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4
Chemical Bonding
and Molecular
Structure
Chemical Bond
It is defined as the attractive force which hold the various chemical
constituents (atoms, ions, etc.) together in different chemical species.
Bond forms to get the stability, with a release of energy.

Kossel-Lewis Approach to Chemical Bonding

According to this theory, atoms take part in the bond formation to
complete their octet or to acquire the electronic configuration of the
nearest inert gas atoms (octet rule). This can be achieved by gaining,
losing or sharing the electrons.

Lewis Symbols
Valence electrons are reported by dots around the chemical symbol of
element, e.g.
• • • •• ••
•B• •C • • • • •
Li •
•F • • Ne •
• ••

Octet Rule
According to Octet rule during the formation of a covalent bond, the
atoms attain an inert gas electronic configuration (valence shell
contains 8e− or shell is completely filled). An atom may attain this
configuration by gaining, losing or sharing electrons with other atoms.
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44 Handbook of Chemistry

Exceptions to the Octet Rule

(i) Incomplete octet of the central atom, e.g. LiCl, BeH 2 and BCl3
Cl
•
•
• • • • •
Li • Cl ; H • Be • H ; Cl • B • Cl
(ii) Odd-electron molecules
•• •• •• •+ •• −
N == O ; O == N O •• ; ClO−2 , He+2
• •• •• ••

(iii) Expanded octet of central atoms

PCl5 SF6 H 2SO4
[10 electrons [12 electrons [12 electrons around
around the around the the S atom]
P atom] S atom]

Ionic Bond
A chemical bond formed by complete transference of electrons from one
atom (metal) to another (non-metal) and hence, each atom acquires the
stable nearest noble gas configuration, is called ionic bond or
electrovalent bond, e.g. formation of sodium chloride
•• ••
Na • + • Cl•• → [Na + •• Cl•• − ]
•• ••
( 2,8,1) ( 2, 8, 7) ( 2, 8) ( 2, 8, 8)

Favourable factors for the formation of ionic bonds

(i) Metal should have low ionisation enthalpy.
(ii) Non-metal must have high electron gain enthalpy.
(iii) The energy released during the formation of 1 mole of crystal
lattice, i.e. lattice enthalpy must be high.

Some elements exhibit variable electrovalency. The reason for this is

unstable configuration of penultimate orbit and inert pair effect.

Ions
Species carrying either positive or negative charge are termed as ions.
Species carrying positive charge are called cations and those carrying
negative charge are called anions. Metals usually form cation while
non-metals (except H) usually form anions.

General Characteristics of Ionic Compounds

(i) Ionic compounds are usually solid in nature.
(ii) Ionic compounds have high melting and boiling points.
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Chemical Bonding and Molecular Structure 45

(iii) Ionic compounds are soluble in polar solvents like water but
insoluble in non-polar solvents like benzene, CCl4 etc.
(iv) Ionic compounds are good conductor in molten state and in
aqueous solution.
(v) Ionic compounds have crystal structure.

Method of Writing Formula of Ionic Compound

(i) Write the symbol of cation at the left and anion at the right.
(ii) Write their electrovalencies in figures on the top of each symbol
as Ax B y .
(iii) Divide their valencies by HCF.
x y
(iv) Now apply criss-cross rule as , i.e. formula is Ay Bx .
A B
3+ 2−
e.g. formula of aluminium sulphate is Al2(SO4 )3 .
Al SO4
Born Haber Cycle
This cycle is based upon the fact that the formation of an ionic
compound may occur either by direct combination of the elements or by
an alternate process in which :
(i) The reactants (metal) are vaporised to convert into gaseous state.
(ii) The gaseous atoms are converted into ion.
(iii) The gaseous ions are combined to form ionic lattice of molecules.
e.g. formation of NaCl can be shown as
1 Q
Na( s) + Cl2( g) → Na +Cl−
2
1
S D
2

Na( g) Cl
I −E
+ −U
Na + Cl−
1
Thus, Q =S + I + D − E −U
2
where, S = enthalpy of sublimation, I = ionisation enthalpy
D = enthalpy of dissociation, E = electron gain enthalpy
U = lattice enthalpy
Q = total enthalpy change.
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46 Handbook of Chemistry

Covalent Bond
A chemical bond formed between two atoms by mutual sharing of
electrons between them so as to complete their octets or duplets, is
known as covalent bond and the number of electrons contributed by
each atom is known as covalency, e.g. formation of Cl2.

Cl + Cl Cl Cl
2,8,7 2,8,7 or
Cl—Cl
In covalent bonding, the shared pairs of electrons present between the
atoms are called bond pairs while unshared or non-bonding electron
pairs are known as lone pairs.

