CHEMICAL BONDING

IONIC BOND ............................................................................................................................................................................... 2

Lattice energy: ............................................................................................................................................................................ 2
Born Haber Cycle ....................................................................................................................................................................... 2
Born-Lande equation ................................................................................................................................................................. 4
COVALENT BOND ...................................................................................................................................................................... 7
Lewis structures:......................................................................................................................................................................... 7
Formal charge:............................................................................................................................................................................ 7
Valence bond theory ................................................................................................................................................................... 8
Hybridisation .............................................................................................................................................................................. 8
Valence Shell Electron Pair Repulsion (VSEPR) theory ...................................................................................................... 11
Molecular orbital (MO) theory ............................................................................................................................................... 13
Polarisation ............................................................................................................................................................................... 15
Dipole moment .......................................................................................................................................................................... 16
Hydrogen bonding .................................................................................................................................................................... 17
van der Waal’s force ................................................................................................................................................................ 17
METALLIC BOND...................................................................................................................................................................... 18
Electron sea theory ................................................................................................................................................................... 19
Band theory ............................................................................................................................................................................... 19

Electronic configuration of Octet rule Lewis electron dot

atoms formula

VSEPR theory
3D shape of molecule

Electronegativity and Molecular Orbital theory

Bond polarity

Polarity of molecule Bonding description of

Valence bond theory molecule
Intermolecular forces and
bulk properties Chemical reactivity

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 IONIC BOND
➢ The chemical bond formed between two or more atoms as a result of the complete transfer of one or more
electrons from one atom to another is called Ionic or electrovalent bond.

➢ According to Kossel’s theory, in the process of formation of ionic bond the atoms acquire the noble gas
electronic configuration by the gain or loss of electrons. Let us consider the formation of NaCl in terms of
Kossel’s Theory.
Na + Cl → Na+ + Cl-
2, 8 1 2, 8 7 2, 8 2, 8, 8
1e- (Ne configuration) (Ar configuration)
➢ An ionic bond usually occurs between a metal and a non-metal. Higher is the difference in electronegativities of
bonded atoms, easier is the formation of ionic bond.

➢ Total number of electrons lose or gained is called electro valency.

➢ The force of attraction is equal in all direction, so ionic bond is non-directional

➢ Ionic compound does not have molecular formula. It has only empirical formula. e.g. NaCl is the empirical
formula of sodium chloride

➢ Conditions for Forming Ionic Bonds:

Lesser Ionisation energy → Greater tendency to form cation.
Higher electron affinity → Greater tendency to form anion
Higher lattice energy → Greater will be the stability or strength of ionic compound.

Lattice energy:
Lattice energy (U) of a crystal is the energy evolved when one mole of an ionic crystal is formed from gaseous ions.
(cations and anions).
(Or)
Lattice energy is the energy required to break one mole of ionic crystal into its constituent gaseous ions.
The lattice energy, ∆U (0 K), of an ionic compound is the change in internal energy that accompanies the formation
of one mole of the solid from its constituent gas-phase ions at 0 K.
Na+ (g) + Cl- (g) → NaCl (S), U= -782 (or) -786 kJ/mol
As per the connections of laws of thermodynamics lattice energy has a negative sign.
Lattice energy cannot be measured directly, but experimental values are obtained from thermodynamic data using the
Born-Haber cycle.

Born Haber Cycle: Born Haber cycle is based on Hess’s law, according to which the overall energy change in
a process depends only on the initial and final states and not on the path taken. The enthalpy of formation is the
algebraic sum of the terms going around the cycle.
This cycle relates the lattice energy of a crystal to other thermochemical data of energy terms involved in building a
crystal lattice.
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The elements in their standard state are first converted to gaseous atoms and then to ions and finally packed into the
crystal lattice.

(I) Sublimation of solid sodium to gaseous sodium atoms.

Na(s) → Na(g); ∆H=108.7 kJ/mol

(II) Ionization of gaseous sodium atom to give sodium ion.

Na(g) → Na+(g) + e- ; ∆H=493.8 kJ/mol

(III) Dissociation of gaseous chlorine molecule into chlorine atoms

1
Cl2(g) → Cl(g) ; ∆H=120.9 kJ/mol
2

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

Cl(g) + e- → Cl- (g) ; ∆H=-379.5 kJ/mol

(V) Formation of NaCl from sodium and chloride ions. (Crystal or lattice formation).
Na+(g) + Cl- (g) → Na+Cl- (s); ∆H=-754.8 kJ/mol
The energy released in this step is lattice energy.
1
The net reaction would be Na(s) + 2Cl2(g) → Na+Cl- (s); ∆H=-410.9 kJ/mol
1 1 ∆Hf
∆Hf = +∆HS + IE + 2HD + EA + U Mg(s) + 2O2 (g) MgO(s)
1
∆Hf = 108.7 + 493.8 + 120.9 -379.5 -754.8 = -410.9 kJ/mol ∆HS 2
HD

Mg(g) O(g)
-U
MX(s) M+(g) + X- (g) E1 -U
I1

-∆Hf +IE -EA Mg+(g) O- (g)

I2 E2
1
1
∆HS + 2HD
M(s) + 2X2 (g) M(g) + X(g) Mg2+(g) + O2- (g)

The enthalpies of sublimation, dissociation and the ionization energy are positive since energy is supplied to the
system. The electron affinity and lattice energy are negative since energy is evolved in these processes.
All the terms except the lattice energy and electron affinity can be measured. By using known crystal structures, it
was possible to calculate the lattice energy and hence values were obtained for the electron affinity.
The cycle is used to calculate the lattice energy for unknown crystal structures.
The lattice energy is used to calculate the solubility of the crystal. When a solid dissolve, the crystal lattice must be
broken up. The ions so formed are solvated (with the evolution of energy). When the lattice energy is high a large
amount of energy is required to break the lattice.
the lattice enthalpy of NaCl is 788 kJ/mole (and Lattice energy = –788 kJ/mol). This means that 788 kJ of energy is
required to separate one mole of solid NaCl into one mole of Na+ (g) and one mole of Cl– to an infinite distance.

