Вы находитесь на странице: 1из 105

Solid State Chemistry

Solid state chemistry is the study of the principles and concepts


underlying the synthesis, structure, bonding, reactivity, and
physical properties of solid state materials.
A subdiscipline of Chemistry, which primarily involves the study
of extended solids (Materials formed under ultrahigh pressure).
Except helium*, all substances form a solid if sufficiently cooled
at 1 atm.
Majority of solids exist in crystalline form where the atoms,
molecules, or ions are arranged in a regular repeating fashion.

The primary focus will be on the structures of metals, ionic


solids, and extended covalent structures, where extended
bonding arrangements dominate.
The properties of solids are related to its structure and bonding.
In order to understand or modify the properties of a solid, we
need to know the structure of the material.
Crystal structures are
crystallography technique.

usually

determined

by

Structures of many inorganic compounds may be initially


described in terms of simple packing of spheres.

X-ray

Brief History and Notable Contributions from Solid State Chemistry


X-ray crystallography in the early 1900s by William Bragg.
Zeolite and platinum-based catalysts for petroleum processing in the
1950s.
High purity silicon, a core component of microelectronic devices in the
1960s
Microwave dielectrics (Wireless communications) in the 1970s and colossal
magnetoresistive
High temperature superconductivity in the 1980s
Giant and colossal magnetoresistive (CMR) materials in the 1990s
Nano-, energy storage and generation and functional materials in the 2000s

Introducti
on
Solids are substances characterised by
i. definite shape
ii. definite volume
iii. non-compressibility
iv. very slow diffusion
v. rigidity and
vi. mechanical strength.

The atoms, molecules or ions in solids are closely packed and cannot move
randomly.
They are held together by strong forces (Intermolecular, interatomic, ionic forces).
Solids can be either crystalline or amorphous.
A crystal or crystalline solid is a solid material whose constituent atoms,
molecules, or ions are arranged in an ordered pattern extending in all three spatial
dimensions.

Examples of large crystals - snowflakes, diamonds, graphite and table salt.

Most inorganic solids are not crystals but polycrystals, i.e. many microscopic
crystals fused together into a single solid.
Examples: most metals, rocks, ceramics, and ice.
A third category of solids is amorphous solids, where the atoms have no
periodic structure. They have completely random particle arrangement.
Examples: glass, wax, and many plastics.
Crystal

Particles

Attractive
forces

Melti
ng
point

Other properties

Ionic

Positive
and
negative
ions

Electrostatic
attractions

High

Hard, brittle, good


electrical conductor in
molten state

London force
and dipoledipole
attraction

Low

non-conductor or
extremely poor
conductor of electricity in
liquid state

Molecula Polar
r
molecules

Quasicrystals (Dan Shechtman


)
A quasicrystal consists of arrays of atoms that are ordered but not strictly
periodic.
They have many attributes in common with ordinary crystals, such as displaying a
discrete pattern in x-ray diffraction, and the ability to form shapes with smooth, flat
faces.
Quasicrystals are most famous for their ability to show five-fold symmetry, which
is impossible for an ordinary periodic crystal

The material Ho-Mg-Zn forms


quasicrystals, which can take on
the macroscopic shape of a
dodecahedron.

Crystalline versus Amorphous solids

Amorphous

Crystalline

Random particle
arrangement

Regular geometry

Do not have sharp M.Pts

Sharp M.Pt

Isotropic

Anisotropic

No cleavage planes

Cleavage planes

No symmetry

Crystal symmetry

Intermolecular interactions
Charge-Dipole Interactions

1/r2

Dipole-Dipole Interactions

1/r3

Intermolecular interactions

London Dispersion Interactions

Hydrogen Bonding Interactions

Crystal Structure

A crystal is a solid substance having a definite geometrical shape with flat faces
and sharp edges.
Crystallography deals with geometry, properties and structures of crystalline
compounds.
Fundamental laws of crystallography
i.Law of constancy of interfacial angles- The shape and size of the crystals
may vary with crystallization conditions, but the interfacial angles ( Angle
between the two intersecting faces) remain constant.

