S O L I D S TAT E

PART VII
14 JULY 2021
 RECAP
• Tetrahedral voids are present at body diagonals of the unit cell, two
at each body diagonal. There contribution is complete towards each
unit cell.
• Octahedral voids are present at edge centres and body centres of
the cubic unit cell.
• Number of octahedral voids is equal to the number of particles and
number of tetrahedral voids is twice the number of particles in a unit
cell.
• Radius of octahedral void r = 0.414 R and
• Radius of tetrahedral void r = 0.225 R where R is the radius of the
particle in a unit cell.
 QUESTIONS

1)What do you mean by close packing in crystal ?

2 )Differentiate between tetrahedral and octahedral voids ?
3 ) Compare HCP and FCC lattices ?
4)Define coordination number ?
5) What is the coordination number in
i. simple cube
ii. HCP
iii.CCP
Packing fraction or Packing efficiency

Packing fraction in simple

cubic

Packing fraction in BCC

Packing fraction in FCC

 Packing fraction or Packing efficiency

Packing Efficiency is defined as percentage of the total

space filled by the particles i.e.
Let edge length of the unit cell =a
and radius of sphere = r
So 2r = a
22
 Packing fraction for FCC unit cell
As the sphere on the face centre is touching the spheres at the corners
evidently AC = 4r But from right angled triangle ABC
Calculation of density of a cubic crystal from its
edge

Edge length of the unit cell = a cm

No. of atoms per unit cell = Z

Atomic mass of the element = M

Numerical: Calculate the density of Aluminum which forms FCC crystal lattice, if
edge length of unit cell is 4.049 Å. (Atomic mass of Al = 26.98 g/mol. Avogadro’s
number = 6.023 x 1023)?

Solution
Given:
Edge length (a) = 4.049 Å = 4.049 x 10−8 cm
Atomic mass of Al (M) = 26.98 g/mol
Z = 4 (FCC)
Avogadro’s number = NA = 6.023 x 1023
To find: Density (d) = ?
V= a3 ..................i
Numerical : An element with density 11.2g cm-3 forms a fcc lattice with edge length
of 4 x 10-8 cm. Calculate the atomic mass of the element. (Given: NA = 6.022 x 1023
mol-1)

Given d = 11.2g /cm-3 , Z = 4 , a = 4 x 10-8 cm

Numerical : Niobium crystallizes in a body centred cubic structure. If density
is 8.55g cm-3, calculate edge length of niobium, given that its atomic mass is
93 u

Given: For ‘bcc’

Z= 2 Density ‘d’= 8.55
g/cm3
Atomic mass ‘M’ = 93 u
NA‘ = 6.022 x 1023mol-1
Edge length= a=?
Numerical : A metallic element has a cubic lattice. Each edge of the unit cell is 2
A˚. The density of the metal is 2.5 g cm-3 . Calculate the number of unit cells in
200 g of metal?
Numerical : Gold crystallizes in an FCC unit cell. What is the edge length of unit cell
(r =0.144 nm) ?

Ans. r = 0.144 nm
a = 2√2 r
= 2 × 1.414 × 0.144 nm = 0.407 nm

Numericals
i.Silver crystallizes in fcc lattice. If edge length of the unit cell is 4.077 x 10 -8 cm, then calculate
the radius of silver atom.

ii.Tungsten crystallizes in body-centred cubic unit cell. If the edge of the unit cell is
316.5 pm, what is the radius of Tungsten atom ?
 QUESTIONS
1. In a solid, oxide ions are arranged in ccp. One sixth of the tetrahedral voids
are occupied by the cation A while one third of the octahedral voids are
occupied by the cation B. What is the formula the compound? (ABO3)
2. If the radius of an atom of an element is 75pm and the lattice type is bcc,
what is the edge of the unit cell? (173.2pm)
3. The edge length of an fcc type unit cell is 1414pm, what will be its radius?
(500pm)
4. What is the percentage of empty space in fcc and bcc?
Numerical: Lets Try
 The density of chromium is 7.2 g cm-3 . If the unit cell is a cubic with
length of 289 pm, determine the type of unit cell. (Atomic mass of Cr = 52
u and NA =6.022 × 1023 atoms mol-1)
Ans : Z =2

 Niobium crystallises in body–centred cubic structure. If density is 8.55 g

cm–3, Calculate atomic radius of niobium using its atomic mass 93 u.
Ans: 1.43 X 10 -8 cm

