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Chemical Bonding IPE
Chemical Bonding IPE
Aditya vardhan
Chemical Bonding 1 adichemadi @ gmail.com
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CHEMICAL BONDING
Chemical Bond : The attraction between two atoms or ions is called a chemical bond. Chemical bond
is formed either due to sharing or transfer of electrons between atoms.
A chemical bond is formed by an atom inorder to get stability by lowering its potential energy.
Atoms (noble gases) with octet configuration in outer shell are stable. Hence every atom tries to get
octet configuration either by losing or gaining or sharing electrons.
N
1) Ionic bond :The electrostatic force of attraction between two oppositely charged ions is called ionic
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bond.
* An ionic bond is formed due to transfer of electrons from one atom to another.
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* The atom which loses electrons will form a cation and the atom which gains electrons will form an
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anion. These oppositely charged ions come closer to each other due to electrostatic force of attraction
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* An ionic bond is formed between two atoms when their electronegativity difference is greater
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than 1.7.
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Pr
2) Covalent Bond : The attraction between two atoms formed due to the sharing of electron pair(s) is
.A
* It is formed when electronegativity difference between two atoms is less than 1.7.
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3) Metallic bond: It is the attraction between metal atoms in a metallic crystal. It is formed between
electropositive metal atoms.
Electrovalency: The number of valence electrons either lost or gained by an atom during the ionic
Prepared by V. Aditya vardhan
Chemical Bonding 2 adichemadi @ gmail.com
bond formation is called electrovalency.
N
2) F + 1e -
F-
HA
z=9
He 2s 2 2p5 He 2s2 2p6
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ed
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3) Li F
LiF
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ep
EM
Pr
Magnesium loses two electrons to get Neon's configuration. Chlorine atom gains one electron to
.A
get Argon's configuration. Thus formed Mg2+ and Cl- ions combine together by forming MgCl2.
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1)
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Mg Mg 2+ + 2e-
z=12
Ne 3s 2 Ne
V.
2) 2 x ( Cl + 1e -
Cl- )
z=17
Ne 3s 2 3p5 Ne 3s2 3p6
3) Mg 2+ 2Cl
MgCl2
2) 3 x( F + 1e -
F- )
z=9
2s 2 2p5
He He 2s2 2p6
3) Al3+ + 3F -
AlF3
N
1)
2x Na Na + + 1e
HA
z=11
1s 2 2s2 2p 6 3s1 1s2 2s 2 2p 6
RD
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2)
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O + 2e
O 2
ar
z 8
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ep
1s 2 2s 2 2p 4 1s2 2s 2 2p 6
EM
Pr
YA
CH
DI
3) 2Na + + O 2-
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Na 2O
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Ionic bond is electrostatic force of attraction between cation and anion. Hence factors
favouring their formation also favour the formation of ionic bond.
4) Octet electronic configuration : The cations with 8 electrons in the outer shell (octet configura-
tion) are highly stable and hence formed readily. Whereas cations with 18 electrons in outer shell
(Pseudo inert gas configuration) are comparatively less stable and hence are not formed easily.
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N
3) Low charge on anion : The formation of highly charged anions is difficult as the addition of succes-
sive electrons to the atoms becomes difficult due to repulsion from electrons in the atom. Hence anion
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with low charge is formed readily.
E.g., Among C4-, N3-, O2- and F- ions, the anion with low charge (F-) is formed readily whereas the
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formation of anion with higher charge (C4-) is difficult.
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i.e., The order of ease of formation is C4- < N3- < O2- < F-
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FAJAN'S RULES
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These rules are used to predict the nature of the bond formed by atoms based on their polarizing
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Pr
E.g. In IA group elements ionic nature increases with increase in the size of cation from Li+ - Cs+.
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i.e, Increasing order of ionic nature : Li+ < Na+ < K+ < Rb+ < Cs+
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less more
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ionic ionic
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The crystal lattice energy of an ionic crystal can be calculated by using Born-Haber cycle. For
example the lattice energy of NaCl can be calculated as follows:
BORN-HABER CYCLE : The principle involved in Born-Haber cylcle is Hess's law of constant
heat summation which can be stated as follows.
Hess's Law : The total energy change in a reaction remains same whether the reaction takes
place in one step or in several steps.
Direct step : NaCl crystals are formed by combining Na metal with chlorine gas in one step. The
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energy evolved during this reaction is called heat of formation ΔH f .
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1
Na s Cl2 g
NaCls ; ΔH f = -410.5 kJ/mol
2 RD
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Indirect method : The formation of NaCl crystals may occur in several steps as follows.
ed
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i) Sublimation of sodium : Solid sodium is first converted gaseous sodium by absorbing 108.7 kJ/
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EM
Pr
Na s
Na g ; ΔHs = + S = +108.7 kJ/mol
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CH
ii) Ionization of sodium : Gaseous sodium atoms are ionized by absorbing 492.82 kJ / mole of
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Na +g + 1e-
Na g ; ΔH i = + I = + 492.82 kJ/mol
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iii) Dissociation of chlorine molecule : One mole of gaseous chlorine molecules are dissociated into
two moles of chlorine atoms by absorbing energy equal to 239.1 kJ/mole. This is called dissociation
V.
energy ΔH d or D .
