Page 1
Scientists are constantly discovering new compounds,
orderly arranging the facts about them, trying to explain
with the existing knowledge, organising to modify the
earlier views or evolve theories for explaining the newly
observed facts.
Unit 4
After studying this Unit, you will be
able to
• unde r s t a nd Kös s e l - Le w i s
approach to chemical bonding;
• e x pl a i n t he oc t e t r ul e and i t s
limitations, draw Lewis structures
of simple molecules;
• explain the formation of different
types of bonds;
• describe the VSEPR theory and
predict the geometry of simple
molecules;
• explain the valence bond
approach for the formation of
covalent bonds;
• predict the directional properties
of covalent bonds;
• explain the different types of
hybridisation involving s, p and
d orbitals and draw shapes of
simple covalent molecules;
• describe the molecular orbital
theory of homonuclear diatomic
molecules;
• explain the concept of hydrogen
bond.
CHEMiCAL BOnDinG AnD
MOLECULAR St RUCt URE
Matter is made up of one or different type of elements.
Under normal conditions no other element exists as an
independent atom in nature, except noble gases. However,
a group of atoms is found to exist together as one species
having characteristic properties. Such a group of atoms
is called a molecule. Obviously there must be some force
which holds these constituent atoms together in the
molecules. the attractive force which holds various
constituents (atoms, ions, etc.) together in different
chemical species is called a chemical bond. Since the
formation of chemical compounds takes place as a result of
combi nat i on of at om s of var i ous el em ent s i n di f f er ent w ays,
it raises many questions. Why do atoms combine? Why are
only certain combinations possible? Why do some atoms
combine while certain others do not? Why do molecules
possess definite shapes? To answer such questions different
theories and concepts have been put forward from time
to time. These are Kössel-Lewis approach, Valence Shell
Electron Pair R epulsion (VSEPR ) Theory, Valence Bond (V B)
Theory and Molecular Orbital (MO) Theory. The evolution
of various theories of valence and the interpretation of
the nature of chemical bonds have closely been related to
the developments in the understanding of the structure
of atom, the electronic configuration of elements and the
periodic table. Every system tends to be more stable and
bonding is nature’s way of lowering the energy of the system
to attain stability.
Unit 4.indd 100 9/12/2022 9:36:09 AM
2024-25
Page 2
Scientists are constantly discovering new compounds,
orderly arranging the facts about them, trying to explain
with the existing knowledge, organising to modify the
earlier views or evolve theories for explaining the newly
observed facts.
Unit 4
After studying this Unit, you will be
able to
• unde r s t a nd Kös s e l - Le w i s
approach to chemical bonding;
• e x pl a i n t he oc t e t r ul e and i t s
limitations, draw Lewis structures
of simple molecules;
• explain the formation of different
types of bonds;
• describe the VSEPR theory and
predict the geometry of simple
molecules;
• explain the valence bond
approach for the formation of
covalent bonds;
• predict the directional properties
of covalent bonds;
• explain the different types of
hybridisation involving s, p and
d orbitals and draw shapes of
simple covalent molecules;
• describe the molecular orbital
theory of homonuclear diatomic
molecules;
• explain the concept of hydrogen
bond.
CHEMiCAL BOnDinG AnD
MOLECULAR St RUCt URE
Matter is made up of one or different type of elements.
Under normal conditions no other element exists as an
independent atom in nature, except noble gases. However,
a group of atoms is found to exist together as one species
having characteristic properties. Such a group of atoms
is called a molecule. Obviously there must be some force
which holds these constituent atoms together in the
molecules. the attractive force which holds various
constituents (atoms, ions, etc.) together in different
chemical species is called a chemical bond. Since the
formation of chemical compounds takes place as a result of
combi nat i on of at om s of var i ous el em ent s i n di f f er ent w ays,
it raises many questions. Why do atoms combine? Why are
only certain combinations possible? Why do some atoms
combine while certain others do not? Why do molecules
possess definite shapes? To answer such questions different
theories and concepts have been put forward from time
to time. These are Kössel-Lewis approach, Valence Shell
Electron Pair R epulsion (VSEPR ) Theory, Valence Bond (V B)
Theory and Molecular Orbital (MO) Theory. The evolution
of various theories of valence and the interpretation of
the nature of chemical bonds have closely been related to
the developments in the understanding of the structure
of atom, the electronic configuration of elements and the
periodic table. Every system tends to be more stable and
bonding is nature’s way of lowering the energy of the system
to attain stability.
Unit 4.indd 100 9/12/2022 9:36:09 AM
2024-25
101
Chemi Cal Bonding a nd m ole Cular Stru Cture 4.1 KÖSSEL-LEwiS AppROACH t O
CHEMiCAL BOnDinG
In order to explain the formation of chemical
bond in terms of electrons, a number of
attempts were made, but it was only in
1916 when Kössel and Lewis succeeded
independently in giving a satisfactory
explan ation . Th ey were th e first to provide
some logical explanation of valence which was
based on the inertness of noble gases.
