CHEMICAL BONDING AND MOLECULAR STRUCTURE

Lewis Symbols: H2, O2, O3, NF3, CO32-, HNO3, NO2-, CO2

Octet Rule: 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.
Covalent Bond: Bond formed between atoms by the sharing of a pair of electrons between
them.

Formal Charge:

Formal charge (F.C.) on an atom in a Lewis structure = [total number of valence electrons in
the free atom] – [total number of valence electrons in the free atom] – ½ [total number of
bonding (shared) electrons]
Limitations of the Octet Rule:
a) The incomplete octet of the central atom: In some compounds, the number of
electrons surrounding the central atom is less than eight.

Eg: LiCl, BeH2 and BCl3.

b) Odd-electron molecules: In molecules with an odd number of electrons, the octet rule
is not satisfied for all the atoms

Eg: NO, NO2

c) The expanded octet: Elements in and beyond the third period of the periodic table
have, apart from 3s and 3p orbitals, 3d orbitals also available for bonding. In a number
of compounds of these elements there are more than eight valence electrons around the
central atom. This is termed as the expanded octet.

Eg: PCl5, SF6

d) Octet rule is based upon the chemical inertness of noble gases. However, some noble
gases (for example xenon and krypton) also combine with oxygen and fluorine to form
a number of compounds like XeF2, KrF2, XeOF2 etc.
e) This theory does not account for the shape of molecules.
 f) It does not explain the relative stability of the molecules being totally silent about the
energy of a molecule.

Ionic and Electrovalent Bond:

Ionic bond will be formed more easily between elements with comparatively low ionization
enthalpies and elements with comparatively high negative value of electron gain enthalpy.
Most ionic compounds have cations derived from metallic elements and anions from non-
metallic elements. Ionic compounds in the crystalline state consist of orderly three-
dimensional arrangements of cations and anions held together by coulombic interaction
energies.

Lattice Enthalpy: The Lattice Enthalpy of an ionic solid is defined as the energy required to
completely separate one mole of a solid ionic compound into gaseous constituent ions.
Bond Parameters:

a) Bond Length: Bond length is defined as the equilibrium distance between the nuclei
of two bonded atoms in a molecule.
• The covalent radius is half of the distance between two similar atoms joined by
a covalent bond in the same molecule.
• The van der Waals radius is half of the distance between two similar atoms in
separate molecules in a solid.
b) Bond Angle: It is defined as the angle between the orbitals containing bonding
electron pairs around the central atom in a molecule/complex ion.
c) Bond Enthalpy: It is defined as the amount of energy required to break one mole of
bonds of a particular type between two atoms in a gaseous state. The unit of bond
enthalpy is kJ mol–1.
d) Bond Order: In the Lewis description of covalent bond, the Bond Order is given by
the number of bonds between the two atoms in a molecule. Isoelectronic molecules
and ions have identical bond orders.
Resonance Structures:

In both structures we have an O–O single bond and a O=O double bond. The normal O–O
and O=O bond lengths are 148 pm and 121 pm respectively. Experimentally determined
oxygen-oxygen bond lengths in the O3 molecule are same (128 pm). Thus the oxygen-
oxygen bonds in the O3 molecule are intermediate between a double and a single bond.
According to the concept of resonance, whenever a single Lewis structure cannot describe a
molecule accurately, a number of structures with similar energy, positions of nuclei, bonding
and non-bonding pairs of electrons are taken as the canonical structures of the hybrid which
describes the molecule accurately. Thus for O3, the two structures shown above constitute the
canonical structures or resonance structures and their hybrid i.e., the III structure represents
the structure of O3 more accurately. This is also called resonance hybrid. Resonance is
represented by a double headed arrow.
Polarity of Bonds: Contrary to this in case of a heteronuclear molecule like HF, the shared
electron pair between the two atoms gets displaced more towards fluorine since the
electronegativity of fluorine is far greater than that of hydrogen. The resultant covalent bond
is a polar covalent bond.

As a result of polarisation, the molecule possesses the dipole moment which can be defined
as the product of the magnitude of the charge and the distance between the centres of positive
and negative charge.

In case of polyatomic molecules the dipole moment not only depend upon the individual
dipole moments of bonds known as bond dipoles but also on the spatial arrangement of
various bonds in the molecule.

a)

The dipole moment in case of BeF2 is zero. This is because the two equal bond dipoles point
in opposite directions and cancel the effect of each other.
In tetra-atomic molecule, for example in BF3, the dipole moment is zero although the B – F
bonds are oriented at an angle of 120o to one another, the three bond moments give a net sum
of zero as the resultant of any two is equal and opposite to the third.

Both NH3 and NF3 molecules have pyramidal shape with a lone pair of electrons on nitrogen
atom. Although fluorine is more electronegative than nitrogen, the resultant dipole moment
of NH3 is greater than that of NF3. This is 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.

