CHAPTER 6

CHEMICAL BONDING
6.1 WHAT IS A CHEMICAL BOND?
When two atoms of same or different elements approach each other, the energy of the
combination of the atoms becomes less than the sum of the energies of the two separate atoms at
a large distance. We say that the two atoms have combined or a bond is formed between the two.
The bond is called a chemical bond. When atoms interact to form a chemical bond, the electrons
in the outer most shell take part in the bond formation and determine the combining capacity or
the ‘valency’ of the atom. Therefore, the outer most shell of any atom is called its valence shell
and the electrons present in the valence shell are called the valence electrons. For this reason,
when we study chemical bonding, we are concerned primarily with the valence electrons of the
atom. Thus a chemical bond may be visualized as an effect that leads to the decrease in the
energy. The combination of atoms leads to the formation of a molecule that has distinct
properties different from that of the constituent atoms.
Why atoms combined to form compounds, clusters, molecules/ polyatomic ions?
-to attain octet (eight) rules
-to have lower energy (to be stable)
-to have net attractive force

Where, A= attraction force, R= repulsion force

Chemical bond is formed when A>R:
Example: H + H H2 (g) but, He + He no reaction since R>A.

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Most atoms are chemically bonded to each other? As independent particles, they are at
relatively high potential energy. However, nature favors arrangements in which potential
energy is minimized. This means that most atoms are less stable existing by themselves than
when they are combined. By bonding with each other, atoms decrease in potential energy,
thereby creating more stable arrangements of matter.
How do atoms combined to form compounds, clusters, molecules/ polyatomic ions?
In chemical bonds, atoms are combined to form compounds, clusters, molecules/ polyatomic
ions by:
 Transferring /losing of their valence electrons.
 Gaining of extra valence electrons
 Sharing of valence electrons
 Coordinating valence electrons
6.2 Types of Chemical Bonding
The forces of attraction that hold atoms together are called chemical bonds. Broadly these forces
of attraction can be categorized as intramolecular forces, which affect the chemical properties
of the species.
There are three main types of chemical bonds – covalent, ionic and metallic bonds. In general,
there is a gradual change from more metallic to more non-metallic property when moving from
left to right across a period and when moving from bottom to top within a group. Three types of
bonding can result from the manner in which the atoms can combine:
6.2.1 IONIC BOND/ELECTROVALENCE BOND-is a type of chemical bond that results
from the electrostatic force of attraction between two oppositely charged ions. It is formed
due to transfer of electrons from one atom (mostly metals) to another (mostly nonmetals) by
losing and gaining of electrons. The atom that loses electrons will form a cation and the atom
that gains electrons will form an anion. These oppositely charged ions come closer to each other
due to electrostatic force of attraction and thus form an ionic bond. In general, an ionic bond is
formed between two atoms that contain greater electronegativity difference and it is between a
metal atom and a nonmetal atom. Example: NaCl, LiF, MgCl2.

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Energetics of Ionic Compound Formation
We have just described the formation of an ionic compound (NaCl) as a result of transfer of
electrons. You may raise a question here that when more energy is required (ionisation energy)
to form a sodium ion from sodium atom, than that released (electron affinity) in the formation
of chloride ion from chlorine atom then how do we say that the formation of NaCl is
accompanied by a decrease in energy? Your question is quite justified but let us assures you that
there is no anomaly. Let us look at the whole process somewhat closely to clarify your doubts.
Born Haber Cycle
Direct experimental determination of the lattice energy of an ionic solid is difficult.
However, this quantity can be indirectly determined from experiment by means of a
thermochemical “cycle” originated by Max Born and Fritz Haber in 1919 and now called the
Born–Haber cycle.

The formation of NaCl from sodium and chlorine can be broken down into a number of steps as:
a) Sublimation of solid sodium to gaseous sodium atoms.

b) Ionization of gaseous sodium atom to give sodium ion.

c) Dissociation of gaseous chlorine molecule into chlorine atoms

d) Conversion of gaseous chlorine atom to chloride ion (addition of electron)

e) Formation of NaCl from sodium and chloride ions.(Crystal or lattice formation).

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The energy released in this step is lattice energy. The energy released when a crystalline solid
forms from ions is related to the lattice energy of the solid. The lattice energy is the change in
energy that occurs when an ionic solid is separated into isolated ions in the gas phase.
The net reaction would be

The overall energy change can be computed by taking the sum of all the energy changes:

Thus we see that the net process of formation of NaCl from sodium and chlorine is accompanied
by a large decrease in the energy. The approach we have just followed is based on the law of
conservation of energy and is known as Born- Haber cycle.

