Solid

State
C.V. Kalyan

Gases do not have definite

shape and volume
Liquids do not have definite shape but
have definite volume
Solids have both definite
shape and volume
C.V. Kalyan

Solids are the

substances that
have definite shape,
volume and ORDER.
Order means that there is a
definite pattern of arranging
the ions, atoms or molecules
that make up the solid and the
pattern extends throughout
C.V. Kalyan

In this lesson we will focus on those

properties of a solid that depend on the
pattern of arrangement of the
constituent ions or atoms and their
nature rather those than that depend on
the amount of solid. Such properties are
called Intensive properties.
C.V. Kalyan

C.V. Kalyan

Unit Cells

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Smallest
Must be
Repeatin
Identical
g
Unit
Must
Must
Link Up
Up
Link
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C.V. Kalyan

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C.V. Kalyan

C.V. Kalyan

THERE ARE
ONLY
SEVEN
SHAPES
IN WHICH
UNIT CELLS
CAN
EXIST

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Cubic
Orthorhombic
Rhombohedral
Tetragonal
Triclinic
Hexagonal
Monoclini

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Crystal
Angles
&
Intercepts
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Lattice
Crystal
Parameters
Systems Interce Angle
pts
s =
=
Cubic
ab

c
= =
Orthorhom ab

bic
c
ab
= =
Rhombohe

c
dral
Tetragonal ab = =

=
c
Hexagonal ab
=
= =
c
Monoclinic ab

c
Triclinic ab

c
a

a
b

Cubic

Orthorho Rhombohe
dral
mbic
c

Tetragonal
c

a
b

Hexagonal Monoclin
ic

Triclinic

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Different
Arrangements
in a shape
(lattice)
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Primitiv
e

Face
Centered

There are not

more than 4 Body
Centered
ways of
arranging
atoms, ions
or molecules
in a given
shape of a
End
unit cell

Centered

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Shape :
Cubic
Arrangement:
Primitive
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Primitive Cubic is also known as Simple

Cubic. Primitive Cubic is defined as a Unit Cell in which the same
type of atoms occupy all the corners of a cube without any
atom of this type having its centre present on the centre of
any face or the centre of the cube.
The contribution of each corner sphere is one eighth for
an Unit Cell. The Rank of Primitive Cubic Unit Cell is 1. If
the Unit Cell length is a and the radius of atom is r then
a=2r
The alternative Unit Cell looks different from the
previous one. In this, one atom is present at the centre
of the cube without any atom of this type having its
centre present on the centre of any face or any corner
of the cube.
Packing fraction of Primitive Cubic Unit Cell is 0.523

Coordination Number an atom in Primitive Cubic Unit

Cell is 6.

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3
2
8

7
6
Unit Cell Shape
View

Total Volume that

all
the
corner
spheres occupy
in

an Unit Cell
This
means
that
effectively there is one
sphere inside the Unit
Cell.
The number effective
spheres in an Unit Cell
is known as the Rank
of the Unit Cell. So the
Rank
of
Primitive
Cubic Unit Cell = 1.

The
sphere which occupied different positions in different unit cells is being

shared by 8 unit cells. Therefore, the volume that the sphere occupies in one Unit
Cell will be th of its Volume.

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Atom Contact
View

a=
2r
Top
View

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Layer Arrangement
View

Let
this
be
Layer Z
Now we place another Layer Z on top
of this one

Layer Side
View
C.V. Kalyan

C.V. Kalyan

Packing
Fraction

Packing fraction is defined as the fraction of the volume of a unit cell that is
occupied by the atoms.
Packing
fraction

So the packing fraction of Primitive Cubic

Unit Cell is 0.523. This means 52.3% of the
Unit cells Volume is being occupied by the
spheres.
10.523 = 0.477 is called the Void Fraction.
This means that 47.7% of the Unit Cells
Volume is empty.

