CHM 1101:

BASIC INORGANIC CHEMISTRY

LECTURE NOTES
By Mr. Musagala Peter
 Course Outline

1. Atomic structure
2. The Periodic Table
3. Simple Bonding theory
4. Molecular orbital
5. The crystalline solid state
6. Practical work

Basic Inorganic Chemistry

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Lecture Notes
 ATOMIC STRUCTURE
Historical discovery of the atom
Democritus (460 – 370 BC) and other Greek philosophers:
• Thought that the material world must be made up of tiny indivisible
particles that they called atomos meaning ‘‘indivisible’’
Plato and Aristotle:
• Formulated the notion that there can be no ultimately indivisible
particles.
Antoine Lavoiser (1700s), Law of conservation of mass
• Matter is not created or destroyed.
Joseph Proust (1700s), Law of constant composition:
• Compounds are composed of atoms in definite ratios.

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Dalton (1766 - 1844)
Postulated as follows
• Each element is composed of extremely small particles called atoms.
• All atoms of a given element are identical.
• Atoms of different elements are different and have different properties
including different masses.
• Atoms of an element are not changed into different types of atoms by
chemical reaction i.e. atoms are neither created nor destroyed in chemical
reaction.
• Cpds are formed when atoms of more than one element combine; a given
cpd always has the same relative number and kind of atoms.
 According to Dalton’s atomic theory, atoms are the basic building
blocks of matter. They are the smallest particles of an element
that retain the chemical identity of the element.
 The Discovery of atomic structure (Electrical structure of atoms)
• A gas was enclosed in a glass tube containing two conducting metal plates/electrodes; the
cathode and anode.
• When a high voltage was applied between the plates, electric current (shown by the bright
luminous discharge) passed through the gas,
• This result suggested that the electric force had broken down atoms into new species that
carry charge. The magnitude of the current was proportional to the amount of gas in the tube.
• When the gas was nearly all removed, the current didn’t go to zero.
• This suggested that the current originated from one of the metal plates.
• These mysterious current carriers appeared to travel in a straight line from the negative
metal plate called the cathode . These current carriers were called cathode rays or beta rays
because they originated from the cathode.
• These cathode rays could not be seen; but their movement could be detected because they
could cause certain materials to fluoresce with green light and produced a luminous spot
where they impinged on the glass tube near the anode.

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Determination of the electronic charge (e): Millikan’s oil Drop
Experiment

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 The Nucleus
•With the growing evidence that the atom is composed of even smaller
particles, attention was given to how the particles fit together.
•In the early 1900s, Thomson reasoned that because electrons comprise
only a small fraction of the mass of an atom, they were responsible for an
equally small fraction of the atom’s size.
•He proposed that the atom consisted of a uniform positive sphere of
matter in which the electrons were embedded. This is called the Plum-
pudding model of the atom.

•In 1910, Rutherford and his co-workers performed an experiment that

disproved Thomson’s model of the atom.

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• He bombarded a thin gold foil with α-particles as shown in the
schematic diagram of the Geiger-Marsden experiment also known
as the Rutherford gold foil experiment below:

Observation:
• Almost all the α-particles passed through without deflection, a
small percentage were found to be slightly deflected on the order
of 1 degree. A small amount of scattering at large angles was
observed.

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From these observations Rutherford postulated that:
Most of the mass of the atom and all of its positive charge reside in a very
small extremely dense region which he called the nucleus.
Most of the total volume of the atom is empty space in which electrons
more around the nucleus.
• Most α – particles passed directly through the foil because they do not
encounter the minute Nucleus they merely pass through the empty space
of the atom.
• Occasionally an α -particle comes into close vicinity of the gold nucleus; the
repulsion between the highly charged gold nucleus and α- particles is
strong enough to deflect the less massive α- particles as shown above.

• Subsequent experimental studies led to the discovery of both positive

particles (protons) and neutral particles (neutrons) in the Nucleus. Protons
were discovered in 1919 by Rutherford, neutrons were discovered by James
Chadwick in 1932.
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Failures of the Rutherford’s model of the atom
• According to the Rutherford’s model of the atom, the atom consisted of
a positively charged Nucleus which constitutes the mass of the atom,
surrounded by negatively charged electrons whose orbits around the
nucleus determined the size of the atom.

This theory contradicts the theory of electromagnetic radiation.

According to the theory of electromagnetic radiation, charged particles
undergoing acceleration would continuously emit radiation and thus
lose energy. The Rutherford ‘atom’ could not have stable existence since
electrons are charged particles and in circling the nucleus are subjected
to acceleration. They would lose energy and spiral into the nucleus with
the subsequent collapse of the atom.
Nature of atomic spectra; which consisted of a series of discrete lines
in different parts of electromagnetic spectrum.

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 Atomic Spectra
• The most important in determining the structure of an atom was the
study of radiation emitted and absorbed by the elements.
• When an element is heated in a flame or a discharge of electricity is
passed through a gas, characteristic colours of light are seen. For
example, a discharge tube containing neon gas glows red, sodium
emits golden yellow light and mercury provides greenish light.
• This light when passed through a suitable prism, it is split into a
pattern of lines of different frequencies of light it contains which are
characteristic of the element. The result is called the atomic
emission spectrum.
• The atoms of an element produce line spectra, called line spectrum.

