The Solid State MODULE - 3

States of Matter

6
Notes

THE SOLID STATE

You are aware that the matter exists in three different states viz., solid, liquid and
gas. In these, the constituent particles (atoms, molecules or ions) are held together
by different forces of attraction between them. However, the nature and magnitude
of the forces varies. In the first two lessons of this module you have learnt about
the gaseous and the liquid states of matter. In this lesson you would learn about
solid state- a compact state of matter. The solids are distinguished from a liquid
or gas in terms of their rigidity which makes them occupy definite volume and
have a well defined shape. In solid state, the constituent particles are in close
contact and have strong forces of attraction between them. Here, you would
learn about structure, classification and properties of solids.

OBJECTIVES
After reading this lesson, you should be able to:
z explain the nature of solid state;
z explain the properties of solids in terms of packing of particles and intermo-
lecular attractions;
z differentiate between crystalline and amorphous solids;
z explain the melting point of a solid;
z classify the crystalline solids according to the forces operating between the
constituent particles;
z define the terms crystal lattice and unit cell;
z describe different types of two dimensional and three dimensional unit cells;
z explain different types of packing in the solids;
z define coordination number;

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z calculate the number of particles in simple cubic, face-centrad cubic and
body centered cubic unit cells;
z relate the density of a solid to the properties of its unit cell;
z calculate the packing efficiency of simple cubic body central cubic and CCP/
HCP lattices;
z define radius ratio;
Notes z correlate the radius ratio with the structure of solids;
z explain the structure of simple ionic compounds;
z explain Frenkel and Schottky defects;
z classify solids on the basis of their electrical and magnetic properties; and
z explain the effect of doping of semiconductors by electron deficit and electron
rich impurities.

6.1 NATURE OF SOLID STATE

You have learnt in lesson 6 that according to Kinetic Molecular Theory, the
gases consist of a large number of molecules, which are in constant random mo-
tion in all directions in the available space. These molecules have very weak or
negligible forces of attraction between them. A sample of gas can be compressed,
as there is a lot of free space between the molecules Fig. 6.1(a) In liquids Fig.
6.1(b) on the other hand the molecules are also in constant motion but this mo-
tion is relatively restricted. Since there is very little free space available between
the molecules the liquids are relatively incompressible.

(a) (b) (c)

Fig. 6.1: A pictorial representation of the three states of matter: (a) gas
(b) liquid and (c) solid state.

In solid state the constituent particles are arranged in a closely packed ordered
arrangement Fig. 6.1 (c) with almost no free space. They can just vibrate about
their fixed positions. These are in close contact and cannot move around like the
molecules of a gas or a liquid. As a consequence, the solids are incompressible,
rigid and have a definite shape. Like liquids, the volume of a solid is independent
of the size or the shape of the container in which it is kept.

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6.2 CLASSIFICATION OF SOLIDS
On the basis of nature of arrangements of the constituent particles the solids
are classified into amorphous and crystalline solids.

6.2.1 Amorphous and Crystalline Solids

In crystalline solids the constituent particles are arranged in a regular and peri-
Notes
odic pattern and give a well defined shape to it. The term ‘crystal’ comes from the
Greek word, krustallos meaning ice. The regular pattern extends throughout the
solid and such solids are said to have long range order. On the other hand, some
solids have only a short range of order. This means that the particles are ar-
ranged regularly in only some regions of the solid and are relatively disordered in
other regions. Such solids are called amorphous solids. In Greek, a means
without and morph means form. Thus the word amorphous means without
form. Sodium chloride and sucrose are common examples of crystalline solids
while glass, fused silica, rubber and high molecular mass polymers are some ex-
amples of amorphous solids.

An important difference between the amorphous and crystalline solids is that

while amorphous solids are isotropic in nature (i.e., these exhibit same value of
some physical properties in all directions) the crystalline solids are anisotropic
(i.e., the values of some physical properties are different in different directions).
Refractive index and coefficient of thermal expansion are typical physical proper-
ties, which have different values when measured along different directions of a
given crystal. Another difference between amorphous and crystalline solids is
that while crystalline solids have a sharp or definite melting point, whereas the
amorphous solids do not have definite melting point, these melt over a range of
temperature.

The crystalline solids can be further classified on the basis of nature of interac-
tion between the constituent particles as discussed below.

6.2.2 Classification of Crystalline Solids

In crystalline solids the constituent particles are arranged in an ordered arrange-
ment and are held together by different types of attractive forces. These forces
could be coulombic or electrostatic, covalent, metallic bonding or weak intermo-
lecular in nature. The differences in the observed properties of the solids are due
to the differences in the type of forces between the constituting particles. The
types of forces binding the constituent particles can be used as a basis for classi-
fication of crystalline solids. On this basis, the crystalline solids can be classified
into four different types- ionic, molecular, covalent and metallic solids. The char-
acteristics and the properties of different types of solids are compiled in Table
6.1.

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Table 6.1: Characteristics and properties of different types of solids.

Type of Constituent Nature of Appearance Melting Examples

Solid Particles interaction Point
between the
particles

Ionic Ions Coulombic Hard and High Sodium chloride,

brittle zinc sulphide, etc
Notes
Molecular Molecules
Non polar van der Waals Soft low Iodine, naphthalene
Polar Dipole-dipole brittle water carbon dioxide.
Covalent Atoms Covalent bond- Hard Very high Diamond, graphite,
ing silica, etc.
Metallic Atoms Metallic bonding Hard and Variable Copper, silver, etc.
malleable

Sodium chloride is an example of an ionic solid because in this case the sodium
ions and chloride ions are attracted to each other by electrostatic interactions.
Iodine on the other hand is an example of a molecular solid because in this the
molecules are held together by weak van der Waals forces. Diamond, with strong
covalent bonds between the constituent carbon atoms is an example of covalent
solids while in metals a large number of positive cores of the atoms are held
together by a sea of electrons.

