OCTAHEDRAL VOIDS (OV)

Simple Cubic Body Centered Cubic Face Centered Cubic Hexagonal Closed Packed Density

Surrounded by 6 spheres
VOIDS Unit Cell (S.C.C.) Unit Cell (B.C.C.) Unit Cell (F.C.C.) Unit Cell (H.C.C.)

C.N. = 6 Z× M
d=
TYPES OF NA × a3
Present on edge centre and body TETRAHEDRAL
body centre of FCC unit UNIT CELLS
VOIDS (TV)
Surrounded by 4 spheres
C.N. = 4 Packging Efficiency
Coordination No.
Lattic Corners Corners + Body Corners + All Corners + Face Centers (C.N.) (P.E.)
Present on body diagonal line at a points Center Face Center + 3 atoms in middle layers
a 3 It is no. of nearest 4
distance of
4
from corner of FCC
 1  1   1 1  1 1  Z× π r3
unit Effective Number 8× 8 = 1 8 × 8 + 1  = 2 8 × 8 + 6× 2  = 3 12× + 2× + 3  = 6 Neighbours of a PE = 3 × 100
     6 2 
of atoms (Z)   lattice point a3

Packing Efficiency 52% 68% 74% 74%

CRYSTALLINE & AMORPHOUS (PE)

SOLIDS STRUCTURE OF VARIOUS IONIC CRYSTALS

Coordination No. 6 8 12 12
CRYSTALLINE AMORPHOUS Crystal
Structure
Lattice
Points
C.N. Number of Formula
Units per unit cell
Example

• Have a long range • Do not have ordered LiCl, KCl

Cl-,-CCP

SOLID STATES
Rock salt
order of particles structure or have a very 6:6 4
NaCl type Na+ -OV RbCl, AgCl
short order
• Anisotropic • Isotropic Zinc-Blende S2--CCP ZnS, Bes,
• True solids • Pseudo solids 4:4 4
Zns type Zn2+-Alternate TV CuCl, CuI
• Sharp melting point • Diffused melting point
• NaCl, Quartz, ZnS • Glass, Rubber, etc. CsCl type Cl--Corners 8:8 1 CsBr, CsI,
(BCC type) Cs+-Body centre CsCN
Molecular Covalent/Network
Fluorite type Ca2+-CCP SrF2, BaF2,
(CaF2) 8:4 4 SrCl2
F-all TV
Ionic Solid Metallic Solids
Anti-Fluorite O2--CCP K2O, Li2O,
4:8 4
type (Na2O) Li+-all TV K2 S
CRYSTAL LATTICE / SPACE
LATTICE
A regular 3-D arrangement of constituent
MAGNETIC & ELECTRICAL PROPERTIES
particles.
DEFECTS IN CRYSTALS
UNIT CELL
STOICHIOMETRIC
Smallest repeating
DEFECTS NON STOICHIOMETRIC MAGNETIC PROPERTIES
unit which repeats
itself over and over DEFECT • Paramagnetic- Weakly attracted by magnetic field. eg. O2, Cu2+ etc.
again to generate
entire crystal.
IN NON-IONIC IN IONIC • Diamagnetic- Weakly repelled by magnetic field. H2O, NaCl, etc.
SOLIDS SOLIDS • Ferromagnetic- permanent magnetism even in absence of magnetic
fields eg. Fe, Ni, CO, CrO2, etc.
Vacancy Interstitial Schottky Frenkel Metal excess Metal deficiency • Ferrimagnetic- Magnetic moment is smaller than that of
Defects Defects Defects Defects Defect Defects ferromagnetic substances. eg. Fe3O4 , MgFe2O4 .
Types of Crystal Lattice/ • Equal no. of • Smaller ion is • Antiferromagnetic- Zero magnetic moment due to equal no. of anti-
• Some of the • Some particles • It may arise either
parallel domains. eg. MnO, etc.
14 Bravis Lattices lattice sites occupy an cations and dislocated from
it's normal site
due to anionic • Occurs due to cationic
anions are vacancies or due to vacancy and presence
are vacant interstial site
missing to an interstitial presence of extra of a cation having
Cubic a=b=c α = β = γ = 90° sites cations at interstitial higher charge.
• Decrease in • increase in
• Decrease in Sites ELECTRICAL PROPERTIES
Tetragonal a=b≠c α = β = γ = 90° density density density • no change density • Appearance in oxides
• Generate F-centres of d-block metals.
• Conductors- Valence bond is partially filled or it overlaps with higher
Orthorhombic a≠b≠c α = β = γ = 90° which are responsible energy unoccupied conduction bands.
Monoclinic a≠b≠c α = γ = β ≠ 90° for colour in crystal
• Insulators- Large energy gap between valance and conduction bands.
Hexagonal a=b≠c α = β = 90° γ = 120° O2- • Semi-conductors- Small energy gap between valance and conduction
bands.
Rhombohedral a=b=c α = β = γ ≠ 90°
e- Fe3+
Triclinic a≠b≠c α ≠ β ≠ γ ≠ 90° • p-type semiconductor: (by doping e- deficient impurities
Fe3+
• n-type semiconductor: (by doping e- rich impurities
 
  SOLID STATE (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)
SOLID STATE
Matter exists mainly in three states, viz. solids, liquids and gases. The existence of matter
in any of these three forms depends upon two factors
1. Intermolecular forces of attraction (keeps particle closer)
2. Thermal energy (keeps particles apart)
Properties Solid Liquid Gases
No free motion Random motion to
(i) Motion of partical. Totally random.
only vibration allow. a limited extent is allowed.
(ii) Inter molecular Intermediate
Very strong Very weak (~ zero)
forces strength
Average separation is almost
(iii) Average separation
x constant so almost fixed No fixed volume.
(volume)
volume.
Definate shape as Average separation is fixed
(iv) Shape location of partical are but location of partical is not No fixed shape.
fixed. fixed so no definate shape..
(v) Effect of change in Liquid are also almost
Are incompressible. Highly compressible.
pressure & temperature. incompressible.
Heat capacity is
Heat capacity is dependent
(vi) Heat capacities almost independent Same as solid.
on process.
of process.
Some common properties of solids, which distinguish them from liquids, gases, are:
 Solids are rigid and have definite shapes.
 Solids have definite volume irrespective of the size or shape of the container in which they
are placed.
 Solids are almost incompressible.
 Solids diffuse very slowly as compared to liquids and gases. Constituent particles are very
closely packed in solids permitting very little space for their movement.
 Solids have a much higher density (mass to volume ratio) than that of gases and liquids.
 Most solids become liquids when heated. Some undergo sublimation on heating. The
temperature at which a solid changes into liquid is called the melting point and the process
is called as melting. Due to the varying natures of solids their melting temperatures vary
considerably.

