Classification of solids:

Crystalline and Amorphous solids:

S.No. Crystalline Solids Amorphous solids

1 Regular internal arrangement of particles irregular internal arrangement of particles
2 Sharp melting point Melt over a rage of temperature
3 Regarded as true solids Regarded as super cooled liquids or pseudo solids
4 Undergo regular cut Undergo irregular cut.

5 Anisotropic in nature Isotropic in nature

Based on binding forces

Crystal Classification
Unit Particles Binding Forces Properties Examples
Atomic Atoms London dispersion forces
Soft, very low melting, poor thermal
Noble gases
and
electrical conductors
Molecular Polar or Vander Waals forces Fairly
(Londonsoft, low to moderately Dry
highice
melting
(solid, methane
non polar molecules
dispersion, dipole dipole
points,
forces
poor thermal and electrical conductors
hydrogen bonds)
Ionic Positive and negative
Ionic bonds
ions Hard and brittle, high melting NaCl,
points,ZnS
high
heats of fusion, poor thermal and electrical
conductors
Covalent Atoms that are connected
Covalent bonds
in Very hard, very high melting points,
Diamond,
poorquartz, silicon
covalent bond network thermal and electrical conductors

Metallic Solids
Cations in electron
Metallic
cloudbonds Soft to very hard, low to very All
highmetallic
meltingelements, for
points, excellent thermal and electrical
example, Cu, Fe, Zn
conductors, malleable and ductile

Bragg Equation:

n = 2dsin,

Where d= distance between the plane

n = order of refraction

= angel of refraction

= wavelength
 Crystal Systems:

Total number of crystal systems: 7

Total number of Bravais Lattices: 14

Crystal Systems
Bravais Lattices Intercepts Crystal angle Example
Cubic Primitive, Face Centered, Bodya Centered
=b=c a = b = g = 90o Pb,Hg,Ag,Au Diamond, NaCl,
ZnS
Orthorhombic b c Enda = b = g = 90o
Primitive, Face Centered, Bodya Centered, KNO2, K2SO4
Centered
Tetragonal Primitive, Body Centered a=bc a = b = g = 90o TiO2,SnO2
Monoclinic Primitive, End Centered abc a = g = 90 , b 90 CaSO4,2H2O
o o

Triclinic Primitive abc abg900 K2Cr2O7, CaSO45H2O

Hexagonal Primitive a=bc 0 o
a = b = 90 , g = 120Mg, SiO2, Zn, Cd
RhombohedraPrimitive a=b=c a = g = 90o, b 90o As, Sb, Bi, CaCO3

Number of atoms in unit cells.

Primitive cubic unit cell:

Number of atoms at corners = 81/8 =1

Number of atoms in faces = 0
Number of atoms at body-centre: =0
Total number of atoms = 1

Body-centred cubic unit cell:

Number of atoms at corners = 81/8 =1
Number of atoms in faces = 0
Number of atoms at body-centre: =1
Total number of atoms = 2

Face-centred cubic or cubic-close packed unit cell:

Number of atoms at corners = 81/8 =1

Number of atoms in faces = 61/2 = 3

Number of atoms at body-centre: = 0

Total number of atoms = 4

Packing Efficiency

Volume occupied by all the atoms present in unit cell / Total volume of unit cell)100
 Relation between edge length a and
Close structure Number of atoms per unit cell z. Packing Efficiency
radius of atom r
hcp and ccp or fcc 4 r = a/(22) 74%
bcc 2 r = (3/4)a 68%
Simple cubic lattice 1 r = a/2 52.4%

Density of crystal lattice:

r =(Number of atoms per unit cell Mass number)/(Volume of unit cell NA)

or

Octahedral and Tetrahedral Voids:

Number of octahedral voids = Number of effective atoms present in unit cell

Number of tetrahedral voids = 2Number of effective atoms present in unit cell

So, Number of tetrahedral voids = 2 Number of octahedral voids.

