2008-2009

APPLIED
PHYSICS

PREPARED BY
Mr. A.CHARIS ISRAEL. M.Sc., B.Ed., (Ph.D.)
Asst. Professor of PHYSICS
Mobile No: +91-9866934653
SECUNDERABAD

1
 UNIT – I (PART – A) BONDING IN SOLIDS 2008-2009

Contents

DEFINITIONS: .................................................................................................................................... 3

TYPES OF BONDING IN SOLIDS: .................................................................................................... 4

FORCES BETWEEN TWO INTERACTING ATOMS ...................................................................... 8

POTENTIAL ENERGY: .................................................................................................................... 10

ESTIMATION OF COHESIVE ENERGY AND DISSOCIATION ENERGY .................................. 11

COHESIVE ENERGY OF IONIC CRYSTALS (NACL): .................................................................. 13

SOLVED PROBLEM: ........................................................................................................................ 15

MADELUNG CONSTANT: ............................................................................................................... 16

QUESTIONS ...................................................................................................................................... 17

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 UNIT – I (PART – A) BONDING IN SOLIDS 2008-2009

UNIT – I PART - A
BONDING IN SOLIDS

DEFINITIONS:
Electro-positive atoms:
The atoms which readily give-up electrons are called Electro-positive atoms, usually
metal atoms.
Ex: Group I & II elements i.e., Na, K, Ca, Cs etc.
Among all elements most electropositive element is Cesium (Cs).
Electro-negative atoms:
The atoms which readily take-up electrons are called Electro-negative atoms, usually
non-metallic atoms.
Ex: Group VI & VII elements i.e., O, F, Cl, Br etc.
Among all elements Fluorine (F) is the most electronegative element.
Electronegativity is used to predict the type of bonding in a molecule:
If the electronegativity difference between two elements is greater than 1.9, then the bond
formed is ionic. If the electronegativity difference between two elements is less than 1.9, then the
bond formed is covalent.
For example: The electronegativity difference between Na (0.9) and Cl (3.0) is 2.1 in NaCl.
So the bond in NaCl is ionic.
Ionization potential or Ionization Energy1:
“The energy necessary to remove the electron from an atom i.e. creating a positive ion is
called ionization energy”.
The element with highest ionization potential value is Helium (He) and Cesium (Cs) has
the least.
Electron affinity:
“The energy given up when a neutral atom gains an electron and becomes a negative ion
is called electron affinity”.
Among all elements Chlorine (Cl) has highest electron affinity and inert gases have zero
electron affinity.
Ionic Size:
Al3+ is smaller than Mg2+
Al3+ and Mg2+ both have 10 electrons. But Al3+ has 13 protons while Mg2+ has 12 protons. Hence
effective nuclear charge in Al3+ is more, which leads to shrinkage of ionic size.
For example, the order of ionic radii varies as Na+ > Mg2+ > Al3+ > Si4+.

1
Ionization potential and Ionization energy are used synonymously. Ionization potential refers to single atom while ionization
energy refers to 1 mole of atoms.

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 UNIT – I (PART – A) BONDING IN SOLIDS 2008-2009

TYPES OF BONDING IN SOLIDS:

Different charge distributions2 between the atoms gives rise to different types of bonding
and can be classified into five types. Also, basing on the bond strengths, atomic bonding can be
grouped into primary and secondary bonding. Primary bondings have the bond energies in the
range of 0.1 - 10 eV/bond and Secondary bondings have the bond energies in the range of
0.01 - 0.5 eV/bond.
PRIMARY BONDINGS3:
(i) Ionic Bonding
(ii) Covalent Bonding
(iii) Metallic Bonding
SECONDARY BONDINGS4:
(iv) Hydrogen Bonding
(v) Van der Waals Bonding

IONIC BONDING:
“The bond formed by the complete transfer of valance electrons from one atom to
another atom, in order to stabilize their outer electronic configurations is called ionic bond5”.
An ionic bonding is the Coulomb electrostatic attractive force6 between a positive ion
(cation) and a negative ion (anion) when they are brought closer to each other. This type of
bonding occurs between electro-positive and electro-negative atoms. The source of cohesive
energy that binds the ionic crystals together is the coulomb electrostatic interaction7 between the
oppositely charged ions.
Examples: NaCl8, KCl, etc9.
The magnitude of this cohesive energy is about 5-10 eV per molecule, for NaCl it is 7.95 eV.
Properties of Ionic Solids:
1) Ionic solids are crystalline10 in nature.
2) They are physically hard11 and brittle.
3) They have high melting and boiling points.

