SOLID STATE

Unit - I Crystal Systems and Structural Analysis (15 Hours)

The growth and form of crystals - the crystal systems and Bravais lattices – Miller indices and labelling
of planes - symmetry properties - crystallographic point groups and space groups - fundamentals of X-
ray diffraction - powder and rotating crystal methods - systematic absences and determination of lattice
types - analysis of X-ray data for cubic system - structure factor and Fourier synthesis - electron and
neutron diffraction and structure determination.
Unit - II Solid State - I (15 Hours)
Types of solids - close packing of atoms and ions - bcc , fcc and hcp voids - Goldschmidt radius ratio -
derivation - its influence on structures - structures of rock salt - cesium chloride - wurtzite - zinc blende
- rutile - fluorite - antifluorite - diamond and graphite - spinel - normal and inverse spinels and
perovskite - lattice energy of ionic crystals - Madelung constant - Born-Haber cycle and its
applications.
Unit - III Solid State - II (15 Hours)
Metallic state - free electron and band theories - non - stoichiometry - point defects in solids - Schottky
and Frenkel defects - linear defects - dislocations - effects due to dislocations - electrical properties of
solids - insulators - intrinsic semiconductors – impurity semiconductors (n and p- type) and
superconductors - elementary study of liquid crystals.

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 SOLID STATE
2.0 INTRODUCTION
Solids are characterized by incompressibility, rigidity and mechanical strength. There are two types
of solids namely amorphous solids and crystalline solids. The following are the important differences
between them.
Crystalline Solids Amorphous solids
1. In crystalline solids the structural units are In amorphous solids the structural units are not
orderly arranged and they have definite geometrical orderly arranged eg. Glass, plastic.
configurations. eg. Sugar, NaCl
2. They have sharp melting point They do not have sharp melting point.
3. They have well defined faces and shapes They do not have well defined faces & shapes.
4. They are anisotropic ie. they exhibit different They are isotropic. ie. They exhibit same physical
physical properties in all directions. properties in all the directions.
5. They have characteristic heats of fusion. They do not have characteristic heats of fusion.
6. They are generally incompressible. They may be compressed to an extent.
7. They give a regular cut when cut with a sharp They give irregular cut.
edged knife. They are regarded as super cooled liquids or pseudo
8. They are regarded as true solids. solids.
IMPORTANT TERMS USED IN SOLID STATE
Space Lattice
An infinite three dimensional array of points showing how atoms or molecules are arranged in a
crystal is known as space lattice. The points are known as lattice points.
Unit cell
It is defined as the smallest fundamental portion of a crystal lattice when repeated in three
dimensions will generate the crystal.
Totally there are 7 classes of unit cells. (a) cubic (b) Triclinic (c) monoclinic (d) orthorhombic (e) tetragonal
(f) hexagonal and (g) rhombohedral
Characteristic parameters of a unit cell
i) Crystallographic axes:- The lines drawn parallel to the lines of intersection of any three faces of the unit
cell which do not lie in the same plane are called crystallographic axes.
ii) Interfacial angles:- The angles between the three crystallographic axes are known as interfacial angles.
iii) Primitives:- The three sides a,b & c of a unit cell are known
as primitives or characteristic intercepts.
Crystallograpic axes OX, OY, OZ Interfacial angles : α, β, γ
Primitives : a, b, c.

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 SEVEN CRYSTAL SYSTEMS
Elements Bravais lattice
S. Crystal of
Axes and angles Examples Nos
No System Symmetr Types
.
y
1 Cubic A=b=c Centre 1 NaCl, KCl 3 1. Simple cube
Α = β = γ = 90o Plane 9 CsCl, ZnS, Pb2 2. Face centered cube
Axes 13 diamond 3. Body centered cube
2 Hexag A=b≠c Centre 1 ZnO, CdS, 1 Hexagonal prism
onal α = β = 90o Plane 7 HgS,
γ = 120o Axes 7 Ice, urea,
graphite
3 Tetrag A=b≠c Centre 1 SnO2 , Ti O2, 2 1. Tetragonal prism
onal Α = β = γ = 90o Plane 5 Sn 2. Body centered tetragonal prism
Axes 5
4 Orthor a≠b≠c Centre 1 KNO3, K2SO4 4 1. Rectangular prism
hombic α = β = γ = 90o Plane 3 BaSO4, 2. Body centered rectangular prism
Axis 3 rhombic 3. Rhombic prism
sulphur 4. Body centered rhombic prism
5 Monoc a≠b≠c Centre 1 Monoclinic 2 1. Monoclinic parallel epiped
linic α = γ = 90o Plane 1 sulphur, 2. Monoclinic one face centered
β ≠ 90o Axis 1 CaSO4 . 2H2O,
NaSO4 10H2O
6 Triclini a ≠ b ≠ c Centre 1 CuSO4 5H2O 1 Triclinic parallel epiped
c α ≠ β≠ γ ≠ 90o K2Cr2O7,
H3BO3
7 Rhomb a=b=c Centre 1 CaCO3 , 1 Rhombohedron
ohedral α = β= γ = ≠ 90o Plane 3 NaNO3 quartz
Axes 4
Cubic System
Crystals belonging to this system are built upon three equal axes at right angles to one another. There are
three types of cubic lattices.

