be defined as the energy required to break up a nucleus into
its component parts (i.e. protons and neutrons).
Nuclear Stability
The principal factor for determining the nuclear stability is the neutron to proton ratio (n:p).
For a stable atom with low atomic number, the n:p value is close to 1. As the atomic number

38
 increases, the n: p ratios of the stable nuclei becomes greater than 1. This deviation occurs because
higher atomic number (in the nucleus of an atom) requires large number of neutrons to stabilize it.
This stabilization is achieved by counteracting the strong repulsion amongst the protons in the
nucleus.
In the graph that follows a plot of the number of neutrons versus the number of protons in
various atoms is shown. The stable nuclei are located in an area of the graph known as the “belt of
stability”. Most of the radioactive nuclei lie outside this belt.
Number of Neutrons (A – Z)

UNSTABLE REGION
(Too many Neutrons: Spontaneous
130 beta emission)
Belt of
stability

110

90
1 : 1 n : p ratio

70

UNSTABLE REGION
50 Too many Protons
(Spontaneous positron emission)
If the n:p ratio is either too high or too low the nuclei tend be unstable and will tend to split to
give30
smaller nuclei. This is called NUCLEAR FISSION. When nuclei divide a high energy radiation
and sometimes sub–atomic particles are emitted from the atom, and this emission of smaller particles
and energy is called radioactivity.
10
39
15 30 45 60 75 90 105
Number of Protons (z)
 Radioactivity can therefore be defined as the spontaneous emission of particles and/or radiation from
the nucleus of an atom. The process is called radioactive decay. Radioactivity was first discovered by
a German scientist called ‘’Wilhelm Roentgen’’ in 1895. There are two types of radioactivity;
Natural radioactivity and Artificial radioactivity.

RADIOACTIVITY
Some minerals or elements naturally emit radiation and particles: this phenomena was
observed by Ernest Rutherford to be of three types (α, β and γ). In an experiment in which he passed
a beam of radiation from a radioactive source through a slit, then through electrically charged plates
unto a photographic plate, he found that the beam had split into three components. The component
that was attracted towards the positive plate he called beta (  ) particles, the one towards the
negative plate alpha (  ) particles, and the one not affected by the charge, gamma (γ) radiation.

PHOTOGRAPHIC
PLATE

β
LEAD BLOCK + ve plate

- ve plate
RADIOACTIVE
SUBSTANCE

Behaviour of Radiation from a Radioactive Source in an Electric Field

ALPHA PARTICLES
 This is a Helium nucleus with a mass of 4 amu and a +2 charge (He2+).
 It normally has a high velocity, 1/20 of the speed of light and it is emitted from the nuclei of
heavier unstable isotopes.

40
  It is highly ionizing as it attracts electrons to form Helium gas. This makes it to have low
penetrating power in the air.
 They travel only short distances in the air (4 to 5 cm).
 Compared to β – particles and γ-radiation,  - particles have relatively low speed and are
involved in frequent collisions with other atoms, which causes them to be stopped easily,
even by a sheet of paper.
  - Particles travel in straight lines.
When heavy unstable elements split to give another element together with  -particles, the decay is
called alpha decay and the mass of the decaying element decreases by four while the atomic number
decreases by two, in addition to the high energy γ- radiation. E.g.
238 234 4
92 U→ 90 Th + 2 He + γ

BETA PARTICLES
 These are fast moving electrons which travel almost at the speed of light.
 They are negatively charged and have practically no mass and are ejected from unstable
nuclei in what is called a beta decay.
 β – Particles do not have much penetrating power, but are more penetrating than -
particles. They need a thin sheet of aluminum of some few millimeters thickness to be
stopped, compared to a piece of paper for  - particles.
 β – particles meander in the air due to their very tiny masses, as can be seen in a cloud
chamber experiment, compared to  - particles that are heavier and go in a straight line.
The loss of β– particles by an unstable isotope is called beta decay. Here, one of the neutrons,
which are neutral, looses an electron to form a positive proton and an electron is emitted.
1 1 0
o  1    1 e

An example of β – decay is:

234 234
90 h  91 a   o1 e  

GAMMA RADIATION
 This is a high energy electromagnetic radiation that accompanies both α – and β decays and
is emitted by nuclei with excess energy. γ - radiation is not a particle.
 γ- Radiation is of very short wavelength with an extremely high penetrating power. It needs
very thick Lead or a block of concrete to stop it.

