CRYSTAL STRUCTURE

Atomic structure
Quantum theory & wave mechanics
Bohr atom
Electron orbits
Orbital shape, density, electron distribution

Interatomic bonds
Ionic bonds
Covalent bonds
Van der Waals bonds
Metallic bonds
Atomic bonding in solids
Ionic
Covalent
Molecular
Metallic
Hydrogen

Ionic crystals
Madelung constant
depends on the geometry of the crystal
structure and is characteristic for a particular
structure type
Example: NaCl structure: = 1.748
CsCl structure: = 1.763
zincblende structure: =
1.748

Madelung constant represents the Coulomb
energy of an ion pair in a crystal relative to the
Coulomb energy of an isolated ion pair
> 1 but not far
Penurunan Madelung constant sbb:
The energy of one ion of charge Z
i
e in a crystal (ex
NaCl) = summation of its interaction with the other j
ions in the crystal

Ei =
(

+
E0
n
j
ij
j
j i
Ri
B
Ri
e eZ Z
t 4
Ionic crystals are
characterized by:
Strong infrared absorption
Transparency in the visible wavelength
Low electrical conductivity at low temp,but
good electrical conductivity at high temp
Compounds of metal ions with group III
anion are strongly ionic.
Ex: NaCl, LiF
Compounds of metals with oxygen are
largely ionic.
Ex: MgO, Al2O3, ZrO2
Compounds with with higher atomic
weight elements of group VI (S, Se, Te)
which have lower electronegativity are
increasingly less ionic.


Ionic bonds
The strength of ionic bonds increases as the
valence increases.
The electron distribution in ions is nearly
spherical
The interatomic bond (since it arises from
coulombic forces) is nondirectional
Covalent crystals
A pair of electron is concentrated in the space
between the atoms
Covalent crystals form when a repetitous
structure can be built up consistently with the
strong directional nature of the covalent
bond
Examples:
C form 4 tetrahedral (covalent)
bond
In methane, CH4: all the tetrahedral bonds are
used up in forming a molecule so that no
electron are available for forming additional
covalent bonds. No covalent crystal can be built
up
In diamond: covalent crystal is formed. Each C is
surrounded by 4 other C atoms. The tetrahedral
(fourfold) coordination doesnot allow dense
packing
Covalent crystal (ex: diamond,
SiC)
Have high hardness
High melting point
Low electrical conductivity (when pure) at low
temp
Formed between atoms of similar
electronegativity which are not close in
electronic structure to inert gas config: C, Ge, S,
Te etc
Molecular bond
In organic molecules, inert gases. Atoms are
bound together in solid phase by means of weak
vd waals forces: weak, compressible, low melting
point, low boiling point.
These forces occur in all crystals and important
only when other forces are absent
In ceramics: the bonding together of silicate
sheet in clays.
Hydrogen bond crystal
In inorganic crystals
H ions form a rather strong bonds between
two anions
Metal crystals

Crystal structures
The most stable crystal structures are those
that have the densest packing of atoms;
consistent with other requirements, such as
the no of bons per atom, atom size and bond
direction.
Crystal structures
Simple cubic
Close-packed cubic
Close-packed hexagonal
Simple cubic structure
48% void space (not very
dense)
6 nearest neighbours

Typical structures with
anions forming simple
cubic
5. Cesium chloride
structure
Formula = AX
e. g. CsCl, CsBr
Anions = simple cubic
Cations = fill all of
the cubic centres
CN = 8 for both
anions and cations
Close-packed cubic structure
26 void volume
12 nearest neighbours
Example of the most simple unit cell: face
centered cubic
For fcc, there are two kinds of interstices:
octahedral and tetrahedral

Close-packed hexagonal
structure

Space lattice
32 permissible arrangements 14 different
Bravais or space lattice, grouped into 6
system:
Triclinic
Monoclinic
Orthorhombic
Tetragonal
Hexagonal
cubic
Grouping of ions and Paulings
Rules
For crystals having a large measure of ionic
bond character (halides, oxides and silicates),
the structure is (in large part) determined on
the basis of how + and ions can be packed
to maximize electrostatic attractive forces
and minimize electrostatic repulsion. The
stable array of ions in a crystal is the one with
the lowest energy.
Ionic crystal structure
Paulings Rules
1
st
rule
Coordination polyhedron of anions is
formed about each cation (and vice versa)
Cation anion distance
Coordination number (CN) = the number of
anions surrounding a cation
A given coordination is stable only when
the ratio of cation to anion radius is greater
than a critical value (#9)
Critical radius ratio govern the
coordination of cation about anion (#9)
Since anions are larger than cations, crit
radius ratio is determined by the
coordination of anions about the cation
cation coordination polyhedron.
Geometry would permit the structure to
form with any one of a number of smaller
coordination number. The most stable
structure however always has the
maximum permissible coordination
number (#9).

