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CHEMISTRY LECTURE NOTES

COURSE : VIKAAS (A)


(LECTURE No. 1 TO 20)
TOPIC : CHEMICAL BONDING
Page # 2
LECTURE # 1
NOTE : All faculty members are required to read unit 4 : Chemical Bonding and
molecular stucture from NCERT text book
CHEMICAL BOND :
A force that acts between two or more than two atoms to hold them together as a stable moleculeis known
as a chemical bond.
Why chemical bond forms between atoms
(A) Potential energy concept : Every system tries to minimise their energy. Here system of
two or more atom undergoes chemical bond formation to get minimise their P.E.
r = distance between two nucleus of different atom.
(B) KOSSEL - LEWIS CONCEPT
* Lewis pictured the atom in terms of a positively charged 'Kernel' (the nucleus plus the inner elec-
trons) and the outer shell that could accommodate a maximum of eight electrons.
* Lewis found that octet of electrons, represents a particularly stable electronic arrangement. To
achieve octet of electron atom can combine either by transfer of valence electrons from one
atom to another (gaining or losing) or by sharing of valence electrons. This is known as octet rule
Lewis Symbols: In the formation of a molecule, only the outer shell electrons take part in chemical combi-
nation and they are known as valence electrons.
For example, the Lewis symbols for the elements of second period are as under:
Ionic bond (Electrovalent bond)
(i) It involves complete transfer of one or more electrons from the valence shell to the other atom.
Ionic bond is always form between electro positive and electro negative elements.
or Mg
+2
(F

)
2
Page # 3
(ii) The capacity of an element is terms of number of loss of e

or gain of electron to form ionic


bond is termed electrovalency
Cavalent bond
(i) A covalent bond is formed by mutual sharing of one of more electron pairs between two atoms
to aquire nearest noble gas configuration.
(ii) Sharing of one e

single bond
two e

Double bond
three e

Triple bond
(iii) Covalent bond energy arises due to forces of attraction between nuclei and shared pair of
electron.
or Cl Cl

8e 8e
Thus in water and carbon tetrachloride molecules, formation of covatent bonds can be represented as:
O
2e

8e

2e

H H
H atom attain a duplet of
electrons and O , the octet
C Cl Cl
Cl
Cl
8e

8e

8e

8e

Each of the four Cl atoms


along with the C atom attains
octet of electrons
For example, in the carbon dioxide molecule, we have two doublebonds between the carbon and oxygen
atoms. Similarly in ethene molecule the two carbon atoms are joined by a double bond.
C
O O
8e

8e

8e

Double bonds in CO molecule


2
or O C O
C C
H H
H H
8e

8e

C H molecule
2 4
C C
H
H
H
H
or
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 N
8e

8e

or
N
N molecule
2
C C
8e

8e

C H molecule
2 2
H
H
or
Page # 4
Co-ordinate bond or dative bond is special type of covalent bond is which shared bond pair of
electron is donated by one atom, called doner and other atom is acceptor.
+ or [ A A B]
H
|
: N H
|
H

F
|
F B
|
F

(
(
(
(

F h
| |
F B N H
| |
F H
NH
3
+ H
+
= NH
3
H
+
or NH
4
+
Ex. Lets try Lewis dot structure of following
(a) O
2
(b) O
3
O
O
O
(c) NF
3

N
F
F
F
(d) CO
3
2

C
O

O
(e) HNO
3
HO N
O
O
(f) CO C O
(g) NO
2

N
O

O
(h) CaF
2
(i) NH
4
NO
3
(j) CuSO
4
Pro. 7 Write the Lewis dot structure of CO molecule.
Sol. Step 1. Count the total number of valence electrons of carbon and oxygen atoms. The outer (valence) shell
configuration 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 : CO
Step 3. Draw a single bond (one shared electron pair) between C and O complete the octet on O , the
remaining two electrons are the lone pair on C.
This does not complete the octed on carbon and hence we have to resort to multiple bonding (in this case
a triple bond) between C and O atoms. This satisfies the octet rule condition for both atoms.
Pro.4.2 Write the Lewis structure of the nitrite ion , NO
2

.
Sol. Step 1. Count the total number of valence electrons of the nitrogen atom , the oxygen atoms and the
additional 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 elecron pair) between the nitrogen and each of the oxygen atoms
completing the octets on oxygen atoms. This , however , does not complete the octet on nitrogen if the
remaininig two electrons constitute lone pair on it.
IONIC BOND (ELECTROVALENT BOND) :
The chemical bond formed between two or more atoms as a result of transfer of one or more electrons
between them.
Page # 5
FAVOURABLE CONDITION :
(i) One of the atom must be electro +ve can easily loose e

s or should have few more e

s than a noble gas. It


should have low I.E value
(ii) Other element should be a electro ve element having high I.E. value, and more negative value of electron
gain enthalpy, having few e

s less than noble gas.