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Co-ordination
Number

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Shape : Cubic
Arrangement: Body
Centered

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BCC Unit Cell is defined as a Unit Cell in which the same type
atoms occupy all the corners of a cube and also the centre of the
cube without any atom of this type having its centre present on
the centre of any face of the cube.

The contribution of each corner sphere is one eighth for

an Unit Cell. The contribution of the Body Centre atom is
1 for the Unit Cell. The Rank of a BCC Unit Cell is 2. The
atoms along the Body Diagonal are in contact with each
other.
The alternate Unit Cell looks identical
to the previous

one with corner and body centred atoms interchanged.

The packing fraction of BCC Unit Cell is 0.68.

Each atom in BCC Unit Cell touches 8 other atoms.
Density of a BCC Unit Cell

C.V. Kalyan

The
volume that a corner sphere occupies in the Unit
Cell will be th of its Volume.
The volume that a centre sphere occupies in the Unit
Cell will be its complete Volume.
Therefore, the Rank of a BCC Unit
Cell will be =
All atoms lying on the Body
diagonal of the Unit Cell are in
contact with each other.

Unit Cell Shape

View

Atom Contact

C.V. Kalyan

Layer Arrangement
View

Let
this
be
X a new layer Y on top of
Now Layer
we place
X. Layer Y has the same arrangement
as X but is put in the groove of X
layer atoms.
Now we place Layer X again on top of
Y.

Top
ViewC.V. Kalyan

Side

C.V. Kalyan

Packing
fraction

Packing
Fraction

So the packing fraction of BCC Unit Cell is

0.68. This means 68% of the Unit cells
Volume is being occupied by the spheres.
10.68 = 0.32 is called the Void Fraction.
This means that 32% of the Unit Cells
Volume is empty.

C.V. Kalyan

Shape : Cubic
Arrangement: Face
Centered

C.V. Kalyan

FCC Unit Cell is defined as a Unit Cell in which the same type
atoms occupy all the corners of a cube and also the centre of
every face of the cube without any atom of this type having its
centre present on the centre of the cube.

The
contribution of each corner sphere is one eighth for

an Unit Cell. The contribution of the Face Centre atom is

for the Unit Cell. The Rank of a FCC Unit Cell is 4. The

atoms along the Face diagonal

are in contact with each
other.
The alternate Unit Cell looks identical to the previous
one with corner atoms becoming face centered and
some face centered atoms becoming corner atoms
The packing fraction of FCC Unit Cell is 0.74.
Each atom in FCC Unit Cell touches 12 other atoms.

Density of a FCC Unit Cell

C.V. Kalyan

The
volume that a corner sphere occupies in the Unit
Cell will be th of its Volume.
The
volume that a face centre sphere occupies in the

Unit Cell will be of its Volume.

Therefore, the Rank of a FCC Unit
Cell will be =
All atoms lying on the Body
diagonal of the Unit Cell are in
contact with each other.

Unit Cell Shape

View

Atom Contact

C.V. Kalyan

C.V. Kalyan

Packing
fraction

Packing
Fraction

So the packing fraction of FCC Unit Cell is

0.74. This means 74% of the Unit cells
Volume is being occupied by the spheres.

10.74 = 0.26 is called the Void Fraction.

This means that 26% of the Unit Cells

Volume is empty.
Face Centered Cubic Unit Cell has the highest Packing Fraction of all the Unit
Cells.

C.V. Kalyan

Co-ordination

Number

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There are in all 7 crystal systems and 4 lattice types. This gives
us 74=28 type of unit cells.

Of these 28, only 14 exist. These are called Bravais

Lattices.

Actually the missing lattices are already there. Each of

the 14 missing lattices are equivalent to those that
already exist as Bravais Lattices.

The rule that is followed to select a particular lattice of a

specific crystal system is (1) Symmetry and (2) size.