2
Transfer of electrons, sharing of electrons, electrons surrounding the positive ion core and formation of dipoles are the
different types of charge distributions.
3
Primary bonds are also called as Interatomic Bonds.
4
Secondary bonds are also called as Intermolecular Bonds.
5
Ionic bond is formed between highly electropositive and highly electronegative elements.
6
In spite of electrostatic attraction there exists a repulsive force between the negatively charged electron clouds which become
operative when the two ions try to overlap.
7
The ions arrange themselves in such a way that the coulomb attraction between ions of opposite sign is stronger than the
coulomb repulsion between ions of the same sign.
8
Crystal structure of NaCl is Face centered cubic with coordination number 6.
9
KBr, MgO, KOH, Al2O3 , (all alkali halides, alkaline oxides) are the few more examples of ionic solids.
10
They usually crystallize in relatively close-packed structures. The structure (simple, body-centered, face-centered etc.,)
actually depends upon the radius ratio of the two ions.
11
On account of strong binding energies the ionic crystals are physically hard, brittle and have a relatively high melting and
boiling points.

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 UNIT – I (PART – A) BONDING IN SOLIDS 2008-2009

4) They are quite poor electrical conductors12 at normal temperatures and at elevated
temperatures ionic conductivity13 results.
5) They are soluble in polar solvents and insoluble in non-polar solvents.
6) They are usually transparent to visible light.
7) The ionic bonds are non-directional14.

COVALENT BONDING:
“The bond formed by sharing of valance electron pairs between two or more similar or
dissimilar atoms such that no net charge is associated with any of the atoms is called covalent
bond15”.
The attractive force between the atoms participating in the covalent bonding is due to the
anti-parallel spins16 of the sharing electrons. In covalent crystals, the total cohesive energy or
binding energy will not only include the energy of bonds but also the energy of interaction
between different bonds. However, in many cases the binding energy is quite close to the sum of
bond energies; this is particularly true for diamond.
Examples: Hydrogen molecule (H2), HCl, etc.17
The binding energy of carbon in diamond is 7.4eV.
Properties of Covalent Solids:
1) The covalent bonds are strongly directional18 in character.
2) Different covalent solids have different bond strengths, hence they exhibit varying19
physical properties.
3) They are hard and brittle, and possess crystalline structures with high20 melting and
boiling points.
4) Electrical conductivity is normally not possible and so these crystals are insulators at
ordinary temperatures.
5) They are soluble in non-polar solvents.
6) When they are doped with certain impurities they become semi-conductors.
7) They are transparent to long-wavelength radiation, but opaque to shorter
wavelengths.

12
Because the valence electrons are bound quite tightly to the ionic nuclei and .hence all ionic solids are electrically neutral.
13
At elevated temperatures however, the ions themselves become mobile and ionic conductivity results. (Conductivity in ionic
solids is due to ions).
14
In ionic crystals, the ions are held together with strong electrostatic forces which have no specific direction and thus the ionic
bonds are non- directional.
15
Since the valence of the atoms forming this bond is the same, it is also called as valence bond. Since the atoms taking part in
covalent bond are identical, this bond is also called as Homopolar bond.
16
As the spin is the intrinsic property in Quantum Mechanics, hence the covalent bonding is the quantum mechanical
phenomenon..
17
S, I, Ge, Si, Diamond, Graphite, H2O,CO2, NH3 etc., are the few more examples of covalent solids and molecules.
18
Covalent bond is formed by the overlapping of orbitals with unpaired electrons. But this overlapping takes place only in the
direction of maximum electron density. Hence covalent bonds are directional.
19
For example, diamond is the hardest substance having high melting points and is best electrical insulator. Tin which is very
soft with low melting point is a good electrical conductor. Silicon and Germanium which are hard with high melting points are
semi-conductors.
20
Ionic compounds have higher melting and boiling points than covalent compounds. This is because ionic solids are held
together by strong electrostatic attractive forces while covalent solids are held by weak van der waals' forces.