Lewis pictured the atom in terms of a
positively charged ‘Kerne l’ (the nucleus plus
the inner electrons) and the outer shell that
could accommodate a maximum of eight
e l e c t r ons . H e , f ur t he r as s um e d t ha t t he s e
eight electrons occupy the corners of a cube
which surround the ‘Kernel’. Thus the single
outer shell electron of sodium would occupy
one corner of the cube, while in the case of
a noble gas all the eight corners would be
occupied. This octet of electrons, represents
a particularly stable electronic arrangement.
Lewis postulated that atoms achieve
the stable octet when they are linked by
chemical bonds. In the case of sodium and
chlorine, this can happen by the transfer of
an electron from sodium to chlorine thereby
giving the Na
+
and Cl
–
ions. In the case of
other molecules like Cl
2
, H
2
, F
2
, etc., the bond
is formed by the sharing of a pair of electrons
between the atoms. In the process each atom
attains a stable outer octet of electrons.
Lewis Symbols: In the formation of a
molecule, only the outer shell electrons take
part in chemical combination and they are
known as valence electrons . The inner shell
electrons are well protected and are generally
not i nvol ved i n t he combi nat i on pr ocess.
G.N. Lewis, an American chemist introduced
simple notations to represent valence electrons
in an atom. These notations are called Lewis
symbols . For example, the Lewis symbols for
the elements of second period are as under:
Significance of Lewis Symbols : The
number of dots around the symbol represents
the number of valence electrons. This number
of valence electrons helps to calculate the
common or group valence of the element.
The gr o up val e nce of t he el e m e nt s i s ge ne r al l y
either equal to the number of dots in Lewis
symbols or 8 minus the number of dots or
valence electrons.
Kössel, in relation to chemical bonding,
drew attention to the following facts:
• In the periodic table, the highly
electronegative halogens and the highly
electropositive alkali metals are separated
by the noble gases;
• The formation of a negative ion from a
halogen atom and a positive ion from
an alkali metal atom is associated with
the gain and loss of an electron by the
respective atoms;
• The negative and positive ions thus
formed attain stable noble gas electronic
configurations. The noble gases (with the
exception of helium which has a duplet
of electrons) have a particul arl y stabl e
outer shell configuration of eight (octet)
electrons, ns
2
np
6
.
• The negative and positive ions are stabilized
by electrostatic attraction.
For example, the formation of NaCl from
sodium and chlorine, according to the above
scheme, can be explained as:
Na ? Na
+
+ e
–
[Ne] 3s
1
[Ne]
Cl + e
–
? Cl
–
[Ne] 3s
2
3p
5
[Ne] 3s
2
3p
6
or [Ar]
Na
+
+ Cl
–
? NaCl or Na
+
Cl
–
Similarly th e formation of CaF
2
may be
shown as:
Ca ? Ca
2+
+ 2e
–
[Ar]4s
2
[Ar]
F + e
–
? F
–
[He] 2s
2
2p
5
[He] 2s
2
2p
6
or [Ne]
Ca
2+
+ 2F
–
? CaF
2
or Ca
2+
(F
–
)
2
the bond formed, as a result of the
electrostatic attraction between the
positive and negative ions was termed as
Unit 4.indd 101 9/12/2022 9:36:09 AM
2024-25
Page 3
Scientists are constantly discovering new compounds,
orderly arranging the facts about them, trying to explain
with the existing knowledge, organising to modify the
earlier views or evolve theories for explaining the newly
observed facts.
Unit 4
After studying this Unit, you will be
able to
• unde r s t a nd Kös s e l - Le w i s
approach to chemical bonding;
• e x pl a i n t he oc t e t r ul e and i t s
limitations, draw Lewis structures
of simple molecules;
• explain the formation of different
types of bonds;
• describe the VSEPR theory and
predict the geometry of simple
molecules;
• explain the valence bond
approach for the formation of
covalent bonds;
• predict the directional properties
of covalent bonds;
• explain the different types of
hybridisation involving s, p and
d orbitals and draw shapes of
simple covalent molecules;
• describe the molecular orbital
theory of homonuclear diatomic
molecules;
• explain the concept of hydrogen
bond.
CHEMiCAL BOnDinG AnD
MOLECULAR St RUCt URE
Matter is made up of one or different type of elements.
Under normal conditions no other element exists as an
independent atom in nature, except noble gases. However,
a group of atoms is found to exist together as one species
having characteristic properties. Such a group of atoms
is called a molecule. Obviously there must be some force
which holds these constituent atoms together in the
molecules. the attractive force which holds various
constituents (atoms, ions, etc.) together in different
chemical species is called a chemical bond. Since the
formation of chemical compounds takes place as a result of
combi nat i on of at om s of var i ous el em ent s i n di f f er ent w ays,
it raises many questions. Why do atoms combine? Why are
only certain combinations possible? Why do some atoms
combine while certain others do not? Why do molecules
possess definite shapes? To answer such questions different
theories and concepts have been put forward from time
to time. These are Kössel-Lewis approach, Valence Shell
Electron Pair R epulsion (VSEPR ) Theory, Valence Bond (V B)
Theory and Molecular Orbital (MO) Theory. The evolution
of various theories of valence and the interpretation of
the nature of chemical bonds have closely been related to
the developments in the understanding of the structure
of atom, the electronic configuration of elements and the
periodic table. Every system tends to be more stable and
bonding is nature’s way of lowering the energy of the system
to attain stability.