Cl 2g
2Cl g ; ΔH d = +D = 239.1 kJ/mol
But the energy required to get one mole of chlorine atoms is equal to
+D 139.2
= = +119.55 kJ/mol
2 2
1 1 +D
Cl 2 g
Cl g ; ΔH d = = +119.55 kJ/mol
2 2 2
Chloride ion formation : The gaseous chlorine atoms are added with electrons to get gaseous chlo-
ride ions. The energy liberated in this process is called electron affinity (ΔH e or E) .
Cl 2 g + e-
Cl- g ; ΔH e = - E = -361.6 kJ/mol
Formation of NaCl Crystals : The gaseous Na+ and Cl- ions unite to form one mole of NaCl crys-
tals. The energy liberated during this process is called lattice energy ΔH u or -U . This value can be
calculated by using Hess's law as follows.
Na +g + Cl- g
NaCl s ; ΔH u = -U
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According to Hess's law the energy change in the steps involved in indirect method.
1
i.e. H f H s H f H d H e H u
2
(or)
D
H f S I E U
2
H d
i.e., U H f H S H i H e
2
U 410.5 108.7 492.82 119.55 (361.6) 769.97 kJ .mol 1
1 Hf
Na(s) + /2Cl2(g) NaCl(s)
N
H d
Hs= +S
HA
2
Na(g) Cl(g)
RD -U
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Hi= +I He= +E
ed
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+ -
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Na (g) + Cl (g)
ep
EM
Pr
Born-Haber cycle
YA
CH
The lattice energy of an ionic crystal is equal to the sum of attractive and repulsive forces in the crystal.
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AZ .Z Be 2
U N o No n
r r
V.
attractive repulsive
force force
Where A = Madelung constant (which depends on geometry of the crystal)
AZ .Z e 2 r n 1
B = Repulsion coefficient
n
(This depends on the structure and approximately proportional to the number of nearest
neighbours)
No = Avogadro's number
Z+ & Z- = Charges on the positive and negative ions respectively.
e = Charge of an electron.
r = Distance between the oppositely charged ions
n = Born exponent (a constant which is usually taken as 9)
AZ .Z e 2 N o 1
U 1 n
ro
CRYSTAL STRUCTURES
Unit cell : The smallest part of the crystal which produces entire crystal upon repeating three dimen-
sionally is called unit cell.
Coordination number : Maximum number of nearest oppositely charged ions surrounding any par-
ticular ion in ionic crystal is called the coordination number of that ion.
r
Limiting radius ratio ( ): The ratio of radius of positive ion to that of negative ion is called limiting
r
N
radius ratio.
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The coordination number and crystal structure of an ionic crystal can be predicted from the limiting
radius ratio value. RD
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r Coordination
Limiting radius ratio ( ) Structure
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r number
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Cl- Cl-
Cs+ 1
Number of Cl- ions = 8 x =1
8
Cl- Cl- Number of Cs+ ions = 1
Cl- Cl-
N
2) Crystal structure of sodium chloride
HA
rNa
* Limiting radius ratio ( )= 0.52
rCl RD
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* The coordination number is equal to 6.
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EM
Pr
YA
1
Na+ Cl- Na+ Number of Cl- ions at corners = 8 x =1
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8
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2
Na+ Cl- Na+
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Formula weight: Ionic compounds contain only ions and there are no molecules in it. Hence their
molar mass is expressed as formula weight instead of molecular weight.
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Covalency : The number of electrons contributed by the atom of an element in the formation of
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covalent compound is known as covalency of that element.
Examples
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1) H2 molecule
* Electronic configuration of hydrogen is 1s1.
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* Each hydrogen atom contribute one electron to form a pair of electrons, which is shared in between
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* Thus in H2 molecule, each hydrogen atom gets its nearest inert gas - Helium's configuration.
EM
Pr
YA
* Covalency of hydrogen is 1.
CH
.
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H. + .H H.H
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.A
or
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H H
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2) Cl2 molecule
V.
2 2 6 2 5
* The electronic configuration of Cl is 1s 2s sp 3s 3p .
7
* In order to get the nearest inert gas- Argon's configuration, each chlorine contributes one electron for
the bond formation.
* Covalency of chlorine is 1.
.. .. .. ..
. + . Cl .
..
..
. . . Cl
..
..
Cl
.. .. Cl ..
or
.. ..
..
. . Cl
..
Cl ..
..
..
.. or H Cl
..
4) Methane (CH4)
2 2 2
* The electronic configuration of carbon is 1s 2s 2p .
4
1
* The electronic configuration of hydrogen is 1s .
* The carbon atom forms four covalent bonds by contributing four of its valence electrons for the bond
formation. It forms 4 bonds with four hydrogen atoms. Thus it gets octet configuration.
* Covalency of carbon is 4.
H H
.x
.
H x C. . x H or H C H
N
x
H
HA
H
5) Ammonia (NH3) : RD
* The electronic configuration of nitrogen is 1s2 2s 2 2p3 .