(iii) Energy released because of the combination of cation and anion should be high.This energy is also defined
in terms of lattice enthalpy.
Lattice Enthalpy
The Lattice Enthalpy of an ionic solid is defined as the energy required to completely separate one mole of
a solid ionic compound into gaseous constituent ions. For example, the lattice enthalpy of NaCI is 788 kJ
mol-1. This means that 788 kJ of energy is required to separate one mole of solid NaCI into one mole of Na
+1
(g) and one mole of Cl

(g) to an infinite distance.


This process involves both the attractive forces between Ions of opposite charges and the repulsive forces
between ions of like charge. The solid crystal being three- dimensional; it is not possible to calculate lattice
enthalpy directly from the interaction of forces of attraction and repulsion only.
Factors associated with the crystal geometry have to be included.
Na
+
(g) + Cl

(g)

NaCl(s) AH = AH
lattice
ve (always)
Mg
2+
(g) + 2Cl

(g)

MgCl
2
(s)
LECTURE # 2
FACTORS AFFECTING L.E.
(i) Lattice energy (L.E.) o
r
1
r = r
+
+ r

= interionic distance
(ii) L.E. o Z
+
, Z

Z
+
charge on cation in terms electronic

charge
Z

charge on anion in terms electronic



charge
(iii) L.E. o cordination number (C.N.)
C.N. of cation is no. of anion surrounding the cation.
C.N. of anion is no. of cation surrounding the anion
C.N. factor is important only in case of sulphates and carbonates of alkaline earth metals and
coordination number is calculated by experimently or by radius ratio.
BeSO
4
< MgSO
4
< CaSO
4
< SrSO
4
< BaSO
4
Size of cation
|
C.N.
|
L.E.
|
(a) NaCl > KCl (size)
(b) NaCl < MgO (size, charge)
(c) NaCl < MgCl
2
(size)
In size and charge, charge will dominate
Na
2
O > NaF
NaCl < Na
2
S
(d) Al
2
O
3
Na
2
O MgO
Al
2
O
3
> MgO > Na
2
O
Note : Dont discuss melting point of ionic compound here.
CALCULATION OF L.E. :
Indirect methods : Born-Haber Cycle ( Hesss law)
Hesss Law the net enthalpy change of a chemical reaction or of any process always remain same
whether the reaction takes place in 1 step or many step
Page # 6
Born Haber Cycle for NaCl (s)
Na (s) +
H
sub
Na(g)
H
I.E.
Na (g) + Cl (g)
+ -
1
2
1
2
Cl (g)
2
H
f
NaCl(s)
H
Eg
H
BE
( )
Cl(g)
H
L.E.
AH
f
enthalpy of formation of any compound is defined as the enthalphy change when 1 mol of that
compound is formed form the elements in their standard states
AH
f
= AH
sub
+ AH
I.E.
+
2
1
AH
BE
+ AH
eg
+ AH
L.E.
+ve/ve
+

+

+ +
Generally +ve +ve +ve +ve/-ve
Q. Born haber cycle for MgCl
2
(s) & calculate its lattice energy in terms AH
Sub
(Mg),
1
E . I
H A
(Mg),
2
E . I
H A (Mg),
AH
eg
(Cl); AH
B.E.
(Cl
2(g)
) + AH
f
(Mg Cl
2
,(s))
Mg (s) + Cl (g)
2
AH
f
MgCl (s)
2
Mg(g)
Mg (g)
+
Mg (g) +
2+
AH
sub
AH
I.E1
AH
I.E2
AH
B.E
2Cl(g)
2 H A
eg
2Cl (g)

AH
L.E
AH
f
= AH
sub
+
1
E . I
H A +
2
E . I
H A + AH
BE
+ AH
eg
+ AH
L.E.
Q. Born haber cycle for Al
2
O
3
(s)
2Al (s) + O (g)
2
AH
f
Al O (s)
2 3
2Al(g)
2Al (g)
+
2Al (g)
2+
2AH
sub
2AH
I.E
1
2AH
I.E2
AH
B.E
3O(g)
3AH
eg
2Al (g) + 3O (g)
3+ 2
AH
L.E
3
2
2AH
I.E3
3
2
3O (g)

3AH
eg
1
2
AH
f
= 2AH
sub
+ 2
1
E . I
H A + 2
2
E . I
H A +
3
E . I
H 2A
+
2
3
AH
BE
+
1
eg
H 3A
+
2
eg
H 3A
+ AH
L.E.
Page # 7
Q. Born haber for NaBr
Na (s) +
H
sub
Na(g)
H
I.E.
Na (g) + Br (g)
+ -
1
2
1
2
Br
2
() !
H
f
NaBr(s)
H
vap
H
Br(g)
1
2
Br (g)
2
H
B.E.
1
2
H
Eg
Born haber for NaI
Na (s) +
H
sub
Na(g)
1
2
1
2
I (s)
2
H
f
NaI(s)
I(g)
1
2
I (g)
2
H
B.E.
1
2
Hsub(I (s)) 2
Ex. MgO found as Mg
2+
O
2
but not as Mg
+
O

