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# 12th Chapter :- 1
Solid State
 Classification of solids On the basis of arrangement
of constituent particles

Crystalline solids Amorphous solids

Substances in which arrangement Amorphous solids do not

of the constituent particles is regular have any regular arrangement or
and extend in all the directions, are have regular arrangement
known as crystalline solids e.g. NaCl. only for short range e.g. Glass.
Amorphous solids Pseudo solids Glass is a
(Super cooled liquids) pseudo solid as it flows
down very slowly

Side view of cut-out Window

 PROPERTIES OF CRYSTALLINE AND AMORPHOUS SOLIDS

Property Crystalline solids Amorphous solids

Amount of heat required
Arrangement Long range order Short range order to melt one mole of solid is
(i.e. properties are same (i.e. properties are same called heat of fusion
over long distances) over shorter distances)

Melts at a definite Melts over a range

Melting point
temperature of temperature
(Inter particle spacing is Inter particle spacing is
equal so all the bonds break at unequal so all the bonds will
the same temperature) not break at the same temperature

Definite heat of Have indefinite

Heat of fusion fusion heat of fusion
Rigid and Compressible to
Compressibility incompressible some extent
Property Crystalline solids Amorphous solids

Cutting with a Smooth planes Rough planes are

sharp edged tool are generated generated
( In crystalline solids some
planes are present along
which they can be cut. )
Isotropy and Isotropic
Anisotropic
anisotropy (Their properties are direction
Due to irregularities
their properties gets averaged
dependent)
out, so they are direction
independent.
They possess
Symmetry They do not
symmetry
Example: plane possess symmetry.
of symmetry
They possess
Interfacial interfacial angles They do not posses
angles α, β, γ. interfacial angles.
 Types of crystalline solids
On the basis of nature of force among constituent particles
crystalline solids are divided into four parts

1. Molecular solids

Non polar Polar Hydrogen bonded

2. Ionic solids

3. Metallic solids

4. Covalent solids
 Type Physical Electrical Melting
Subtypes Bonding Examples
of Nature Conductivity Point
Solid
(1) Molecular (ii) Polar Dispersion or Ar, CCl4 ,
Soft Insulator Ver
solids London forces H2,I2,CO2
y
(Molecules) low
(i) Non polar Dipole-dipole HCl, SO2 Soft Insulator Low
interactions
(iii) Hydrogen Hydrogen H2O (ice) Hard Insulator Low
bonded bonding

Dispersion forces are Dipole-dipole interaction Hydrogen bonding is

weak forces hence is stronger than stronger than non polar
these solids are soft dispersion forces and polar interaction
 Type Physical Electrical Melting
Constituents Bonding Examples
of Nature Conductivity Point
Solid
(2) Ionic Ions Coulombic NaCl, MgO, Hard but Insulators in High
Solids or ZnS, CaF2 brittle solid state but
Electrostatic conductors in
molten state and
in aqueous
solution

(3) Metallic Positive ions Metallic Fe, Cu, Hard but Conductors in Fairly
Solids in a sea of bonding Ag, Mg malleable solid state as high
delocalized and ductile well as in molten
electrons state
Electrostatic forces are very
strong force of attraction
 Type Physical Electrical Melting
Constituents Bonding Examples
of Nature Conductivity Point
Solid
(4) Covalent Atoms Covalent SiO2(quartz), Hard Insulators Ver
or bonding SiC, y
Network solids C(diamond), high
AlN
C(graphite) Soft Conductor
(exception)
 CRYSTAL LATTICE
:
The regular arrangement of the building blocks (atoms/ions/molecules)
inside the crystalline solid.
Basically crystal
The smallest part of a lattice which can be
lattice is the entire
repeated in all the directions to generate the
structure of solid.
entire lattice is called UNIT CELL.
If the wall of the house is
the entire lattice then its
smallest unit is BRICK.

