COHESIVE ENERGY

At the end of this chapter you should be able to

Understand cohesive energy
Explain types of bond
Derive expression for Cohesive energy
Apply the cohesive energy to NaCl.

C1.CRYSTAL BINDING

What holds a crystal together? What are the conditions under which a crystal is
stable? We shall discuss these aspects. The attractive electrostatic interaction
between the negative charges of the electrons and the positive charges of the nuclei is
entirely responsible for the cohesion of solids.
Magnetic and gravitational forces do not play any role worth considering. Exchange
energy Vander walls forces, covalent bonds and resonance stabilization energies
come into play only in special situations. The difference between different forms of
solids is caused by the differences in the distribution of the valence electrons and the
ion cores.
C2.COHESIVE ENERGY
A crystal consists of atoms or molecules bound together by certain forces. These
forces or bonds determine the arrangement of the constituent atoms i.e. crystal
structure. Forces that hold the crystalline atoms/molecules together are called
cohesive forces.
The total energy of a crystal consists of its kinetic energy and potential energies. It is
called the crystal energy. It includes the energy of interaction when the atoms come
together.
The energy of the same atoms that constitute the crystal when free (i.e. infinitely far
apart) is called the free atom energy.
The difference between the free atom energy and the crystal energy is called the
cohesive energy.
The inert gas crystals like He, Ne, and Xe have cohesive energies in the range 3-4
kJ/mol. They are weakly bound. Carbon silicon and Germanium are strongly bound.
Their cohesive energies are in the range 370 700 kJ/mol. The alkali metal crystals
have intermediate values ( 100 kJ/mol) of cohesive energy.
C3.TYPES OF BONDING
Bonds are two types the primary bonds that are interatomic in nature and the
secondary bonds that are intermolecular in nature.
There are four different types of bonding
(i) Ionic (ii) Covalent (iii) Metallic (iv) Vanderwaals.
Ionic bonding:
Ionic crystals consist of positive and negative ions in a periodic array. The ionic
bonding is a result of an atom losing one or more electrons and another capturing
them. For this to occur, the exchange must be energetically favourable. This means

that if one starts with two neutral atoms say Na and Cl and goes through the process
of ionizing one of them then giving the resulting electron or electrons to be other and
bringing the two ions together the overall energy of the bound pair must be less than
the energy of the initial state of two neutral atoms.
For example: Sodium chloride is a typical example of ionic crystal. Imagine that Na
and Cl atoms are free i.e., distance of separation is infinity. To remove an electron
from the neutral sodium atom i.e. ionization energy is equal to 5.1 ev.
This leads to Na + 5.1 eV Na++eThe electron so removed has to be added to the neutral chlorine atom. In the process
an energy of 3.6 eV is released as the electron affinity of chlorine is 3.6 eV Cl + eCl-+3.6 eV. Thus an energy of 1.5 e V(5.1-3.6 eV) has to be spent to create
Na+and Cl- at infinity. Therefore Na+Cl +1.5 eV Na++Cl-.
Even though the Na+and Cl- ions are far apart the electrostatic attraction brings them
together and keeps them at the equilibrium distance. At the equilibrium the potential
energy is minimum as energy is released in the formation of Nacl molecule.
Covalent bond: It is another important and a very strong type of bond. A good example of this is the
hydrogen molecule (H2). The covalent bond comes here because 1st electrons of both
hydrogen atoms are in orbit around both nuclei. Therefore one or the other of the
electrons spends part of its time between the two nuclei attracting both of them and
thus binding them. One way to understand why this takes place is by considering the
tendency of the atoms to have filled sub shells. The hydrogen atom needs one more
electron to fill the 1st sub shell and thus achieve the inert electronic configuration of
helium. Lacking any other sources of electrons, it will try to capture the extra
electron from the adjacent hydrogen atom. Of course the other atom will try to do the
same and they compromise by sharing both electrons.
For example
The best examples of covalent bonding in solids are offered by carbon in the diamond
structure, silicon and germanium.
Si

Si

Si

Si

Si
SI

Si

Si

Si

METALLIC BOND:
The metallic bond can be thought as the limiting case of covalent bond in which
electrons are shared by all the ions in the crystal. When a crystal is formed of atoms
that have a few weakly bond electrons in the outer sub shells. These electrons
become free from the individual atoms, which thereupon acquire stable closed sub
shell configurations. The energy needed to liberate these loosely bond electrons is
more than compensated for by the decrease in energy resulting from the binding.
We can visualize the metallic bonding as follows:

The liberated electrons move through the entire crystal, visiting each positive ion at
some time or other. We thus have a situation where an array of heavy positive ions is
permeated by a sea of highly mobile negative electrons. It is the electrostatic
attraction between the electron sea and the positive ions that prevents the break down
of the entire structure, which would result from the repulsion of the positive ions.
The electrons provide the glue that keeps the structure together.
The metallic bond is in many ways. Similar to the ionic bond in the sense that the
main role is played by the electrostatic attraction between unlike charges; however,
there is a big difference whereas in the ionic crystal the position of the positive and
negative charges and therefore the directionality of the forces is fixed in the metallic
bond they are not. The electronic attraction comes from all directions. This is
important because it explains why a small deformation in a nearly perfect metal
crystal does not cause a fracture. Whether we compress, twist or pull a piece of
metal. The cohesive forces are still there and coming from all directions. Pure metals
are ductile and malleable.
MOLECULAR OR VANDER WAALS BOND:
When the outer sub-shells of an atom are not filled, the atom tries to fill them by
associating with an atom that can supply one or more electrons. The two atoms
become bonded in the process. What happens if the atom has an outer sub shell that
is completely filled and difficult to excite such as in the case with rare gases. The
answer is that it is very difficult for them to bond and therefore to form molecules and
solids. However they (except Helium) can form solids at very low temperatures by
another mechanism. The mechanism is generally known as dipole dipole
interaction and the resulting forces are called Vander walls or London forces. Two
molecules or atoms with no permanent dipole moment, such as rare gases can still
attract each other. Even though the electron distribution is symmetric on the average
the electrons themselves are in constant motion and at any given instant one part of
the molecule can be more negative than another. In the polar molecule, the charge