Law of rational indices


All faces cut a given axis at distances from the origin, which bear a simple ratio to
one another

Miller indices of a given crystal face are inversely proportional to the intercepts of that
face on the various axes.

When a face intersects


i.all crystallographic axes, it has Miller Indices (hkl).
ii. two crystallographic axes and parallel to the third, has Miller Indices (0kl),
(h0l), (hk0).
iii. one crystallographic axis and parallel to others two, has Miller Indices
(h00), (00l), (0k0).

Miller Indices for planes


(0,0,1)

(0,3,0)

(2,0,0)

Find intercepts along axes 2:3:1


Take reciprocal 1/2:1/3:1
Convert to smallest integers in the same ratio 3:2:6
Enclose in parenthesis (326)

Intercepts 1
Plane (100)
Family {100} 3

Intercepts 1 1
Plane (110)
Family {110} 6

Intercepts 1 1 1
Plane (111)
Family {111} 8
(Octahedral plane)

Miller indices

It is possible to choose along the three coordinates unit distances from the origin
(a, b and c), which may or may not be of same length, such that the ratio of the
three intercepts of any plane in the crystal is given by (ha:kb:lc), where h, k and l
are integral numbers.
Say for a plane that makes intercepts 2a, 2b & 3c respectively, then the ratio of
the intercepts in terms of the standard is 2:2:3. The coefficients of a,b & c are
known as Weiss indices.
Miller indices are obtained by taking the reciprocal of Weiss indices and
multiplying throughout by the least common multiple to obtain integral values.

Miller indices
Positions within the unit cell are
specified in terms of
translations along the three
lattice vectors, e.g. the atoms
in a bcc unit cell are at (0,0,0)
and (,,).
Lattice planes are indexed by
their intercepts of the
coordinate axes. Lattice planes
are identified by their Miller
indices, (h k l). To obtain the
indices of a lattice plane, the
reciprocals of the intercepts are
taken, and the set of smallest
integers giving the same ratio
between them is determined.
These are the Miller indices for
the lattice plane, usually
represented as (h k l).

Tetrahedron inscribed inside a cube


with bounding planes belonging to the
{111} family

8 planes of {111} family forming a


regular octahedron

The (111) planes:

Law of symmetry
All crystals of the same subtance possess the same elements of symmetry
Three main types of symmetry
Plane of symmetry
Axis of symmetry
Centre of symmetry

Axes of Symmetry:
Proper axes of rotation (Cn)
Rotation with respect to a line (axis of
symmetry) which molecules rotate.
Cn is a rotation of (360/n), where n is the
order of the axis.
C2 = 180 rotation, C3 = 120 rotation, C4
= 90 rotation, C5 = 72 rotation, C6 = 60
rotation
Each rotation brings you to the
indistinguishable state for original

Planes and Reflection ()


Molecules contain mirror planes, the
symmetry element is
called a mirror plane or plane of symmetry.
h(horizontal): plane perpendicular to
principal axis
d(dihedral), v(vertical): plane colinear
with principal axis
v: Vertical, parallel to principal axis
d: parallel to Cn and bisecting two C2'
axes

Inversion, Center of Inversion (i)


A center of symmetry: A point at the center
of the molecule. (x,y,z) (-x,-y,-z).
Center of inversion can only be in a
molecule. It is not necessary to have an
atom
in the center (e.g. benzene).
Tetrahedrons, triangles, and pentagons
don't have a center of inversion symmetry

Ru(CO)6

C2H6

Symmetry
Symmetry is useful when it comes to describing the
shapes of both individual molecules and regular
repeating structures.
Point symmetry - is the symmetry possessed
by a single object that describes the repetition
of identical parts of the object.
Symmetry operations are actions such as
rotating an object or molecule.
Symmetry elements arenthe rotational
axes, mirror planes, etc., possessed by objects
Schoenflies (or Schnflies) notation Sn: one of
two conventions commonly used to describe
point groups used in spectroscopy.
Herman-Mauguin can describe the point
symmetry of individual molecules, and also the
relationship of different atoms to one another
in space (space symmetry). HermannMauguin
notationdescribe the space group of a crystal lattice
and is used in crystallography.