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Electronic structure of the hydrogen atom
• The single electron of the hydrogen atom rotates in certain orbits around
the nucleus called permissible orbits.
• These permissible orbits are called energy levels and are given quantum
numbers 1, 2, 3, 4, …. Or they are designated by letters K, L, M, N, …
respectively
• Under normal conditions, the electron occupies the energy level nearest to
the nucleus i.e. energy level 1 or K, referred to as the ground state
• When an electric discharge is passed through hydrogen atoms, electrons
absorb energy and jump to higher energy levels. The electron is said to be
promoted to a higher energy level and the process is called excitation.
• While in the higher energy levels, the electron is unstable, it falls to the
ground state. The fall may take place in one step or in stages.
• According to which level it falls, the electron gives out some or all of its
surplus energy in form of radiation giving rise to the emission spectrum
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Limitations of Bohr’s Theory
• The theory explains the spectrum of hydrogen and spectra of hydrogen like
elements (He , Li , ) satisfactorily. The model however cannot explain the spectra
+ 2+

of elements that contain two or more electrons. Each line in the spectrum
consists of two more closely spaced lines. This is called the fine structure. The
Bohr model with one quantum number cannot explain the fine structure.
• When the spectrum of an element is observed in a magnetic field, the lines
undergo splitting. This is called the Zeeman effect. Similar splitting is observed in
the electric field . This is called the Stark effect. The Bohr model could not provide
satisfactory explanation to the Zeeman and stark effects.
• To account for the fine structure of the spectrum, a quantum number (l)is
introduced in addition to n.

• To explain the Zeeman and stark effects one more quantum number (m) is
introduced on ad hoc basis.
• A modification of the Bohr’s theory was first made by Sommerfield and
subsequently a more satisfactory explanation came from the application of wave
mechanics.

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Principal quantum number Level of shell Maximum number of

electrons N = 2n2

1 K 2
2 L 8
3 M 18
4 N 32
5 O 50
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Principal quantum number() Values of Corresponding

( 0, 1, 2….., n – 1) sub-levels

1 0 s
2 0, 1 s, p
3 0, 1, 2 S, p, d
4 0, 1, 2, 3 S, p, d, f
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• n Allowed values of Total allowed values of
(2+1)
Possible values of

1(K) 0 (s) 1 0
2(L) 0 (s) 1 0
1 (p) 3 -1, 0, +1
3(K) 0 (s) 1 0
(L) 1 (p) 3 -1, 0, +1
(M) 2 (d) 5 -2, -1, 0, +1, +2
4 (K) 0 (s) 1 0
(L) 1 (p) 3 -1, 0, +1
(M)
2 (d) 5 -2, -1, 0, +1, +2
(N)
3 (f) 7 -3, -2, -1, 0, +1, +2,
+3

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2. Using quantum numbers; show that the third shell contains 18
electrons.
Solution:

There are 18 values of s, therefore the 3 orbit contains 18 electrons.

rd

Trial question:
Using quantum numbers; show that the second and fourth shell contain 8
and 32 electrons respectively.
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Arrangement of electrons in a shell
Shell Quantum No. Sub-shell No. of e-s in No. of e-s in
sub-shell complete
shell
K 2 2
1 0 0 -½
1 0 0 +½
L 2 0 0 +½ 2
2 0 0 -½
2 1 -1 + ½
2 1 -1 - ½ 8
2 1 0 +½
2 1 0 -½ 6
2 1 +1 + ½
2 1 +1 - ½

M 3 0 0 +½ 2
3 0 0 -½
3 1 -1 +½
3 1 -1 -½
3 1 0 +½
3 1 0 -½ 6
3 1 +1 +½
3 1 +1 -½
3 2 -2 +½
3 2 -2 -½ 18
3 2 1 +½
3 2 1 -½
3 2 0 +½
3 2 0 -½ 10
3 2 +1 +½
3 2 +1 -½
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3 2 +2 -½
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 Aufbau order of sub-shells for feeding in electrons

To fill electrons, follow the arrow.

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• Plot of N/z ratio for the different isotopes

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Assignment:
Read and make notes on the uses of radioisotopes (Hand in the
next lecture at 8:00 am)
Note:
The decay of a radioactive element is a random process, it is
not affected by external conditions such as temperature and
pressure changes
The process follows first order kinetics. The rate of decay
decreases with time.
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 THE PERIODIC TABLE
• It is a classification of the elements in order of increasing atomic number.
• This arrangement results into families of elements with similar chemical
properties forming groups of the Periodic table. For example the elements
C, Si, Sn, Ge and Pb form hydrides of the form EH suggesting they belong
4

to the same group; the elements N, P, As and Sb form hydrides of the form
EH also suggest that they belong to the same group
3

• This classification of elements was devised by Dmitri Mendeleev (1869)

• Assignment: Read about the Mendeleev Periodic Table.