6.3 PROPERTIES OF CRYSTALLINE SOLIDS

You are familiar with the following properties of solids on the basis of han-
dling solids in day to day work.
z Solids are rigid in nature and have well defined shapes
z Solids have a definite volume irrespective of the size and shape of the
container in which they are placed
z Solids are almost incompressible.
You are familiar with a number of crystalline solids like sugar, rock salt, alum,
gem stones, etc. You must have noticed that such solids have smooth surfaces.
These are called ‘faces’ of the crystal. These faces are developed in the process of
crystal formation by ordered arrangements of the constituent particles. It is gen-
erally observed that the faces of crystals are developed unequally. The internal
angle between a pair of faces is called interfacial angle and is defined as the
angle between the normals to the intersecting faces. An important characteristic
of crystalline solids is that irrespective of the size and shape of the crystal of a
given substance, the interfacial angle between a pair of faces is always the same.

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This fact was stated by Steno as the law of constancy of interfacial angles (Fig.
6.2).

Fig. 6.2 The constancy of interfacial angles Notes

6.3.1 Melting Point of a Solid

What is the effect of heat on a solid? You would have observed that when a solid
is heated it becomes hot and eventually gets converted into a liquid. This process
of conversion of a solid to a liquid on heating is called melting. You would also
have observed that different solids need to be heated to different extents to con-
vert them to liquids. The temperature at which a solid melts to give a liquid is
called its melting point. Every solid is characterized by a definite melting point.
This in fact is a test of the purity of the solid. The melting point of a solid gives
us an idea about the nature of binding forces between constituent particles of the
solid. Solids like sodium chloride ( m.p = 1077 K ) have very high melting points
due to strong coulombic forces between the ions constituting it. On the other
hand molecular solids like naphthalene ( m.p. = 353 K) have low melting points.
The effect of heat on a solid can be understood in terms of energy and motion of
the constituent particles. You are aware that in a solid the constituent particles
just vibrate about their mean position. As the heat is supplied to the solid, the
constituent particles gain energy and start vibrating more vigorously about their
equilibrium positions. As more and more heat is supplied, the energy keeps on
increasing and eventually it becomes greater than the binding forces between
them. As a consequence the solid is converted into a liquid.

INTEXT QUESTIONS 6.1

a) Differentiate between solid, liquid and gaseous state.
b) How are solids classified on the basis of the intermolecular forces.
c) What is Steno’s law of constancy of interfacial angles?

6.4 CRYSTAL LATTICE AND UNIT CELLS

You know, the crystalline solids have long-range order and the closely packed
constituent particles are arranged in an ordered three dimensional pattern. The

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structure of the crystalline solids can be represented as an ordered three dimensional
arrangement of points. Here each point represents the location of a constituent
particle and is known as lattice point and such an arrangement is called a crystal
lattice or space lattice or simply a lattice.

6.4.1 Two Dimensional Lattice and Unit Cells

Notes To understand the meaning of the term lattice, let us first start with a two
dimensional lattice. A two dimensional lattice has a set of points arranged in
a regular pattern on a plane or a surface (in two dimensions). One such lattice
is shown in Figure 6.4(a). The arrangement of lattice points is as shown in Fig.
6.4(a). When these lattice points are joined, the geometry of the lattice becomes
clear (Fig. 6.4(b). The entire pattern can be generated by repeating a set of four
points. On joining these points we get a unit cell of the lattice (shown in dark).
The unit cell of a two dimensional lattice is a parallelogram which is defined
in terms of two sides a and b and the angle between them γ. Only five types
of unit cells are possible in two dimensional lattice. These are shown in Fig.
6.4(b).

b
y
a
(a) (b)

Fig. 6.3 (a) A two dimensional lattice (b) and its unit cell

a b a
y
90°
a a
a=b 90° a=b
y = 90° a y ¹ 90°
a¹b
y = 90°

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b
a
y 60°
a a
a¹b a=b Notes
y ¹ 90° y = 60°

Fig. 6.4: Five types of two dimensional unit cells

6.4.2 Three Dimensional Lattice and Unit Cells

In three dimensions, the crystal structure of a solid is represented as a three
dimensional array of lattice points. Remember that the lattice points represent the
positions of the constituent particles of the solid (Fig. 6.5(a)).

(a) (b)

Fig. 6.5: Schematic representation of a three dimensional crystal lattice.

In a crystal lattice we can select a group of points which can be used to generate
the whole lattice. Such a group is called repeat unit or the unit cell of the crystal
lattice. The shaded region in the Fig. 6.5(a) represents a unit cell of the crystal
lattice. The unit cell is characterized by three distances along the three edges of
the lattice (a, b and c) and the angles between them (α, β and γ) as shown in the
Fig. 6.5(b). We can generate the whole crystal lattice by repeating the unit cell in
the three directions.
On the basis of the external appearance the known crystals can be classified into
seven types. These are called crystal systems. In terms of the internal structure
also the crystal lattices contain only seven types of unit cells. The seven crystal
systems and the definition of their unit cells in terms of their unit distances and
the angles are compiled in Table 6.2. The seven simple unit cells are given in Fig.
6.6.

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Table 6.2: The seven crystal systems and their possible lattice types.

Systems Axes Angles Possible lattice

types
Cubic a=b=c a = β = γ = 90° P, F, I
Tetragonal a=b≠c a = β = γ = 90° P, I
Orthorhombic a≠b=c a = β = γ = 90° P, F, I, C
Notes Rhombohedral a=b=c a = β = γ ≠ 90° P
Hexagonal a=b≠c a = β = 90°; γ = 120° P
Monoclinic a≠b=c a = γ = 90°; β ≠ 90° P, I
Triclinic a≠b≠c a ≠ β ≠ γ ≠ 90° P

* P= primitive, I= body centered, F= face centered and C= side centered

The unit cell shown in Fig. 6.5 and the ones given in Fig..6.5 have the lattice
points at the corners only.

c
c
a
a 120o a
a b a
a
Cubic Orthorhombic Hexagonal

c
c c
a
b g b b a a
b a a
a a a

Triclinic Monoclinic Tetragonal Rhombohedral

Fig. 6.6 : The primitive unit cells; the relative dimensions of the three repeat distances (a, b
and c) and the angles between them (a, β and γ) are given in Table 6.2.