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Born-Lande equation
The ions are treated as point charges and the electrostatic (coulombic) energy ‘E’ between two ions of opposite
charge is calculated.
𝑍 +𝑍−𝑒 2
𝐸=− 𝑟

where
Z+ and Z- are the charges on the positive and negative ions
e is the charge on an electron
r is the interionic distance
For more than two ions, the electrostatic energy depends on the number of ions and also on A their arrangement in
space.
𝑁0 𝐴𝑍 + 𝑍 − 𝑒 2
For one mole, the attractive energy is 𝐸 = − 𝑟

Where

N0 is the Avogadro constant (The number of molecules in a mole – 6.023 × 1023 mol-1)

A is the Madelung constant (which depends on the geometric arrangement of the ions in the lattice)

negative sign in the above equation is due to energy is given out when a crystal is formed.

Coulombic interactions are not the only forces operating in a real ionic lattice. The ions have finite size, and electron–
electron and nucleus–nucleus repulsions also arise; these are Born forces. when the inter-ionic distance becomes
small enough for the ions to touch, they begin to repel each other. this repulsion originates from the mutual repulsion
of the electron clouds on the two atoms or ions. the repulsive forces increase rapidly as r decreases.
𝐵
The repulsive force is given by 𝑟 𝑛

where B is a constant (Repulsion coefficient) that depends on the structure, and n is called born exponent.
𝑁0 𝐵
For one-gram molecule the total repulsive force is 𝑟𝑛

The total energy holding the crystal together is lattice energy (U) this is the sum of the attractive and the repulsive
forces.

𝑁0 𝐴𝑍 + 𝑍 − 𝑒 2 𝑁0 𝐵
𝑈=− + (1)
𝑟 𝑟𝑛
Attractive Repulsive
force force
𝑑𝑈
At equilibrium = 0, and the equilibrium distance r=r0
𝑑𝑟

𝑑𝑈 𝑁0 𝐴𝑍 + 𝑍 − 𝑒 2 𝑛𝑁0 𝐵
= -𝑟 =0
𝑑𝑟 𝑟0 2 0
𝑛+1

rearranging the above equation gives repulsive coefficient B

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 𝐴𝑍 + 𝑍 − 𝑒 2 𝑟0 𝑛−1
𝐵= 𝑛

substituting the value of B in (1), we get

𝑁0 𝐴𝑍 + 𝑍 − 𝑒 2 1
𝑈=− (1 − 𝑛)
𝑟0

This equation is called the Born-Lande equation, it allows lattice energy to be calculated from a knowledge of the
geometry of the crystal, and hence the Madelung constant.
when using S.I units, the equation takes the form
𝑁0 𝐴𝑍 + 𝑍 − 𝑒 2 1
𝑈=− (1 − 𝑛)
4𝜋𝜀0 𝑟0

where 𝜀0 is the permittivity of free space = 8.854 × 10-12 Fm-1.

In an ionic crystal the force of any one ion will be determined not only by the oppositely charged ions directly
surrounding it but also by the other ions (both positive and negative ions) at greater distance. Thus, in an ionic crystal
not only two separate ions are to be considered but the whole crystal must be considered.

(1) The lattice energy varies directly as the product of the ionic charges of the ionic crystal. Higher is the charge
on ions, higher is the lattice energy. High lattice energy – ions are held tightly together and the tendency
of the solid to split into ions by dissolution is less.
LiF < CaF2 < MgO
Increasing Lattice energy High solvation energy – tendency of solid to split into ions and then
to get hydrated is also high.
(2) Lattice energy varies inversely as the interionic distance 𝑟0 . An ionic solid with smaller ions will have higher
lattice energy.
LiF > LiCl > LiBr > LiI
Decreasing order of lattice energy

(3) Crystals with a high lattice energy usually melt at high temperature and are very hard. The higher is the lattice
energy, the more stable is the ionic bond. (Lattice energy ∝ strength of ionic bond)

(4) If lattice energy of an ionic solid is smaller than the solvation (hydration) energy, the ionic solid will dissolve
in the solvent.
Solvation energy: The energy released when a compound is dissolved in a solvent.
1
𝐿𝑎𝑡𝑡𝑖𝑐𝑒 𝑒𝑛𝑒𝑟𝑔𝑦 ∝
𝑠𝑜𝑙𝑢𝑏𝑖𝑙𝑖𝑡𝑦
In a number of cases, the results obtained from Born-Lande equation are different from experimental values. so, this
equation is modified. other equations used for the purpose are Born-Mayer equation and Kapustinskii equation.
𝑁0 𝑀𝑍 + 𝑍 − 𝑒 2 𝜌
Born -Mayer equation: 𝑈 = (1 − 𝑟 )
4𝜋𝜀0 𝑟0 0

𝜌 = constant dependent on the compressibility of crystal. Lattice energy decreases down the group since the
r0 = distance to closest ions size of ions increases.