Format of the Modern Periodic Table

The layout of the Periodic Table reflects the electronic structure of the
atoms of the elements

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General structure of Periodic Table

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Block s p d
Number of electrons in the valence G G
shell

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Periodic Properties
• Characteristic properties of atoms which show regular
variations with atomic number. These properties are of
considerable importance for understanding the
chemical properties of the elements.
• The important periodic properties are:
Atomic radius and ionic radius
Ionization Energy (I.E) / potential
Electron affinity
Electronegativity
Polarisability

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Atomic radius and ionic radius
 The atomic radius of an atom refers to the metallic and
covalent radius.
 The metallic radius of a metallic element is defined as half the
experimentally determined distance between the centres of
nearest-neighbour atoms in the solid.
 The covalent radius of a non-metallic element is defined as
half the internuclear distance between neighbouring atoms of
the same element in a molecule.
• The atomic and ionic radii increase down a group and decrease
from left to right across a period.
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Variation of first ionization energy with atomic
number

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From the graph:
• The helium atom has the highest ionization potential than any
other atom
Reason:
It has a nuclear charge of +2, its electrons reside in the lowest
energy level close to the nucleus.
• The noble gases have the highest ionization potential than any
other atom in their respective periods.
Reason:
Electrons in the noble gases are held in shells that are
completely filled.

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Example:
Using the following bond energies:
a) Calculate the electronegativity difference hydrogen and
chlorine
b) If the electronegativity of hydrogen is 2.1, calculate the
electronegativity of chlorine ( 1 kJmol-1 = 0.23901 k Calmol-1)
Bond Bond Energy (kJmol-1)
H – Cl 428
H–H 432
Cl - Cl 239

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Bond Bond energy/ Bond energy /kCalmol-1

kJmol-1
H – Cl 428
H–H 432
Cl – 239
Cl

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Trial Question:
The table below shows some bonds and their bond energies
Bond Bond energy (kJmol-1)
H–H 432
Cl – Cl 239

H–S 363
S – Cl 255
(S8) 226

a) Calculate the electronegativity difference between :

(i) Hydrogen and Sulphur
(ii) Chlorine and Sulphur

b) Determine the electronegativity of sulphur if the

electronegativity of hydrogen is 2.1.
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Pauling scale of Electronegativities

Element H
2.1
Element Li Be B N O F
1.0 1.5 2.0 3.0 3.5 4.0
Element Na Cl
0.9 3.0
Element K Br
0.8 2.0

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3. Calculate the effective nuclear charge on a
(i) 4s electron,
(ii) 3d in a V atom.
Solution:
(i) Write down the electron configuration with appropriate
groupings:
(1s)2, (2s, 2p)8, (3s, 3p)8, (3d)3, (4s, 4p)2-1
Then S = (1 × 0.35)+(11 × 0.85) + (10 × 1.00) = 19.7
Therefore , Z eff = Z − S = 23 − 19.7 = 3.3
(ii) Write down the electron configuration with appropriate
groupings:
(1s)2, (2s, 2p)8, (3s, 3p)8, (3d)3-1, (4s, 4p)2
Then S = (2 × 0.35)+(18 × 1.00) + (2 × 0.00) = 18.7
Therefore , Z eff = Z − S = 23 − 18.7 = 4.3
Note:
• From the answer in (i) and (ii) it can be noted the effective nuclear
charge on a 3d electron is higher than that on a 4s electron.
Therefore, it is easier to lose a 4s electron than a 3d electron. The
ground state electron configuration of the V+ ion is 3d34s1 rather
than 3d24s2
• The values of Zeff calculated this way are generally lower than
those given in Table below although they do follow the same
pattern. This approximation does not, take into account the
difference between s and p orbitals or the effects of spin
correlation.
• With knowledge of Z eff the electronegativity of the element can
be calculated.
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Exercise:
Calculate the effective nuclear charge on the
(a) 2p electron in fluorine
(b) 4s electron in calcium
(c) 3d electron in scandium
(d) 4s electron in copper
(e) 6s electron in platinum
 Effective nuclear charge, Z for selected elements
eff

H He
Z 1 2
1s 1.00 1.69
Li Be B C N O F Ne
Z 3 4 5 6 7 8 9 10
1s 2.69 3.68 4.68 5.67 6.66 7.66 8.65 9.64
2s 1.28 1.91 2.58 3.22 3.85 4.49 5.13 5.76
2p 2.42 3.14 3.83 4.45 5.10 5.76
Na Mg Al Si P S Cl Ar
Z 11 12 13 14 15 16 17 18
1s 10.63 11.61 12.59 13.57 14.56 15.54 16.52 17.51
2s 6.57 7.39 8.21 9.02 9.82 10.63 11.43 12.23
2p 6.80 7.83 8.96 9.94 10.96 11.98 12.99 14.01
3s 2.51 3.31 4.12 4.90 5.64 6.37 7.07 7.76
3p 4.07 4.29 4.89 5.48 6.12 6.76

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• Across the period effective nuclear charge increases. This is
because the shielding remains almost the same for the valence
electrons.
• Down a group Z eff decreases from one element to the next.