CLASSIFICATION OF SOLIDS
Solids are divided into two classes, namely
crystalline and amorphous solids. A solid is said to
be crystalline if the constituents arrange
themselves in regular manner throughout the three-
dimensional network. The ordered arrangement of
building constituents extends over a large distance
(long range order). On the other hand, in amorphous
solids, the arrangement of building constituents is not regular (short range order).
 
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i) Crystalline solids: A crystallline solid is a homog geneous so ch the constituent pa

olid in whic articles
(atoms, io
ons or mole
ecule) are arranged
a in a definite repeating pattern.
Examplee: Diamondd, Quartz, NaCl,
N K2SOO4 etc.

General characteri
c istics of Crystalline
C e solids:
i) A crysttalline solid
d is a homo
ogeneous solid
s in whiich the con
nstituent p
particles (ii.e. atoms, ions or
moleculess) are arran nged in a de
efinite rep
peating patttern in all dimensions.
d .
ii) The tottal intermoolecular foorce of atttraction in i crystalline solid iis maximum m thus im mparting
maximum stability, the force es responsible for th he stabilityy involves iionic bondss, covalent bonds,
hydrogen n bonds and d Van der Waal’s
W forcees.
iii)A crysttalline solidd usually coonsist of a large nummber of sm mall tiny crrystals called unit ceell, each
having a definite
d characteristiic geometrical shape.
iv) Crystalline solid hash regula
ar arrangem ment of particles which repea ats periodiically over entire
crystal, thus
t exhibitting short-- and long--range ordder.
v) Crystalline solids have
h sharp melting point, thus haave definitte heat of ffusion.
a true solids.
vi) Crystalline solids are
o cutting gives a clea
vii) Crystaalline solid on an cleavage
e.
viii) Crystaalline solid shows
s different physsical properrties in different direection, thiss type of behavior
b
is called anisotropy
a y and the suubstances exhibiting this type of o behaviorr are called d anisotrop
pic. The
 
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SOLID STATE (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)
properties like electrical conductivity, refractive index, thermal expansion etc. have different value
in different direction.
ix) Two or more crystalline substances having same crystal structure are said to be isomorphous.
Isomorphous substance contains constituent atom of same atomic ratio.
Example: a) NaF and MgO (Ratio is 1:1)
b) NaNO3 and CaCO3 (Ratio is 1:1:3)
c) K2SO4 and K2SeO4 (Ratio is 2:1:4)
d) Cr2O3 and Fe2O3 (Ratio is 2 : 3)
Exceptional: NaCl and KCl have all properties identical [same atomic ratio, similar molecular
formula or similar chemical properties] but are not isomorphous.
x) A single substance that crystallizes in two or more forms under different conditions is called
polymorphous. (allotropic forms)
. Example: a) Carbon has two allotropes graphite and diamond.
b) Sulphur has two polymorphic forms monoclinic and rhombic.
c) CaCO3 and SiO2 have two allotropic forms.

ii) Amorphous solids: Substances that appear like solids but do not have perfectly ordered
crystalline structure and no regular arrangement of constituent particles in structure is called
amorphous solids.
Example: Tar, glass, plastic, rubber, butter etc.

General characteristics of amorphous solids:

i) Amorphous substances appear like solids but they do not have perfectly ordered crystalline
structure, hence they are not real solids.
ii) An amorphous solid does not have regular arrangement of constituent particles.
iii) The arrangement of constituent particles like atoms or molecules has only short-range order
hence periodically repeating regular pattern is only over a short distance.
iv) Regular patterns are scattered and hence the arrangement is disordered.
v) Amorphous solids are called supercooled liquids of very high viscosity or pseudo solids.
vi) Physical properties do not change with change in directions hence amorphous solids are isotropic
in nature.
vii) Amorphous solids behave like fluids and very slowly float under gravity.
viii) Amorphous solids do not have sharp melting points.
ix) When cut, they split into pieces with irregular and rough surfaces.

Uses of amorphous solids:

i) Most widely used amorphous solid are the inorganic glasses viz. construction, house-ware,
laboratory ware, etc.
ii) Used as rubber in making tyres, shoe soles, etc.
iii)Used in plastics.
iv) Amorphous silica used for converting sunlight into electricity (in photovoltaic cell).

 
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B

A
B A
B

 
SOLID STATE (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)
Anisotropy: The ability of crystalline solids to change their physical properties when measured in
different directions is called anisotropy.
Explanation: This property is due to different arrangement of
constituents in different directions.
Different types of particles fall on the way of measurements in
different directions. Hence, the composition of crystalline solids
changes with directions changing their physical properties.
Isotropy: The ability of amorphous solids to have same physical
properties when measured in different directions is called isotropy.
Explanation:This property is due to no regular arrangement of
particles in any direction. Hence the properties like electrical
conductivity, thermal expansion are identical in all the direction.

Difference between Crystalline and Amorphous Solid:

Crystalline solid Amorphous solids
True solid Pseudo solids, super cooled liquid [In
between solid & liquid]
1 The constituent partical (atoms, molecule, ion) 1 No particular pattern is followed
follow a definite repetiting arrangement. partical are random arranged.
2 These have long range order. 2 They have short range order no long
range order are found.