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 UNIT – I (PART – A) BONDING IN SOLIDS 2008-2009

METALLIC BONDING:
“The bond formed by sharing a number of valence electrons21 with a number of atoms22
in a solid is called metallic bond”.
The metallic bonding is the Coulomb electrostatic force of attraction between the
negative electron cloud23 and the positive ions24. Metallic bond is also called as incomplete or
unsaturated25 covalent bond26. The source of cohesive energy or binding energy in metals is
the same as in electron pair bonds with a difference that there is an additional property of finding
the electrons in the low potential energy regions between the ions. Metallic bonds are weaker
than ionic and covalent bonds, but stronger than Van der Waals bonds.
Examples: Sodium (Na), Aluminum (Al), etc.27
The binding energies of sodium and aluminum are 1.3eV and 3.23eV respectively.
Properties of Metallic Solids:
1) Metallic solids are crystalline in nature.
2) They possess a high degree of crystal symmetry28.
3) They possess high electrical and thermal conductivities29.
4) Unlike ionic and covalent solids, the metallic solids are soft, malleable30 and ductile.
5) The metals are opaque to all electromagnetic radiations from very low frequency to
the middle ultraviolet frequencies, beyond which they are transparent.
6) They are not soluble in polar and non-polar solvents.

HYDROGEN BONDING:
“The bond formed between two similar atoms31 with the hydrogen atom in-between32 as
the positive end of the dipole is called hydrogen bond”.
OR
The weak intermolecular forces of attraction (electrostatic) that exists between ‘H’ atom
of one molecule and a more electronegative atom of another molecule is called hydrogen bond.
In hydrogen bonding, the hydrogen atom with its single 1s orbital cannot form more than
one pure covalent bond; hence the attraction of two atoms must be largely due to electrostatic
forces.

21
No valence electron is associated with a specific atom and hence these electrons do not promote the formation of any
permanent bond between the atoms.
22
The bonding in metals must be thought in terms of all the atoms in the solids taken together.
23
The free electrons in metals are also termed as free electron gas or a sea of mobile electrons.
24
Positive ions are also termed as kernels.
25
It is unsaturated because of many vacancies in their outermost electron shells and hence their bonds do not exhibit directional
preferences.
26
According to L. Pauling, metallic bond is considered as “highly delocalized covalent bond”.
27
Potassium, copper, silver, gold, iron, nickel, tungsten, titanium etc., are few more examples of metallic solids.
28
This symmetry is due to the symmetrical arrangements of positive ions.
29
This is due to the enormous number of free electrons present in the metals.
30
Unlike other crystals, metallic crystal can be deformed without fracture since the electron gas behaves as a lubricant which
permits the atoms to slide on one another.
31
The atoms involved are electro-negative atoms such as Oxygen, Fluorine and Nitrogen.
32
Under certain circumstances, the hydrogen atom appears to be attracted simultaneously by rather strong forces to two other
atoms, which serves as a bridge between two species and is considered as a basis for the bond between two atoms.

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 UNIT – I (PART – A) BONDING IN SOLIDS 2008-2009

Examples: Water molecule in the form of ice, Hydrogen difluoride (HF2-), etc.33
The binding energy of hydrogen atom in hydrogen bonding is of the order 0.1eV.
Properties of Hydrogen bonded Solids:
1) The hydrogen bonds are directional.
2) Hydrogen bonded solids can be crystalline or non-crystalline in nature.
3) They possess low melting points.
4) They are very good insulators of electricity.
5) They are transparent to visible light.
6) They are soluble in polar and non-polar solvents.

