Unit-5 Chemical Bonding and Shapes of Molecules 9 Hours

Valence Shell and Valence Electron;

The outermost shell of an atom is called valence shell and the electrons which belong to the valence
shell are called valence electrons. Valence electrons take part in chemical combination. The reactivity
of an atom depends up on the number of valence electron.
Octet Theory:
The tendency of an atom to have eight electrons in their outermost (valence shell) shell is known as
octet rule and the theory related to this rule is known as octet theory. The main points of this rule are.
1. Atoms with 8 electrons in their valence shell (except helium) are chemically stable.
2. Atoms with less than 8 electrons in their outermost shell are chemically active and take part in
chemical combination.
3. Atoms having less than 4 electrons in outermost shell usually tend to lose electrons while atoms
having more than 4 electrons in their outermost shell usually tend to gain electrons and having 4
electrons in their outermost have tendency to share electrons during chemical combination.
4. Transfer or sharing of electrons gives a stable electronic configuration of 8 electrons in valence
shell of both combining atoms.

Failure (exception) of octet rule:

Some compounds are stable even though constituent atoms do not follow octet rule. Some of them are,
1. Compounds of hydrogen: Hydrogen atom doesn’t attain 8 electrons rather it attain two electrons
(duplet) in its outermost shell in H2, HF, HCl etc.

H H F
H

2. Molecules having incomplete octet: Octet rule could not explain the formation of molecule that
contain electron deficient central atoms such as BeCl 2, BF3, NO, NO2, etc.

Cl Be Cl

3. Molecules having super octet state:

Octet rule could not explain the existence of molecules in which central atom has more than eight
electrons such as PCl5, ClF3, FCl3, SF6, IF7 , etc in which central atoms have 10, 10,10, 12, 14
electrons respectively.

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Chemical Bond:
The binding force between two chemical species (atoms, ions) which is formed by either sharing or
transfer of valence electron(s) is called chemical bonding.
On the basis of mode of formation, chemical bonds are of following three types
1. Electrovalent or ionic bond.
2. Covalent bond.
3. Co-ordinate covalent bond or dative bond.

Electrovalent or ionic bond

The chemical bond which is formed by the complete transfer of one or more valence electrons from one
atom to other atom is known as electrovalent bond or ionic bond. This type of bond is usually formed
between a metal and a non metal atom in which metal atom changes into cation (positive ion) and non
metal changes into anion (negative ion) .For example, bond in NaCl, KCl, MgCl 2, CaCl2,NaBr,Na2S ,
FeCl2, FeCl3, AlCl3 etc.

+ -
Na + Cl Na Cl Na Cl
(2,8,1) (2,8,7) Lewis formula (Ionic Bond)
(Electron dot formula)

Characteristics of ionic bond:

1. It is formed by complete transfer of electron between two combining atoms.
2. It is non directional.
3. There is no fixed geometry of molecule in ionic compounds.
4. Ionic molecules do not exhibit isomerism due to non direction nature of ionic bond.
5. The number of electrons gained or lost by an atom is known as electrovalency.

Ionic compound
The compounds which are formed by the complete transfer of electrons from one atom to the another
between combining atoms are called as ionic compound or the compounds that are formed by existence
of electrostatic force of attraction or ionic bond between combining atoms are called ionic compounds.
For example, NaCl, KCl, NaBr CaCl2. Etc
Characteristics of ionic compounds
1. Nature of bond: There is existence of ionic bond in the ionic compounds.
2. Physical state: Ionic compounds usually exist in crystalline solid form at room temperature.
3. Solubility: They are soluble in water and other polar solvent but are insoluble in organic solvent
like benzene, chloroform etc.
4. High melting and boiling point: Ionic compounds have high m.p. and b.p. due to strong
electrostatic force of attraction between cation and anion.

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 5. Electrical conductivity: Ionic compounds can conduct electricity in molten state or in their aqueous
solution however they can’t conduct electricity in solid state it is because cations and anions are
strongly attracted by each other and so can’t move freely in solid state while these ions are far
apart to each other and can freely move in the aqueous solution or in molten state due to less
electrostatic force of attraction.. Therefore ionic solid are bad conductor in solid but good
conductors in molten or aqueous solution.
6. Nature of reaction: Ionic compounds show ionic reaction in which ions involve in chemical
combination.
Na+ (aq.) + Cl-(aq.) + Ag+ (aq.)+ NO3- (aq.)  NaNO3 (aq.) + AgCl↓(aq.)