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Variation of electronegativity across a period and down a
group in the Periodic Table
• Electronegativity of the elements increases across a period in the
periodic table. Trend in electronegativity is related to the size of the
atom and its electron configuration; small atoms with almost full
electron shells are likely to attract an electron towards themselves.
This is due to increased effective nuclear charge.
• Large atoms with few valence electrons have a small tendency to
attract electrons towards themselves. This is due to decreasing
effective nuclear charge. Consequently, electronegativity decreases
down a group in the P. Table.
Note:
Fluorine has the highest electronegativity value; while cesium has
the lowest value.
The 3 highly electronegative elements are F, O and N
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• In a single covalent bond, each atom contributes an electron to
the pair it shares with its neighbors. However, in some cases
one atom contributes both electrons.
• If only one atom contributes the pair of electrons to be shared,
the resultant covalent bond is called a Dative (or coordinate)
covalent bond.
The octet Rule
It states that:
Each atom shares electrons with neighbouring atom(s) to
achieve a total of eight valence electrons i.e an octet (valence
shell containing 8 e-s).

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Examples:
• Nitrogen has 5 valence electrons and needs 3 more
electrons to complete its octet.
• Chlorine (and the halogens) have 7 valence electrons and
needs a share in one more electron to complete its octet
• Oxygen has 6 valence e-s and needs 2 e-s to complete its
octet.
• Argon has 8 valence electrons and has no tendency to
share electrons because it already has a complete octet.
• Hydrogen has one electron; and need one e- to complete
the Helium like structure i.e. a duplet rather than an octet
of electrons.

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Exceptions to the Octet Rule
• When empty d orbitals are available (e.g. period 3 elements and later), more
than 8 electrons can be accommodated around an atom. The molecule is
said to have an expanded octet.
• The 5 bonds between phosphorus and chlorine in PCl5 require P to use its d
orbital to accommodate an additional pair of electrons beyond the octet.
• Other molecules with expanded octets are SF4, AsF6- , ICl4-, SF6, IF7, [XeF8]2-,
ClF3

The octet rule does not apply when molecules have an incomplete octet (a
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valence shell with fewer than 8 electrons).
• Boron forms compounds (e.g. BCl3) in which it has only 6 valence electrons;
beryllium forms compounds in which it has 4 electrons around Be e.g. BeF2

• For molecules with an odd number of valence electrons, complete pairing is

impossible and an octet around eachChemistry
Basic Inorganic atomLecture
cannotNotes be achieved. Example: 125
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This applies to Cl Br I molecules
2 2 2

Note:
• Each X atom has 3 lone pairs of electrons.
• The number of valence electrons of an atom is equal to the roman
group number of that atom
• The lone pairs of electrons on the small fluorine atoms repel one
another and almost overcome the favourable attractions that hold the
fluorine atoms together in the molecule. This repelling effect explains
why fluorine gas is so reactive.

Assignment:
Write Lewis structures for the following diatomic molecules
HCl, Br , O , CO, N , CN , HO
2 2 2
- -

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Writing Lewis structures for polyatomic molecules and ions
• Determine the total number of electrons by adding the number of
valence electrons.
Each H atom supplies one electron.
Each main group element supplies its Roman group number of electrons.
For a cation subtract one electron for each positive charge.
For each anion add one electron for each negative change.
Divide the total number of electrons by 2 to get the number of electron
pairs.

• Write chemical symbols of the atoms to show which atoms are

neighbours
The less electronegative atom is in the centre of the molecule e.g. SO2 is
OSO and not SOO, CO2 is OCO not COO.
Exceptions are H2O with O in the centre, NH3 with N in the centre.

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• Distribute the electron pairs so that there is one pair of electrons
forming a single bond between each pair of atoms bonded
together and then supply electron pairs (to form lone pairs or
multiple bonds) until each atom has an octet.
Each bonding pair (:) is then represented by a single line (–)
The net charge of a polyatomic ion is supposed to be possessed by the
ion as whole and not by a particular individual atom.

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T h i s ar r an g em en t d o es n o t
H : C : N:
co m p l ete n i tr o g en 's o ctet

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If there not enough electron pairs, use one or more of the electron pairs to
form multiple bonds.
The H atom has already completed its duplet, so try putting all three
remaining e- pairs on the N atom.
H : C : N: T h i s ar r an g em en t d o es n o t
Also try : co m p l ete car b o n 's o ctet

We rearrange the electron pairs to form multiple bonds between carbon and
nitrogen.

H : C : : : N : w r i tten as H C N :

Note:
The nitrogen atom and carbon atom each achieve an octet.

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Generally:
• Terminal halogen atoms in a molecule always have 3 lone pairs.

i.e.
• Terminal oxygen and sulphur atoms form either one or two
bonds and have either 3 or two lone pairs respectively.

• Terminal nitrogen atoms may have up to 3 bonds.

Examples and exercises:
Write the Lewis structure for each of the following molecules/ions
(a) hypochlorous acid, HClO. Sulphur trioxide, SO3
(b) Oxygen difluoride, OF2 Phosgene, COCl2
(c) Suphuric acid HClO3
(d) POCl3 H2SO3
(e) CH2Cl2 AsO33-
(f) XeF2 BrO3-
(g) ClO2- SO42-
(h) CO32- PO43-
(i) ClO4- ClO3-
(j) NO+
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• Use the remaining 8 electron pairs to complete the octets of the
O atoms, one O atom needs two electron pairs, the other two
need 3 electron pairs each to complete their octets.