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1
* The electronic configuration of hydrogen is 1s ,
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* In the formation of Ammonia molecule, nitrogen atom contributes 3 of its electrons to form three
EM
Pr
bond pairs which are shared with hydrogen atoms. Thus nitrogen forms 3 single bonds with three
YA
* Covalency of nitrogen is 3.
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.A
.. ..
W
.N.
AD
H x x H or H N H
.
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H H
V.
5) H2O molecule
* Electronic configuration of oxygen is 1s2 2s 2 2p 4 .
6
1
* Electronic configuration of Hydrogen is 1s .
* In the formation of water molecule, oxygen atom contributes two electrons to form two bond pairs
which are shared with hydrogen atoms. Thus two bonds are formed by oxygen atom to get the configu-
ration of neon. There are also two lone pairs on oxygen atom.
* Covalency of oxygen is 2.
.. ..
H .O.
x x H or H O H
.. ..
6) Oxygen molecule (O2)
2 2 4
* The electronic configuration of oxygen is 1s 2s 2p .
6
* In the formation of oxygen molecule, each oxygen atom contributes 2 electrons to form 2 bond pairs.
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Thus a double bond is formed between oxygen atoms. Thus each oxygen atom gets Neon's configura-
tion.
.. . . .. .. ..
.. .
O .O.. or O
.. O
..
7) Nitrogen molecule (N2)
* The Electronic configuration of nitrogen is 1s2 2s 2 2p3 .
5
* In the formation of Nitrogen molecule, each nitrogen atom contributes 3 electrons to form 3 bond
pairs. Thus a triple bond between nitrogen atoms is formed. Each nitrogen atom gets Neon's configura-
tion.
or
...
...
.. N N N N
..
..
..
8) Carbon dioxide (CO2)
N
2 2 2
* Electronic configuration of carbon is 1s 2s 2p .
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4
2 2 4
* Electronic configuration of oxygen is 1s 2s 2p .
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6
ed
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* In carbon dioxide, carbon atom forms double bond with each oxygen. Thus both oxygen and carbon
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ep
.. .. ..
YA
..
or C O
CH
O
..
O
..
O C
..
..
..
..
..
..
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AD
2 2 2
* Electronic configuration of carbon is 1s 2s 2p
4
V.
.. .. .. ..
Cl . . Cl or Cl Be Cl
..
..
Be
..
..
x x
.. .. .. ..
BCl3 (Boron trichloride)
2 2 1
* Electronic configuration of Boron is 1s 2s 2p .
3
2 2 6 2 5
* Electronic configuration of chlorine is 1s 2s sp 3s 3p .
7
* In BCl3 molecule, boron contributes 3 of its valence electrons and forms three bond pairs with
chlorine atoms. There are only six electrons in the valence shell of boron atom in BCl3. But still it is
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stable. It is an electron deficient compound. It is also the violation of octet rule.
* Covalency of boron is 3.
HA
..
RD ..
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Cl
..
..
Cl
..
..
.
ed
.. .. .. ..
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x
. . Cl or Cl
..
B Cl B
a..r
..
Cl
..
x x
.. .. .. ..
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ep
EM
Pr
2 2 6 2 3
* Electronic configuration of phosphorus is 1s 2s 2p 3s 3p .
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5
.A
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2 2 6 2 5
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7
In the formation of PCl5 molecule, phosphorus contributes five electrons in it's valence shell and
V.
forms five bonds with chlorine atoms. There are 10 electrons in the valence shell of phosphorus in this
molecule. It is a stable molecule and violates octet rule.
* Covalency of phosphorus in this molecule is 5.
.. ..
Cl
..
..
.. Cl
..
..
..
. .. ..
Cl . Cl
..
x
.
..
Cl
..
.. x Cl
..
x .. or ..
P .. P
x x
. .. .. ..
.. .
Cl Cl
..
..
Cl Cl
..
..
.. .. .. ..
F F
F * F F F
* * or
S
* *
S
F * F F F
F F
N
Conclusion: Lewi's electronic theory could not explain the shapes and bond angles of molecules. It
HA
also could not explain why some molecules are stable eventhough they violate octet rule.
I.C
_ _
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x
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x
ep
O O
EM
Pr
.. .. x
C xx O C O
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H .S. x or
CH
x x H or H S H
.. .. Ox O
x _
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Hydrogen sulphide _
.A
Carbonate ion
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3) SiCl4 4) HCOOH
V.
.. ..
Cl O O
..
..
Cl ..
..
..
.. .x .. ..
x.
Si . x Cl Cl Si Cl H C OR H C
..
Cl
..
or
..
..
.. .x .. .. ..
Cl O H O H
..
..
Cl
..
..
..
..
Silicon tetrachloride Formic acid
5) NF3 6) HNO3
.. xx .. xx + +
. N . F F N F O N O H O N O H
..
F x
..
x
.. . .. or
x
` O O
F F - -
Nitrogen trifluoride Nitric acid
7) CO 8) O3
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:
:
::: : : O :O
: :
O:
: :
C O or C O or :
: :
:
:
:
O O
: O
:
:
Carbon monoxide molecule Ozone molecule
-1 +
8) NO2 9) NH4
+ +
- H
- H
O N O or O N O ..