Such unit cells are called primitive (P) unit cells. Sometimes, the unit cell of a
crystal contains lattice point(s) in addition to the ones at the corners. A unit cell
containing a lattice point each at the centers of its faces in addition to the lattice
points at the corners is called a face centered (F) unit cell. On the other hand a
unit cell with lattice points at the center of the unit cell and at the corners is
called a body centered unit cell (I). In some cases, in addition to the lattice
points at the corners there are two lattice points located at the centers of any two
opposite faces. These are called as end centered (C) unit cells. The possible
lattice types in different crystal systems are also indicated in Table 6.2. The seven
crystal systems when combined with these possibilities give rise to 14 lattice
types. These are called Bravais lattices.

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6.5 NUMBER OF ATOMS IN CUBIC UNIT CELLS
Of the seven crystal systems, let us discuss unit cells belonging to the cubic crys-
tal system in somewhat details. As you can see from Table 6.2 that in the cubic
crystal system the three repeat distances are equal and all the three angles are
right angles. The unit cells of three possible lattice types viz., primitive or simple
cubic, body centered cubic and the face centered cubic, belonging to cubic crys-
tal system are shown in Figure 6.7. Notes

(a) (b) (c)

Fig. 6.7: (a) primitive or simple (b) body centered and (c) face centered
cubic unit cells.

Number of atoms per unit cell

As you know that in unit cells the atoms can be on the corners, in the body
center and on face centers. All the atoms do not belong to a single unit cell.
These are shared amongst different unit cells. It is important to know the number
of atoms per unit cell. Let us learn how to compute these for different cubic unit
cells.
(a) Simple Cubic Unit Cell
The simple or primitive unit cell has the atoms
at the corners of the cube (Fig. 6.7 (a)). A lattice
point at the corner of the unit cell is shared by
eight unit cells as you can see from the encircled
atom in the Fig. 6.8. Therefore, the contribution
of an atom at the corner to the unit cell will be
1/8. The number of atoms per unit cell can be
calculated as follows:
Fig. 6.8: A corner lattice point is
Number of corner atoms = 8 shared by eight unit cells
1
Contribution of each corner atom =
8
1
The number of atoms in a simple cubic unit cell = 8 × =1
8
(b) Body Centered Cubic Unit Cell
A body centered cubic (bcc) unit cell has lattice points not only at the corners but

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also at the center of the cube( Fig. 6.7 (b)). The atom in the center of the cube
belongs entirely to the unit cell, i.e., it is not shared by other unit cells. Each
corner atom, on the other hand, as in the case of simple cubic unit cell, is shared
by eight unit cells. Thus the number of atoms per unit cell can be calculated as
Number of corner atoms = 8
1
Notes Contribution of each corner atom =
8
1
∴ Contribution of all the corner atoms to the unit cell = 8 × =1
8
Number of atoms at the center of the cube = 1
Contribution to the unit cell = 1 ( as it is not shared)
The number of atoms in a body centered cubic unit cell = 1 + 1 = 2
(c) Face Centered Cubic Unit Cell
A face centered cubic ( fcc) unit cell has atoms not only at the corners but also at
the center of each face. Thus it has eight lattice points at the corners and six at
the face centers (Fig. 6.7 (c)). A face centered lattice point is shared by two unit
cells, as shown in Fig. 6.9.

Fig. 6.9: A face centered lattice point is shared by two unit cells

Number of corner atoms = 8

1
Contribution of each corner atom =
8
1
Contribution of all the corner atoms to the unit cell = 8 × =1
8
Number of atoms at the face center = 6
1
Contribution of each atom at the face centre =
2
1
Contribution of all the face centered atoms to the unit cell = 6 × =3
2
The number of atoms points in a face centered cubic unit cell = 1 + 3 = 4

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The number of atoms per unit cell in different types of cubic unit cells is given in
Table 6.3.
Table. 6.3: Number of atoms per unit cell

S.No. Type of unit cell No. of atoms per unit cell

1. Simple cubic 1
2. Body centered cubic 2 Notes
3. Face centered cubic 4

6.6 CALCULATION OF DENSITY OF UNIT CELL

Mass
Density =
Volume
(i) Volume of Unit cell
If the edge length of the cubic unit cell is ‘a’ its volume is a3
(ii) Mass of the Unit cell
Let the molar mass of substance = M

M
∴ Mass of one atom or molecule =
NA

Where NA = Avogadro’s constant.

Let the number of atoms or molecules of the substance present per unit cell = z
(See table 6.3 for values of z for different type of cubic unit cells)

∴ Mass of unit cell = ( number of atoms/molecules present per unit cell )

× ( mass of one atom/molecule )

z⋅M
=
NA
(iii) Density
Mass of one unit cell
Density =
Volume of one unit cell
z⋅M
d=
a3 ⋅ N A
Density of the unit of cell of a substance is the same as the density of the
substance. In case of ionic substances, the formula unit is taken as one particle.
(For example, formula unit of NaCl = 1Na+ + 1Cl– ions; of Na2SO4 = 2Na+
+ 1SO42– ions).

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The above relation can be used to calculate z and hence the nature of cubic lattice
if d and M are known or M if d and z are known
Example. The unit cell of a metallic element is face centred cubic and the side
of the cube is 540.2 pm. Calculate the density of the metal in gcm–3 if its relative
atomic mass is 202.4.

Notes Solution
z⋅M
d=
a3 ⋅ N A
Given:
Side of the cube = a = 540.2 pm = 540.2 × 10–10 cm
Number of atoms per unit cell of a face-centred cubic unit cell = z = 4
Molar mass of the element, M = 202.4 g mol–1
Putting these values in the above relation

4 × 202.4 g mol−1
d=
(540.2 × 10−10 cm)3 × (6.022 × 10−23 mol−1 )
= 8.53 g cm −3

6.7 CLOSE PACKED STRUCTURES OF SOLIDS

In the process of the formation of a crystal the constituent particles get packed
quite closely. The crystal structures of the solids can be described in terms of a
close packing of identical spheres as shown in Fig. 6.10. These are held together
by forces of attraction. Let us learn about the possible close packed structures of
solids and their significance.