No table of contents entries found. “The bond formed between the atoms or molecules34 due to
the dipolar forces35 is called molecular or van der waals bond”.
The molecular bonding is the instantaneous dipole interactions36 between the atoms or
molecules in the solids. Van der waals bonding is typically an order of magnitude weaker than
the hydrogen bonding.
Examples: Solid Neon, solid methane (CH4) and solid Argon are the best examples of this class.
Properties of Solids with Van der Waals bonding:
1) Van der waals bonds are non-directional.
2) Van der waals bonded solids are electrical insulators because the electrons are
localized.
3) Due to the presence of weak forces they are soft and mechanically weak.
4) They have low melting points.
5) They are soluble in both polar and non-polar solvents.
6) They are usually transparent to light.

33
potassium dihydrogen phosphate (KH2PO3), H2O, NH3 (ammonia molecules) are the other few examples of hydrogen bonding
molecules.
34
These atoms or molecules have no tendency to lose or even share their valence electrons with other atoms or molecules in the
solid.
35
The dipole moment is the source of an electrostatic dipole field which in turn may induce a dipole moment in another atom or
molecule. The interaction between original and induced dipole moment is attractive and is called as dipolar forces or van der
waals forces.
36
These interactions are primarily due to non-uniformities in the electrostatic charge distributions which are caused by the
momentary shifts of the electrons and nuclei towards the opposite ends of the atom, producing so called dipoles.

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 UNIT – I (PART – A) BONDING IN SOLIDS 2008-2009

FORCES BETWEEN TWO INTERACTING ATOMS

There exist two types of forces37 between interacting atoms.
(i) Attractive force
(ii) Repulsive force

Resultant force = attractive force + repulsive force

Attractive force:
The atoms with less stable electronic configuration, try to have stable electronic
configuration. In this attempt, they will attract other atoms to form a stable compound where
attractive forces begin to act. This attractive force exists only when the atoms are at far distances
and is electrostatic in nature.
A
Attractive Force = m
r
Repulsive force:
When atoms approach each other, their negatively charged electron shells come much
closer than their positive nuclei. Thus repulsive force between the two atoms is due to the
overlapping of the electron shells.
B
Repulsive force = − n
r
Resultant force:
The two atoms approach each other to a stable condition and have minimum energy. Now
the bonding force, F(r) between two atoms may be represented by the general equation
A B 38
Resultant force, F ( r ) = m − n (n > m)
r r
where ‘A’, ‘B’, ‘m’ and ‘n’ are constants that depend on the type of bond and ‘r’ is centre-to-centre spacing between
two atoms.
At larger separation, the attractive force predominates and the two atoms approach until
they reach equilibrium spacing ‘ro’. If they continue to approach further, the repulsive force
predominates, tending to push them back to their equilibrium spacing ‘ro’.
At the equilibrium spacing ‘ro’, the resultant force F(r) is Zero.39
i.e., F (ro ) = 0
‘ro’ is of the order 10-10 m i.e. 1Ao. For different bonds ‘ro’ varies between 1 Ao and 4 Ao.

37
Just by casual thinking we may draw two conclusions from the very existence of solids: Firstly, there must act attractive force
between the atoms or molecules in a solid which keep them together and secondly, there must also be the repulsive forces
between them since large external pressures are required to compress a solid to any appreciable extent.
38
Since the attractive forces in interatomic bonds are largely electrostatic, ‘m’ is usually 2 following Coulomb’s inverse square
law of electrostatics. The value of ‘n’ is not so easy to approximate, but it takes values from 7 to 10 for metallic bonds and
10 to 12 for ionic and covalent bonds.
39
the attractive and repulsive forces are equal in magnitude.

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 UNIT – I (PART – A) BONDING IN SOLIDS 2008-2009

Variation of interatomic force F(r) with interatomic spacing ‘r’:

F

A
Attractive Force,
rm
A B
Resultant Force, F ( r ) = m − n
r r

ro
O r
F(ro ) = 0 Fmax

B
Repulsive Force, −
rn

Fig. 1
The above figure shows the variation of resultant force between atoms. To separate the
atoms completely from the structure, a force Fmax is to be applied. This force corresponds to the
cohesive strength of the material.
Equilibrium spacing, ro:
The general expression for the bonding force between two atoms is
A B
F (r ) = m − ( n > m)
r rn
At equilibrium spacing r = ro , F (ro ) = 0
Hence,
A B
m =
ro ron
B
ron − m =
A
1
 B  n− m
ro =  
 A
The above equation represents the equilibrium spacing between two atoms.