Coordination numbers and radius ratio:

Coordination numbers
Geometry Radius ratio (x) Example
2 Linear x < 0.155 BeF2
3 0.155 x < 0.225 AlCl3
Planar Triangle
4 0.225 x < 0.414 ZnS
Tetrahedron
4 0.414 x < 0.732 PtCl42-
Square planar
6 0.414 x < 0.732 NaCl
 Octahedron
8 Body centered cubic 0.732 x < 0.999 CsCl

Classification of Ionic Structures:

Structures Descriptions Examples

- +
Rock Salt Structure Anion(Cl ) forms fcc units and cation(Na ) occupyNaCl,octahedral
KCl, LiCl, RbCl
voids. Z=4 Coordination number =6
Zinc Blende Structure Anion (S2-) forms fcc units and cation (Zn2+) occupy ZnSalternate
, BeO
tetrahedral voids Z=4 Coordination number =4
Fluorite Structures Cation (Ca2+) forms fcc units and anions (F-) occupy CaFtetrahedral
2, UO2, and ThO2
voids Z= 4 Coordination number of anion = 4 Coordination
number of cation = 8
Anti- Fluorite Structures Na2O, K2O and Rb2O.
Oxide ions are face centered and metal ions occupy all the
tetrahedral voids.
Cesium Halide Structure Halide ions are primitive cubic while the metal ion Alloccupies
Halides the
of Cesium.
center of the unit cell.
Z=2
Coordination number of = 8
Pervoskite Structure One of the cation is bivalent and the other is tetravalent.
CaTiO3,The
BaTiO3
bivalent ions are present in primitive cubic lattice with oxide ions
on the centers of all the six square faces. The tetravalent cation is
in the center of the unit cell occupying octahedral void.
Spinel and Inverse Spinel Spinel :M2+M23+O4, where M2+ is present in one-eighthMgAl2of O4 , ZnAl2O4, Fe3O4,FeCr2O4 etc.
3+
tetrahedral voids in a FCC lattice of oxide ions and M ions are
Structure present in half of the octahedral voids. M2+ is usually Mg, Fe, Co,
Ni, Zn and Mn; M3+ is generally Al, Fe, Mn, Cr and Rh.
 Defects in crystal:

Any departure from perfectly ordered arrangement of the constituent particles in the crystal called imperfection
or defect.

The defects in the crystal are arises when crystallization takes place at the fast or moderate rates because the
constituent particles does not get sufficient time to arrange in perfect order.

Types of the point defects:-

1. Stoichiometric defects 2. Non stoichiometric defects 3. Impurity defects

1. Stoichiometric- Defects If imperfection in the crystal are such that the ratio between cation and onions
remains same. Stoichiometry of substance do not disturbed defect is called stoichiometric defect these defects
are of the following types.

1. Schottky Defects

Some of the lattice points in a crystal are unoccupied, which is called lattice vacancy or holes
Appears in ionic compounds in which anions and cations are of nearly same size.
Decreases the density of lattice
Electrical neutrality is same
Electrical conductance slightly increases.
Entropy increases.

Conditions- Strong should have strong ionic characters,

cation and anion should have similer in size and coordination
number should be high.

Examples: NaCl and KCl,CsCl AgBr

2. Frenkel Defects

Ion dislocate from its position and occupies an interstitial position between the lattice points
Appears in crystals in which the negative ions are much larger than the positive ion.
Does not affect density of the crystal.

Conditions- should have difference in size, low coordination number,electrical conductance increases more
than schottky
Examples: AgBr, ZnS

Important points

Schottky defect appears more often than frenkel defect because wnergy needed to form a schottky defect is
much less than that needed to form a frenkel defect.AgBr shows both schottkey and frankel defect.
Due to defects or holes lowers the lattice energy and stability of the crystal
Due to closeness of similar charge di electric constant increase

Non stoichiometric defects:-

If a result of the imperfactions in the crystal the ratio, of the cations and anions becomes difference from that
indicated by ideal chemical formula. The defects are called non-stoichiometric defects.
They are of two types:-

i. Metal excess defects:- A negative ion may be missing from its lattice site, leaving a hole which is
occupied by an electron, there by maintain the electrical neutrality.

Metal excess due to anion- The interstitial sites containing the electron thus trapped in the anion vacancies are
called the F centers. {F- Farbe-which means colour}They are responsible for imparting colour to the
crystals.Li excess in LiCl makes it pink , potassium in KCl makes it violet.