CRYSTAL STRUCTURE

Atoms and ions will be viewed as hard spheres. In the case of


pure metals, the packing pattern often provides the greatest spatial
efficiency (closest packing).
Ionic crystals can often be viewed as a close-packed arrangement
of the larger ions, with the smaller ions placed in the holes of
the structure.

CRYSTAL STRUCTURE

Crystals contain highly ordered molecules or atoms held together by noncovalent interactions

NaCl . has the cubic structure

Crystal lattice is a highly ordered three dimensional structure, formed by its


constituent atom or molecules or ions

An infinite set of points (represent the constituents of the crystal) repeated


regularly along a line (1D), in a plane (2D) or along the three coordinates in
space(3D).

Unit cell is the smallest building unit in space of crystal which when repeated
over and over again in 3 dimensions results in a space lattice of the crystalline
substance.

A crystalline solid possesses rigid and long-range order. In a crystalline solid,


atoms, molecules or ions occupy specific (predictable) positions.
An amorphous solid does not possess a well-defined arrangement and long-range
molecular order.
A unit cell is the basic repeating structural unit of a crystalline solid.

At lattice points:

lattice
point

Unit Cell

Unit cells in 3-dimensions

Atoms

Molecules

Ions

The simplest repeating unit in a crystal is called a unit cell. Each unit cell
is defined in terms of lattice points the points in space about which the
particles are free to vibrate in a crystal.
The structures of the unit cell for a variety of salts are shown below.

Types of Crystal Structure


1.

Cubic
- sodium chloride

4.

Rhombic
- iodine

2.

Tetragonal
- urea

5.

Monoclinic
- sucrose

3.

Hexagonal
- iodoform

6.

Triclinic
- boric acid

7.

Trigonal

Unit cell in 3D lattice is characterised by the lengths a, b and c and the


angles , and . Collectively known as unit cell parameters.
A total of seven crystal lattices are constructed from these parameters.

Bravais Lattices
1.

End-centred
i.

Monoclinic

ii.

orthorombic

2.

Face-centred
i.

Cubic (NaCl)

ii.

Orthorombic

3.

Body-centred
i.

Cubic tetragonal

ii.

Orthorombic

Total of 14 possible types of


unit cells

For drugs, only 3 types:


1.

Triclinic

2.

Monoclinic

3.

Orthorombic

The unit cell is the


simplest repeating unit
in the crystal.
Opposite faces of a
unit cell are parallel.
The edge of the unit
cell
connects
equivalent points.

Three types of crystal structure

Shared by 8 unit
cells

Shared by 2 unit
cells

When silver crystallizes, it forms face-centered cubic cells. The unit cell edge
length is 408.7 pm. Calculate the density of silver.

d=

V = a3

atoms/unit cell in a face-centered cubic cell

m = 4 Ag atoms x

d=

m
V

= (408.7 pm)3 = 6.83 x 10-23 cm3

107.9 g

mole Ag

1 mole Ag
6.022 x 1023 atoms

7.17 x 10-22 g
6.83 x 10

-23

cm

= 7.17 x 10-22

= ___________________

Extra distance =

BC + CD =

2d sin

= n

(Bragg Equation)

X rays of wavelength 0.154 nm are diffracted from a crystal at an angle of 14.170.