7. Brittleness: Generally ionic compounds are brittle in nature. When force is applied, similar
charged ions come together and repulsion force results the breaking of crystal.
8. Non directional character: The ionic bond is non directional in nature since an ion can attract
other opposite charged ions equally from any direction.
9. Isomerism: They do not show isomerism due to non direction nature of ionic bond.
10. Isomorphism: Ionic compounds formed from ions having similar electronic configuration
possess identity of crystalline form which is termed as isomorphism. For e.g.

i). NaF and MgO

Na+ F- Mg+2 O2-
(2,8) (2,8) (2,8) (2,8)
ii). CaCl2 and K2S
Cl- Ca2+ Cl- K+ S2- K+
(2,8,8) (2,8,8) (2,8,8) (2,8,8) (2,8,8) (2,8,8)

Covalent Bond:
The chemical bond which is formed by the mutual sharing of valence electrons between two
combining atoms is known as covalent bond. Each combining atom contributes equal number of
electrons for sharing. For example,
Formation of Cl2, F2, H2, O2, N2, H2O, NH3, CH4, HCl molecules etc.

i. Formation of H2 molecule:

H H H H
H + H

Lewis structure Covalent bond

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 ii. Formation of Cl2 molecule

Cl Cl
Covalent bond

iii. Formation of ammonia molecule

Characteristics of covalent bond:

1. It is formed by the mutual sharing of valence electrons between two combining atoms.
2. It is directional.
3. There is fixed geometry of molecule of covalent compound.
4. Covalent compound exhibits isomerism due to directional characters of covalent bond
5. The number of share electrons by an atom is called covalency.

Covalent compound:
The compounds which are formed by the mutual sharing of electrons between combining atoms are
known as covalent compounds. For example, CH4, CCl4, CO2, H2S, C2H6, NH3 etc.
Characteristics of covalent compounds
1. Nature of bond: Covalent compounds consists of covalent bond.
2. Physical state: Covalent compounds exist in all three states gas, liquid or liquid.
3. Low boiling and melting point: covalent compounds usually have low m. p. and b. p. since
molecules are bounded by weak vander waal’s force.
4. Solubility: Covalent compounds are soluble in organic (non polar) solvent like benzene,
chloroform but insoluble in polar solvent like water.
5. Electrical conductivity: covalent compounds are bad conductor since they can’t furnish free ions
but graphite can conduct electricity though it is covalent due to presence one free electron in
each carbon.
6. Nature of reaction: Molecules involve in chemical combination in which old bonds are broken
and new bonds are formed. They show molecular reaction.

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 7. Directional character: covalent bonds are rigid and directional since shared pair of electrons are
localized in fixed direction in the space between the nuclei of two atoms.
8. Isomerism: covalent compounds possess isomerism because covalent bonds are rigid and
directional and hence can form different arrangement of atoms in the space.
9. Soft and non brittle: Covalent compounds are usually soft and non brittle.

Lewis structure of some covalent compounds:

Co-ordinate covalent bond or dative bond:

The chemical bond formed by sharing of valence electrons between two atoms in which shared pair of
electrons is contributed only by one of the two atoms and other atom simply participates in sharing is
known as co-ordinate covalent bond or dative bond. The atom which donates shared pair of electrons is
called donor and it must already be octet while the atom which accepts electron pair in order to attain
octet is called acceptor. Co-ordinate covalent bond is represented by an arrow (→) pointing from donor
atom towards the acceptor atom. Some examples

i. In O3 molecule

ii. In SO3 molecule:

Characteristics of co-ordinate covalent bond.

1. It is formed by the sharing of a pair of electron between combining atoms in which only one
atom contributes electron for sharing.
2. It is directional.
3. It is semi ionic bond.
4. Molecules exhibit isomerism due to directional character of co-ordinate covalent bond.