Mg
2+
O
2


L.E. is very large (-ve)
Mg
+
O

L.E. is ve
General characteristics of ionic compounds :
(a) Physical state (b) Melting and boiling points
(c) Conductance (d) Crystal structure
(e) Brittlrness (f) Solubility
(g) Isomorphism
Solvation or Hydration :
Whenever any compound generally ionic or polar covalent is dissolved in an polar solvent or in water then.,
different ions of the compound will get separated and will get surrounded by polar solvent molecules. This
process is known as solvation or hydration. Energy released in this process is known as solvation energy or
hydration energy
The ionic compound will be soluble only if solvation energy (H.E.) is more than the lattice energy
Page # 8
Factors affecting solvtion energy or hydration energy.
S.E. o Z
+
Z

o
|
.
|

\
|

+
+ r
1
r
1
o
|
|
.
|

\
|
e

r
1
1
(nature of solvent) where c
r
is dielectric constant.
Greater the polarity, greater will be e
r
e
r

|
1/ e
r

+
, 11/e
r |
S.E.
|
H
2
O CH
3
OH C
2
H
5
OH C
6
H
6
er 81 34 27 34
Applications of Hydration energy
(a) Size of the hydrated ions: Greater the hydration of the ion greater will be its hydrated radii
Li
+
(aq) > Na
+
(aq)
(b) Mobility of the ion: more is the hydration smaller will be the mobility of the ions
Li
+
(aq) < Na
+
(aq) < K
+
(aq) < Rb
+
(aq) < Cs
+
(aq)
(c) Electrical conductance : is related to mobility so follows the same order
LECTURE # 3
Now we have

L.E. o
+
+ r r
1
and S.E. o
|
.
|

\
|
+
+
r
1
r
1
From these 2 equations, it can be mathematically proved that if the difference between the radii of Cation &
Anion is large then, solvation energy will dominate and if radii are comparable or difference is small, then
lattice energy will dominate
Greater the difference between radii, greater will be solubility
100 10 100 20 100 30 100 40
Cs F > Cs Cl > Cs Br > Cs I
L.E.
110
1
120
1
130
1
140
1
S.E.
10
1
100
1
+
20
1
100
1
+
30
1
100
1
+
40
1
100
1
+
decreament in solvation energy > decreament in lattice energy
Solubility Orders.
Increase difference in radii
|
solubility
|
and viceversa
i. LiF LiI increses
ii. NaF NaI increase
iii. LiF CsF increase
iv CsF CsI decrease
v LiI CsI decrease
vi Be(OH)
2
Ba(OH)
2
increase
vii LiOH CsOH increase
viii BeSO
4
BaSO
4
decrease
white ppt
ix LiClO
4
CsClO
4
decrease
Page # 9
Explain by Fazans rule, because of covalent character
|
solubility !
x BeF
2
BeI
2
decrease
xi AgF AgI decrease
Q. NaF Na[BF
4
]

which is more soluble


Ans. Na[BF
4
]

difference will
|
solubility
|
Q. Which is more soluble CsI
3
or [N(CH
3
)
4
]
+
I
3

Ans. CsI
3
Note : It has generally observed that larger cation will be thermally stable with the larger anion and
smaller will be stable with the smaller anion.
e.g. [N(CH
3
)
4
]
+
I
3

more stable than CsI


3
.
Facts about solubility in H
2
O :
a All the salts of NH
4
+
, alkalimetals are soluble except LiF, Li
3
PO
4
, Li
2
C
2
O
4
, Li
2
CO
3
b All the NO
3

, ClO
4

, CH
3
COO

are soluble
c S
2
( sulphides) of NH
4
+
, alkalimetals or alkaline earth metal are soluble
rest are insoluble
d Sulphates of all elements are soluble except
" " " # " " " $ %
. whiteppt
2 2 2 2
Pb , Ca , Sr , Ba
+ + + +
e Hydroxides of NH
4
+
, alkalimetals and Ba(OH)
2
are soluble rest are insoluble
f Halides are generally soluble except AgCI(white), AgBr(pale yellow), AgI(yellow) and PbI
2
(yellow)
Ex. Which salt is insoluble in the following reaction
(i) BaCl
2
+ Na
2
SO
4
BaSO
4
+ 2NaCl
(ii) BaCl
2
+ 2AgNO
3
2AgCl + Ba(NO
3
)
2
(iii) (NH
4
)
3
PO
4
+ 3LiCl 3NH
4
Cl + Li
3
PO
4
(iv) Na
2
CO
3
+ (CH
3
COO)
2
Pb PbCO
3
+ 2CH
3
COONa
(v) Ba(OH)
2
+ MgCl
2
Mg(OH)
2
+ BaCl
2
Ans. (i) BaSO
4
(ii) AgCl (iii) Li
3
PO
4
(iv) PbCO
3
(v) Mg(OH)
2
Ex. Predict the product of decomposition of given polyhalides
Rb
+
[ICl
2
]