Of the five different types of energies involved, two (sublimation and dissociation energies)
generally have low values than the rest. Therefore, the three energy terms i.e., ionization energy,
electron affinity and lattice energy are important in determining the formation of an ionic
compound.
Favorable condition for ionic bond formation
 Low ionization energy of the metals
 High electro-affinity of the nonmetals
 High lattice energy
 High electro-negativity difference between a metal and a nonmetal atom

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6.2.2 Covalent Bond- is the chemical bond formed between two atoms due to the sharing of
electron pair(s). It is formed between two atoms that contain the same or small difference in
electronegativity. Bonding between two atoms of the same element is completely covalent. In
covalent bond, single, double, triple and quadruple bonds are formed. There are different types of
covalent bonds like polar and non-polar and coordinate covalent bonds.
A polar-covalent bond is a covalent bond in which the bonded atoms have an unequal attraction
for the shared electrons. Example: hydrogen-chlorine bond (H δ+-Clδ⁻). Polar covalent bonding
occurs because one atom has a stronger affinity for electrons than the other. When electrons are
shared but shared unequally.
Non-polar covalent bond is a covalent bond in which the bonding electrons are shared equally
by the bonded atoms, resulting in a balanced distribution of electrical charge. Example;
hydrogen-hydrogen bond (H: H), Cl2. The electrons are shared equally.

Coordinate Covalent bond - A coordinate covalent bond (also called a dative bond) is formed
when one atom donates both of the electrons to form a single covalent bond. These electrons
originate from the donor atom as an unshared pair. Both the ammonium ion and hydronium ion
contain one coordinate covalent bond each.

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6.2.3 Metallic Bond- It is the attraction between metal atoms in a metallic crystal. Metallic Bond
is the attraction between motion of ions and the surrounding sea of electrons. It is formed
between electropositive metal atoms of same or different elements. The valence electrons of pure
metals are not strongly associated with particular atoms. This is a function of their low ionization
energy. Electrons in metals are said to be delocalized (not found in one specific region, such as
between two particular atoms). Since they are not confined to a specific area, electrons act like a
flowing “sea”, moving about the positively charged cores of the metal atoms. Delocalization can
be used to explain conductivity, malleability, and ductility. In general, the greater the number of
electrons per atom that participate in metallic bond the stronger the metallic bond. E.g. the metal
atoms Na, Cu, Ag, and Fe etc. are bound to each other in their crystals by metallic bond.
How metallic bond is different from ionic and covalent bonds?
Is metallic bonding responsible to form compounds?
Comparison of Ionic versus Covalent Compounds
Ionic bonding Covalent bonding
 Formed between high electropositive  Formed between two electronegative
metal and high electronegative nonmetals
nonmetals  They are gases, liquids, or solids with low
 They are solids with high melting melting points (typically _300°C)
point (typically _400°C).  Many are insoluble in polar solvents such
 Many are soluble in polar solvents as water
such as water.  Most are soluble in nonpolar solvents,
 Most are insoluble in nonpolar such as hexane, and CCl4.
solvents( C6H14, CCl4)  Molten compounds don‘t conduct
 Molten /aqueous compounds conduct electricity because they don‘t contain
electricity well because they contain mobile charged particles (ions).
mobile charged particles (ions).  They are often formed between two
 They are often formed between two elements with similar electro negativities
elements with quite different EN, (EN), usually nonmetals
usually a metal and nonmetals

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6.3 Lewis Definition of Covalent Bonding
An American chemist named Gilbert N. Lewis developed the Lewis bonding theory in which
electrons are represented as dots. The molecules represented are called Lewis structures or Lewis
electron-dot formulas. Today we use Lewis structures to determine how atoms are arranged in a
molecule and to predict the 3D shape of molecules. Nonmetal atoms form bonds to achieve a
Noble Gas electron configuration. However, instead of taking electrons away from one another
to form ions, they simply share the electrons in a covalent bond. Lewis defined a covalent bond
as an interaction of two atoms which are held together by a pair of electrons located between the
two atoms. The two electrons are shared by the two atoms. The following generalizations are
helpful in constructing Lewis structures:
1. Count the total number of valence electrons present in the compound by adding the total
valence electrons of each atom.
2. Determine the number of pairs (single bonds) by dividing the total valence electrons by two.
3. Predict the central atom based on the electronegative. The least electronegative atom in a
molecule is often located in the central position and the more electronegative atoms occupy the
outer (terminal) positions.
4. Connect all atoms by drawing single bonds between all atoms, and then distribute the
remaining valence electrons as lone pairs around outer atoms and around the central atom so
each has an octet.
5. If there are not enough electrons for each atom to have an octet, make double or triple bonds
between central atom and surrounding atoms. The great majority of inorganic compounds can be
described by Lewis structures where each atom achieves a closed shell electronic configuration.
Example: Draw the Lewis structured of HNO3, CF4, CH2O, ClO4-, SO3, NO2-, H2O and BF3.
Resonance Structures
We have assumed up to this point that there is one correct Lewis structure. Now we turn our
attention to Resonance structures: the structure the same relative placement of atoms but
different locations of bonding and non-bonding electron pairs. Systems which have more than
one Lewis structure are Resonance Structures. Resonance is delocalization of electrons through
double bond. NO3- is a classic example of resonance:

