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4. CHEMICAL BONDING AND MOLECULAR STRUCTURE

Chemical bond
The attractive force which holds various constituents (atoms, ions etc.) together in different chemical
species is called a chemical bond.

Valence electrons: In the formation of a molecule only the outer shell electrons take part in chemical
combination and they are known as valence electrons.
Note: The inner shells electrons are well protected and are generally not involved in the combination
process.

Lewis symbols: G.N. Lewis an American chemist introduced simple notations to represent valence
electrons in an atom. These notations are called Lewis symbols.
Ex: Lewis symbols for the elements of second period are

Electrovalent bond: The bond formed as a result of electrostatic attraction between the positive
and negative ions was termed as the electrovalent bond.

Note: The electrovalence is equal to the number of unit charge (s) on the ion.

Ex: Ca2  2F  Ca2(F ) 2

Calcium is assigned a positive electrovalence of two while chlorine a negative electrovalence of one.
1. The formation of NaCl from sodium and chlorine, according to the above scheme can be explained
as
Na  Na  e
[Ne] 3s1 [Ne]
[2,8,1] [2,8]
Cl  e  Cl
[Ne] 3s2 3p5 [Ne] 3s2 3p6 or (Ar)
[2, 8, 7] [2, 8, 8]
i.e. Na  Cl  NaCl or NaCl

2. Formation of CaF2
Ca  Ca2  2e
[Ar] 4s2 [Ar]
 
Fe   F
[He] 2s22p5 [He] 2s22p6 or [Ne]
i.e. Ca2  2F  CaF2 or Ca2(F )2

Factors favouring the formation of ionic or electrovalent bonds

1. Donor atom must be highly electropositive i.e.; it must have low ionization energy so that the
cation is formed easily.
2. Acceptor atom must have large electron affinity so that the anion is formed easily.
3. Difference in the electronegativity between the two atoms must be large.
4. Lattice energy of the compound should be large.
5. Larger cation and smaller anion favour ionic bond formation.
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Octet rule
Kossel and Lewis in 1916 developed an important theory of chemical combination between atoms
known as electronic theory of chemical bonding.
According to this theory 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 (Lewis-Langmuir concept)

The bond formed by mutual sharing of one or more electron pairs between the participating atoms is
called covalent bond. The compound thus formed are called covalent compounds.
A covalent bond is represented by writing a continuous line between the two atoms.
Ex.: Hydrogen molecule

Or H—H
Lewis dot structure and formation of covalent bond
The dots represent electrons. Such structures are referred as Lewis dot structures.
The Lewis dot structures can be written for the molecules in which the combining atoms may be
identical or different.

The important condition of Lewis dot structures is

1. Each covalent bond is formed as a result of sharing of an electron pair between the atoms.
2. Each combining atom contributes at least one electron to the shared pair.
3. The combining atoms attain the outer-shell noble gas configuration as a result of the sharing of
electrons.
Ex: 1) When two atoms share one electron pair they are said to be joined by a single covalent bond.

a)

8e- 8e-
Or Cl — Cl

b) c)

H atoms attain a duplet

of electrons and O Each of the four Cl atoms
attains the octet. along with the C atom
attains octet of electrons.
2. If two atoms share two pairs of electrons the covalent bond between them is called a double bond.
Ex: a) CO2

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b) C2H4 molecule

3. When combining atoms share three electron pairs a triple bond is formed.

Lewis representation of simple molecules (The Lewis structures)

The Lewis dot structures provide a picture of bonding in molecules and ions in terms of the shared
pairs of electrons and the octet rule.

The Lewis representation of some molecules

Molecule/ion Lewis dot structure Lewis
representation
H2 H: H [duplet of
H—H
electrons]
O2

O3

NF3

CO2
3

HNO3

Problems
1. Write the Lewis dot structure of CO
Step 1: The total valence electrons available are 4+6 = 10
Step 2: The skeletal structure of CO is written as C O
Step 3: Draw a single bond between C and O and complete the octet on O, the
remaining two electrons are the lone pair of C.

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This does not complete the octet on carbon and hence we have to resort to multiple bonding between
C and O. This satisfies the octet rule condition for both atoms.

2. Write the Lewis structure of the nitrite ion NO-2

Step 1: Count the total number of valence electron of nitrogen and oxygen atom and the
additional one negative charge.
N(2s , 2p ), O(2s22p4 )
2 3

 5  (2  6)  1  18 electrons
Step 2: The skeletal structure of NO-2 is written as O N O
Step 3: Draw a single bond between the nitrogen and each of the oxygen atoms
completing the octet on oxygen atoms. This however does not complete the octet
on nitrogen, if the remaining two electrons constitute lone pair on it.