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(i) Simple cubic crystal (SC) : In this the atoms are present only at the corners. In a simple
cubic structure, each corner atom is shared by eight surrounding cubes, it contributes for 1/8
of an atom. Thus each simple cube has (8 x 1/8) = 1 atom per unit cell in a crystalline solid.

(ii) Body Centred Cubic Crystal (BCC)

A BCC structure possess 8 corner atoms along with one body centre atom. Eight corner
atoms contribute 1 atom per unit cell. The centre atom also contributes one per unit cell. Hence
the number of atoms per unit cell is 2.
(iii) Face Centred Cubic Crystals (FCC)
A FCC structure posses 8 corner atoms along with 6 atoms, one each at the centre
of each face. The 8 corner atoms contribute for 1/8 of an atom and thus only one atom per
unit cell. Each of six face centred atom is shared by two adjacent unit cells and so it
contributes ½ of its share for each unit cell. ie. a total of 6 x ½ = 3 atoms per unit cell.
Hence, the number of atoms per unit cell in FCC structure are (i) 3 face centred and (ii) 1 corner atom ie. 4
atoms per unit cell.
Co-ordination number
Coordination number is defined as the number of nearest neighbours that an atom has in a unit cell.
Co.No.
a) Simple cubic structure 6
b) Body centred cubic structure 8
c) Face centred cubic structure 12
Characteristic of cubic lattices
Simple
Characteristics Body centred cube Face centred cube
cube

1. Unit cell volume a3 a3 a3

2. Lattice points per unit cell 1 2 4
3. Nearest neighbour distance a

4. Coordination number 6
8 12
5. Second nearest neighbour distance
a a

6. Number of second neighbours

12 6 6

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Close packing arrangements (hcp, ccp)
The close packing arrangements describe how the atoms are closely arranged
in a crystal occupying minimum amount of space.
First layer is formed by placing a number of spheres in such away that each
sphere is in contact with six other spheres of the same layer. In such an arrangement
obviously depressions will be formed in between the spheres. The second layer is
formed by placing the spheres in the depressions on the top of the first layer. Again in
the second layer also, each sphere is in contact with six other sphere of the same layer.
There are two ways in which the third layer can be arranged on the top of the second layer. If the spheres
in the third layer are arranged exactly above the spheres in the first layer, the arrangement is known as
hexagonal close packing hcp arrangement. This arrangement is also known as ABABAB….. arrangement . If
the spheres in the third layer are arranged not exactly above the spheres in the first layer but in a position
different from the position of spheres in the first and second layer, such an arrangement is called cubic close
packing ccp or face centred cubic, fcc arrangement. This arrangement is also known as ABCABC…..
arrangement
Arrangement of third layer in hcp & ccp

Packing Fraction or Packing Efficiency

It is defined as the fraction of the total volume occupied by the molecules in a crystal system. Packing
density = υ / V
Let us calculate the packing fraction for simple cube, body centred and fcc systems.
Packing density of simple cubic structure
Let „a‟ be the cube edge of unit cell and „γ‟ the atomic radius. In SC structure, the unit cell contains one atom on
the average. Volume of atoms in unit cell (V) = 1 x 4/3 π γ3
For SC structure : γ = a/2 V = 4/3 π (a/2) 3 = π a3 /6 ; Volume of unit cell = V = a3

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This reveals that 52% of the unit cell is occupied by atoms and 48% is empty.