 Silver metal crystallises with a face centred cubic lattice. The length of
unit cell is found to be 4.077x10-8 cm. calculate atomic radius and
density of silver.
Ans : r =1.44
X 10 -8 cm Density = 10.58 g cm-3
IMPERFECTIONS/DEFECTS IN SOLIDS
• Although crystalline solids have short range as well as long
range order in the arrangement of their constituent
particles, yet crystals are not perfect . Crystals have defects
in them.
• The defects are basically irregularities in the arrangement
of constituent particles. Broadly speaking, the defects are
of two types, namely, point defects and line defects.
IMPERFECTIONS/DEFECTS IN SOLIDS
• Point defects are irregularities or deviations from ideal
arrangement around a point or an atom in a crystalline
substance, whereas
• Line defects are the irregularities or deviations from ideal
arrangement in entire rows of lattice points. These irregularities
are called crystal defects.
IMPERFECTIONS/DEFECTS IN SOLIDS

• Types of Point Defects

• Point defects can be classified into three types :
(i) Stoichiometric defects
(ii) Non-stoichiometric defects
(iii) Impurity defects
IMPERFECTIONS/DEFECTS IN SOLIDS

• TYPES OF
STOICHIOMETRIC
DEFECTS
IMPERFECTIONS/DEFECTS IN SOLIDS
• Stoichiometric Defects
• If imperfections in the crystal are such that the ratio
between the cations and anions remains the same as
represented by the molecular formula and stoichiometry
of the crystal is not changed , the defects are called
stoichiometric defects. They are also called intrinsic or
thermodynamic defects. Basically these are of two
types:
• Vacancy defects
• Interstitial defects
IMPERFECTIONS/DEFECTS IN SOLIDS
• Vacancy Defect:
– When some of the lattice sites are vacant, the crystal is said
to have vacancy defect . This results in decrease in density
of the substance. This defect can also develop when a
substance is heated.
IMPERFECTIONS/DEFECTS IN SOLIDS
• Interstitial Defect:
• When some constituent particles (atoms or molecules)
occupy an interstitial site, the crystal is said to have
interstitial defect. This defect increases the density of
the substance.
 IMPERFECTIONS/DEFECTS IN SOLIDS
• Vacancy and Interstitial defects are shown
by non-ionic solids. Ionic solids must
always maintain electrical neutrality ,so,
rather than simple vacancy or interstitial
defects, they show these defects as
Schottky and Frenkel defects.
• Schottky Defect
– If in an ionic crystal, equivalent number
of cations and anions are missing from
the lattice site so that the electrical
neutrality is maintained, it is called
Schottky defect.
IMPERFECTIONS/DEFECTS IN SOLIDS

• Types of compounds showing Schottky Defect:

• Ionic compounds having
 High coordination number and
 Small difference in the size of cations and anions e.g.
 NaCl, KCl, KBr, AgBr and CsCl
IMPERFECTIONS/DEFECTS IN SOLIDS
• Frenkel Defect
– If an ion is missing from its lattice site (causing a vacancy
there)and it occupies an interstitial site, this is called Frenkel
Defect.
– The electrical neutrality and stoichiometry of the compound
are maintained.
IMPERFECTIONS/DEFECTS IN SOLIDS

• Types of compounds showing Frenkel Defect:

• Ionic compounds having
– Low coordination number and
– Large difference in the size of cations and anions e.g.
– AgCl, AgBr, AgI and ZnS
 IMPERFECTIONS/DEFECTS IN SOLIDS
• Effect on Density
• Effect on Density
 As the number of ions decreases as
 Since no ions are missing from the
a result of this defect, the mass
crystal, therefore density of the
decreases but volume remains the
crystal remains unchanged.
same. Hence, the density of the
solid decreases.
IMPERFECTIONS/DEFECTS IN SOLIDS
• Consequences of Schottky and Frenkel Defects
• Solids having these defects conduct electricity to some extent
due to movement of an ion from its lattice site to a hole,
creating a new hole. In this way, a hole moves across the crystal
resulting in movement of the charge in the opposite direction.
• Due to presence of holes, the stability of the crystal decreases
as lattice energy decreases.
• In Frenkel defect, similar charges come closer resulting in
increase of dielectric constant.
SLIDE TITE
We are going to have a
great year learning
together!
THANK
YOU