Hence, we have to resort to multiple bonding between nitrogen and one of the oxygen atoms. This
leads to the following Lewis dot structures.

3. NH 4
+

Step 1: Total valence electrons = 5 + 4 – 1 = 8

Step 2: Skeletal structure:

Step 3: Shared electrons and Lewis structure

4. HCN
Total no. of valence electrons: 1 + 4 + 5 = 10
Skeletal structure H C N
Lewis structure H: C : : : N : H—CN:
Shared & unshared Lewis structure
electrons
2-
5. SO4
Total number of valence electrons: 6 + 4 (6) + 2 = 32

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Skeletal structure

Lewis structure

6. ClO 4
-

Total valence electrons 7 + 4(6) + 1 = 32

Skeletal structure :

Lewis structure :

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.
i.e.
Formal charge  total number of   total number of    1  total number of 
 on an atom in a   valence electrons   non-bonding  2  bonding (shared) 
Lewis structure  in the free atom  (lone pair) electrons    
electrons
OR
1
FC  V  L  (S)
2
1. Write the formal charges on atoms in ozone molecule.
The Lewis structure of O3 may be drawn as

The atoms have been numbered as 1, 2 & 3.

1
a) The formal charge on the central 'O' atom marked 1  6  2  (6)  1
2
1
b) The formal charge on the end 'O' atom marked 2  6  4  (4)  0
2
c) The end 'O' atom marked 3  6  6  1 (2)  1
2
Hence, we represent O3 along with the formal charges as

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1. Write the formal charges on atoms in carbonate ion.

Lewis structure of CO23 ion is

Formal charge on ‘C’ atom = V  L  1 (S)  4  0  1 (8)  0

2 2
1
Formal chare on single bonded ‘O’ atoms = 6  6  (2)  1
2
Formal charge on double bonded ‘O’ atom = 6  4  1 (4)  0
2

Limitations of octet rule

1. Formation of compounds with electron deficient atoms or incomplete octate of the central atom
In some compounds the number of electrons surrounding the central atom is less than eight. This is
especially the case with elements having less than 4 valence electrons.

2. Formation of odd-electron molecules

In molecules with an odd number of electrons like nitric oxide (NO) and nitrogen dioxide (NO2), the
octet rule is not satisfied for all the atoms.

3. Formation of super octet (expanded octet) molecules

Violation of octet rule is also observed in case of compounds like PF5, SF6 and IF7 where the central
atoms have more than eight electrons in their valence shell.

10 electrons around the P atom.

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4. The octet rule is based on the chemical inertness of noble gases. However, some noble gases
also combine with oxygen and fluorine to form a number of compounds like XeF2, KrF2, XeOF2
etc.
5. This theory does not account for the shape of molecules.
6. It does not explain the relative stability of the molecules, being totally silent about the energy
of a molecule.

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 and vice versa.
Ex.: NaCl  Na  Cl :  H  788 kJ mol 1
(s) (g) (g) lattice

Bond parameters
1. Bond length: Bond length is defined as the equilibrium distance between the nuclei of two bonded
atoms in a molecule.
2. Bond angle: It is defined as the angle between the orbitals containing bonding electron pairs
around the central atom in a molecule/complex ion.
The bond angle is expressed in degrees or minutes or seconds.
It gives some idea regarding the distribution of orbitals around the central atom in a molecule or
complex ion and it helps us in determining its shape.

Ex: H — O — H bond angle in H2O can be represented as

Bond order
The number of bonds present between two atoms in a molecule is known as bond order.
Ex: The bond order of H2, O2 and N2 is 1, 2, 3 respectively.
Note: With increase in bond order, bond enthalpy increases and bond length decreases and the
molecule becomes more stable.
Isoelectronic molecules and ions have identical bond
+
orders.
Ex: F and O2 have bond order 1. N , CO and NO have bond order 3.
2 2 2

Resonance structure
1. Resonance structure of O3 molecule

2. Resonance structure of CO2-

3
ion.

I, II & III represent the three canonical forms.

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3. Resonance structure of CO2 molecule

Note: Resonance stabilizes the molecules 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.

Covalent character of an ionic bond (Fajan’s rules)

Covalent character of an ionic bond depends on polarizing power of a cation and the polarizability of
an anion. Greater the polarizing power and high polarizability favours the covalency in ionic bond.

According to Fajan’s rules

1. Smaller the cation favours covalency.
Ex: Among LiCl and KCl, LiCl is covalent while KCl is ionic.
2. Larger the anion favours covalency.
Ex: Among the lithium halides the order of covalent character is LiF < LiCl < LiBi < LiI.
3. Larger charge on either ion or both the ions favour covalency.
Ex: NaCl (ionic) < MgCl2 < AlCl3 (covalent)
4. Covalency is favoured if the cation does not have noble gas configuration.
+ +
Ex: Among CuCl and NaCl, Cu ion has greater polarizing power than Na . Hence CuCl has
covalent character while NaCl has ionic character.