Types of Covalent Bonds

(a) Non-polar Covalent Bond
If the covalent bond is formed between two homonuclear atoms,
i.e. between atoms of exactly equal electronegativity, e.g. H 2 , Cl2 etc.
(b) Polar Covalent Bond
If a covalent bond is formed between the different atoms, the shared
pair is displaced towards the more electronegative atom causing
greater concentration of electron density around the more
electronegative atom. Such a covalent bond develops some ionic
character and is called polar covalent bond, (e.g. H—Cl).

Properties of Covalent Compounds

(i) In general, covalent compounds exist in the liquid or gaseous
state at room temperature due to magnitude of intermolecular
forces.
(ii) Covalent compounds have low melting and boiling points.
(iii) Covalent compounds are generally poor conductors of electricity
because they do not contain free electrons or ions to conduct
electricity.
(iv) They are soluble in non-polar solvents like benzene but usually
insoluble in water.

Formal Charge on an Atom in a Molecule/Ion

Formal charge (F.C.) on an atom in a Lewis structure
= [total number of valence electrons in the free atom]
– [total number of non-bonding (lone pair) electrons]
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Chemical Bonding and Molecular Structure 47

1
– [total number of bonding (shared) electrons]
2

O
O O
1
F.C. on O2 = 6 − 2 − ( 6) = + 1
2
 1 
F.C. on O2 = 6 − 4 + × 4 = 6 − 6 = 0
 2 
 1 
F.C. on O3 = 6 − 6 + × 2 = 6 − 7 = − 1
 2 
Hence, O3 along with the formal charges can be represented as follows:
δ+
O
δ–
O O

Bond Characteristics
Bond Length
In a covalently bonded molecule, distance between the nuclei of the two
atoms is known as bond length. Bond length increases with increase in
the size of bonded atoms and decreases with an increase in the number
of bonds between bonded atoms.

Bond type Covalent bond length (in pm)

C—H 107 pm
C—C 154 pm
C== C 133 pm
C≡≡ C 120 pm

Bond length is determined by X-ray diffraction or electron diffraction

methods.

Bond Angle
In a covalently bonded molecule having more than two atoms, the bonds
form an angle with each other, which is known as bond angle. In
general an increase in the size of central atom decreases the bond angle.
Factors affecting bond angle (i) Lone pair repulsion (ii) hybridisation of
central atom. It is determined by X-rays diffraction method.
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48 Handbook of Chemistry

Bond Order
It is defined as the number of covalent bonds present in a molecule.
1
Bond order = [Number of electrons in bonding orbitals
2
– Number of electrons in anti-bonding orbitals]
1
Bond order ∝
bond length
If bond order comes out to be zero, the molecule does not exist.

Bond Enthalpy
It is the amount of energy released when one mole of covalent bonds is
formed while the bond dissociation enthalpy is the amount of energy
required to break one mole of bonds of the same kind so as to separate
the bonded atoms in the gaseous state.
The bond enthalpy and bond dissociation enthalpy are equal in
magnitude and opposite in sign.

Bond dissociation enthalpy is determined by thermal or spectroscopic

methods.
As the bond order increases, bond enthalpy also increases and bond
length decreases.
Factors affecting bond enthalpy
(i) atomic size
(ii) electronegativity
(iii) extent of overlapping
(iv) bond order

Fajan’s Rule
The partial covalent character of ionic bonds was discussed by Fajan’s
in terms of following rules:
The smaller the size of 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 or anion, the greater the covalent
character of the ionic bond.

Resonance
According to the concept of resonance, a single Lewis structure cannot
explain all the properties of the molecules. The molecule is then
supposed to have many structures, each of which can explain most of
the properties.
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Chemical Bonding and Molecular Structure 49

The actual structure lies in between of all these contributing structures
and is called resonance hybrid and the different individual structures
are called resonating structures or canonical structures. This
phenomenon is known as resonance.
O O O
O O O O O O
(I) (II) (III)
Resonance in ozone molecule
Resonance stabilises the molecule as the energy of the resonance
hybrid is less than the energy of any single canonical structure.
Resonance averages the bond characteristics as a whole.
The difference in the energy of the resonance hybrid and the most
stable contributing structure (having least energy) is called resonance
energy. Greater the resonance energy, greater is the stability of the
molecule.