Assuming that n = 1, what is the distance (in pm) between layers in the crystal?

n = 2d sin

d=

n=1

= 14.170

1 x 154 pm

2sin

2 x sin14.17

= 0.154 nm = 154 pm

= ____________

Types of Solids
Ionic Crystals or Solids

Lattice points occupied by cations and anions

Held together by electrostatic attraction

Hard, brittle, high melting point

Poor conductor of heat and electricity

CsCl

ZnS

CaF2

Types of Solids
Molecular Crystals or Solids

Lattice points occupied by molecules

Held together by intermolecular forces

Soft, low melting point

Poor conductor of heat and electricity

Types of Solids
Network or covalent Crystals or Solids

Lattice points occupied by atoms

Held together by covalent bonds

Hard, high melting point

Poor conductor of heat and electricity

carbon
atoms

diamond

graphite

Types of Solids
Metallic Crystals or Solids

Lattice points occupied by metal atoms

Held together by metallic bond

Soft to hard, low to high melting point

Good conductor of heat and electricity

Cross Section of a Metallic Crystal


nucleus &
inner shell e-

mobile sea
of e-

Types of Crystals

Types of Crystals and General Properties

Radius ratios, coordination numbers, and


coordination environment for both the
cations and anions for four representative
AB-type ionic lattices.

Different types of Lattice planes


Interplanar spacing

Extended Covalent Arrays


Several elements for covalently
bonded solids at room temperature,
including B, C, Si, Ge, P, As, Se, Te.
Unit cell of C (diamond).
All C-C bond length are identical (1.54
).
Covalent C-C bonds are strong and
the
rigid 3D network of atoms give
diamond
the hardest substance known and it
also
has a high melting point.
Unit cell of C (graphite).
All C-C bond length are identical (1.42
A).
Two dimensional layers of carbon

Covalent Network Crystals


A
covalent
network
crystal
is
composed of atoms or groups of atoms
arranged into a crystal lattice held
together by an interlocking pair of
covalent bonds.
Covalent bonds, the sharing of one or
more pairs of electrons in a region of
overlap between two or more atoms,
are directional interactions as opposed
to ionic and metallic bonds that are
nondirectional.
These interactions are directional in
nature.
Compounds
that
form
covalent
network crystals include SiO2, C, Si,
BN.

Metallic Crystals
The structure of metals may be
visualized as a lattice of cations held
together by a Fermi sea (of
electrons).
The electrons are no longer
associated with any particular cation.
Valence electrons are delocalized
about the lattice of cations.
This type of electron movement
enables high conductivity typically
associated with metals.

Ionic crystals
Na+

Ionic bonds are nondirectional the


electrostatic forces dominate.
Many salts form ionic crystals NaCl,
CsCl, CaF2, KNO3, and NH4Cl.

Cl-

Ionic bonding in
NaCl

An amorphous solid does not possess a well-defined arrangement and long-range


molecular order.
A glass is an optically transparent fusion product of inorganic materials that has cooled
to a rigid state without crystallizing

Crystalline
quartz (SiO2)

Non-crystalline
quartz glass

Formu
la

Cation :
anion
Coordinati
on

Type and number


of holes occupied

Examples:
Cubic close
packing

Examples:
Hexagonal
close packing

MX

6:6

All octahedral

4:4

Half tetrahedral;
every
alternate site
occupied

Sodium chloride:
NaCl,
FeO, MnS, TiC
Zinc blende: ZnS,
CuCl, -AgI

Nickel arsenide:
NiAs, FeS, NiS
Wurtzite: ZnS,
-AgI

MX2

8:4
6:3

All tetrahedral
Half octahedral;
alternate layers have
fully occupied sites

Fluorite: CaF2, ThO2,


ZrO2, CeO2
Cadmium chloride:
CdCl2

None
Cadmium iodide:
CdI2

MX3

6:2

One-third octahedral;
alternate pairs of
layers
have two-thirds of
the
octahedral sites
occupied.

Bismuth iodide:
BiI3, FeCl3, TiCl3,
VCl3.

M 2 X3

6:4

Two-thirds octahedral

Corundum: Al2O3, -Fe2O3,


V2O3, Ti2O3, Cr2O3

ABO3

Structures
related to close-packed arrangements
of anions
Two-thirds octahedral
Ilmenite: Fe O
2

Lattice Packing

Elemental Cu and Ni each uses fcc packing and


both have very similar lattice parameters (e.g.
internuclear distances).
If we heat the two elements to melting and then
mix together and cool slowly, the fcc packing is
retained, but with a random placement of the two
elements.
Known as a solid solution alloy.