3 These are produced by slow cooling under 3 Rapid or suddenly cooling of the liquid
controlled condition of liquid. The crystalline generate the amorphous solid.
structure is also dependent on conditions.
Same substance can have different crystalline
structure in different condition.
Different crystalline structure of the same
substance are called its polymorphic forms &
this is known as polymorphism.
4 These have fixed or sharp melting point and 4 These have a range of temperature in
enthalpy of fusion. which they melts as. There melting
point and enthalpy of fusion is not
Cooling Curve : fixed.
Liquid Transition
From liquid to solid Liquid Liquid + solid
Temp. (Transition)
(T0) Temp.
solid T1
T2 solid
only
t1 t2 t1 t2
Time Time

5 These are anisotropic : Physical properties 5 These are isotropic :

will have different values in different direction. All different physical properties are
same in all different direction.

Reason : Due to random arrangement

of partical.

Ex. : Ag, Fe, Cu, NaCl, H2O (s), Dimond,

Quartz, Sucrose (Sugar)

Ex. : Glass, Plastic, Amorphous silica,

Rubber, Starch.

 
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Types of crystalline solids: They are classified into four main types as follows:
i) Molecular solids: They are further classified into three types:
a. Polar molecular solids.
b. Non-polar molecular solids.
c. Hydrogen bonded molecular solids.
ii) Ionic solids.
iii)Metallic solids.
iv) Covalent solids.
Molecular solids:
i) Here the constituent particles are molecules of same compound.
ii) Depending upon the type of molecules involved in crystal formation and the nature of
intermolecular force of attraction between the neighboring molecules, they are further sub-divided
as :
a) Non-polar molecular solids:
1. These are those crystalline solid in which the constituent particles are either atoms [Noble gases]
or non-polar molecules [H2, Cl2, I2, CH4, etc.] or weakly polar molecules like CO or other
hydrocarbons.
2. They are formed at relatively lower temperature and are in usually gaseous state at normal
temperature.
3. In these atoms or non-polar molecules are held by weak London forces.
4. These are generally soft, having low m.p and b.p and are non-conductor of electricity.
5. As polar molecules exist in gaseous state, polar molecular solids is obtained by subjecting the gas
high pressure and low temperature.

b) Polar-molecular solids:
1. They crystalline solid in which the constituent particles are polar molecules [HCl, SO2,]
2. In polar molecule there is separation of charges, in which the opposite charges of neighboring
molecules are brought closer.
3. The forces holding these molecules are dipole-dipole forces of attraction, this force of
attractionis stronger than London forces.
4. These solids show following characteristic:
i) They are soft.
ii) Their melting point and boiling point are comparatively higher than non-polar molecular solids
but lowerthan ionic and metallic.
iii) They also exist as liquid or gases at room temperature.
iv) They are non-conductor of electricity.
v) They possess permanent dipole moment.

c) Hydrogen bonded molecular solids:

1. In these solids, the constituent particles are such molecules which contain hydrogen atom linked
to a highly electronegative atom [O, N or F]. Example: solid ice, NH3, etc.
2. In these, molecules are held by hydrogen bond in which the H atom of one molecule is bonded to
electronegative atom of another molecule.

 
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SOLID STATE (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)
3. This intermolecular force of attraction existing among the molecules is strong hydrogen bonds.
4. Characteristic of hydrogen bonded molecular solid :
i) They exist as volatile liquid or soft solids at room temperature.
ii) They are non-conductors of electricity.
iii) Their melting point and boiling are usually higher than non-polar molecular solids and polar
molecular solids.
5. They solidify on cooling.

Ionic solids:
i) In these crystalline solids, the constituent particles are positive and negative ions i.e. cations and
anions. e.g. Na+ and Cl– ions in case of NaCl.
ii) These ions in the solid are held in their lattice points by strong electrostatic force of attraction
resulting into well-ordered three-dimensional arrangement of ions.
iii)All salts are crystalline in nature and are called Ionic solids.
iv) In Ionic solids, the charges on the ions and the arrangement of ions are in such a manner that
they balance each other and hence the molecule is electrically neutral.
v) The arrangement of ions in the solid depends upon:
a) Size of cation and anion
b) charges on the ion
c) ease with which anion is polarized (i.e. polarizability of anions).
vi) Ionic solids are hard and brittle and have high melting point and boiling point.
vii) They are electrical insulators in solid state because their ions are not free to move.
viii) In aqueous solution or in molten state as the ions become free, they are good conductor of
electricity.
ix) They are soluble in polar solvent but insoluble in non-polar solvent.
x) On application of shearing force, ionic crystals undergo distortion and fracture in crystal
structure.

Metallic solids:
i) In metallic solids the constituent particles are positively charged metal ion and free electron.
ii) Due to low ionization energy of metal atom the metal atom loses their valence electron and
becomes positively charged ions.
iii)Thus electrons lost are delocalized over the crystal space and flows throughout the crystal like
water in sea, hence also called sea of free electrons.
iv) The force of attraction between positively charged metallic ion and negatively charged sea of
delocalized electron is called metallic bond.
v) If energy is supplied, valence electron from sea of electrons move from one place to another, this
presence of mobile electrons makes all the metal good conductor of heat and electricity.
vi) On application of shearing force, the layers slide on one another and hence the structure is not
fractured imparting the properties of malleability and ductility.
vii) They have high melting point, boiling point and density.
viii) The mixtures of metals can be fused together to form alloys, which exhibit all properties of
metals.

 
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SOLID STATE (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)
ix) They possess lusture and colour. [Gold metal exhibit yellow lusture and copper has reddish
lusture].
x) Metallic bonds are stronger than ionic and covalent bond.

Covalent solids or Network solids:

i) These are crystalline solids in which the constituent particles are non-metal atoms linked to the
adjacent atoms by covalent bonds throughout the crystal forming a giant three-dimensional
structure.
ii) Hence covalent solids are called giant solids and the constituting molecules are called giant
molecules.
iii)Since covalent bonds are strong and directional, atoms are held strongly at their lattice positions.
iv) They are hard or brittle depending on the event of bonding.
v) They have high melting points.
vi) They act as good conductors of electricity or insulators depending upon the availability of free
electrons.
Examples diamond, graphite, Silicon carbide (carborundum), fullerene, boron nitride, etc.