Pauling,s 2
nd
Rule
Local electrical neutrality
The formal charge of cation divided by its CN
= ionic bond strength (#10)
Example: Si, valence 4; tetrahedral coordination
bond strength = 4/4 = 1
Al
3+
, octahedral coordination; bond strength = 3/6
= , regardless whether all coordinating anions
are of the same species.
In a stable structure, the total strength of
the bonds reaching an anion from all
surrounding cations should be equal to the
charge of the anion.
Example: SiO2 two bonds of strength 1 reached
the shared O ion from the surrounding Si ions
2 x 1= 2 == valence of O.
Implying that in Si2O7 no additional cation may
be bonded to the shared O
MgAl2O4 (spinel structure). Each O
2-
is
surrounded by one Mg
2+
which donate bond of
strength 2/4 and three Al
3+
which donate three
bonds of strength 3/6: 2 == (1)(2/4) + (3)(3/6)
#10
Paulings 3
rd
rule
The separation of cations within the
polyhedron decreases as the polyhedron
successively shared corners, edges and faces
and the repulsive interaction between cations
accordingly increases
Pauling,s 4
th
rule
Polyhedron formed about cations of lowest
CN and high charge tend to be linked by
corner
--- the repulsive interaction between a pair of
cations increases as the square of their charge and
that the separation of caations within a
coordinated polyhedron decreases as the CN
becomes smaller
Pauling,s 5
th
rule
The number of different constituents in a
structure tends to be small
--- follow from the difficulty encountered in
efficiently packing into a single structure ions and
coordination polyherda of different size.
Oxide structures
Rock salt
Wurtzite
Zincblende
Spinel
Corundum
Rutile
Cesium chloride
Fluorite

Antifluorite
Perovskite
Ilmenite

Derivative structures,
mechanism
Substitution of different atoms
Omission of atoms
Addition of an atom to an unoccupied site
(stuffing)
Distortion of an atomic array
Silicate structures
Radius ratio Si-O = 0.29 tetrahedral
coordination (CN = 4)
Bond strength = 4/4 = 1 O may be
coordinated with only two Si low CN of O
makes silica not so dense

Silicates classification
are based on the number of shared O ions per
[SiO4] tetrahedra (bridging oxygen).
Silicates characteristics largely depend on
the nature of the tetrahedral arrangement.
Inversely, the characteristics and behaviour
of silicates provide many clues to their
internal structure.

Silicates classification
1. Independent silicates (orthosilicates)
2. Ring silicates (cyclosilicates)
3. Chain/linear silicates (polysilicates)
4. Layer/sheet silicates (phyllosilicates)
5. Framework silicates

Orthosilicates
The silica tetrahedra do not share any O bonds

examples
Cyclosilicates
the tetrahedra are joined forming ring, each
tetrahedron shares two O with the adjacent
tetrahedra. The rings are complex groups of
(SiO
3
)
3
-6
or (SiO
3
)
6
-12
. Charges are balanced by
metal ions holding the rings together in a
crystal structure.
examples
polysilicates
a linear open structure of tetrahedra in which
each tetrahedron share two O with its adjacent
tetrahedra. In effect a giant negative ion is
created with an indefinite number of tetrahdera,
each carrying 2 negative charges. The chains are
aligned and held together by metal ions other
than silicon.
pyroxenes
Phyllosilicates
are formed when each tetrahedron shares 3 O with
other tetrahedra. The resulting giant negative ions
extends imdefinitely in 2D. The sheet consists of
(Si2O5)
-2
units held together in stacks by metal
ions.
Framework silicates
the tetrahedra shares all of its 4 O with
the other tetrahedra forming a framework
structure extending in 3D. Al can substitute
Si as the centre of the tetrahedra. If part
of the [SiO4] tetrahedra are substituted by
[AlO4]
-
tetrahedra, the corresponding
minerals are termed aluminosilicates. As Al
has 3 positive charges while the 4 O give 4
negative charges, the resultant tetrahedra
has to be charge-balanced by a cation,
usually of the alkali and alkaline-earth
metals.
Silica, crystalline SiO2
Polymorphs: quartz, tridymite and
cristobalite, each exist in two or three modif.
SiO2, silica are both monotropic and
enantiotropic. and quartz are two stable
form of silica showing enantiotropic
behaviour.
and cristobalite are two metastable form
of silica which are enantiotropic wrt one
another but monotropic to the stable forms
of and quartz.
enantiotropy
Type of polymorphism in which each phase
posses a definite range of stability
It is a common type

Monotropy
One that posseses more than one crystalline
form but where one form is stable over the
whole temp range and the other form is
merely metastable at all temp
Derivative structures, of
silicates
Structures that are derived from a more
simple one; by distortion or by substitution of
different chemical species.
Examples: quartz, tridymite and cristobalite,
all have low-temp structures that are
distorted from the more symmetrical high-
temp structures (Fig 2-32)
Examples; in stuffed silica structures in
which Si
4+
is replaced by Al
3+
.
LiAlSiO
4
, eucryptite, is a stuffed derivative
of quartz
Clay minerals