3.

Bonding in Crystals: [5 hours]

3.1 Equilibrium lattice constant,

3.2 Different types of bonding (ionic, covalent, metallic, hydrogen) in

crystals and lattice energy,

3.3 Bonding in Crystals of Inert gases

BONDING IN SOLIDS

In solids, bonding between atoms is very strong. Generally, there are two types of bonding in
solids. They are,

i) Primary bonding
ii) Secondary bonding

Under equilibrium distance, two atoms are fixed and net force, F = 0. i.e., attractive force
balances the repulsive force. In this case, potential energy becomes minimum. We consider
attractive force as -ve and repulsive force as +ve.

When the atoms are at far distance, then the force between the atoms is attractive and as it
approaches closer, it becomes repulsive. At r = re , attractive force balances the repulsive
force. Repulsive forces are short range forces.

!"
𝐹 = − !#

!"
𝐹|#$#! = − !# % =0
#$#!

The variation of resultant force and potential energy between atoms with their
separation is shown in the figure below.
Primary bonds (strong) are formed due to sharing or transfer of electrons (covalent, ionic and
metallic bond). Secondary bonds (weak) are formed by attractive forces between +ve and -ve
charges i.e., interaction of atomic or molecular dipoles (Hydrogen, Van-der Waals bond).

Equilibrium lattice constant

The total energy released in the formation of crystal by all individual neutral atoms
constituting the crystal is called lattice energy.

If we neglect the kinetic energy of the inert gas atoms, the cohesive energy of an inert gas
crystal is given by summing the Lennard-Jones potential over all pairs of atoms in the crystal.
If there are N atoms in the crystal, the total potential energy is,

'( ,
' ) )
𝑈%&% = ( 𝑁(4𝜖) ,∑´. .* +
/ − ∑´. .* +
/ 0 (1)
"# "#

where pijR is the distance between reference atom i and any other atom j, expressed in terms
of the nearest-neighbor distance R. The factor 1/2 occurs with the N to compensate for
counting twice each pair of atoms. (S´ means 𝑖 ≠ 𝑗).

In fcc structure (inert gases), there are 12 nearest neighbors and the nearest neighbors
contribute most of the interaction energy of inert gas crystals.

∑´. 𝑝/. 0'( = 12.13188

and ∑´. 𝑝/. 0, = 14.45392 (2)

If we take Utot in (1) as the total energy of the crystal, the equilibrium value Re is given by
requiring that Utot be a minimum with respect to variations in the nearest-neighbor distance
R.

!"$%$ ) &' ))
𝐹|+$+! = − !+
% = 0 = - 2N 𝜖 =12 × 12.13 ?+&(@ − 6 × 14.45 ?+* @B (3)
+$+!

At R = Re, on solving, we get,

+!
)
= 1.09 (4)

This value is same for all elements with fcc structure.

Cohesive Energy (Energy of dissociation)

The cohesive energy of a solid is defined as the energy which will be given out in the process
of formation of a crystal by bringing neutral atoms from infinity to the position of eqbm.
separation.
The cohesive energy of inert gas crystals at absolute zero and at zero pressure is obtained by
substituting (2) and (4) in (1):

) '( ) ,
𝑈%&% (𝑅) = 2𝑁𝜖 E12.13 ?+@ − 14.45 ?+@ F (5)

and, at R = Re,

Utot (Re ) = - (2.15)(4N𝜖) (6)

the same for all inert gases. This is the calculated cohesive energy when the atoms are at rest.

Note:

• ϵ is the well depth and a measure of how strongly the two particles attract each other.
• σ is the distance at which the intermolecular potential between the two particles is
zero (Figure B). σ gives a measurement of how close two nonbonding particles can
get and is thus referred to as the van der Waals radius. It is equal to one-half of the
internuclear distance between nonbonding particles.

Ionic Bonding:

Ionic bonds are formed when atoms that have low ionization energies, and hence lose
electrons readily, interact with other atoms that tend to acquire excess electrons. The former
atoms give up electrons to the latter. Thus the atoms become positive and negative ions
respectively. These ions come together in an equilibrium configuration in which the attractive
forces between positive and negative ions predominate over the repulsive forces between
similar ions.