Unit 4.indd 100 9/12/2022 9:36:09 AM
2024-25
101
Chemi Cal Bonding a nd m ole Cular Stru Cture 4.1 KÖSSEL-LEwiS AppROACH t O
CHEMiCAL BOnDinG
In order to explain the formation of chemical
bond in terms of electrons, a number of
attempts were made, but it was only in
1916 when Kössel and Lewis succeeded
independently in giving a satisfactory
explan ation . Th ey were th e first to provide
some logical explanation of valence which was
based on the inertness of noble gases.
Lewis pictured the atom in terms of a
positively charged ‘Kerne l’ (the nucleus plus
the inner electrons) and the outer shell that
could accommodate a maximum of eight
e l e c t r ons . H e , f ur t he r as s um e d t ha t t he s e
eight electrons occupy the corners of a cube
which surround the ‘Kernel’. Thus the single
outer shell electron of sodium would occupy
one corner of the cube, while in the case of
a noble gas all the eight corners would be
occupied. This octet of electrons, represents
a particularly stable electronic arrangement.
Lewis postulated that atoms achieve
the stable octet when they are linked by
chemical bonds. In the case of sodium and
chlorine, this can happen by the transfer of
an electron from sodium to chlorine thereby
giving the Na
+
and Cl
–
ions. In the case of
other molecules like Cl
2
, H
2
, F
2
, etc., the bond
is formed by the sharing of a pair of electrons
between the atoms. In the process each atom
attains a stable outer octet of electrons.
Lewis Symbols: In the formation of a
molecule, only the outer shell electrons take
part in chemical combination and they are
known as valence electrons . The inner shell
electrons are well protected and are generally
not i nvol ved i n t he combi nat i on pr ocess.
G.N. Lewis, an American chemist introduced
simple notations to represent valence electrons
in an atom. These notations are called Lewis
symbols . For example, the Lewis symbols for
the elements of second period are as under:
Significance of Lewis Symbols : The
number of dots around the symbol represents
the number of valence electrons. This number
of valence electrons helps to calculate the
common or group valence of the element.
The gr o up val e nce of t he el e m e nt s i s ge ne r al l y
either equal to the number of dots in Lewis
symbols or 8 minus the number of dots or
valence electrons.
Kössel, in relation to chemical bonding,
drew attention to the following facts:
• In the periodic table, the highly
electronegative halogens and the highly
electropositive alkali metals are separated
by the noble gases;
• The formation of a negative ion from a
halogen atom and a positive ion from
an alkali metal atom is associated with
the gain and loss of an electron by the
respective atoms;
• The negative and positive ions thus
formed attain stable noble gas electronic
configurations. The noble gases (with the
exception of helium which has a duplet
of electrons) have a particul arl y stabl e
outer shell configuration of eight (octet)
electrons, ns
2
np
6
.
• The negative and positive ions are stabilized
by electrostatic attraction.
For example, the formation of NaCl from
sodium and chlorine, according to the above
scheme, can be explained as:
Na ? Na
+
+ e
–
[Ne] 3s
1
[Ne]
Cl + e
–
? Cl
–
[Ne] 3s
2
3p
5
[Ne] 3s
2
3p
6
or [Ar]
Na
+
+ Cl
–
? NaCl or Na
+
Cl
–
Similarly th e formation of CaF
2
may be
shown as:
Ca ? Ca
2+
+ 2e
–
[Ar]4s
2
[Ar]
F + e
–
? F
–
[He] 2s
2
2p
5
[He] 2s
2
2p
6
or [Ne]
Ca
2+
+ 2F
–
? CaF
2
or Ca
2+
(F
–
)
2
the bond formed, as a result of the
electrostatic attraction between the
positive and negative ions was termed as
Unit 4.indd 101 9/12/2022 9:36:09 AM
2024-25
102 chemistry the electrovalent bond. t he electrovalence
is thus equal to the number of unit charge(s)
on the ion. Thus, calcium is assigned a
positive electrovalence of two, while chlorine
a negative electrovalence of one.
Kösse l ’s post ul at i ons pr ovi de t he basi s f or
th e modern con cepts regard ing ion-formation
by electron transfer and the formation of ionic
crystallin e compou nd s. His views h ave proved
to be of great value in the understanding and
systematisation of the ionic compounds. At
the same time he did recognise the fact that
a large number of compounds did not fit into
these concepts.
4.1.1 Octet Rule
Kössel and Lewis in 1916 developed an
important theory of chemical combination
between atoms known as electronic theory
of chemical bonding. According to this,
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.
4.1.2 Covalent Bond
Langmuir (1919) refined the Lewis
postulations by abandoning the idea of
the stationary cubical arrangement of the
octet, and by introducing the term covalent
bond . The Lewis-Langmuir theory can be
understood by considering the formation of
the chlorine molecule, Cl
2
. The Cl atom with
electronic configuration, [Ne]3s
2
3p
5
, is one
electron short of the argon configuration.