Fig. 6.10 : Arrangement of identical spheres in one dimension

A linear horizontal arrangement of identical spheres in one dimension forms a

row (Fig. 6.10). A two dimensional close packed structure can be obtained by
arranging a number of such rows to form a layer. This can be done in two pos-
sible ways. In one of these, we can place these rows in such a way that these are
aligned as shown in (Fig. 6.11 (a)). In such an arrangement each sphere is in
contact with four other spheres. This arrangement in two dimensions is called
square close packing.

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Notes
(a) (b)
Fig. 6.11 : (a) Square close packing and (b) hexagonal close packing of identical
spheres in two dimensions

In the other way we can place the spheres of the second row in the depressions
of the first row and so on and so forth (Fig. 6.11(b)). You may notice that
in such an arrangement each sphere is in contact with six other spheres. Such
an arrangement in two dimensions is called hexagonal close packing. In such
a packing, the spheres of the third row are aligned with the first row. You may
also have noticed that in the hexagonal close packed the spheres are more
efficiently packed. In Fig. 6.11 an equal number of identical spheres are arranged
in two different types of packing.
A three dimensional structure can be generated by placing such two dimensional
layers on top of each other. Before we move on to the three dimensional packing
let us look at the hexagonal close packed layer some what more closely (Fig.
6.12).
You may note from Fig. 6.12 that in a hexagonal close packed layer there are
some unoccupied spaces or voids. These are triangular in shape and are called
trigonal voids. You can further note that there are two types of triangular voids,
one with the apex pointing upwards and the other with the apex pointing down-
wards. Let us call these as X type and Y type voids respectively as marked in the
Fig. 6.12.

IIIrd row

IInd row

Ist row

Fig. 6.12 : A hexagonal Close Packed layer showing two types of triangular voids.

Close Packed Structures in three dimensions

Let us take a hexagonal close packed layer and call it A layer and place another
hexagonal close-packed layer (called the B layer) on it. There are two possibilities.

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1. In one, we can place the second layer in such a way that the spheres of the
second layer come exactly on top of the first layer.
2. In other, the spheres of the second layer are in such a way that these are on
the depressions of the first layer. The first possibility is similar to square
close packing discussed above and is accompanied by wastage of space. In
the second possibility when we place the second layer into the voids of the
Notes first layer, the spheres of the second layer can occupy either the X or Y type
trigonal voids but not both. You may verify this by using coins of same
denomination. You would observe that when you place a coin on the trigonal
void of a given type, the other type of void becomes unavailable for placing
the next coin (Fig. 6.13).

Fig. 6.13 : Two layers of close packed spheres , the second layer occupies only one
type (either X or Y ) of triangular voids in the first layer.

In this process, the sphere of second layer covers the trigonal voids of the first
layer. It results into voids with four spheres around it, as shown in Fig. 6.14(a).
Such a void is called a tetrahedral void since the four spheres surrounding it are
arranged on the corners of a regular tetrahedron, Fig. 6.14(b). Similarly, the trigonal
voids of the second layer will be placed over the spheres of the first layer and give
rise to tetrahedral voids.

(a) (b)
Fig. 6.14 : A tetrahedral void

In a yet another possibility, the trigonal voids of the first layer have another
trigonal void of the opposite type (X type over Y and Y type over X type) from
the second layer over it. This generates a void which is surrounded by six spheres,
Fig..6.15 (a). Such a void is called an octahedral void because the six spheres

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surrounding the void lie at the corners of a regular octahedron, Fig..6.15 (b).

Notes
(a) (b)
Fig. 6.15 : An octahedral void

A closer look at the second layer reveals that it has a series of regularly placed
tetrahedral and octahedral voids marked as ‘t’ and ‘o’ respectively in Fig. 6.16.

Fig. 6.16 : The top view of the second layer showing the tetrahedral
and octahedral voids.

Now, when we place the third layer over the second layer, again there are two
possibilities i.e., either the tetrahedral or the octahedral voids of the second layer
are occupied. Let us take these two possibilities. If the tetrahedral voids of the
second layer are occupied then the spheres in the third layer would be exactly on
top (i.e., vertically aligned) of the first or A layer The next layer ( 4th layer)
which is then placed would align with the B layer. In other words, every alternate
layer will be vertically aligned. This is called AB AB …. pattern or AB AB ….
repeat. On the other hand if the octahedral voids of the second layer are occu-
pied, the third layer is different from both the first as well as the second layer. It
is called the C layer. In this case the next layer, i.e., the fourth layer, howsoever
it is placed will be aligned with the first layer. This is called ABC ABC …. pattern
or ABC ABC.. …. repeat. In three dimensional set up the AB AB …. pattern or
repeat is called hexagonal closed packing ( hcp) (Fig. 6.10 (c) ) while the ABC
ABC …. pattern or repeat is called cubic closed packing (ccp) (Fig. 6.17 (a)).

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A Layer
A-Layer

C Layer A Layer
B-Layer
C Layer
Notes B Layer A-Layer
A Layer B Layer

A Layer

(a) (b) (c)

Fig. 6.17 : (a) Cubic closed packing (ccp) as a result of ABC pattern of close packed spheres;
(b) the layers in (a) tilted and brought closer to show fcc arrangement
(c) hexagonal closed packing (hcp) as a result of ABAB pattern of close packed
spheres.

This process continues to generate the overall three dimensional packed struc-
ture. These three dimensional structures contain a large number of tetrahedral
and octahedral voids. In general there is one octahedral and two tetrahedral voids
per atom in the close packed structure. These voids are also called as interstices.
As mentioned earlier, the identical spheres represent the positions of only one
kind of atoms or ions in a crystal structure. Other kind of atoms or ions occupy
these interstices or voids.
In the close packed structures (hcp and ccp) discussed above, each sphere is in
contact with six spheres in its own layer ( as shown in Fig. 6.12) and is in contact
with three spheres each of the layer immediately above and immediately below it.
That is, each sphere is in contact with a total of twelve spheres. This number of
nearest neighbor is called its coordination number. The particles occupying the
interstices or the voids will have a coordination number depending on the nature
of the void. For example an ion in a tetrahedral void will be in contact with four
neighbors i.e., would have a coordination number of four. Similarly the atom or
ion in an octahedral void would have a coordination number of six.