Atomic Packing Factor (APF):SC

Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres
• APF for a simple cubic structure = 0.52
volume
atoms atom
a 4
unit cell 1 p (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.24,
Callister & Rethwisch 8e. Chapter 3 - 8

Packing density of body Centred cubic structure

The unit cell of bcc structure contains 2 atoms on the average.
Volume of atoms in the unit cell (V) = 2 x 4 / 3 π r3

Volume of unit cell V = a3

Thus reveals that 68% of the unit cell is occupied by atoms and 32% is empty.

Body Centered Cubic Structure (BCC)

• Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

ex: Cr, W, Fe (), Tantalum, Molybdenum

• Coordination # = 8

Adapted from Fig. 3.2,

Click once on image to start animation Callister & Rethwisch 8e.
(Courtesy P.M. Anderson)
2 atoms/unit cell: 1 center + 8 corners x 1/8
Chapter 3 - 9

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Packing density of face centred cubic structure
The unit cell of fcc structure contains 4 atoms on the average.
Volume of atoms in the unit cell V = 4 x 4 / 3 π r3

Volume of unit cell V = a3

This reveals that 74% of unit cell is occupied by atoms and 26% is empty.

Face Centered Cubic Structure (FCC)

• Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

ex: Al, Cu, Au, Pb, Ni, Pt, Ag

• Coordination # = 12

Adapted from Fig. 3.1, Callister & Rethwisch 8e.

Click once on image to start animation
(Courtesy P.M. Anderson) 4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

Chapter 3 - 11

Radius Ratio
The radius ratio is the ratio of the radius of smaller ion, usually cation to that of larger ion, usually
anion. It is given by
P=r+/r–

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The limiting radius ratio that can tolerate a given coordination number is listed below.
Coordination number Geometry Limiting radius
(CN) ratio
2 Linear 0.0 – 0.15
3 Triangular 0.15 – 0.22
4 Tetrahedral 0.22 – 0.414
4 Square planar 0.22 – 0.414
6 Octahedral 0.414 – 0.73
8 Cubic 0.73 – 1.0

Radius Ratio for NaCl structure

Consider ∆ ABC only
AC2 = AB2 + BC2
( 4r - )2 = [ 2 (r+ + r -)]2 + [2(r+ + r - )] 2
16 r - 2
= 8 ( r + + r -)2
√2 r - = r+ + r -

Cubic Coordination
Body diagonal =

A = 2r -
Body diagonal = 2( r+ + r - )

r+ + r - =

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Applications of radius ratio
1) This helps to rationalize the structure
2) This helps to predict the coordination number.
1) Let us take the example of NaCl crystal. Here
Na+ ion will prefer octahedral hole in closepacked void of Cl- ions.

Therefore it is 6 Coordinates
2). The radius ratio will predict how many anions can fit around a cation and vice versa (Number of nearest
neighbours) consider NaCl.

This lies in the range of 0.414 – 0.73. So the coordination number is six. Since it is 1:1 salt, the
coordination number Cl - ion should also be six.
Goldschmidt radius ratio
Every compound can be identified by a unique arrangement of the atoms in the crystal structure, which
determines the inter–atomic distances and the compositional ratios and thus helps understanding specific
material properties. For this reason, crystal structure determination and analysis are essential not only from a
mere crystallographic viewpoint, but also for numerous fields of materials research, chemistry, physics and life
sciences.

Goldschmidt's radius ratio (or) tolerance factor is an indicator for the stability and distortion of
crystal structures. It was originally only used to describe perovskite structure, but now tolerance factors are also
used for ilmenite. Alternatively the tolerance factor can be used to calculate the compatibility of an ion with a
crystal structure. The first description of the tolerance factor for perovskite was made by Victor Moritz
Goldschmidt in 1926. The evaluation of crystal structures can be facilitated by various tools and indicators. For
instance, Goldschmidt tolerance factor (T ) of perovskite compounds ABX3 (A and B: metal cations, X:
chalcogen or halogen group) is widely used to assess the geometric stability and distortion of crystal structures
in terms of the constituent ionic packing.

Mathematical expression
The Goldschmidt tolerance factor (t) is a dimensionless number that is calculated from the ratio of
the ionic radii.

√ ( )

rA is the radius of the A-cation.

rB is the radius of the B-cation.
r0 is the radius of the anion (usually oxygen).