Example:- When NaCl is heated in an atmosphere of Na vapours. The excess of Na atoms deposition the
surface of NaCl crystal Cl- ions then diffuse to the surface where the combine with Na+ ions which becomes
due to losing electrons.

These electrons loses by Na atom are diffuse back into the crystal and occupy the vacant site created by Cl-
ions and imparts Yellow colour to NaCl crystal

ii. By presence of extra cation in interstitial sites:-

Metal excess may also be caused by an extra cation occupying the interstial site. For example when ZnO is
heated it loses oxygen and turns yellow due to following
ZnO Zn+2 + (1/2)O2 + 2e-
The excess interstitial sites and the electrons in neighbouring interstitial sites.

Impotant points-
Such crystal can conduct electricity to some extant and can be used as semiconductors
Appeared coloured due to presence of free electrons.

Metal deficiency defect:-this defect can occur in two ways first defect occurs when the metal shows the
variable valancy. Due to metal deficiency the compounds obtained are non stoichiometric. For example it is
difficult to prepare ferrous oxide with ideal composition because ferum exists as both Fe+2 and Fe+3 ions thus
we obtain Fe0.95O or FexO with x = 0.93 to 0.96(due to variable oxidation states )

Second due to an extra anions occupying interstitial sites-

Impurity defects or extrinsic defects:-

These defects are arises when foreign atoms are present at the lattice site in place of the host atom. Or it is
present at the vacant interstitial site example n type semi conductor, p type semi conductor.
The process of adding impurities to the crystalline is called as doping.

In case of ionic solids the impurities are introduced by adding impurity of ions. If the impurity ions are in
different valnce state from that of host ions. Vacancies are created if mole ten NaCl containing a little impurity
of SrCl2 and is allowed to cool. The vacancies of Na+ ions are created and these are occupied by sr+2 ions.

Introducing Impurity in covalent solids:-

i. Doping with electron rich impurities (formation of n type semi conductor):-

Group in elements like silicon or germanium has 4 electrons in valance Shell. Thus it form four covalent bonds
with neighbouring atoms. When it is doped by group 15 element like P or As, the silicon or germanium atom at
some lattice sites are substituted by P or As.

Now doped atom have 5 valence electrons after forming four covalent bonds. The fifth free electron is gets
delocalized. This increases conductivity of silicon.

As conductivity is increases due to electrons thus the germanium crystal doped with e- rich impurity are called
n type semi conductors.

ii. Doping with electron deficit impurities:- (P type semi conductor)

If group 14 element like silicon are doped with 3 valance electron containing 13 group elements like Al or Ga.

Due to three valance electron all atom forms 3 valance bond with 3 silicon atoms. Thus a hole is get created at
the site of fourth electron is missing. This is called electron hole or electron vacancy.

If an electron jump from neighbouring site to fill this hole a another hole is generated at that site and it
continues.

Thus if electric field is applied the electrons move towards +vely charged plate and electron holes move
towards negative charged plate as they carry +ve charge. Thus a semiconductor with increased conducting is
formed and called P type semiconductor.
Defect or Imperfection:-

Any departure from perfectly ordered arrangement of the constituent particles in the crystal
called imperfection or defect.
The defects in the crystal are arises when crystallization takes place at the fast or moderate
rates because the constituent particles does not get sufficient time to arrange in perfect
order.

There are mainly two types of defects:-

1. Point defect:-When the deviation or irregularities exists from ideal arrangement around a
point or an atom in a crystalline substance the defect is called the point defect.
2. Line defect:- When the deviation from the ideal arrangement exists in the entire row of
lattice points the defect is called as line defect.

Types of the point defects:-

1. 1. Stoichiometric defects
2. 2. Non stoichiometric defects
3. 3. Impurity defects

Stoichiometric defect:-

If imperfection in the crystal are such that the ratio between cation and onions remains same.
Stoichiometry of substance do not disturbed defect is called stoichiometric defect these
defects are of the following types.

1. Vacancy defect:-
When is in a crystalline substance, some of the lattice sites are vacant the crystal is said to
have vacancy defect it results in decrease of density of substance.