INTEXT QUESTIONS 6.2

(a) What is the difference between the square close packed and hexagonal close
packed structures?
(b) Which of the above two, is more efficient way of packing?
(c) Clearly differentiate between, trigonal, tetrahedral and octahedral voids.

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6.8 PACKING EFFICIENCY
In all closed packed structures there are always some voids or empty spaces.
The percentage of the total space that is filled by the constituent particles is
called the packing efficiency. It is calculated from the following relation:
filled space
Packing efficiency = × 100%
total space Notes
It depends upon the nature of crystal lattice. For the three types of cubic lattices,
the calculations are given below:
(1) Packing Efficiency of Simple Cubic Lattice
In simple cubic lattice, the constituent particles occupy only the corner positions
of the cubic unit cell. These particles touch one another along the edge of the
cube as shown in the Figure 6.18. Let a be the edge length of the cube and
r the radius of the particle then
a = 2r

C
B

H A

F
C

E D

Fig. 6.18: Simple cubic unit cell

The volume of the cube = (edge length/side)3 = a3 = (2r)3 = 8r3

No. of constituent particles present in each unit cell = 1
4 3
The volume of the filled space = volume of 1 particle = πr
3
filled space
Packing efficiency = × 100
total space
4 3
πr
3 π
= 3
× 100 = × 100
8r 6
= 52.36% = 52.4%

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(2) Packing Efficiency of Body Centred Cubic Lattice

G
B

H A

c
Notes c

F b C

E a D

Fig. 6.19. Body centred cubic until cell.

The body centred cubic unit cell has constitutent particles present at all its
corners as well as at its body centre. The particle at the body-centre touches
the particle at corner positions. Thus, the particles are in contact along the body-
diagonal of the cube. Consider the body-diagonal AF along which the contact
between the central particles with those at corners A and F has been shown in
Fig. 6.19.
∴ Length of body-diagonal AF = c = 4 r (6.1)
(Whole of the central particle (2r) and one-half of each of the two corner particle
(r + r) occupy the body-diagonal)
Length of the body-diagonal
In the triangle EFD on the face CDEF, EF ⊥ ED.

∴ FD2 = EF2 + ED2

b 2 = a 2 + a 2 = 2a 2
Where a is the edge-length or side of the cube.

In the triangle AFD, AD ⊥ FD

∴ AF2 = AD2 + FD2

c 2 = a 2 + b 2 = a 2 + 2a 2 = 3a 2

∴ c = 3a (6.2)

But c = 4r

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4r
∴ a= (6.3)
3

The number of constituent particles in a body-centred cubic unit cell = 2

4
∴ Volume of filled space = 2 × π r 3 (6.4)
3
Notes
3
⎛ 4r ⎞
Volume of the cubic unit cell = a3 = ⎜ ⎟ (6.5)
⎝ 3⎠
4
2 × π r3
filled space 3
Packing efficiency = × 100 = 3
×100
total space ⎛ 4r ⎞
⎜ ⎟
⎝ 3⎠
8 3
πr 3π
= 3 ×100 = × 100 = 68.0%
64 3 8
r
3 3
(3) Packing Efficiency of CCP and HCP Lattices
Cubic close packed or face centred cubic (FCC) and hexagonal close packed
lattices have equal packing efficiency. Packing efficiency of face centred cubic
(FCC) or cubic close packing (CCP) unit cell can be calculated with the help
of Figure 6.20. Let the edge length or the side of the cubic unit cell be a and
its face diagonal AC be b. In the triangle ABC, AB ⊥ BC, therefore,

AC2 = AB2 + BC2

b 2 = a 2 + a 2 = 2a 2
or b = 2a. (6.6)
G
B
A
H

F C

E D

Fig. 6.20: Face centred cubic or cubic close packing unit cell

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Unit cell of fcc (or ccp) lattice has constituent particles at all the corners and
at the centre of each face.
The particle of face-centre touches the particles occupying the corner positions
of the same face.

∴ Length of the face diagonal AC = b = 4r (6.7)

Notes
Where r is the radius of the constitutent particle (whole of central particle, 2r,
and one-half of each of the two corner particles, r + r)
From equations 1 and 2

b = 4r = 2a
4r
or a= = 2 2r (6.8)
2
The number of constituent particles in a face centred cubic unit cell = 4

4
∴ The Volume of filled space = 4 × π r 3
3

Volume of the cubic unit cell = (side)3 = a3 = (2 2r )3

4
4 × π r3
filled space 3
Packing efficiency = × 100 = ×100
total space (2 2r )3
16
π π
= 3 × 100 = = 74%
16 2 3 2
Packing efficiencies of the three types of cubic lattices are summarized in the
table 6.4.
Table 6.4: Packing efficiency of cubic unit cells

S.No. Lattice Packing Efficiency %

1. Simple Cubic 52.4%
2. Body Centred Cubic 68.0%
3. Face Centred Cubic or 74.0%
Cubic close packing

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6.9 STRUCTURES OF IONIC SOLIDS
In case of ionic solids that consist of ions of different sizes, we need to specify
the positions of both the cations as well as the anions in the crystal lattice. There-
fore, structure adopted by an ionic solid depends on the relative sizes of the two
ions. In fact it depends on the ratios of their radii (r+/r-) called radius ratio. Here
r+ is the radius of the cation and r- is that of the anion. The radius ratios and the
corresponding structures are compiled in Table 6.5. Notes
Table 6.5 : The radius ratios (r + /r–) and the corresponding structures
Radius ratio (r+/r–) Coordination number Structure adopted

0.225 – 0.414 4 Tetrahedral

0.414 – 0.732 6 Octahedral

0.732 – 0.91 8 Body centered cubic

>=1.00 12 Cubic Close Packed structure

The common ionic compounds have the general formulae as MX, MX2, and
MX3, where M represents the metal ion and X denotes the anion. We would
discuss the structures of some ionic compounds of MX and MX2 types.