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Co-ordinate covalent compound
The compounds which consist of at least one or more co-ordinate covalent bond in addition with other
covalent bond are known as co-ordinate covalent compound. For example,

Characteristic of co-ordinate covalent compounds

1. Physical state: Generally co-ordinate covalent compounds exist in liquid and gaseous state.
2. Solubility: They are sparingly soluble in water and organic solvent since they semi polar or semi
ionic in nature.
3. Electrical conductivity: They are poor conductor in nature.
4. M.P. and B.P.: they lower m. p. and b.p. than ionic compounds but higher than covalent
compounds.
5. Directional character: Co-ordinate covalent bond is rigid and direction.
6. Isomerism: They possess isomerism due to rigid and directional bond.
7. Molecular reaction: They show molecular reaction mechanism.

Lewis structure of some co-ordinate covalent compounds

i. NO ii. NO2 iii. N2O iv). N2O3 v. N2O4 vi. N2O5 vii.HNO3
2- 2- - +
viii . HNO2 ix. H2SO4 x. SO4 xi. CO3 xii.NO3 xiii.NH4 ix. (NH4)2SO4
xv. MgCO3 xvi. H2SO3 XVI. H3PO4

Bond Characteristics:
i. Bond length:
Bond length or bond distance is the average distance between the nuclei of two bonded atoms in a
molecule or chemical species. In general, a single bond is longer than the double bond and double is
longer than triple bond. The bond length is inversely related to bond strength and bond enthalpy.

C C C C C C

Bond length : Single bond > Double bond > Tripple bond

Bond enthalpy: Single bond < Double bond < Tripple bond

The bond length between any two atoms depends upon the electronegativity of bonding atoms,
neighbouring substituent, orbital hybridization and resonance. For example, the bond length of C-H
bond in methane and in chloroform is different. Replacement of hydrogen atom by chlorine atom
causes different bonding environment resulting into different bond length.

Bond length is measured in the order of picometer (pm) or Bohr radius. A Bohr radius is 1 amu
length.

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 1 Bohr radius (1amu) = 52.91 pm
For example,
Common single bond length of C-C = 154 pm or 2.91 Bohr radius.
ii. Ionic Charater:
Partial ionic character of covalent compounds:
Covalent compounds which are formed by mutual sharing of electrons between dissimilar atoms having
different electro negativity exhibit partial ionic character. In this case, shared pair of electrons is
displaced towards more electronegative atom and it acquires partial negative charge while the less
electro negative atom acquires partial positive charge and hence covalent molecule shows partial ionic
character. For example, HCl, HBr, HI, NH3, H2O etc
 
H Cl

The extent of ionic character depends upon the difference of electro negativities of two combining
atoms. Greater the difference of electro negativity, greater is the percentage of ionic characters. It has
been observed that a bond has 50% ionic character and 50% covalent character if the difference in
electro negativities of the participating atoms is 1.7. On the other hand if difference is more than 1.7,
ionic character is dominance and if difference is less than 1.7, covalent character is dominance.
Percentage ionic character and difference in electro negativity is given below.
Electro negativity difference 3 2.3 1.7 1.1 0.6 0.2
% ionic character 99 75 50 25 10 1

Polar and non polar covalent compound:

Polar covalent compound:
The covalent compounds that are formed by sharing of electrons between dissimilar atoms of different
electro negativity in which more electronegative atom acquires partial negative charge and less
electronegative atom acquires partial positive charge, are known as polar covalent bond. The different
poles i. e. partial negative charge and partial positive charge are developed due to unequal distribution
of bonded pair of electrons. Some examples of polar covalent compounds are HCl, H 2O, HBr, NH3, HI
etc.
Non polar covalent compound:
Covalent compounds that are formed by sharing of electrons between similar atoms, in which shared
pair of electrons are localized at equal distance from nuclei of both participating atoms, are called non
polar covalent compounds. Such molecules have no any kinds of charge at atoms. Some examples of
non polar covalent compounds are H2, Cl2, O2, N2 etc.
iii. Dipole Moments:
The degree of polarity or ionic character in a covalent bond is expressed in term of dipole moment.
Dipole moment is defined as the product of the magnitude of charge of any one of atoms and the
distance between them. It is denoted by Greek letter  (meu) and it unit is Debye or D. Mathematically
it can be expressed as

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 q+ q-
A B
d

=q  d
Where, q= magnitude of chare on any one of atoms (order of 10 -10 esu)
d=distance between both (order of 10 -8 cm)
Hence, 1D = 10-10  10-8 = 1  10-18 esu cm
Dipole moment is a vector quantity and is represented by an arrow with crossed tail ( ) pointing
from positive atom to negative atom.

