SOLID STATE

Solids are the substances under atmospheric pressure whose melting

point is above the room temperature. Only vibrational motions exists in solids.
The characteristics of solids are
1. They have definite shape, mass and volume.
2. Inter atomic/ionic/molecular distance is less
3. They have strong forces of attractions between the constituent particles and
the particles are at fixed positions.
4. They are generally incompressible and are rigid.
CLASSIFICATION OF SOLIDS :– Solids are classified in two ways as
1. Based on the arrangement of constituent particles, solids are classified into
two types as
A) CRYSTALLINE SOLIDS :– These are the solids in which the constituent
particles are arranged in an orderly manner and they have long range order
which means that, there is regular pattern of arrangement of particles which
repeats periodically over entire crystal.
Ex : Quartz glass, Diamond, NaCl, Metallic crystals etc.
B) AMORPHOUS SOLIDS :– These are the solids in which the constituent
particles are not arranged in an orderly manner and they have short range
order which means that, the regular and periodically repeating pattern is
observed over a short distance.
Ex : Glass, Plastics, Rubber, Graphite etc.

Crystalline compounds have sharp melting point where as amorphous

solids have a range of melting point. Amorphous solids on heating become
crystalline solids at some temperature.
Crystalline solids are “anisotropic”. i.e, some of physical properties like
electrical resistance, refractive index etc. show different values when measured
along different directions in the same crystal, it is due to different arrangement
of particles in different directions. Amorphous solids are “Isotropic” i.e, the

1
physical properties show same value even when measured along different
directions due to short range order.
Amorphous solids have tendency to flow but very slowly. These are called
pseudo solids or super cooled liquids.

S.NO PROPERTY CRYSTALLINE SOLIDS AMORPHOUS SOLIDS

1. Nature These are true solids These are Pseudo
solids/super cooled liquids
2. Order of arrangement They have long range They have short range order
order
3. Structure They have definite They have no regular
geometry structure
4. Heat of fusion They have definite heat of They do not have definite
fusion heat of fusion
5. Anisotropy They are anisotropic They are isotropic
6. Cleavage When cut with sharp tool, When cut with sharp tool,
they split into two pieces & they split into two pieces &
newly formed pieces have newly formed pieces have
plain and smooth surfaces irregular surfaces.
7 Melting point They have sharp melting They have melting point in a
point range of temperature.
8 Examples NaCl, KCl, Quartz, CaF2, Rubber, Glass, Plastic etc
ZnS
CLASSIFICATION OF CRYSTALLINE SOLIDS:-
Crystalline solids are classified into 4 types based on the nature of inter
molecular forces.
1. IONIC SOLIDS:- These are the solids in which the constituent particles
are ions and are bound together by strong electrostatic force of attraction.
These are hard & brittle, hence have high melting points /boiling points.
Since the ions are not free to move, they do not conduct electricity in
solid state, but conducts in fused state or aqueous solution.
Ex : All ionic compounds.
2. METALLIC SOLIDS: There are the solids in which the metals ions are
bound together by sea of mobile electrons. Each metal atom contributes
one or more electrons to this sea of mobile electrons. They are good
conductors of heat & electricity.
3. MOLECULAR SOLIDS: These are the solids in which the constituent
particles are molecules. These are further classified into different types as
A. NON-POLAR MOLECULAR SOLIDS:- These solids contains non-polar
molecules which are held together by London forces. They are soft and
non-conductors, have low melting points/boiling points. These are
generally liquids or gases at room temperature & pressure.
Ex: H2, Cl2, I2, etc
B. POLAR MOLECULAR SOLIDS:- These solids consists of molecules
formed by polar covalent bonds and the molecules are held together
by strong dipole-dipole attraction. These are also soft and non

2
 conductors, but their melting points/boiling points are higher than
non-polar molecular solids SO2, NH3, HCL.
C. HYDROGEN BONDED MOLECULAR SOLIDS: These are the solids
containing polar molecules which are bound together through strong
hydrogen bonds. These are non-conductors of electricity. These are
generally liquids or soft solids under room temperature & pressure.
Ex:- H2O.
4.COVALENT OR NETWORK SOLIDS:- These are the solids in which
constituent particles are atoms of non-metals or molecules of non-metals
obtained through covalent bonds. Constituent particles in these solids are
bound together through covalent bonds. These are giant molecular solids.
These are very hard and have very high melting points. These are
insulators.
Ex: Diamond, SiC, SiO2, BN, AIN etc.
Graphite is also a covalent solid but it is a good conductor.

Brag’s Equation :– ( *** 4 Marks )

The structure of solids can be determined by x – ray
crystallographic studies. In crystals, the atoms or ions are arranged in a
regular pattern. When the x – rays are incident on the crystals, these rays
strike the atoms or ions and then get diffracted. The diffracted rays
undergo constructive interference.