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Example: Write two equivalent Lewis structures for the ozone, O 3. Describe its resonance
hybrid structure.
Exceptions to the Octet Rule
1. Electron-Deficient Molecules: gaseous molecules containing either Be or B as the central
atom; have fewer than 8 electrons around the Be or B (4e around Be and 6e- around B) (BF3).
2. Odd-Electron Molecules: have an odd number of valence electrons; examples include free
radicals, which contain a lone (unpaired) electron and are paramagnetic (use formal charges to
locate the lone electron) (NO2). Example: CH3, OH, H, NO2 etc.
3. Expanded Valence Shells: for molecules that have more than 8 electrons around the central
atom; use empty outer d orbitals; occurs only with a central atom from Period 3 or higher (SF 6,
PCl5). Eg: PCl5, SF6, H2SO4, H3PO4

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6.4 Covalent Bond Parameters
A covalent bond between two specific atoms has certain properties that are approximately the
same in all the molecules in which that bond occurs. For example, C-H bond has about same
energy a length in all organic molecules, and O-H bonds are similar, no matter in which
compound they occur. These characteristic features are called bond parameters. Each covalent
bond is characterized by the following parameters which are called covalent bond parameters.
(1) Bond order
Bond order is the number of bonds present between two atoms in a molecule or ion. Generally,
bond order has an integral value. For example,
Bond order = 1
Bond order is 1 (one) when there is only one covalent bond (sigma bond) between the two
bonded atoms. H2, Cl2, NH3 are some such examples. These are called single bonds.

In NH3 molecule, there are three single N–H bonds.

Bond order = 2
Bond order is 2 (two) when there are two covalent bonds between the two bonded atoms. Of the
two, one is a sigma bond and the other is a pi bond. These are called double bonds. Examples are
as follows.

Bond Order = 3
Bond order is 3 (three) when there are three bonds between the two bonded atoms. Out of these,
one is a sigma bond and two are pi bonds. These are called triple bonds. Examples are given
below.

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(2) Bond Length
Bond length is the distance between the nuclei of the two bonded atoms. It is expressed in
picometer (pm). Bond lengths are determined experimentally using x-ray diffraction or the
analysis of molecular spectra. Bond length depends upon the sizes of the bonded atoms and the
bond order of the bond linking them.
Bonds between heavy atoms tend to be longer than those between light atoms because heavy
atoms have more electrons and hence greater atomic radii. The greater the bond order, the
smaller is the bond length. Multiple bonds are shorter than single bonds between the same pair of
elements because the additional bonding electrons bind the atoms together more closely. For
bonds between the same pairs of atoms, the stronger the bond the shorter it is.

EXERCISE: Consider the molecules N2H4, N2, and N2F2. Which molecule has the shortest
nitrogen–nitrogen bond? Which has the longest nitrogen–nitrogen bond?
(3) Bond Angle
It is the angle between the two bonds in a molecule. Since covalent bonds are formed through
overlapping of orbitals, it may also be defined as the angle between the two orbitals that contain
bonding electrons and overlap with atomic orbitals of other atoms. Bond angle between two
bonds or bonding orbitals is shown below

The bond angle between two O–H bonds in H 2O molecule is 104.5°, between N–H bonds in NH 3
molecule is 107.3° and between C–H bonds in CH4 is 109°28’.

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(4) Bond Enthalpy ΔaH
The strength of covalent bond is measured by bond enthalpy ∆H a; it is the amount of energy
required for breaking one mole of bonds of a particular type in gaseous molecules. It is also
called bond dissociation enthalpy, and is applicable to simple molecules, containing only one
bond of the particular type.
For example, the bond enthalpy of Cl–Cl bond in Cl 2 is 243 kJ mol–1, of O=O in O2 is 498 kJ
mol–1 and of N≡N bond in N 2 is 946 kJ mol–1. Multiple bonds are stronger than single bonds,
bond enthalpy decrease as number of bond decrease. For example, N2>O2>Cl2
A difficulty arises in using this definition in case of molecules that contain more than one bond
of the same type. H2O molecule has two O–H bonds and the two bonds require different amounts
of energies to break.