6.9.1 Structures of the Ionic Compounds of MX Type

For the MX type of ionic compounds three types of structures are commonly
observed. These are sodium chloride, zinc sulphide and caesium chloride struc-
tures. Let us discuss these in some details.

(a) Caesium Chloride Structure

In CsCl the cation and the anions are
of comparable sizes (the radius ratio
= 0.93) and has a bcc structure in
which each ion is surrounded by 8 Caesium Ion
ions of opposite type. The Cs+ ions
is in the body center position and
eight Cl– ions are located at the Chloride Ions
corners (Fig. 6.21) of the cube. Thus
it has a coordination number of 8. Fig. 6.21: Caesium chloride structure

(b) Sodium Chloride Structure

In case of NaCl the anion (Cl–) is much larger than the cation (Na+). It has a
radius ratio of 0.52. According to Table 3.3 it should have an octahedral ar-
rangement. In sodium chloride the( Cl–) form a ccp (or fcc) structure and the
sodium ion occupy the octahedral voids. You may visualise the structure having

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chloride ions at the corners and the face centers and the sodium ions at the edge
centers and in the middle of the cube (Fig. 6.22).

Notes

Fig. 6.22 : Sodium chloride structure.

(c) Zinc Sulphide Structure

In case of zinc sulphide the radius ratio is just = 0.40. According to Table 3.3
it should have an tetrahedral arrangement. In Zinc sulphide structure, the
sulphide ions are arranged in a ccp structure. The zinc ions are located at the
corners of a tetrahedron, which lies inside the cube as shown in the Fig. 6.23.
These occupy alternate tetrahedral voids.

Fig. 6.23 : Zinc Sulphide structure.

6.9.2 Structure of Ionic Compounds of MX2 type

(a) Calcium fluoride or fluorite structure
In this structure the Ca2+ ions form a fcc arrangement and the fluoride ions are
located in the tetrahedral voids (Fig. 6.24).

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Notes

Fig. 6.24 : Calcium fluoride or Fluorite structure; calcium ions occupy the corners of the
cube and face centers The F- ions are on the corners of the smaller cube which
dipict the positions of tetrahedral void.

(b) Antifluorite Structure

Some of the ionic compounds like Na2O have antifluorite structure. In this struc-
ture the positions of cations and the anions in fluorite structures are interchanged.
That is why it is called antifluorite structure. In Na2O the oxide ions form the
ccp and the sodium ions occupy the tetrahedral voids (Fig. 6.25).

Fig. 6.25: Antifluorite structure adopted by Na2O; The oxide ions occupy the corners
of the cube and face centers and the Na+ ions ( shown in black ) are on
the corners of the smaller cube.

6.10 DEFECTS IN IONIC CRYSTALS

You have learnt that in a crystalline solid the constituent particles are ar-
ranged in a ordered three dimensional network. However, in actual crystals
such a perfect order is not there. Every crystal has some deviations from the
perfect order. These deviations are called imperfections or defects. These
defects can be broadly grouped into two types. These are stoichiometric and

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non-stoichiometric defects depending on whether or not these disturb the
stoichiometry of the crystalline material. Here, we would deal only with sto-
ichiometric defects. In such compounds the number of positive and negative
ions are in stoichiometric proportions. There are two kinds of stoichiometric
defects, these are
z Schottky defects
Notes z Frenkel defects
(a) Schottky defects : This type of defect are due to the absence of some
positive and negative ions from their positions. These unoccupied lattice sites
are called holes. Such defects are found in ionic compounds in which the
positive and negative ions are of similar size e.g., NaCl and CsCl. The num-
ber of missing positive and negative ions is equal. The presence of Schottky
defects decreases the density of the crystal [Fig. 6.26(a)].
(b) Frenkel defects : This type of defect arise when some ions move from
their lattice positions and occupy interstitial sites. The interstitial sites refer
to the positions in between the ions. When the ion leaves its lattice site a hole
is created there. ZnS and AgBr are examples of ionic compounds showing
Frenkel defects. In these ionic compounds the positive and negative ions are
of quite different sizes. Generally the positive ions leave their lattice posi-
tions, as these are smaller and can accommodate themselves in the interstitial
sites. The Frenkel defects do not change the density of the solids [Fig. 6.26(b)].

A– B– A– B– A– A– B– A– B– A–
A
– – – – – – – –
B A B B B A B B

A– A– B– A– A– B– A– B– A–

B
–
A
–
B
–
A
–
B
–
B
–
A– B
–
A– B
–

(a) (b)

Fig. 6.26: Stoichiometric defects a) Schottky and b) Frenkel defects

These defects cause the crystal to conduct electricity to some extent. The
conduction is due to the movement of ions into the holes. When an ion moves
into a hole it creates a new hole, which in turn is occupied by another ion, and the
process continues.

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INTEXT QUESTIONS 6.3

(a) What do you understand by crystal lattice?
b) What is a unit cell ?
c) How many atoms are there in a fcc unit cell?
Notes

6.11 ELECTRICAL PROPERTIES

Conductance of electricity is an important property of a substance. Solids show
a very wide range of conductivities from a high of 107 to a low of 10–20 s m–
1, thus spanning 27 orders of magnitude. Based upon their ability to conduct

electricity, solids may be classified into three categories; conductors, insulators

and semiconductors.

6.11.1 Conductors' Insulators and Semiconductors

(i) Conductors

These are the solids with conductivities ranging from 104 to 107 S m–1. Metals
conduct electricity through movement of their electrons and are called electronic
conductors. Ionic solids conduct electricity when in molten state or dissolved
in water, through movement of their ions. They are called electrolytic conductors.

(ii) Insulators

These are the solids with extremely low conductivities ranging from 10–20 to
10–10 S m–1. Insulators are used to provide protective covering on conductors.