Unit cell
3–D unit cells

Various lattices can be formed by varying the c

unit cell parameters. b

a

1) Edge lengths = a, b, c

2) Interfacial angles = α, β, γ

3) Location of atoms/ions w.r.t each

other.
By varying first 2 parameters we get 7 types
of unit cells called crystal systems.
 Crystal Systems

Crystal system Edge lengths Interfacial angles

Cubic a=b=c α = β = γ = 90o
Tetragona a=b≠c α = β = γ = 90o
l
Orthorhombic a≠b≠c α = β = γ = 90o
(Rhombic)
Trigonal a=b=c α = β = γ ≠ 90o
(Rhombohedral)
 Crystal Systems

Crystal system Edge lengths Interfacial angles

Hexagonal a=b≠c α = β = 90; γ = 120o

Monoclinic a≠b≠c α = γ = 90; β ≠ 90o

Triclini a≠b≠c α ≠ β ≠ γ ≠ 90o

c
Note :

7 types of crystal systems These 14 lattices

are called
But only half of BRAVAIS
these are found to LATTICES.
4 subtypes exist i.e. 14.

7 × 4 = 28 Possible variations
Location of atoms in unit cell :

(1) Simple cubic : Atoms / ions are present at corners only.

This in found in all 7

crystal systems

(2) Body centered : Atoms / ions are present

at corners + body center. This is found in
cubic, tetragonal
and orthorhombic
systems.
Location of atoms in unit cell :

(3) Face centred : Atoms / ions are present at corners + face centers.

This is found in
cubic and orthorhombic
systems.

(4) End centred : Atoms / ions are present

are corners and only at two opposite faces.

This is found
in orthorhombic and
monoclinic systems.
 Contribution of different lattice points in cubic unit cell :

CORNER
ATOM
FACE CENTRE

BODY CENTRE

EDGE CENTRE
 Contribution of different lattice points in cubic unit cell :

There are 8 corners in a cube.

CORNER Each atom at the corner is shared among 8 unit
ATOM cells so its contribution to one unit cell is 1/8.

There are 6 faces in a cube.

FACE CENTRE Each face is shared between 2 unit cells,
so its contribution to one unit cell = 1/2
 Contribution of different lattice points in cubic unit cell :

BODY CENTRE There is 1 body center in a cube. Whole of the

atom is found inside the unit cell, so
contribution to one unit cell = 1

EDGE CENTRE There are 12 edges in a cube. Each edge is

shared among 4 unit cells, so contribution
to one unit cell = 1/4
 Types of cubic unit cell
In actual practice
Cubic unit cell is the simplest of all 7 types of unit cells with
these spheres touch
a=b=c and α = β = γ = 90º each other.

Simple cubic (SC) : Atoms / ions are present at corners only.

a = 2r r

edge length radius of sphere(atom)

RANK (Z) :
It is effective number of spheres in one unit cell.

Example :

There are 8 spheres at 8 corners in simple cubic unit cell and the
contribution of each sphere in one unit cell
is 1/8th only.

1
Rank (Z) = 8 × = 1
8

⇒ Effectively there is only 1 sphere in 1

unit cell.
Packing fraction :
It is the fraction of volume occupied by the spheres in a unit cell.

Volume of spheres in 1 unit cell

P.F. =
Volume of cube
Volume of cube =
a3 4 πr3
Volume of 1 sphere =
3
Effective number of spheres = Z
4 πr3
So, total volume of spheres = Z ×
3
Packing fraction :
Z × (4/3)π r3
P.F. =
a3

Packing fraction for SC :

Put Z = 1 , a = 2r
1 × (4/3)π r3 π
P.F. = = = 0.52
(2r)3 6

So, 52% of the space is occupied by the

spheres and rest space is empty.
Empty spaces are called as voids.
What are the types of cubic unit cell ?

Body center cube (BCC) :

Rank & Packing fraction for BCC :

Body center cube (BCC) :
The spheres are present at corners + body center.