Lattice Packing

Elemental Cu and Au each uses fcc packing but


have very different lattice parameters (Au >>
Cu).
Upon reaction (melt and cool) yields a
specifically ordered arrangement = an
intermetallic compound, which may not conform
to oxidation state rules.

hexagonal close
packed (hcp)
ABABAB
Space Group:
P63/mmc

HCP

cubic close
packed (ccp)
ABCABC
Space Group:
Fm3m

In ionic crystals, ions pack themselves so as to maximize the attractions and


minimize repulsions between the ions.
A more efficient packing improves these interactions.
Placing a sphere in the crevice or depression between two others gives
improved packing efficiency.

A ccp structure has a fcc unit cell.

Different Types of Crystal


Lattices

Close
Packing

Holes in Close Packed


Crystals
There are two
types of holes
created by a closepacked
arrangement.
Octahedral holes
lie within two
staggered
triangular planes
of atoms.

Holes in Close Packed


Crystals
The coordination
number of an atom
occupying an
octahedral hole is
6.
For n atoms in a
close-packed
structure, there are
n octahedral holes.

Octahedral Holes
The green atoms are
in a cubic closepacked arrangement.
The small orange
spheres show the
position of octahedral
holes in the unit cell.
Each hole has a
coordination number
of 6.

Octahedral Holes
The size of the octahedral hole =
0.414 r
where r is the radius of the cubic
close-packed atom or ion.

Holes in Close Packed


Crystals
Tetrahedral holes are formed by a planar
triangle of atoms, with a 4th atom covering
the indentation in the center. The resulting
hole has a coordination number of 4.

Tetrahedral Holes
The orange spheres
show atoms in a
cubic close-packed
arrangement. The
small white spheres
behind each corner
indicate the
location of the
tetrahedral holes.

Tetrahedral Holes
For a close-packed
crystal of n atoms,
there are 2n
tetrahedral holes.
The size of the
tetrahedral holes =
0.225 r
where r is the radius
of the close-packed
atom or ion.

Atoms/Unit
Cell
For atoms in a cubic unit cell:
Atoms in corners are within the cell

For atoms in a cubic unit cell:


Atoms on faces are within the cell
For atoms in a cubic unit cell:
Atoms in corners are within
the cell
Atoms on faces are within the
cell
Atoms on edges are within
the cell

# of Atoms/Unit Cell
For atoms in a
cubic unit cell:
Atoms on faces
are within the
cell

# of Atoms/Unit Cell
A facecentered cubic
unit cell contains
a total of 4
atoms: 1 from
the corners, and
3 from the faces.

# of Atoms/Unit Cell
For atoms in a cubic unit cell:
Atoms in corners are within
the cell
Atoms on faces are within
the cell
Atoms on edges are within
the cell

Other Metallic Crystal


Structures
Body-centered cubic unit cells have an
atom in the center of the cube as well as
one in each corner. The packing efficiency
is 68%, and the coordination number = 8.

Other Metallic Crystal


Structures
Simple cubic (or primitive cubic) unit cells
are relatively rare. The atoms occupy the
corners of a cube. The coordination number
is 6, and the packing efficiency is only
52.4%.

Polymorphism
Many metals exhibit different crystal
structures with changes in pressure
and temperature. Typically, denser
forms occur at higher pressures.
Higher temperatures often cause
close-packed structures to become
body-center cubic structures due to
atomic vibrations.

Atomic Radii of Metals


Metallic radii are defined as half
the internuclear distance as
determined by X-ray crystallography.
However, this distance varies with
coordination number of the atom;
increasing with increasing
coordination number.