H Cl

For HCl  =1.03  10-18 esu cm

= 1.03 D

Application of dipole moment

Some applications are
1. Determination of polar and non polar molecules: Molecules having some value of dipole
moment are polar while molecules having zero value of dipole moment are non polar. For, e.g. H 2,
N2, Cl2 etc are non polar as their dipole moment is zero and HCl, HBr, NH3 etc are polar as they
have some value of dipole moment.
2. Determination of ionic character in covalent compound: The dipole moment provides idea
about ionic character of covalent bond. Higher the value of dipole moment, larger is the ionic
character of covalent compound.
3. Determination of geometry of molecules: The dipole moment gives the idea about geometry and
shape of molecule.
i. Molecules having linear geometry: The resultant dipole moment of tri atomic molecules like CO 2,
CS2, etc is zero. Therefore, they have linear geometry. (This means each polar bond in such
molecules lies opposite direction so as to cancel dipole moment of each other and hence give linear
geometry)

     
O C O S C S
 =0 D  =0D

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 ii. .Molecules having trigonal planar geometry: Resultant dipole moment of some molecules
like BF3, BH3 etc is zero which indicates that three bond pairs of electrons are directed along
each corner of equilateral triangle so as cancel dipole moment of each other. The bon angle of
each bond is 120O.
F

F F
 =0D
Special bonds
1. Hydrogen bond
2. Metallic bond
3. Vander waal’s force (bond)

1. Hydrogen bond:
The weak force of attraction between hydrogen covalently bonded with more electronegative
element and more electronegative elements like N, O, F etc in the same or different molecule is
known as hydrogen bond.

. . . . . . .H Cl . . . . . . . . . . . .H Cl. . . . . . . .H Cl . . . . . .
Hydrogen bond

Conditions for hydrogen bonding

i. Hydrogen atom should already be covalently bonded with more electro negative element
ii. The electronegative element should have smaller size.

Type of hydrogen bond

There are two types of hydrogen bond.
i. Intermolecular hydrogen bond
ii. Intra molecular hydrogen bond

i. Intermolecular hydrogen bond:

The weak attraction force between hydrogen (already covalently bonded with more electronegative
elements) and more electronegative elements like N, O, F, etc of different molecules of either same
or different compound is called intermolecular hydrogen bond.

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 H O H O H O

H H H

Intermolecular hydrogen bond

-----H O------------H Cl-------------H O----------H Cl------

H H

Intermolecular hydrogen bond

Some points:
i. It results the association of molecules. So, it has effect on viscosity and surface tension.
ii. It affects the boiling point and melting point.
iii. It affects the solubility of compounds.

Effect of intermolecular H-bond

i. It results the association of molecule. So, it increases viscosity and surface tension
ii. It increases b.p and m.p. of compounds.
iii. It increases solubility of compounds in water.

ii. Intra molecular Hydrogen bond: The hydrogen bond which is formed between hydrogen (already
covalently bonded with more electro negative elements) and more electronegative element within
the same molecule is known as intra molecular hydrogen bond.

Intermolecular H-
O H bond
O
N

o-nitrophenol

Some points:
1. It does not aggregate molecules.
2. It does not affect the melting point, boiling point and solubility

Application of hydrogen bond:

1. Increase in viscosity and surface tension:

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 Molecules of compounds get associated due to intermolecular hydrogen bonds which results
increase in viscosity surface tension of liquid compound. For example, glycerol is more viscous
than alcohol because there is large number of intermolecular hydrogen bonds between glycerol
molecules than in alcohol.
2. Increase in boiling point and melting:
Boiling and melting point of compounds increases due to presence of intermolecular hydrogen
bonds. It requires extra amount of heat energy to break down intermolecular hydrogen bond.
3. Effect on physical state :
H2O is liquid at room temperature but H2S is gas because H2O can form inters molecular hydrogen
bonds between water molecules but H2S can’t form intermolecular hydrogen bonds rather H2S
molecules are attracted by very weak Vander Waal’s force of attraction. Therefore, H 2O is liquid
but H2S is gas at room temperature.