H x .N. x H or H N H
.
x
Nitrite ion
H H
N
gativity and the electron pairs are shared equally. It is calculated as follows:
HA
1
Qf = N A - N LP - N BP
2 RD
Where NA = Number of electrons in the valence shell of free atom.
VA by
OM
NLP = Number of electrons in the lone pairs (unshared pairs).
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ep
Examples:
EM
Pr
1) PH3 molecule
YA
.. ..
.A
H x .P. x H H P H
.
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x or
W
H H
V.
1 6
Formal charge on 'P' = N A - N LP - N BP 5 2 0
2 2
1 2
N BP 1 0 0
Formal charge on 'H' = N A - N LP -
2 2
2) N2O molecule: It exists in following two resonance forms.
For the following first resonance form:
- + - +
:
:
:
:N N O
: or : N : :N : :O :
(1 ) (2 ) (1 ) (2 )
1 4
Formal charge on first nitrogen 'N(1)' = N A - N LP - N BP 5 4 1
2 2
1 8
Formal charge on second nitrogen 'N(2)' = N A - N LP - N BP 5 0 1
2 2
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1 4
Formal charge on 'O' = N A - N LP - N BP 6 4 0
2 2
:
:N N O
:
or :N : ::
N
:
O
:
(1 ) (2)
:
(1 ) (2 )
1 6
Formal charge on first nitrogen 'N (1)' = N A - N LP - N BP 5 2 0
2 2
1 8
Formal charge on second nitrogen 'N (2) ' = N A - N LP - N BP 5 0 1
2 2
1 2
Formal charge on 'O' = N A - N LP - N BP 6 6 1
2 2
N
HA
Hence the formal charges vary with structural environment.
I.C
electron pairs present in the valence shell of central atom of that molecule.
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3) The electron pairs in the valence shell the repel each other and determines the shape of the molecule.
CH
The magnitude of the repulsion depends upon the type of electron pair.
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4) The bond pair is attracted by nuclei the occupies less space and hence it causes less repulsion.
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Whereas, the lone pairs are only attracted by one nucleus and hence occupy more space. As a result,
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structure, whereas the symmetry is distorted when there are lone pairs along with bond pairs.
6) The bond angle decreases due to the presence of lone pairs.
7) The repulsion increases with increase in the number of bonds between two atoms.
E.g. Triple bond causes more repulsion then double bond which in turn causes more repulsion than
single bonds.
8) The repulsion between electron pairs increases with increase electronegativity of central atom and
hence the bond angle increases.
9) Shapes of molecules can be predicted from the number of electron pairs in the valence shell of central
atom as follows:
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THE GEOMETRY OF MOLECULES CONTAINING ONLY BOND PAIRS IN THE CENTRAL ATOM
Number of
Formula Molecular geometry Examples
bond pairs
2 AB2 Linear B A B BeCl2, BeF2
B
Trigonal
3 AB3 BF3, BCl3
planar A
B B
4 AB4 Tetrahedral A
B
CH4, CCl4
B
B
N
B
HA
B
Trigonal
5 AB5 B A PCl5, PF5
bipyramidalRD B
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B
ed
I.C
B
ar
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ep
B B
EM
Pr
B B
DI
B
W IT
.A
W
AD
W
V.
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N
5 3 2 AB3E2 T-Shape ClF3
o -
2 3 AB2E3 Linear 180 XeF2, I3
HA
Square o
5 1 AB5E 90 BrF5
pyramidal
6 RD
Square o
VA by
4 2 AB4E2 90 XeF4
OM
planar
ed
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ep
Explanatory examples:
DI
1) BeCl2: The valence shell of central atom, beryllium contains only two bond pairs. Hence it is linear
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.A
180o
Cl Be Cl
V.
Linear molecule
2) BF3: The valence shell of the central atom - boron contains only three bond pairs. Hence it's shape
is trigonal planar with 120o bond angle.
Cl
Cl
120o Cl
3) CH4: The valence shell of the central atom - carbon contains only four bond pairs. Hence it is
tetrahadral in shape with 109o28' bond angle.
The bond pairs are arranged tetrahedral symmetry so as to minimize repulsions. If the bond pairs
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are arranged in square plane, the angles between them will be only 90o and the repulsions will be more
than in case of tetrahedral arrangement. Hence tetrahedral structure is more favorable than square
planar structure.
109o28'
C
H
H
H
Tetrahedral structure of methane
4) NH3: There are three bond pairs and one lone pair in the central atom, nitrogen. The bond angle is
N
decreased from 109o28' to 107o48' due to repulsion caused by lone pair.
HA
RD
VA by
N
OM
H H
ed
I.C
107o48'
ar
H
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ep
5) H2O: There are two bond pairs and two lone pairs in the central atom, oxygen. The bond angle is
decreased from 109o28' to 104o28' due to repulsion caused by two lone pairs.
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.A
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AD
W
O
V.
H
o
104 28'
H
Angular shape of water molecule
Note: The 's' orbitals can only form bonds, whereas the p, d & f orbitals can form both and π
bonds.