Atomic Radii of Metals


Goldschmidt radii correct all metallic
radii for a coordination number of 12.
Coord
12
8
6
4

#
Relative radius
1.000
0.97
0.96
0.88

Most Common MX
Structures
NaCl structure
Na+ in fcc lattice
Cl- in Oh holes

CsCl structure
Cl- in simple cubic lattice
Cs+ in cubic hole

Zinc blende (ZnS) structure


S-2 in fcc lattice
Zn+2 in alternating Td holes

Most Common MX2 Structures

Fluorite (CaF2) structure


Ca+2 in fcc lattice
F- in all Td holes
Rutile (TiO2) structure
Ti+2 in body centered cubic lattice
Oxygens in lower symmetry array.

Common Crystal Types

1. The Rock Salt (NaCl)


structureThe coordination
number is 6 for both
ions.

Common Crystal Types

2. The CsCl structureChloride ions occupy the


corners of a cube, with a cesium
ion in the center (called a cubic
hole) or vice versa. Both ions
have a coordination number of 8,
with the two ions fairly similar in
size.

Common Crystal Types


3. The Zinc-blende or Sphalerite structureAnions (S2-) ions are in a face-centered cubic
arrangement, with cations (Zn2+) in half of the
tetrahedral holes.

Common Crystal Types


4. The Fluorite (CaF2) and Antifluorite structures
A face-centered cubic arrangement of Ca2+
ions with F- ions in all of the tetrahedral holes.

Common Crystal Types


4. The Fluorite (CaF2) and Antifluorite
structures
The antifluorite structure reverses the
positions of the cations and anions. An
example is K2O.

The rock-salt crystal structure. Each atom has six


nearest neighbors, with octahedral geometry.

rNa= 0.102 nm ; rCl= 0.181 nm


rNa/rCl= 0.564
cations (Na+) prefer octahedral sites

MgO and FeO also have the NaCl structure

AX Crystal Structures
Since 0.732 < 0.939 < 1.0, cubic
sites preferred. So each Cs+has 8
neighbor ClAXType Crystal Structures include
NaCl, CsCl, and zinc blende

AX2Crystal Structures
Fluorite structure

Calcium Fluorite (CaF2)


Cations in cubic sites
UO2,ThO2, ZrO2, CeO2
Antifluorite structure positions of cations and anions re

ABX3Crystal Structures
Perovskite structure
Ex: complex oxide BaTiO3

SPINELS
Class of minerals of general formula A2+B3+2O2-4
Crystallise in the cubic (isometric) crystal system, with the oxide anions arranged in a
cubic close-packed lattice and the cations A and B occupying some or all of the
octahedral and tetrahedral sites in the lattice.
A and B can be divalent, trivalent, or quadrivalent cations, including magnesium, zinc,
iron, manganese, aluminium, chromium, titanium, and silicon.
Although the anion is normally oxide, the analogous thiospinel structure includes the
rest of the chalcogenides.
A and B can also be the same metal under different charges, as is the case with
magnetite, Fe3O4 (as Fe2+Fe3+2O2-4), which is the most abundant member of the Spinel
group.
Spinels are grouped in series by the B cation.
A common example of a normal spinel is MgAl2O4.
Mg2+
Al3+
O2-

Spinel is the name given to the mineral MgAl2O4. It has a common structural
arrangement shared by many oxides of the transition metals with formula
AB2O4.
In the normal pattern the oxygens form a cubic close packed (ABCABC or face
centred) array and the Mg(II) and Al(III) sit in tetrahedral (1/8 occupied) and
octahedral (1/2 occupied) sites in the lattice, giving a Unit Cell with 8 Mg's, 16
Al's and 32 O's.
An inverse spinel is an alternative arrangement where the divalent ions swap
with half of the trivalent ions so that the M(II) now occupy octahedral sites
i.e. B(AB)O4. NiFe2O4
In this case Ni(II) is octahedral and half of the Fe(III) are tetrahedral.
Complexes that share this structure include a number of 1st row TM oxides and
sulfides.