D d C

Consider the diagram, the 1st and 2nd waves reach the crystal
surface and they undergo constructive interference. The two waves are
parallel and travel the same distance till the wave front AD. The 2 nd wave
travels more distance than the 1st wave by an extra distance of DB + BC
after crossing the grating for it to interfere with 1st wave in a constructive
manner. Then only they can be in the same phase with one another. If
the two waves are to be in phase, the path difference between the two
waves must be equal to the wavelength (λ) or an integral multiple of it.
i.e n λ. Where n= 1,2,3 ….

3
 Therefore n λ = DB + BC
Since AB = ‘d’
DB = BC = d sin θ
DB + BC = 2 d sin θ
n λ = 2 d sin θ This is known as Bragg’s equation
n = 1, 2, 3, 4
θ = angle of diffraction
d= inter atomic distance in an unknown crystal and it can
be calculated.
The value of ‘d’ can be determined from the values of λ and θ, from which the
crystal structure can be deduced.
CRYSTAL LATTICES & UNIT CELL:-
The regular & repeating pattern of constituent particles in a three
dimensional arrangement is called “Crystal Lattice”.
Characteristics of Crystal Lattice:-
a) Each point in a crystal lattice represents the constituent particles.
b) Each point in a lattice is called Lattice point or Lattice site.
c) Lattice points are joined by straight lines to bring out the geometry of the
lattice.
The smallest portion of crystal lattice which when repeated in three
dimensions generates the entire crystal lattice is called “unit cell”.
A unit cell is characterised by
1. Its dimensionally along three edges a, b and c. These edges may or may
not be mutually perpendicular.
2. Angles between the edges α,β and ϒ
These a unit cell is characterised by 6 parameters (a,b,c and α,β and ϒ )
There are only 14 possible three dimensional lattices. These are called Bravais
Lattices (after the French mathematician who first described them). The
following are the characteristics of a crystal lattice:
(a) Each point in a lattice is called lattice point or lattice site.
(b) Each point in a crystal lattice represents one constituent particle which may
be an atom, a molecule (group of atoms) or an ion.
(c) Lattice points are joined by straight lines to bring out the geometry of the
lattice.
Unit cells can be broadly divided into two categories, primitive and centred unit
cells.
(a) Primitive Unit Cells
When constituent particles are present only on the corner positions of a unit
cell, it is called as primitive unit cell.
(b) Centred Unit Cells
When a unit cell contains one or more constituent particles present at positions
other than corners in addition to those at corners, it is called a centred unit
cell. Centred unit cells are of three types:

4
(i) Body-Centred Unit Cells: Such a unit cell contains one constituent particle
(atom, molecule or ion) at its body-centre besides the ones that are at its
corners.
(ii) Face-Centred Unit Cells: Such a unit cell contains one constituent particle
present at the centre of each face, besides the ones that are at its corners.
iii) End-Centred Unit Cells: In such a unit cell, one constituent particle is
present at the centre of any two opposite faces besides the ones present at its
corners.
There are 14 types of lattices called “Bravais lattices” and are grouped into 7
types

S.No Type of unit cell Relation Angle between α

between edge β ϒ
lenths a, b, c
1 Cubic a = b = c α = β = ϒ = 900
2 Tetragonal a = b ≠ c α = β = ϒ = 900
3 Orthorhobic a ≠ b ≠ c α = β = ϒ = 900
4 Monoclinic a ≠ b ≠ c α = ϒ = 900 ; β ≠
900
5 Triclinic a≠b≠c α ≠ β ≠ ϒ ≠ 900
6 Hexagonal a=b≠c α = β = 900 ; ϒ =
1200
7 Rhombohegral a=b=c α = β = ϒ ≠ 900
CALCULATION OF CONTRIBUTION OF ATOMS TO THE UNIT CELL :–

1. Corner atom is shared by 8 unit cells. Hence its contribution to the unit cell
is 1/8.
2. An atom on the face is shared by two unit cell. Hence its contribution to the
unit cell is ½
3. An atom with in the body is not shared by any other unit cell. Hence its
contribution to the unit cell is 1.
4. An atom on the edge is shared by four other unit cells. Hence its
contribution to the unit cell is ¼.
CALCULATION OF NUMBER OF ATOMS PRESENT PER UNIT CELL :–
1. In simple cubic lattice :– A simple cubic lattice has atoms only at the
corners. Hence it has 8 atoms. As the contribution of each corner atom is
1/8.
 The number of atoms present in the unit cell is 8 x 1/8 = 1