Dipole moment
Molecules of the type X-Y having two polar ends with partial positive and negative charges are
called dipoles or polar molecules. The degree of polarity is measured in terms of its dipole moment
().
Dipole moment is defined as the product of net positive (or negative) charge and the distance
between the two charged ends.
Dipole moment () = (charge on the polar ends) x (distance between the ends)
=xl
The unit of dipole moment is debye (D). The SI unit of dipole moment is coulomb metre.
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1 D = 3.355 x 10 Cm
Dipole moment is represented by an arrow (with + on the tail) drawn above the molecule pointing
towards the negative end.

For homodiatomic molecules like H2, Cl2, N2, etc.,  = 0. They are non-polar.
Heterodiatomic molecules like HF, HCl, HBr, etc., have a finite dipole moment.
HF HCl HBr HI
1.91D 1.08D 0.80D 0.42D

The decrease in the dipole moment from HF to HI is due to decrease in electronegativities of the
halogen atoms from F to I.
 is a vector quantity and has both magnitude and direction. Hence, in polyatomic molecules
with two or more polar bonds. The overall dipole moment is the vector sum of the dipole moments of
the constituent bonds. In such cases, dipole moment depends on bond moments and also on the
geometry of molecules.

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Dipole moment of CO2

CO2 molecule is linear and the bonds are identical. Hence, the two bond dipoles act in opposite
directions and cancel each other. Therefore, the net dipole moment of the molecule is zero.
Although the molecule has polar covalent bonds, the net dipole moment is zero and hence, it is
regarded as non-polar molecule.

Dipole moment of H2O

H2O molecule has bent structure. Hence, individual bond
moments do not cancel each other. Such molecules (with
distorted structure) possess a finite value of dipole moment which
depends upon the magnitude of the bond moments (or bond
dipoles) and the bond angle.

Dipole moment of BF3

The dipole moment of BF3 is zero indicating the
symmetrical (planar triangle) structure. In BF3, each B–F
bond has a bond dipole. The resultant of any two B–F
bond dipoles neutralizes the third B–F bond dipole
leading to the zero value of the net dipole moment.

Dipole moment of NH3

A definite value of dipole moment of NH3 suggests that its structure is non-planar.
NH3 is found to have pyramidal structure. In this geometry, the resultant of two
bond dipoles do not cancel the third bond dipole. Moreover, the lone pair of electrons also have a
dipole. Hence, the net dipole moment of NH3 molecule is the resultant of the bond moments of the
three N–H bonds and due to the lone pair.

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
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resultant dipole moment of NH3 (4.90 x 10 C m) is
greater than that of NF3. In NH3, 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:

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Applications of dipole moment

Measurement of dipole moment is helpful in predicting the geometry of the molecule.
1. Zero dipole moment of CO2 indicates linear structure.
2. Zero dipole moments for BF3, C6H6 and CH4 account for their symmetric structure.
3. Finite values of dipole moments for H2O and SO2 rule out the possibility of linear structure.
4. It is helpful in predicting ionic character of a molecule.
5. It helps to distinguish between polar and non-polar molecules.

The valence shell electron pair repulsion (VSEPR) theory

Postulates of VSEPR theory
1. The geometry and shape of the molecule depend upon the number of electron pairs (bonded
as well as non-bonded) in the valence shell of the central atom.
2. Pairs of electrons in the valence shell repel one another since their electron clouds are
negatively charged.
3. In order to minimize repulsion, these electron pairs tend to occupy such positions in space
where the distance between them is maximum.
4. The valence shell is taken as a sphere with the electron pairs localizing on the spherical
surface at maximum distance from one another.
5. A multiple bond is treated as a single electron pair and the two or three electron pairs of a
multiple bond are treated as a single super pair.

Ex:

6. 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 decreases in the order.

Lone pair (lp) – lone pair (lp) > lone pair (lp) – bond pair (bp) > bond pair (bp) – bond pair (bp)

Total Bond Lone

number pairs pairs
Geometry of the Geometry (shape)
of examples
electron pairs (Molecular of the molecule
electron
formula)
pairs
2 0
2
(AB2)

3 0

3
(AB3)

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2 1

(AB2L)

4 0

4
(AB4)

3 1

(AB3L)

2 2

(AB2L2)

5 0

(AB5)

4 1

(AB4L)

3 2

(AB3L2)

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2 3 XeF2
(I, Br, ICl )
3 3 2
(AB2L3)

6 0
6 SF6

(AB6)
Octahedral

5 1
ClF5

(AB5L)

(AB4L2) XeF4

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Valence Bond Theory (VBT)