 
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SOLID STATE
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2
TERM
MS AND CONCEPT
TS
Space latttice or crrystal latttice:
It may be e defined as a regular three--dimension nal arrange
ement of constituen nt particle
es of a
solid subsstancein sppace.
The positions which h are occuupied by attoms, ions or molecu
ules in the
e crystal lattice are
e called
lattice pooints or lattice site
es.
Lattice point
p Lines
La
attice are used
d to represent
P
Point geometry of crystal

Characterristics of Crystal la
attice:
1. Lattice points or lattice sitees: The cryystal lattic
ce of a sub
bstance is representeed by show
wing the
position of
o the partticle in space. These positions a are represeented by po
oints and are
a referreed to as
Lattice points.
p
2. Each po oint in a crystal
c latttice represents one constituen nt particle
e which maay be an atom,
a a
molecule (group of a
atoms) or an
a ion.
3. Lattice points are joined by straight
s lin
nes to bring
g out the ge
eometry off the molec
cule.

Unit Cell:: It is the smallest portion of a crystal lattic

ce which, when rep
peated in
n three
dimensio
ons produc ces crysta
al lattice.

Characte eristics of aracterized by follow

f Unit celll: A unit cell is cha wing parammeters,
1. Edges or
o edge le ength:The e intersecction of twwo faces of
o crystall lattice iss called ass edge.
The threee edges denoted
d b a, b and
by d c repressent the dimensions
d s (lengths)) of the un nit cell
along thrree axes. These
T edgges may orr may not be mutually perpend dicular.
2. Angles between the edgess (or plane es): Therre are threee angles between thet edges of the
unit cell represennted as α , β and γ . The crysttal is defined with
the help of these parameters of its unit
u cell.
a) The ang
gle α is be dges b and c.
etween ed
b) The ang
gle β is be dges a and c.
etween ed
c) The ang
gle γ is be
etween ed
dges a and b.

 
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A space laattice can

n be sub-divided into
o a numbe
er of smalll cells known as unitt cells. It can be
defined asthe
a smalllest block
k from wh e crystal can be bu
hich entire uilt up by its transllational
repetition
n in three dimension ns
TYPES OF
O LATTI
ICES AND
D TYPES OF
O UNIT
T CELL

(i) Primitiive or sim

mple Unit Cells: Inn a primittive unit cell,
c the ssame type
e of partiicles is
present at all the corners of the unit cell.

(ii) Non-pprimitive oor centere

ed unit ceells:
There arre three types of noon-primitivve unit cellls as follo
ows:
(a) Face Centered:
C :Whenatomsarepressentinall 8 8-corners and six fa
ace cente
ersin a cub
bic unit
cell then
n this arra
angement is
i known as FCC.

 
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(b) Body Centered(BCC):When atoms are present at 8 corners as well as in the body centre
in a cubic unit cell then this arrangement is known as BCC.

(c) End-Centered:Inadditiontoparticlesatthe corners, there are particles at the centers of

two oppositefaces.
 

 

 

 

SEVEN CRYSTAL SYSTEMS

By considering the symmetry of the axial distance and the axialangles between the edges,
the various crystals can be divided into 7 systems. Although each system is expected to have
4 different unit cell, but actually all of them cannot exist in each case and only 14 different
type of lattices called Brava is lattice had been established.
There are 14 possible three-dimensional lattices. These are called Bravais Lattices.
Serial No. Crystal System Possible variations Edge lengths Axial angles Examples
Primitive NaCl
1 Cubic Body – Centered a=b=c α = β = γ = 90 o
ZnS
Face – Centered Cu
Primitive SnO2
2 Tetragonal a=b≠c α = β = γ = 90 o
Body – centered TiO2
Primitive Rhombic Sulphur
Body – Centered KNO3
3 Orthorhombic a≠b≠c α = β = γ = 90 o
Face – Centred BaSO4
End – Centred MgSO4.7H2O
α = β = 90 o

4 Hexagonal Primitive a=b≠c Graphite, ZnO

γ = 120 o

Calcite (CaCO3)
5 Rhombohedral or Trigonal Primitive a=b=c α = β = γ ≠90 o
Cinnabar (HgS)
Primitive Monoclinic sulphur
α = γ = 90 o

6 Monoclinic a≠b≠c
End – Centred β ≠90 o Na2SO4.10H2O

Primitive K2Cr2O7, H3BO3

7 Triclinic a≠b≠c α ≠ β ≠ γ ≠90

 
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a=b=c Three a=b=c
All sides are angles All sides are
of equal length; changed of equal length;
all angles are all angles
c a 90° c a  =  =  = 90°

b I F b P
P
Cubic Trigonal (Rhombohedral)

One side One side length changed

two angles fixed at 90°
is
one fixed at 120°
changed

General case : Special case

a=b=c All sides are
One side is a=bc
  different lengths; c
different length;  =  = 90°
all angles are
all angles are c a different  = 90°
90°  a a a
b P b P
Three unit cells are
Tetragonal Triclinic Hexagonal shown to give the
hexagon
Length of another side is
changed
Two side lengths made
the same; one angle
fixed at 120°

All sides are of

abc different lengths
One angle  =  = 90°
Three sides are of changed
different lengths;   90°
c a all angles are 90° 
c  c
a a
b P I F C
C b P b
Orthorombic
Monoclinic
CALCULATION OF NUMBER OF PARTICLES IN A UNIT CELL (Z)
In a crystal, atom located at the corner and face center of a unit cell are shared by other
cells and only a portion of such an atom actually lies within a given unit cell.
(i)A face-centered point is shared by two unit cells and only one half of it is present in given
unit cell, hence the contribution of the particle per unit cell is 1/2.
2 3
1 4

5
6
8 7
(ii) A point along an edge is shared by four-unit cells and only one-fourth of it lies within one
cell,hence the contribution of the particle per unit cell is 1/4.