2. In body centred cubic lattice :– A body centered cubic lattice has 8

atoms on the corners and one atom within the body
a) Contribution of 8 corner atoms = 8 x 1/8 = 1
b) Contribution of body centered atom = 1 x 1 = 1
 The number of atoms present per unit cell = 1 + 1 = 2
3. In face centred cubic lattice :– A face centered cubic lattice has 8
atoms on the corners and 6 atoms on the faces ( one on each face )
a) Contribution of 8 corner atoms = 8 x 1/8 = 1
b) Contribution of body centered atom = 6 x 1/2 = 3
 The number of atoms present per unit cell = 1 + 3 = 4

5
 NOTE :– The number of atoms present in unit cell are in the same ratio as
the stoichiometry of the compound. Hence it helps to predict the formula of
a compound.
PROBLEMS :–
1. A compound is formed by the elements A and B has a cubic structure in
which ‘A’ atoms are at the corners and ‘B’ atoms are on the faces. Derive
the formula of the compound.
a) Number of ‘A’ atoms on the corners = 8 x 1/8 = 1
b) Number of ‘B’ atoms on the faces = 6 x 1/2 = 3
 The formula of the compound is AB3 .

2. A cubic solid is made up of two elements X and Y. X atoms are present

at the body centre and Y atoms are present on the corners of the cube .
Deduce the formula of the compound and coordination number of X and Y.
a) Number of ‘Y’ atoms on the corners = 8 x 1/8 = 1
b) Number of ‘X’ body centered atoms = 1x1 = 1
 The formula of the compound is XY and coordination number is 8.

3. A compound formed by elements X and Y crystallises in cubic structure

where ‘Y’ atoms are on the corners and ‘X’ atoms are at alternate faces.
Find the formula of the compound.
a) The number of ‘Y’ atoms are = 8 x 1/8 = 1
b) There are only two ‘X’ atoms at alternate faces. Therefore, the number
of atoms of ‘X’ are = 2 x ½ = 1
 The formula of the compound is XY.
4. Calculate the number of atoms in a cubic based unit cell having one atoms
at each corner and two atoms on each body diagonal.
a) The number of atoms at the corner = 8 x 1/8 = 1
b) There are 4 diagonals. Thus there are 8 atoms within the body
of unit cell which are not shared by any other unit cells. Hence = 8 x 1
= 8
 The number of atoms present per unit cell = 1+8 = 9

5. A compound is made up of two elements A and B crystallises in the cubic

structure. Atoms of ‘A’ are present on the corners as well as on the faces
while atoms of ‘B’ are on the edges as well as at the centre of the body.
Find the formula of the compound
a) Number of atoms of ‘A’ at the corner = 8 x 1/8 = 1
b) Number of atoms of ‘A’ at the faces =6x½ = 3
c) Number of atoms of ‘B’ at the edges = 12 x ¼ = 3
d) Number of atoms of ‘B’ at the body centre = 1 x 1 = 1
 The ratio of A : B = 4 : 4 i.e 1 : 1. Hence the formula of the
compound is AB.

6. A body centred cubic solid is made up of two elements A and B. Atoms of ‘A’
occupy two corners. If the remaining positions in the unit cell are occupied by
atoms of ‘B’ , suggest the formula of the compound.
a) Atoms of ‘A’ occupying only two corners = 2 x 1/8 = ¼.
b) Atoms of ‘B’ are occupying 6 corners and one body centre = 6 x 1/8 + 1 x 1
i.e = ¾ + 1 = 7/4

6
  The ratio of A : B = ¼ : 7/4 = 1 : 7. Hence the formula of the
compound is AB7 .

CLOSE PACKED STRUCTURES :

(a) Close Packing in One Dimension
There is only one way of arranging spheres in a one dimensional close packed structure, that is to
arrange them in a row and touching each other.