Examples
1) H2 molecule
* Electronic configuration of hydrogen is 1s1.
* In the formation of hydrogen molecule, two half filled 1s orbitals of hydrogen atoms overlap along the
internuclear axis and thus form a s-s bond.
H + H H H
N
1s orbital 1s orbital s s bond
HA
2) Cl 2 molecule
* Electronic configuration of Cl is 1s2 2s2 2p6 3s2 3px2 3py2 3pz1
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* The two half filled 3pz atomic orbitals of two chlorine atoms overlap along the internuclear axis and
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thus by forming a p-p bond.
ed
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Cl + Cl Cl Cl
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3) HCl molecule
* Electronic configuration of hydrogen is 1s1.
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* The half filled 1s orbital of hydrogen overlap with the half filled 3pz atomic orbital of chlorine atom
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AD
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H + Cl H Cl
4) O2 molecule
* Electronic configuration of O is 1s2 2s2 2px2 2py1 2pz1
* The half filled 2px orbitals of two oxygen atoms overlap along the internuclear axis and form
p-p bond. The remaining half filled 2pz orbitals overlap laterally to form a π p-p bond. Thus a double
bond (one and one ) is formed between two oxygen atoms.
p p bond
p p bond
O + O O O
5) N2 molecule
* Electronic configuration of N is1s2 2s2 2px1 2py1 2pz1
* p-pbond is formed between two nitrogen atoms due to overlapping of half filled 2px atomic
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Chemical Bonding 20 adichemadi @ gmail.com
orbitals axially. The remaining half filled 2py and 2pz orbitals form two π p-p bonds due to lateral
overlapping. Thus a triple bond (one and two )is formed between two nitrogen atoms.
p p
p p
p p
N N
Valence bond theory could not explain the structures and bond angles of molecules with more than
three atoms. E.g. It could not explain the structures and bond angles of H2O, NH3 etc.,
Inorder to explain the structures and bond angles of molecules, Linus Pauling modified the valence
bond theory by proposing hybridization concept.
N
HA
HYBRIDIZATION
The intermixing of atomic orbitals of almost equal energies of an atom to give an equal
number of identical and degenerate hybrid orbitals is called hybridization.
RD
VA by
OM
Characteristics of hybridization :
ed
I.C
1) Pure atomic orbitals of same atom should participate in the hybridization.
ar
3) The number of hybrid orbitals formed is equal to the number of atomic orbitals participating in the
EM
Pr
hybridization.
YA
CH
6) The filling of electrons into hybrid orbitals follows Pauli's exclusion principle and Hund's rule of
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maximum multiplicity.
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TYPES OF HYBRIDIZATION
1) 'sp' hybridization
* Intermixing of one 's' and one 'p' orbitals of almost equal energy to give two identical and degen-
erate hybrid orbitals is called 'sp' hybridization.
* These sp-hybrid orbitals are arranged linearly at 180o of angle.
* They possess 50% 's' and 50% 'p' character.
Examples:
1) BeCl2
* Electronic configuration of 'Be' in ground state is 1s2 2s2
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* Electronic configuration of 'Be' in excited state is 1s 2 2s1 2p1x
sp
hybridization
(2σ bonds)
* In the excited state, beryllium undergoes 'sp' hybridization by using a 2s and a 2p orbitals. Thus two
half filled 'sp' hybrid orbitals are formed. These are arranged linearly.
* These half filled sp-orbitals form two sp p bonds with two 'Cl' atoms.
* Thus BeCl2 is linear in shape with the bond angle of 180o.
sp p sp p
N
HA
Cl Be Cl
BeCl2
Hybridization - sp
RD
VA by
180o
OM
Shape - linear
ed
Cl Be Cl
I.C
Bond angle - 180o
ar
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ep
Linear molecule
EM
Pr
YA
2) Acetylene (C2H2)
CH
sp
hybridization
(2σ bonds) pure
orbitals
form
2 bonds
* Each carbon atom undergoes 'sp' hybridization by using one 2s and one 2p orbitals in the excited
state. Thus two half filled 'sp' orbitals are formed. These are arranged linearly.
The two carbon atoms form one sp sp bond with each other by using sp-orbitals. They also form
two p p bonds by overlapping half filled pure p-orbitals ( 2py and 2pz). Thus a triple bond (1 & 2 )
is formed between carbon atoms.
Each carbon also forms a sp s bond with the hydrogen atom.
Thus acetylene molecule is linear with 180o bond angle.
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p p
p p
sp s sp sp
H C C H
C2 H 2 - Acetylene
Hybridization - sp
Shape - linear
180o
Bond angle - 180o
H C C H
N
HA
sp2 hybridization :
* Intermixing of one 's' and two 'p' orbitals of almost equal energy to give three identical and degener-
RD
ate hybrid orbitals is known as sp2 hybridization.
VA by
OM
* The three sp2 hybrid orbitals are oriented in trigonal planar symmetry at angles of 1200 to each other.
ed
* sp2 hybrid orbitals have 33.3% 's' character and 66.6% 'p' character.
I.C
ar
AD
ep
EM
Pr
YA
+ +
CH
DI
W IT
.A
W
AD
Examples:
V.