1 2


4 3

 
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C (IIT-JEE) EXAMS (2021 - 2022)
2
(iii)A poin
nt that lies at the e corner of a unitt cell is shared
s am
mong eighht-unit cells and
thereforre, only one eighthh of each such poin given unit cell, hence the
nt lies witthin the g
contribu
ution of thhe particle
e per unitt cell is 1//8.
6 8

5 7
2
 4

1 3

(iv) A boddy-centered point lies entire es one complete

ely within the unit cell and contribute
point to the cell.
2
 3
1 4

5 6
8 
7
  Type of Lattice ppoint  Conntribution to
o one unit ceell 
Face‐center  1/22 
Edge  1/44 
Corneer     1/88 
Body Center  1 
i. Calculatiion of nummber of particles
p p unit ce
per ell in a primitive
p c
cubic unit cell:
In this type
t of uniit cell, the
ere are eig
ght particles at the corners oof the unitt cell.
 Numbe er of partticles per unit cell = No. of particles
p in unit cell x share of particles per
unit cell
=8x = =1 particle

ii. Calculatiion of num

mber of particles
p p unit ce
per ell in a Body-
B cenntred cubiic unit celll:
This type
e of unit cell
c has 8 particles at the corners andd 1 particle
e at the
centre of the unitt cell.
 Numbe cles per unit cell =8 x
er of partic +1x 1
= 2 partic
cles.

iii. Calculatiion of num

mber of particles
p p unit ce
per ell in a Face-
F cenntred cubic unit cell:
This type of unit cell has 8 particles at
a the corrners and 6 particle
es at
centre of 6 faces of the unit cell.
 Numbe
er of partic c =8
cles unit cell x +6x
=1 +3
=4 particles.
 
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Calcula
ation of nu
umber of particles in a unit cell
Type of u
unit cell  Latttice  points  at  Lattice p
points at face‐ Lattice  points  at  body  ZZ  =  no.  of  lattiice  points  per  unit 
corners  centerred  centered  cell 
SC  8  0  0  1
8 1 
8
BCC  8  0  1  1
8 1 1 2 
8
FCC  8  6  0  1 1
8 6 4 
8 2

CALCULA ATION OF F NEARES ST NEIGH HBOURS

Note: In a simple cube, the atoms at the corners touch each oth her. But, the atoms at the
corners of f face cenntered cubbe and bod dy centereed cube do o not touch each othher. In fcc
c, each
sphere at the corne er touchess the threee spheress at the fa ace centrees of thre
ee adjuringg faces
similarly, in bcc, all the atomss at the co
orners touuch the ce entral spheere.
The relattionship between th he nearest neighbo or distance (d) and the radius of atom (for
crystals of
o pure ele ements) annd the edg ge of unit cell (a) are
e given be
elow:
1] Simple e Cube:
d = AB = a
r = a/2

2] Face Centered
C Cube:
d= in right
r angled
d C2 = AB2 + B
ABC AC BC2
AC2 = a2 + a2 = 2a2
AC √2. a
AC √2. a a d a
d ∵ r
2 2 √
√2 2 2√2
3] Body Centered
C C
Cube: d
In right an
ngled C, AC2 = AB
ABC B2 + BC2 = 2a2
AC √2. a
In right angled
a AD
DC
2
C + DC = (√2.a) 2 + a2
AD = AC 2 2

√3. a d √3
AD 3a  AD
D √3. a  d r a
2 2 4

(i) Close packing

p in
n two dimeensions:
Initiallytthe sphere
es arrangee themselvves in a ro
ow to form
m an edge o
of the cry
ystal.
There arre two way ys to build
d a crystal plane

 
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(a) Sphere is packed in such a way that the rows have a horizontal as well as vertical
alignment. In this arrangement, the spheres are found to form square. This type of packing
is also called square close packing.

The number of spheres which are touching a given sphere is called co-ordination number.
Thus, the coordination number of each sphere in square close packing is four.
(b) The sphere is packed in such a way that the spheres in the second row are placed in the
depressions between the spheres of the first row and so on. This gives rise to hexagonal
close packing of spheres and the coordination number of each sphere is six.

(ii) Close packing in three dimensions:

It is clear from the figure (X) that there are two types of voids or hollows in the first layer.
These are marked as b and c. All the hollows are equivalent but the sphere of second layer
may be placed either on hollows which are marked b or on the other set of hollows marked c.
The second layer is indicated as dotted circles in figure (Y).

 
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a a a a a a a a a a
c c c c c c c c
b b b b b b
a a a a a a a a
c c c c c c
b b b b b b b b
a a a a a a a a a a

(X) (Y)
When a third layer is to be added, again there two types of hollows available. One type of
hollows marked ‘c’ are unoccupied hollows of the first layer. The other type of hollows are
hollows in the second layer (marked a). Thus, there are two alternatives to build the third
layer.
(i) When the third layer is placed over the second layer so as to cover the tetrahedral or ‘a’
voids, a three-dimensional closest packing is obtained where the spheres in every third
layer are vertically aligned to the first layer. This arrangement is called ABAB.,…pattern
or hexagonal (HCP) close packing(calling first layer as A and second layer B).

 
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(a) For HCP geometry Coordination number = 12
(b) For HCP geometry no. of atoms per unit cell
1 1
12 corners 2 face centres 3 inside the body 1 6
6 2
(c) For HCP geometry packing efficiency = 74 %
(ii) When the third layer is placed over the second layer such that the spheres cover the
octahedral or ‘a’ voids, a layer different from A and B is formed. This pattern is called
ABCABC……pattern or cubic close packing (CCP).
The ABC ABC....... packing has cubic symmetry and is known as cubic close packing (ccp). The
cubic close packing has face centered cubic (fcc) unit cell.

Cubic close packing (ccp)  


 
(i) For CCP geometry coordination number = 12 
(ii)For CCP geometry no. of atoms per unit cell = 4(as calculated before)  

(iii)For CCP geometry packing efficiency = 74 % 


 
VOIDS
In the close packing of spheres, certain hollows are left vacant. These holes or voids in the
crystals are called interstitial sites or interstitial voids.
(i) Triangular (ii) tetrahedral
(iii) Octahedral (iv) cubical void
(i) Triangular: The vacant space (void) formed by touching three spheres.
0.155

 
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(ii) Tetrahedral:The vacant space among four spheres having tetrahedral arrangement is
called tetrahedral site or tetrahedral hole. For tetrahedral void 0.225.