close packing of spheres in one dimension

In this arrangement, each sphere is in contact with two of its neighbours. The number of
nearest neighbours of a particle is called its coordination number. Thus, in one dimensional close
packed arrangement, the coordination number is 2.
(b) Close Packing in Two Dimensions
Two dimensional close packed structure can be generated by stacking (placing) the rows of
close packed spheres. This can be done in two different ways.
(i) The second row may be placed in contact with the first one such that the spheres of the second
row are exactly above those of the first row. The spheres of the two rows are aligned horizontally as
well as vertically. If we call the first row as ‘A’ type row, the second row being exactly the same as
the first one, is also of ‘A’ type. Similarly, we may place more rows to obtain AAA type of
arrangement.
In this arrangement, each sphere is in contact with four of its neighbours. Thus, the two
dimensional coordination number is 4. Also, if the centres of these 4 immediate neighbouring
spheres are joined, a square is formed. Hence this packing is called square close packing in two
dimensions.
(ii) The second row may be placed above the first one in a staggered manner such that its spheres
fit in the depressions of the first row. If the arrangement of spheres in the first row is called ‘A’
type, the one in the second row is different and may be called ‘B’ type. When the third row is
placed adjacent to the second in staggered manner, its spheres are aligned with those of the first
layer. Hence this layer is also of ‘A’ type. The spheres of similarly placed fourth row will be aligned
with those of the second row (‘B’ type). Hence this arrangement is of ABAB type. In this
arrangement there is less free space and this packing is more efficient than the square close
packing. Each sphere is in contact with six of its neighbours and the two dimensional coordination
number is 6. The centres of these six spheres are at the corners of a regular hexagon, hence this
packing is called two dimensional hexagonal close packing. It can be seen that in this layer there
are some voids (empty spaces). These are triangular in shape. The triangular voids are of two
different types. In one row, the apex of the triangles are pointing upwards and in the next layer
downwards.

(a) Square close packing of spheres in two dimensions (b) hexagonal close packing of spheres in
two dimensions

7
 (c) Close Packing in Three Dimensions
All real structures are three dimensional structures. They can be obtained by stacking two
dimensional layers one above the other. In the last Section, we discussed close packing in two
dimensions which can be of two types; square close-packed and hexagonal close-packed. Let us see
what types of three dimensional close packing can be obtained from these.
(i) Three dimensional close packing from two dimensional square close-packed layers: While placing
the second square close-packed layer above the first we follow the same rule that was followed
when one row was placed adjacent to the other. The second layer is placed over the first layer such
that the spheres of the upper layer are exactly above those of the first layer. In this arrangement
spheres of both the layers are perfectly aligned horizontally as well as vertically. Similarly, we may
place more layers one above the other. If the arrangement of spheres in the first layer is called ‘A’
type, all the layers have the same arrangement. Thus this lattice has AAA.... type pattern. The
lattice thus generated is the simple cubic lattice, and its unit cell is the primitive cubic unit cell.
(ii) Three dimensional close packing from two dimensional hexagonal close packed layers: Three
dimensional close packed structure can be generated by placing layers one over the other.
(a) Placing second layer over the first layer
Let us take a two dimensional hexagonal close packed layer ‘A’ and place a similar layer above it
such that the spheres of the second layer are placed in the depressions of the first layer. Since the
spheres of the two layers are aligned differently, let us call the second layer as B. It can be observed
that not all the triangular voids of the first layer are covered by the spheres of the second layer.
This gives rise to different arrangements. Wherever a sphere of the second layer is above the void
of the first layer (or vice versa) a tetrahedral void is formed. These voids are called tetrahedral
voids because a tetrahedron is formed when the centres of these four spheres are joined.
At other places, the triangular voids in the second layer are above the triangular voids in the first
layer, and the triangular shapes of these do not overlap. One of them has the apex of the triangle
pointing upwards and the other downwards. These voids have been marked as ‘O’. Such voids are
surrounded by six spheres and are called octahedral voids. The number of these two types of voids
depend upon the number of close packed spheres.
Let the number of close packed spheres be N, then:
The number of octahedral voids generated = N
The number of tetrahedral voids generated = 2N
(b) Placing third layer over the second layer
When third layer is placed over the second, there are two possibilities.
(i) Covering Tetrahedral Voids: Tetrahedral voids of the second layer may be covered by the
spheres of the third layer. In this case, the spheres of the third layer are exactly aligned with those
of the first layer. Thus, the pattern of spheres is repeated in alternate layers. This pattern is often
written as ABAB ....... pattern. This structure is called hexagonal close packed (hcp) structure. This
sort of arrangement of atoms is found in many metals like magnesium and zinc.
(ii) Covering Octahedral Voids: The third layer may be placed above the second layer in a manner
such that its spheres cover the octahedral voids. When placed in this manner, the spheres of the
third layer are not aligned with those of either the first or the second layer. This arrangement is
called “C’ type. Only when fourth layer is placed, its spheres are aligned with those of the first layer.
This pattern of layers is often written as ABCABC ........... This structure is called cubic close packed
(ccp) or face-centred cubic (fcc) structure. Metals such as copper and silver crystallise in this
structure. Both these types of close packing are highly efficient and 74% space in the crystal is filled.
In either of them, each sphere is in contact with twelve spheres. Thus, the coordination number is
12 in either of these two structures.
8
Formula of a compound and number of voids filled : –
Earlier in the section, we have learnt that when particles are close packed resulting in either
ccp or hcp structure, two types of voids are generated. While the number of octahedral voids
present in a lattice is equal to the number of close packed particles, the number of tetrahedral
voids generated is twice this number. In ionic solids, the bigger ions (usually anions) form the close
packed structure and the smaller ions (usually cations) occupy the voids. If the latter ion is small
enough then tetrahedral voids are occupied, if bigger, then octahedral voids. Not all octahedral or
tetrahedral voids are occupied. In a given compound, the fraction of octahedral or tetrahedral voids
that are occupied, depends upon the chemical formula of the compound, as can be seen from the
following examples. We know that close packed structures have both tetrahedral and octahedral
voids. Let us take ccp (or fcc) structure and locate these voids in it.
(a) Locating Tetrahedral Voids : Let us consider a unit cell of ccp or fcc lattice. The unit cell is
divided into eight small cubes.
A compound is formed by two elements X and Y. Atoms of the element Y (as anions) make ccp and
those of the element X (as cations) occupy all the octahedral voids. What is the formula of the
compound? The ccp lattice is formed by the element Y. The number of octahedral voids generated
would be equal to the number of atoms of Y present in it. Since all the octahedral voids are
occupied by the atoms of X, their number would also be equal to that of the element Y. Thus, the
atoms of elements X and Y are present in equal numbers or 1:1 ratio. Therefore, the formula of the
compound is XY.
Atoms of element B form hcp lattice and those of the element A occupy 2/3rd of tetrahedral voids.
What is the formula of the compound formed by the elements A and B? The number of tetrahedral
voids formed is equal to twice the number of atoms of element B and only 2/3rd of these are
occupied by the atoms of element A. Hence the ratio of the number of atoms of A and B is 2 ×
2/3):1 or 4:3 and the formula of the compound is A4B3.