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In an ideal cubic perovskite structure the axis of the unit cell (a) can be described with the following equation:
√ ( ) ( )

Goldschm
idt
Structure Explanation Example Example lattice
tolerance
factor (t)
A ion too big
Hexagonal or
>1 or B ion too BaNiO3 -
Tetragonal
small.

A and B ions
SrTiO3
0.9-1 Cubic have ideal
BaTiO3
size.

A ions too GdFeO3 (Ort

Orthorhombic/ small to fit horhombic)
0.71 - 0.9
Rhombohedral into B ion CaTiO3 (Orth
interstices. orhombic)

A ions and B Ilmenite,

Different
<0.71 have similar FeTiO3 (Trig -
structures
ionic radii. onal)

The T is defined by ratios of constituent ionic radii of A, B and X as T = (RA + RX)/√2(RB + RX),

where RA, RB and RX are the ionic radii of A, B and X, respectively.

From the following figure, the ideal perovskite compounds adopt a cubic close packed structure
with T = 1. When the ratio of the ionic radii deviates from the ideal value (T ≠ 1), a geometric strain and crystal
distortions arise. As the deviation from T = 1 becomes greater, the crystal adopts structures of lower symmetry
than the cubic one. Thus by calculating T, the crystalline structure can be predicted and its geometric strain and
stability evaluated. At the same time, the T can be used to estimate the compatibility of different ions with a
crystalline structure. Because of its simplicity and practicality, the T is used extensively in a wide variety of
fundamental and applied studies

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 (a) concept of T, (b) loosely packed crystal structure with a small radius of A with T < 1 and tightly
packed crystal structure with a large radius of A with T > 1, and (c) concept of the IFF in an ideal cubic
perovskite structure with a lattice constant a and Z = 1 (purple sphere: A; lime spheres: B; black spheres: X;
Grey cuboid: Vunit/Z; purple + lime + 3 × black spheres: Vion). The IFF shows spherical ionic volume fraction in
the crystal structure (grey cuboid).

STRUCTURE OF NaCl

 Chloride ions are ccp type of arrangement, i.e., it contains chloride ions at the corners and at the center
of each face of the cube.
 Sodium ions are so located that there are six chloride ions around it. This equivalent to saying that
sodium ions occupy all the octahedral sites.
 As there is only one octahedral site for every chloride ion, the stoichiometry is 1 : 1.
 For sodium ions to occupy octahedral holes and the arrangement of chloride ions to be close packed the
radius ratio, rNa+/rCl-, should be equal to 0.414. The actual radius ratio 0.525 exceeds this limit. To
accommodate large sodium ions, the arrangement of chloride ions has to slightly open up.

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  It is obvious from the diagram that each chloride ion is surrounded by six sodium ions which are
disposed towards the corners of a regular octahedron. We may say that cations and anions are present in
equivalent positions and the structure has 6 : 6 coordination.
 The structure of sodium chloride consists of eight ions a unit cell, four are Na+ ions and the other four
are Cl- ions.

In this structure, each corner ion is shared between eight unit cells, each ion a face of the cell by two cells,
each ion on a edge by four cells and the ion inside the cell belongs entirely to that unit cell.

Most of the alkali halides, alkaline earth oxides, and sulphides exhibit this type of structure. Other compounds
which crystallize in sodium chloride type of structure are NH4Cl, NH4Br, NH4I, AgF, AgCl and AgBr

STRUCTURE OF CsCl
The structure of CsCl is shown in the figure at the left and its unit cell representation is shown in figure at the
right.

Figures. (left) Structure of CsCl and (right) unit cell representation of CsCl.

The structure can be described as:

 The cesium ions from the simple cubic arrangement.

 Chloride ions occupy the cubic interstitial sites, i.e., each chloride ion has eight cesium ions as its
nearest neighbours.
 If we consider the figure at left it can be observed that each cesium ion is surrounded by eight chloride
ions which are also disposed towards the corners of a cube.
 It may be concluded that both type of ions are in equivalent positions, and the stoichiometry is 1:1. The
coordination is 8:8.

Other examples of this type of structure are CsBr and CsI. This structure is observed only when the cations are
comparable in size to the anions.

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The Wurtzite structure

Figure. Unit cell representation of Wurtzite structure.