RbCl + ICl

halide with stable lattice ( having ions of comparable radii) are produced
Li Be F
Na Mg Cl Na
+
< F

~

K
+
K Ca Br K
+
< Cl


~
Rb
+
Rb Sr I
Cs Br At
K
+
[Br ICl]


A

KCl + IBr
COVALENT CHARACTER IN IONIC COMPOUNDS (FAJANS RULE) :
! There is no compound which is 100% ionic.
! Covalent character in ionic compound can be explained with the help of Fajans rule.
According to Fajans rules, covalent character will be more if
Cation Anion
(i) Small size (i) Large size
(ii) More charge (ii) More charge
(iii) Pseudo inert gas configuration of cation
More distortion of anion, more will be polarisation then covalent character increases.
Page # 10
Factors affecting the polarisation :
(i) Small size of cation " polarisation.
e.g. BeCl
2
MgCl
2
CaCl
2
SrCl
2
BaCl
2
Size of cation
|
Polarisation
+
Covalent character
+
(ii) Large size of anion " polarisation
e.g.
(iii) Charge on cation or anion " polarisation.
(a) Charge on cation :
NaCl MgCl
2
AlCl
3
Na
+
Mg
+2
Al
+3

Charge of cation
|
Polarisation
|
Covalent character
|
(b) Charge on anion :
AlF
3
Al
2
O
3
AlN
F

, O
2
, N
3

Charge on anion
|
Polarisation
|
Covalent character
|
(iv) Cation which has pseudo inert gas configuration, shows more polarising power in comparison of cation that
has inert gas configuration. CuCl > NaCl (Covalent character)
ion configurat gas
ion configurat gas inert inert Pseudo
8e 18e
p s 2 , s 1 Na d p 3s ] Ne [ Cu

6 2 2 10 6 2
= =
+ +
Application & Exceptions of Fajans Rules :
Applications :
(i) Ag
2
S is less soluble than Ag
2
O in H
2
O because Ag
2
S is more covalent due to bigger S
2
ion.
(ii) Fe(OH)
3
is less soluble than Fe(OH)
2
in water because Fe
+3
is smaller than Fe
+2
and thus charge is more.
Fe(OH)
3
is more covalent than Fe(OH)
2
.
(iii) The colour of some compound can be explained on the basis of polarisation of their bigger negative ions.
For ex : AgCl is white AgBr, AgI, Ag
2
CO
3
are yellow
The bigger anions are more polarised.
and hence their electrons get excited by partial absorption of visible light
! similarly, SnCl
2
is white but SnI
2
is red.
PbCl
2
is white but PbI
2
is yellow.
Page # 11
(iv) Variation of M.P. [M.P. of covalent < M.P. of ionic] :
BeCl
2
, MgCl
2
, CaCl
2
, SrCl
2
, BaCl
2
>>
ionic charater | , ' r
+
ion | & r

ion = constant MP |
CaF
2
, CaCl
2
, CaBr
2
, CaI
2
>>
Covalent character | M.P. + ' r

ion | & r
+
ion = constant
(v) Thermal stability of carbonates ionic character
Li
2
CO
3
< Na
2
CO
3
< K
2
CO
3
< Rb
2
CO
3
< Cs
2
CO
3
Li
2
CO
3

A
Li
2
O + CO
2
|
LECTURE # 4
COVALENT BOND :
Theories explaning the nature of covalent bond are as follows
g
g
g
M
Draw Lewis dot structures
Each bond Is formed as a result of sharing of an electron pair between the atoms.
Each combining atom contributes 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.
TO DECIDE THE CENTRAL ATOM
(1) In general the least electronegative atom occupies the central position in the molecule/ion. For ex-
ample in the NF
3
and CO
3
2
, nitrogen and carbon are the centra atoms whereas fluorine and oxygen occupy
the terminal positions.
(2) Generally the atom which is/are less in number acts as central atom
(3) Generally central atom is the atom which can form maximum number of bonds( which is generally equal
to the number of electrons present in the valence shell of the atom).
(4) Atom of highest atomic number or largest atom atom generally acts as central atom.
Hence we can say that Flourine and Hydrogen can never act as central atoms.
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 pairs. The basic requirement being that each bonded atom
gets an octet of electrons.
Lewis representations of a few molecules/ions are given in the following Table
Page # 12
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 difference between the number of valence electrons of that atom in an isolated or free state
and the number of electrons assigned to that atom in the Lewis structure. It is expressed as :