CALCULATION OF SPACE OCCUPIED i.e PACKING FRACTION OR

PACKING EFFICIENCY OR PACKING DENSITY :–

The ratio of volume occupied by the atoms in the unit cell(  ) to the total
volume of the unit cell ( V ) is called packing fraction.
v No of atoms per unit cell x volume of sphere (atoms )
Packing fraction = =
V Total volume of the unit cell
4 3
nx r
= 3 Where ‘n’ = No of atoms
a3
‘a’ = Unit cell edge length.

Packing fraction in simple cubic unit cell :–

Consider the edge length of unit cell is = ‘a’
Radius of atom is = ‘r’
As spheres (atoms) are touching each other.  a = 2r.
In case of simple cubic cell, the number of
atoms per unit cell = 1
4 3
1x r
 Packing fraction = 3
a3

9
 a = 2r  a 3 = ( 2r )
3
or a 3 = 8 r 3

4 3 4 3
1x r 1x r 1 x 4 r 3 
Thus Packing fraction = 3 = 3 = 3 = = 0.524 i.e
a3 8r 3 3x8r 6
52.4%
Remaining 47.6% is empty space or void.

Packing fraction in face centered cubic ( FCC )unit cell :–

Consider the edge length of unit cell is = ‘a’

Radius of atom is = ‘r’
FCC unit cell has four atoms per unit cell,
therefore n = 4 As sphere on the face is
touching the spheres at the Corners but
corner spheres are not touching each other
Face diagonal (AC) = 4r
But for right angle triangle AC2 = AB2 + BC2
4r
AC = 2 a ; 2 a = 4r ; a =
2
3
3  4  3 32 3
a =  r ; a3 = r
 2 2
4 3 16 3
Total volume of all atoms = 4 r = r
3 3
16 3
r 16  2 2
Packing fraction = 3 = = = 0.74 = 74%
32 3 3 x 32 6
r
2
The remaining 26% is empty or void.
NOTE :– Packing fraction of hcp and ccp is same as fcc.
Packing fraction in body centered cubic ( BCC )unit cell :–
Consider the edge length of unit cell is = ‘a’
Radius of atom is = ‘r’
BCC unit cell has four atoms per unit cell,
therefore n = 2 As sphere an the body centre
is touching the spheres at the corners but corner
spheres are not touching each other
Body diagonal (AD) = 4r
For face diagonal AC = AB2 + BC 2 = 2a
For body diagonal AD = AB 2 + BC 2 + CD2 = 3a
4r  4  3
3
64 3 64 3
 3a = 4r ; a= ; 3
a =   r ; a3 = r3 ; a = r
( 3)
3
3  3 3 3
4 8
Total volume of all atoms = 2  r3 =  r3
3 3
10
 8 3
r 3
Packing fraction = 3 = = 0.68 ; 68 %
64 3 8
r
3 3
The remaining 32% is empty space or void.

NUMBER OF VOIDS FILLED AND FORMULA OF THE COMPOUND :–

If the cube contains ‘n’ number of atoms, then,

Number of octahedral voids = ‘n’ and Number of tetrahedral voids = ‘2n’.

