Crystallography

Shamima Akhter Urmi, Lecturer, GCE

 c

Shamima Akhter Urmi, Lecturer, GCE

• Unit Cell:
• Smallest group of atoms which has the overall symmetry of a crystal, and from
which the entire lattice can be built up by repetition in three dimensions.
• Basic Building block of the crystal structure.

• Lattice Parameter:
 The lengths of the unit cell along its edges.
 a, b, c are the lattice parameters.

Shamima Akhter Urmi, Lecturer, GCE

Cubic Cells

Shamima Akhter Urmi, Lecturer, GCE

Simple Cubic Structure (SC)

8x1/8 Corner atom = 1 atom per unit cell

Shamima Akhter Urmi, Lecturer, GCE

Body Centered Cubic Structure (BCC)

8x1/8 Corner atom+1 Centre atom=2 atoms per unit cell

Shamima Akhter Urmi, Lecturer, GCE

Face Centered Cubic Structure (FCC)

8x1/8 Corner atom+6x1/2 Face atom=4 atoms per unit cell

Shamima Akhter Urmi, Lecturer, GCE

Hexagonal Closed Packed Structure (HCP)

6x1/6 Corner atom (Top layer)+ 6x1/6 Corner atom (Bottom layer)+ 3
Centre atom (Middle layer)+2x1/2 Centre atom (From Top & Bottom
layer)=(1+1+3+1)=6 atoms per unit cell
Shamima Akhter Urmi, Lecturer, GCE
 Coordination Number

 Number of atoms or ions

immediately surrounding
a central atom in a
complex or crystal.

Shamima Akhter Urmi, Lecturer, GCE

CN of SC Unit Cell: 6

Shamima Akhter Urmi, Lecturer, GCE

CN of BCC Unit Cell: 8

Shamima Akhter Urmi, Lecturer, GCE

CN of FCC unit Cell: 12

Shamima Akhter Urmi, Lecturer, GCE

CN of HCP unit Cell: 12

Shamima Akhter Urmi, Lecturer, GCE

Solid Soluion

Shamima Akhter Urmi, Lecturer, GCE

 Solvent atom

Solute atom

(a) Substitutional solid solution (b) Interstitial solid solution

Shamima Akhter Urmi, Lecturer, GCE

Solid Solution:
 A solid-state solution of one or more solutes in a solvent.
 Such a multi-component system is considered as solution rather than a compound 
 when the crystal structure of the solvent remains unchanged by addition of the solutes and
 when the chemical components remain in a single homogeneous phase

Shamima Akhter Urmi, Lecturer, GCE

substitutional solid solution
• When the atoms of solute substitute for the atoms of the solvent in its lattice, the solution
is called substitutional solid solution.
• The solute may incorporate into the solvent crystal lattice substitutionally by replacing a
solvent particle in the lattice.
• In substitutional solid solution, the arrangement of the solute atoms may be disordered
(random) or ordered.
• Some alloy systems exhibit complete solid solubility (e.g. Cu-Ni, Cd-Mg), others show
only limited solubility at any temperature.
• Several factors determine the limits of solubility. These are expressed as a series of rules
often called William Hume-Rothery Rules

Shamima Akhter Urmi, Lecturer, GCE

Interstitial solid solution
• Solute atoms fit in between the voids (interstices) of solvent atoms.
• Solvent atoms in this case should be much larger than solute atoms.
• When the atoms of the solute occupy the interstitial spaces in the lattice of the solvent, it is known
as interstitial solid solution.
• Only H, Li, Na and B form interstitial solid solution.

Shamima Akhter Urmi, Lecturer, GCE

Hume Rothery Rules

Shamima Akhter Urmi, Lecturer, GCE

 Hume-Rothery Rule for substitutional solid solution
• Hume-Rothery Rule 1:Atomic Size Factor (the 15%) Rule
Extensive substitutional solid solution occurs only if the relative difference between the atomic diameters
(radii) of the two species is less than 15%. If the difference > 15%, the solubility is limited.
Comparing the atomic radii of solids that form solid solutions, the empirical rule given by Hume-Rothery is
given as:

• Hume-Rothery Rule 2: Crystal Structure Rule

For appreciable solid solubility, the crystal structures of the two elements must be identical.

Shamima Akhter Urmi, Lecturer, GCE

• Hume-Rothery Rule 3: Valency Rule

A metal will dissolve a metal of higher valency to a greater extent than one of lower valency. The
solute and solvent atoms should typically have the same valence in order to achieve maximum
solubility.