According to Valence Bond Theory
1. A covalent bond is formed due to the overlapping of atomic orbitals of the two combining
atoms each of them containing one unpaired electron.
2. The new orbital formed due to the overlapping of the two atomic orbitals is called a bond
orbital which will be common to both the atoms.
3. The strength of the bond depends on the extent of overlapping of the atomic orbitals. Greater
the degree of overlapping, stronger will be the bond formed.
4. The two electrons involved in bond formation must have opposite spins.
5. Covalent bond is directional in nature and lies in the direction of the maximum overlapping
of atomic orbitals.
Depending upon the manner in which overlapping takes place, covalent bonds are of two types
namely,
a)  - covalent bond or  - bond
b)  - covalent bond or  - bond

Overlapping of atomic orbitals

When two atoms approach each other to form a bond, due to their atomic orbitals overlap. The
overlap between the atomic orbitals can be positive, negative or zero depending upon the
characteristics of the orbitals participating in overlap.
1. Positive overlap: It involves the overlap of the lobes of same signs. It leads to attractive
interaction.
2. Negative overlap: It involves the overlap of the lobes of opposite signs. It leads to repulsive
interactions.
3. Zero overlap: This arises out of phase due to direction of approach.

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Types of overlapping and nature of covalent bonds

The covalent bond may be classified into two types depending upon the types of overlapping.
1) Sigma () bond 2) Pi () bond

1. Sigma () bond: This type of covalent bond is formed by the end to end (head-on) overlap of
bonding orbitals along the inter-nuclear axis. This is called as head-on overlap or axial overlap.
The sigma bond is formed by any one of the following types of combination of atomic orbitals.
a) s-s overlapping: In this case there is overlap of two half-filled s-orbitals along the inter-nuclear
axis.
Ex: formation of H2

b) s-p overlapping: This type of overlap occurs between half-filled s-orbitals of one atom and half-
filled p-orbitals of another atom.
Ex: formation of HF molecule.

c) p-p overlapping: This type of overlap takes place between half-filled

p-orbitals of the two approaching atoms.
Ex: formation of F2 molecule

2. Pi () bond: A covalent bond formed by overlapping of two half-filled p-atomic orbitals sideways
(laterally) is called a -bond.

In the formation of  bond the atomic orbitals overlap in such a way that their axis remains parallel to
each other and perpendicular to the inter-nuclear axis.
Ex: Formation of O2 molecule

Strength of Sigma and Pi bond

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.

Differences between  &  bonds

 bond  bond
1. -bond is formed by the axial overlap of -bond is formed by the lateral
s-s or p-p or s-p orbitals of two atoms. (sideways) overlap of p-p orbitals.
2. -bond is stronger due to greater -bond is weaker due to relatively
overlapping of atomic orbitals less overlapping of atomic orbitals.
3. There can be only one -bond between There can be one or two -
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two atoms bonds between two atoms

4. The -bond can be formed with -
The -bond can be formed alone.
bond.
5. The free rotation of the atoms around - Free rotation of the atoms around
bond is possible. -bond is not possible.

Hybridization
The process of intermixing of the orbitals of slightly different energies so as to de-
distribute their energies resulting in the formation of new set of orbitals of equivalent energies and
shape is called hybridization.
The atomic orbitals combine to form new set of equivalent orbitals known as hybrid orbitals; the
hybrid orbitals are used in bond formation.

Important conditions for hybridization

1. The orbitals present in the valence shell of the atom are hybridized.
2. The orbitals undergoing hybridization should have almost equal energy.
3. Promotion of electron is not essential condition prior to hybridization.
4. It is not necessary that only half-filled orbitals participate in hybridization. In some cases,
even filled orbitals of valence shell take part in hybridization.

Salient features of hybridization

1. The number of hybrid orbitals is equal to the number of the atomic orbitals that get
hybridized.
2. The hybridized orbitals are always equivalent in energy and shape.
3. The hybrid orbitals are more effective in forming stable bonds than the pure atomic orbitals.
4. 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
hybridization indicates the geometry of the molecules.

sp3 Hybridization
3
Mixing of one s-orbital and three p-orbitals of an atom to form four identical orbitals is called sp
3
hybridization. The new orbitals formed are called sp hybrid orbitals. They are directed in space
o
towards the four corners of a regular tetrahedron making an angle of 109 28'.
Formation of methane
1s2 2s2 2p2

6C: Carbon ground state:

C*: Carbon excited state:

Undergo hybridation
After Hybridization:
Four sp3 hybrid orbitals
3
The 2s orbital and three 2p orbitals combine to form four sp hybrid orbitals which are oriented
3
towards the corners of a tetrahedron. Each sp hybrid orbital has one electron. These hybrid orbitals
overlap with 1s orbitals of four H-atoms.