Calculation of bond order for molecules showing resonance :

Bond order
total number of bonds between two atoms in all the structures
=
total number of resonating structures

Dipole Moment (µ)

It is defined as the product of the magnitude of the charge and the
distance between the centres of positive and negative charges.
µ = charge (Q ) × distance of separation (r )
Dipole moment is expressed in Debye (D).
1 D = 1 × 10−18 esu-cm = 3.33564 × 10−30 C-m
where, C is coulomb and m is meter.
(The shift in electron density is symbolised by broken arrow)
In chemistry, presence of dipole moment is represented by the crossed
arrow ( →
| ) put on Lewis structure of molecule. The cross is on
positive end and arrow head is on negative end.
NH3 has higher dipole moment than NF3 .

N N
H H F F
H F

Resultant dipole moment,

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50 Handbook of Chemistry

2 2
µ = µ 1 + µ 2 + 2 µ 1µ 2 cos θ

Applications of Dipole Moment

1. Dipole moment is helpful in predicting the geometry of the
molecule.
2. Dipole moment helps in determining the polarity.
Hannay-Smith equation
Per cent ionic character = 16 [X A − X B ] + 3.5 [X A − X B ]2
where, X A and X B are the electronegativities of atoms.

Per cent ionic character can also be calculated by dipole moment as

observed dipole moment
Per cent ionic character = × 100
calculated dipole moment
3. Non-polar molecule has zero dipole moment like BF3 , CCl4, etc.
F

B O C O
µ=0
F F
µ=0
4. cis and trans isomers can be distinguished by dipole moments
usually cis isomer have higher dipole moment and hence, higher
polarity.
5. Dipole moment is greatest for ortho isomer; zero for para isomer;
and less than that of ortho, for meta isomer.

The Valence Shell Electron Pair Repulsion

(VSEPR) Theory
According to this theory,
1. The geometry of a molecule or ion depends on the number of
electron pairs in the valence shell of its central atom.
2. To attain minimum repulsive state, electron pairs try to stay as
far away as possible.
3. If the central atom is surrounded by only bonded electron pairs of
similar atoms, the repulsive interactions are similar and the
molecular geometry is regular.
4. If the central atom is surrounded by only bonded electron pairs of
dissimilar atoms, the repulsive interactions are not equivalent
and hence, the geometry of molecule will not be regular.
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Chemical Bonding and Molecular Structure 51

5. If the central atom is surrounded by both bonded pairs (bp) as
well as lone pairs (lp) of electrons, repulsive interactions are not
equivalent and hence, geometry of the molecule will be irregular.
The repulsive interactions decrease in the order
lp – lp > lp – bp > bp – bp
Shapes (Geometry) of Molecules Containing Bond Pairs Only
or Bond Pairs and Lone Pairs
Total number Number Number
Geometry (shape) of the Illustrative
of electron of bond of Lone
molecule examples
pairs pairs pairs
2 2 0 B—A—B BeF2 , CO2 , BeCl2
Linear
3 3 0 B B BF3, AlCl 3, SO 3
A

B
Triangular planar
2 1 SO2 , O 3, NO2

A
B B
Bent (V-shape)
4 4 0 B CH 4 , SiF4 , NH 4+

A
B B
B
Tetrahedral
3 1 NH 3, PCl 3, NCl 3,
PH 3
A
B B
B
Trigonal pyramidal
2 2 H2O, H2S

A
B
B
Bent
Contd.…
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52 Handbook of Chemistry

Total number Number Number

Geometry (shape) of the Illustrative
of electron of bond of Lone
molecule examples
pairs pairs pairs
5 5 0 B PCl 5
B
A B
B
B
Trigonal bipyramidal
4 1 B SF4
B
A
B
B
See saw
3 2 B ClF3, BrF3

B B

B
T-shaped
2 3 B XeF2 , I−3 , ICl2−

B
Linear
6 6 0 B SF6

B B
A
B B
B
Octahedral
5 1 B BrF5, ClF5
B B
A
B B
Square pyramidal

Contd.…
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Chemical Bonding and Molecular Structure 53

Total number Number Number
Geometry (shape) of the Illustrative
of electron of bond of Lone
molecule examples
pairs pairs pairs
4 2 XeF4
B B
A
B B