In case of ionic compounds usually anions are present in the packing and
cations occupy the voids.

If the cations are small in size, they may occupy tetrahedral voids and if
the cations are large enough to occupy tetrahedral voids, then, they occupy
octahedral voids. It is not necessary that, only tetrahedral voids or octahedral
voids are may be occupied and also all the voids must be occupied. Only a
fraction of total volume may be occupied.
Knowing the fraction of the voids occupied, the formula of the compound
can be calculate.
PROBLEMS : –
1. A compound is formed by two elements X and Y. Atoms of element ‘Y’ ( as
anions ) make ccp and those of the element ‘X’ ( as cations ) occupy all the
octahedral voids. What is the formula of the compound ?
Solution : Suppose number of atoms of ‘Y’ = n, then
Number of octahedral voids are = n
As all the octahedral voids are occupied by the atoms of ‘X”. Therefore the
number of atoms of ‘X’ is also n. Hence the ratio of X : Y = n : n = 1 : 1.
Hence the formula of the compound is ‘XY’.
2. A compound is formed by two elements A and B. Atoms of element ‘B’ form
hcp lattice and those of the element ‘A’ occupy 2/3 of tetrahedral voids. Find
the formula of the compound.
Solution : Suppose number of atoms of ‘B’ = n, then
Number of tetrahedral voids are = 2n
As atoms of ‘A’ occupy 2/3 of tetrahedral voids.  The number of atoms of
‘A’ = 2/3 x 2n= 4/3 n.
The ratio of A : B = 4/3n : n i.e 4/3 : 1 or 4 : 3. Hence the formula of
the compound is A4B3.
3. In a crystalline compound anions ‘B’ are arranged in ccp. Cations ‘A’ are
equally distributed between octahedral voids and tetrahedral voids. If all the
octahedral voids are occupied, what is the formula of the compound ?
Solution : Consider the number of anions ‘B’ = n, then
Number of octahedral voids is = n and Number of tetrahedral
voids is = 2n
As octahedral and tetrahedral voids are equally occupied by cations
‘A’ and all the octahedral voids are occupied ( given ), therefore

11
 ‘n’ cations of ‘A’ are occupied in octahedral voids and ‘n’ cations are occupied
in tetrahedral voids.
Corresponding to ‘n’ anions of ‘B’ there should be n + n = 2n cations of ‘A’ .
Thus the ratio of
A : B = 2n : n i.e 2 : 1.
Hence the formula of the compound is A2B
CALCULATION OF DENSITY FROM EDGELENGTH :–
The density of the crystal can be calculated by knowing edge length of the
unit cell, type of the crystal structure and number of particles present per unit
cell.
Let, Edge length of the unit cell = ‘a’ ; Number of particles per unit cell = ‘z’
Atomic mass of an element = ‘M’ ; Avogadro’s number = N0
Mass of each atom = M/N0
zxM
Mass of ‘z’ no.of atoms = Volume of unit cell = a3
N0
Density (d or  ) = Mass/Volume
z xM z xM
d= ( For compounds ) OR d= ( For elements )
N0 a 3 N 0 a 3 10−30

The number of particles present per unit cell is

1. For simple cubic unit cell = 1
2. For FCC unit cell = 4
3. For BCC unit cell = 2

PROBLEMS ON DENSITY :–

1. Silver forms ccp lattice with an edge length of 408.6 pm. Calculate the
density of silver. At.mass of silver is 107.8.
Solution : For cubic crystalline packing (ccp) which is equivalent to FCC Z = 4.
a = 408.6 pm or 408.6 x 10-10 cm
z xM 4 x 107.8
d= ; d= = 10.5 g/cc
6.023x1023 x ( 408.6 x10−10 )
3
N0 a 3
Sodium has BCC structure with nearest neighbour distance 365.9 pm. Calculate
its density.
2
Solution : For BCC a = d ; a = 1.155 x d ; i.e a = 1.155 x 365.9 = 422.6 pm
3
and Z = 2, M = 23 and a3 = 422.6 x 10 -10 cm
z xM 2 x 23
d= ; d= = 36.77 g/cc
6.023x1023 x ( 422.6 x10−10 )
3
N0 a 3
2. CsCl has cubic structure. Its density is 3.99 g/cc. Find the distance between
Cs+ and Cl- ions.
Solution. For simple cubic lattice Z = 1, M = 133 = 35.5 = 168.5
z xM z xM
d= ; a3 = ;
N0 a 3 N0 d
12
 1 x 168.5 168.5 x 10−23
3
a = 23
3
; a = ; a 3 = 70.12 x 10−24
6.023x10 x 3.99 240.3