1) BCl3
* Electronic configuration of 'B' in ground state is 1s2 2s2 2p1
* Electronic configuration of 'B' in excited state is 1s2 2s12px12py1
sp2
hybridization
(3σ bonds)
In the excited state, Boron undergoes sp2 hybridization by using a 2s and two 2p orbitals. Thus
three half filled sp2 hybrid orbitals which are oriented in trigonal planar symmetry are obtained.
Boron forms three σ sp2 -p bonds by using sp2 hybrid orbitals with three chlorine atoms. Each
chlorine atom uses it's half filled p-orbital for the bond formation.
Thus the shape of BCl3 is trigonal planar with Cl-B-Cl bond angles equal to 120o.
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Cl
Cl
B
B
Cl
120o Cl
Cl Cl
N
HA
BCl3 - Boron trichlorine
RD
VA by
hybridization - sp 2
OM
ed
EM
Pr
2) Ethylene (C2H4).
YA
sp2
V.
hybridization
(3σ bonds)
pure
orbital
forms
one bond
* In the excited state, each carbon in ethylene undergoes sp2 hybridization by mixing 2s and two 2p
orbitals. Thus three half filled sp2 hybrid orbitals are formed in trigonal planar symmetry. There is also a
half filled 2pz orbital on each carbon.
* The carbon atoms form a sp2 -sp 2 bond with each other by using hybrid orbitals.
The remaining pure atomic orbitals overlap laterally and form a p-p bond.
* There is a double bond (1 & 1 ) between two carbon atoms.
* Each carbon atom also forms two sp 2 -s bonds with two hydrogen atoms.
* Thus ethylene molecule is planar with H-C-H & C-C-H bond angles equal to 120o.
* All the atoms are present in one plane.
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p p
H H
sp 2 sp 2 H H C2 H 2 - Ethylene
o
C C 120
C C sp 2 s Hybridization - sp 2
H H
Shape - planar
H H
Bond angle - 120o
Planar structure of ethylene molecule
sp3 hybridization:-
* Intermixing of one 's' and three 'p' orbitals of almost equal energy to give four identical and degener-
ate hybrid orbitals is called sp3 hybridization.
* Thus formed four sp3 hybrid orbitals are oriented in tetrahedral symmetry with 109028' angle with
N
each other.
HA
* In these orbital the ‘s’ character is 25% and ‘p’ character is 75%.
RD
VA by
+ + + OM
ed
I.C
ar
AD
ep
EM
Pr
YA
Examples:
W IT
.A
Methane (CH4)
W
AD
sp3
hybridization
(4σ bonds)
* In the excited state, the carbon atom undergoes sp3 hybridization by mixing one ‘2s’ and three 2p
orbitals. Thus four half filled sp3 hybrid orbitals are formed in tetrahedral symmetry.
* Each of these form σsp3 - s bond with hydrogen atom. Thus carbon forms four bonds with four
hydrogen atoms.
* Methane molecule is tetrahedral in shape with 109028' bond angle.
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H H
sp3 s
109o28'
CH 4 - Methane
C C
H H Hybridization - sp3
H H Shape - Tetrahedral
H H Bond angle - 109o 28 '
Tetrahedral structure of methane
2) Ethane (C2H6)
* Electronic configuration of 'C' in ground state is 1s2 2s2 2p2
* Electronic configuration at 'C' in excited state is 1s2 2s1 2p3
N
2s 2px 2py 2pz
HA
sp3
hybridization
RD
VA by
(4σ bonds)
OM
ed
I.C
* In the excited state, each carbon atom undergoes sp3 hybridization by using one 2s and three 2p
ar
orbitals. Thus four half filled sp3 hybrid orbitals are formed in tetrahedral symmetry around each car-
AD
ep
bon.
EM
Pr
YA
* The two carbon atoms form a σsp3 - sp3 bond with each other by overlapping sp3 hybrid orbitals
CH
axially.
DI
W IT
Each carbon atom also forms three σsp3 -s bonds with hydrogen atoms.
.A
W
AD
* Thus there is tetrahedral symmetry around each carbon with HCH and HCC bond angles equal
W
to 1090 28' .
V.
H H
sp3 sp 3 H 109o28' H
sp3 s 109o28'
C C C
C H H H
H
H H
H H
Structure of Ethane molecule
C 2 H 6 - Ethane
Hybridization - sp3
Bond angle - 109o 28 '
3) Ammonia (NH3)
* Electronic configuration of nitrogen is 1s2 2s2 2px1 2py1 2pz1
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sp3
hybridization
(3σ bonds)
* Nitrogen undergoes sp3 hybridization by using one 2s and three 2p orbitals. Thus formed four sp3
orbitals are arranged in tetrahedral symmetry. Among them three are half filled and one is full filled.
* Nitrogen forms 3 σsp3 -s bonds with three hydrogen atoms by using three half filled hybrid orbitals.
The bond angle is decreased from 1090 28'to 1070 48' due to the repulsion caused by lone pair.
Thus ammonia acquires trigonal pyramidal shape.