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 1202𝛾𝑍𝑐 𝑍𝑎 0.345 120,200𝛾𝑍𝑐 𝑍𝑎 34.5
Kapustinskii equation: 𝑈 = (1 − 𝑟 +𝑟 ) (Or) 𝑈= (1 − 𝑟 +𝑟 )
𝑟𝑐 +𝑟𝑎 𝑐 𝑎 𝑟𝑐 +𝑟𝑎 𝑐 𝑎

𝛾 = Number of ions in the formula for the compound.

Problems

(1) Sodium fluoride adapts the NaCl structure type. Estimate the lattice energy of NaF using an electrostatic model.
N0 = 6.023 × 1023 mol-1, A = 1.7476, e = 1.602 × 10-19 C, 𝜀0 = 8.854 × 10-12 Fm-1, n = 7, Na-F distance = 231pm
𝑁0 𝐴𝑍 + 𝑍 − 𝑒 2 1
on substituting the above values in the given equation, 𝑈 = − (1 − 𝑛) ≈ -901kJmol-1.
4𝜋𝜀0 𝑟0

(2) Estimate the lattice energy of KF (NaCl structure) using an electrostatic model; K-F distance – 266pm.
(3) Given that the standard enthalpy of formation at 298K of CaF2 is -1228kJmol-1, determine lattice energy.
1
given: I1 = 589.8, I2 = 1145, E1 = -141, E2 = +798, ∆HS = 178, 2HD = 249

Values of the Born exponent, n, given for an ionic compound MX in terms of the electronic configuration of
the ions [M+][X-]. The value of n for an ionic compound is determined by averaging the component values,
5+9
e.g. for LiCl, n = 2 = 7
Electronic configuration Examples of ions n (no. units)
of the ions in an ionic
compound MX
[He][He] H-, Li+ 5
[Ne][Ne] F-, O2-, Na+, Mg2+ 7
[Ar][Ar], or [3d10][Ar] Cl-, S2-, K+, Ca2+, Cu+ 9
[Kr][Kr] or [4d10][Kr] Br-, Rb+, Sr2+, Ag+ 10
[Xe][Xe] or [5d10][Xe] I-, Cs+, Ba2+, Au+ 12

Madelung Constant: These values are derived by considering the coordination environments (near and far
neighbours) of ions in the crystal lattice.
Madelung constants (A) are numerical and have no units.
Structure type Madelung constant (A)
Sodium chloride (NaCl) 1.7476
Caesium chloride (CsCl) 1.7627
Wurtzite (α-ZnS) 1.6413
Zinc blende (ß-ZnS) 1.6381
Fluorite (CaF2) 2.5194
Rutile (TiO2) 2.408*
Cadmium iodide (CdI2) 2.355*
* For these structures, the value depends slightly on the lattice parameters for the unit cell.

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 COVALENT BOND
➢ A covalent bond is formed by mutual sharing of one (or) more electron pairs between two atoms so that each atom
involved in bonding attains nearest noble gas configuration in order to gain stability.

➢ When two atoms of non-metals bond, a large amount of energy is needed for either atom to lose an electron. So,
two non-metal atoms don’t transfer electrons to fill their outermost energy levels. Instead, the atoms bond by
sharing electrons with one another.

➢ The sharing of one, two and three electron pairs between two atoms give rise to the formation of single, double
and triple bond respectively.

➢ The covalent bond energy arises due to van der Waals forces of attraction between nuclei and shared pair of
electrons.
In a covalent species, electrons are shared
➢ Covalent bond is rigid and directional in nature. between atoms.
In an ionic species, one or more electrons
➢ Conditions for the formation of covalent bond: are transferred between atoms to form
The bonded atoms must have same or almost same electronegativity. ions.

compounds having valency of central atom higher than 3 are generally covalent.
➢ Covalency: The number of valence electrons shared by atom to complete its octet. (or) the number of covalent
bonds formed by an atom in a molecule.
Covalency of an atom = 8 – group number. (This relation is not valid for H and noble gases.)
some elements show more than one covalency because of excitation of electrons into vacant d-orbitals present in
valence shell.

Lewis structures:
Lewis presented a simple, but useful, method of describing the arrangement of valence electrons in molecules. The
approach uses dots (or dots and crosses) to represent the number of valence electrons, and the nuclei are indicated by
appropriate elemental symbols. A basic premise of the theory is that electrons in a molecule should be paired; the
presence of a single (odd) electron indicates that the species is a radical.
H H

O H O H

where each line stands for one pair of electrons, i.e. a single covalent bond. Pairs of valence electrons which are not
involved in bonding are lone pairs.

Formal charge:
It allows us to determine the location of charge in a molecule. The formal charge of an atom in a polyatomic
molecule or ion may be defined as the difference between the number of valence electrons and the number of
electrons assigned to that atom in the Lewis structure.
It is expressed as: Formal charge = Number of valence e– on neutral atom – (2  Lone pairs) – Bond pairs.
If there are more than one possible Lewis structures for a molecule having same number of bonds, the better structure
is one which has the least formal charge on each individual atom. It takes energy to get a separation of charge in the
molecule (as indicated by the formal charge) so the structure with the least formal charge should be lower in energy
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and thereby be the better Lewis structure. The non-zero formal charge on any atoms in the molecule are written near
the atom.