a = 3 70.12 x 10−24 ; a = 3 70.12 x 10−8 ; a = 4.124 x 10−8 cm

3a
For BCC d= = 0.866 a i.e d= 0.866 x 4.124 x 10 -8 = 3.57 x
2
10-8 cm OR 3.57 pm
3. Calculate Avogadro’s number from the following data. Density of NaCl is
2.165 g/cc, Distance between Na+ and Cl- ions is 281 pm.
Solution : NaCl is FCC type of crystal. Hence Z = 4 , M = 58.5.
Edge is the distance from Na+ to Na+ or Cl- to Cl-
Therefore edge length of unit cell = 2 x 281 = 562 pm or 562 x 10-10 cm.
z xM z xM 4 x 58.5
d= ; N0 = = −10
= 6.09 x 10 23
N0 a 3 da 3
2.165 (562 x 10 )

4. An element has a bcc structure with cell edge of 288 pm. The density of the
element is 702 g/cc. How many atoms are present in 208 g of element ?
Solution : For bcc Z = 2 ; a = 288 x 10-10 cm, d = 7.2 g/cc
7.2 x 6.023 x 1023 ( 288 x 10−10 )
3
ZM d N0 a 3
d= ; M= ; M=
N0 a 3 Z 2
d = 51.8 g/mole
51.8 g of element contains 6.023 x 1023 atoms
208 g of element contains = ?
208 x 6.023 x 1023
= = 24.18 x 1023 atoms
51.8

5. The density of KBr is 2.75 g/cc. The length of edge of unit cell is 654 pm.
Predict the type of cubic lattice.
Solution : Molecular weight of KBr ( M ) = 119
2.75 x 6.023 x 1023 ( 654 x 10−10 )
3
ZM d N0 a 3
d= ; Z= ; Z= = 3.89  4
N0 a 3 M 119
Since Z = 4, therefore KBr has FCC cubic crystalline lattice structure.
Imperfections in Solids :-
In which ever manner the crystals are formed, they have some defects in
them i.e irregularities in the arrangement of particles and are called “Crystal
defects”. These are of two types.
Point defects :- These are the defects which arises due to irregularities from
ideal arrangement around a point.
Line defects : These are the defects which arises due to irregularities from
ideal arrangement in some rows .
Point defects are of three types as
A) Stoichiometric defects : These are the point defects that do not disturb
the stoichiometry of the crystal. These are called Intrinsic or
thermodynamic defects. These are two types.
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1) Vacancy defect : This defect arises when some of the lattice points are
vacant. This results in decrease in density of the soild.
2) Interstitial defect :- This defect arises when some of the constituent
particles occupy an interstitial sites. This results in increase in density of
the crystal.
The above defects are shown by non ionic solids. Ionic solids show the
following defects
a) FRENKEL DEFECT :- It is an interstitial defect
which arises due to dislocation of an ion
(Usually a smaller ion i.e cation ) from its
normal site to an insterstitial site. It creates
a vacancy defect at its normal site. It does,t
change the density of the crystal.
Frenkel defect is shown by the ionic solids in
which there is large difference in the size of the ions.
Ex :- ZnS, AgCl, AgBr, AgI etc

b) SCHOTTKY DEFECT :- It is a vacancy

defect which arises due to missing of ions
from crystal lattice. In order to maintain
electrical neutrality, the number of missing
cations and anions are equal.
Schottky defect is shown by ionic solids,
in which cation and anion are of almost same
size. Ex: NaCl KCl, AgBr etc.
AgBr shows both Frenkel as well as Schottky defect.

B) Impurjty Defect :- It arises due to the presence of impurities in the

crystal lattice. For example, if molten NaCl is crystalised in presence of
SrCl2, some of the sites of Na+ ions are occupied by Sr2+ ions. Each Sr2+
replaces two Na+ ions and occupies the site of one Na+ ion and the other
site remain vacant. The cationic vacancies produced are equal to the
number of Sr2+ ions.
C) Non – Stoichiometric Defects :- These are the defects which arises due
to non-stoichiometric ratio of constituent particles in the crystal lattice of
certain solids. These are of two types,
i) Metal Excess Defect :- It is due to anionic vacancies. Alkali metal
halides like NaCl, KCl show this types of defect. When crystals of NaCl are
heated in an atmosphere of sodium, some sodium atoms are deposited on
the surface of NaCl crystal. Now the Cl-1 ions diffuse to the surface of
crystal and combine with sodium ions which are formed by the loss of
electron by Na atoms. The released electrons diffuse into the crystal and
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 occupy anionic sites ( Cl-1 sites ). The anionic sites occupied by
unpaired electrons are called “ F – Centres ”.
ii) Metal Deficiency Defect : Certain metal compounds which contain less
amount of metal as compared to the stoichiometric proportion. For
example Ferrous oxide (FeO) which is mostly found with a composition of
Fe0.95O. It may range from Fe0.93O. to Fe0.96O.