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 UNIT – I (PART – A) BONDING IN SOLIDS 2008-2009

POTENTIAL ENERGY:
Variation of Potential Energy U(r) with interatomic distance ‘r’:
U Fig. 2
b
Repulsive Energy,
rn
a b
Potential Energy, U ( r ) = − m
+ n
r r
r = ro
O r
U =0
Umin
a
Attractive Energy, −
rm
When two atoms approach other, some work is said to be done either on the system or by
the system. This work done is stored in the form of potential energy. Basing on the work done,
potential energy is divided into two types
i) Attractive Potential Energy
ii) Repulsive potential energy
Total Potential Energy = Attractive Energy + Repulsive Energy
Attractive Potential Energy:
During their approach, the atoms do the work of attraction. This work done by the atoms
is stored in the form of attractive potential energy. At large separations this energy is zero, but
a
decreases gradually at shorter distances according to the expression − m
r
Repulsive Potential Energy:
When the atoms are so close to each other, such that the outer electrons of each atom can
interact, repulsive forces begin to act. Hence some external work must be done to bring the
atoms together, when they repel each other. This external work done is stored in the form of
repulsive potential energy. At shorter distances this increases more rapidly40 than the attractive
b
potential according to the expression
rn
Hence the total potential energy is given by
a b
U (r ) = − m
+ n (n > m)
r r
At equilibrium position i.e. at r = ro , the total potential energy is minimum i.e. U (ro ) = Umin .

40
This is because, the positive charges on the nuclei repel each other very strongly when ‘r’ becomes small.

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 UNIT – I (PART – A) BONDING IN SOLIDS 2008-2009

Cohesive Energy or Binding Energy and Bond dissociation energy:

“The energy released when a molecule is formed from two atoms is called cohesive
energy”.
“The energy necessary to dissociate the molecule into isolated neutral atoms is called
dissociation energy”.
These energies are equal in magnitude but with opposite signs. These energies are of the
order of a few electron volts (eV) in magnitude.

ESTIMATION OF COHESIVE ENERGY AND DISSOCIATION ENERGY

Expression for the equilibrium spacing of two atoms for which the potential energy is
minimum:
Let us consider a general situation of two identical atoms. These two atoms comes closer
to each other in accordance with the force relation
A B
F (r ) = M
− (N > M )
(1)
r rN
The work done in moving through a small distance dr , due to this force is stored in the form of
potential energy du ( r ) given by
du ( r ) = F ( r ) dr
Hence the potential energy of the molecule is
U (r ) = ∫ du(r ) = ∫ F (r ) dr
 A B
= ∫  r M
−  dr
rN 
 −A  1  B  1
=   M −1 +   N −1 + C
 M −1 r  N −1  r
−a b
U (r ) = m
+ n + C
(2)
r r
 A   B 
where a =  , b =   , m = M − 1 and n = N − 1 .
 M −1   N −1 
We know that at infinite distance the potential energy is zero i.e. when r = ∞ , U = 0
substituting ' r ' and 'U ' in eq(2), we have C = 0
Therefore eq(2) can be written as,
−a b
U (r ) = m
+ n
(3)
r r
where the first term is the attractive energy and the second term is the repulsive energy.
We know that the condition for the potential energy to have minimum value is