Valence bond theory

The theory given by Lewis explained the structure of molecules. however, it failed to explain the chemical bond
formation. similarly, VSEPR theory explained the shape of simple molecules. it also failed to explain the geometry of
complex molecules. hence, the theory of valence bonds is introduced by Heitler and London, further developed by
Linus Pauling.
(A) Orbital overlapping theory
According to atomic orbital theory, the covalent bond is formed by the overlapping (orbitals share a common region)
of atomic orbitals having electrons with opposite spins belonging to the external shells of two atoms of same (or) of
different kinds. After overlapping, the electron−pair belongs to both the orbitals of two atoms.
➢ A covalent bond is formed by the overlapping of two half-filled valence atomic orbitals of two different atoms.

➢ The electrons in the overlapping orbitals gets paired and confined between the nuclei of two atoms.

➢ The electron density between two bonded atoms increases due to overlapping. this confers stability to the
molecule. p, d and f are directional orbitals ➔More
overlapping
➢ Greater the extent of overlapping, stronger is the bond formed.
s orbital is non directional ➔ Less overlap
➢ In case the atomic orbitals possess more than one unpaired electron, more than one bond can be formed and
electrons paired in the valence shell cannot take part in such a bond formation.

➢ The direction of the covalent bond is along the region of overlapping of the atomic orbitals i.e. covalent bond is
directional.

➢ There are two types of covalent bonds based on the pattern of overlapping

(i) 𝜎 − 𝑏𝑜𝑛𝑑 : The covalent bond formed due to overlapping of atomic orbitals along the internuclear axis. it is the
stronger bond and cylindrically symmetrical around the internuclear axis, and the electrons in it have zero orbital
angular momentum about the axis.

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

(B) Hybridisation theory

Hybridisation
The mixing of atomic orbitals of same atom to produce new orbitals of equivalent energy and shape is called as
Hybridisation. This concept was given by Linus Pauling in 1937. This concept not only predicts the correct shapes
but also explains the actual microscopic observations of the geometry of molecules. The different cases of
hybridisation arise by mixing of s, p and d orbitals are discussed below.
p-s p-p
Consider an example of BeCl2, Cl ---Be ---Cl
if it is formed without hybridisation, then both the Be-Cl bonds should have different parameters. practically, bond
strength and distance of both the Be-Cl bonds are same
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sp hybridisation: A sp hybrid orbital is formed when in an atom one s and one p orbital mix with
each other to form two equivalent orbitals. Two such orbitals, i.e., sp hybrid orbitals are most stable
when they adopt an angle of 180 between them so that they are at the maximum distance apart. It means that the
molecule involving sp hybrid orbitals will be linear in shape. e.g. BeCl2

sp2 hybridisation: One 2s orbital and two 2p orbitals hybridise to give three sp2 hybridized orbitals.
this is called sp2 hybridisation. These three sp2 hybrid orbitals are at angle of 120° & giving trigonal
planar shape. e.g. BF3

sp3 hybridisation: This type of hybridisation results from mixing of one s and three p orbitals of outer (valence)
shell of an atom.

Let us consider the formation of CH4 molecule. The outer-shell configuration of C atom in ground state is 2s2 , 2p1x ,
2p1y. Note that 2pz orbital is empty. One of the electrons in the 2s2 orbital is excited (or promoted) to this vacant 2pz
orbital.
1 e- is excited to 2pz orbital ↑ ↑ ↑
↑↓ ↑ ↑ ↑
(Requires energy)
2s2 2p1x 2p1y 2pz 2s1 2p1x 2p1y 2p1z
Ground state Excited state

After the electron is promoted, all the four orbitals are mixed to give four equivalent hybrid orbitals (all of them are
of equal energy) called as sp3 hybrid orbitals. These four hybrid orbitals are directed at the corners of a regular
tetrahedron. This is best geometry for four bonded pairs to be at the maximum distance apart and thus minimize the
repulsion and hence the energy of the system is minimized. Each of four sp3 orbitals in carbon can now combine with
a 1s orbital of a hydrogen atom, forming four equivalent CH bonds involving sp3−s overlapping and forming four
sigma bonds. The extent of overlapping by hybrid orbitals is very high due to their strong orientation in space.

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sp3d hybridisation: one s orbital, three p orbitals and one d orbital are mixed to give five
new hybrid orbitals which are equivalent in shape and energy called as sp3d hybrid orbitals.

Out of these five hybrid orbitals, three hybrid orbitals are at 120° angle and two hybrid orbitals
are perpendicular to the plane of three hybrid orbitals i.e. trigonal planar, the shape of molecule
becomes trigonal bipyramidal.
In this hybridisation dz2 orbital is hybridised with s and p orbitals. e.g. PCl5

sp3d2 hybridisation: one s-orbital, three p-orbitals & two d-orbitals are mixed to give six new
hybrid orbitals known as sp3d2 hybrid orbitals.

