Ch – 4

Chemical Bonding and Molecular Structure

➢ Introduction:-
• Chemical Bond is the attractive force that binds different atoms or ions
together to give rise a chemical compound. The stronger the bonding
between the constituents, the more stable would be the resulting
compound.
• When the forces are attractive in nature, energy decreases and stability
increases. When the forces are repulsive in nature, energy increases
and stability decreases.

➢ Kossel-Lewis Approach to Chemical Bonding:-

• In the periodic table, the highly electronegative halogens and the highly
electro-positive alkali metals are separated by noble gases.
• Formation of an anion and cation by the halogens and alkali metals are
formed by gain of electron and loss of electron respectively.
• Both the negative and positive ions acquire the noble gas configuration.
• The negative and positive ions are stabilized by electrostatic attraction
Example,

• The bond formed, as a result of the electrostatic attraction between the

positive and negative ions was termed as the electrovalent bond. The
electrovalence is thus equal to the number of unit charge on the ion.
• Atoms can combine either by transfer of valence electrons from one atom to
another (gaining or losing) or by sharing of valence electrons in order to
have an octet in their valence shells. This is known as octet rule.
• The dots represent valence electrons. Such structures are referred to as
Lewis dot structures.

➢ Covalent Bond—Lewis-Langmuir Concept:-

• When the bond is formed between two or more atoms by mutual
contribution and sharing of electrons, it is known as covalent bond.
• If the combining atoms are same the covalent molecule is known
as homoatomic. If they are different, they are known as
heteroatomic molecule.
➢ Formal Charge:-
• The formal charge of an atom in a polyatomic molecule or ion may be
defined as the difference between the number of valence electrons of that
atom in an isolated or free state and the number of electrons assigned to
that atom in the Lewis structure.
 • Limitations of the Octet Rule:-
(i) The incomplete octet of the central atoms: In some covalent
compounds central atom has less than eight electrons, i.e., it has an
incomplete octet. For example,

(ii) Odd-electron molecules: There are certain molecules which have odd
number of electrons the octet rule is not applied for all the atoms.

(iii) The expanded Octet: In many compounds there are more than eight
valence electrons around the central atom. It is termed as expanded octet.

➢ Resonance Structures:-
There are many molecules whose behaviour cannot be explained by a single-
Lewis structure. For example, Lewis structure of Ozone represented as follows:
 • According to the concept of resonance, whenever a single Lewis structure
cannot explain all the properties of the molecule, the molecule is then
supposed to have many structures with similar energy. Positions of
nuclei, bonding and nonbonding pairs of electrons are taken as the
canonical structure of the hybrid which describes the molecule
accurately.
• For O3, the two structures shown above are canonical structures and the III
structure represents the structure of O3 more accurately. This is also
called resonance hybrid.

➢ Polarity of Bonds:-
The existence of a hundred percent ionic or covalent bond represents an
ideal situation. In reality no bond or a compound is either completely
covalent or ionic. Hence, Dipole Moment is used to find out partial ionic
character present in covalent bond.
• Dipole moment is defined as the product of magnitude of the positive or negative
charge and the distance between the charges.
Dipole moment (µ) = charge (Q) × distance of separation (r)
Dipole moment is usually expressed in Debye units (D).
1 D = 3.33564 × 10-30 C m; where C is coulomb and m is meter.
• In case of NH3 and NF3 molecule. Both the molecules have pyramidal shape with
a lone pair of electrons on nitrogen atom and fluorine is more electronegative than
nitrogen, still dipole moment of NH3 is greater than NF3.
• This because in case of NH3 the orbital dipole due to lone pair is in the same
direction as the resultant dipole moment of the N – H bonds, whereas in NF3 the
orbital dipole is in the direction opposite to the resultant dipole moment of the
three N–F bonds. The orbital dipole because of lone pair decreases the effect of
the resultant N – F bond moments, which results in the low dipole moment of NF3
as represented below :
 • Similarly, ionic bonds also have partial covalent character. The partial
covalent character of ionic bonds was discussed through Fajan’s
rules.