C.V. Kalyan

Crystal
Systems
Cubic
Orthorhom
bic
Rhombohe
dral
Tetragonal

Bravais Lattices
Primitive, Body Centred & Face
Centred
Primitive, Body Centred , Face
Centred & End Centred
Primitive
Primitive & Body Centred

Hexagonal

Primitive

Monoclinic
Triclinic

Primitive & End Centred

Primitive
C.V. Kalyan

The Curious Case of

Missing Lattices

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End
Centered =
Tetragonal
Cubic
Primitive
Cubic is not chosen because End centered
Cubic voilates the symmetry elements of
cube.

C.V. Kalyan

End
Centered
=
Tetragonal
Tetragonal
Primitive

Face
Centered
=
Body
Centered
Tetragonal
Tetragonal

C.V. Kalyan

Body
Centered
=
End
Centered
Monoclinic
Monoclinic

Face
Centered
=
End
Centered
Monoclinic
Monoclinic

C.V. Kalyan

Body
Centered
= Primitve Triclinic
Triclinic

End
Centered
=
Primitve Triclinic
Triclinic

C.V. Kalyan

Face
Centered
= Primitve Triclinic
Triclinic

Body
Centered
Hexagonal

C.V. Kalyan

Crystal
Systems
Cubic

Rhombohedral

Tetragonal
Hexagonal
Triclinic
Monoclinic

Missing
lattices
End Centred

Equivalent
lattice
Tetragonal
Primitive

Body Centred
End Centred
Face Centred
End Centred
Face Centred
Body Centred
End Centred
Face Centred

Rhombohedral
Rhombohedral
Primitive
Primitive
Triclinic
Primitive

Any Centred
Body Centred
Face Centred

Tetragonal Primitive
Tetragonal Body
CentredEnd
Monoclinic
Orthorhombic
Centered
PrimitiveEnd
Monoclinic
Centred
Triclinic
Primitive
Monoclinic End
C.V. Kalyan Centred

Let this be Layer A

FCC-Layer Arrangement
View

C.V. Kalyan

We create another layer same as A. We choose any one void and place the new layer
over the void. We select the yellow voids. Since this layer is not superimposing on A
layer we shall call it B Layer.

C.V. Kalyan

Now we create another layer same as A. There are two voids

generated by layer B. Blue voids and red voids. Lets put Layer C by
selecting blue voids.

C.V. Kalyan

On top of C layer we repeat ABCABC. This is the layer view of FCC.

One FCC unit cell contains four layers.-ABCA. This arrangement is
called Cubic Close Packing.

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C.V. Kalyan

C.V. Kalyan

Let this be Layer A

C.V. Kalyan

We create another layer same as A. We choose any one void and place the new layer
over the void. We select the yellow voids. Since this layer is not superimposing on A
layer we shall call it B Layer.

C.V. Kalyan

Now we create another layer same as A. There are two voids generated by
layer B. Blue voids and red voids. Putting spheres in blue voids got us FCC.
Now we place the third layer on the red voids.

C.V. Kalyan

This generates another A layer. This packing is called Hexagonal Close

Packing. This is the Layer arrangement view of Hexagonal Primitive.

C.V. Kalyan

Shape :
Hexagonal
Arrangement:
Primitive

C.V. Kalyan

Hexagonal Primitive Unit Cell is defined as a Unit Cell in which

the same type atoms occupy all the corners of a Hexagonal
lattice without any atom of this type having its centre present on
the centre of any face or the centre of the Unit Cell.

The
contribution of each corner sphere is one sixth for

an Unit Cell. The contribution of the Face Centre atom is

for the Unit Cell. The contribution of second layer atoms
is 3. Rank of Hexagonal Primitive Unit Cell is 6.
The actual Unit Cell is one-third of the hexagonal
shaped unit cell. Actual Rank is 2.
The packing fraction of Hexagonal Primitive Unit Cell is
0.74.
Each atom in Hexagonal Primitive touches 12 other
atoms.