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3
Due to sp hybridization, CH 4 molecule has tetrahedral structure with
HĈH = 109o28'.

sp3 hybridization in H2O

Electronic configuration of O is

3
The four oxygen orbitals [one 2s and three 2p] undergo sp
3
hybridization forming four sp hybrid orbitals. Out of which two
contain a pair of electrons and two contains one electron each.
3
These four sp hybrid orbitals acquire a tetrahedral geometry.
Due to the lp-lp repulsion the bond angle in this case is reduced to
o o
104.5 from 109 .28' and the molecule thus acquires a V-shape or
angular geometry.

sp3 hybridization in NH3

Electronic configuration of N is

Out of the four sp3 hybrid orbitals one hybrid orbital

contain lone pair of electrons and 3 hybrid orbitals contains
unpaired electrons. These 3 hybrid orbitals contain one
electron each overlap with 1s orbitals of hydrogen atoms to
form three N-H sigma bonds due to the presence of a lone
pair of electrons the molecule gets distorted and the bond
o o
angle is reduced to 107 from 109 .28'. The geometry of
such a molecule will be trigonal pyramidal.

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sp2 Hybridization
2
Mixing of one s-orbital and two p-orbitals of an atom to form three identical sp hybrid orbitals is
called sp2-hybridization.
All the three hybrid orbitals are in the same plane and are directed towards the three corners of an
o
equilateral triangle with the bond angle 120 . The unhybridized p z orbital lies perpendicular to the
2
plane of sp hybrid orbitals.
Example: Formation of BCl3 molecule

5B: Boron in ground state:

B*: Boron in excited state:

After Hybridization:

three sp2 hybrid orbitals

2
The 2s orbital and two 2p orbitals combine to form three sp hybrid orbitals. These hybrid orbitals are
2
oriented towards the corners of an equilateral triangle. Each sp hybrid orbital has one unpaired
electron. These hybrid orbitals form three B-Cl -bonds by overlapping with 2p orbitals of three Cl-
atoms.

2
Due to sp hybridization, BCl 3 molecule has trigonal planar structure with ClB̂Cl = 1200 .

Formation of C2H4 molecule

6C: Carbon in ground state:

C*: Carbon in excited state:

After Hybridization: pz orbital is unhybridized

three sp2 hybrid orbitals

2 2
The 2s orbital and two 2p orbitals combine to form three sp hybrid orbitals. After sp hybridization,
2 o
each C-atom has three sp hybrid orbitals oriented at an angle of 120 in the same plane and one
unhybridized pz orbital which remains perpendicular to the plane of the hybrid orbitals.

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2 2
A sp hybrid orbital of one C-atom overlaps with a sp hybrid orbital of the other carbon atom to
form C-C  bonds. After forming -bonds, each C-atom is left with one unhybridized pz orbital.
Sideways overlapping of pz orbitals takes place to form a -bond.

2
Due to sp hybridization, Ethene has trigonal planar structure. -electron density lies above and
below the plane.

sp hybridization
Mixing of one s-orbital and one p-orbital of an atom to form two sp hybrid orbitals is called sp
o
hybridization. The two sp hybrid orbitals are directed linearly with an angle of 180 . Hence, the
molecule with sp hybridization will have linear structure.
The other two unhybridized p-orbitals lie mutually perpendicular to each other.

Formation of BeCl2 molecule

2 2
In BeCl2, central atom is Be (Z=4, 1s , 2s ). It has two electrons in the valence shell.

Be: Beryllium in ground state:

Be*: Beryllium in excited state:

sp-hybrid orbitals
After Hybridization:

BeCl2 molecule:
two sp hybrid orbitals overlapped
with two 3pz orbitals of Chlorine
One of the 2s orbital electron is shifted to vacant 2p x orbital. Half-filled 2s and 2px orbitals mix
together to give two sp hybrid orbitals containing one electron each. The half-filled 3pz orbital of the
two chlorine atoms overlap with the two sp hybrid orbitals to form two Be—Cl sigma bonds. The
molecule is linear with
o
Cl—Be—Cl bond angle 180 .

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Formation of C2H2 molecule

6C: Carbon in ground state:

C*: Carbon in excited state:

py and pz orbital is unhybridized
After Hybridization:
two sp hybrid orbitals
The 2s-orbital and one 2p-orbital combine to give two sp hybrid orbitals with linear orientation
o
(180 ). After sp hybridization, each C-atom has two sp hybrid orbitals and two mutually
perpendicular unhybridized p-orbitals.
sp hybrid orbital of one C-atom overlaps with a sp hybrid orbital of the other carbon atom to form C-C
 bond. The remaining sp hybrid orbital of each C-atom overlaps with s-orbital of H-atom to form C-H
-bond. After forming -bonds, each C-atom is left with two unhybridized p-orbitals which are at right
angles to one another. The unhybridized p-orbitals overlap laterally (sideways) to form two -bonds.