(iii) Semiconductors

These are the solids with intermediate conductivities ranging from 10–6 to 104
S m–1. Although semiconductors have low conductivities, they find vide
applications in solid state devices like diodes and transistors. Their conductivities
can be modified by introduction of a suitable impurity.

6.11.2 Conduction of Electricity in Metals

Metals conduct electricity through movement of their electrons. In unit 5 you
have learnt that when two atoms come closer, their atomic orbitals overlap and
they form an equal number of molecular orbitals. One-half of these have lower
energy while the other half have higher energy than the energy of the atomic
orbitals. As the number of molecular orbitals increases, the energy-separation
between them decreases.

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In a piece of metal, the number of metal atoms is very large and so is the number
of their valence orbitals. This results in formation of an equally large number
of molecular orbitals which are so close to one-another that they form a
continuous band. The band in which the valence electrons are present is called
valence band. Electrons present in this band are strongly bound to the nucleus
and cannot conduct electricity. The band formed by vacant molecular orbitals
of higher energy is called conduction band. When electrons reach conduction
Notes band from valence band on excitation, they become loosely bound to the nucleus
and can conduct electricity by moving under the influence of an electric field.
Such electrons are also called free electrons. Conductivity of a solid depends
upon how easy or difficult it is for the valence electrons to jump to the
conduction band. See figure 6.27.
Conduction band

Empty
band
Empty
band

Forbidden band
(Large energy gap) Small energy gap
Emergy

Filled
band

Partially Overlapping
filled bands
band
Metal Insulator Semiconductor
(a) (b) (c)

Fig. 6.27: Valence and conduction bands in (a) metals, (b) insulators and
(c) semi conductors.

(i) In conductors either the valence band is only partially filled or it overlaps
a vacant conduction band of slightly higher energy. In both the cases its
electrons can easily flow under the influence of electric field and the solid
behaves as a conductor (Fig. 6.27(a))
(ii) In insulators the gap between the valence band and conduction band is
large. Due to this the valence electrons cannot jump to the conduction band
and conduct electricity (Fig. 6.27(b))
(iii) In semiconductors the gap between the valence band and nearest
conduction band is small (Fig. 6.27(c)). On applying the electric field, some
electrons can jump to the conduction band and provide low conductivity.
On increasing the temperature more electrons can jump to the conduction
band and the conductivity increases. Silicon and germanium show this type
of behaviour. They are called intrinsic semiconductors.

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6.11.3 Doping of Semiconductors
Conductivities of silicon and germanium are too low to be put to any practical
use. Their conductivities can be improved by introduction of controlled
quantities of impurities which are either electron-rich or electron-deficit with
respect to these elements. This process is known as doping.
(a) Doping with electron–rich impurities
Notes
Silicon and germanium both belong to group 14 of the periodic table and have
4 valence electrons each. In their crystal lattice each silicon (or germanium) atom
forms four covalent bonds with its neighbours (Fig. 6.23(a)) when it is doped
with a group 15 element like As or P, whose each atom carries 5 valence electrons
which is one more than Si. After sharing its four electrons with four neighbouring
Si atoms, it has 9 electrons in its valence shell (Fig. 6.28(b)) which is highly
unstable electronic configuration. The ninth electron being highly unstable roams
freely in the whole of the crystal lattice randomly. In the presence of an electric
field this electron (mobile electron) moves from negative to positive terminal and
increases the conductivity of Si (or Ge). Since the increased conductivity of Si
(or Ge) is due to negatively charged mobile electrons, the Si doped with electron
rich impurity becomes a n-type semiconductor.
Positive hole
Silicon atom Mobile electron (no electron)

: : : : : : : : : : : :
:

: : : : : : As : : : : B : :
:

: : : : : : : : : : : :
:

: : : : : : : : : : : :
:

Perfect crystal n-type p-type

(a) (b) (c)
Fig. 6.28: Creation of n-type and p-type semiconductors

(b) Doping with electron-deficit impurities. When Si (or Ge) is doped with
a group 13 element like B or Al containing 3 valence electrons (1 electron less
than Si/Ge), this results in creation of one-electron vacancy in the structure
which is called an electron hole (Fig. 6.28(c)). An electron from its neightbouring
atom can come and occupy it, leaving a hole at its original position. Electrons
can randomly occupy holes and the hole would appear to move randomly. On
applying an electric field, the electrons move from negative to positive terminal
and the hole would appear move in the opposite direction, i.e., from positive
to negative terminal and would behave as if it is positively charged. Such
semiconductors are called p-type semiconductors. The movement of electrons
and the hole increases the conductivity of Si. Semiconductors like Si, doped

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with electron-deficit or electron-rich impurities are called extrinsic
semiconductors.

Applications of n-type and p-type semiconductors

Due to their special properties, n-and p-type semiconductors find several
applications.
Notes (i) Diodes: Diode is a combination of a n-type and a p-type semiconductor.
Diodes are used as rectifier to convert an AC signal to a DC signal.
(ii) Transistors. Transistors are made by combination of 3 layers of
semiconductors. Transistor of n-p-n type is made by sandwiching a layer
of p-type semiconductor between two layers of n-type semiconductors and
of p-n-p type by sandwiching a layer of n-type semiconductors between
two layers of p-type semiconductor. Transistors are used as detectors and
amplifiers of radio or audio frequency signals. They are used in circuits of
solid state devices.
(iii) Solar cells. Solar cells are photo diodes which have a special property of
emitting electrons when sunlight falls on them. They are used to convert
solar energy into electricity.