Density of a HCP Unit

C.V. Kalyan

The
volume that a corner

sphere occupies in the Unit

Cell will be th of its Volume.

a = 2r

The
volume that a face center

sphere occupies in the Unit Cell

will be of its Volume.
Volume occupied by the B
layer atoms in an unit cell =
3
Rank =

Unit Cell Shape

View

Atom Contact

C.V. Kalyan

a = 2r

A
O

30o

D
O

C.V. Kalyan

O
A

30oD

C.V. Kalyan

Packing
fraction

Packing
Fraction

So the packing fraction of Hexagonal

Primitive Unit Cell is 0.74. This means 74%

of the Unit cells Volume is being occupied
by
the spheres.
10.74
= 0.26 is called the Void Fraction.
This means that 26% of the Unit Cells
Volume is empty.
Hexagonal Primitive Unit Cell has the highest Packing
Fraction
of all the Unit Cells.
C.V.
Kalyan

Two
types
voids:
Octahedral

of

Void
s

Tetrahedra
l
Found only in FCC & Hexagonal primitive
unit cells
Octahedral
void in
FCC
One octahedral void is
found at the center of
every edge of the unit cell.
There 12 edges in a cube.
Each edge is shared by 4
unit
cells.
Effective
octahedral
voids
from
edge
centers

C.V. Kalyan

There is one octahedral void at the

centre of the unit cell which has a
100% contribution to the unit cell.
Total octahedral voids in a FCC unit cell
is = 3 + 1 = 4.
Number of octahedral voids in a unit
cell = rank of the unit cell.

C.V. Kalyan

Tetrahedral
FCC

void

Number of Tetrahedral voids in a FCC

unit cell = 8 (assuming each corner as
origin)
Number of Tetrahedral voids in a unit
cell = 2 number of Octahedral Voids

in

C.V. Kalyan

Tetrahedral
FCC

void

in

C.V. Kalyan

Octahedral void in
HCP
Assuming the 3D hexagonal lattice to be the unit cell we should expect 6
octahedral voids in Hexagonal Primitive and 12 Tetrahedral Voids. For the
actual unit cell it would be 2 and 4 respectively.

Octahedral
void

3 octahedral voids between Layers A and B. 3 more

between the B and upper A layer. Total is 6.
For the rhombus type unit cell total octahedral
voids per unit cell is 2.

C.V. Kalyan

Tetrahedral
HCP

void

in

There are 4 tetrahedral voids inside the

unit cell and 6 on the tip of the hexagon
with a contribution of one third.
Total tetrahedral voids in HCP per unit
cell =12

C.V. Kalyan

Why Octahedral voids are = rank of a unit cell and tetrahedral voids are = 2
rank of
a unitincell?
Each
sphere
Close packing Arrangement is involved with 14 voids.
Of this 6 are octahedral void. Because a sphere would take up all the six
positions in the octahedral voids as the arrangement as maximum symmetry.
It would be associated with 8 tetrahedral void
because it will take all the 4 positions in a single
triangular arrangement and four more in the other
triangular arrangement.

Since 6 atoms form an octahedral void, each atom contributes one-sixth to the void.
The atom is involved in 6 octahedral void so effectively each atom has a
contribution to 1 octahedral void. For a given triangular arrangement an atom
C.V. orientation
Kalyan
contributes one-fourth to the void. So in each triangular
an tom has one

Radius
Ratios

C.V. Kalyan

Minimum Radius Ratio ( for various coordination numbers.

