ESO 205

Nature and Properties of Materials

Prof. Kaustubh Kulkarni

Department of Materials Science and Materials
Indian Institute of Technology Kanpur

Email: kkaustub@iitk.ac.in

Course Website: lattice.mse.iitk.ac.in/~sangals

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 Structure of Ionic Solids
• Consist of Cations (+ve) and Anions (-ve)
• Each ion wants to be surrounded by as
many ions of opposite sign as possible
• No. of anions surrounding a cation is
called “Coordination number” or “Ligancy”
• Ligancy depends upon
– Charge on the ions
– Relative sizes of the two types of ions 2
 Producing Local Ionic Packing
• Conditions for stable ion- configurations
– A cation should touch all the anions surrounding it
(assumed to be hard spheres)

– Anions touch each other in limiting case and as close

as possible otherwise

– As many anions as possible surround a central cation

for the maximum reduction in electrostatic energy

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 Ligancy Rules: Radius ratio
Ligancy Range of Configuration
radius ratio
2 0-0.155 Linear

3 0.155-0.225 Triangular

4 0.225-0.414 Tetrahedral

6 0.414-0.732 Octahedral

8 0.732-1.0 Cubic

12 >1.0 FCC or HCP

Most common coordinations are 4, 6 and 8

 NaCl Crystal: Rocksalt Structure
rNa+
=0.54 Between 0.414 and 0.732
rCl -
+ -
Octahedral Coordination: Each Na cation surrounded by six Cl anions

- +
Cl Na

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FCC positions for Cations
 Charge Neutrality
• Charge neutrality is ensured by long range
arrangement
• Na+ ions at the FCC positions
• 4 Na+ ions per unit cell

• Cl- ions at the Centres of edges, each shared by

four unit cells

• 12/4=3
• One entire ion at body center

• 3+1=4 Cl- ions per unit cell

• One octahedral site per FCC lattice position

• All octahedral sites have to be occupied by cations in NaCl to maintain6charge

neutrality
 Charge Neutrality
• One octahedral site per FCC lattice position
• Right Fraction of octahedral sites have to be occupied by to maintain charge neutrality

Crystal rc/ra Anion Packing Fraction of octahedral sites

occupied by cations
NaCl 0.54 FCC All

MgO 0.59 FCC All

CdCl2 0.57 FCC Half

Al2O3 0.43 HCP Two-thirds

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 CsCl Crystal
rCs+
=0.91 Between 0.732-1
rCl -
+ -
Cubic Coordination: Each Cs cation surrounded by eight Cl anions

Cube corner positions for Anions

-
Cl
+ Cations are located at the body center
Cs

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 ZnS: Zincblend or Sphalerite
rZn2+
=0.48 Between 0.414-0.732
rS 2-
3
Octahedral Coordination Suggested by Ligancy rule but Covalent charatcer dominates and tetrahedral packing taken for sp

bonding
2-
S

FCC positions for Anions

2+
Zn
Cations are located at alternate tetrahedral sites

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STRUCTURE OF
SILICATES
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 Silicates
• Noncrystalline:
– Glasses

• Crystalline
– Quartz
– Cristobalite
– Tridymite

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 Silicates: Basic Unit
• Si-O bonds are 50% ionic and 50% covalent
• Tetrahedral coordination
– Satisfies the Ligancy rule (rc/ra = 0.29) (between 0.225-0.414)
– Satisfies orientation for SP3 bonds

• a tetravalent Si ion bonded to four divalent oxygen

• (SiO4)
4-

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 Structure of Silica

• 4+
Each Si ion contained entirely in a tetrahedron
• 2-
Each of the four O ion shared by two tetrahedra
• 4+ 2-
Thus one Si ion and two O ions per tetrahedron maintaining the charge neutrality 13
Glasses: Network Modifiers

Si - O - Si + Na2O ® Si - O.Na + Si - O.Na

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