Square planar

Valence Bond Theory of Covalent Bond

According to this theory, a covalent bond is formed by the overlapping
of two half-filled atomic orbitals having electrons with opposite spins.
It is based on wave nature of electron.
(i) Sigma Bond (σ bond)
This type of covalent bond is formed by head-on overlap, i.e. end to end
overlap along the internuclear axis. Sigma bond can be formed by any
one of the following types of combinations of atomic orbitals :
(a) s-s overlapping (b) s-p overlapping (c) p-p overlapping (axial)
The strength of σ bond depends upon the extent of overlapping
between atomic orbitals. The greater the extent of overlapping, the
stronger is the σ bond.
(ii) Pi Bond (π bond)
It is formed by the sidewise or lateral overlapping between p-atomic
orbitals [p-p side by side or lateral overlapping]
π bond is a weaker bond than σ bond.
Comparison of Sigma and Pi Bonds
Sigma bond Pi bond
1. This bond is formed by overlapping of orbitals This bond is formed by sideway
along their internuclear axis. overlapping of atomic orbitals.
s-p
or
s-s
p-orbital p-orbital p-p
p-p
2. Free rotation along a σ bond is possible. Free rotation about a π bond is not
possible.
3. Sigma bond consist of only one electron cloud Pi ( π) bond consists of two electron
symmetrical about the internuclear axis. clouds, one above the plane of atomic
nuclei and the other below it.
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54 Handbook of Chemistry

Limitations of VBT
It fails to explain
1. The magnetic properties of some molecules.
2. Bonding in electron deficient compounds.

Hybridisation
It is defined as the mixing of the atomic orbitals belonging to the same
atom but having slightly different energies so that a redistribution of
energy takes place between them resulting in the formation of new
orbitals of equal energies and identical shapes. The new orbitals thus
formed are known as hybrid orbitals and are more stable.

Method for Finding the Hybridisation

Apply the following formula to find the hybridisation of central atom.
 number of valence electrons of central atom 
1 
Z =  + number of monovalent atoms attached to it 
2 
 + negative charge if any − positive charge if any
Value of Z 2 3 4 5 6 7
Hybridisation sp sp2 sp3 sp3 d sp3 d 2 sp3 d3
Examples
1
Hybridisation of N in NH3 = [5 + 3 + 0 − 0] = 4 ⇒ sp3
2
1
Hybridisation of S in SO2−
4 = [6 + 0 + 2 − 0] = 4 ⇒ sp3
2
Some Common Types of Hybridisation
with Shapes and Examples
Representing directions of
Types of Atomic orbitals
hybrid orbitals formed Examples
hybridisation involved
alongwith bond angles
sp one s + one p 180° BeCl2 , BeH2 , C 2H2

Linear

sp2 one s + two p BF3, BCl 3, C 2H 4 , CO2−

3

120°

Triangular planar
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Chemical Bonding and Molecular Structure 55

Representing directions of
Types of Atomic orbitals
hybrid orbitals formed Examples
hybridisation involved
alongwith bond angles
sp 3 one s + three p CH 4 , CCl 4 , SnCl 4 , NH 4+
109°28′

Tetrahedral
dsp2 one d + one s + 90° XeF 4
two p

Square planar
3
sp d one s + three p PCl 5, PF5
+ one d 90°
120°

Trigonal bipyramidal

sp 3d2 one s + three p 90° SF6, [CrF6] 3–

+ two d

Octahedral

Coordinate or Dative Bond

It is a type of covalent bond in which the electron pair (lone pair) is
donated by one atom but shared by both the atoms so as to complete
their octets, e.g.
•• •• ••
(i) NH3 → BF3 (ii) •• O == O → O ••
donor acceptor ••

Molecular Orbital Theory

According to this theory, the atomic orbitals combine to form the
molecular orbitals. The number of molecular orbitals formed is equal to
the number of atomic orbitals involved. Molecular orbital of lower
energy is known as bonding molecular orbital and that of higher
energy is known as anti-bonding molecular orbital. Aufbau rule,
Pauli’s exclusion principle and Hund’s rule are all applicable for
molecular orbitals.
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56 Handbook of Chemistry

Formation of Molecular Orbtials :

Linear Combination of Atomic Orbitals (LCAO)
1. The molecular orbitals are formed by LCAO (Linear combination
of atomic orbitals) method, i.e. by addition or subtraction of wave
functions of individual atoms, thus
ψ MO = ψ A ± ψ B
ψb = ψA + ψB [constructive interference]
ψa = ψA − ψB [destructive interference]
ψA + ψA
ψA

Addition (Bonding
molecular
Constructive orbital)
ψB interference

(a)
ψA

ψA – ψA
(Antibonding
Subtraction
molecular
Destructive orbital)
interference

ψB

(b)

2. The shape of molecular orbitals is governed by the shape of

atomic orbitals, e.g. s-s and p-p overlapping.
(i) Combination between 1s and 1s atomic orbitals gives σ1s and
*
σ 1 s orbitals.
(Bonding
+ + + molecular
1s 1s σ1s orbitals)
Addition
(Antibonding
+ – + + molecular
1s 1s σ 1s orbitals)
Subtraction
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Chemical Bonding and Molecular Structure 57