41
  γ - Radiation travels at the speed of light and has no charge or mass.

POSITRION EMISSION AND ELECTRON CAPTURE

There are two other types of radioactive decay processes that occur, in addition to  , β, and γ
- radiations.
1) Positron emission is when a proton in the nucleus is converted into a neutron and in the process a

positron is ejected ( 10 e
). A positron is the exact opposite of an electron in terms of charge (+ ve) but has the same mass.
When a positron is ejected, a decrease in the atomic number is observed since the proton is
converted to a neutron. There is however no change in mass number. For example
1 1 0
1   o  1 e
40
19   40 0
18 r  1 e

2) When a proton in the nucleus captures an inner shell electron and is thereby converted to a
neutron, the process is called electron capture. Here also, the atomic number decreases by one, since
a proton is converted to a neutron, but the mass number remains unchanged.
1 0 1
1    1 e o 
197
e.g. 80  g   10e 197
79 u

A summary of radioactive decay process is shown below:

process symbol Change in Change in mass Change in neutron
atomic no no no
 - Emission 4
2 e or -2 -4 -2
β – Emission +1 0 -1
o
1e or   oo 

o
1e or  
γ – Emission 0 0 0
E.C

Positron Emission -1 0 +1
Electron Capture -1 0 +1

APPLICATIONS OF RADIOACTIVITY
There are many good uses for radioactive isotopes if handled properly. Otherwise, they can
be very harmful biologically.

42
 1. Controlled application of radioisotopes used include Iodine- 131, Cobalt – 60, Cesium – 137
for disease treatment e.g. cancer, etc.
2. Medical equipments like surgical equipments are sterilized using radiation. Food is also
preserved by radiation with γ – rays.
3. Radioisotopes are used as tracers where they detect leaks in water pipes or oil pipelines. A
Geiger – Muller counter can detect where the radiation is leaking thereby avoiding the
uprooting of the whole pipeline.
4. Radioisotopes like Iodine – 131 (a β and γ - emitter) is used as a tracer by medical
practitioners for diagnosing thyroid disease while agriculturists use phosphate that is labeled
with P – 32 to determine how plants use fertilizers and grow in order to improve yields.
5. Metal crack, particularly in aircrafts, can be detected using X – rays. This helps in preventing
aircrafts having accidents since the X – rays can detect small cracks in the metals that cannot
be seen with the naked eye.
6. Carbon – 14 is used to compute the ages of archeological materials. Since its half – life and
rate of decay are known; analyzing the content of C -14 in an archeological material and
comparing it with the known content in all living materials can give a reasonable age of the
archeological material.
7. Nuclear power is used in providing electricity for many nations

INTRODUCTION TO TRANSITION METALS

In the periodic table, lying between the S – block and P – block elements are a group of
elements called transition elements. Transition elements are those that contain an incomplete d –
subshell or f – subshell in at least one of their compounds. Those with the incomplete f – subshell are
called the f – block transition elements or inner transition elements.
There are four rows or series of transition elements in the periodic table, and we shall be
more concerned with the d –block elements, the first row for that matter. Since Zn, Cd, and Hg have
fully filled d sub-shells, they are not considered to be transition metals.
Transition metals have many uses; like in the making of iron tools, copper wire, Silver
jewelry, coins etc. Some are also used as catalysts for important industrial reactions. Many like iron
have biological importance, as it is present in hemoglobin.
ELECTRONIC CONFIGURATION
After Calcium (Ar [4S2]), the next element in scandium. Here, the next orbital to be filled
after the 4S2 is the d sub-shell. This is due to the fact that the 4S orbital has a lower potential energy