The shape of molecule obtained from above six hybrid orbitals will be symmetrical octahedral
and the angle between all hybrid orbitals will be 90°.
Two 'd' orbital participates in this hybridisation are dx2-y2 and dz2. e.g. SF6

sp3d3 hybridisation: one s-orbital, three p-orbitals & three d-orbitals are mixed to give seven new hybrid orbitals
known as sp3d3 hybrid orbitals.
These seven sp3d3 orbitals are configurated in pentagonal bipyramidal shape. Five bond angles are of 72° & ten bond
angles of 90°.
d-orbitals used in this hybridisation are dxy, dx2-y2 & dz2. e.g. IF7

1
The angle of hybridised orbitals is derived by: Cos𝛼 = -(𝑚)

where ‘m’ is number of p orbitals involved in hybridisation.

sp hybridisation: Cos𝛼 = -1 ∴𝛼 = 180°
𝑠
Percentage s character: Cos𝜃 = 𝑠−1
𝑝−1
Percentage p character: Cos𝜃 = 𝑝

Bond-length: It is defined as the equilibrium distance between the nuclei of two bonded atoms in a molecule.
Bond-angle: It is defined as the angle between the orbitals containing bonding electron pairs around the central
atom in a molecule/complex ion.

Bond-energy: The amount of energy required to break one mole of the bond and separate
the bonded atoms in the gaseous state is known as the bond energy of that particular bond.
it is expressed in kJ mol–1 (in SI units) or in kcal mol–1.

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Valence Shell Electron Pair Repulsion (VSEPR) theory
This theory was put forth by Sidgwick and Powell in 1940 to explain the shapes of molecules. It was later refined and
extended by Nyholm and Gillespie in 1957. This theory focuses on the electron pairs present in the valence shell of
the central atom of the molecule.
Lewis electron structures predict the number and types of bonds, whereas VSEPR can predict the shapes of many
molecules and polyatomic ions.

Assumptions
➢ The shape of the molecule is determined by repulsions between all of the electron pairs present in the valence
shell.
(The 𝜎-bond pairs and lone pairs on the central atom are oriented as far apart from each other as possible in order
to minimize the repulsive forces between them.)

➢ 𝜋-bonds are not considered, as they form a single repulsive unit along with their associated 𝜎-bond pairs.
(bond angles involving single bonds are generally smaller than those of multiple bonds)
triple bond–single bond > double bond–single bond > single bond–single bond.

➢ lone pair – lone pair repulsions > lone pair – bond pair repulsions > bond pair – bond pair repulsions.
(A lone pair of electrons takes up more space around the central atom than a bond pair, since the lone pair is
attracted to one nucleus while the bond pair is shared by two nuclei)

➢ The magnitude of repulsions between bond pairs of electrons depends on the electronegativity difference between
the central atom and the other atoms attached to it.
(As the electronegativity difference between E and L increases [as L becomes more electronegative] the bond
pair is displaced towards L and away from E. this reduces the repulsive effect with other bond pairs leading to
decrease in ∟L-E-L)

➢ If the radius of E decreases (or) radius of L increases, the mutual electronic and steric repulsions between the
polarized ligands increases, causing in ∟L-E-L. At a high coordination number this value can exceed the
repulsion by the lone pair at which point the lone pairs becomes stereo chemically inactive.
(E – Central atom, L – Ligands (or) atoms attached to central atom.)

Number of Molecular Spatial representation. Hybridisation Ideal Symmetry

electron pairs geometry bond
(bp: lp) angle
2: 0 Linear sp 180° 𝐷∞ ℎ

3: 0 Trigonal sp2 120° 𝐷3 ℎ

planar

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 2: 1 Bent sp2 120° 𝐶2 𝑣

4: 0 Tetrahedral sp3 109.5° 𝑇𝑑

3: 1 Trigonal sp3 109.5° 𝐶3 𝑣

pyramidal

2: 2 Bent sp3 109.5° 𝐶2 𝑣

5: 0 Trigonal sp3d 90°, 120° 𝐷3 ℎ

bipyramidal

4: 1 See-saw sp3d 90°, 120° 𝐶2 𝑣

3: 2 T-shaped sp3d 90°, 120° 𝐶2 𝑣

2: 3 Linear sp3d 90°, 120° 𝐷∞ ℎ

6: 0 Octahedral sp3d2 90° 𝑂ℎ

5: 1 Square sp3d2 90° 𝐶4 𝑣

pyramidal

4: 2 Square planar sp3d2 90° 𝐷4 ℎ

7: 0 Pentagonal sp3d3 72°, 90° 𝐷5 ℎ

bipyramidal

6: 1 distorted sp3d3 72°, 90°

octahedral

8: 0 Square sp3d4 70.5°,

antiprism 99.6°,
109.5°

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 (1) CH4 (2) ICl2-
C – s2p2 = 4e- I – s2p5 =7e-
H – s1 1×4 = 4e- Cl – s2p5 1×2 = 2e- [ number of available states]
8e- Anionic charge = 1e-
4 𝜎 − 𝑏𝑜𝑛𝑑 𝑝𝑎𝑖𝑟𝑠. 10e-
2 𝜎 − 𝑏𝑜𝑛𝑑 𝑝𝑎𝑖𝑟𝑠 + 3 lone pairs.