(ii) Combination between 2s and 2s orbitals gives σ 2 s and σ* 2 s

orbitals.
(iii) Combination between 2 pz and 2 pz atomic orbitals gives
σ 2 pz and σ * 2 pz orbitals

– + + – – + – (Bonding π-molecular
Addition σ 2pz orbitals)

– + + + – + + (Antibonding
π-molecular
Subtraction σ 2pz orbitals)
(iv) Combination between 2 px and 2 px atomic orbitals gives
π2 px and π * 2 px orbitals.
+ + (Bonding
+
+ π-molecular
– orbitals)
– – π 2px

+ –
+
– (Anti-bonding
+ + π-molecular
–
– + orbitals)
π 2px

2 py atomic orbitals will also overlap in the same way and thus,
resulting molecular orbitals are π2 py and π* 2 py .
If molecular orbital has symmetry with respect to centre, it is called
gerade ( g ) otherwise ungerade (u). All σ bonding and π* anti-bonding
MO are g while all π bonding and σ* anti-bonding MO are u.

Electronic Configuration and Bond Order

(BO) of Molecules
The order of energy of molecular orbitals has been determined
experimentally by spectroscopy for the elements of the second period.
The increasing order of energies of the molecular orbitals in
homonuclear diatomic molecules is

σ1s < σ* 1s < σ 2s < σ* 2s < σ 2 pz < ( π 2 px ≈ π 2 py ) < ( π* 2 px ≈ π* 2 py ) < σ* 2 pz

[For O2 , F2 , Ne2 more than 14 electrons]
σ1s < σ* 1s < σ 2s < σ* 2s < ( π 2 px ≈ π 2 py ) < σ 2 pz < ( π* 2 px ≈ π* 2 py ) < σ* 2 pz
[For B2 , C2 , N 2 upto 14 electrons]
N − N*
Bond order (BO) = b a
2
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58 Handbook of Chemistry

A positive bond order, (i.e. N b > N a* ) means a stable molecule while a

negative (i.e. N b < N a* ) or zero, (i.e. N b = N a* ) bond order means
unstable molecule.

Molecular species having unpaired electrons are paramagnetic, while

if all the electrons in the orbitals are paired then the molecule is
diamagnetic.

Hydrogen Bond
It is defined as the force of attraction existing between hydrogen atom
covalently bonded to highly electronegative atom (N, O or F) and the
electronegative atom belonging to another molecule of the same or
different substance. It is represented by dotted lines. The chains
possess a zig-zag structure.
δ δ
δ F δ δ F δ
H H δ H H δ
F F
Hydrogen bond is purely electrostatic and a weak bond. The strength
of the strongest hydrogen bond is about 5-10 kcal per mol. The more
the electronegativity of atom involved in H-bonding, the more is the
bond strength, e.g.
H- - -F > H- - - O > H- - -N
10 kcal/mol > 7 kcal/mol > 2.0 kcal/mol
Types of hydrogen bonds are:

Intermolecular H-bonding
H-bonding involving two or more different molecules. e.g. o-nitrophenol.

Intramolecular H-bonding
H-bonding within a same molecule. e.g., p-nitrophenol

Applications of Intermolecular H-bonding

(i) Melting point and boiling point of water Water has the
lowest molecular weight among the hydrides of group 16
elements yet it has the highest melting and boiling points. It is
due to intermolecular H-bonding in H 2O.
(ii) Ice has less density than water In crystal structure of ice,
every water molecule is associated with four other water
molecules by H-bonding in a cage like tetrahedral structure. On
melting the ice, H-bonds are broken and space between water
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Chemical Bonding and Molecular Structure 59

molecules decreases and density of water increases up to 4°C.
Above 4°C, more H-bonds are broken, the water molecules get
apart from each other and the density again decreases. Thus,
water has maximum density at 4°C.
(iii) Melting point and boiling point of alcohols The marked
difference between the melting and boiling points of alcohols is
also due to H-bonding.

Applications of Intramolecular H-bonding

Volatile character of nitrophenols o-nitrophenol is more volatile
(b.p. 214°C) as compared to meta (b.p. 290°C) and para (b.p. 279°C). It
is due to chelation (ring like structure).
δ
O
Hδ
Oδ
N

O
In meta and para isomer, chelation is not possible due to the formation
of desired size of ring.

Metallic Bond
The attractive force that binds the metal ions to the mobile electrons is
called metallic bond. The positive metal ions are called positive cores or
kernels and mobile electrons are electron pool or electron gas.
Electron-sea theory of metallic bond explains number of the
properties of the metal.
Strength of bonds
Ionic bond > covalent bond > metallic bond > H-bond