The formation of the Cl
2
molecule can be
understood in terms of the sharing of a pair
of electrons between the two chlorine atoms,
each chlorine atom contributing one electron
to the shared pair. In the process both
chlorine atoms attain the outer shell octet of
the nearest noble gas (i.e., argon).
t he dots represent electrons. Such
structures are referred to as Lewis dot
structures.
The Le w i s dot s t r uc t ur es c an be w r i t t en f or
other molecules also, in which the combining
atoms may be identical or d i f f e r e n t . T h e
important conditions being that:
• Ea c h bo nd i s f o r m e d a s a r e s ul t o f s ha r i ng
of an electron pair between the atoms.
• Each combining atom contri butes at least
one electron to the shared pair.
• The combining atoms attain the outer-
shell noble gas configurations as a result
of the sharing of electrons.
• Thus in water and carbon tetrachloride
mol ecules, formation of covalent bonds
can be represented as:
or Cl – Cl
Covalent bond between two Cl atoms
t hus, when two atoms share one
electron pair they are said to be joined by
a single covalent bond. In many compounds
we have multiple bonds between atoms. The
formation of mu ltip le b on ds envisages sh a rin g
of more than one electron pair between two
atoms. if two atoms share two pairs of
electrons, the covalent bond between them
is called a double bond. For example, in the
carbon dioxide molecule, we have two double
bonds between the carbon and oxygen atoms.
Similarly in ethene molecule the two carbon
atoms are joined by a double bond.
Double bonds in CO
2
molecule
Unit 4.indd 102 9/12/2022 9:36:09 AM
2024-25
Page 4
Scientists are constantly discovering new compounds,
orderly arranging the facts about them, trying to explain
with the existing knowledge, organising to modify the
earlier views or evolve theories for explaining the newly
observed facts.
Unit 4
After studying this Unit, you will be
able to
• unde r s t a nd Kös s e l - Le w i s
approach to chemical bonding;
• e x pl a i n t he oc t e t r ul e and i t s
limitations, draw Lewis structures
of simple molecules;
• explain the formation of different
types of bonds;
• describe the VSEPR theory and
predict the geometry of simple
molecules;
• explain the valence bond
approach for the formation of
covalent bonds;
• predict the directional properties
of covalent bonds;
• explain the different types of
hybridisation involving s, p and
d orbitals and draw shapes of
simple covalent molecules;
• describe the molecular orbital
theory of homonuclear diatomic
molecules;
• explain the concept of hydrogen
bond.
CHEMiCAL BOnDinG AnD
MOLECULAR St RUCt URE
Matter is made up of one or different type of elements.
Under normal conditions no other element exists as an
independent atom in nature, except noble gases. However,
a group of atoms is found to exist together as one species
having characteristic properties. Such a group of atoms
is called a molecule. Obviously there must be some force
which holds these constituent atoms together in the
molecules. the attractive force which holds various
constituents (atoms, ions, etc.) together in different
chemical species is called a chemical bond. Since the
formation of chemical compounds takes place as a result of
combi nat i on of at om s of var i ous el em ent s i n di f f er ent w ays,
it raises many questions. Why do atoms combine? Why are
only certain combinations possible? Why do some atoms
combine while certain others do not? Why do molecules
possess definite shapes? To answer such questions different
theories and concepts have been put forward from time
to time. These are Kössel-Lewis approach, Valence Shell
Electron Pair R epulsion (VSEPR ) Theory, Valence Bond (V B)
Theory and Molecular Orbital (MO) Theory. The evolution
of various theories of valence and the interpretation of
the nature of chemical bonds have closely been related to
the developments in the understanding of the structure
of atom, the electronic configuration of elements and the
periodic table. Every system tends to be more stable and
bonding is nature’s way of lowering the energy of the system
to attain stability.
Unit 4.indd 100 9/12/2022 9:36:09 AM
2024-25
101
Chemi Cal Bonding a nd m ole Cular Stru Cture 4.1 KÖSSEL-LEwiS AppROACH t O
CHEMiCAL BOnDinG
In order to explain the formation of chemical
bond in terms of electrons, a number of
attempts were made, but it was only in
1916 when Kössel and Lewis succeeded
independently in giving a satisfactory
explan ation . Th ey were th e first to provide
some logical explanation of valence which was
based on the inertness of noble gases.
Lewis pictured the atom in terms of a
positively charged ‘Kerne l’ (the nucleus plus
the inner electrons) and the outer shell that
could accommodate a maximum of eight
e l e c t r ons . H e , f ur t he r as s um e d t ha t t he s e
eight electrons occupy the corners of a cube
which surround the ‘Kernel’. Thus the single
outer shell electron of sodium would occupy
one corner of the cube, while in the case of
a noble gas all the eight corners would be
occupied. This octet of electrons, represents
a particularly stable electronic arrangement.
Lewis postulated that atoms achieve
the stable octet when they are linked by
chemical bonds. In the case of sodium and
chlorine, this can happen by the transfer of
an electron from sodium to chlorine thereby
giving the Na
+
and Cl
–
ions. In the case of
other molecules like Cl
2
, H
2
, F
2
, etc., the bond
is formed by the sharing of a pair of electrons
between the atoms. In the process each atom
attains a stable outer octet of electrons.