Likewise, there are three N–H bonds in NH3 and four C–H bonds in CH4. Each one of these
bonds requires a different amount of energy to break. In such cases, average bond enthalpy is
considered. It is defined as the average energy per bond required to dissociate one mole of bonds
in gaseous atoms.

For example in case of water molecule

502+ 427
Average bond enthalpy of O–H bond ¿ = 464.5 kJ mol–1
2
Some bond enthalpy values are given below:

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Another factor which affects bond strength is existence of lone pair. The lone pairs on
neighboring atoms repel one another, so there is stronger force pushing the atoms apart when
number of lone pairs increase. For example the number of lone pair in nitrogen, oxygen and
fluorine increase in order: N2<O2<F2, so, bond enthalpy decrease in the order of N2>O2>F2.
Charge distributions in compounds
The properties of molecules, like the properties of atoms, are essentially the properties of their
electron distribution.
Ionic versus covalent bonding
No actual bond is purely ionic or covalent. We have noted that whether two elements form ionic
or covalent compound depends on the difference in their electronegativities. The bond between
atoms that differ in electronegativity by less than about 1 can be referred as covalent. When
electronegativity difference more than 2 it can be referred as ionic bond.
Polarizability and polarizing power
The origin of covalent character of an ionic bond lies in the distortion of electron cloud under the
influence of an electric charge. This property of an electron cloud to get distorted is called its
polarizability and the process of distortion of electron cloud is called polarization. The power
of an electric charge to distort an electron cloud is called its polarizing power. In an ionic
compound cations and anions are formed as a result of loss and gain of electrons, respectively.
Each ion tries to polarize the electron cloud of the other.
Atoms and ions that readily undergo large distortions are said to be highly polarizable. Ions that
can cause large distortions are said to have a high polarizing power.
Generally, cations have greater polarizing power due to their small size and hence high charge
density. Anions are more easily polarized. Due to their large size, the electrons in anions are
more loosely bound to the nucleus than in cations. Cation attracts the electron cloud of the anion

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and this result in its polarization and the electron cloud spreads out towards cation in between the
two ions. Thus the electron lost by cation does not fully belong to the anion but partially comes
back towards cation and is shared by it. This results in some covalent character in the ionic bond.
The more the polarization, the more is the covalent character.
Dipole moments
Charge separation in a covalent bond results the formation of an electrical dipole (two equal but
opposite charges with a small distance between them). Each electrical dipole is characterized by
its dipole moment which is defined as
Dipole Moment (μ) = Magnitude of charge (Q) × Distance of Separation (r)
An electric dipole is positive charge next to unequal but opposite negative charge. The
magnitude of electric dipole is reported as electric dipole moment µ (the Greek letter mu) in
units called debye (D).
1 D = 3.336 × 10-30 C m
The dipole moment depends upon the difference in electronegativities of the two bonded atoms.
It can be seen from the data given below

A polar bond is covalent bond between atoms that have partial electric charges. In polar bond
he bonding electrons spend more time near one atom than the other. For example, in the case of

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the HCl molecule, the bonding electrons spend more time near the chlorine atom than the
hydrogen atom.

Polar molecule is a molecule with non zero electric dipole moment. Examples: cis-C 2H2Cl2, N2O,
NH3, CH3Cl.
Non polar molecule is a molecule which has zero electric dipole moment. Examples: trans-
C2H2Cl2, CO2, BF3, CH4, PCl5, SF6
6.5 Assessing charge distribution
Formal charge is a simple way of assigning the ownership of electrons to the atoms in
molecule. The formal charge of an atom in a Lewis formula is the hypothetical charge you obtain
by assuming that bonding electrons are equally shared between bonded atoms and that the
electrons of each lone pair belong completely to one atom.
An atom’s formal charge is the electrical charge difference between the valence electrons in an
isolated atom and the number of electrons assigned to that atom in a Lewis structure. It helps to
check whether the Lewis structure is stable or not. The smallest formal charge is the more stable
in Lewis structure regardless numerical sign. A more negative formal charge should reside on an
atom with a larger EN value.