➢ Valence Shell Electron Pair Repulsion (VSEPR) Theory:-

Sidgwick and Powell proposed a simple theory based on the repulsive
interactions of the electron pairs in the valence shell of the atoms. The main
postulates of VSEPR theory are as follows:-
(i) The exact shape of molecule depends upon the number of electron pairs
(bonded or non-bonded) around the central atoms.
(ii) The electron pairs have a tendency to repel each other since they exist
around the central atom and the electron clouds are negatively charged.
(iii) Electron pairs try to take such position which can minimize repulsion
between them.
(iv) The valence shell is taken as a sphere with the electron pairs placed at
maximum distance.
(v) A multiple bond is treated as if it is a single electron pair and the electron
pairs which constitute the bond as single pairs.
The repulsive interaction of electron pairs decreases in the order:
l.p. – l.p. > l.p. – b.p. > b.p. – b.p.

➢ Valence Bond Theory:-

Valence bond theory was introduced by Heitler and London and
developed by Pauling and others. It is based on the concept of atomic
orbitals and the electronic configuration of the atoms.
• Let two hydrogen atoms A and B having their nuclei NA , NB and electrons
present in them are eA and eB .As these two atoms come closer new
attractive and repulsive forces begin to operate.
(i) The nucleus of one atom is attracted towards its own electron and the
electron of the other and vice versa.
(ii) Repulsive forces arise between the electrons of two atoms and nuclei of
two atoms. Attractive forces tend to bring the two atoms closer whereas
repulsive forces tend to push them apart.
• Orbital Overlap Concept
According to orbital overlap concept, covalent bond formed between atoms
results in the overlap of orbitals belonging to the atoms having opposite
spins of electrons. Formation of hydrogen molecule as a result of overlap of
the two atomic orbitals of hydrogen atoms is shown in the figure that
follows:
 Stability of a Molecular orbital depends upon the extent of the overlap of the
atomic orbitals.
• Types of Orbital Overlap:-
Depending upon the type of overlapping, the covalent bonds are of two
types, known as sigma (σ ) and pi (π) bonds.
(i) Sigma (σ bond): Sigma bond is formed by the end to end (head-on)
overlap of bonding orbitals along the internuclear axis. The axial overlap
involving these orbitals is of three types:-
• s-s overlapping: In this case, there is overlap of two half-filled s-orbitals
along the internuclear axis.

• s-p overlapping: This type of overlapping occurs between half-filled s-

orbitals of one atom and half-filled p-orbitals of another atoms.

• p-p overlapping: This type of overlapping takes place between half-filled p-

orbitals of the two approaching atoms.
 (ii) pi (π bond): π bond is formed by the atomic orbitals when they overlap
in such a way that their axes remain parallel to each other and perpendicular
to the internuclear axis. The orbital formed is due to lateral overlapping or
sideways overlapping.

• Strength of Sigma and pi Bonds:-

Strength of a bond depends upon the extent of overlapping. In case of sigma
bond, the axial (head on) overlapping of orbitals takes place to a larger
extent. Hence, it is stronger as compared to the pi bond where the extent of
sideways (lateral) overlapping occurs to a smaller extent.

➢ Hybridisation:-
Hybridisation is the process of intermixing of the orbitals of slightly
different energies so as to redistribute their energies resulting in the
formation of new set of orbitals of equivalent energies and shape.
• Salient Features of Hybridisation
(i) Orbitals with almost equal energy take part in the hybridisation.
(ii) Number of hybrid orbitals produced is equal to the number of atomic
orbitals mixed,
(iii) Geometry of a covalent molecule can be indicated by the type of
hybridisation.
(iv) The hybrid orbitals are more effective in forming stable bonds than the
pure atomic orbitals.
• Conditions necessary for Hybridisation
(i) Orbitals of valence shell take part in the hybridisation.
(ii) Orbitals involved in hybridisation should have almost equal energy.
(iii) Promotion of electron is not necessary condition prior to hybridisation.
(iv) In some cases filled orbitals of valence shell also take part in
hybridisation.
• Types of Hybridisation
(i) sp hybridisation: When one s and one p-orbital hybridise to form two
equivalent orbitals, the orbital is known as sp hybrid orbital, and the type
of hybridisation is called sp hybridisation. Each of the hybrid orbitals
formed has 50% s-character and 50% p-character. This type of
hybridisation is also known as diagonal hybridisation. Eg. BeCl 2

(ii) sp2 hybridisation: In this type, one s and two p-orbitals hybridise to
form three equivalent sp2 hybridised orbitals. All the three hybrid orbitals
formed has 33% s character and 67% p-character and remain in the same
plane making an angle of 120°. Eg. few compounds in which
sp2 hybridisation takes place are BF3, BH3, BCl3 carbon compounds
containing double bond etc.
 (iii) sp3 hybridisation: In this type, one s and three p-orbitals in the valence
shell of an atom get hybridised to form four equivalent hybrid orbitals.
There is 25% s-character and 75% p-character in each sp3 hybrid
orbital. The four sp3 orbitals are directed towards four corners of the
tetrahedron. The angle between sp3 hybrid orbitals is 109.5°. A
compound in which sp3 hybridisation occurs is, (CH4). The structures of
NH2 and H2O molecules can also be explained with sp3 hybridisation.