Geometry – lone pair + bond pair

Shape – only bond pair (exclude lone pair)
Tetrahedral – sp hybridisation
3

Linear – sp3d hybridisation

Bent rule: More electronegative atom prefers to stay in the hybrid orbital having less s-character and more
electropositive (Less electronegative) atom prefer to that hybrid orbital which is having more s-character.
High electronegative atom → axial position, lone pairs → equatorial
sp3d hybridisation (Group hybridisation)

dp hybridisation sp2 hybridisation

(axial bond) (equatorial bond)

Molecular orbital (MO) theory

Molecular orbital theory was developed mainly by Hund and Mullikan in 1932 and later on developed by Lennard
Jones and Coulson. According to this theory the atomic orbitals combine and form a resultant orbital known as the
molecular orbital in which the identity of both the atomic orbitals is lost. All the electrons pertaining to both the
atoms are considered to be moving along the entire molecule under the influence of all the nuclei. The combination of
atomic orbitals occurs by LCAO (Linear combination of atomic orbitals) method.
In an atomic orbital the movement of an electron is influenced by only one positive nucleus while that of an electron
in a molecular orbital is influenced by two or more nuclei depending on the number of atoms contained in the
molecule. Thus, atomic orbitals are monocentric while molecular orbitals are polycentric.
➢ The combining atomic orbitals must have the same or nearly the same energy and same symmetry about the
molecular axis also the combining atomic orbitals must overlap to the maximum extent.

➢ Number of atomic orbitals = number of molecular orbitals.

➢ Each MO occupy maximum two electrons and follows Aufbau principle, Pauli’s exclusion principle and Hund’s
rule of maximum multiplicity.
If Bond order is positive value (Nb – Na) then the molecule is stable else it is unstable.

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Count the number of electrons in the outer shell of both the atomic orbitals and those electrons are to be
accommodated in the molecular orbitals. The higher electronegative atomic orbitals would be of lower energy
than the corresponding atomic orbitals. Due to this energy difference, the bonding and antibonding molecular receive
different contributions from atomic orbitals. The bonding orbitals receive more contribution from atomic orbitals of
lower energy, than the antibonding molecular orbitals which would be closer to another atomic orbitals in energy.
The bonding molecular orbitals would have more characteristics of atomic orbitals of high electronegative atom and
antibonding molecular orbitals would have more characteristics of atomic orbitals of the other atomic orbital.

𝜎1𝑠 2 , 𝜎 ∗ 1𝑠 2 (KK), 𝜎2𝑠 2 , 𝜎 ∗ 2𝑠 2 , 𝜎2𝑝𝑧 2 𝜋2𝑝𝑥 2 , 𝜋 ∗ 2𝑝𝑥 2 , 𝜎 ∗ 2𝑝𝑧 2

𝜋2𝑝𝑦 2 𝜋 ∗ 2𝑝𝑦 2

1
Bond order = 2 (𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑜𝑐𝑐𝑢𝑝𝑦𝑖𝑛𝑔 𝑏𝑜𝑛𝑑𝑖𝑛𝑔 𝑜𝑟𝑏𝑖𝑡𝑎𝑙 −
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑜𝑐𝑐𝑢𝑝𝑦𝑖𝑛𝑔 𝑎𝑛𝑡𝑖𝑏𝑜𝑛𝑑𝑖𝑛𝑔 𝑜𝑟𝑏𝑖𝑡𝑎𝑙)

If electrons are paired up – diamagnetic

if electrons are unpaired - paramagnetic

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Polarisation
When two oppositely charged ions (cation and anion) of the ionic molecule come closer to each other, the cation
attracts the electron charge cloud of the outer most shell of the anion towards itself and hence the symmetrical shape
of the anion gets distorted (deformed or polarised).
The phenomenon in which the symmetrical shape of the anion gets deformed by the approach of the cation closer to it
is called polarisation (distortion or deformation) of the anion.
The ability of a cation to polarize an anion is called its polarising power or polarising ability.
The tendency of an anion to get polarized by a cation is called its polarisability.

Factors affecting the magnitude of polarising power

➢ Higher is the positive charge on the cation, more
strongly it attracts the outermost shell electron
cloud of the anion towards itself.

➢ Smaller is the size of a cation, more strongly it

attracts the outermost shell electron cloud of the
anion towards itself.

➢ The cation having ns2 np6 d10 as its valence-shell

configuration will polarise the given anion to a
greater extent than the cation having ns2 np6 as its
valence-shell configuration. ns2p6dl0configuration
is called pseudo inert gas configuration.

d-electrons shield the nucleus poorly as compared to s and p-electrons. thus d-electrons present in an 18-electron
cation has poorer shielding of the nucleus than the s and p-electrons present in 8-electron cation. Consequently the
18-electron cation would have more greater polarising power than the 8-electron cation.

Fajan’s rules of covalency

In 1924, Fajan told that there are certain conditions which if fulfilled by the cation and anion of a given ionic
molecule, make the ionic bond partially covalent (polar covalent) or purely covalent. These conditions are called
Fajan’s rules.
According to this rule a molecule is predominantly covalent if smaller the size of cation, larger the size of anion,
greater the charge on cation and anion and ion does not having inert gas configuration.
We can also say that these factors favour polarisation.