Example Calculate the formal charges on carbonate ion

Solution:
The C atom:
The C atom has four valence electrons and there are no nonbonding electrons on the atom in the
Lewis structure.
Formal charge = 4- ½(8)-0 = 0
The O atom in C=O:

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The O atom has six valence electrons and there are four nonbonding electrons on the atom.
Formal charge =6- ½(4)-4 = 0
The O atom in C-O: This atom has six nonbonding electrons and the breaking of the single bond
transfers another electron to it.
Formal charge = 6- ½(2)-6 = -1

Thus, we can write as

You can also use formal charges to help you choose the most likely skeleton structure from
several possibilities. The Lewis structure of covalent molecules and molecular ions in which
formal charges of the individual atoms are closest to zero are likely to have the lowest energy.
Example
Draw the most likely Lewis structure for formaladehyde (CH2O).
Solution
There are two possible skeletal structures. First we draw the Lewis structures for each of these
possibilities

In (a) Because C has four valence electrons, the formal charge on the atom is 4 -5 = -1, and
formal charge on O atom 6-5 = 1.
In (b) the C atom has formal charge is 4 - 4 = 0, The O atom has again 6 - 6 = 0 formal charge.
Thus, even though both structures satisfy the octet rule, (b) is the more likely structure because it
carries no formal charges.
Example: NCO- has three possible resonance forms.

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Forms B and C have negative formal charges on N and O. These forms are more important than
Form A. Form C has a negative charge on O which is more electronegative than N. Therefore,
Form C contributes the most to the resonance hybrid and stable.

6.6 Structure of Molecules

Molecular geometry is the three-dimensional arrangement of atoms in a molecule. A molecule’s
geometry affects its physical and chemical properties, such as melting point, boiling point,
density, and the types of reactions it undergoes. In general, bond lengths and bond angles must
be determined by experiment. The shape of simple covalent molecules can be predicted by using
different bonding theories. However, there is a simple procedure that enables us to predict with
considerable success the overall geometry of a molecule or ion if we know the number of
electrons surrounding a central atom in its Lewis structure. There is a simple model that allows
you to predict shapes from Lewis structure is valence-shell electron-pair model (VSEPR). The
basis of this approach is the assumption that electron pairs in the valence shell of an atom repel
one another. This valence-shell electron- pair model usually predicts the correct general shape of
a molecule. It does not explain chemical bonding, however.
6.6.1 Valence shell electron Pair repulsion (VSEPR) Model
This model provides a method for predicting the shape of molecules, based on the electron pair
electrostatic repulsion. It was described by Sidgwick and Powell in 1940 and further developed
by Gillespie and Nyholm in 1957. The VSEPR method predicts shapes that compare favorably
with those determined experimentally. However, this approach at best provides approximate
shapes for molecules, not a complete picture of bonding. Electrons repel each other because they
are negatively charged. The quantum mechanical rules force some of them to be fairly close to
each other in bonding pairs or lone pairs, but each pair repels all other pairs.
This theory focuses on the electron pairs present in the valence shell of the central atom of the
molecule and can be stated in terms of two postulates:

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POSTULATE 1
The electron pairs (both bonding and non-bonding) around the central atom in a molecule
arrange themselves in space in such a way that they minimize their mutual repulsion. In other
words, the chemical bonds in the molecule will be energetically most stable when they are as far
apart from each other as possible. Different molecules would have different shapes depending on
the number of valence shell electrons involved.
POSTULATE 2
The repulsion of a lone pair of electrons for another lone pair is greater than that between a bond
pair and a lone pair which in turn is greater than between two bond pairs. The order of repulsive
force between different possibilities is as under.
lone pair - lone pair > lone pair - bond pair > bond pair - bond pair
Steps to Apply the VSEPR Model
➥ 1 Draw the Lewis structure for the molecule.
➥ 2 Count the electron pairs and arrange them in the way that minimizes repulsion (that is, put
the pairs as far apart as possible).
➥ 3 Determine the positions of the atoms from the way the electron pairs are shared.
➥ 4 Determine the name of the molecular structure from the positions of the atoms.
A molecule can be described by the generic formula AX mEn, where A is the central atom, X
stands for any atom or group of atoms surrounding the central atom, and E represents a lone pair
of electrons. The steric number (SN= m + n) is the number of positions occupied by atoms or
lone pairs around a central atom.
VESPR predicts the following geometries depending on the lone pairs and bond pairs as shown
below.