Note:
The net charge of a polyatomic ion is supposed to be possessed by the ion
as whole and not by a particular individual atom in a Lewis structure.
The Lewis structure for the carbonate ion is

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That of the phosphate ion is

Formal Charge (check james, pfenning and silver)

It refers to the apparent electronic charge of each atom in a molecule, based
on the electron-dot structure (Lewis structure)

To calculate the formal charge of an atom in a molecule /ion;

 Assign all the unshared (non-bonding) electrons to the atom on which are they found
 Assign half of the bonding electrons to each atom in the bond.
 Formal charge is calculated from the expression:

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Example:
Calculate the formal on the C and N atoms in the cyanide ion.
Soln.
Write the Lewis structure ion first i.e.
[ : C : : : N :]-

Therefore, formal charge on C is -1.

Similarly, the formal charge on the N atom = 5 – 5 = 0
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Note:
• The sum of formal charges on an ion equals the charge on the
ion; for a molecule the sum of formal charges on the atoms
equals 0

• When several Lewis structures are possible, the most stable one
will be that in which:
The atoms bear formal charges close to 0,
Any negative formal charge resides on the more electronegative
atom(s).
Example:

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Example:
The possible Lewis structures of the carbon dioxide molecule are:

O C O
The preferred structure is
Reason:
The atoms carry 0 formal charge.
Assignment:
Write the Lewis structures of the thiocyanate ion. Which of the structures is
preferred. Give reason(s) for your answer.

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• The lone pairs (LP) tend to take up more space around the
central atom because they are closer to the nucleus than the
bonding pair although the true origin of the effect is not clear.
To apply the VSEPR model;
Write the Lewis structure for the molecule / ion.
Count the total number of electron-domains around the central atom.
Each nonbonding electron pair, single bond, double bond or triple bond
should be counted as an electron domain.
Determine the electron-domain geometry by arranging the total number
of electron domains so that the repulsions among them are minimized.
Use the arrangement of the bonded atoms to determine the molecular
geometry.
The positions of the atoms and hence the shape of the molecule are
then dictated by the positions of the bonding electron pairs.

Basic Inorganic Chemistry Lecture Notes 143

Illustration:

The NH3 molecule has four electron pairs that are disposed
tetrahedrally but since one of them is alone pair, the molecule
is classified as trigonal pyramidal; one apex of the pyramid is
occupied by the lone pair as shown in the illustration.
Similarly the H2O molecule has a tetrahedral arrangement of
its electron pairs around the O atom but two of the pairs are
lone pairs. The molecule is classified as Angular or bent.

Basic Inorganic Chemistry Lecture Notes 144

 Shapes of simple molecules
No. of e- Molecular Number of No. of VSEPR model formula, Examples and shape
domains geometry sigma bonds LP
around the (bonding
central atom domains)
1 Linear 1 A – X e.g. ClF, BrCl, HF, BrF
2 Linear 2 0 AX2E0 e.g. CO2, BeCl2, HgCl2

X A X

3 Trigonal 3 0 AX3E0 e.g. BF 2- -

3,CO3 , SO3, NO3
X

planar
A

X X
X

O
Bent 2 1 AX E
A
e.g. NO -, NSF,SnCl ,NO , O O
X 2 1 2 X
X 2 2 3

Basic Inorganic Chemistry Lecture Notes 145

4 Tetrahedral 4 0 AX4E0 e.g. CH4, SiCl4, NH4+, PO43-,
SO42-, ClO4-
H

C
H H
X
X e.g. H
X

Trigonal pyramidal 3 1 AX3E1 e.g. NH3, PCl3, XeO3

N
H H

X H
X
X e.g.

Bent /V-shape / 2 2 AX2E2 e.g. H2O, Cl2O, SCl

O
2
H
Angular X
H
X

e.g.
Cl

Cl
5 Trigonal 5 0 AX5E0 e.g. PCl5, SOF4 P Cl

bipyramidal Cl

Cl

Basic Inorganic Chemistry Lecture Notes 146

e.g.
Seesaw / 4 1 AX4E1 e.g. SF4, TeCl4
Distorted F

tetrahedral
S F

Cl

e.g. F

T- shape 3 2 AX3E2 e.g. ClF3, BrF3, BrCl3

Cl F

e.g.

I I I

Linear 2 3 AX2E3 e.g. XeF2, I3-

e.g.

Basic Inorganic Chemistry Lecture Notes 147

 Square pyramidal 5 1 AX5E1 e.g. ClF5, BrF5, ICl5

Square planar 4 2 AX5E1 e.g. XeF4

7 Pentagonal 7 0 AX7E0 e.g. IF7

bipyramidal

8 Square 8 0 AX7E0 e.g. TaF83-

antiprismatic
Basic Inorganic Chemistry Lecture Notes 148
• For trigonal bipyramidal and pentagonal bipyramidal molecules;
we distinguish between axial electron pairs which lie along the
axis of the molecule and Equatorial election pairs. The lone
pairs occupies the Equatorial site.
• In an octahedral basic shape (6 electron pairs around the central
atom) a single lone pair can occupy any position but a second
lone pair will occupy the position directly trans (opposite) to the
first L.P which results in a square – planar structure.