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 UNIT – I (PART – A) BONDING IN SOLIDS 2008-2009

dU
= 0
dr
dU
This happens at equilibrium position r = ro , i.e. = 0
dr r =ro
from eq(3),
dU am bn
= m +1
− n +1 = 0
(4)
dr r =ro r r
am bn
=
r m +1 r n +1
 b  n 
ron− m =   
(5)
 a  m 
1
 bn  n − m
ro =  
(6)
 am 
This is the expression for the equilibrium spacing of two atoms for which the potential
energy is minimum.
The cohesive energy and dissociation energy can be calculated as below:
Using eq(3) at r = ro , we have
−a b
U ( ro ) = m
+ n
(7)
ro ro
Rearranging the eq(5), we get
1  1   a  m 
n
=  m    
ro  ro   b  n 
Substituting this equation in the above eq(6), we have
−a  1   a  m 
U (ro ) = m
+ b  m    
ro  ro   b  n 
a  m
U (ro ) = − m 1 −  (n > m)
(8)41
ro  n 
This energy corresponding to the equilibrium position i.e. r = ro , is called Cohesive energy.
The dissociation energy of the molecule is given by

a  m a  m
U (ro ) = − m 
1−  = m 
1−  (n > m)
(9)
ro  n  ro  n 

41
The negative sign indicates that the total binding energy is essentially attractive in nature. Since m ≠ n the attractive and
repulsive energies are not equal though the attractive and repulsive forces are equal in equilibrium.

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 UNIT – I (PART – A) BONDING IN SOLIDS 2008-2009

To show that n > m :

Since U is minimum at r = ro ,
U must also satisfy the condition,
 d 2U 
 2  > 0
(10)
 dr r =ro
Differentiating Eq. (4) and applying the condition given by Eq.(10), we get
 d 2U  -am(m + 1) bn(n + 1)
 2  = m+ 2
+ > 0
 dr r =r ro ron+ 2
o
−am(m + 1)ron+2 + bn(n + 1)rom+ 2 > 0
bn(n + 1)rom+2 > am(m + 1)ron +2
bn(n + 1) > am(m + 1)ron−m
Substituting for ro from Eq. (6), we get
 b  n 
bn(n + 1) > am(m + 1)   
 a  m 
( n + 1) > ( m + 1)
i.e. n > m
(11)42

COHESIVE ENERGY OF IONIC CRYSTALS (NaCl):

AZ1Z2e2
The attractive potential energy of ionic crystals is −
(1)
4π ∈0 r
where ‘A’ is Madelung constant43, ‘Z1 , Z2’ are valencies of corresponding ions, ‘e’ is the electronic
charge.
B
The repulsive energy between the ions is
(2)
rn
where ‘n’ is called Born repulsive exponent.
Therefore the total energy of ionic crystals is
AZ Z e2 B
U (r ) = − 1 2 +
(3)
4π ∈0 r rn

For Uni-valent crystals (such as NaCl), Z1 = Z2 = 1.

For 1 Kilo mole Eq. (1) can be written as
 Ae2 B
U (r) = N − + n
(4)
 4π ∈0 r r 
where ‘N’ is the Avagadro number.

42
This indicates that the forces between the atoms are mostly electrostatic in nature.
43
The value of madelung constant ‘A’ purely depends on the geometrical arrangement of ions in the crystal
(i.e. structure of the crystal).

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 UNIT – I (PART – A) BONDING IN SOLIDS 2008-2009

At equilibrium position i.e. r = ro , the potential energy equation can be written as

 Ae2 B
U (ro ) = N − + n
(5)
 4π ∈0 ro ro 
To find the value of ‘B’:
To evaluate the repulsion constant ‘B’, let us consider the fact that at equilibrium separation
i.e. at r = ro , the potential energy is minimum.
Hence,
dU (r )
= 0
dr r =ro

dU ( r )  Ae 2 
= N − ( −1) ro−2 + B ( − n )ro− n−1  = 0
dr r = ro  4π ∈0 
 Ae2 Bn 
N 2
− n +1  = 0
(6)
 4π ∈0 ro ro 
In Eq. (6) N ≠ 0 hence,
 Ae 2 Bn 
 2
− n +1  = 0
 4π ∈0 ro ro 
Ae2 ron+1
= B
4π ∈0 ro2 n
Ae 2 ron −1
B =
(7)
4π ∈0 n
Now, substituting the value of ‘B’ in Eq. (5), we get
 Ae2 Ae2ron−1 
U (ro ) = N − + n
 4π ∈0 ro 4π ∈0 nro 

 Ae2 Ae2 
U (ro ) = N − + 
 4π ∈0 ro 4π ∈0 ron 

NAe2  1
U (ro ) = − 1 − n 
(8)44
4π ∈0 ro
where ‘A’ is madelung constant of ionic crystal.
The above Eq. (8) represents the cohesive energy per 1kilomole of ionic crystal.