Spinel (AB2O4) structures


Normal Spinel: MgAl2O4
Similar structures include FeCr2O4, Mn3O4,
FeCr2S4, ZnAl2S4 and ZnCr2Se4

Inverse Spinel Co3O4


Examples of inverse spinel structures include
Fe3O4, TiMn2O4, TiFe2O4, TiZn2O4 & SnZn2O4
Examples of partially inverse spinel
structures include MgFe2O4, MnFe2O4 and
NiAl2O4

Normal spinel structures are usually cubic close-packed oxides with one
octahedral and two tetrahedral sites per oxide.
The tetrahedral points are smaller than the octahedral points. B3+ ions occupy the
octahedral holes because of a charge factor, but can only occupy half of the
octahedral holes.
A2+ ions occupy 1/8 of the tetrahedral holes. A common example of a normal
spinel is MgAl2O4.
Inverse spinel structures however are different in the cation distribution, in that all
of the A cations and half of the B cations occupy octahedral sites, while the other
half of the B cations occupy tetrahedral sites. A common example of an inverse
spinel is Fe3O4, if the Fe2+ (A2+) ions are d6 high-spin and the Fe3+ (B3+) ions are d5
high-spin.

Spinels

Spinel

Magnetite is another compound with mixed-valent iron atoms .


It has the AB2X4 spinel structure

Magnetite has the empirical formula Fe3O4 , or Fe2+(Fe3+O2)2 , ferrous


ferrite . Its formula as a spinel would be Fe3+tetFe2+octFe3+octO4 , where
"tet" and "oct" stand for tetrahedral and octahedral coordinations by
the oxide anions . In the above model , the blue spheres represent the
tetrahedral iron(III) cations , and the red spheres are the octahedrally
coordinated iron(II) and (III) cations . The oxide anions are shown as
the green spheres . Because of the fortuitous inverse nature of the
magnetite structure , ferrous and ferric cations are both in the similar
octahedral coordination by oxides . In "normal" spinels , such as the
mineral spinel itself (magnesium aluminate) , the A cation is
tetrahedral and the M cations are both octahedral :

This close-packed spheres representation provides a wider view


of the spinel structure , showing the regular packing order of the
tetrahedral and octahedral cations among the anions .

Point defects in non-ionic and ionic solids occur in different ways, as described by following chart:

(i) Stoichiometric Defects : Also called intrinsic or


thermodynamic defects. Due to this defects the stoichiometry (i.e.,
the ratio of cations and anions as per the chemical formula) of the
solid is not disturbed.
Non-ionic solids show following defects:
(A) Vacancy Defects : This defect arises due to a vacancy created
in the lattice site. This results in decrease in density of the
substance. Generally, this defect arises on heating of a substance.
(B) Interstitial Defect : When some atoms or molecules occupy
the interstitial site, this is called interstitial defects. Due to this
defect density of the substances increases.

Ionic solids have following defects instead of the above two


defects because they must maintain electrical neutrality.
(C) Frenkel Defect : Also called dislocation defect because in this
defect cation (smaller ion) is dislocated from its normal site to an
interstitial site. Thus vacancy defect arises at the original site
while interstitial defect at the new location. Due to this defect
there is no change in the density of substance. This defect is
shown by the ionic compounds having large difference in the size
of ions. For example ZnS, AgCl, AgBr, AgI, etc.
(D) Schottky Defect : Basically it is a vacancy defect but in this
case number of missing cations and anions are equal so that
electrical neutrality of the substance is maintained. Like vacancy
defect, Schottky defect also decreases the density of the
substance. There is one Schottky defect per ions. This defect is
shown by the ionic compounds having cations and anions of
almost similar size. For exampleNaCl, KCl, CsCl, AgBr, etc.

Schottky defect of crystals


Equal number of cations and anions are missing from lattice sites.
Electrical neutrality is maintained.
Decreases density of the material.
Schottky defects are found in NaCl, KCl, KBr etc.

Frenkel DefectAn ion missing from the lattice occupies any interstitial void.
Electrical neutrality and stoichiometry remains same.
Density is not affected.This defect are found in AgCl, AgBr etc.
This defect are found in AgCl, AgBr etc.

Оценить