H2S

Vander waal’s force

H2S

4. Solubility of covalent compounds:

The covalent compounds which can form inter molecular hydrogen bonds with water molecules are
soluble in water but the covalent compounds which are unable to form intermolecular hydrogen
bonds with water molecules are insoluble in water.
Various organic compounds such as carboxylic acids, alcohols, amines, etc are soluble in water as
they can form intermolecular hydrogen bonds with water molecules.

H O H O

H C2H5

Intermolecular hydrogen bond between water and alcohol molecules

2. Metallic bond: kernel

mobile electrons

fig: electron sea model

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The strong electrostatic force of attraction between positive kernels (metallic ion) and mobile free
electrons which binds metal atoms together resulting hardness and solid properties is known as metallic
bond. According to Drude (1900) and Lorentz (1916), metal consists of positive charged metallic ions
(kernels) in which valence electrons are moving on the surface of metal as like gas molecule. So this
model is called electron sea model or electron gas model.
Properties of metal
1. Metallic luster: When light falls on the metal surface, the free electron absorb light and get
vibrated. These vibrating electrons immediately emit radiation due to which metal surface
appears shinning.
2. Electrical an thermal conductivity: When the electricity is applied, the free electrons in the
metal start moving from negative terminal to the positive terminal.
3. Thermal conductivity: when a end of a metal is heated, the free mobile electrons move rapidly
towards cooler end and transfer heat to the adjacent electron by colliding with it.
4. Malleability and ductility: when the stress is applied on metal, the lattice of kernels slips on
each other layers and the free mobile electron immediately occupy their positions without
destroying lattice of crystal and metal become sheet or wire.
5. High tensile strength: the property by virtue of which metal can be stretched without breaking is
known as tensile. This property is due to the strong electro static force of attraction between
positive kernel and mobile electrons.
6. Hardness: Metals are very hard due presence of strong electro static force of attraction between
positive kernels and mobile electrons.

3. Vander waal’s force:

The very weak force of attraction between instantaneous dipoles and induced dipoles developed in
covalent molecules are called Vander waal’s force or London force.
The rapid movement of electrons results unsymmetrical distribution of electron density in atoms of
molecule which leads separation of negative and positive poles temporary. This temporary dipole is
called instantaneous dipole which influences the electron distributions of other close molecules. As a
result dipoles appear on the molecule which is termed as induces dipole

Vander waal’s force

Instantaneous dipole Induced dipole

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Some important points
1. It is an instantaneous force of attraction.
2. Vander waal’s force of attraction is weaker than hydrogen bond.
3. Vander waal’s force of attraction increases with increasing surface area of molecules and
polarity in the molecule.

Vander waal’s force increase the melting point and boiling point of molecules. For example, the order
of boiling and melting point of halogen molecules is
I2 > Br2 > Cl2
Order of surface area is I2 > Br2 > Cl2
Order of vander waal’s force is I2 > Br2 > Cl2
Molecular solids:
The solids which consist of molecules as constituent held by weak Vander Waal’s force of attraction
are known as molecular solids. For e.g. ice, sugar, iodine solid, dry ice, etc.
Properties
i) They have low m.p. and b.p.
ii) They are generally soft.
iii) They are bad conductor of electricity.
iv) They are volatile and have low heat of vaporization.

Resonance:
The phenomenon in which single molecule can be represented by two or more structures as a result of
delocalization of pi (  ) electrons, lone pair of electrons and odd electron in the molecule is known as
resonance and the different structures of a molecule represented by resonance phenomenon are known
as resonance structure or canonical structure. The two resonating structures are denoted by double
headed arrow and intermediate structure among the resonance structure is called resonance hybrid.
Some example
1. Resonance in O3
2. Resonance in SO3
3. Resonance of SO2
4. Resonance in CO3 - -
5. Resonance of SO4- -
6. Resonance in NO3-
7. Resonance of PO4- -

Hybridization:
The phenomenon of intermixing of the two or more different orbitals of comparable energies of an atom to
produce new hybrid orbitals of same shape, size and equivalent energy is known as hybridization.

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Conditions of hybridization

1. The orbital should have comparable energy undergo in hybridization.

2. Orbital of valence shell take part in hybridization.
3. The orbitals of same atom take part in hybridization
4. Both half filled as well as completely filled orbitals can take part in hybridization.
5. The hybrid orbitals have equal energies and identical shape.
6. The number of hybrid orbitals is equal to the number of orbital taking part in hybridization.