Properties:

i) Ionic bonds are very strong.

ii) Most ionic solids are hard, brittle and have high melting points.
iii) They are soluble in polar liquids like water.
iv) Their electrical conductivity is much smaller than that of metals at room
temperature. But in contrast to metals, the conductivity of ionic crystals increases
with increasing temperature. At elevated temperatures, the ions themselves
become mobile and ionic conductivity results.
v) They are transparent over wide range of em-spectrum including visible light.
vi) Ionic solids crystallize in close-packed structures, of which the NaCl and CsCl
structures are the commonest.

Let us consider the case of sodium chloride which is a typical example of an ionic crystal.
Here, a single valence electron is transferred from the sodium atom to the chlorine atom.
The Na+ and Cl– ions so formed are arranged in a face-centred cubic structure as shown
in figure.

Cl

Na

Sodium Chloride Crystal

The principal contribution to the cohesive energy of an ionic crystal is the electrostatic
potential energy Ucoulomb of the ions. Let us consider an Na+ ion in NaCl. Its nearest
neighbours are six Cl– ions, each one the distance r away. The potential energyof the Na+ ion
,2 '
due to the 6Cl– ions is given by, 𝑈' = − 345 #
6
The next nearest neighbours are 12 Na+ ions, each one at distance Ö2 r away. The potential
'(2 '
energy of the Na+ ion due to the12 Na+ ions, , 𝑈( = + 378
+ √(#

Then there are 8 Cl– ions at Ö3 r distance, 6 Na+ ions at 2r distance and so on. When the
summation is continued over all the + and – ions in a crystal of infinite size, the result is

,2 ' '(2 ' :2 ' ,2 '

Ucoulomb = − 345 + 378 − 378 + 378 - ……….
6# + √(# + √;# + (#

2' , '( : ,
= − 378 # = − + − +⋯B
+ √' √( √; √3

2'
= −1.748 378+ #

2'
= −𝛼 378+ #

This result holds for the potential energy of a Cl- ion also. α is called the Madelung constant
of the crystal. It has the same value for all crystals of the same structure. For simple crystal
structures α lies between 1.6 and 1.8.

Two ions cannot continuously approach each other under coulomb attraction on account of
the exclusion principle. When they are at a certain small distance apart, they begin to repel
each other with a force which increases rapidly with decreasing internuclear distance r. The
potential energy contribution of the short-range repulsive forces can be expressed
approximately as,

𝐵
𝑈#2* =
𝑟<

where B is a constant and n is a number (n ≈ 9, From compressibility of ionic crystal).

Hence, total energy, U = Ucoulomb + Urep

2' =
= −𝛼 378+ #
+ #,

!"
We know, %
!# #$#!
= 0 at equilibrium separation.

>2 ' <=

So that, 378+ #+ '
−# ,-&
=0
+

>2 ' <0'

B= 𝑟
378+ < 6

The total potential energy at the equilibrium separation is,

 >2 ' >2 ' #+ ,.& >2 ' '
𝑈 = − 378 + 378 ,
= − 378 =1 − <B
+ #+ + < #+ + #+

This is the magnitude of the energy needed to separate an ionic crystal into individual ions
(not into atoms). In an NaCl crystal, the equilibrium distance r between ions is 2.81 × 10– 10
0

m, α = 1.748 and n ≈ 9, 1/4πε0 = 9 × 109 Nm2 C– 2.

The potential energy of an ion of either sign is,

>2 ' ' ?×'6/ × '.B3: ×('.,×'6.&/ )' '

U = − 378 =1 − <B = = − (.:'×'6.&+
=1 − ?B = - 7.96 eV.
+ #+

Because we may not count each ion more than once, only half this potential energy, or – 3.98
eV, represents the contribution per ion to the cohesive energy of the crystal.

Some energy is needed to transfer an electron from a Na atom to a Cl atom to form a Na+ –
Cl– ion pair. This electron transfer energy is the difference between the + 5.14 eV ionization
energy of Na and the – 3.61 eV electron affinity of Cl, or + 1.53 eV. Each atom thus
contributes + 0.77 eV to the cohesive energy.

∴ the total cohesive energy per atom in the NaCl crystal is

Ecohesive = (– 3.98 + 0.77) eV/atom = – 3.21 eV/atom.