The spheres touch each other at body diagonal.

Length of body diagonal = a √3

⇒ 4r = a√3
Body center cube (BCC) :

1
Rank (Z) = 8 × + 1×1 =2
8

Spheres Contribution Spheres at Contribution of

at 8 corners of a sphere body center a sphere at
at corner body center
So, effectively there are 2 spheres in 1 unit cell.
Packing fraction for BCC :
4
Z× π r3
3
P.F =
. a3
4r
Put Z = 2 , a =
√3
4 π r3
2× π √3
3
P.F = = = 0.68
. 4r 3 8
√3
⇒ 68% of the space is occupied by the
spheres and rest is empty.
What are the types of cubic unit cell ?

Face centered cube (FCC) :

Rank & Packing fraction for FCC :

Face centered cube (FCC) :
Spheres are present at corners + face centers.

Here, the spheres touch along face diagonal.

Length of face diagonal = a √2 4r = a√2
Face centered cube (FCC) :

1 1
Rank (Z) = 8 × + 6× =4
8 2

Spheres Contribution 6 Spheres Contribution of

at corners of each sphere at 6 faces each sphere
at corner at face
 Face centered cube (FCC) :
Packing fraction
Z × (4/3)π r3 4r
P.F = Put Z = 4 , a =
a3 √2
.
4 × (4/3) π r3 √2 π
= =
4r 3 6
√2

∴ Packing fraction = 0.74

⇒ 74% of the space is occupied by the

spheres and rest space is empty.
 Summary
Relation between Rank Packing
Structure
‘a’ and ‘r’ (Z) fraction
π
SC 2r = a 1 0.52
6

BCC 4r = a √3 2 √3 π 0.68
8
√2 π
FCC 4r = a √2 4 0.74
6

Most efficient packing takes place in FCC

Density of cubic crystals
Mass of spheres M is the
Density = atomic mass
Volume of cube
Volume of cube =
a3
Mass of NA atoms = M g/mol
M
Mass of 1 atom = g
NA
Effective number
of atoms in 1 unit cell = Z
M
Total = Z×
mass NA
Density of cubic crystals

M
Z×
NA We must take
Density(ρ) = care of units
a3

M×Z
Density(ρ) =
a3 × NA

If ρ = g/cm3 then M= g/mol , a = cm

If ρ = kg/m3 then M= kg/mol , a = m
Q. The unit cell of Al is a cube with edge length 405 pm. The density of
aluminum is 2.7 g/cm3 What is the structure of aluminum crystals ?
Solution :
Z=4
a = 405 pm = 405 × 10–12 m = 405 × 10–10 cm
∴Structure of aluminum
M×Z crystal is FCC
ρ=
a3 × NA
27 × Z
2.7 =
(405 × 10–10)3 × 6.022 × 1023

Z = 4
Packing in solids

Start with

Square Close Packing

 One Dimension

Linear Arrangement

x - axis

z - axis
Coordination number = 2

y - axis
 Two dimension Every one dimensional layer is
stacked above each other.
Coordination number = 4

x - axis

z - axis

y - axis
Two dimension
The holes are
square shaped.
A
A
The size of hole is
A comparable to the
A size of sphere.

Square Close Packing

AAAA Type PLANAR Arrangement

PACKING IN
SOLIDS

Hexagonal Close Packing

 Two dimension

Coordination number = 6

x - axis

z - axis

y - axis
Two dimension

The crest of one row is

A in contact with depression
of another row.
B
A
B
A

ABAB Type PLANAR Arrangement

Two dimension

A Hexagonal Close Packing

B
A
The holes are triangular shaped.
B The size of hole is negligible to the size of sphere.
A

ABAB Type PLANAR Arrangement

PACKING IN THREE DIMENSION

Square Close Packing

Three dimension

AAAA Arrangement

A
A
A
A
A
Three dimension

AAAA Arrangement
 Three dimension

AAAA Arrangement
Square Close Packing
A
A
A
A
A
Coordination Number = 6?
PACKING IN THREE DIMENSION

Hexagonal Close Packing

Three dimension
Three dimension
Three dimension
ABAB Type Arrangement

A
B
A
B
A

SIDE VIEW
Coordination Number = 12 Hexagonal Close Packing
 VOIDS

⮚ Even in the most efficient packing (CCP or HCP) only 74%

of the space is occupied.
⮚ Rest space is empty and this empty space is called void.