Types of hybridization.
Depending upon the types of orbitals involved in the hybridization process, hybridization is classified into
following three types.
1.sp hybridization: The hybridization in which one s-orbital and one p-orbital of comparable energies of an
atom intermix to produce two sp-hybrid orbitals of same shape, size and equivalent energy is known as sp
hybridization.

y
Y Z
Z
180O
X sp hybridization
X
SP- hybrid orbitals
s-orbital p-orbital

Feature of sp-hybridization
1. Molecule has linear geometry
2. Bond angle of such molecule is 1800
3. S and P characters are 50-50% respectively
4. Atom with sp hybridization has relative high electro negativity

Some examples
1. Formation of BeF2 molecule
Be=1s2 2s2
1s 2s 2px 2py 2pz
Ground state Be =

1s 2s 2px 2py 2pz

Excited state Be=

SP- hybridization

2pY 2pZ
In BeF2 molecule =
SP SP
1s
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Two half filled hybrid orbital of Be undergo head to head overlapping with half filled p-orbital of two fluorine
atoms to form linear BeF2 molecule.
Orbital geometry of BeF2
F + Be F
+

180O
F Be F F Be F
Linear geometry of BeF2
Linear orbital geometry

2. SP2 hybridization: The process of intermixing of one s-orbital and two p-orbitals to form three sp2 hybrid
orbitals of same shape, size and equivalent energies is known as sp2 hybridization.

y Z y z
120O
x +

Features of sp2 hybridization

1. Molecule has trigonal planar geometry
2. Bond angle in such molecule is 1200
3. S and p characters are 33.33 and 66.67% respectively
For example
Formation of BF3 molecule
B= 1s2 2s2 2p1
1s 2s 2px 2py 2pz
Ground state B=

1s 2s 2px 2py 2pz

Excited state B=

SP2 hybridization

In BF3 molecule=
1s sp2 sp2 sp2 2p

Three half filled hybrid orbitals of B undergo head to head overlapping with half filled orbital of three fluorine
atoms to form trigonal planar molecule
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 F

3 F + B
B
Three F atoms

F F

Orbital picture of BF3

Trigonal planar geometry

B
120
F F
Trigonal planar
3
3. SP hybridization: The phenomenon which involves intermixing of one s-orbital with three p-orbitals of
the same atom to form four sp3 hybrid orbitals is known SP3. These four hybrid orbitals lie in tetrahedral
arrangement.

Features of sp3 hybridization

1. Molecule has tetrahedral structure.
2. Bond angle of the molecule is 109.5o
3.s and p characters are 25% and 75% respectively.
For examples, CCl4, CH4, H2O, NH3 molecules.
Formation of CH4 molecule
Carbon atom undergoes sp3 hybridization at excited state to form four sp3 hybrid orbitals. Each hybrid orbital
contains single electron and combines with 1s orbital of H atoms to form CH4 molecule. The geometry of
molecule is tetrahedral with bond angle 109.5o between each C-H bond.

In ground state C =

In excited state C =

Sp3 hybridyzation

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 CH4 molecule =

109.5
C C
H H

H
Fig: Tetrahedral geometry

Deviated geometry of molecules with lone pair of electrons:

1. Molecule of water

Oxygen atom undergoes sp3 hybridization to form four sp3 hybrid orbitals. Two hybrid orbitals contain single
electron in each which combine with 1s orbital of H atoms to form two O-H sigma bonds and other two hybrid
orbitals contain non bonded pair of electrons (lone pair) in each. Presence of two lone pair of electrons causes
repulsion between them which reduce bond angle between two O-H bonds to 104.5 o from 109.5o. Hence, water
molecule is angular (V- shape) shape.

1s 2s 2p
Ground state O=

Sp3 hybridyzation
1s
O
H2O molecule =
104.5O
H H
Fig: angular shape

2. Molecule of H2S

Sulphur atom undergoes sp3 hybridization to form four sp3 hybrid orbitals. Two hybrid orbitals contain single
electron in each which combine with s orbital of H atoms to form two S-H sigma bonds and other two hybrid
orbitals contain non bonded pair of electrons (lone pair) in each. Presence of two lone pair of electrons causes

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repulsion between them which reduce bond angle between two S-H bonds to 920 from 109.5o. Hence, H2S
molecule is angular (V- shape) shape.