Table 6.1. Arrangements of Electron pairs about a central atom (A) in a molecule and geometry
of some simple molecules and ions in which the central atom has no lone pairs

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Table 6.2: Geometry of simple molecules and ions in which the central atom
has one or more lone pairs of electrons

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The VSEPR Model and Multiple Bonds

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VSEPR model Treats double and triple bonds as single bonds. To see how these molecules are
handled by this model, let’s consider the NO 3- ion, which requires three resonance structures to
describe its electronic structure:

The NO3- ion is known to be planar with 120-degree bond angles:

This planar structure is the one expected for three pairs of electrons around a central atom, which
means that a double bond should be counted as one effective pair in using the VSEPR model.
This makes sense because the two pairs of electrons involved in the double bond are not
independent pairs. Both the electron pairs must be in the space between the nuclei of the two
atoms to form the double bond. In other words, the double bond acts as one center of electron
density to repel the other pairs of electrons.
Example: Predict the molecular structure of the sulfur dioxide molecule. Is this molecule
expected to have a dipole moment?
Solution
First, we must determine the Lewis structure for the SO 2 molecule, which has 18 valence
electrons. The expected resonance structures are

To determine the molecular structure, we must count the electron pairs around the sulfur atom. In
each resonance structure the sulfur has one lone pair, one pair in a single bond, and one double

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bond. Counting the double bond as one pair yields three effective pairs around the sulfur. A
trigonal planar arrangement is required, which yields a V-shaped molecule:

Thus the structure of the SO2 molecule is expected to be V-shaped, with a 120-degree bond
angle.
Limitations
1. This approach is time-consuming, because it requires handling all valence electrons.
2. It is easy to make simple arithmetic mistakes when you work with large numbers.
3. The number of electrons around the central atom in a molecule can often be ≠ 8 (e.g. 6, 10,
12), that can be confusing and make you feel unsure.
4. Accurate Lewis structures can be difficult to draw for many compounds. This can complicate
making the decisions about the shape.
6.6.2 Valence Bond theory and Hybridization
The valence bond theory was proposed by Heitler and London to explain the formation of
covalent bond quantitatively using quantum mechanics. Later on, in the 1930s, Linus Pauling
improved this theory by introducing the concept of hybridization. According to valence bond
theory, covalent bonds are formed between the two atoms by the overlap of half-filled valence
atomic orbitals of each atom containing one unpaired electron.
Hybridization- is the intermixing of two or more pure atomic orbitals of an atom with almost
same energy to give same number of identical and degenerate new type of orbitals. The new
orbitals formed are also known as hybrid orbitals.
Two types of covalent bonds are formed based on the pattern of overlapping orbitals. These are:
(i) σ-bond: The covalent bond formed due to overlapping of atomic orbital along the inter
nucleus axis is called σ-bond. It is a stronger bond and cylindrically symmetrical. Depending on

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the types of orbitals overlapping, the σ-bond is divided into following types:

(ii) π-bond: The covalent bond formed by sidewise overlapping of atomic orbitals is called π-
bond. In this bond, the electron density is present above and below the internuclear axis. It is
relatively a weaker bond since the electrons are not strongly attracted by the nuclei of bonding
atoms.

Types of Hybridization
During hybridization, the atomic orbitals with different characteristics are mixed with each other.
Hence there is no meaning of hybridization between same types of orbitals i.e., mixing of two’s’
orbitals or two 'p' orbitals is not called hybridization. However, orbital of’s’ type can mix with

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the orbitals of 'p' type or of’d’ type. Based on the type and number of orbitals, the hybridization
can be subdivided into following types.
Sp Hybridization- Intermixing of one 's' and one 'p' orbitals of almost equal energy to give two
identical and degenerate hybrid orbitals is called 'sp' hybridization. These sp-hybrid orbitals are
arranged linearly at 180o of angle. They possess 50%’s’ and 50% 'p' character.

E.g., BeF2; Be is the central atom in this compound and normally Be has 4 atomic number, then
its electronic configuration is 1s2, 2s2. Thus, Be contains 2 es at the ground state before bonding
in 2s orbital. But at the exited state (during reaction) one electron promotes to the empty 2p
orbital in order to share these two electrons with two chlorines.

sp2 Hybridization-Intermixing of one 's' and two 'p' orbitals of almost equal energy to give three
identical and degenerate hybrid orbitals is known as sp 2 hybridization. The three sp2 hybrid
orbitals are oriented in trigonal planar symmetry at angles of 120 o to each other. The sp2 hybrid
orbitals have 33.3%’s’ character and 66.6% 'p' character.

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Example: BF3,

Sp3 Hybridization-In sp3 hybridization, one’s’ and three 'p' orbitals of almost equal energy
intermix to give four identical and degenerate hybrid orbitals. These four sp 3 hybrid orbitals are
oriented in tetrahedral symmetry with 109 o28'angle with each other. The sp3 hybrid orbitals have
25%’s’ character and 75% 'p' character.

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Example: CH4

sp3d hybridization: The bonding in PC15 may be described using hybrids of the 3s, 3p and 3d
atomic orbitals for P-see below.

sp3d2 hybridization: In a similar way the structure of SF 6 can be described by mixing the 3s,
three 3p and two 3d orbitals, that is sp3d 2 hybridization.