➢ Formation of Molecular Orbitals:-

The formation of molecular orbitals can be explained by the linear combination
of atomic orbitals(LCAO). Combination takes place either by addition or by
subtraction of wave function as shown below:

The molecular orbital formed by addition of atomic orbitals is called bonding

molecular orbital while molecular orbital formed by subtraction of atomic orbitals
is called antibonding molecular orbital.
 • Conditions for the combination of atomic orbitals
(1) The combining atomic orbitals must have almost equal energy.
(2) The combining atomic orbitals must have same symmetry molecular axis.
(3) The combining atomic orbitals must overlap to the maximum extent.

• Types of Molecular Orbitals

Sigma (σ) Molecular Orbitals: They are symmetrical around the bond-axis.
pi (π) Molecular Orbitals: They are not symmetrical, because of the
presence of positive lobes above and negative lobes below the molecular
plane. The distribution of electrons among various molecular orbitals is
called electronic configuration of the molecule.

• Stability of Molecules

The increasing order of energies of various molecular orbitals for O2

and F2 (≥ 14 electrons) is given below:
σ (1s) < σ∗ (1s) < σ (2s) < σ∗ (2s) < σ (2pz) < [π (2px) = π (2py)]
< π∗ (2px) = π∗ (2py)] < σ∗ (2pz)
Similarly, for Li2, Be2, B2, C2, N2 type molecules (≤ 14 electrons)
σ (1s) < σ∗ (1s) < σ (2s) < σ∗ (2s) < [π (2px) = π (2py)] < σ (2pz)
< π∗ (2px) = π∗ (2py)] < σ∗ (2pz)

• Bond Order
Bond order is defined as half of the difference between the number of
electrons present in bonding and antibonding molecular orbitals.
Bond order (B.O.) = 1/2 [Nb - Na]
The bond order may be a whole number, a fraction or even zero.

• Nature of bond, bond length and magnetic behaviour

Integral bond order value for single double and triple bond will be 1, 2 and 3
respectively. Bond order is inversely proportional to bond-length. Thus,
greater the bond order, smaller will be the bond-length. If all the molecular
orbitals have paired electrons, the substance is diamagnetic. If one or more
molecular orbitals have unpaired electrons, it is paramagnetic e.g. O2
➢ Bonding in Some Homonuclear (Diatomic) Molecules:-
(1) Hydrogen molecule (H2): It is formed by the combination of two hydrogen
atoms. Each hydrogen atom has one electron in 1s orbital, so, the electronic
configuration of hydrogen molecule.

This indicates that two hydrogen atoms are bonded by a single covalent bond.
Bond dissociation energy of hydrogen has been found = 438 kJ/mole.
Bond-Length = 74 pm.No unpaired electron is present therefore, it is diamagnetic.

(2) Helium molecule (He2): Each helium atom contains 2 electrons, thus in
He2 molecule there would be 4 electrons. The electrons will be accommodated
in σ(1s) and σ*(1s) molecular orbitals:
➢ Hydrogen Bonding:-
Hydrogen bond can be defined as the attractive force which binds hydrogen
atom of one molecule with the electronegative atom (F, O or N) of another
molecule. Hydrogen bond is represented by a dotted line (– – –).
• In HF molecule, hydrogen bond exists between hydrogen atom of one

molecule and fluorine atom of another molecule. It can be depicted as

• The magnitude of H-bonding depends on the physical state of the
compound. It is maximum in the solid state and minimum in gaseous state.

• Types of H-Bonds:-
(i) Intermolecular hydrogen bond: It is formed between two different
molecules of the same or different compounds. For Example, in HF
molecules, alcohol or water molecules etc

(ii) Intramolecular hydrogen bond: In this type, hydrogen atom is in

between the two highly electronegative F, N, O atoms present within the
same molecule. For example, in o-nitrophenol, the hydrogen is in between
the two oxygen atoms.