Basic Inorganic Chemistry Lecture Notes 149

•

Basic Inorganic Chemistry Lecture Notes 150

•
•

Basic Inorganic Chemistry Lecture Notes 152

Limitations of the VSEPR model of molecular shapes
• It can not be used to predict the actual bond angle adopted by
the molecule.
• There are also problems with hydrides and fluorides.

Basic Inorganic Chemistry Lecture Notes 153

 Valence bond theory (VBT)
• According to the VBT, a covalent bond is formed when a valence atomic orbital of
one atom merges with that of another atom. The atoms are said to share a region
of space or to overlap.
• The overlap of orbitals allows two electrons of opposite spins to share the
common space between the nuclei forming a covalent bond. i.e. a covalent bond
is formed by overlapping of two half-filled atomic orbitals of two different or same
atoms
• The electrons in the overlapping orbitals get paired and are confined between the
nuclei of the two atoms.
• The electron density between two bonded atoms increases due to overlapping
giving the molecule more stability and the greater the stability the stronger the
bond.
• The direction of the covalent bond in long the region of overlapping of the atomic
orbitals.

Examples:

Basic Inorganic Chemistry Lecture Notes 154

•

Basic Inorganic Chemistry Lecture Notes 155

•

Basic Inorganic Chemistry Lecture Notes 156

Examples:
Hydrogen molecule:

Similarly the bond in hydrogen chloride results from the overlap of the 1s orbital of H and one of the
lobes of the 3p orbital of Chlorine.
The bond in chlorine molecule results from the overlap of two 3p orbitals from two Cl atoms. The
formation of covalent bonds in two molecules is illustrated below.

Basic Inorganic Chemistry Lecture Notes 157

•

Basic Inorganic Chemistry Lecture Notes 158

•

Basic Inorganic Chemistry Lecture Notes 159

• This version of the VBT was limited to diatomic molecules only. It could
not explain the structures and bond angles of molecules with more than
three atoms. E.g. it could not explain the structures and bond angles of
H2O, NH3 etc.
• In order to explain the structures and bond angles of molecules, Linus
Pauling modified the valence bond theory using hybridization concept.

HYBRIDIZATION:
The mixing of two or more atomic orbitals of an atom with almost same energy
to give the same number of identical and degenerate orbitals called hybrid
orbitals.

• The mixing or hybridization of atomic orbitals is a mathematical concept

based on quantum mechanics. During this process, the wave functions, Ψ of
atomic orbitals of same atom are combined to give new wave functions
corresponding to hybrid orbitals.

Basic Inorganic Chemistry Lecture Notes 160

Note:
• The hybrid orbitals are filled with those electrons which were
present in the pure atomic orbitals forming them and the filling
up follows Pauli's exclusion principle and Hund's rule.
• The hybrid orbitals participate in the σ bond formation with other
atoms.
• The number of hybrid orbitals formed is equal to the number of
pure atomic orbitals that undergo hybridization.
• Hybrid orbitals have characteristics of atomic orbitals and have
identical shapes; usually with one big lobe and a small lobe.
• In bonding atomic orbitals of different atoms combine to form
the bond while during hybridization atomic orbitals of the same
atom are mixed.

Basic Inorganic Chemistry Lecture Notes 161

Types of Hybridization
• sp hybridization
It refers mixing of one s and one p orbitals of almost equal energy to give
two identical and degenerate hybrid orbitals is called sp hybrid orbitals.
sp hybrid orbitals are arrange linearly make angle of 180o and possess
50% s- and 50% p character.

• The two sp hybrid orbitals are shown together in the illustration

Basic Inorganic Chemistry Lecture Notes 162

Examples:
Formation of beryllium chloride

• Ground state electronic configuration of Be is 1s2 2s2 ; on excitation,

promotes one of its 2s orbital electron into the empty 2p orbital giving the
excited state electronic configuration 1s2 2s1 2p1.
• Then mixes one s orbital with one p orbital to form two half-filled sp
hybrid orbitals which are arranged linearly around the Be atom.
• These half filled sp-orbitals form two σ bonds with two Cl atoms i.e.

Basic Inorganic Chemistry Lecture Notes 163

 sp2 hybridization
It refers mixing of one s and two p orbitals of almost equal energy to give three
identical and degenerate hybrid orbitals is called sp2 hybrid orbitals.
sp2 hybrid orbitals arrange themselves making an angle of 120o

Examples: Formation of the borane (BH3) molecule

• Ground state electronic configuration of B is 1s22s22p1
• On excitation, boron promotes one of its 2s orbital electron into
the empty 2py orbital giving the excited state electronic
configuration:1s22s12px12py1.
• It then mixes one s orbital with two p orbital to form three half-
filled sp2 hybrid orbitals.
• The three sp2 hybrid orbitals arrange themselves making an angle
of 120o
• These half-filled sp2-orbitals form three σsp-s bonds with 3 H atoms
forming the is trigonal planar molecule.
Basic Inorganic Chemistry Lecture Notes 164
Illustration:

Trial question:
With the aid of relevant diagram(s), briefly explain how the
boron trichloride molecule is formed by hybridization.
Basic Inorganic Chemistry Lecture Notes 165
 Sp3 hybridization
It refers mixing of one s and three p orbitals of almost equal energy to
give four identical and degenerate hybrid orbitals is called sp3 hybrid
orbitals.
Example:
Formation of methane

• Ground-state e- configuration. of carbon: 1s22s22px12py12pz0

• On absorbing 402 kJ mol-1 carbon promotes one electron from the

2s orbital to the pz to give the excited state e- Confn. of carbon :
1s22s22px12py12pz1

• In the excited state carbon mixes one s orbital with three p orbitals
(sp3 hybridization) = four degenerate orbitals called sp3 hybrid
orbitals

Basic Inorganic Chemistry Lecture Notes 166

• The four hybrid orbitals arrange themselves tetrahedrally around
the carbon atom as shown below.