Lewis Symbols: In the formation of a
molecule, only the outer shell electrons take
part in chemical combination and they are
known as valence electrons . The inner shell
electrons are well protected and are generally
not i nvol ved i n t he combi nat i on pr ocess.
G.N. Lewis, an American chemist introduced
simple notations to represent valence electrons
in an atom. These notations are called Lewis
symbols . For example, the Lewis symbols for
the elements of second period are as under:
Significance of Lewis Symbols : The
number of dots around the symbol represents
the number of valence electrons. This number
of valence electrons helps to calculate the
common or group valence of the element.
The gr o up val e nce of t he el e m e nt s i s ge ne r al l y
either equal to the number of dots in Lewis
symbols or 8 minus the number of dots or
valence electrons.
Kössel, in relation to chemical bonding,
drew attention to the following facts:
• In the periodic table, the highly
electronegative halogens and the highly
electropositive alkali metals are separated
by the noble gases;
• The formation of a negative ion from a
halogen atom and a positive ion from
an alkali metal atom is associated with
the gain and loss of an electron by the
respective atoms;
• The negative and positive ions thus
formed attain stable noble gas electronic
configurations. The noble gases (with the
exception of helium which has a duplet
of electrons) have a particul arl y stabl e
outer shell configuration of eight (octet)
electrons, ns
2
np
6
.
• The negative and positive ions are stabilized
by electrostatic attraction.
For example, the formation of NaCl from
sodium and chlorine, according to the above
scheme, can be explained as:
Na ? Na
+
+ e
–
[Ne] 3s
1
[Ne]
Cl + e
–
? Cl
–
[Ne] 3s
2
3p
5
[Ne] 3s
2
3p
6
or [Ar]
Na
+
+ Cl
–
? NaCl or Na
+
Cl
–
Similarly th e formation of CaF
2
may be
shown as:
Ca ? Ca
2+
+ 2e
–
[Ar]4s
2
[Ar]
F + e
–
? F
–
[He] 2s
2
2p
5
[He] 2s
2
2p
6
or [Ne]
Ca
2+
+ 2F
–
? CaF
2
or Ca
2+
(F
–
)
2
the bond formed, as a result of the
electrostatic attraction between the
positive and negative ions was termed as
Unit 4.indd 101 9/12/2022 9:36:09 AM
2024-25
102 chemistry the electrovalent bond. t he electrovalence
is thus equal to the number of unit charge(s)
on the ion. Thus, calcium is assigned a
positive electrovalence of two, while chlorine
a negative electrovalence of one.
Kösse l ’s post ul at i ons pr ovi de t he basi s f or
th e modern con cepts regard ing ion-formation
by electron transfer and the formation of ionic
crystallin e compou nd s. His views h ave proved
to be of great value in the understanding and
systematisation of the ionic compounds. At
the same time he did recognise the fact that
a large number of compounds did not fit into
these concepts.
4.1.1 Octet Rule
Kössel and Lewis in 1916 developed an
important theory of chemical combination
between atoms known as electronic theory
of chemical bonding. According to this,
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.
4.1.2 Covalent Bond
Langmuir (1919) refined the Lewis
postulations by abandoning the idea of
the stationary cubical arrangement of the
octet, and by introducing the term covalent
bond . The Lewis-Langmuir theory can be
understood by considering the formation of
the chlorine molecule, Cl
2
. The Cl atom with
electronic configuration, [Ne]3s
2
3p
5
, is one
electron short of the argon configuration.
The formation of the Cl
2
molecule can be
understood in terms of the sharing of a pair
of electrons between the two chlorine atoms,
each chlorine atom contributing one electron
to the shared pair. In the process both
chlorine atoms attain the outer shell octet of
the nearest noble gas (i.e., argon).
t he dots represent electrons. Such
structures are referred to as Lewis dot
structures.
The Le w i s dot s t r uc t ur es c an be w r i t t en f or
other molecules also, in which the combining
atoms may be identical or d i f f e r e n t . T h e
important conditions being that:
• Ea c h bo nd i s f o r m e d a s a r e s ul t o f s ha r i ng
of an electron pair between the atoms.
• Each combining atom contri butes at least
one electron to the shared pair.
• The combining atoms attain the outer-
shell noble gas configurations as a result
of the sharing of electrons.
• Thus in water and carbon tetrachloride
mol ecules, formation of covalent bonds
can be represented as:
or Cl – Cl
Covalent bond between two Cl atoms
t hus, when two atoms share one
electron pair they are said to be joined by
a single covalent bond. In many compounds
we have multiple bonds between atoms. The
formation of mu ltip le b on ds envisages sh a rin g
of more than one electron pair between two
atoms. if two atoms share two pairs of
electrons, the covalent bond between them
is called a double bond. For example, in the
carbon dioxide molecule, we have two double
bonds between the carbon and oxygen atoms.
Similarly in ethene molecule the two carbon
atoms are joined by a double bond.
Double bonds in CO
2
molecule
Unit 4.indd 102 9/12/2022 9:36:09 AM
2024-25
103
Chemi Cal Bonding a nd m ole Cular Stru Cture when combining atoms share three
electron pairs as in the case of two nitrogen
atoms in the n
2
molecule and the two
carbon atoms in the ethyne molecule, a
triple bond is formed.