The salient features of its structure are:

 Sulfur atoms form the hcp type of arrangement and are yellow spheres in the diagram.
 Zinc atoms are violet spheres and are located that there are four sulphur atoms around each zinc atom. It
may be said that zinc atoms occupy tetrahedral sites.
 As there are two tetrahedral sites available for every sulphur atom, zinc atoms occupy only half of
tetrahedral sites. The alternate tetrahedral sites remain vacant. The stoichiometry of the compound is
1:1.
 Each zinc atom is surrounded by four sulphur atoms and in turn each sulphur atom is also surrounded by
four zinc atoms (which are also disposed towards the corners of a regular tetrahedron). The coordination
of the compound is 4:4. Again we may say that cations and anions are in equivalent positions.
 It may be concluded that the structure of Wurtzite is very similar to the structure of zinc blende. The
only difference is in the sequence of the arrangement of close packed layers of sulphur atoms. In zinc
blende, sulphur atoms follow the sequence ABCABC... etc. whereas in wurtzite the sequence is
ABABAB... etc.

Other examples of this type of structure are ZnO, CdS, CdTe and BeO

ZINC BLENDE STRUCTURE

A unit cell representation of zinc blende is shown in the figure.
The sulphur atoms are yellow and zinc atoms are gray. The salient features of its structure are:
 The zinc atoms are ccp type of arrangement, i.e., zinc atoms at the corners and at the center of each face
of the cube.
 Sulphur atoms are so located that there are four zinc atoms around it. Or it may be said that sulphur
atoms occupy tetrahedral sites and their coordination number is four.

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  As there are eight tetrahedral sites available; four sulphur atoms occupy only half of tetrahedral sites. So
the stoichiometry of the compound is 1:1. Only alternate tetrahedral sites are filled by sulphur atoms.

Figure. Unit cell representation of zinc blende structure.

 Each zinc atom is surrounded by four sulphur atoms and in turn each sulphur atom is also surrounded by
four zinc atoms which are also disposed towards the corners of a regular tetrahedron. We may say that
cations and anions are present in equivalent positions and the coordination of zinc blende structure is
described as 4:4.
 For the arrangement of sulphur atoms to be truly close packed and zinc atoms to occupy tetrahedral
voids, the radius ratio (rZn2+/zS2-) should be 0.40. This value is greater than 0.225 and so we may say
that the arrangement of sulphur atoms is not actually close packed.
This structure is found in 1:1 compounds in which the cation is smaller than the anion. Examples include
copper(I) halides (CuCl, CuBr, CuI), silver iodide and beryllium sulphide.

RUTILE STRUCTURE (TiO2)

The rutile structure is shown in the following figure. In this structure, each Ti4+ ion is surrounded by six
O2- ions arranged octahedrally and each O2- ion is surrounded by the Ti4+ ions arranged in a plane triangular
manner. Thus, the coordination numbers of Ti4+ and O2- are 6 and 3.
The structure of titanium dioxide cannot be considered to be cubic as one of the axes is shorter than the
other by 30 percent.

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STRUCTURE OF FLUORITE.
This structure is shown in the following Fig. The fluoride structure is found when the radius ratio is 0.73
or above.

In the fluoride structure, each Ca2+ ion is surrounded by eight F- ions at the corners of a body centred
cubic arrangement while each F- ion is surrounded by four Ca2+ ions arranged tetrahedrally. Thus, the
coordination numbers of Ca2+ and F- are 8 and 4. Such an arrangement is known as 8 : 4 arrangement. Calcium
ions in fluoride structure are arranged in face-centred cubic close packed (ccp) type of arrangement. As there
are two tetrahedral sites available for every calcium ion, the fluoride ions occupy all the tetrahedral sites Thus,
the stoichiometry of the compound is 1 : 2.
Others compounds showing this type of structure are SrF2, BaF2, BaCl2, SrCl2, CdF2, HgF2 and PhF2.

STRUCTURE OF ANTI FLUORITE

Regarding to some metal oxides, like LiO2 , an inverse ratio of cations and anions is found. This type is so
called: antifluorite. The locations of the cations and the anions are inversed. Depending on that, the coordination
will be (4:8). The cations occupy all tetrahedral holes in the ccp array. In the solid state lithium oxide adopts an
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antifluorite structure which is related to the CaF. Fluorite structure with Li cations substituted for fluoride
anions and oxide anions substituted for calcium cations.