The counting is based on the assumption that the atom in the molecule owns one electron of each shared
pair and both the electrons of a lone pair.
Let us consider the ozone molecule (O
3
). The Lewis structure of O
3
, may be drawn as :
The atoms have been numbered as 1. 2 and 3. The formal charge on:
The central O atom marked 1 = 6 2
2
1
(6) = + 1
The end O atom marked 2 = 6 4
2
1
(4) = 0
The end O atom marked 3 = 6 6
2
1
(2) = 1
Hence, we represent O
3
along with the formal charges as follows:
We must understand that formal charges do not indicate real charge separation within the molecule. Indicatng
the charges on the atoms in the Lewis structure only helps in keeping track of the valence electrons in
Page # 13
themolecule. Formal charges help in the selection of the lowest energy structure from a number of
possible Lewis structures for a given species. Generally the lowest energy structure is the one with the
smallest formal charges on the atoms. The formal charge Is a factor based on a pure covalent view of bonding
in which electron pairs are shared equally by neighbouring atoms.
Ex. Calculate the formal charge on the all atoms present in the molecules.
(a) NO
3

(b) NH
4
+
(c) N
3

Ans. (a) (b) (c)

N =
+
N
=

N
Limitations of the Octet Rule
The octet rule, though useful, is not universal. It is quite useful for understanding .the structures of most of
the organic compounds and it applies mainly to the second period elements of the periodic table. There are
three types of exceptions to the octet rule.
1. The incomplete octet of the central atom
In some compounds, the number of electrons surrounding the central atom Is less than eight. This is espe-
cially the case with elements having less than four valence electrons. Examples are LiCl. BeH
2
and BCl
3
.

Li. Be and B have 1,2 and 3 valence electrons only. Some other such compounds are AlCl
3
and BF
3
.
2. Odd-electron molecules
In molecules with an odd number of electrons like nitric oxide. NO and nitrogen dioxide. NO
2
, the octet rule
is not satisfied for all the atoms
2
O Cl
.
3. The expanded octet/ super octet / hypervalent compound
Elements in and beyond the third period of the periodic table have, apart from 3s and 3p orbitals, 3d orbitals
also available for bonding. In a number of compounds of these elements there are more than eight valence
electrons around the central atom. This is termed as the expanded octet. Obviously the octet rule does not
apply in such cases.
Some of the examples of such compounds are: PF
5
SF
6
, H
2
SO
4
and a number of coordination compounds.
Interestingly, sulphur also forms many compounds in which the octet rule is obeyed. In sulphur dichloride,
the S atom has an octet of electrons around it.
4. Other drawbacks of the octet theory
It is clear that octet rule is based upon the chemical Inertness of noble gases. However, some noble gases
(for example xenon and krypton) also combine with oxygen and fluorine to form a number of compounds like
XeF
2
, KrF
2
, XeOF
2
etc.,
This theory does not account for the shape of molecules.
It does not explain the relative stability of the molecules being totally silent about the energy of a molecule.
Page # 14
MODERN CONCEPT OF COVALENT BOND (VBT) :
(Do not take much time here to discuss with the students)
As we know that Lewis approach helps in writing the structure of molecules but it fails to explain the
formation of chemical bond. It also does not give any reason for the difference in bond dissociation enthalpies
and bond lengths in molecules like H
2
(435.8 kJ mol

, 74 pm) and F
2
(150.6 kJ mol

, 42 pm). although in both
the cases a single covalent bond is formed by the sharing of an electron pair between the respective atoms.
It also gives no idea about the shapes of polyatomic molecules.Similarly the VSEPR theory gives the
geometry of simple molecules but theoretically, it does not explain them and also it has limited applications.
To overcome these limitations the two Important theories based on quantum mechanical principles are
Introduced. These are valence bond (VB) theory and molecular orbital (MO) theory.
Valence bond theory was introduced by Heitler and London (1927) and developed further by Pauling and
others. A discussion of the valence bond theory is based on the knowledge of atomic orbitals, electronic
configurations of elements (Units 2), the overlap criteria of atomic orbitals, the hybridization of atomic orbitals
and the principles of variation and superposition. A rigorous treatment of the VB theory in terms of these
aspects is beyond the scope of this book. Therefore, for the sake of convenience, valence bond theory has
been discussed in terms of qualitative and non-mathematical treatment only. To start with, let us consider
the formation of hydrogen molecule which is the simplest of all molecules. Consider two hydrogen atoms A
and B approaching each other having nuclei N^ and Ny and electrons present in them are represented by e
and e^. When the two atoms are at large distance from each other, there is no interaction between them. As
these two atoms approach each'other, new attractive and repulsive forces begin to operate.
Attractive forces arise between:
(i) nucleus of one atom and its own electron that is N
A
e
A
and N
B
e
B
.
(ii) nucleus of one atom and electron of other atom i.e., N
A
e
B
. N
B
e
A
.
Similarly repulsive forces arise between
(i) electrons of two atoms like e
A
e
B
,
(ii) nuclei of two atoms N
A
N
B
.
Attractive forces tend to bring the two atoms close to each other whereas repulsive forces tend to push them
apart (Fig. 4.7).
Fig- 4.7 Forces of attraction and repulsion during the formation of H
2
molecule.
Experimentally it has been found that the magnitude of new attractive force is more than the new repulsive
forces. As a result, two atoms approach each other and potential energy decreases. Ultimately a stage is
reached where the net force of attraction balances the force of repulsion and system acquires minimum
energy. At this stage two hydrogen atoms are said to be bonded together to form a stable molecule having
the bond length of 74 pm.
Since the energy gets released when the bond is formed between two hydrogen atoms, the hydrogen mol-
ecule is more stable than that of isolated hydrogen atoms. The energy so released is called as bond en-
thalpy, which is corresponding to minimum in the curve depicted in Fig. 4.8. Conversely. 435.8 kJ of energy
is required to dissociate one mole of Hg molecule.
H
2
(g) + 435.8 kJ mol