ELECTRICAL PROPERTIES OF SOLIDS :- Solids are classified into three

types on the basis of their electrical conductivities.
1) Conductors :- These are the solids with high conductivities ranging
between 104 to 107 ohm-1m-1. Metals have conductivities in this range,
hence metals are good conductors.
2) Insulators :- These are the solids with very low conductivities ranging
between 10-20 to 10-10 ohm-1m-1.
3) Semiconductors :- These are the solids with conductivities ranging
between 10-6 to 104 ohm-1m-1.
Conduction of Electricity in Metals :- Conduction in metals ( Metallic
conduction ) is due to the movement of electrons. Metals conduct electricity
in solid as well as molten state. The extent of conductivity of metal depends
on the availability of valence electrons.
The atomic orbitals containing electrons merge to form molecular
orbitals which are so close in energy to each other and form a band called
“Valence band”. If it is partly filled or overlaps with higher energy unoccupied
band called “Conduction band”, then the electrons flow easily under applied
potential and the metal shows conductivity.
If the gap between valence band and conduction band is so large,
electrons cannot jump to it and such a substance has very small conductivity
and behaves as an Insulator.
Conduction of Electricity in Semiconductors :-
The gap between valence band and conduction band in
semiconductors is small and electrons can jump to conduction band and show
some conductivity and it increases with increase of temperature because
more number of electrons jump into the conduction band.
Silicon and Germanium show this type of conductivity and called
Intrinsic semiconductors. The conductivity of these semiconductors can be
increased by adding some amount of suitable impurity. The process of
increasing conductivity of semiconductor by adding impurity is called
“Doping”. The impurity which is electron rich or electron deficient as
compared to the intrinsic semiconductor can be used for doping.
a) Electron rich impurities , n – type semiconductors :- Si and Ge contain
four valence electrons each in their crystals and are used for the formation
of four covalent bonds with its neighbours. When doped with a group 15
elements like ‘P’ or ‘As’ which contain 5 valence electrons, they occupy
some of lattice sites of the crystal. Four out of five electrons are used for
bonding with four neighbour Si or Ge atoms. The 5 th electron is extra and
becomes delocalised. These delocalised electrons increases the conductivity
of doped semiconductor. The increase in conductivity is due to negatively
charged electron, hence Si or Ge doped with electron rich impurity is called
“n – type” semiconductor.

15
 b) Electron deficient impurities , p – type semiconductors :-
Si and Ge can also be doped with group 13 elements like B or Al or Ga
which contain only three electrons in the valence shell. The place where
fourth electron missing is called Electron hole or Electron vacancy. An
electron from neighbouring atom can move and fill the electron hole.
Under the influence of electric field, electrons move towards the positively
charged plate through electron holes. This type of semiconductors are
called P – type semiconductors.

MAGNETIC PROPERTIES :- Every substance has some magnetic property

associated with it. It is due to electrons in it. Each electron behaves like a tiny
magnet. Its magnetic momentum is due to orbital angular momentum and spin
angular momentum.
On the basis of magnetic properties, the substances are classified into
different types.
1. Paramagnetism :- Substances which are attracted by applied magnetic
field are called “Paramagnetic substances”. It is due to the presence of
unpaired electrons.
2. Diamagnetism : Substances which are repelled by applied magnetic field
are called “Diamagnetic substances”. It is due to the presence of paired
electrons.
3. Ferromagnetism : Substances which are strongly attracted by applied
magnetic field are called “ Ferromagnetic substances”. Only few
substances like Iron, Cobalt, Nickel, Gadalonium etc., show
ferromagnetism. These substances can be permanently magnetised.
In solid state, the metal ions of ferromagnetic substances are
grouped together into small regions called “Domains”. Each domain acts
as tiny magnet. In an unmagnetised ferromagnetic substance, the
domains are randomly arranged while under the influence of magnetic
field, the domains get orderly oriented in the direction of magnetic field.
The ordering of domains persists even when the magnetic field is removed
and the substance become permanent magnet.

4. Antiferromagnetism : These are the substances in which the domains

are oppositely arranged with equal number and cancel out each others
magnetic moment. Ex : MnO

16
5. Ferrimagnetism :- These are the substances in which the domains are
aligned in parallel and antiparallel directions in unequal numbers. These
are weakly attracted by magnetic field. Ex: Fe2O3, MgFe2O3, NiFe2O3 etc.

17