• The unpaired electrons of carbon combine with four other

atoms to form compounds e.g. 4 H to form methane, CH4

Basic Inorganic Chemistry Lecture Notes 167

sp3d hybridization
It refers mixing of one s, three p and one d orbitals to give five identical
and degenerate hybrid orbitals is called sp3d hybrid orbitals. The five
sp3d arrange in trigonal bipyramidal symmetry, three are arranged in
trigonal plane, the remaining two orbitals are present above and below
the trigonal plane at right angles shown below.

Basic Inorganic Chemistry Lecture Notes 168

 Example:
Formation of phosphorus pentachloride (PCl5)

• Ground-state e- configuration. of P: [Ne]3s23p3

• P promotes one electron from the 3s orbital to the 3d to give the

excited state e- confn. of P : [Ne] 3s13px13py13pz13d1

• In the excited state P mixes one s orbital with three p orbitals and one
d (sp3d hybridization) = five degenerate orbitals called sp3d hybrid
orbitals.
• By using these half-filled sp3d orbitals, phosphorous forms five σsp3d-p
bonds with chlorine atoms. Each chlorine atom makes use of half-
filled 3pz orbital for the bond formation. The shape of PCl5 molecule is
trigonal bipyramidal with 120o and 90o of Cl - P - Cl bond angles.

Basic Inorganic Chemistry Lecture Notes 169

The trigonal bipramidal structure of PCl5

Basic Inorganic Chemistry Lecture Notes 170

sp3d2 hybridization
• Refers to mixing of one s, three p and two d orbitals to give six
identical and degenerate hybrid orbitals called sp3d2 hybrid orbitlas.
• The six sp3d2 orbitals are arranged in octahedral symmetry by
making 90o angles to each other. This arrangement can be visualized
as four orbitals arranged in a square plane and the remaining two are
oriented above and below this plane perpendicularly as shown below.

Basic Inorganic Chemistry Lecture Notes 171

Example:
Formation of sulphur hexafluoride
• The ground state electronic configuration of S: 1s 2s 2p 3s 3p 3p 3p . 2 2 6 2
x
2
y
1
z
1

• In the excited state, sulphur promotes two electrons into two of the 3d
orbitals (one from 3s and one from 3p ) to give the excited state
x

electronic configuration 1s 2s 2p 3s 3p 3p 3p 3d .
2 2 6 1
x
1
y
1
z
1 2

• S by mixes one 3s, three 3p and two 3d orbitals(sp d hybridization) 3 2

forming six half-filled sp d hybrid orbitals are arranged in octahedral

3 2

symmetry.
• Sulfur atom forms six σ 3 2
sp d -p bonds with 6 fluorine atoms by using these
sp d orbitals.
3 2

• Each fluorine atom uses is half-filled 2p orbitals for the bond formation.
z

• SF is octahedral in shape with bond angles equal to 90 as shown below.

6
o

Basic Inorganic Chemistry Lecture Notes 172

Formation of SF6 by sp3d2 hybridization

Basic Inorganic Chemistry Lecture Notes 173

sp3d3 hybridization
• Refers to mixing of one s, three p and three d orbitals to give seven
identical and degenerate hybrid orbitals called sp3d3 hybrid orbitals.
• The seven sp3d3 which are oriented in a pentagonal bipyramidal symmetry.

• Five among the sp3d3 orbitals are arranged in a pentagonal plane by

making anglesof72o.
• The remaining are arranged perpendicularly above and below this
pentagonal plane as shown below.

Basic Inorganic Chemistry Lecture Notes 174

Formation of iodine heptafluoride by sp3d3 hybrization
• The electronic configuration of Iodine atom in the ground state is:
[Kr]4d105s25p5.
• However, the formation of IF7 requires 7 unpaired electrons; therefore, the
iodine atom promotes three of its electrons (one from 5s orbital and two
from 5p sublevel) to give the excited state electronic configuration of Iodine
as: [Kr]4d105s15p35d3.