(iii) Octahedral: This type of site is formed at the centre of six sphere. The void formed
by two equilateral triangles with apices in opposite direction is called octahedral site or
rvoid
octahedral hole. For octahedral void
rsphere
0.414
 O 
O  O
 O 

O  O
 O 
O  O

 O 
O  O
 O 
Octahedral void
rvoid
iv) Cubical void:Vacant space (void) formed by touching eight spheres
rsphere 0.732

Note:If a close packing (array) is made up of n number of atoms or ions then it has n no.
ofoctahedral voids and 2n no. of tetrahedral voids.

DENSITY OF UNIT CELL

 The length of edge of the cell= a cm
 Volume of unit cell = a3 cm3

Density

 Mass of unit cell = number ofatoms in a unit cell  mass of each atom = Z.m




 Mass of one atom m ′

 Density Z → Number of atoms per unit cell.

 
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PACKING EFFICIENCY
Packing efficiency is the % of total space occupied by particles. Both types of close packing
(hcp and ccp) are equally efficient and occupy 74% of available value. In bcc, the efficiency
is 68% while is simple cubic structure, it is 52.4%
Vol. occupied by all atoms in unit cell v
Packing ef iciency
Total vol. of unit cell V
Let a be the cube edge length and r the radius of atom.
V =volume of unit cell = a3; Volume of sphere,v πr
a. Packing efficiency in CCP or FCCarrangement:
Both type of close packing (hcp and ccp) are equally efficient. Let us
calculate the efficiency of packing in ccp structure.
In ccp, the unit cell is face centred. In face centred cubic unit cell, there
are four spheres per unit cell. Let ‘r’ is the radius of sphere and ‘a’ be the
edge length of the cube.
Volume of the sphere =
Total four spheres per unit cell of fcc, volume of it = 4 x
In a face centred cubic unit cell, the spheres at corners are in
contact with the sphere at the centre of the face and the particles
at the corners are not in touch with each other.
Therefore we can find the radius of the sphere as follows:
From Δle ABC, AC2 = AB2 + BC2
 b 2 = a2 + a2
 b2 = 2a2
 b = √2
Since b = 4r, we have
 4r = √2
r = √

r =
√
or a =
√
√ √
 a= or a =
√ √

 a=2 2 r

Packing Efficiency = 100 3 100
√

100 100 74.04%

√ √

Packing Efficiency = 74.04% OR 74%

 
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A a

b C

D c

 
SOLID STATE (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)
b) HCP arrangement:
Volume of unit cell base area height 6√34 4 2/3 24√2r
1 1 4
no. of atoms in hcp 12 2 3 1 6 v 6 4πr 8πr
6 2 3
8πr π
Packing ef iciency 100 100 74%
24√2r 3√2

c) BCC arrangement:
InBody centred cubic unit cell, atoms are located at the corners of the cube and 1 particle at the
centre of the cube.
Number of particles per unit cell of BCC structure = 2
 Volume occupied by spheres = 2× πr = πr
Where r  radius of the spheres.
Edge length of cube = a
In a body centred cubic unit cell, the spheres at the corners are not touching
each other but are in contact with the sphere at the centre of the cube.
From the figure, we can find, Face-diagonal as, from Δle ABC,
AC2 = AB 2 + BC2 = a2 +a2
b2 = 2a2
For body diagonal consider the Δle ACD, Body diagonal CD can be calculated as CD2 = AC2 + AD2
c2 = b2 + a2 = 2a2 +a2
 CD = c = √3 = √3
 CD =√3 = 4r
 4r = √3
3
 r= a or a=
√
r
4
 Volume of unit cell = a3 =
√
a =
√
Volume of space occuped by atoms in one unit cell
Packing Efficiency = 100
Volume of one cubic unit cell
πr 8πr √
Packing Efficiency = 64 x 100 = x 100
64 x 3 r
√

Packing efficiency = 67.98 % ≃ 68 %

d) Simple cubic arrangement: In simple cubic unit cell, atoms arelocated only at the corners of the
cube. The particles touch one another along the edge.
If edge length of the cube= a, and radius of each particle is r; then a is
related to r as a = 2r
The volume of the cubic unit cell = a3 = 2r3 = 8r3
Since a simple cubic unit cell contains only 1 atom
4 3
The volume of the occupied space = πr
3
 
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Volume of space occuped by atom 4/3πr 4πr
Packing Efficiency = 100% = ×100 = ×100
Volume of cubic unit cell 8r 8r

= ×100 = 52.36%

RADIUS RATIO RULES

In ionic crystals, the coordination numbers as well as the geometrical shapes of the crystals
depend mainly on the relative sizes of the ions. The ration of the radii of the positive and
negative ions is called radius ratio.
Radius of postive ion cation r
Radius ratio
Radius of negative ion anion r
Common coordination numbers are 3, 4, 6 and 8.
Limiting  radius ratio  Co‐ord. No.  Shape  Example  

i)   < 0.155  2  Linear    BeF2 

ii)   0.155 – 0.225  3  Trigonal planar  B2O3 
iii)   0.225 – 0.414  4  Tetrahedral  ZnS 
iv)   0.414 0.732  6  octahedral  NaCl 
v)   0.732 0.999  8  B.C.C.    CsCl 

STRUCTURE OF IONIC COMPOUNDS

(A) Ionic Compounds of AB type:
These compounds can have following three type of structures.
1] Rock salt structure (NaCl):
+
a) Cl¯ is forming a FCC unit cell in which Na is in the Cl–

+ Na+
octahedral voids. The co-ordination number of Na is 6 and that
of Cl¯ would also be 6.
r
b Ratio of ionic radii 0.525 Crystal structure of NaCl
r
1
c No. of sodium ions 12 At edge centre 1 At body centre 1 4
4
1 1
No. of Cl ions 8 At corners 6 At face centres 4
8 2
(Thus formula is Na4Cl4 i.e. NaCl)
d) Most of the halides of alkali metals and oxides of alkaline-earth metal have this type of
structure.e.g. NaI, KCl, RbI and RbF. FeO also has rock-salt structure in which oxide ions
2+
are arranged in ccp and Fe ions occupy octahedral voids.