• Hume-Rothery Rule 4: The Electronegativity Rule

Electronegativity difference close to 0 gives maximum solubility. The more electropositive one
element and the more electronegative the other, the greater is the likelihood that they will form an
intermetallic compound instead of a substitutional solid solution. The solute and the solvent should
lie relatively close in the electrochemical series

Shamima Akhter Urmi, Lecturer, GCE

 Hume-Rothery Rule for Innterstitial solid solution

Similar to substitutional solid solution Hume-Rothery rules can be applied for interstitial solid solutions:
Interstitial solid solutions are formed if
• A solute is smaller than pores in the lattice of a solvent;
• A solute has approximately the same electronegativity as a solvent.
There are very few elements that create ions, small enough to fit in interstitial positions, therefore,
appreciable solubility is rare for interstitial solid solutions.

Shamima Akhter Urmi, Lecturer, GCE

Interstitial Sites

(a) Tetrahedral Site (b) Octahedral Site

Shamima Akhter Urmi, Lecturer, GCE
Shamima Akhter Urmi, Lecturer, GCE
BCC: Octahedral sites
• 6 face position (6x1/2=3)+ 12 edge position (12x1/4=3)=6 octahedral sites.

Shamima Akhter Urmi, Lecturer, GCE

BCC: Tetrahedral sites

• Total 6 faces
• Each face contain 4 sites
• Total (6x4)/2=12 tetrahedral sites.

Shamima Akhter Urmi, Lecturer, GCE

FCC: Octahedral sites

• 1 center +12x1/4 edge position

• Total 1+3=4 octahedral sites.

Shamima Akhter Urmi, Lecturer, GCE

FCC: Tetrahedral sites

• 4+4=8 Tetrahedral sites.

Shamima Akhter Urmi, Lecturer, GCE

HCP: Octahedral sites

Shamima Akhter Urmi, Lecturer, GCE

HCP: Tetrahedral sites

• 3+3=6 red atoms+1+1=2 yellow

atoms+ 12x1/3=4 blue atoms
• Total 6+2+4=12 tetrahedral sites

Shamima Akhter Urmi, Lecturer, GCE

Comparison of different structure
SC BCC FCC HCP
No. of atoms 1 2 4 6

CN 6 8 12 12

a 2r 4r/√3 2√2r 2r

APF 52% 68% 74% 74%

Octahedral site - 6 4 6

Tetrahedral site - 12 8 12

Stacking A-A A-B A-B-C A-B

Shamima Akhter Urmi, Lecturer, GCE

Atomic Packing Factor (APF)

Volume occupied by the atoms in a unit cell

APF= Unit cell volume

Volume of an atom × No of atoms in a unit cell

= Unit cell volume

Shamima Akhter Urmi, Lecturer, GCE

AX Type Structures

Shamima Akhter Urmi, Lecturer, GCE

 Rocksalt Structure (6:6) Nickel Arsenide Structure (6:6)
Examples Cation Position Anion Position
Examples Cation Anion Position
• NaCl Position
• KCl
• LiF • NiAs
• KBr • FeS
• MgO • FeSe
• CaO • CoSe All Octahedral
All Octahedral HCP
• SrO FCC sites
sites
• BaO
• MnO
• FeO
• CoO
• NiO etc.

Shamima Akhter Urmi, Lecturer, GCE

Rocksalt structure
Na
Cl

Shamima Akhter Urmi, Lecturer, GCE

Nickel Arsenide Structure

Shamima Akhter Urmi, Lecturer, GCE

Shamima Akhter Urmi, Lecturer, GCE
Zinc Blende structure

Shamima Akhter Urmi, Lecturer, GCE

Wurtzite structure

Shamima Akhter Urmi, Lecturer, GCE

Cesium Chloride structure

Shamima Akhter Urmi, Lecturer, GCE

AmXp Type Structures

Shamima Akhter Urmi, Lecturer, GCE

 Fluorite Structure (8:4)
Examples Cation Position Anion Position
• CaF2
• ThO2 ½ Cubic SC
• CeO2
• UO2
• ZrO2 All Tetrahedral
FCC
• HfO2 sites

Anti Fluorite Structure (8:4)

Examples Cation Position Anion Position
• Li2O All Tetrahedral
• Na2O FCC
sites
• K2O
• Rb2O SC ½ Cubic

Shamima Akhter Urmi, Lecturer, GCE

Fluorite structure Anti Fluorite structure

Shamima Akhter Urmi, Lecturer, GCE

FCC
Cation

Anion

Fluorite structure

Shamima Akhter Urmi, Lecturer, GCE

Cadmium Iodide Structure (6:3)

Examples Cation Anion Position

Position
• CdI2
• TiS2
• ZrS2 ½ Octahedral
• MgI2 sites HCP
• VBr2 (3 among 6)

