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Crystal Structures
Lattice - A collection of points that divide space into smaller
equally sized segments.
Basis - A group of atoms associated with a lattice point.
- it has a chemical composition that is either the same as
the formula unit, or an integer multiple of the formula unit.
Unit cell - A subdivision of the lattice that still retains the overall
characteristics of the entire lattice.
Arrangements in which atoms contact at least six other atoms will be referred to as
Close Packed.
(c) 2003 Brooks/Cole Publishing / Thomson Learning™
8 cubes model
RC/RA =0.8
CN=8
A.3) Zinc Blende structure
• looks like FCC, but with other atoms in different holes.
Also SiC
Applications:
opacifying pigment for paints, paper and fabric
B.3 TiO2 unit cell
n’ (1) = 2 ; n’ = 2
Anion balance: Number of anion in the unit cell
Therefore, based on
n’ (2) = 4 ; n’ = 2 calculations, the number of
formula units equals 2.
C) AmBnXp structures – Same cations with differing valences
are incorporated in an anion sublattice.
C.1: perovskites
ABO3 is the chemical formula with structure considered
as FCC-derivative.
Titanates and Zirconates are used in electroceramic
applications.
Lead titanate-lead zirconate solid solutions have been
used as speakers and microphones, sonar transducers,
ultrasonic cleaners, and actuators for high precision
positioning.
• A ternary (3 component) structure:
Perovskite.
The perovskite unit cell showing the A and B site cations and
oxygen ions occupying the face-center positions of the unit cell.
Note: Ions are not show to scale.
C.2: Spinels
---- normal spinel– cubic close packed anion
arrangement
The unit cell contains eight FCC oxygen
subcells in a cubic array. It has 32 octahedral (1/2
occupied) interstices and 64 tetrahedral interstices
(1/8 occupied).
** where all of the B atoms occupy octahedral sites and all of the A atoms
occupy tetrahedral sites
AB2O4 - normal
A: M2+ (Fe, Mg)
B: M3+ (Al, Fe, Cr)
Spinel structure – top view
Inverse-spinels
** all of the A and half of the B atoms (in AB2O4) occupy the octahedral
sites and the other half of the B atoms occupy the tetrahedral sites
DEFECT-SPINEL FORMULA:
Density
n' ( M C M A )
weight of ions within unit cell
volume of unit cell VC N Av
Where n’= number of formula units within the unit cell
M C = sum of atomic weights of all cations within unit cell
a M 4(A Na A Cl )
V a3 NA
4 ions (22.99 35.45) g/mol
2[(0.102x1 0 7 0.181x10 7 )]cm 3 (6.023x10 23 )ions/mol
2.14 g/cm 3
(actual 2.16g/cm 3 )
(c) 2003 Brooks/Cole Publishing / Thomson Learning
Corundum structure of alpha-alumina (α-AI203).
Given: a and c and density of alumina
find the APF.
Surprise Quiz:
Solution:
Assignment:
Allotropic or Polymorphic
Transformations
Rule 3
Shared edges, and particularly faces of two anion polyhedra in a
crystal structure decreases its stability
Figures for rule 3
Rule 4
In a crystal structure containing several cations, those of high valency
and small coordination number 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. Thus, if they do not
share polyhedral elements they can be better shielded from the effects of
other positive charges in the crystal structure.
Rule 5, The principle of Parsimony
The number of different kinds of constituents in a crystal tends to be
small.
- This means that there are only a few different types of cation and anion sites in a
crystal. Even though a crystal may have tetrahedral sites, octahedral sites, and cubic
sites, most crystals will be limited to this small number of sites, although different
elements may occupy similar sites.
1. Diamond
Diamond film by CVD
2. Graphite
Discovered in 1985
3. Fullerenes 20 hexagons + 12 pentagons
FCC packing
Buckytubes, ...
(c) 2003 Brooks/Cole Publishing / Thomson Learning
(a) Tetrahedron and (b) the diamond cubic (DC) unit
cell. This open structure is produced because of the
requirements of covalent bonding.
A test of the radius ratio rules for binary 1:1 compounds
Reasons for inadequacy of prediction
based on radius ratio:
Silica (SiO2)
Quartz,
Cristobailite,
tridymite
Layer silicates
Kaolinite clay
Ionic-covalent
Sheet structures!
Van der Wall: between the double-layers e.g., Mica
Salient points for NBOs:
1) The number of NBOs is proportional to the number of moles
of alkali or alkali-earth metal oxide added.
2) The addition of alkali or alkali-earth metal oxides to silica
must increase the overall O/Si ratio of the silicate.
3) Increasing the number of NBOs results in the progressive
breakdown of the silicate structure into smaller units.
Si4+
O2-