Structure of Spinel and Inverse Spinel

The compound MgAl2O4 which occurs in nature as the mineral spinel has a structure based on a „ccp‟
array of oxide ions. One of the tetrahedral holes are occupied by Mg2+ ions and one half of the octahedral holes
are occupied by Al3+ ions. This structure are a modification to be discussed below is adopted by many other
mixed metal oxides of the type “M11M111O4” (eg. FeCr2O4, ZnAl2O4 and CoCO2 O4) by some of the type M21
M1V O4 (eg. Na2MoO4 and AgMoO4). This structure is often symbolized as A[B2]O4 where square brackets
enclose the ions in the octahedral interstrces.
An important variant is the inverse Spinel structure B[AB]O4, in which half of the „B‟ ions are in
tetrahedral sites and the „A‟ ions are in octahedral ones along with other half of the B1 ions. This often happens
when the „A‟ ions have a stronger preference for octahedral co-ordination than the „B1 ions so far as is known
all M11M211O4 (eg. Fe111 (Co11Fe111)O4 Fe111 (Fe11Fe111) O4 and Fe111[Ni11 Fe111]O4] and also M1V M211 O4 (eg.
Zn [ZnTi])4] spinels are inverse

There are also many compounds of the „A‟ spinel structures in which only a fraction of the „A‟ ions are
in tetrahedral sites. This occurs when the preferences of both „A‟ and „B‟ ions for octahedral and tetrahedral
sites do not differ markedly.

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Pervoskite (ABO3) Strucutre
Perovskites having the general formula ABX3 (eg. CaTiO3) have larger A ions occupying 12 coordinate
holes and smaller B ions in octahedral 6 coordinate holes in a cubic structure. The X ion is generally O2- or F- in
a Fluoride Perovskite (eg. NaFeF3). The structure is distorted without symmetric centre and has overall
permanent electric

Polarization. These polar crystals are ferromagnets with larger number of spins aligned parallely along with the
aligned electrical polarization. The piezo electric perovskites change dimensions in an electric field, or generate
a electric field when the crystal is under stress. BaTiO3 , NaNbO3 ,NaTiO3 ,KTiO3 are some piezo electric
perovskites. They find application in pressure transducers, sound detectors and micromanipulators.

Lattice Energy in Ionic Solids

The stability of an ionic solid is measured in terms of its lattice energy (U0). It is defined as the energy
released when on mole of an ionic crystal is formed from one mole of gaseous positive and one mole of
gaseous negative ions, when these are separated from each other by infinite distance. Greater the value of
lattice energy, more stable, more stable is the ionic solid. The lattice energy of sodium chloride is -185
kcal/mole. The negative sign indicates that the process is exothermic and that the energy of the system is
lowered as the solid is formed. The high value suggests the stability of the solid.
Qualitatively speaking, the force of attraction between oppositely charged ions is determined by
 their ionic radii,
 the charges on the ions.
 It is given by the relationship,

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  where q1, q2, are the charges on ions and r is the interionic distance.
 It may be observed that if the radii of the ions are large, the force of attraction will be less. This is better
illustrated if we compare the stability of NaCl and CsCl. The force of attraction between the Large Cs+
ions and Cl- ions will be less than that between the smaller Na+ ions and Cl- ions. As result, CsCl is less
stable than NaCl. We may say that the stability of an ionic solid increases with decreasing interionic
distance for crystals with similar charges.
 The role played by charges on the ions (on the stability of solids) is demonstrated if we compare the
lattice energies of BaO and NaCl, since both have very similar internuclear distances (NaCl=2.81 Å and
BaO=2.77 Å). Since BaO consists of doubly charged Ba2+ and O2-ions, the force of attraction is much
larger than that in NaCl which contains singly charged ions. Hence, BaO is more stable than NaCl
(melting point; NaCl=800 °C, BaO=1921 °C). The stability of an ionic solid increases with increasing
nuclear charge for crystals with similar interionic distances.

The Born-Haber Cycle

The formation of an ionic solid MX from its elements may be formulated by two different path interrelating
different thermochemical quantities.

Figure. Born-Haber cycle for the formation of an ionic solid MX.

The various terms are:

 S = Sublimation energy of the metal

Since energy is required for the process (endothermic), its value is reported as a positive quantity.
 D = Dissociation energy of X2 gas into atoms
This process is also endothermic and its value is reported as a positive quantity.
 I = Ionization energy, i.e., energy required for the removal of an electron from an isolated gaseous atom
M. The process is endothermic and is reported as a positive quantity.