43
 than the 3d orbital. However, once the 4S orbital is filled, it has higher energy content than the 3d
orbital.
Except in the case of Cr, and Cu, Hunds rule is followed in the filling of the 3d orbital, as one
electron is filled to each of the five 3 –d orbitals, before a second electron is added to any one of
them. For the Cr and Cu, repulsion between the electrons are minimized by half – filling each orbital
of a sub-shell. The half filled and fully filled 3d orbitals give rise to extra stability.
VIIIB
IIIB IVB VB VIB VIIB IB IIB
21 45 22 47.9 23 50.9 24 52 25 54.7 26 27 58.9 28 58.7 29 63.5 30 65.4
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc

ELEMENT GROUP VALENCE ELECTRONIC CONFIGURATION

M M2+ M3+
Sc IIIB 3d 1452 3d1 3d0
Ti IVB 3d 2452 3d2 3d1
V VB 3d3452 3d3 3d2
Cr VIIB 3d5451 3d4 3d3
Mn VIIIB 3d5452 3d5
Fe VIIIB 3d6452 3d6
Co VIIIB 3d7452 3d7
Ni VIIIB 3d8452 3d8
Cu IB 3d10451 3d9
Zn IIB 3d10452 3d10

Expected outer configuration Observed outer configuration

C ↑ ↑ ↑ ↑ ↑↓ ↑ ↑ ↑ ↑ ↑ ↑
r 3d 4s
3d 4s

Expected outer configuration

Observed outer configuration
Cu ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑↓
↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑
3d ↓
4s
3d 4s
GENERAL PROPERTIES OF TRANSITION METALS
Because transition metals have incompletely filled d sub-shells or give rise to ions with
incomplete d sub-shells, this attribute is responsible for several common notable properties in
transition metals. These common properties include;

44
 1. They are all metals. This is not surprising since their outermost shell contains so few
electrons. They are hard, brittle and have high melting point. This can be explained due to the
extremely small size of the atoms and partly due to the existence of strong metallic bonding
between the ions. An exception is Mercury, which is a liquid at room temperature.
2. They are all good conductors of and heat electricity.
3. They have high melting points, boiling points and density.
4. They are often coloured, especially in their hydrated forms. The coloured components may
be simple positive ions(e.g. Fe2+, Cu2+) or negative polyatomic ions (e.g. MnO-4, Cr2O2-7)
containing d – block elements. The colour results from electron jumps, or transition, between
the two closely spaced d- orbital energy levels.
5. They form alloys with each other and other elements of the periodic table.
6. They have catalytic properties. The d-block elements and their compounds are common
catalysts for both homogeneous and heterogeneous reaction in industry and biological system.
Platinum, Nickel, Iron, Manganese(iv) Oxide and vanadium(v) oxide are important heterogonous
catalysts used in many industrial process
7) They have variable oxidation states, presumably because some of or all the 3d electrons can also
be used along with the 4s electrons in chemical bonding. Manganese, e.g, has oxidation numbers of
+2, +3, +4, +5, +6, +7, corresponding to the use of none, one, two, three, four, and five 3d electrons
respectively.
8) They are very good in forming complexes due to their small size and highly charged ions which
also have vacant low energy orbitals (to accept lone pairs of electron from ligand molecules during
complex formation).
A metal complex is a structure consisting of a central metal atom or ion (usually metallic),
bonded to molecules or anions called ligands or complexing agents. A ligand is an ion or molecule
containing at least one atom having a lone pair of electrons which can be donated to the central metal
atom or ion to form a dative covalent bond. Examples of ligands include NH3, H2O, CO, CN-, Cl-,
OH- etc. Example of metal complexes include; Potassium hexacyanoferrate (iii) [K3(Fe(CN)6)] and
Trichlorotriammine cobalt (iii) [CoCl3 (NH3)3 ]
9) Many of the compounds of transition elements are paramagnetic, i.e they are weakly attracted by
a magnet.
10) They form non-stoichiometric compounds. These are chemical compounds formed by transition
metals that their elemental composition cannot be represented by a ratio of well-defined natural

45
numbers and therefore violates the law of definite proportions. E.g. YBa2Cu3O7-x where x can be any
number from 1-6.

46