Co-ordination Number
3

Cations with radius ratios less than 0.155 with respect to

an Anion can only have coordination number of 2 with
that anion. Cations with Radius Ratios more will be in
contact with 3 anions but the anions would not be in
contact with each other. C.V. Kalyan

Co-ordination Number 4 (Tetrahedron)

C.V. Kalyan

Co-ordination
(Octahedron)

Number

(Square

Planar)

C.V. Kalyan

or

Co-ordination Number 8

C.V. Kalyan

Radius
Ratios

>
0.155
[0.1550.225)
[0.2250.414)
[0.4140.732)
[0.732-

Co-ordination
number

2 or 3
2 or 3 or 4
(Tetrahedron)
2 or 3 or 4 (Tetrahedron) or 4
(sq. planar) or 6
2 or 3 or 4 (Tetrahedron) or 4
C.V. Kalyan

Structure of some Ionic

Compounds

C.V. Kalyan

Rock
(NaCl)

Salt
Cl- ions form FCC Lattice and Na+ ions
are present in Octahedral Voids.
No. of Cl- per unit= 4
cellof Na+ per unit = 4
No.
cell
formula is NaCl
=6
Coordination no. of
Na+
Coordination no. of Cl- = 6

For an ionic Compound of the type AxBy the

ratio of coordination number of A to that
of B is y:x.
Other
compounds
which
have
this
structure are: all halides of alkali metals
except cesium halide, all halides of Silver,
all oxides of alkaline earth metals except
beryllium oxide.
C.V. Kalyan

Zinc
(ZnS)

Blende
S2- ions form FCC Lattice and Zn2+ ions
are present in half of tetrahedral voids.

No. of S2- per unit

=4
cell
No. of Zn2+ per unit = 4
cell
formula is
ZnS
=4
Coordination no. of Zn2+
=4
Coordination no. of
S2- compound
Other
which
have
structure is: BeO

C.V. Kalyan

this

Fluorite
(CaF2)

Ca2+ ions form FCC Lattice and F- ions

are present in all the
tetrahedral
voids.
No. of Ca2+ ions per unit
=4
cell
=8
No. of F- per unit cell
formula is
CaF2
=4
Coordination no. of
F
=8
Coordination
no. of
Ca2+
Other
compounds
which
have
this
structure are: UO2, ThO2, PbO2, HgF2 etc.

C.V. Kalyan

Anti
(Li2O)

Fluorite
Opposite of Fluorite. Cations and
Anions
interchange
positions
in
Fluorite.
No. of O2- ions per unit
=4
cell
No. of Li+ per unit = 8
cell
formula is
Li2O
=4
Coordination no. of
+
Li
=8
Coordination
no. of
O2Other compounds which have this
structure are: Na2O, K2O, Rb2O.

C.V. Kalyan

Cesium
(CsCl)

Halide

Cl- is Primitive Cubic and Cs+ is also

Primitive Cubic.
No. of Cl- per unit = 1
cell
No. of Cs+ per unit = 1
cell

formula
is
CsCl
Coordination no. of = 8
Cs+
=8
Coordination no. of
ClOther compounds which have this structure
are: all halides of Cesium and Ammonium

C.V. Kalyan

Defec
(i) Lattice of
ts
atoms

(a) Vacancy

an atom is missing from its

position
density decreases
percentage
occupancy
decreases

(b)
interstitial

Self
an atom leaves its lattice site & occupies
interstitial space
density & percentage occupancy remains same

C.V. Kalyan

Defec
ts

(c)
Substitution
impurity
foreign atom substitutes a host atom & occupies
its lattice
density
& percentage occupancy may change
(c) Interstitial impurity
foreign atom occupies occupies the interstitial
space
density & percentage occupancy increases

C.V. Kalyan

Defec
(i) Ionic
ts
structures

(a)
Schottky
Defect
Cation anion pair are missing
electro
neutrality
maintained
density decreases

(d) Interstitial Impurity Defect

is

H2 is trapped in TiC

(b)
Frenkel
Defect
ion
leaves
lattice
position
interstitial
space is maintained
electro neutrality
density
(c) maintained
Substitutional

Impurity

Defect
Ba2+ is replaced by Sr2+
electro
neutrality
maintained
density changes

is

&

density
increases
occupies

(e) F-Centre
electron replaces anion
electro
neutrality
maintained
density decreases
colour is imparted

C.V. Kalyan

is