 E = Electron affinity, i.e., amount of energy released when a neutral gaseous atom gains an electron. The
process is exothermic and its value is given as a negative quantity.

 U0 = Lattice energy; it is the amount of energy released when one mole of gaseous positive and negative
ions condense to form an ionic solid.

The process is exothermic and its value is always negative.

 ΔHf = Heat of formation; it is defined as the amount of energy released when one mole of a substance is
formed from its elements.

This is a single step reaction. Energy is released in the process and its value is reported as a negative
quantity.

Since the two processes are independent of each other, the two can be equated, i.e., heat of formation of MX
must be equal to the summation of all other terms.
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The lattice energy of a solid can be calculated with the help of other thermochemical quantities which can be
measured experimentally. The quantitative value of each term (along with their signs) are substituted in
previous equation.
As an example we may calculate the lattice energy of NaCl crystal from the following data by the use of Born-
Haber cycle.

Now substituting the values in expression

Role of Lattice Energy

 Stability of ionic solids: Greater the lattice energy, greater is the stability of an ionic solid. Because
more energy will be needed to pull apart the +ive and -ive ions.
 Melting points: Salts with high lattice energies require a greater input of thermal energy to breakdown
the crystal lattice. Consequently, salts have high melting points.
 Solubilities of ionic solids: The magnitude of lattice energy of a solid may give us an idea about the
solubility of that substance in different solvents. Ionic solids in general are insoluble in non-polar
(covalent) solvents such as carbontetrachloride, where as these are soluble in polar solvent, the strong
forces of attraction between its ions (lattice energy) must be overcome. This energy can be overcome by
the ion-solvent interactions. The solvation of ions is referred to in terms of solvation energy which is
always negative, i.e., energy is released in the process. The amount of solvation energy depends upon
the nature of the solvent. In case of non-polar solvents, the solvation energy is small and it is not
sufficient to overcome the lattice energy of solid, thereby the substance does not dissolve. The solvation
energy increases if the solvent has high dipole moment or high polarizability. As a general rule, we may
say that for a solid to dissolve in a particular solvent its solvation energy should be greater than the
lattice energy of that solid.

Applications of Born – Haber cycle-

i) It can be used to determine electron gain enthalpy , ionisation energy and lattice energy.
ii) It can be used to explain the stability of molecules.

Madelung constant
The Madelung constant is used in determining the electrostatic potential of a single ion in a crystal by
approximating the ions by point charges. Because the anions and cations in an ionic solid are attracting each
other by virtue of their opposing charges, separating the ions requires a certain amount of energy. This
energy must be given to the system in order to break the anion-cation bonds. The energy required to break
these bonds for one mole of an ionic solid under standard conditions is the lattice energy.

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The Madelung constant allows for the calculation of the electric potential Vi of all ions of the lattice felt by
the ion at position ri

where rij =|ri - rj| is the distance between the ith and the jth ion. In addition,
zj = number of charges of the jth ion, e = 1.6022×10−19 C
−10
4 π ϵ0 = 1.112×10 C²/(J m).
If the distances rij are normalized to the nearest neighbour distance r0 the potential may be written

with being the (dimensionless) Madelung constant of the ith ion

The electrostatic energy of the ion at site then is the product of its charge with the potential acting at its site

There occur as many Madelung constants Mi in a crystal structure as ions occupy different lattice sites. For
example, for the ionic crystal NaCl, there arise two Madelung constants – one for Na and another for Cl.
Since both ions, however, occupy lattice sites of the same symmetry they both are of the same magnitude
and differ only by sign. The electrical charge of the Na+ and Cl− ion are assumed to be one fold positive and
negative, respectively, ZNa = 1 and ZCl = -1 . The nearest neighbour distance amounts to half the lattice
parameter of the cubic unit cell r0 = a/2 and the Madelung constants become

The prime indicates that the term j = k = l = 0 is to be left out. Since this sum is conditionally convergent it
is not suitable as definition of Madelung's constant unless the order of summation is also specified. There
are two "obvious" methods of summing this series, by expanding cubes or expanding spheres. The latter,
though devoid of a meaningful physical interpretation (there are no spherical crystals) is rather popular
because of its simplicity. Thus, the following expansion is often found in the literature

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