H(g) + H(g)
Page # 15
Fig. 4.8 The potential energy curve for the formation of H
2
molecule as a function of internuclear distance of
the H atoms. The minimum in the curve corresponds to the most stable state of H
2
.
4.5.1 Orbital Overlap Concept
In the formation of hydrogen molecule, there is a minimum energy state when two hydrogen atoms are so
near that their atomic orbltals undergo partial interpenetration. This partial merging of atomic orbitals is
called overlapping of atomic orbitals which results in the pairing of electrons. The extent of overlap decides
the strength of a covalent bond. In general, greater the overlap the stronger is the bond formed between two
atoms. Therefore, according to orbital overlap concept, the formation of a covalent bond between two atoms
results by pairing of electrons present In the valence shell having opposite spins.
Main points of valency bond theory :
(i) A covalent bond is formed by partial overlapping of two atomic orbitals
(ii) More is the extent of overlapping between the two atomic orbital, stronger will be bond.
< < [Principal Quantum no. same, n = 2]
(o) (o) (o)
' s orbital are spherical in nature so they are least diffused hence it will provide less area for overlapping.
(iii) Orbitals which are undergoing overlapping must be such that
(a) Each orbital should have one electron with opposite spin
(for formation of covalent bond)
(b) One orbital have pair of electron and the other orbital have no electron
(for formation of co-ordinate bond)
(iv) If the overlapping is along the molecular axis then bond will be sigma (o) & in the perpendicular direction,
it will be pi(t) bond.
Page # 16
! Examples of overlapping of pure atomic orbitals.
(i) H
2
(ss) H = H =
(ii) HCl gas molecule (s-p)
(iii) F
2
, Cl
2
, Br
2
, I
2
(p-p)
F
2
Cl
2
Br
2
I
2
2p-2p 3p-3p 4p-4p 5p-5p
4.5.4 Types of Overlapping and Nature of Covalent Bonds (NCERT Theory)
The covalent bond may be classified into two types depending upon the types of overlapping :
(i) Sigma(o) bond, and (ii) pi (t) bond
(i) Slgma(o) bond : This type of covalent bond is formed by the end to end (hand-on) overlap of bonding
orbitals along the intemuclear axis. This is called as head on overlap or axial overlap. This can be formed by
any one of the following types of combinations of atomic orbitals.
" s-s overlapping : In this case, there is overlap of two half filled s-orbitals along the intemuclear axis as
shown below :
" s-p overlapping: This type of overlap occurs between half filled s-orbitals of one atom and half filled p-
orbitals of another atom.
" p-p overlapping : This type of overlap takes place between half filled p-orbitals of the two approaching
atoms.
(iii) pi(t) bond : In the formation of t bond the atomic orbitals overlap in such a way that their axes remain
parallel to each other and perpendicular to the intemuclear axis. The orbitals formed due to sidewise
overlapping consists of two saucer type charged clouds above and below the plane of the participating
atoms.
Page # 17
4.5.5 Strength of Sigma and pi Bonds
Basically the strength of a bond depends upon the extent of overlapping- In case of sigma bond, the overlaping
of orbitals takes place to a larger extent. Hence, it is stronger as compared to the pi bond where the extent
of overlapping occurs to a smaller extent. Further, it is important to note that pi bond . between two atoms is
formed in addition to a sigma bond. It is always present in the molecules containing multiple bond (double or
triple bonds)
4.5.3 Overlapping of Atomic Orbitals
When two atoms come close to each other. there is overlapping of atomic orbitals. This overlap may be
positive, negative or zero depending upon the properties of overlapping of atomic orbitals. The various ar-
rangements of s and p orbitals resulting in positive, negative and zero overlap are depicted in Fig. 4.9.
The criterion of overlap, as the main factor for the formation of covalent bonds applies uniformly to the
homonuclear/heteronuclear diatomic molecules and polyatomic molecules. In the case of polyatomic mol-