Fajans Rule:

• The smaller the size of the cation and the larger the size of the anion, the greater the
covalent character of an ionic bond.
• The greater the charge on the cation, the greater the covalent character of the ionic
bond.
• For cations of the same size and charge, the one, with electronic configuration of
typical of transition metals, is more polarising than the one with a noble gas
configuration, ns2 np6, typical of alkali and alkaline earth metal cations.
THE VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR) THEORY

The main postulates of VSEPR theory:

• The shape of a molecule depends upon the number of valence shell electron pairs
(bonded or nonbonded) around the central atom.
• Pairs of electrons in the valence shell repel one another since their electron clouds are
negatively charged.
• These pairs of electrons tend to occupy such positions in space that minimise repulsion
and thus maximise distance between them.
• The valence shell is taken as a sphere with the electron pairs localising on the spherical
surface at maximum distance from one another.
• A multiple bond is treated as if it is a single electron pair and the two or three electron
pairs of a multiple bond are treated as a single super pair.
• Where two or more resonance structures can represent a molecule, the VSEPR model
is applicable to any such structure.
• The repulsive interaction of electron pairs decrease in the order: Lone pair (lp) – Lone
pair (lp) > Lone pair (lp) – Bond pair (bp) > Bond pair (bp) – Bond pair (bp)

No. of Electron Pairs Shape Bond Angle

Linear 1800
2
Trigonal Planar 1200
3
Tetrahedral 109.50
4
Trigonal Bipyramidal 1200, 900
5
Octahedral 900
6

Predict the shape of the following molecules using VSEPR Model:

Molecules with Bond pair electrons only: BeCl2, BF3, CH4, PCl5, SF6

Molecules with Bond pair and lone pair electrons: NH3, H2O, SF4, ClF3, BrF5, XeF4

VALENCE BOND THEORY

Let us consider the formation of hydrogen molecule.

Consider two hydrogen atoms A and B approaching each other having nuclei NA and NB and
electrons present in them are represented by eA and eB. When the two atoms are at large
distance from each other, there is no interaction between them. As these two atoms approach
each other, new attractive and repulsive forces begin to operate.
Attractive forces arise between:

(i) nucleus of one atom and its own electron that is NA – eA and NB– eB.
(ii) nucleus of one atom and electron of other atom i.e., NA– eB, NB– eA.

Similarly repulsive forces arise between

(i) electrons of two atoms like eA – eB.

(ii) nuclei of two atoms NA – NB.

Attractive forces tend to bring the two atoms close to each other whereas repulsive forces
tend to push them apart.

Experimentally it has been found that the magnitude of new attractive force is more than the
new repulsive forces. As a result, two atoms approach each other and potential energy
decreases. Ultimately a stage is reached where the net force of attraction balances the force
of repulsion and system acquires minimum energy. Since the energy gets released when the
bond is formed between two hydrogen atoms, the hydrogen molecule is more stable than that
of isolated hydrogen atoms. The energy so released is called as bond enthalpy.
Orbital Overlap Concept:

The partial merging of atomic orbitals is called overlapping of atomic orbitals which results
in the pairing of electrons. The extent of overlap decides the strength of a covalent bond.

When orbitals of two atoms come close to form bond, their overlap may be positive, negative
or zero depending upon the sign (phase) and direction of orientation of amplitude of orbital
wave function in space.

Types of Overlapping and Nature of Covalent Bonds:

The covalent bond may be classified into two types.

Sigma(σ) bond : s-s, s-p, p-p overlapping.

Sigma type of covalent bond is formed by the end to end (head-on) overlap of bonding
orbitals along the internuclear axis. This is called as head on overlap or axial overlap.

pi(π) bond : p-p overlapping.

In the formation of π bond the atomic orbitals overlap in such a way that their axes remain
parallel to each other and perpendicular to the internuclear axis.

Strength of Sigma and pi Bonds:

Basically the strength of a bond depends upon the extent of overlapping. In case of sigma
bond, the overlapping of orbitals takes place to a larger extent. Hence, it is stronger as
compared to the pi bond where the extent of overlapping occurs to a smaller extent.

In the formation of multiple bonds between two atoms of a molecule, pi bond(s) is formed in
addition to a sigma bond.
HYBRIDISATION

Hybridisation is defined as 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 hybridization:

 a) The number of hybrid orbitals is equal to the number of the atomic orbitals that get
hybridised.
b) The hybridised orbitals are always equivalent in energy and shape.
c) The hybrid orbitals are more effective in forming stable bonds than the pure atomic
orbitals.
d) These hybrid orbitals are directed in space in some preferred direction to have
minimum repulsion between electron pairs and thus a stable arrangement. Therefore,
the type of hybridisation indicates the geometry of the molecules.

Important conditions for hybridization:

a) The orbitals present in the valence shell of the atom are hybridised.
b) The orbitals undergoing hybridisation should have almost equal energy.
c) Excitation of electron is not essential condition prior to hybridisation.
d) It is not necessary that only half filled orbitals participate in hybridisation. In some
cases, even filled orbitals of valence shell take part in hybridisation.

• sp hybridisation:
This type of hybridisation involves the mixing of one s and one p orbital resulting in
the formation of two equivalent sp hybrid orbitalsEach sp hybrid orbitals has 50% s-
character and 50% p-character. They possess linear geometry. This type of
hybridisation is also known as diagonal hybridisation.
Eg: BeCl2