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Pi - Bonds in hybridization: Pi – Bonds never included in hybridization but apart from this all
the orbitals in the outer shell are hybridized. Consider the structure of the carbon dioxide
molecule. Since C is typically four-valent and O is typically two-valent, the bonding can be
simply represented
O=C=O
Triatomic molecules must be either linear or angular. In CO 2, the C atom must be excited to
provide four unpaired electrons t" form the four bonds required.

There are two  bonds and two  bonds in the molecule. Pi orbitals are ignored in determining
the shape of the molecule. The remaining s and p orbitals are used to form the  bonds. Then sp
hybridization is formed.
In the sulphur trioxide molecule SO3 valency requirements suggest the structure

The central S atom must be excited to provide six unpaired electrons to form six bonds.

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The three  bonds are ignored in determining the shape of the molecule. The three  orbitals are
directed towards the corners of an equilateral triangle, and the SO 3 molecule is a completely
regular plane triangle. The  bonds shorten the bond lengths, but do not affect the shape. This
approach explains the o bonding and shape of the molecule.
Hybridization provides a useful and convenient method of predicting the shapes of molecules. It
must be noted that though it is valuable in predicting and describing the shape, it does not
explain the reason for the shape.
Based on the type of hybridization we can predict the shape of simple molecules.

Limitation of VBT
 The theory is unable to adequately explain electronic and magnetic properties of
complexes.
 VBT is widely used inorganic and main group element chemistry.
 In transition metal chemistry VBT is superseded by the Crystal Field Theory (CFT).
6.6.3 Molecular Orbital Theory
The Molecular Orbital Theory, initially developed by Robert S. Mullikan, incorporates the wave
like characteristics of electrons in describing bonding behavior. In molecular orbital theory, the
bonding between atoms is described as a combination of their atomic orbitals. While the valence
bond theory and Lewis structures sufficiently explain simple models; the Molecular Orbital
theory provides answers to more complex questions. In the molecular orbital theory, the
electrons are delocalized since they are not assigned to a particular atom or bond. Instead, the
electrons are smeared out across the molecule.
The molecular orbital theory allows one to predict the distribution of electrons in a molecule
which in turn can help to predict molecular properties such as shape, magnetism, and Bond
Order.
Bonding and Antibonding Molecular Orbitals (MOs)

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Bonding Molecular Orbital – MOs with electron density concentrated in the regions between
atoms. Bonding MOs have lower energy and greater stability than the atomic orbitals from which
it was formed.
Antibonding Molecular Orbital – MOs with electron density concentrated in regions other than
between the atoms. Anitbonding MOs have higher energy and lower stability than the atomic
orbitals from which it was formed.

Linear Combination of Atomic Orbitals (LCAO)

According to wave mechanics, the atomic orbitals can be expressed by wave functions (ψ’s)
which represent the amplitude of the electron waves. These are obtained from the solution of
Schrödinger wave equation. However, since it cannot be solved for any system containing more
than one electron, molecular orbitals which are one electron wave functions for molecules are
difficult to obtain directly from the solution of Schrödinger wave equation. To overcome this
problem, an approximate method known as linear combination of atomic orbitals (LCAO) has
been adopted.

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Let us apply this method to the homonuclear diatomic hydrogen molecule. Consider the
hydrogen molecule consisting of two atoms A and B. Each hydrogen atom in the ground state
has one electron in 1s orbital. The atomic orbitals of these atoms may be represented by the wave
functions ψA and ψB. Mathematically, the formation of molecular orbitals may be described by
the linear combination of atomic orbitals that can take place by addition and by subtraction of
wave functions of individual atomic orbitals as shown below:
ψMO = ψA + ψB
Therefore, the two molecular orbitals σ and σ* are formed as:
σ = ψA + ψB
σ* = ψA – ψB
The molecular orbital σ formed by the addition of atomic orbitals is called the bonding molecular
orbital while the molecular orbital σ* formed by the subtraction of atomic orbital is called
antibonding molecular orbital as depicted in the figure below.

Figure 6.1. Formation of bonding (σ) and antibonding (σ*) molecular orbitals by the linear
combination of atomic orbitals ψA and ψB centered on two atoms A and B respectively.
Three conditions are essential for overlap bonding MO.
1. The symmetry of the orbitals must be such that regions with the same sign of + overlap.
2. The energies of the atomic orbitals must be similar. When the energies differ by a large
amount, the change in energy on formation of the molecular orbitals is small and the net
reduction in energy of the electrons is too small for significant bonding.