⮚ The size of void can be expressed in terms of radius ratio i.e. r/R

R = radius of r = radius of
surrounding sphere spheres that can exactly
fit in the void.

⮚ There are various types of voids depending upon

their size and no. of spheres.
 VOIDS
The size of void can be expressed in terms of radius ratio i.e. r/R
1) TRIGONAL VOID
Trigonal void is a void surrounded by 3 spheres

600

Coordination number of Trigonal void = 3

If we join the centers of spheres of radius R,
we get an equilateral triangle.
2) TETRAHEDRAL VOID
It is a void surrounded by 4 spheres.
Hence, Coordination number = 4
These voids are located in FCC near every corner.
Tetrahedral void
If we move from a corner along the body diagonal, we will
find this void at 1/4th distance from corner.
The ‘T’ type of void in hexagonal packing
was tetrahedral void.
It is surrounded by
spheres located at 1
Tetrahedral voids
corner and 3 faces to
FCC lattice points
which that corner is common.
 2) TETRAHEDRAL VOID

Rank of FCC, Ζ = 4
No. of Tetrahedral voids = 8

No. of Tetrahedral voids = 2× Z

Similarly, Rank of HCP, Z =

6
No. of Tetrahedral voids = 12

There are two tetrahedral voids per sphere.

3) OCTAHEDRAL VOIDS

In hexagonal packing ‘O’ type of void are octahedral void.

This void is surrounded by 6 spheres i.e. Coordination number = 6

But in FCC they are located at 2 positions.

 3) OCTAHEDRAL VOIDS

(1) At body center All face centered spheres touch this void.
: At edge center the void in surrounded by 2 corner
(2)At edge center :
spheres and 4 face centered spheres.

The void at the edge center will

not be completely inside 1 unit cell.
At edge center It is shared among 4 unit cells.

At body center

But in FCC they are located at 2 positions.

 3) OCTAHEDRAL VOIDS
No. of Octahedral voids in unit cell =
There is exactly 1
1 octahedral void
12 × + 1× 1 = 4 per sphere in FCC
4

12 void at Contribution of 1 sphere Contribution of one

12 edges one void at edge at center sphere at center

We know that rank of FCC, Z = 4

⇒ No. of octahedral voids = Z
For HCP, Z =
6
⇒ No. of octahedral voids = 6
 Imperfections in solids .. ...
. ...
Vacancie .....
Defects can be due s
Interstitial Sites
.....
to

. . . .
Vacancies occur when positions that . ... .
should contain atoms or ions are vacant.
. . . .
Atoms or ions in a crystal may occupy
. . . .
positions called interstitial sites that are
located between the regular positions.
Classification of Defects

Defects are of two types

Stoichiometric Non–Stoichiometric
defects defects

Stoichiometric Defects
These defects do not disturb the stoichiometry
of solid. It is of 2 types:
Schottky Defect Frenkel Defect
 Schottky Defect It is a
vacancy defect.
Number of missing cations and anions are
equal.
So, solid is still
Density of substance decreases due to this defect.
electrically neutral.

This defect is shown by

ionic substances in which
cation and anion are of
almost similar sizes.

E.g. NaCl, KCl, AgBr etc.

Frenkel Defect

Smaller ion is dislocated from its normal site to an

interstitial site creating a vacancy at its original site. M+

What do you think about density of solid ?

Will it change or not?

Density of solid will not change as

number of ions are still the same.

This type of defect is shown by ionic substances

in which there is a large difference in size of ions.