44
The negative sign indicates that the energy is attractive in nature. The dissociation energy of ionic crystals is
NAe2  1 
U (ro ) = 1−
4π ∈0 ro  n 

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 UNIT – I (PART – A) BONDING IN SOLIDS 2008-2009

SOLVED PROBLEM:
Calculate the cohesive energy of NaCl from the following data:
Equilibrium separation between the ion pair , ro = 0.281 nm
Ionization energy of Na = 5.14 eV
Electron affinity of Cl = 3.61 eV
Born repulsive exponent, n =9
Madelung constant, A = 1.748
SOLUTION:
Cohesive energy per molecule of NaCl is
Ae2  1
U (ro ) = 1 − n 
4π ∈0 ro

We know,
e = 1.602 x 10 −19 C
∈o = 8.85 x 10−12
ro = 0.281nm = 0.281 x 10−9 m,
A = 1.748
n =9
Hence cohesive energy per molecule of NaCl is
1.748 x (1.602 x 10−19 )2 (8 / 9)
=
4π x 8.85 x 10−12 x 0.281 x 10−9
3.98762 x 10−38
=
31.2632 x 10−21
= 0.12755 x 10 − 17 J
0.12755 x 10−17
= eV
1.602 x 10−19
= 7.96 eV

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 UNIT – I (PART – A) BONDING IN SOLIDS 2008-2009

MADELUNG CONSTANT:
It is a function of crystal structure and can be calculated from the geometrical
arrangement of ions in the crystal.
Evaluation of madelung constant ‘A’ for NaCl:
Na+
Cl-
r

Fig. 3

Consider the Sodium Chloride crystal as shown in the fig. 3. Let the distance
between two successive ions in NaCl crystal lattice be ‘r’. Let us take a sodium ion named ‘C’,
which is surrounded by six chlorine ions at a distance ‘r’.
6e2
The coulomb energy due to these six chlorine ions is − .
4π ∈0 r
12e 2
Further the coulomb energy due to twelve sodium ions at a distance 2r is .
4π ∈0 2r

Similarly, the coulomb energy due to eight chlorine ions which are at a distance 3r is
8e 2
−
4π ∈0 3r
Further Na at ‘C’ is surrounded by six sodium ions at a distance of 2r and so on.
Thus the total energy of Na at position ‘C’ is given by
e2  6 12 8 6 24 
U =−  − + − + − ...
4π ∈0 r  1 2 3 4 5 
In the above equation the bracketed term is a natural number whose value depends on the
structure of the crystal, called Madelung Constant ‘A’.
Therefore, the value of madelung constant for NaCl crystal is
 6 12 8 6 24 
A=  − + − +  = 1.7475
 1 2 3 4 5

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 UNIT – I (PART – A) BONDING IN SOLIDS 2008-2009

QUESTIONS
1) Explain the different types of bondings in solids with suitable examples.
2) Explain the forces between the two interacting atoms when they are brought nearer to
form a molecule.
3) Plot and explain the variation of
(i) Attractive potential energy
(ii) Repulsive potential energy
(iii) Resultant potential energy
with the interatomic distance, when two atoms are brought nearer.
4) Illustrate graphically the variation of
(i) Attractive force
(ii) Repulsive force
(iii) Resultant force
with the spacing between two interacting atoms.
5) Derive the expression for the equilibrium spacing of two atoms for which the potential
energy is minimum and hence obtain the dissociation energy.
6) What is cohesive energy? Assuming a suitable model for interatomic forces derive an
expression for the cohesive energy.
7) Derive an expression for the cohesive energy of an ionic crystal.
8) Evaluate the value of madelung constant for NaCl crystal.

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