MSE 631a IIT Kanpur

Electroceramic Materials &

Applications (MSE 631a)
2023-24, Semester II
Instructor: Dr. Shobit Omar

Venue: T112
Lecture 2
MSE 631a Question IIT Kanpur
Question 1: Identify octahedral and tetrahedral sites in hexagonal
closed packed crystal structure
# Tetrahedral sites = 2 +2 +2 +2 +2 +2 =12

x x x
Tetrahedral
voids x x
x x x
x x

MSE 631A 10th January 2024 Venue-T112 Lecture 2

MSE 631a Question IIT Kanpur
Identify octahedral sites in hexagonal closed packed crystal structure

Number of octahedral sites =

1x3 +1 x3=6

MSE 631A 10th January 2024 Venue-T112 Lecture 2

 Stability of Ionic Crystal
MSE 631a IIT Kanpur
Structures
Why ionic crystal structure is preferred over the same number
of isolated molecules?

Energetic Stability?

A+ B-

The interaction energy of a pair of anion and cation consists of

two terms: electrostatic attractive energy and repulsion energy

Constant
Z M Z X e2 B
E=− + n Born Exponent

4 o r r

MSE 631A 10th January 2024 Venue-T112 Lecture 2

MSE 631a Potential Energy Curve IIT Kanpur

Coloumbic Repulsive
Interaction Interaction

Z M Z X e2 B
E=− + n
4 o r r
MSE 631A 10th January 2024 Venue-T112 Lecture 2
MSE 631a Madelung Constant IIT Kanpur
Madelung constant is defined as the ratio of the electrostatic
interaction energy of an ion pair in a crystal to the electrostatic
interaction energy of an isolated pair at the same separation.

Electrostatic Z M Z X e2 Interaction energy

Interaction energy Ecol = −  of an isolated pair
of an ion pair in a 4 o r MX
crystal
Zi Z j
A = − Rij = rij r
i Z i Z j rij

If A (Madelung constant) > 1 then crystal is energetically stable

MSE 631A 10th January 2024 Venue-T112 Lecture 2

MSE 631a Madelung Constant IIT Kanpur
Linear array of ions in AB type compound
Reference ion

A+ B- A+ B- A+ B- A+ B- A+

Zi Z j
A = −
i Z i Z j rij
A = 2  [1 − 1 / 2 + 1 / 3 − 1 / 4...]
2 3 4
x x x
ln(1 + x) = x − + − + ...
2 3 4
A = 2 ln 2
MSE 631A 10th January 2024 Venue-T112 Lecture 2
MSE 631a Madelung Constant IIT Kanpur
Madelung constant in NaCl structure

Rij = rij r
3r

r
2r

A = −(6 / 2)(−1) / 1 − (12 / 4)(1) / 2 − (8 / 8)(−1) / 3

= 1.456
Doubling the cell edge,

A = 1.75
MSE 631A 10th January 2024 Venue-T112 Lecture 2
 Stability of Ionic Crystal
MSE 631a IIT Kanpur
Structures
Structure Co-ordination Madelung Constant
number

NaCl 6:6 1.747

CsCl 8:8 1.763 When the energy

difference between
Zinc Blende 4:4 1.638
two structures of
the same
Wurtzite 4:4 1.641
compound is
Fluorite 8:4 2.519 negligible then
polymorphism
Rutile 6:3 2.408 occurs

MSE 631A 10th January 2024 Venue-T112 Lecture 2

MSE 631a Lattice Energy IIT Kanpur
2
ZM Z X e NB
E = − N + n
4 o r r
N is the number of
ion pairs
dE Z M Z X e2 nNB
= 0 = − N + n +1
dr 4 o r 2 r
Z M Z X r n −1e 2 Z M Z X e2  1 
B= E = − N 1 − 
4 o 4 o r  n 
Average value of n is taken as 8

Q: For MgO, r = 210 pm and A = 1.748. Estimate the lattice

energy/mol.
MSE 631A 10th January 2024 Venue-T112 Lecture 2
MSE 631a Homework Question IIT Kanpur
Question 1: Estimate the Madelung constant for following
array of ion.

A+2 B-2 A+2 B-2 A+2 B-2 A+2 B-2 A+2 B-2

Reference ion

MSE 631A 10th January 2024 Venue-T112 Lecture 2

MSE 631a Pauling’s Rule IIT Kanpur
These are a set of five general statements which allow us to predict the
structure in which a compound is likely to crystallize.
Corners of a
Rule 1. Around every cation, a Triangle (3) < 0.225
coordination polyhedron of anions forms,
in which the cation-anion distance is Corners of a 0.414-
determined by the radius sums and the Tetrahedral (4) 0.225
coordination number of cation is
Corners of a 0.732 -
determined by the cation/anion radius
Octahedral (6) 0.414
ratio.
Corners of a
Cube (8) 1-0.732
The co-ordination number is
indicated by the radius ratio of co-
ordinating ions Corners of a ~1
Cuboctahedron (12)

MSE 631A 10th January 2024 Venue-T112 Lecture 2

MSE 631a Pauling’s Rule IIT Kanpur
Rule 2. An ionic structure will be stable to the extent that the sum of the
strengths of the electrostatic bonds that reach an ion equal the charge on
that ion.