N
HA
N sp3 s N NH 3 - Ammonia
H H H Hybridization - sp3
H 107o48'
RD Shape - Trigonal pyramidal
H
VA by
OM
H Bond angle - 107o 48'
ed
I.C
Trigonal pyramidal structure of ammonia molecule
ar
AD
ep
sp3
W
hybridization
(2σ bonds)
V.
* Oxygen atom undergoes sp3 hybridization by mixing a 2s and three 2p orbitals and forms four sp3
hybrid orbitals arranged in tetrahedra symmetry. Among thenm two are half filled and the remaining two
are completely filled.
Oxygen forms two σsp3 -s bonds with hydrogen atoms by using half filled hybrid orbitals.
The bond angle is decreased from 1099 28' to 1040 28' due to repulsions caused by two lone
pairs. Thus water molecule gets angular shape (V shape).
sp 3 s O water - H 2 O
O
H Hybridization - sp3
H o
104 28' shape - Angular
H
H Bond angle - 104o 28'
Angular shape of water molecule
sp3d Hybridization
* The intermixing of one 's', three 'p' and one 'd' orbitals to give five identical and degenerate hybrid
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orbitals is called sp3d hybridization.
* Thus formed sp3d orbitals are arranged in trigonal bipyramidal symmetry. Among them, three are
arranged in trigonal plane and the remaining two orbitals are present perpendicularly above and below
the trigonal plane.
Examples:
1) PCl5 (phosphorus pentachloride)
N
* E.configuration of 'P' in ground state is 1s2 2s2 2p6 3s2 3p3
HA
* E.configuration of 'P' in excited state is 1s2 2s2 2p6 3s1 3p3 3d1
RD 3s 3p 3d
VA by
OM
ed
sp3d
I.C
ar
hybridization
AD
(5σ bonds)
ep
EM
Pr
YA
* In the excited state, phosphorus undergoes sp3d hybridization by using a 3s, three 3p and one 3d
CH
* By using these half filled sp3d orbitals, phosphorous forms five σsp3d - p bonds with chlorine atoms.
W IT
.A
Each chlorine atom makes use of half filled 3pz orbital for the bond formation.
W
AD
W
* The shape of PCl5 molecule is trigonal bipyramidal with 1200 and 900 of Cl - P - Cl bond angles.
Cl
V.
sp3d2 hybridization
* Intermixing of one 's', three 'p' and two 'd' orbitals of almost same energy by giving six identical and
degenerate hybrid orbitals is called sp3d2 hybridization.
* These six sp3d2 orbitals are arranged in octahedral symmetry by making 900 angles to each other.
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Examples:
1) Sulfur hexa flouride (SF6)
* E.configuration of 'S' in ground state is 1s2 2s2 2p6 3s2 3p4
* E.configuration of 'S' in 2nd excited state is 1s2 2s2 2p6 3s1 3p3 3d2
N
3s 3p 3d
HA
sp3d2
hybridization
RD (6σ bonds)
VA by
OM
* In the second excited state, sulfur under goes sp3d2 hyrbidization by mixing a 3s, three 3p and two 3d
ed
I.C
orbitals. Thus formed six half filled sp3d2 hybrid orbitals are arranged in octahedral symmetry.
ar
AD
ep
Sulfur atom forms six σsp3d 2 - p bonds with 6 fluorine atoms by using these sp3d2 orbitals. Each
EM
Pr
F
.A
sp3d 2
W
Hybridization -
S
shape - Octahedral
F F Bond angle - 90o
V.
* The atom which donates the electron pair is called as donor, whereas the atom which accepts that
pair is called as acceptor.
* Both donor and acceptor will share the electron pair.
* Coordinate bond is also known as dative bond.
* It is represented by an arrow pointing towards the acceptor.
Examples:
1) Formation of Ammonium ion (NH4+)
* Ammonium ion is formed when ammonia reacts with hydrogen ion. In the formation of ammonium
N
ion, the sp3 orbital with a lone pair on nitrogen overlaps with the empty 1s orbital of hydrogen ion to
form a coordinate covalent bond.
HA
H3N: + H+ [H3N H]+ (or) [NH4]+
RD
VA by
OM
Donor Acceptor Ammonium ion
ed
I.C
* Ammonium ion contains 4 bond pairs in the valence shell of nitrogen atom and hence it is tetrahedral
ar
AD
in shape with 109o28' bond angles. The hybridization of nitrogen will remain sp3 only.
ep
EM
Pr
YA
+
CH
H
DI
W IT
109o28'
.A
N
W
AD
H
H
W
Note: In NH4Cl, there are three covalent bonds, one coordinate covalent bond and an ionic bond.
Ionic bond is present between NH4+ and Cl- ions.
* The hybridization in boron is changed from sp2 to sp3 during the formation of coordinate covalent
bond. Hence the geometry around boron in the complex formed will be tetrahedral.
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H H
H H
N B
H H
3) Formation of Hydronium ion
* The sp3 orbital containing lone pair on oxygen in water molecule overlaps with the empty 1s orbital on
hydrogen ion to form a coordinate covalent bond.
:
:
H2O: + H+ [H2O H]+ or H3O+
Donor Acceptor Hydronium ion
2) Formation of [AlCl4]-
* The chloride ion (Cl-) donates a lone pair of electrons to the empty 'p' orbital of aluminium in AlCl3.