2. Interstitial defect:-

o When some extra constituent particles are present in the interstitial site the crystal
is said to be have interstitial defect.
o This defect increases density of the crystal
o These above types of defects are shown only by non ionic solids.

3. Schottky defect:-

o If in an ionic crystal of the type A+B- equal number of cations and anions are missing
from the lattice site. So that electrical neutrality is remained is called schottky
defect.
Compounds exhibiting schottky defect are NaCl, KCl
o Which compounds have small difference in size of cation and anions show defect.

Frenkel defect:- If an ion is missing, from its lattice site and is occupies the interstitial site,
electrical neutrality as well as Stoichiometry of the compound are maintained this type of
defect is called frenkel defect. It is also called dislocation defect.
Example:-
(AgCl, AgBr, AgI, ZnS) shows this defect which have a large difference in size of cations
and anions.

Main points of difference between schottky and frankel defect

Non stoichiometric defects:-

If a result of the imperfactions in the crystal the ratio, of the cations and anions becomes
difference from that indicated by ideal chemical formula. The defects are called non-
stoichiometric defects.

They are of two types:-

i. Metal excess defects:-

A negative ion may be missing from its lattice site, leaving a hole which is occupied by an
electron, there by maintain the electrical neutrality.
The interstitial sites containing the electron thus trapped in the anion vacancies are called
the F centers. They are responsible for imparting colour to the crystals.
Example:- When NaCl is heated in an atmosphere of Na vapours. The excess of Na atoms
deposition the surface of NaCl crystal Cl- ions then diffuse to the surface where the combine
with Na+ ions which becomes due to losing electrons.
These electrons loses by Na atom are diffuse back into the crystal and occupy the vacant site
created by Cl- ions and imparts Yellow colour to NaCl crystal

ii. By presence of extra cation in interstitial sites:-

Metal excess may also be caused by an extra cation occupying the interstial site. For
example when ZnO is heated it loses oxygen and turns yellow due to following ZnO Zn+2 +
(1/2)O2 + 2e-
The excess interstitial sites and the electrons in neighbouring interstitial sites.
Metal deficiency defect:- This defect occurs when the metal shows the variable valancy. Due
to metal deficiency the compounds obtained are non stoichiometric. For example it is
difficult to prepare ferrous oxide with ideal composition because ferum exists as both Fe+2
and Fe+3 ions thus we obtain Fe0.95O or FexO with x = 0.93 to 0.96

Impurity defects:-

These defects are arises when foreign atoms are present at the lattice site in place of the host
atom. Or it is present at the vacant interstitial site example n type semi conductor, p type
semi conductor.

The process of adding impurities to the crystalline is called as doping.

In case of ionic solids the impurities are introduced by adding impurity of ions. If the
impurity ions are in different valnce state from that of host ions. Vacancies are created if
mole ten NaCl containing a little impurity of SrCl2 and is allowed to cool. The vacancies of
Na+ ions are created and thses are occupied by sr+2 ions.

Introducing Impurity in covalent solids:-

i. Doping with electron rich impurities (formation of n type semi conductor):-

 o Group in elements like silicon or germanium has 4 electrons in valance Shell. Thus it
form four covalent bonds with neighbouring atoms. When it is doped by group 15
element like P or As, the silicon or germanium atom at some lattice sites are
substituted by P or As.
o Now doped atom have 5 valence electrons after forming four covalent bonds. The
fifth free electron is gets delocalized. This increases conductivity of silicon.
o As conductivity is increases due to electrons thus the germanium crystal doped with
e- rich impurity are called n type semi conductors.

ii. Doping with electron deficit impurities:- (P type semi conductor)

o If group 14 element like silicon are doped with 3 valance electron containing 13
group elements like Al or Ga.
o Due to three valance electron all atom forms 3 valance bond with 3 silicon atoms.
Thus a hole is get created at the site of fourth electron is missing. This is called
electron hole or electron vacancy.
o If an electron jump from neighbouring site to fill this hole a another hole is
generated at that site and it continues.
o Thus if electric field is applied the electrons move towards +vely charged plate and
electron holes move towards negative charged plate as they carry +ve charge. Thus
a semiconductor with increased conducting is formed and called P type
semiconductor.