N
2
molecule
C
2
H
2
molecule
4.1.3 Lewis Representation of Simple
Molecules (the Lewis Structures)
t he Lewis dot structures provide a picture
of bonding in molecules and ions in terms of
the shared pairs of electrons and the octet
rule. While such a picture may not explain
the bonding and behaviour of a molecule
completely, it does help in understanding the
formation and properties of a molecule to a
large extent. Writing of Lewis dot structures of
molecules is, therefore, very useful. The Lewis
dot structures can be written by adopting the
following steps:
• The total number of electrons required
for writing the structures are obtained
by adding the valence electrons of the
combining atoms. For example, in the CH
4
molecule there are eight valence electrons
available for bonding (4 from carbon and
4 from the four hydrogen atoms).
• For anions, each negative charge would
mean addition of one electron. For cations,
each positive ch arge wou ld resu lt in
subtraction of one electron from the total
number of valence electrons. For example,
for the CO
3
2–
ion, the two negative charges
indicate that there are two additional
electrons than those provided by the
neutral atoms. For NH
4
+
ion, one positive
charge indicates the loss of one electron
from the group of neutral atoms.
• Knowing the chemical symbols of the
combining atoms and having knowledge
of the skeletal structure of the compound
(known or guessed intelligently), it is easy
to distribute the total number of electrons
as bonding shared pairs between the
atoms in proportion to the total bonds.
• In general the least electronegative atom
occupies the central position in the
molecule/ion. For example in the NF
3
and
CO
3
2–
, nitrogen and carbon are the central
atoms whereas fluorine and oxygen
occupy the terminal positions.
• After accounting for the shared pairs of
electrons for single bonds, the remaining
electron pairs are either utilized for
multiple bonding or remain as the lone
pai r s . The basi c r e qui r e m e nt bei ng
that each bonded atom gets an octet of
electrons.
Lewis representations of a few molecules/
ions are given in Table 4.1.
table 4.1 the Lewis Representation of
Some Molecules
* Each H atom attains the configuration of helium
(a duplet of electrons)
C
2
H
4
molecule
Unit 4.indd 103 9/12/2022 9:36:10 AM
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Page 5
Scientists are constantly discovering new compounds,
orderly arranging the facts about them, trying to explain
with the existing knowledge, organising to modify the
earlier views or evolve theories for explaining the newly
observed facts.
Unit 4
After studying this Unit, you will be
able to
• unde r s t a nd Kös s e l - Le w i s
approach to chemical bonding;
• e x pl a i n t he oc t e t r ul e and i t s
limitations, draw Lewis structures
of simple molecules;
• explain the formation of different
types of bonds;
• describe the VSEPR theory and
predict the geometry of simple
molecules;
• explain the valence bond
approach for the formation of
covalent bonds;
• predict the directional properties
of covalent bonds;
• explain the different types of
hybridisation involving s, p and
d orbitals and draw shapes of
simple covalent molecules;
• describe the molecular orbital
theory of homonuclear diatomic
molecules;
• explain the concept of hydrogen
bond.
CHEMiCAL BOnDinG AnD
MOLECULAR St RUCt URE
Matter is made up of one or different type of elements.
Under normal conditions no other element exists as an
independent atom in nature, except noble gases. However,
a group of atoms is found to exist together as one species
having characteristic properties. Such a group of atoms
is called a molecule. Obviously there must be some force
which holds these constituent atoms together in the
molecules. the attractive force which holds various
constituents (atoms, ions, etc.) together in different
chemical species is called a chemical bond. Since the
formation of chemical compounds takes place as a result of
combi nat i on of at om s of var i ous el em ent s i n di f f er ent w ays,
it raises many questions. Why do atoms combine? Why are
only certain combinations possible? Why do some atoms
combine while certain others do not? Why do molecules
possess definite shapes? To answer such questions different
theories and concepts have been put forward from time
to time. These are Kössel-Lewis approach, Valence Shell
Electron Pair R epulsion (VSEPR ) Theory, Valence Bond (V B)
Theory and Molecular Orbital (MO) Theory. The evolution
of various theories of valence and the interpretation of
the nature of chemical bonds have closely been related to
the developments in the understanding of the structure
of atom, the electronic configuration of elements and the
periodic table. Every system tends to be more stable and
bonding is nature’s way of lowering the energy of the system
to attain stability.
Unit 4.indd 100 9/12/2022 9:36:09 AM
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101
Chemi Cal Bonding a nd m ole Cular Stru Cture 4.1 KÖSSEL-LEwiS AppROACH t O
CHEMiCAL BOnDinG
In order to explain the formation of chemical
bond in terms of electrons, a number of
attempts were made, but it was only in
1916 when Kössel and Lewis succeeded
independently in giving a satisfactory
explan ation . Th ey were th e first to provide
some logical explanation of valence which was
based on the inertness of noble gases.