92O
H H
Fig: angular shape

3. Molecule of ammonia

In ammonia molecule, nitrogen atom has four sp3 hybrid orbitals. Among them, three hybrid orbitals contain
single electron in each which combine with 1s orbital of three H atoms to form three N-H sigma bonds and
remaining one hybrid orbital contains non bonded pair of electrons (lone pair). Presence of lone pair of electrons
causes repulsion between lone pair and bond pair electrons. Since repulsion of electrons follow the order of L.P-
L.P> L.P.-B.P>B.P-B.P, therefore bond angles between N-H bonds reduces to 107.5 o from 109.5o. Hence,
ammonia molecule has trigonal pyramidal structure.

N
N
OR
H H
H
H H

H
Fig: Trigonal pyramidal

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4. Molecule of ethene (CH2=CH2)

Both carbon atoms of ethene have three sp2 hybrid orbitals. One sp2 hybrid orbital of each carbon atom combine
together to form C-C sigma bond and other two hybrid orbitals of both carbon atoms combine with 1s orbital of
two H atoms to form two C-H sigma bonds to each carbon. The remaining unhybridized p-orbital of both
carbons overlap laterally above and below the plane of sigma bonds to form one pi bond between two carbon
atoms.

H
H


C C

H H

Py Py

Orbital geometry of ethene

4. Molecule of ethyne:

Both carbon atoms of ethyne molecule have two sp hybrid orbitals. One sp hybrid orbital of each carbon atom
combine together to form C-C sigma bond and other one hybrid orbital of each carbon atom combine with 1s
orbital one H atom to form one C-H sigma bond to each carbon atom. The remaining two unhybridized p-orbitals
of both carbon atoms overlap laterally above and below the plane of sigma bonds to form two pi bonds between
two carbon atoms.


H C C H

Pz Pz

Py Py
Orbital geometry of ethyne

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Types of Covalent bond
On the basis of types of overlapping of orbitals, covalent bonds are of two types

1. Sigma (σ)bond
2. Pi (π) bond
1. Sigma (σ)bond:
The covalent bond formed by head –to-head overlapping of two half-filled orbitals along inter nuclear axis is
called sigma bond.

Feature of sigma bond.

i. It is stronger bond than pi bond.

ii. It may or may not be polar.
iii. It doesn’t involve in resonance.
iv. It can be rotated.
Formation of sigma bond

Sigma bond is formed in three different ways by overlapping of half filled orbitals. Both s and p orbitals involve
in formation of sigma bond.

i. S-S overlap: Half filled S-orbital of one atom overlaps with half filled s-orbital of another atom to form
sigma bond. For e.g formation of H2 molecule
S-S overlapping
+ H-H
+
Sigma bond
bond

ii.S-P overlap: Half filled s-orbital of one atom overlaps with half filled P- orbital of another atom along inter
nuclear axis to form sigma bond. For e.g. Formation of HCl molecule.

 p overlapping
+ s   H-Cl

iii)P-P overlapping: One half filled P-orbital of an atom overlaps with half filled P-orbital of another atom above
and below the inter nuclear axis to form sima bond .For e.g formation of F 2 molecule,Cl2molecule.

p  p overlapping
+ +   

F-F

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 2. Pi(π) bond:

The covalent bond formed by sideways (lateral) overlapping of both lobes of two half filled p-orbitals above
and below the inter nuclear axis is known as Pi (π) bond.

π -bond

p  p overlapping
+    
 inter nuclear axis

Feature of Pi bond

i. It is weaker bond than the sigma bond.

ii. It is formed by lateral overlapping of two half filled p-orbitals.
iii. Overlapping occurs above and below inter nuclear axis.
iv. It can’t be rotted.
v. It involves in resonance.
Difference between pi and sigma bonds
Sigma bond Pi bond

1. It occurs head to head overlapping of two half 1.It occurs laterally overlapping of two half filed p-
filled orbitals along nuclear axis. orbital perpendicular to the inter nuclear axis

2. It is stronger than the pi bond due to maximum 2. It is weaker than the sigma bond due to low
overlapping. extent of overlapping.