asymmetry is fixed, where as in nonpolar molecule there is a constantly shifting

charge asymmetry. When two such non polar molecules are close together so that
adjacent ends always have opposite signs thus mutually inducing dipoles with
resulting attraction.

Dipole

Dipole

Inter atomic force: The force acting in between two adjacent atoms
Inter atomic distance: the distance between centers of two adjacent atoms
C4.INTERATOMIC FORCE Vs INTER ATOMIC DISTANCE
Both attractive and repulsive forces operate between the atoms of a solid. Attractive
forces keep the atoms together while repulsive forces come into play when the atoms
are brought close to each other. In order to understand the nature of these two forces
let us consider a simple system of two atoms A and B
A
The force of attraction between atoms is Fa M ---(1) where a is a constant and
r
B
the force of repulsion is Fr N ----(2) Where B is constant
r

Attractive Force

Fmax
Resultant Force

Repulsive Force

F gives the net force acting in between atoms =

A B
-------(3)
rM rN

A, B, M and N are constants and Characteristic of the molecule (A-B). The value of
N is greater than M. Typical values are M=2 and N = 7 to 10.
At Equilibrium Separation r0:
When r = r0, F(r) = 0 from equation (3)
A
B
A
B
B
0 = M N or M = N or r0N M =
A
r0
r0
r0
r0
1

B N M
r0 =
-------(4)
A
Potential Energy
The Potential energy between the atoms U can be obtained by integrating equation (3)
W.R.T. r thus
B
A
U = F (r )dr = M N dr
r
r
Ar 1 M Br 1 N
M
N
= [ Ar Br ]dr =

+ c Where c is constant of integration

1 M 1 N
A
B
A 1 B 1
= -
=a;
=b; M-1 =m; N-1= n
+
+ c Let
M 1
N 1

M 1
N 1
M 1 r
N 1 r
a b
then U= m + n +c -------(5) Where a and b are attractive and repulsive force
r
r
constants .m and n are positive integers.
The value of c can be obtained by applying boundary conditions in equation (5)
When r = ,U(r)=0 and c=0
a b
a
So U= m + n -----(6) in equation (6) the quantity m represents attractive potential
r
r
r
b
energy and n represents repulsive potential energy
r

Repulsive potential energy

Resultant potential energy

r0

Attractive potential energy

C5.CALCULATION OF COHESIVE ENERGY OR MINIMUM POTENTIAL ENERGY

The potential energy is minimum [Umin] for a separation of r0. This spacing r0 is
called equilibrium spacing of atoms. At r = r0, potential energy is negative, hence a
positive amount of energy Umin is needed to separate the atoms. When the atoms are at
equilibrium then the potential energy between the atoms is minimum [Umin] and it is
a b
represented asU (r0). So U (r0)= Umin= m + n .(7)
r0
r0
Where r0 is the equilibrium separation between the atoms. This energy (Umin) is called
bonding energy or Cohesive energy or Dissociation energy of the atoms because this is
the energy with which the two atoms bond together and that amount of energy is required
to separate them U(r0) is calculated in the following way.
Differentiating equation (6) with respect to r gives.
dU
am
bn
= m+1 n +1 --------------(8)
dr r
r
At equilibrium separation equation (8) becomes

am
bn
dU
=

dr r = r0
r0m +1
r0n +1

=0 or

am
r0m +1

bn
r0n +1

b n
or r0n = r0m --------(9) substituting equation(9) in (7) gives
a m
a b a m a a m
U min = m + m = m + m
r0
r0 b n r0
r0 n

a m
1 --------(10)
n
r0m
This is the expression for cohesive energy of a molecule containing two atoms in a
molecule.
C6.BOND ENERGY OF NACL
=

Sodium chloride is a typical example of ionic crystal. Imagine that Na and Cl atoms
are free i.e., distance of separation is infinity. To remove an electron from the neutral
sodium atom i.e. ionization energy is equal to 5.1 eV.
This leads to Na + 5.1 eV Na++e-

The electron so removed has to be added to the neutral chlorine atom. In the process
an energy of 3.6 eV is released as the electron affinity of chlorine is 3.6 eV Cl + eCl-+3.6 eV. Thus an energy of 1.5 e V(5.1-3.6 eV) has to be spent to create
Na+and Cl- at infinity. Therefore Na+Cl +1.5 eV Na++Cl-.

Even though the Na+and Cl- ions are far apart the electrostatic attraction brings them
together and keeps them at the equilibrium distance. At the equilibrium the potential
energy is minimum as energy is released in the formation of Nacl molecule. It is
called bond energy. The potential energy at the equilibrium can be calculated using
the standard formula V = - e2/4oro
Substitution of e = 1.6 x 10-19 C o = 8.85 and assuming a value of 0.24 nm for ro we
get V = -6eV. The energy released in the formation of Nacl = 5.1 eV 3.6 eV 6 eV
= -4.5 eV. This is equal to cohesive or bond energy of NaCl molecule.