Shamima Akhter Urmi, Lecturer, GCE

 Rutile Structure (6:3)

Examples Cation Position Anion Position

• TiO2
• GeO2
• PbO2
• VO2
• RuO2 ½ Octahedral
Distorted FCC
• NbO2 sites
Ti • MnO2

Shamima Akhter Urmi, Lecturer, GCE

 Cation has charge of 4+.
 CN of cation is 6.
 Anion has CN=2x6/4=3.
 A CN of 3 can not be achieved in the
cubic/hexagonal close-packed arrangement.
 So a distorted close-packed structure results by
anions.
 Cations fill only half the octahedral positions.

Shamima Akhter Urmi, Lecturer, GCE

 Corundum Structure (6:4)
Examples Cation Position Anion Position
• Al2O3
• Cr2O3
• Fe2O3 2/3 Octahedral
• V2O3 HCP
sites (4 among 6)
• Rh2O3
• Ti2O3

Shamima Akhter Urmi, Lecturer, GCE

AmBnXp Type Structures

Shamima Akhter Urmi, Lecturer, GCE

 Perovskite Structure (12:6:6)

Examples Ba
• BaTiO3
• CaTiO3
• SrTiO3
• SrZrO3 Ti
• SrSnO3

Shamima Akhter Urmi, Lecturer, GCE

 Spinel Structure (4:6:4)

Examples
• FeAl2O4
• ZnAl2O4
• MgAl2O4

Shamima Akhter Urmi, Lecturer, GCE

How Spinel structure is formed?
 O ions form FCC (4 (n) atoms in a sub cell; 4x8=32 atoms in 8 unit cells)
 One FCC sub cell contains n octahedral sites (4)[12x1/4 in edges and corners + 1 in center] and 2n
tetrahedral sites (2x4=8) [2 in each corners]
 4+8=12 interstitial sites should be filled by cations in one cell.
 Total 4x8=32 octahedral and 8x8=64 tetrahedral sites in 8 cells.
 Actually 32+64=96 interstitial sites should be filled by cations.
 In each cell 2 octahedral and 1 tetrahedral sites are occupied. In 8 unit cells total (2x8)=16 octahedral and
(1x8)=8 tetrahedral sites are occupied.
 A (II) cation fills 1/8 (8/64)of the tetrahedral sites
 B (III) cation fills 1/2 (16/32) of the octahedral sites

Shamima Akhter Urmi, Lecturer, GCE

Inverse Spinel Structure (6:6:4)
Examples
• FeMgFeO4
• MgTiMgO4

• A (II) cation and ½ B (III) cation fills the octahedral sites.

• ½ B (III) cation fills the tetrahedral sites

Shamima Akhter Urmi, Lecturer, GCE

 Diamond Structure

 Metastable carbon polymorph at room temperature.

 Its structure is a variant of zinc blende structure.
 C atoms occupy all the positions of Zn and S.
 So each C atom is surrounded by 4 C atoms.
 Bond is totally covalent.

Shamima Akhter Urmi, Lecturer, GCE

 Graphite Structure

 More stable at room temperature than diamond.

 Graphite structure is composed of layers of
hexagonally arranged C atoms.
 Within a layer each C atom is bonded to 3 co planer
neighbor atoms by covalent bonds.
 The 4th bonding is a weak van der waals type bonding
between the layers.

Shamima Akhter Urmi, Lecturer, GCE

Shamima Akhter Urmi, Lecturer, GCE
Construction of crystals from closed packed
hexagonal layers of atoms

Shamima Akhter Urmi, Lecturer, GCE

Shamima Akhter Urmi, Lecturer, GCE
Shamima Akhter Urmi, Lecturer, GCE
Construction of crystals from square
layers of atoms

Shamima Akhter Urmi, Lecturer, GCE

Silicate Structures
Silica

A silicon–oxygen tetrahedron.

Shamima Akhter Urmi, Lecturer, GCE

Silica Glasses

Schematic representation of ion positions in a sodium–silicate glass.

Shamima Akhter Urmi, Lecturer, GCE

Simple Silicates

Five silicate ion structures formed from tetrahedra. SiO44

Shamima Akhter Urmi, Lecturer, GCE

Layered Silicates:

Schematic representation of the two-dimensional silicate Structure of kaolinite clay

sheet structure having a repeat unit formula of (Si2O5)2

Shamima Akhter Urmi, Lecturer, GCE

Crystallinity in Polymers

Shamima Akhter Urmi, Lecturer, GCE

Shamima Akhter Urmi, Lecturer, GCE