3. It is formed by S-S,S-P and P-P overlapping. 3. It is formed by p-p overlapping only and s-
orbital can’t form pi bond.
4 .Electrons of sigma bond are located between
nuclei of bonded atoms. 4. Electrons of pi bond are located above and below
the inter nuclear axis.
5. It can be rotted.
5. It can’t be rotated.
6. It does not involve in resonance.
6.It involve in resonance.

Valence Shell Electron Pair Repulsion (VSEPR) theory

This theory was proposed by Sidgwick and Powell in 1940 and further developed by Gillespie and
Nyholm in 1957.This theory explains molecular shape and bond angles more exactly on the basis of
electrostatic attraction between electron pairs around the central atom.

VSEPR theory states that, “The electron pairs (both lone pairs and shared pairs) surrounding the central
atom will be arranged in space as far apart as possible to minimize the electrostatic repulsion between
them”.

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Postulates of VSEPR theory

1. There is spatial arrangement of electrons pairs (lone pairs and shared pairs) around the central atom.
2. Atoms of molecules are arranged in such a way that repulsion between electron pairs is minimum as
much as possible.
3. The order of repulsion between electron pairs are L.P.-L.P.>L.P.-B.P.>B.P.-B.P.
4. If lone pair of electrons is/are present in the central atom, then the structure of molecule gets deviated
from ideal geometry.
5. The shape of molecule is determined by the repulsion between all types of electron pairs present
around the central atom.
6. The molecules or ions containing 2,3,4,5 and 6 bonded electron pairs in central atom have linear,
trigonal planar, tetrahedral, trigonal bipyramidal and octahedral geometry respectively.

Geometry of some molecules in the light of VSEPR theory

1. Shape of BeF2:

Lewis structure of BeF2

F Be F

Central atom berilium has two bonded pair of electrons. To minimize repulsion, bonded pair of
electrons get stretched to form an angle 180o and the BeF2 molecule assumes linear structure.

180o
F Be F
Linear geometry

2. Shape of BF3

Lewis structure of BF3

F B F

The central atom boron contains three bond pairs of electrons. To minimize repulsion, three bonded
pairs of electrons get stretched to assume trigonal planar geometry with bond angle 120 o between each
B-Fbonds.

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 F

B
120
F F
Fig. Trigonal planar geometry
3. Shape of CH4

Lewis structure of CH4 is

H

H C H

Central atom carbon has four bonded pairs of electrons which cause repulsion equally to each other.
Therefore, to have a minimum repulsion between them, four bonded pairs electrons are stretched
symmetrically in the space and form an angle of 109.5o with each other and hence molecule have
regular tetrahedral geometry. H

109.5 C

H H

H
Tetrahedral geometry

Deviated geometry of molecule (with lone pair of electrons)

4. Shape of H2O

Lewis structure of H2O is

H O H

Central atom oxygen contains four pair of electrons i.e. two bonded pair of electrons and two lone pair
of electrons. The expected geometry of water is tetrahedral but the presence of two lone pair of
electrons causes the repulsion in the order of L.P.-L.P.>L.P.-B.P.>B.P.-B.P. and hence tetrahedral
shape gets distorted to an angular shape with bond angle 104.5 o between two O-H bonds.

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 O

104.5o
H H
Fig. Angular shape of H2O

5. Shape of ammonia

Lewis structure of NH3

Central atom nitrogen contains four pairs of electrons i.e. three bonded pair of electrons and one lone
pair of electrons. The expected geometry of NH3 molecule is regular tetrahedral but presence of one
lone pair of electrons cause repulsion in the order of L.P.-L.P.>L.P.-B.P.>B.P.-B.P. and hence
tetrahedral shape gets distorted to trigonal pyramidal geometry with bond angle 107.5 o between each
N-H bond.

N̈

H 107.5 o H

5. Shape of CH2=CH2

Each carbon atom in ethylene molecule has three bonded pairs of electrons (double bond is counted as a
single pair because it causes the repulsion like a single bond pair).To have minimum repulsion, the
bonded pair of electrons get stretched so as to form trigonal planar with bond angle 120 o.

H H

120o C=C

H H

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Limitation of VSEPR theory

1. It cannot explain the shape of molecules having very polar bonds, e.g. Li 2O should have the same
structure as H2O but actually it is linear.
2. It fails to explain the shape of molecules having extensive delocalized pi electron system.
3. This theory is unable to predict the shape of certain transition metal complex.
4. It does not help in determining the exact bond angle.

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