Due to sp hybridization, acetylene has linear structure.

sp3d hybridization
Overlapping of one s, three p and one d orbital to give five sp3d hybridized orbitals is called sp3d
hybridization.
3
The set of 5 sp d hybrid orbitals which are directed towards the five corners of a trigonal
bipyramidal.
3
All the bond angles in trigonal bipyramidal geometry are not equivalent. In PCl5 the five sp d orbitals
of phosphorus overlap with the singly occupied p orbitals of chlorine atoms to form five P-Cl sigma
o
bonds. Three P-Cl bond lie in one plane and make an angle of 120 with each other, these bonds are
turned as equatorial bonds. The remaining two P-Cl bonds one lying above and the other lying below
o
the equatorial plane, make an angle of 90 with the plane. These bonds are called axial bonds.
Example: Formation of PCl5 molecule

15P Phosphorus in ground state:

*P: Phosphorus in excited state:

sp3d hybridization
After hybridization: sp3d hybrid orbitals
PCl5 molecule:

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five sp3d hybrid orbitals overlapped with five 3pz

orbitals of chlorine

Shape: Trigonal bipyramidal 



o
Bond angles : Axial bond angle: 90
o
Equatorial bond angle: 120
Bond length : axial bond length is longer than equatorial bond length. They are two in number.
Equatorial bond is identical and they are 3 in number.

sp3d2 hybridization
Example: Formation of SF6

16S Sulphur in ground state [Ne]3s23p4:

*S: Sulphur in excited state:

After hybridization: 6sp3d2 hybridization

SF6 molecule: six sp3d2 hybrid orbitals overlapped
with six 2p1z orbitals of F
3 2
The six sp d hybrid orbitals overlap with singly occupied 2p1z orbitals of F to form stable SF6
molecule.
Shape: Regular octahedron
o
Bond angle: All bond angle is equal to 90
Bond length: All bonds are of equal length

Molecular orbital theory

This theory was developed by F. Hund and R.S. Mulliken in 1932. The salient features of this theory
are;
1. The electrons in a molecule are present in the various molecular orbitals as the electrons of
atoms are present in the various atomic orbitals.

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2. The atomic orbitals of comparable energies and proper symmetry combine to form a
molecular orbital.
3. While an electron in an atomic orbital is influenced by one nucleus, in a molecular orbital it
is influenced by two or more nuclei depending upon the number of atoms in the molecule.
Thus, an atomic orbital is monocentric while a molecular orbital is polycentric.
4. The number of molecular orbitals formed is equal to the number of combining atomic
orbitals. When two atomic orbitals combine two molecular orbitals are formed. One is known
as bonding molecular orbital while other is called anti-bonding molecular orbital.
5. The bonding molecular orbital has lower energy and hence greater stability than the
corresponding antibonding molecular orbital.
6. The molecular orbitals are filled in accordance with the Aufbau principle, obeying the
Pauli's exclusion principle and the Hund's rule.

Difference between atomic and molecular orbitals

Atomic orbitals Molecular orbitals
Atomic orbitals are mono centric Molecular orbitals are polycentric
They are less stable They are more stable
Shapes of atomic orbitals are simple Shapes of molecular orbitals are complex
Different atomic orbitals are represented as s, Different molecular orbitals are designated as:
p, d and f orbitals (i) Sigma bonding and antibonding
molecular orbitals are represented as 
and * respectively.
(ii) Pi bonding and antibonding molecular
orbitals are represented as  and *
respectively.

Formation of molecular orbitals by linear combination of atomic orbitals (LCAO)

According to wave mechanics, atomic orbitals are considered
as electron waves and are represented by the wave function
.
Molecular orbitals are formed by the linear combination of
atomic orbitals in two ways. Molecular orbitals are formed
by the addition of wave function of atomic orbitals
(symmetric combination) as well by the subtraction
(asymmetric combination) of wave function of atomic
orbitals.
Mathematically, combination of two atomic orbitals
A and B is represented as
MO = A  B
= A + B
* = A - B
Molecular orbitals formed by the addition of wave functions
of atomic orbitals are known as bonding molecular orbitals
( or b) and the molecular orbitals formed by the subtraction of wave
function of atomic orbitals is known as antibonding molecular orbitals (* or a).
Differences between bonding and anti-bonding molecular orbitals
Bonding molecular orbitals Antibonding molecular orbitals
These are formed by the addition of wave These are formed by the subtraction of wave
functions of atomic orbitals (symmetric function of atomic orbitals (asymmetric
combination) combination)