• The iodine atom them mixes one s orbital, three p orbitals and two d orbital
to give 7 half filled sp3d3 hybrid orbitals ( sp3d3 hybridization) which arrange
in pentagonal bipyramidal symmetry around the iodine atom.
• These will form 7 σsp3d3-p bonds with fluorine atoms.
• Thus the shape of IF7 is pentagonal bipyramidal. The F-I-F bond angles in the
pentagonal plane are equal 72o, whereas two fluorine atoms are present
perpendicularly to the pentagonal plane above and below as shown below.
Basic Inorganic Chemistry Lecture Notes 175
Formation of iodine heptafluoride by sp3d3 hybrization

Basic Inorganic Chemistry Lecture Notes 176

 Molecular orbital theory of bonding (MOT)

Basic Inorganic Chemistry Lecture Notes 177

• Atomic orbitals of two or more atoms combine to form
molecular orbitals only when the have:
Close distance
Similar energy
Matching symmetry
Matching geometry
• The number of MOs produced is equal to the number of atomic
orbitals that combined.
Examples of combination of atomic orbitals
1. s – s combination of atomic orbitals

Basic Inorganic Chemistry Lecture Notes 178

•

Basic Inorganic Chemistry Lecture Notes 179

Combination of p and p orbitals
Combination of p orbitals along the axis joining the nuclei
produces sigma MOs while lateral overlap of atomic orbitals
produces pi MOs

Basic Inorganic Chemistry Lecture Notes 180

• Formation of pi

Basic Inorganic Chemistry Lecture Notes 181

Combination of p and d atomic orbitals
• This produces one bonding MO and one anti-bonding MO.
• The lateral overlap of atomic orbitals produces pi Mos.
• Occurs in compounds of transition metal and other compounds e.g. P and
S oxoacids and oxides.

Basic Inorganic Chemistry Lecture Notes 182

•

Basic Inorganic Chemistry Lecture Notes 183

•
MOs MOs

 Formed by the overlap of the lobes of atomic  Formed by overlap of the lobes of atomic
orbitals pointing along the internuclear axis. orbitals perpendicular to the line joining the
nuclei.

 The electron density is concentrated between  The electron density is zero between the two
the two nuclei nuclei

 All bonding Mos are symmetric about the  MOs have no symmetry about the internuclear
internuclear axis axis

 All antibonding MOs are unsymmetric  All antibonding MOs are symmetric

Basic Inorganic Chemistry Lecture Notes 184

Molecular orbital diagram
• A diagram representing energies of atomic orbitals and
molecular orbitals at a particular internuclear distance between
the atom.
• In the MO diagram, the energies of the MOs are shown in the
middle of the diagram and the energies of atomic orbitals are
shown on either side of the MOs.
• The atomic orbitals are ordered in terms of their energy.
• The most stable valence atomic orbitals are placed lowest as
shown in the diagram below.

Basic Inorganic Chemistry Lecture Notes 185

Molecular orbital diagram

Basic Inorganic Chemistry Lecture Notes 186

• Molecules are built up by adding electrons in the MOs in the
same way as atoms are built up by adding electrons to atomic
orbitals
• The Aufbau principle is used to obtain the electron configuration
of some diatomic molecules
• A bonding MO is lower in energy than the atomic orbitals from
which it is composed
• Electrons in this type of orbital favour bonding
• An anti-bonding MO is higher in energy than the atomic orbitals
from which it is composed
• Electrons in this type of orbital favour the separated atoms(they
are anti-bonding)

Basic Inorganic Chemistry Lecture Notes 187

•

Basic Inorganic Chemistry Lecture Notes 188

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Basic Inorganic Chemistry Lecture Notes 189

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Basic Inorganic Chemistry Lecture Notes 190

•

Basic Inorganic Chemistry Lecture Notes 191

A general molecular orbital energy level diagram for the formation of
X2 in which the valence orbitals of atom X are 2s and 2p

Basic Inorganic Chemistry Lecture Notes 192

•

Basic Inorganic Chemistry Lecture Notes 193

Assignment:
1. (a) Draw the energy level diagrams for the F2 and Ne2
molecules
(b) Write the electron configurations of the molecules
(c) Calculate the bond order for each molecule.
2. (a) Draw the MO energy diagram for the NO molecule.
(b) Write electron configuration of the molecule
(c) Is the molecule paramagnetic or not. Give a reason for your
answer
(d) Write the electron configuration of the molecule and calculate
the bond order.
(e) What is the significance of the bond order obtained?
(f) Calculate the bond order of the O2+ . Explain your answer.
Comparison between VBT and MOT for covalent bond formation
Similarities
• Both theories explain the nature and formation of covalent bond in a
molecule
• Both theories assume that the bond is formed only when the atomic
orbitals of two atoms possess:
Nearly same energy
Appropriate symmetry about the molecular axis
Good overlap with each other
• Both theories consider the concentration of electron density
between the nuclei which develops attraction.
• Both theories consider directional character of the covalent bond
• Both theories use Aufbau principle in filling electrons in the atom
orbitals and molecular orbitals.

Basic Inorganic Chemistry Lecture Notes 195

 Differences between the VBT and MOT
VBT MOT

• Overlapping of atomic orbitals takes place Overlapping and combination of atomic orbitals takes
place
• Atoms retain their individual character Atoms lose their individual character in formation of a
when linked to other atoms chemical bond and MOs are formed.

• Atomic orbitals are monocentric. An MOs are polycentric. An electron moves in the field of
electron moves in the field of one nucleus more than one nucleus
only.
• Electron pairs are localized between the Electrons are delocalized over all atoms
two atoms.

• It is an old model It is a modern and more popular model

• It is used for qualitative consideration It is used for semi-quantitative and quantitative results

• It gives a simple pictorial representation It has greater conceptual and mathematical simplicity
of molecular structure than the VBT

Basic Inorganic Chemistry Lecture Notes 196