E.g. ZnS, AgCl, AgBr etc.

Note: AgBr shows both type of defects.

Non–Stoichiometric Defects
These defects disturb the stoichiometry of solid. It is of 2 types:
Metal excess defect Metal deficiency defect

Metal excess defects

The defects in which number of metal cations
are more than the number of anions.
It is of two types:
a) Due to anionic vacancies

b) Due to extra cations

a) Due to anionic vacancies

The anion is missing from its lattice site leaving

an e– behind so that charge remains balanced.

The site containing the electrons are called

F–centers because they are responsible ‘F’ Stands for
for imparting color to the crystals. Farbenzenter meaning color.

This defect is similar to Schottky defect as

here also ion is leaving the lattice.
So this defect is found in crystals having
Schottky defect e.g. NaCl, KCl
(b) Due to extra cations
A+ B+ A+ B+
A+
An extra cations may be occupying the interstitial B+ A+ B+ A+

site and an e– is present in another interstitial site. A+ B+ A+

e–B +

B+ A+ B+ A+
So crystal is
electrically neutral. Zn2+ will go to
interstitial site and e– will
Since interstitial site is occupied by an ion, so this go to another site.
defect in found in crystals having Frenkel defect.

Example
Δ 1
ZnO Zn2+ + O2 + 2e–
2
Metal deficiency defect:

This defect occurs when metal shows variable valency.

E.g. FeO is mostly found as Fe0.93O to Fe0.96O.

This is because some of the Fe2+ are replaced by Fe3+.

But charge should remain balanced.

E.g. For every 3 Fe2+ we have 2 Fe3+
thereby creating a vacancy of 1.
 ELECTRICAL PROPERTIES
CONDUCTORS
Valence band and conduction band are very
close to each other or overlap with each other.
Very less energy is required to excite the
electrons from valence band to conduction band.
Electrons are delocalized in conduction band.
They are good conductors of heat and
electricity.

Examples: Iron, Copper etc.

 INSULATOR
Valence band and conductionSband are relatively
far from each other.
More amount of energy is required to promote
electron from valence band to conduction band.
No electrons in Conduction Band.

Bad conductor of heat and

electricity

Examples: Glass, Rubber etc.

 SEMICONDUCTORS
Spacing between valence band and
conduction band is very small.
Thus electrons can be excited from valence
band to conduction band easily.
But number of electrons for conductivity
is relatively less as compared to metals.
Addition of impurities
Examples Silicon, Germanium etc. to any semiconductor is
called doping.
:
However, the conduction can be increased
by adding impurity like Arsenic or Boron
in the conduction band of semi conductors.
 DOPING ⮚ If an impurity is added from group
13 to SILICON or GERMANIUM, it is
p – Block elements called p-type semi conductor
⮚ If an impurity is added from group
Impurity Impurity 15 to SILICON or GERMANIUM, it is
called n-type semi conductor
 n-type semiconductor
Si Si Si
⮚ Silicon has 4 valence electrons

⮚ If we dope Si withn an element of group 15 Si

Si
Si
i.e. Arsenic
⮚ Arsenic valence electrons = 5
Si Si Si

⮚ Due to negatively charged extra electron,

it is called n-type semiconductor
⮚ Conduct through normal e– conduction mechanism As
 p-type semiconductor
Si Si Si

⮚ Silicon has 4 valence electron.

If this is now doped with Boron
(Valence electron = 3), At one place there Si Si Si
is no electron. There is vacancy or hole.

⮚ Now to form covalent bond it borrows an electron

from neighbouring silicon Si Si Si

⮚ This creates vacancy at the site from where

electron is donated
B

⮚ Under the influence of electric field, holes moves

⮚ This type of semi conductors are
towards negatively charged plate and it would
called p-type semiconductors.
appear as if they are positively charged.
DHOOM Machale…….Dhoom Machale……...DHOOOOOOOM
85