Lewis pictured the atom in terms of a
positively charged ‘Kerne l’ (the nucleus plus
the inner electrons) and the outer shell that
could accommodate a maximum of eight
e l e c t r ons . H e , f ur t he r as s um e d t ha t t he s e
eight electrons occupy the corners of a cube
which surround the ‘Kernel’. Thus the single
outer shell electron of sodium would occupy
one corner of the cube, while in the case of
a noble gas all the eight corners would be
occupied. This octet of electrons, represents
a particularly stable electronic arrangement.
Lewis postulated that atoms achieve
the stable octet when they are linked by
chemical bonds. In the case of sodium and
chlorine, this can happen by the transfer of
an electron from sodium to chlorine thereby
giving the Na
+
and Cl
–
ions. In the case of
other molecules like Cl
2
, H
2
, F
2
, etc., the bond
is formed by the sharing of a pair of electrons
between the atoms. In the process each atom
attains a stable outer octet of electrons.
Lewis Symbols: In the formation of a
molecule, only the outer shell electrons take
part in chemical combination and they are
known as valence electrons . The inner shell
electrons are well protected and are generally
not i nvol ved i n t he combi nat i on pr ocess.
G.N. Lewis, an American chemist introduced
simple notations to represent valence electrons
in an atom. These notations are called Lewis
symbols . For example, the Lewis symbols for
the elements of second period are as under:
Significance of Lewis Symbols : The
number of dots around the symbol represents
the number of valence electrons. This number
of valence electrons helps to calculate the
common or group valence of the element.
The gr o up val e nce of t he el e m e nt s i s ge ne r al l y
either equal to the number of dots in Lewis
symbols or 8 minus the number of dots or
valence electrons.
Kössel, in relation to chemical bonding,
drew attention to the following facts:
• In the periodic table, the highly
electronegative halogens and the highly
electropositive alkali metals are separated
by the noble gases;
• The formation of a negative ion from a
halogen atom and a positive ion from
an alkali metal atom is associated with
the gain and loss of an electron by the
respective atoms;
• The negative and positive ions thus
formed attain stable noble gas electronic
configurations. The noble gases (with the
exception of helium which has a duplet
of electrons) have a particul arl y stabl e
outer shell configuration of eight (octet)
electrons, ns
2
np
6
.
• The negative and positive ions are stabilized
by electrostatic attraction.
For example, the formation of NaCl from
sodium and chlorine, according to the above
scheme, can be explained as:
Na ? Na
+
+ e
–
[Ne] 3s
1
[Ne]
Cl + e
–
? Cl
–
[Ne] 3s
2
3p
5
[Ne] 3s
2
3p
6
or [Ar]
Na
+
+ Cl
–
? NaCl or Na
+
Cl
–
Similarly th e formation of CaF
2
may be
shown as:
Ca ? Ca
2+
+ 2e
–
[Ar]4s
2
[Ar]
F + e
–
? F
–
[He] 2s
2
2p
5
[He] 2s
2
2p
6
or [Ne]
Ca
2+
+ 2F
–
? CaF
2
or Ca
2+
(F
–
)
2
the bond formed, as a result of the
electrostatic attraction between the
positive and negative ions was termed as
Unit 4.indd 101 9/12/2022 9:36:09 AM
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102 chemistry the electrovalent bond. t he electrovalence
is thus equal to the number of unit charge(s)
on the ion. Thus, calcium is assigned a
positive electrovalence of two, while chlorine
a negative electrovalence of one.
Kösse l ’s post ul at i ons pr ovi de t he basi s f or
th e modern con cepts regard ing ion-formation
by electron transfer and the formation of ionic
crystallin e compou nd s. His views h ave proved
to be of great value in the understanding and
systematisation of the ionic compounds. At
the same time he did recognise the fact that
a large number of compounds did not fit into
these concepts.
4.1.1 Octet Rule
Kössel and Lewis in 1916 developed an
important theory of chemical combination
between atoms known as electronic theory
of chemical bonding. According to this,
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.
4.1.2 Covalent Bond
Langmuir (1919) refined the Lewis
postulations by abandoning the idea of
the stationary cubical arrangement of the
octet, and by introducing the term covalent
bond . The Lewis-Langmuir theory can be
understood by considering the formation of
the chlorine molecule, Cl
2
. The Cl atom with
electronic configuration, [Ne]3s
2
3p
5
, is one
electron short of the argon configuration.
The formation of the Cl
2
molecule can be
understood in terms of the sharing of a pair
of electrons between the two chlorine atoms,
each chlorine atom contributing one electron
to the shared pair. In the process both
chlorine atoms attain the outer shell octet of
the nearest noble gas (i.e., argon).
t he dots represent electrons. Such
structures are referred to as Lewis dot
structures.
The Le w i s dot s t r uc t ur es c an be w r i t t en f or
other molecules also, in which the combining
atoms may be identical or d i f f e r e n t . T h e
important conditions being that:
• Ea c h bo nd i s f o r m e d a s a r e s ul t o f s ha r i ng
of an electron pair between the atoms.
• Each combining atom contri butes at least
one electron to the shared pair.
• The combining atoms attain the outer-
shell noble gas configurations as a result
of the sharing of electrons.