Lattice Energy of Ionic Crystal (From Born’s Theory)

Lattice energy is the energy evolved when a crystal is formed from individual ions (not
atoms). According to Born-Madelung theory, the interaction energy (Ui) on the ion ‘i’ due to
all other ions is given by;

𝑈0 = ∑21 𝑈01 (𝑖 ≠ 𝑗)

For ionic crystals, there are two types

of energies,

i) Coulomb interaction energy

E'
= ±# (cgs)
"#

.3"#
ii) Central field repulsive energy between nearest ions is = 𝜆𝑒 4

Where 𝜆 and b are empirical parameters with b as range of repulsive interaction

and 𝜆 as energy strength.
.3"#
E'
Total energy of an ith atom, 𝑈/. = 𝜆𝑒 4 ±#
"#
 The total lattice energy Utot of a crystal composed of N molecules (2N ions) is;
−𝑟𝑖𝑗 2
Utot = N Ui = N ∑21 𝑈01 = N ∑21[ 𝜆𝑒 𝑏 ± 𝑟𝑞 ]
𝑖𝑗

For convenience, we introduce a dimensionless quantity Pij such that, rij = R Pij. Where R is
nearest neighboring separation.
J
0+H"# 𝑞(
𝑈%&% = 𝑁 Q R𝜆𝑒 I ± U
𝑅𝑃/.
.

Assuming the repulsive interaction is effective only for nearest neighbors,

Pij = 1 then rij = R and also considering Z nearest neighbors of the ith ion,
J
0+H"#
0+K
𝑁 Q V𝜆𝑒 I W = 𝑁 𝑍𝜆𝑒 I
.

J
0+ 𝑞(
∴ 𝑈%&% = 𝑁(𝑍𝜆𝑒 I −Q± )
𝑅𝑃/.
.

.;
E'
𝑈%&% = 𝑁(𝑍𝜆𝑒 4 − 𝛼 +
) (1)

'
Where 𝛼 = ∑J. ∓ H is Madelung constant and also known as Coulomb energy constant.
"#

At equilibrium separation, R = R0 , the crystal energy is minimum.

!"$%$
i.e., !+
% =0
+$++

0+K ' L>E '

or, =𝑁𝑍𝜆𝑒 I (− )
I
+ +'
B =0
+$++

L 0++K L>E '

or, I 𝑍𝜆𝑒 I = ++ '

0++K I>E '

or, 𝑒 I = ' (2)
MN++

Hence, equation (1) with R = R0 becomes,

.;+
E' I>E ' E' I>E ' E'
𝑈6 = 𝑁(𝑍𝜆𝑒 4 − 𝛼 + ) = 𝑁(𝑍𝜆 ' −𝛼+ ) = 𝑁= + ' −𝛼+ B
+ MN++ + + +

L>E ' I
𝑈6 = − ++
=1 − + B (3)
+
 L>E '
Equation (3) gives the lattice energy of ionic crystal and the term − ++
is Madelung energy.

The cohesive energy per ion pair is given by,

>E ' I
=− ++
=1 − + B (cgs)
+

>E ' I
= − 37O =1 − + B (SI)
+ ++ +

𝜆 and b can be determined from experimental data of lattice constant and compressibility.

Covalent Bonding:

In the covalent bond, atoms are held together by the sharing of electrons. Each atom
participating in a covalent bond contributes an electron to the bond and gives inert gas like
structure. The binding of molecular hydrogen (H2) is a simple example of covalent bond. The
strongest binding occurs when the spins of the two electrons are antiparallel. The binding
depends on the relative spin orientation not because there are strong magnetic dipole forces
between the spins, but because the Pauli principle modifies the distribution of charge
according to the spin orientation. This spin-dependent coulomb energy is called the exchange
interaction.

In the H2 molecule, two electrons are shared by the two atoms as shown in figure.

As these electrons circulate, they spend more time between the atoms (in fact between the
protons) than elsewhere and this produces an attractive force. Thus covalent crystals are
composed of neutral atoms having slightly overlapping electron clouds. Diamond, germanium,
silicon, and silicon carbide (SiC) are examples of covalent crystals.