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3. The distance between the atoms must be short enough to provide good overlap of the orbitals,
but not so short that repulsive forces of other electrons or the nuclei interfere. When these
conditions are met, the overall energy of the electrons in the occupied molecular orbitals will be
lower in energy than the overall energy of the electrons in the original atomic orbitals, and the
resulting molecule has a lower total energy than the separated atoms.
Types of Bonds in Molecular orbital
1) Sigma Bonds
Molecular orbitals that are symmetrical about the axis of the bond are called sigma molecular
orbitals, often abbreviated by the Greek letter σ. There are two types of sigma orbitals formed,
antibonding sigma orbitals (abbreviated σ*), and bonding sigma orbitals (abbreviated σ). In
sigma bonding orbitals, the in phase atomic orbitals overlap end to end causing an increase in
electron density along the bond axis. In sigma antibonding orbitals (σ*), the out of phase overlap
of orbitals interfere destructively which results in a low electron density between the nuclei. In
the s-orbital, the sigma boding orbital can be represented as σs and the antibonding will be
written as σ*s. Sigma bonding orbitals and antibonding orbitals can also be formed between p
orbitals. Sigma molecular orbitals formed by p orbitals are often differentiated from other types
of sigma orbitals by adding the subscript p below it as σ*2p.
2) Pi Bonds
The pi bonding bonds as a side to side overlap, which then causes there to be no electron density
along the axis, but there is density above and below the axis. In the pi bonding, there are an
overlap of atomic orbitals in between py-py and pz-pz orbitals to form π2py, π2pz bonding and
π*2py, π*2pz antibonding molecular orbitals. The 2p z-2pz overlap is similar to the 2p y-2py overlap
because it is just the orbitals of the 2pz rotated 90 degrees about the axis.
Bond Order: Bond Order indicates the strength of the bond. The higher the bond order the
stronger the bond. Bond order can be calculated as follows:
number of electrons∈bonding−number of electrons∈antibinding
Bond order=
2
Example: H2, BO =½ (2 –0) = 1 H–H single bond will be formed.
Bond order determines the stability of the molecule. If the bond order is zero, then no bonds
are produced and the molecule is not stable (for example He 2). If the bond order is 1, then it is a
single covalent bond. The higher the bond order, the more stable the molecule is. An advantage

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of molecular orbital theory when it comes to bond order is that it can more accurately describe
partial bonds (for example in H2+, where the Bond Order=1/2), than Lewis Structures.
Rules of MOT: MO Theory has five basic rules:
1. The number of molecular orbitals = the number of atomic orbitals combined.
2. Of the two MO's, one is a bonding orbital (lower energy) and one is an antibonding orbital
(higher energy).
3. Electrons enter the lowest orbital available.
4. The maximum # of electrons in an orbital is 2 (Pauli Exclusion Principle).
5. Electrons spread out before pairing up (Hund's Rule).
Drawing Molecular Orbital Diagrams
 Determine the number of electrons in the molecule.
 Fill the molecular orbitals from bottom to top until all the electrons are added. Describe
the electrons with arrows. Put two arrows in each molecular orbital, with the first arrow
pointing up and the second pointing down.
 Orbitals of equal energy are half filled with parallel spin before they begin to pair up.
Molecular orbital energy level diagram for homonuclear and heteronuclear diatomic
molecules
Homonuclear diatomic molecules are molecules made up of the same or identical elements. E.g.,
H2, N2, O2, F2, Cl2, Br2, and [Link] molecular electronic configuration of molecules is determined
using spectroscopic data. For period 2 diatomic molecules up to and including N 2 the electronic
configuration is: σ2s, σ *2s, π2p, σ 2p, π*2p, σ *2p. For period 2 diatomic molecules O 2, F2, and
Ne2: π2p and σ 2p change order and the electronic configuration is: σ 2s, σ *2s, σ 2p, π2p, π*2p,
σ *2p as shown in the table below. Hetronuclear diatomic molecules are molecules formed from
two different elements. In heteronuclear diatomic molecules, mixing of atomic orbitals only
occurs when the electronegativity values are similar.

Examples

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32
In heteronuclear diatomic molecules, the more electronegative element makes a greater
contribution to the bonding MO‘s, and the less electronegative one makes a greater contribution
to the antibonding MO‘s. The bonding MO‘s have energies similar to those of the contributing
AO‘s of the more EN atom. The antibonding MOs have energies close to those of the
contributing AO‘s of the less electronegative atom.

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Exercise: Draw the MO energy level diagram, predict the magnetism, calculate the band order
and determine the stability of the following molecules. NO +, NO-, O2-2, O2 +2, CO, HF, Be2, C2,
H2+ and CO+.

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