 
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2] Caesiu um chlorid de structuure (CsCl):
(a)CsCl haas body-ce entered cu ubic (bcc)) arrangemment. Thiss structure has 8: 8 co-ordin nations,
C + ion is touching eight
i.e., each Cs e Cl– io ach Cl– ion
ons and ea ns in touch C + ions. (bcc).
hing eight Cs (
  
b 0.933   
   Cs+
    Cl—  
    
  

    
    
(b)
   One unit cell
c
(a)

1
c No. of Cl ions 8 At corneers 1
8
f Cs+ ions = 1 (At the
No. of e body cenntre) × 1 = 1
No. of
f CsCl unit per unit cell
c =1
(d) Compoounds havinng this typ ucture are CsBr, CsI
pe of stru I, TlCl, and
d TlBr.

3] Zinc blende
b strructure orr Sphaleriite structture (ZnS)):
(a)Sulphide ions are
a face centered and zinc c is prese
ent in alte etrahedral voids.
ernate te
b 0.40
– 1 1
c No. of S2 ions 8 at corn
ners 6 at face centres 4
8 2
2+
No. of
f Zn ions = 4 (within the bod dy) × 1 = 4
No. of
f ZnS unitss per unit cell = 4
(Formula is Zn4S4, i.e. ZnS
S)
(d) Ionic
c solids having zinc blende
b strructure are CuCl, CuBr, CuI & AgI

(B) Ionic Compoundds of AB2 type:

Fluorite structure
e (CaF2):
(a) The cations arre arrange ed in cubiic close pa cp) while tthe anion occupies all the
acking (cc
tetraheddral voids. Calcium fluoride
f ha
as 8: 4 co--ordination
n. (ccp)
(b) In un
nit cell no. of calcium
m ions 8 8 at cornerss 6 at face centtres 4
No. of
f fluoride ions = 4 (wwithin the body) × 1 = 4
No. of
f CaF2 unitts per unitt cell = 4
(c) Com
mpounds having
h uorite strructure are SrF2,
flu Ca2+
BaCl2, Ba
aF2, PbF2 a
and CdF2.  F—

 
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(C) Ionic Compounds of A2B Type:
Antifluorite Structure:
In Antifluorite structure e.g., (Na2O)
(a) The anions are arranged in cubic close packing (ccp)
while the captions occupy allthe tetrahedral voids. O2–
(b) Na2O has 4: 8 co-ordinations  Na+

(c) Compounds having ant fluorite structures are: Li2O, K2O,

Rb2O and Rb2S
Sr.  Type of crystal  Ions occupying voids  ions forming close   Coord no. 
packing  (cation: anion)  
+ ‐
1.  Rock salt (AB) (NaCl)   Na  ions occupy  Cl   6: 6 
octahedral voids 
2.  Cesium chloride (AB)   Cs+ ion occupy cubic  Cl‐  8: 8 
(CsCl)   hde 
2+ 2‐
3.  Sphalerite (AB) (ZnS)   Zn  occupy tetrahedral  S   4: 4 
voids alternatively 
ˉ 2+
4.  Fluorite (AB2) (CaF2)   F occupy tetrahedral  Ca   8: 4 
voids 
5.  Antifluorite (A2B)   Cations occupy  Anions  4: 8 
(Na2O)   telrahedrd voids 

IMPERFECTIONS OR DEFECTS IN SOLIDS

At absolute zero, crystals tend to have a perfectly ordered arrangement. This arrangement
corresponds to state of lowest energy. As the temperature increases, the crystals start
deviating from the perfectly ordered arrangement. Any deviation from the perfectly
ordered arrangement constitutes a defect or imperfection. These defects are sometimes
called thermodynamic defects because the number of these defects depends on the
temperature. Crystals may also possess addition defects due to the presence of impurities.
Many properties of crystalline solids such as electrical conductivity and mechanical strength
can be explained in terms of imperfections. Imperfections not only modify the properties of
solids but also give rise to new properties. The defect which arises due to the irregularity in
the arrangement of atoms or ions are called atomic imperfections.
These imperfections in the crystalline solid are called defects in crystalline solid. The
defects in crystalline solids are of two types viz.,
a. Point defect
b. Line defect
Point Defect: This defect is produced because of the faulty arrangement of a point i.e.
constituent practice like atom, ion or molecules in a crystalline solid.
The point defects are classified into three types:
Types of point Defects:
i) Stoichiometric defects.These are those defects in which the stoichiometry of the solid
is not disturbed as a result of the defect.

 
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ii) Non-stoichiometry defects. These are those in which the stoichiometry is disturbed due
to the defect.
iii) Impurity defect. These arise when some foreign material is added into the crystal.

Types of Stoichiometric defect

(i) Vacancy defect is a stoichiometric defect generated
during crystallization, in which some of the places of the
constituent particle remain unoccupied. This defect
results in the decrease of density of thecrystal than
expected. This defect possibly occurs when a substance is
heated.
(ii) Interstitial defect: Interstitial defect is a type of
stoichiometric defect, in which the constituent particles
(atoms or molecules) occupy an interstitial site (occupies
the space between the lattice site). This defect results in
the increase of density of the crystal than expected.
In case of ionic solids, always electrical neutrality must be maintained. The above two
defects in case of ionic solids can be explained as follows:
a) Schottky defect:
It is due to equal number of cations and anions missing from their lattice sties. As a result,
density decreases. This type of defect is shown by ionic compounds which have high
coordination number and small difference in the size of cations and anions, e.g., NaCl, KCl,
KBr, AgBr and CsCl.

b) Frenkel defect:
It arises when cations are missing from their lattice sites and occupy interstitial sites. As a
result, density remains unchanged. This defect is also called dislocation defect as smaller
ions (usually cations) are dislocated from normal sites to interstitial sites.