N
Thus a coordinate bond is formed. During the bond formation, the 'p' orbital containing the lone pair on
chloride ion overlaps the empty 'p' orbital of aluminium.
HA
RD _
Cl
VA by
OM
Cl _ :
Cl
Pr : :
ed
Cl Al + : Cl : Al Cl :
I.C :
ar
Cl Cl
AD
ep
AlCl4-
EM
Acceptor donor
YA
Planar Tetrahedral
CH
DI
W IT
* The hybridization in aluminium is changed from sp2 to sp3 during the formation of coordinate covalent
.A
More examples:
SO2 and SO3 also considered to have coordinate covalent bonds according to octet rule as shown
V.
below.
O
:
S S
O O O O
N
increasing order of energy.
8) The degenerate molecular orbitals posses same energy and are filled with electrons according to
HA
Hund's rule. But they may be arranged in different directions.
9) The MO's which have lower energy than AO's are called bonding orbitals, whereas those with
RD
higher energy are known as anti bonding orbitals. The number of bonding orbitals formed is equal to
VA by
OM
the number of anti bonding orbitals.
ed
The orbitals which are not involved in the combination are called non bonding orbitals.
I.C
ar
Bonding orbitals < Non bonding orbitals < Anti bonding orbitals
EM
Pr
YA
Bonding orbitals
10) The bond order of the molecule can be calculated by using the following formula.
number of bonding electrons - number of antibonding electrons
Bond order (B.O) =
2
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N
combined, whereas anti bonding molecular orbitals are formed when the orbitals with different signs of
HA
wavefunctions are combined.
Depending on the pattern of overlapping, number of nodes and symmetry, the molecular orbitals
are again divided into two types viz., & . RD
VA by
σ -Molecular orbitals
OM
-Molecular orbitals are formed due to linear combination of atomic orbitals along the inter-
ed
I.C
nuclear axis of bonded atoms. They have cylindrical symmetry about the axis. Bonding orbital is
ar
AD
Illustrations:
EM
Pr
YA
+ + + + +
DI
+
W IT
.A
+
W
AD
s
W
s s
bonding orbital
V.
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+ - + - + -
+
s s
s *
anti bonding
orbital
+ + +
+ + - + -
+
-
p s p
s
bonding orbital
- -
+ - -
N
+ + - + -
HA
p s p *
s
bonding orbital
OM
ed
+
+ -
I.C
- + + - - ++ - -
+
ar
AD
ep
p p p
EM
Pr
bonding orbital
YA
CH
DI
W IT
+
.A
- + - + - +- + - + - +
W
AD
p*
W
p p
anti bonding
orbital
V.
π -Molecular orbitals
-Molecular orbitals are formed due to sidewise overlapping of atomic orbitals on either sides of
the internuclear axis of bonded atoms. The electron density is concentrated on either side of the axis.
Bonding orbital is designated as , whereas antibonding orbital is designated as * .
Illustrations:
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Combination of two 'p' orbitals above and below the internuclear axis
+
+
+
+
+
- -
- - - -
p
bonding orbital
- -
+
+
-
+
+
N
-
+
- -
+
HA
p*
anti bonding
orbital
RD
VA by
OM
ed
I.C
DIFFERENCES BETWEEN σ AND π MOLECULAR ORBITALS
ar
AD
3. Rotation about the internuclear axis is Rotation about the internuclear axis is
W IT
.A
symmetrical. unsymmetrical.
W
But for elements heavier than nitrogen i.e., from oxygen onwards, the order will be as follows:
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2 py *2 p y
1s *1s 2 s *2 s 2 px *2 px
2p *2 p
z z
1) MOED of H2
*1s
Energy H H
1s 1s
N
HA
1s
RD H2
VA by
OM
* Electronic configuration of H2 molecule is 1s 2 *1s 2
ed
I.C
ar
2-0
YA
= 1
CH
2
DI
2) MOED of N2
W
V.
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*2 p x
*2 p y *2 pz
2 px
2 p y 2 pz
N
*2 s
HA
Energy
2s RD 2s
VA by
OM
2s
ed
I.C
ar
AD
ep
EM
Pr
YA
CH
*1s
DI
W IT
.A
1s 1s
W
AD
W
1s
V.
10 - 4
* Bond order (B.O) = 3
2
* Hence there is a triple bond in N2 molecule.
2) MOED of O2
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*2 p x
*2 p y *2 pz
2 p y 2 pz
2 px
N
*2 s
HA
Energy
2s RD 2s
VA by
OM
2s
ed
I.C
ar
AD
ep
EM
Pr
YA
CH
*1s
DI
W IT
.A
1s 1s
W
AD
W
1s
V.
10 - 6
* Bond order (B.O) = 2
2
* Hence there is a double bond in O2 molecule.
* It is paramagnetic due to presence of two unpaired electrons.
HYDROGEN BONDING
The electrostatic force of attraction between partially positively charged hydrogen in a polar
molecule and an electronegative atom is called hydrogen bond.
It is represented by dotted line.