Properties:

1) Covalent bond is a strong bond. Cohesive energies of 6 to 12 eV/atom are typical of

covalent crystals, which is more than the usual cohesive energies in ionic crystals. All
covalent crystals are hard, have high melting points, and are insoluble in all ordinary
liquids.
2) Covalent bonds are strongly directional.
3) The other important characteristic property of the covalent bond is its saturability.
Saturability means that each atom can form covalent bonds only with a limited number
of its neighbours.
4) The conductivity of covalent crystals varies over a wide range. Some crystals are
insulators (diamond) and some are semiconductors (Ge). The conductivity increases
with the increase of temperature.
 5) The optical properties of the covalent crystals are characterized by high refractive index
and high dielectric constant. Covalent crystals are transparent to long-wavelength
radiation but opaque to shorter wavelengths

Vander Waals Bonding

Noble gas atoms which have close shell structure and are represented as spherical rigid
charge distributions. Such electron distributions are reluctant to overlap when any two atoms
are brought close to each other. But there must be some attractive forces between atoms
bringing about the cohesion and finally the solidification.

The van der Waals forces are weak forces arising out of the attractive interaction between
fluctuating electric dipoles. By chance, for a fraction of the second, there could be more number
of electrons on one side of the nucleus than on the other. This destroys the spherical symmetry
of the electron charge distribution and momentarily displaces the centre of the negative charge
(the electrons) from the centre of the positive charge (the nucleus). Thus, an atom becomes a
tiny electric dipole which is capable of inducing an electric dipole moment in the neighbouring
atom. The two dipoles attract each other, though weakly, resulting in the van der Waals binding.
As the electron charge distribution keeps fluctuating, the electric dipoles in question are called
fluctuating dipoles.

Suppose we have two atoms 1 and 2 of a noble gas separated by distance r. As described
above, when atom 1 acquires an instantaneous electric dipole moment p1; an instantaneous
electric dipole moment p2 may be induced in atom 2 because of the polarization caused by
the electric field E of the atomic dipole 1 at atom 2. We know in electrostatics that the
interaction energy of two dipoles p1 and p2 (= − p × E ) varies with separation as 1/r6. This
2
interaction energy is essentially the van der Waals binding energy of the two atoms.

METALLIC BOND

The metallic bond is similar to the covalent bond, but it is quite different in others. In the
covalent bond, two atoms are linked together by pairs of electrons shared between them. In
metallic bonding, the valence electrons, which hold the atoms together are not bound to
individual atoms or pairs of atoms but move freely throughout the whole metal. The similarity
to the covalent bond lies in the sharing of electrons. The difference is that electrons belong to
the metal as a whole rather than to any particular atom.
Metallic elements have low ionization energies and hence, in this bonding, atoms of the same
element or different elements give their valence electrons to form an electron cloud or say
“electron gas” throughout the space occupied by atoms. Having given up their valence
electrons, the atoms are in that they are primarily electrostatic, but are between the ions and the
electrons.

Most of the atoms in metals have one or two valence electrons. These electrons are loosely held
by their atoms and therefore, can be easily released to the common pool to form an electron
cloud. The electrostatic interaction between the positive ions and the electron gas holds the
metal together. The high electrical and thermal conductivities of metals follow from the ability
of the free electrons to migrate through their crystal structures while all the electrons in ionic
and covalent crystals are bound to particular atoms.

PROPERTIES OF METALLIC CRYSTALS

1. Bonding energies and melting temperatures are found very wide in these bonding
2. Due to the symmetrical arrangements of the positive ions in a space lattice, metals are
crystalline.
3. Metallic bonds being weak, metals have a melting point moderate to high, i.e., the
melting points of metallic crystals are lower than those of the electrovalent crystals.
4. Since a large number of free electrons are available, metallic crystals have high
electrical conductivity.
5. Metallic crystals have higher thermal conductivity because of the availability of large
number of free electrons which act as carriers of heat.
6. Metals are opaque to light since the light energy is absorbed by free electrons.
Copper, sodium, silver, aluminum, etc. are examples of metallic crystals.

HYDROGEN BONDING

Hydrogen bond is formed under certain conditions when a single hydrogen atom appears to be
bonded to two distinct electronegative atoms. This configuration is represented as X – H ... Y
where X is called ‘donor’ while Y is called ‘acceptor’. The weaker of the two bonds (shown by
dotted line) is the hydrogen bond while the other (shown by a full line) is a strong covalent
bond. H2O (ice), NH3 and HF are examples of hydrogen-bonded crystals. These bonds are
stronger than van der Waals bonds but weaker than ionic or covalent bonds.