Electrostatic bond strength = Charge on the ion / Co-ordination number

Example:
Na+ is surrounded by 6 Cl- ion

Electrostatic bond strength = 1/6

(From each Na+ to Cl-)

How many Na+ ions surrounds Cl-?

Using Rule 2,
Number of Na+ surrounding Cl- = 1/(1/6) = 6

MSE 631A 10th January 2024 Venue-T112 Lecture 2

MSE 631a Pauling’s Rule IIT Kanpur

Rule 3. Co-ordination polyhedra prefer linkage when they share corners

rather than edges, and edges rather than faces.

Positively charge cation comes closer if polyhdrons share edges and faces.

MSE 631A 10th January 2024 Venue-T112 Lecture 2

MSE 631a Pauling’s Rule IIT Kanpur
Rule 4. In a crystal structure containing several cations, those of high
valency and small coordination numbers tend not to share polyhedral
elements.

Sharing of polyhedral elements for cations of high charge will place

cations close enough together that they may repel one another.

Polyhedral
Element
Rules 1 through 4 maximize
the cation - anion attractions
and minimize the anion-
anion and cation-cation
repulsions

MSE 631A 10th January 2024 Venue-T112 Lecture 2

MSE 631a Pauling’s Rule IIT Kanpur
Rule 5 : Also, called “Rule of Parsimony”.
The number of essential different kinds of constituents in a crystal
tends to be small.
Constituent refers to coordination polyhedral. There may be two or
three types of polyhedra, such as tetrahedra or octahedra, but there
will not be many different types.
Question
Question 2: In TiO2, O2- is surrounded 3 Ti4+ ions. Using this
information, predict the polyhdra Ti4+ ion will form with O2-.

Bond strength = 2/3

(from each O2- to Ti4+ ion)

Using Pauling Rule 2,

Number of O2- surrounding each Ti4+ = 4/(2/3) = 6

MSE 631A 10th January 2024 Venue-T112 Lecture 2
MSE 631a Background on IIT Kanpur
Crystal Structures
Pauling’s rules apply to compounds in which the bonding is
primarily ionic.

Fraction of ionic character = 1 − exp[ −0.25( X M − X X ) 2 ]

Electronegativity

SiC (12%), BN (22%), MgO (73%), BaO (82%), SiO2 (51%), Al2O3 (63%)

1. Anion is the large ion compared to cations

2. Anion forms a scaffold with the cations filling the interstices
between the anions

MSE 631A 10th January 2024 Venue-T112 Lecture 2

MSE 631a Ionic Radius IIT Kanpur

Do not use the value of ionic radius given in radom internet website !!

MSE 631A 10th January 2024 Venue-T112 Lecture 2

MSE 631a Rock Salt Crystal Structure IIT Kanpur
Rock Salt Structure

Example: NaCl, MgO, LiF, etc.

Co-ordination: 6,6

Anion Packing: FCC lattice

Cation Packing: Occupying all

the octahedral sites

Interpenetrating fcc lattice of

anion and cation

rNa +
= 0.56  0.414
rCl −
CN of Na+ should be 6
MSE 631A 10th January 2024 Venue-T112 Lecture 2
MSE 631a CsCl Crystal Structure IIT Kanpur
CsCl Structure
Example: CsCl, CsBr etc.
Co-ordination: 8,8

Anion Packing: Primitive cubic

Interpenetrating simple cubic

lattice of anion and cation

rCs +
= 0.94  0.732
rCl −
Structure for 8-coordinate cations

MSE 631A 10th January 2024 Venue-T112 Lecture 2

MSE 631a Anti-Fluorite Crystal Structure IIT Kanpur
Anti-fluorite Structure

Example: Li2O, Na2O, K2O etc.

Co-ordination: 4,8

Anion Packing: FCC lattice

Cation Packing: Occupying all

the tetrahedral Sites

rLi+
= 0.414  0.732
rO 2−
CN of Li+ should be 4
MSE 631A 10th January 2024 Venue-T112 Lecture 2
MSE 631a Fluorite Crystal Structure IIT Kanpur
Fluorite Structure
Example: CaF2, CeO2, ZrO2 etc.
Co-ordination: 8,4
Cation Packing: FCC lattice
Anion Packing: All the
tetrahedral sites
Anion Packing: Primitive cubic
Cation Packing: Half the center
of the cube

rCa 2+ 100
= = 0.8  0.732
rF − 130
CN of Ca2+ should be 8

MSE 631A 10th January 2024 Venue-T112 Lecture 2

MSE 631a Zinc Blende Crystal Structure IIT Kanpur
Zinc Blende Structure

Example: ZnS, BeO etc.