• Thus in water and carbon tetrachloride
mol ecules, formation of covalent bonds
can be represented as:
or Cl – Cl
Covalent bond between two Cl atoms
t hus, when two atoms share one
electron pair they are said to be joined by
a single covalent bond. In many compounds
we have multiple bonds between atoms. The
formation of mu ltip le b on ds envisages sh a rin g
of more than one electron pair between two
atoms. if two atoms share two pairs of
electrons, the covalent bond between them
is called a double bond. For example, in the
carbon dioxide molecule, we have two double
bonds between the carbon and oxygen atoms.
Similarly in ethene molecule the two carbon
atoms are joined by a double bond.
Double bonds in CO
2
molecule
Unit 4.indd 102 9/12/2022 9:36:09 AM
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103
Chemi Cal Bonding a nd m ole Cular Stru Cture when combining atoms share three
electron pairs as in the case of two nitrogen
atoms in the n
2
molecule and the two
carbon atoms in the ethyne molecule, a
triple bond is formed.
N
2
molecule
C
2
H
2
molecule
4.1.3 Lewis Representation of Simple
Molecules (the Lewis Structures)
t he Lewis dot structures provide a picture
of bonding in molecules and ions in terms of
the shared pairs of electrons and the octet
rule. While such a picture may not explain
the bonding and behaviour of a molecule
completely, it does help in understanding the
formation and properties of a molecule to a
large extent. Writing of Lewis dot structures of
molecules is, therefore, very useful. The Lewis
dot structures can be written by adopting the
following steps:
• The total number of electrons required
for writing the structures are obtained
by adding the valence electrons of the
combining atoms. For example, in the CH
4
molecule there are eight valence electrons
available for bonding (4 from carbon and
4 from the four hydrogen atoms).
• For anions, each negative charge would
mean addition of one electron. For cations,
each positive ch arge wou ld resu lt in
subtraction of one electron from the total
number of valence electrons. For example,
for the CO
3
2–
ion, the two negative charges
indicate that there are two additional
electrons than those provided by the
neutral atoms. For NH
4
+
ion, one positive
charge indicates the loss of one electron
from the group of neutral atoms.
• Knowing the chemical symbols of the
combining atoms and having knowledge
of the skeletal structure of the compound
(known or guessed intelligently), it is easy
to distribute the total number of electrons
as bonding shared pairs between the
atoms in proportion to the total bonds.
• In general the least electronegative atom
occupies the central position in the
molecule/ion. For example in the NF
3
and
CO
3
2–
, nitrogen and carbon are the central
atoms whereas fluorine and oxygen
occupy the terminal positions.
• After accounting for the shared pairs of
electrons for single bonds, the remaining
electron pairs are either utilized for
multiple bonding or remain as the lone
pai r s . The basi c r e qui r e m e nt bei ng
that each bonded atom gets an octet of
electrons.
Lewis representations of a few molecules/
ions are given in Table 4.1.
table 4.1 the Lewis Representation of
Some Molecules
* Each H atom attains the configuration of helium
(a duplet of electrons)
C
2
H
4
molecule
Unit 4.indd 103 9/12/2022 9:36:10 AM
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104 chemistry problem 4.1
W r i t e t he Le w i s dot st r uc t ur e of C O
molecule.
Solution
Step 1. Count the total number of valence
electrons of carbon and oxygen atoms.
The outer (valence) shell configurations
of carbon and oxygen atoms are: 2s
2
2p
2
and 2s
2
2p
4
, respectively. The 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 (one shared
electron pair) betw een C and O and
complete the octet on O, the remaining
two electrons are the lone pair on C.
Th is does n ot complete th e octet on
carbon and hence we have to resort to
multiple bonding (in this case a triple
bo nd) bet w ee n C and O at om s . Thi s
sati sfies t he oct et rul e condi t i on f or bot h
atoms.
problem 4.2
Write the Lewis structure of the nitrite
ion, NO
2
–
.
Solution
Step 1. Count the total number of
valence electrons of the nitrogen atom,
t he ox y g e n at o m s and t he add i t i o na l one
negative charge (equal to one electron).
N(2s
2
2p
3
), O (2s
2
2p
4
)
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 (one shared
electron pair) between the nitrogen and
e a c h o f t he ox y g e n at o m s co m pl e t i ng t he
octets on oxygen atoms. This, however,
does not complete the octet on nitrogen
if the remaining two electrons constitute
lone pair on it.
H ence w e have t o resort t o mul t i pl e
bonding between nitrogen and one of
the oxygen atoms (in this case a double
bond). This leads to the following Lewis
dot structures.
4.1.4 Formal Charge
Lewis dot structures, in general, do not
represent the actual shapes of the molecules.
In case of polyatomic ions, the net charge is
possessed by the ion as a whole and not by
a particular atom. It is, however, feasible to
assign a formal charge on each atom. The
formal charge of an atom in a polyatomic
molecule or ion may be defined as the
di f f er ence betw een the number of val ence
electrons of that atom in an isolated or free
state and the number of electrons assigned
to that atom in the Lew is structure. It is
expressed as :
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
— (1/2)
total number of
bonding (shared)
electrons
Unit 4.indd 104 9/12/2022 9:36:10 AM
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