ecules like CH
4
, NH
3
and H
2
O, the VB theory has to account for their characteristic shapes as well. We know
that the shapes of CH
4
, NH
3
, and H
2
O molecules are tetrahedral, pyramidal and bent respectively. It would
be therefore interesting to find out if these geometrical shapes can be explained in terms of the orbital
overlaps.
! Following overlappings are not allowed.
(A) Zero overlapping :
(a) (i)
(ii) Also in an s-orbital, + is positive throughout but in p-orbital it is positive and negative
Total overlapping will zero
(b) this type of overlapping is not allowed.
Because it is neither along the molecular axis nor to it.
(B) Negative overlapping :
not allowed
not allowed
not allowed
Q. Count the t & o bonds in N C C C C N
Ans. 6 t & 5 o
Page # 18
LECTURE # 5
4.5.2 Directional Properties of Bonds
As we have already seen the formation of covalent bond depends on the overlapping of atomic orbitals. The
molecule of hydrogen is formed due to the overlap of 1s-orbitals of two H atoms, when they combine with
each other.
In case of polyatomic molecules like CH
4
, NH
3
and H
2
O the geometry of the molecules is also important in
addition to the bond formation. For example why is it so that CH
4
molecule has tetrahedral shape and HCH
bond angles are 109.5 ? Why is the shape of NH
3
molecule pyramidal ?
The valence bond theory explains the formation and directional properties of bonds in polyatomic molecules
like CH
4
, NH
3
and H
2
O , etc. in terms of overlap and hybridisation of atomic orbitals.
NEED OF NEW CONCEPT (HYBRIDISATION) :
The valance bond theory (overlapping concept) explains satisfactorily the formation of various molecules but
it fails to account the geometry and shapes of various molecules. It does not give the explanation why BeCl
2
is linear , BF
3
is planar, CH
4
is tetrahedral , NH
3
is pyramidal and water is V shaped molecule.
In order to explain these cases , the valance bond theory has been supplemented by the concept of hybrid-
ization. This is a hypothetical concept and was introduced by Pauling & Slater.
Let us first consider the CH
4
(methane) molecule. The electronic configuration of carbon in its ground state is
[He]2s
2
2p
2
which in the excited stale becomes [He] 2s
1
2p
x
1
2p
x
1
2p
x
1
. The energy required for this excitation
is compensated by the release of energy due to overlap between the orbitals
of carbon and the hydrogen.The four atomic orbitals of carbon, each with an unpaired electron can overlap
with the 1 s orbitals of the four H atoms which are also singly occupied. This will result in the formation of tour
C H bonds. It will , however , be observed that while the three p orbitals of carbon are at 90 to one another,
the HCH angle for these will also be 90
0
That Is three C H bonds will be oriented at 90
0
to one another. The
2s orbital of carbon and the 1s orbital of H are spherically symmetrical and they can overlap in any direction.
Therefore the direction of the fourth C H bond cannot be ascertained. This description does not fit in with the
tetrahedral HCH angles of 109.5. Clearly, it follows that simple atomic orbital overlap does not account for
the directional characterisics of bonds in CH
4
. Using similar procedure and arguments, it can be seen that in
the case of NH
3
and H
2
O molecules, the HNH and HOH angles should be 90. This is in disagreement with
the actual bond angles of 107
0
and 104.5 in the NH
3
and H
2
O molecules respectively.
Hybridisation
Inter Mixing of pure atomic orbitals before bonding to produce new hybrid orbitals, specially for bonding
purpose
Postulates
(i) It is a hypothetical concept
(ii) Only those orbitals can take part in hybridisation which have comparable ( almost equal ) energies. So,
orbitals must be having same principal quantum number or these can be a maximum different of unity (if d
orbitals are involved)
(iii) The number of hybrid orbitals generated will be equal to the number of pure atomic orbitals taking part in
hybridisation.
(iv) All three type of orbitals (having a pair of e