Co-ordination: 4,4

Anion Packing: FCC lattice

Cation Packing: Half the

tetrahedral positions

rZn2+
= 0.34  0.225
rS 2−

CN of Zn2+ should be 4

MSE 631A 10th January 2024 Venue-T112 Lecture 2

MSE 631a Diamond Crystal Structure IIT Kanpur
Diamond Crystal Structure
Example: Diamond, Si, etc.
Co-ordination: 4,4
Bonding: Covalent Bond
Number of atoms per unit cell: 8

Co-ordinates:
(0, 0, 0)
(½, ½, 0)
(½, 0, ½)
(0, ½, ½)
(¼, ¼, ¼)
(¾, ¾, ¼)
(¼, ¾, ¾)
(¾, ¼, ¾)

MSE 631A 10th January 2024 Venue-T112 Lecture 2

MSE 631a Wurtzite Crystal Structure IIT Kanpur
Wurtzite Crystal Structure
Example: ZnS, ZnO, CdS etc.
Co-ordination: 4,4

Anion Packing: HCP lattice

Cation Packing: ½ Tetrahedral

sites (Corner sharing)

rZn2+
= 0.34  0.225
rS 2−
Madelung constant of Zinc Blende
(1.638) and Wurtzite (1.641) structures CN of Zn2+ should be 4
are similar. Compounds of one structure
often have a polytype of other.
MSE 631A 10th January 2024 Venue-T112 Lecture 2
MSE 631a NiAs Crystal Structure IIT Kanpur
NiAs Crystal Structure
Example: NiAs, etc.
Co-ordination: 6,6

Anion Packing: HCP lattice

Cation Packing: Octahedral sites

As Co-ordinates:
(0, 0, 0)
(2/3, 1/3 , 1/2)
Ni Co-ordinates:
(1/3, 2/3, 1/4)
(1/3, 2/3, 3/4)

MSE 631A 10th January 2024 Venue-T112 Lecture 2

MSE 631a CdI2 Crystal Structure IIT Kanpur

CdI2 Crystal Structure Example: CdI2, CaI2, FeI2 etc.

Co-ordination: 6,3

Anion Packing: HCP lattice

Cation Packing: ½ Octahedral

sites (alternating layers)
I Co-ordinates:
(0, 0, 0)
(2/3, 1/3 , 1/2)
Cd Co-ordinates:
(1/3, 2/3, 3/4)

MSE 631A 10th January 2024 Venue-T112 Lecture 2

MSE 631a Perovskite Structure IIT Kanpur

AMX3 Crystal Structure Example: CaTiO3, etc.

Multivalent Cations: A & M

A Cation Packing: Simple cubic

M Cation Packing: Body-centered
position
X Anion Packing: Face centered
position
Coordination of M: 6
Coordination of A: 12
Coordination of X: 2

MSE 631A 10th January 2024 Venue-T112 Lecture 2

MSE 631a Spinel and Inverse Spinel AB2O4 IIT Kanpur
Spinel Structure
Example: MgAl2O4 Made of 8-unit cells of anion fcc
Mg8Al16O32
Anion Packing: FCC lattice
Di-valent cation: 1/8 of the tetrahedral sites Mn2+ = Ar3d5
Tri-valent Cation: 1/2 of the octahedral sites Co2+ = Ar3d7

Inverse Spinel Structure

Example: Fe3O4 Use as a semiconducting oxides
and is black in color
Anion Packing: FCC lattice
Di-valent cation: 1/4 of the octahedral sites
Tri-valent Cation: 1/4 of the octahedral sites + 1/8 of tetrahedral sites

eg 4s + 4p
Fe2+ = Ar3d6 Six orbitals of d2sp3
Interact with the empty orbitals of
t2g
surrounding anions to enhance the bond
strength
MSE 631A 10th January 2024 Venue-T112 Lecture 2
MSE 631a Corundum Structure IIT Kanpur
Al2O3 Side View
Top View

Anion Packing: HCP lattice

Cation Packing: Occupying 2/3 of the octahedral sites

MSE 631A 10th January 2024 Venue-T112 Lecture 2

MSE 631a Rutile Crystal Structure IIT Kanpur

Example: TiO2, etc.

Co-ordination: 6,3

Cation Packing: Body-centered

tetragonal

Anion Packing: Trigonal planar

co-ordination

rTi 4+
= 0.43  0.414
rO 2−
CN of Ti4+ should be 6
Ti
O
MSE 631A 10th January 2024 Venue-T112 Lecture 2