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Energy of bonding molecular orbitals is less Energy of antibonding molecular orbitals is

than corresponding atomic orbitals more than the corresponding atomic orbitals.
Electrons in the bonding molecular orbitals Electrons in the antibonding molecular
contribute to bond formation. orbitals do not contribute to bond formation.
They are represented as ,  They are represented as * and *

Conditions for the formation of molecular orbitals

1. Combining atomic orbitals must have comparable energy.
This means that 1s orbital can combine with another 1s orbital but not with 2s orbital. This is because
1s orbital has less energy than 2s orbital.
2. Combining atomic orbitals must have the same symmetry around the molecular axis.
This means that 2px orbital of one atom can combine with 2px orbital of another atom but 2px cannot
combine with 2py or 2pz because of their different symmetries.
3. Atomic orbitals must overlap to the maximum extent.
Greater the extent of overlap, the greater will be the electron density between the nuclei of a
molecular orbital.

Types of molecular orbitals

1.  molecular orbitals: Molecular orbitals formed by the addition of wave functions of atomic
orbitals along the molecular axis are called sigma bonding molecular orbitals (). Molecular orbitals
formed by the subtraction of the wave functions atomic orbitals along the molecular axis are sigma
antibonding molecular orbitals (*).
2.  molecular orbitals: Molecular orbitals formed by the lateral overlap of atomic orbitals are pi
() molecular orbitals. Addition of the wave functions of atomic orbitals laterally result in pi bonding
molecular orbitals () and subtraction of the wave functions of atomic orbitals laterally results in pi
antibonding molecular orbitals (*).

Differences between  and  molecular orbitals

 molecular orbital  molecular orbital
These are formed by the overlap of atomic These are formed by the lateral overlap of
orbitals along the intermolecular axis. atomic orbitals
Overlapping of atomic orbitals in maximum. Overlap of atomic orbital is partial.

Energy level of molecular orbital 

Order of increasing energy of molecular Order of increasing energy of molecular

orbitals in O2, F2, molecules orbitals in H2, He2, Li2, Be2, B2, C2 & N 2,
  *    *    [  ]  molecules
1s 1s 2s 2s 2pz 2px 2py   *    *  [   ]   
[*  * ] * 1s 1s 2s 2s 2px 2py 2pz
2p x 2py 2pz
[*2px  *2py ]  *2p z
Significance of molecular orbital theory
Based on the electronic configuration of a molecule, it is possible to predict the following parameters
about a molecule.
(i) Bond order: It is one half of the difference in the number of electrons in bonding orbitals (Nb)
and the antibonding orbitals (Na).
1
Bond order = (N b  Na )
2
i.e., a) The molecule is stable if Nb is greater than Na and
b) The molecule is unstable if Nb is less than Na.
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(ii) Stability of a molecule: If number of electrons in bonding molecular orbital is greater than the
number of electrons in antibonding molecular orbitals, then the molecule is stable.
(iii) Nature of bond and bond length: The bond length decreases with increase in the number of
bonds between two atoms.
iv) Magnetic property of the molecule: If there are unpaired electrons in the molecule, then, it is
paramagnetic. If all the electrons are paired, then, the molecule is diamagnetic.

Bonding in some homonuclear diatomic molecules

The bond order, stability and magnetic character of molecules of first and second period elements in
the periodic table can be determined from the electronic configuration and molecular orbital energy
level diagrams.

(i) Hydrogen molecule (H2)

Atomic number of H = 1
Total number of electrons in the H2 molecule
1 + 1 = 2,
Electronic configuration: 1s2 , 1s* 0 .
1 1
Bond order = (N  N )  (2  0)  1
b a
2 2
There is a single bond between two hydrogen
atoms in the hydrogen molecule.
Molecule is stable and is diamagnetic since the
electrons are paired.

(ii) On the basics of the MOT show that He2

Molecule not stable or He2 molecule does
not exist.
Atomic number of He = 2
Total number electrons in
He2 = 2 + 2 = 4
Electronic configuration, 1s2 , 1s2
*

1 1
Bond order = (N b  Na )  (2  2)  0
2 2
He2 molecule does not exist since bond order is zero.
He is diamagnetic since all the electrons are paired.

(iii) Lithium molecule ( Li2 )

2 1
The electronic configuration of lithium is 1s , 2s . There are six electrons in Li 2. The electronic
configuration of Li2 molecule, therefore, is
Li : ( )2 ( * )2 ( )2
2 1s 1s 2s

The above configuration is also written as KK( 2s )2 where KK represents the closed K shell
structure( 1s)2 ( *1s)2 .
From the electronic configuration of Li2 molecule, it is clear that there are four electrons present in
bonding molecular orbitals and two electrons present in antibonding molecular orbitals. Its bond
order, therefore, is ½ (4-2) = 1. It means that Li2 molecule is stable and since it has no unpaired

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electrons it should diamagnetic. Indeed, diamagnetic Li2 molecules are known to exist in the vapour
phase.