s or having a unpaired e

or completely empty can take part in


hybridisation.
empty orbitals are used in coordination compounds
(v) The hybrid orbital generated will be represented by
nucleus
bigger lobe will
be used for bonding
(vi) Since hybrid orbitals have been generated for the bonding purpose. So, bond formed by a hybrid orbitals are
stronger than bond formed by pure atomic orbitals
(vii) The orientations of hybrid orbitals generated will be dependent on type of atomic orbitals and on number of
atomic orbitals taking part in hybridisation
Page # 19
s + p 2 new sp hybridised orbitals
(sp hybridisation)
s +2p

3 new sp
2
hybridised
(sp
2
hybridisation)
s + 3p 4 new sp
3
hybridised
s + 3p + d

sp
3
d
s + 3p + 2d

sp
3
d
2
s + 3p + 3d

sp
3
d
3
d + s + 2p

dsp
2
The orientation of hybridised orbitals will be such that there will be minimum repulsion between any two
hybridised orbitals s + p s + p
x
SP
180
x axis
s + p
Y
Yaxis
s + 2p s + p
x
+ p
y

in x - y plane
120
s + p
y
+ p
z
in y z plane
s + p
x
+ p
z
in x z plane
sp
3
s + p
x
+ p
y
+ p
z
directed along the 4 corners of tetrahedron
(viii) hybridised orbitals will be generally used for making o bond and for t bond pure p-orbitals will be used
sp -sp bond
2 2
t
(unstable)
Calculation of state of Hybridisation :
Steric number rule
Steric number of any atom in a molecule = number of atoms bonded to an atom + number of lone pair left on
the atom after bonding
S.N = 2 SP.
S.N. = 3 SP
2
S.N. = 4 SP
3
S.N. of central atom will decide the shape or structure of the molecule
Page # 20
Ex. (a) CO
2
O
:
: C O
:
:
(SP )
2
S.N. = 3
(S+Px+Pz)
SP
(S+Px)
S.N. = 3 (SP )
2
(S+Px+Py)
S.N of C=2
xy plane
:
:
:
:
x-z
plane
t(xy)
py
t(xz)
x axis
o
o
(s + px + pz) (s + px) (s + px+ py)
(b) SF
6
S
F
F
F
F
F
S.N. = 4(SP )
3
S.N. = 6
(SP d )
3 2
(c)
F
B
F F
S.N = 3 (SP)
2
S.N.= 4 (SP)
3
(d) SO
2
S
O O :
:
:
:
:
<120
S.N = 3 (SP )
2
S.N = 3(SP )
2
(e) SO
3
S
O O
:
:
:
:
:
120
S.N = 3 (SP )
2
S.N = 3(SP )
2
O
:
:
(f) CN

: C N
:
S.N + 2
(SP)
S.N = 2
(SP)
Or
: C N
:
.x
Out of C & N less E.N. element i.e C will donate its !.P.
(g) NH
3
N
:
S.N = 4 (SP )
3
H
H
H
(h) NH
4
+
N S.N = 4 (SP )
3
H
H
H
H
+
Page # 21
sp hybridisation :
This type of hybridisation involves the mixing of one s and one p orbital rcsull.ingin the formation of two
equivalert sp hybrid orbitals. The suitable orbiials for sp hybridisation are s and p
z
, if the hybrid orbitals arc to
lie along the z-axis. Each sp hybrid orbitals has 50% s-character and 50% p-character. Such a molecule in
which the central atom is sp-hybridised and linked directly to two other central atoms possesses linear
geometry. This type of hybridisation is also known as diagonal hybridisation.
The two sp hybrids point in the opposite direction along the z-axis with projecting positive lobes and very
small negative lobes, which provides more effective overlapping resulting in the formation of stronger bonds.
Example of a molecule having sp hybridisation
BeCl
2
: The ground state electronic configuration of Be is 1s
2
2s
2
. In the exited state one of the 2s-electrons
is promoted to vacant 2p orbital to account for its divalency. One 2s and one 2p-orbitals get hybridised to
form two sp hybridised orbitals. These two sp hybrid orbitals are oriented in opposite direction forming an
angle of 180. Each of the sp hybridised orbital overlaps with the 2p-orbital of chlorine axially and form two
Be-Cl sigma bonds. This is shown in Fig
Fig.4.10 (A) Formation of sp hybrids from s and p orbitals ; (B) Formation of the linear BeCl
2
molecule.
Examples of SP hybridisation.
(a)
C
SP
H C N, H C C H
(b) = C = O = C = O H
2
C = C = CH
2
Q. Will all the 4 H atom in propadiene be coplanar
Ans. NO
C C C
H
H H
H
sp p
x z
sp
x s
p
p
x
y
p
y Pz
xz
xy
(c)
C
+
(ion radical
S.N =2(sp)
+

2
CH
(d) C
.
2
CH .
( triplet carbene)
C
:
S.N. = 3
(sp )
2 ) Carbene glet (sin
CH :
2
C
:
Total spin multiplicity of any molecule = 2S + 1
S = |summation of all the spins|
Triplet S = (

+
2
1
2
1
= 1
Total spin multiplicity = 3 (triplet)
Singlet S = zero
Total spin multiplicity = 1 (singlet)
Page # 22
Q. Which is more stable
triplet carbene or singlet carbene?
Ans. triplet carbene
(f) BeCl
2
(g)
: Cl Be Cl
:
::
: :
S.N= 4(SP )
3
S.N = 2
(SP)
In solid state, BeCl
2
is formed in form of polymer (BeCl
2
)
n
Be Be Be Be Be Be Be
Cl Cl Cl Cl Cl Cl Cl
Cl Cl Cl Cl Cl Cl Cl Cl
S.N = 4 (SP )
3
Bond angle 90 95
(g) N
2

: N N :
S.N = 2 (SP)
(h) Azide ion N
3

N
3
(nitride ion)
: N
x.
N N:
:
: N
: N
.x
x.
N
N
N
N
:
:
:
SP

N =
+
N
=

N SP

+
SP
In azide ion, both NN bond lengths are equal and it is a linear ion.
(i) Hydroazoic acid (HN
3
)
N
H
N
+
N
:
120
Its a bent molecule
2 N N bond length are not equal as in one bond there is extra electrostatic attraction which
+
the bond
length.
It will be planar molecule
Q. CH
3
CN is a weaker lewis base than CH
3
NH
2
Sol.
SP
: N C CH
3
+

:
SP
3
N
H
H
H C
3
N
sp
>
3
sp
N E.N order
more E.N., lesser will be tendency to donate the l.p.