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Dipole moment
A molecule with positive and negative charge centers in equilibrium is called as dipole and is characterised by
possessing a quantity dipole moment (µ) defined as the product of the magnitude of charge (q) and the distance (d)
separating the centers of positive and negative charges.  = q × d.
Its unit in CGS system is Debye (D). 1 D = 1 × 10−18 esu.cm. The charge q is measured in esu. The distance d is
measured in cm and is of order of 1 Å, i.e., 10−8 cm. The direction of dipole moment is from +ve end to –ve end.
Note: Charge on 1 electron = 1.6 × 10−19 C = 4.8 × 10−10 esu. In cgs system there are two units of charge
In S.I units µ is expressed in coulomb meter (Cm) (1) esu – electrostatic system of unit (also
called stat coulomb or franklin)
dipole moment is a vector quantity, denoted
(2) emu – electromagnetic unit (abcoulomb)
by cross arrow, the head of the arrow pointed
1 coulomb – 3×109 esu (or) 10-1 emu.
towards more electronegative atom.
covalent molecules having bond dipoles are classified into two categories: 𝜇𝑟𝑒𝑠𝑢𝑙𝑡𝑎𝑛𝑡 = √𝜇1 2 +𝜇2 2 +2𝜇1 𝜇2 cos𝜃
(a) Polar molecules (b) Non-polar molecules
A molecule is said to be polar if the net dipole moment of a molecule is not equal to zero. (net  0).
example: HF, H2O, NH3, CH3OH, etc.
If there are no polar bonds or lone pairs on the central atom, the molecule cannot be polar. and even if these are
present, they may be arranged in such a manner that their polarities should not cancel each other.
A molecule is non−polar if its net dipole moment is equal to zero. (net = 0).
example: H2, Cl2, BF3, CO2, BeCl2, etc.

The dipole moment of a molecule, (zero or non-zero), depends upon the structure or shape (or on geometry) of the
molecule.
For example, H2O is polar whereas HgCl2 is non−polar. The difference lies in the shapes of two molecules. H2O is
angular (  0) and HgCl2 is linear ( = 0). Both have polar bonds, O−H bond in water while Hg−Cl bond in
mercuric chloride, but due to structure of HgCl2 being linear, the dipole moments of two bond dipoles cancel each
other whereas in water, due to angular shape the dipole moments of two bond dipoles do not cancel and give rise to
a net dipole moment.

Applications
(i) To decide polarity of the molecule: Molecules having zero dipole moment () are said to be non-polar
molecules and those having R  0 (resultant dipole moment) are polar in nature.
(ii) To determine percentage of ionic character: The value of dipole moment can be used for determining the
amount of ionic character in a bond.
𝐸𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡𝑎𝑙 𝑣𝑎𝑙𝑢𝑒 𝑜𝑓 𝑑𝑖𝑝𝑜𝑙𝑒 𝑚𝑜𝑚𝑒𝑛𝑡
𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝑖𝑜𝑛𝑖𝑐 𝑐ℎ𝑎𝑟𝑎𝑐𝑡𝑒𝑟 = × 100
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑣𝑎𝑙𝑢𝑒 𝑜𝑓 𝑑𝑖𝑝𝑜𝑙𝑒 𝑚𝑜𝑚𝑒𝑛𝑡
(iii) To determine geometry of molecules: The values of dipole moments provide value information about the
structure of molecules.
CO2, CS2 molecules are linear as value of their dipole moments are zero. H2O is not a linear molecule as it has
dipole moment.
(iv) To distinguish between cis and trans isomers: For trans isomer, R = 0, for cis isomer, R  0.

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Hydrogen bonding
It is a special type of attraction between a hydrogen atom bonded to a strongly electronegative atom (like
nitrogen, oxygen or fluorine) and the unshared pair of electrons on another electronegative atom. Hydrogen bond is a
weak bond, the strength being just about 4-25 kJ mol–1. It is quite small as compared to the covalent bond, which
needs a few hundreds of kJ mol–1 of energy to break. However, it is strong enough to be responsible for the high
boiling points of H2O and HF etc.
When a hydrogen atom is bonded to an element having an electronegativity of about 2.6 or higher (F, O, N, Cl, or S),
the polarity of the bond is sufficient that the hydrogen carries a positive charge that enables it to be attracted to a pair
of electrons on another atom. That attraction is known as a hydrogen bond.
Due to the difference in the electronegativity between hydrogen and the other electronegative atom, the bond
connecting them becomes polar. The hydrogen atom acquires a positive charge while the electronegative atom bears
the negative charge. Hydrogen bonding results from the electrostatic interaction between the positively charged
hydrogen atom and the negatively charged electronegative atom.
If the hydrogen bond is formed between two different molecules it is called intermolecular hydrogen bond. When
the hydrogen bond exists within the same molecule, it is called intramolecular hydrogen bonding.

Intramolecular hydrogen bonding – boiling and melting point of the substance decreases
Intermolecular hydrogen bonding – boiling and melting point of the substance increases

van der Waal’s force

The attractive forces between two separate molecules operate at longer distances where no orbital overlap can occur.
these attractive forces are thus much weaker and are called intermolecular forces (or) van der Waal’s forces of
attraction.
These are the weakest type of inter molecular forces that exist among the molecules which being significant change
in physical properties.
inert gases do not form any type of bond but may exist in liquid and solid states. This shows that the atoms of inert
gases are attracted by each other through some type of inter molecular forces.
(A) Dispersion forces: These are electrostatic in nature and result from an attraction between induced dipoles in
adjacent molecules. The induced dipole originates in a molecule when the electrons of the neighboring molecule are
momentarily unequally distributed. The neighbor is said to have an instantaneous dipole and it can induce dipole in
the first molecule.
These forces are very weak in nature and exists only at low temperature.
it exists among the non-polar molecules like H2, O2, Cl2 etc. in solid or liquid states.