(iv) Carbon molecule (C2)

2 2 2
The electronic configuration of carbon is 1s 2s 2p . There are twelve electrons in C 2. The electronic
configuration of C2 molecule, therefore, is
C : ( )2 ( * )2 ( )2 ( * )2 (π2p2  π2p2 )
2 1s 1s 2s 2s x y
or KK( )2 ( * )2 (π2p2  π2p2 )
2s 2s x y
1
The bond order of C2 is  (8  4)  2 and C2 should be diamagnetic. Diamagnetic C2
2
molecules have indeed been detected in vapour phase. It is important to note that both the bonds of
double bond in C2 are pi bonds because of the presence of four electrons in two pi molecular
orbitals. In most of the other molecules, a double bond is made up of a sigma bond and a
pi bond. In a similar fashion, the bonding in N2 molecule is discussed.
The molecular orbital configuration, the bond order and magnetic character of Li2 , Be2 , B2
and C2 are as indicated in the following table:
Bond order
Molecular orbital 1
Molecule = (N - N ) Magnetic character
configuration b a
2
KK(2s ) 2
Li2 1 Diamagnetic
Be2 KK( ) ( )
2 * 2
Zero Be2 does not exist
2s 2s

B2 KK( 2s )2 ( 2s
* )2 (π )1  (π )1 1 paramagnetic
2p2x 2py2

C2 KK( )2 ( * )2 (π )2  (π )2 2 Diamagnetic
2s 2s 2p x 2py

In the above molecular orbital configuration, KK represents the bonding and antibonding molecular
orbitals formed by the combination of 1s atomic orbitals.

Nitrogen molecule
Number of electrons in nitrogen atom = 7
Number of electrons in nitrogen molecule = 7 + 7 = 14
Electron configuration of nitrogen molecule is ( )2 ( * )2 ( )2 ( * )2 [(π2  π2 )] ( )2
1s 1s 2s 2s
  2p x 2pz 2 2
2py

Or KK (2s ) (2s ) [(π 2p  π 2p )] (2pz )

2 * 2 2 2
2
2
2
x y

1
Bond order = (N b  Na )
2
1
 (10  4)  3
2
The molecule is highly stable as bond order is 3 and the two nitrogen atoms are held by triple bond,
one sigma bond and two pi bonds. All the electrons are paired in the molecule and it is diamagnetic.
(v) Oxygen molecule
Number of electrons in oxygen atom (O) = 8
Number of electrons in oxygen molecule ( O2 ) = 8 + 8 = 16
Electronic configuration of oxygen molecule is:
( )2 ( * )2 ( )2 ( * )2 ( )2 [(π2p2  π2p2 )] (π* 2p1  π* 2p1 )
1s 1s 2s 2s 2pz x y x y

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Or KK ( )2 ( * )2 ( )2 [(π2p2  π2p2 ) ] (π* 2p1  π* 2p1 )

2s 2s 2pz x y x y
1 1
Bond order = (N  N )  (10  6)  2
b a
2 2
The molecule is stable as bond order is two and the two oxygen atoms are held by a double
bond, one sigma bond and one pi bond. Since there are two unpaired electrons, the molecule is
paramagnetic.

H-bond: 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.

Cause of formation of H-bond

When highly electronegative elements attached to a H-atom to form covalent bond, the e- of the
covalent bond are shifted towards the more electronegative atom. This partially positively
charged H-atom forms a bond with other more electronegative atom.
H-atom acts as a bridge between the two highly electronegative atoms.

Types of hydrogen bonding

There are two types of hydrogen bonding. They are:
(i) Intermolecular hydrogen bonding
(ii) Intramolecular hydrogen bonding

Intermolecular hydrogen bonding

If hydrogen bonding exists between two molecules of the same or different substances, then it is
called intermolecular hydrogen bonding.
Examples: Hydrogen fluoride
In water molecule, the central oxygen atom is covalently bonded to two hydrogen atoms and then to
two more hydrogen atoms of neighbouring molecules through hydrogen bonds.

Due to intermolecular hydrogen bonding, the association of molecules takes place. Energy is required
to separate the molecules. Therefore, compounds with intermolecular hydrogen bonding have high
boiling points.

Intramolecular hydrogen bonding

If hydrogen bonding exists within the molecule, then, it is called intramolecular hydrogen bonding.

Intramolecular hydrogen bonding decreases the possibility of association of the molecules to a large
extent. Therefore, compounds with intramolecular hydrogen bonding have low boiling points.

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