6.12 MAGNETIC PROPERTIES

All substances are affected (attracted or repelled) by a magnetic field. Magnetic
properties present in any substance are due to the electrons present in it. Each
electron in an atom behaves like a tiny magnet. Electrons are negatively charged
particles. When an electron revolves around nucleus and spins about its own
axis, two types of magnetic moments are created – orbital magnetic moment
due to its revolution around the nucleus and spin magnetic moment due to its
spin. Overall magnetic properties of a substance depend upon the orientation
of these tiny magnets.
On the basis of magnetic properties, all substances can be classified into five
categories:
(i) paramagnetic, (ii) diamagnetic, (iii) ferromagnetic, (iv) antiferromagnetic and
(v) ferrimagnetic

6.12.1 Paramagnetic Substances

On placing these substances in a magnetic field, these are weakly attracted by
it. O2, Cu2+, Fe3+ and Cr3t are some examples of paramagnetic substances
Paramagnetism is due to the presence of one or more unpaired electrons in an
atom, molecule or ion.

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6.12.2 Diamagnetic Substances
When placed in a magnetic field, diamagnetic substances are weakly repelled
by it. H2O, NaCl and C6H6 are some examples of such substances. Diamagnetism
is shown by substances in which all the electrons are paired.

6.12.3 Ferromagnetic Substances

When placed in a magnetic field, ferromagnetic substances are strongly attracted Notes
by it. Fe, Ni, Co, Gd, MnAs, CrBr3 and CrO2 are such substances. These
substances can be permanently magnetized. In solid state, the metal ions of
ferromagnetic substances are grouped together into small regions called
domains. In each domain, the individual magnetic moments of the metal ions
are directed in the same direction and they add up. As a result, each domain
acts as a tiny magnet. Ordinarily, these domains are randomly oriented which
cancels out their magnetic moment. When

(a)

(b)

(c)

Fig. 6.29 Arrangement of magnetic moments of domains in (a) ferromagnetic, (b) anti
ferromagnetic and (c) ferrimagnetic substances

placed in a magnetic field, all the domains get oriented in the direction of the
magnetic field. This adds up their magnetic moments and makes them strong
magnets (Fig. 6.29(a)). They lose their ferromagnetism on being given mechanical
jerks or on heating above a certain temperature, called Curie temperature they
become paramagnetic.

6.12.4 Antiferromagnetic Substances

Some substance that have domains in them like ferromagnetic substances but
their domains are oppositely oriented and cancel out the magnetic moments of
each other (Fig. 6.29 (b)) are caled antiferro magnetic substances. FeO, MnCl2,
MnO, Mn2O3 and MnO2 are examples of antiferromagnetic substances. They
also become paramagnetic on heating above a certain temperature.

6.12.5 Ferrimagnetic Substances.

Some substances like Fe3O4 (magnetite) and ferrites (MFe2O4 where M is a
bivalent cation like Cu2+, Zn2+) show an intermediate behavior between that

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of ferromagnetic and antiferromagnetic substances. These substances are quite
strongly attracted by magnetic field as compared to paramagnetic substances
but weakly as compared to ferromagnetic substances. Their domains are aligned
in parallel and antiparallel directions in unequal numbers (Fig. 6.29(c)). They
also become paramagnetic on heating above a certain temperature.

Notes
WHAT YOU HAVE LEARNT
z In solid state the constituent particles are arranged in a closely packed or-
dered arrangement with almost no free space. These are held together by
strong forces of attraction and vibrate about their fixed positions. Solids are
incompressible and rigid and have definite shapes.
z Solids are classified into amorphous and crystalline solids. The crystalline
solids have long range order while amorphous solids have only short range
order.
z The crystalline solids can be classified into four different types- ionic, mo-
lecular, covalent and metallic solids on the basis of nature of forces of
attraction between the constituent particles.
z The temperature at which a solid melts to give a liquid is called its melting
point.
z The three dimensional internal structure of a crystalline solid can be repre-
sented in terms of a crystal lattice in which the location of each constituent
particle is indicated by a point.
z The whole crystal lattice can be generated by moving the unit cell in the
three directions.
z The crystal structures of the solids can be described in terms of a close-
packing of identical spheres.
z In three dimensions there are two ways of packing identical spheres. These
are hexagonal closed packing (hcp) and cubic closed packing (ccp). The hcp
arrangement is obtained by ABAB repeat of the two dimensional layers
whereas the ccp arrangement is obtained by ABCABC repeat.
z On the basis of the external appearance the known crystals can be classified
into seven types called crystal systems.
z The unit cells of cubic crystal system has three possible lattice types. These
are simple cubic, body centered cubic and the face centered cubic.
z The atoms at the corner of a cubic unit cell is shared by eight unit cells while
a face centered atom is shared by two unit cells. The atom at the body center,
on the other hand is exclusive to the unit cell as it is not shared.

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z The number of atoms per unit cell for the simple cubic, bcc and fcc unit cells
are 1,2 and 4 respectively.
z The structure adopted by an ionic solid depends on the ratios of their radii
(r+/r-), called radius ratio.
z The structures of some simple ionic solids can be described in terms of ccp
of one type of ions and the other ions occupying the voids.
z Actual crystals have some kind of imperfections in their internal structure. Notes
These are called defects.
z There are two types of defects called stoichiometric and non-stoichiometric
defects depending on whether or not these disturb the stoichiometry of the
crystalline material.
z There are two kinds of stoichiometric defects, these are called Schottky
defects and Frenkel defects.
z Solid can be classified as conductors, insulators and semiconductors on the
basis of their electrical conductivities.
z Electrical properties of solids can be explained with the help of band theory.
z On the basis of their interaction with external magnetic field, solids can be
classified as paramagnetic, diamagnetic, ferromagnetic, ferrimagnetic and
antiferromagnetic substances.

TERMINAL EXERCISES
1. Outline the differences between a crystalline and an amorphous solid.
2. How can you classify solids on the basis of the nature of the forces between
the constituent particles?
3. What do you understand by the melting point of a solid ? What information
does it provide about the nature of interaction between the constituent particles
of the solids?
4. What do you understand by coordination number? What would be the coor-
dination number of an ion occupying an octahedral void.?
5. Explain the following with the help of suitable examples.
(a) Schottky defect
(b) Frankel defect
6. Explain why a particular solid behaves as conductor or semiconductor or
insulator on the basis of band theory.
7. What are (i) paramagnetic (ii) diamagnetic and (iii) ferromagnetic substances?

CHEMISTRY 205