(B) Dipole – Dipole forces: These kinds of intermolecular forces operate between polar molecules. when
molecules are built up of atoms with large difference in electronegativity, the bond gets permanently polarised.
electrostatic attractions between the oppositely charged ends of permanent dipoles. This type of attraction is weaker
than the ion-dipole attraction.
it exists between polar molecules and due to this force gas can be liquified.

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(C) Ion-Dipole forces: negative ends of dipolar molecules like H2O, NH3 may be attracted towards metal ions to
form metal hydrates (or) metal ammoniates. The weak attraction occurs due to the lone pair electron density of H2O
(or) NH3 facing the cations.
Polar molecules are attracted by ions. The negative pole is attracted by cation and positive pole attracted by the anion.
This type of attraction is called ion dipole attraction, ion-dipole attraction is observed generally in the process of
solvation when sodium chloride (Na+ Cl–) is dissolved in water because negative poles of water aggregate around Na+
ions and positive poles around Cl– ions
it exists between an ion and a polar molecule; its strength depends on (i) size of ion (ii) charge on the ion (iii) dipole
moment of the polar molecule.

(D) Ion-Induced dipole attraction: When non polar molecules come in contact with ions, its electron cloud
gets polarised and the oppositely charged end of it is attracted by the ion.

(E) Dipole – Induced dipole interaction: This type of weak interaction exists between a molecule with a
permanent dipole and a molecule (or) atom without one. The polar molecule may distort the electron density of the
second molecule (or) atom towards its positive end so that the centers of positive and negative charge in the second
molecule does not coincide as in the absence of the polar molecule. thus, a dipole is induced. an attraction now results
between the permanent dipole and the induced dipole. The forces responsible for the formation of noble gas hydrates
belongs to this class.
it exists between polar and non-polar molecules.

METALLIC BOND
Molecular orbitals are formed by the interaction of atomic orbitals. the bonding orbital is separated from antibonding
orbital by several electron volts. when three atomic orbitals from three atoms combine to form MOs, we get three
orbitals, a bonding, a nonbonding and an antibonding orbital. when N atomic orbitals from N atoms interact, they
give N molecular orbitals. when N becomes very large, as in the case of a solid, there will be a large number of
orbitals in a given range of energy (between El and Eh) this collection of orbitals or energy levels is called as (energy)
band. rather than the discrete energy levels of small molecules. These bands contain the electrons from the atoms.
The highest energy band containing electrons is called the valence band; the next higher, empty band is called the
conduction band.

Metallic bond is not ionic because

(i) Ionic bond is not formed between two same atoms.
(ii) Ionic solids do not conduct electricity in solid state.
(iii) ionic solids are brittle while metals are malleable.

Metallic bond is not covalent because

(i) The octet of metal atom can’t be completed by mutual sharing of electrons.
(ii) X-ray study of metal crystals reveals that one atom is surrounded by 8 (or) 12 atoms but metals have a few
valence electrons and can’t bind with such a large number of atoms.
(iii) Lighter covalent compounds are liquids (or) gases but metals are solids (except mercury and gallium)

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 To explain metallic bond, two theories have been proposed
(A) Electron sea theory (or) electron gas theory
(B) Band theory

Electron sea theory

Drude (1900) regarded a metal as a lattice with electrons moving through it in much the same way as molecules of
gas are free to move. The idea was refined by Lorentz in 1923, who suggested that metals comprised a lattice of rigid
spheres (Positive ions), embedded in a gas of free valency electrons which could move in the interstices. This model
explains the free movement of electrons, and cohesion results from electrostatic attraction between the positive ions
and the electron cloud. These mobile electrons behave like ideal gas and they regularly move at random. these mobile
electrons present between cations are responsible for attraction between these ions, which are known as metallic
bonds.
The strength of metallic bond increases with increase in the number of mobile electrons between two cations.

Band theory
Band theory of metallic bond is an extension of molecular orbital theory to metallic structure. atoms held by metallic
bond have same symmetry and same energy and so they combine to form molecular orbitals (bonding and
antibonding MOs). these orbitals collectively form energy bands. The energy levels in a band is equal to the number
of atoms in the metal. The highest energy band containing electrons is called the valence band; the next higher, empty
band is called the conduction band. Thus, in conduction band, a number of empty energy levels are there in which
electrons can move and this movement of electrons from one level to another allows the passage of current.
The minimum differences between energies of valence band and conduction band is known as band gap (or) energy
gap and the value of energy gap determine the electrical conductivity of different materials. smaller is the band gap,
higher is the conductivity. the energy gap decreases as we move down in the group and i.e., why C is insulator, Si and
Ge are semiconductor and Sn is conductor.
The electrical attraction between delocalised electrons (i.e. mobile electrons) and the positive part of the atom
(i.e. kernel) is called metallic bond. Strength of metallic bond depends upon number of metallic bonds per atom.

Electropositive + Electronegative ➔Ionic bond

Electronegative + Electronegative ➔ Covalent bond

Electropositive + Electropositive ➔ Metallic bond

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