 
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Types of Non-stoichiometricDefects:
These arre of two types
t
i) Metal excess: T These def fects arisse when tthere are excess m metal ionss in the crystal.
c
These deefects arise in two ways:
w
a) By anioon vacancies: It arises due to
t a negative ion misssing fromm the
lattice siite leavingg a hole which iss occupied d by elecctron thereby
maintainin
ng electrrical neuttrality. The
T lattic
ce sites occupied d by
electrons are calle ed F-centtres as th hey are rresponsibleforcolour of
Crystal:
Ex: When n NaCl is heated in the atmo osphere of f sodium vapors,
v sodium
atoms gett deposite ed on the surface of
o the cry ystal. The Cl¯ ions ffrom
the crystal lattice leave their sites annd diffusee to the surface.
s T
These
Cl¯ ions combine
c with the so
odium atom ms and these Na attoms ionizes and the electron ns that
are releassed are tra t anion vacancies..These are
apped by the e called f centers
b) By pre
esence of extra cattions in th he intersttitial sitess:
Excess metal
m ionss are entrrapped intto the vac cant interrstitials sites and electrons
e in the
neighbou
uring interrstitial sites to main
ntain electtrical neuttrality.
For exam
mple, when n ZnO is heated, it loses
l O2 and turns yellow
y due to the following reaction:

The Zn2+ ions occuupy certaiin interstitial sitesswhereas electrons released will occupy the
neighborin
ng sites in the latttice. On heating
h he crystal turns yellow, due to transittion of
th
freeelectrons from
ma lower ennergy statte.

b) Metal Deficienc cy due to cations va acancies:

This defeect occurss when the metal shows va ariable va
acancy, i.e
e.,
transition
n metals, e.g.,
e in FeO
O, FeS, NiO etc. This is becau
use in FeO
O,
2+ 3+
3 Fe ion ns may be e replaced
d by 2 Fee ions too maintain
n electrica
al
neutrality
y. That is why we never havve the ideea compossition FeOO.
Instead, we
w have Fe exO with x = 0.93 to 0.96.

 
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Types of Impurity defects:
Impuritiess are adde
ed to chan
nge the properties of
o the crysstals. The
e process is called do
oping.

i) In ionic
c solids: F
For examp
ple, SrCl2 may
m be add
ded to Na Na+ ions will be repla
aCl. Two N aced by
2+
one Sr ion thereby creatin
ng a whole
e (a cation vacancy) and
a impartting condu
uctivity.

ii) In covvalent soliids:

a) Dopingg with eleectron ric ch impuritties: For example, Group 14 4 elementts like Si or Ge
(having 4 valence electros) may be doped d witth Group 15 elemen nts like P ores (ha aving 5
valence electrons). For everry atom of Group 114 replace ed by tha at of Grou up 15 onee extra
electron is present making it n-type se emiconducttor
b) Dopingg with elec ctron defficit impurrities: Forr example, when Grroup 14 ele ements is doped
with Grouup 13 eleme ents like B,
B Al or Ga a (having 3 valence electrons)
e ), for everry atom of
f Group
14 replaceed by thatt of Group p 13, a hole
e is create ed. On app
plying elec
ctric field, electron
ns move
to occupy these holes. Thus, holes movve towards the nega ative plate
e as if theey carry positive
p
charge. Hence, we get
g p-type e semicondductors.

PROPERT
TIES OF S
SOLIDS
(i) Electric
cal Propertties: Solidss can be brroadly classified into three type
es, on the basis of ele
ectrical
conductivitty.
(a) Metals (conductorrs)
(b) Insulattors
(c) Semi-co onductors
6 8 –1 –1
Electrical conductivitty of meta
als is very
y high and is of the order of 10 –10 ohm
m cm where
eas for
–12 –1 –1
insulators, it is of the order of 10 ohm cm
c . Semi-conductorss have intermediate conductivity
c y in the
2 –9 –1 –1
0 –10 ohm cm . Elect
range of 10 trical condu
uctivity of solids may
y arise throough the motion of ele ectrons
and holes (positive)
( o through the motion
or n of ions. T
The conducction throug gh electronns is called
d n-type
n and through (positive) holes is called p-ty
conduction ype conducttion. Pure ionic solids where con nduction
 
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can take place only through movement of ions are insulators. The presence of defects in the crystal
structure increases their conductivity.
The conductivity of semi-conductors and insulators is mainly due to the presence of interstitial
electrons and positive holes in the solids due to imperfections. The conductivity of semi-conductors
and insulators increases with increase in temperature while that of metals decrease.

(ii) Magnetic Properties:

 Diamagnetic Materials: Materials which are weakly repelled by the magnetic field are called
diamagnetic materials. e.g. Cu+, TiO2, NaCl and benzene. They do not have unpaired electrons.
 Paramagnetic Materials:The materials which are weakly attracted by magnetic field are called
paramagnetic materials. These materials have permanent magnetic dipoles due to presence of
2+ 2+
atoms, ions or molecules with unpaired electron. e.g. O2, Cu , Fe etc. But these materials lose
their magnetism in the absence of magnetic field.
 Ferromagnetic Materials: The materials which show permanent magnetism even in the absence of
magnetic field are called ferromagnetic materials. These materials are strongly attracted by the
magnetic field. e.g. Fe, Co, Ni and CrO2. Ferromagnetism arises due to spontaneous alignment of
magnetic moments of ions or atoms in the same direction.

 
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 Alignment of magnetic moments in opposite directions in a compensatory manner and
resulting in zero magnetic moment gives rise to anti-ferromagnetism.
for example,MnO,Mn2O3 andMnO2.
 Alignment of magnetic moments in opposite directions resulting in a net magnetic moment
due to unequal number of parallel and anti-parallel magnetic dipoles give rise to ferri-
magnetism e.g. Fe3O4.
Ferromagnetic and ferrimagnetic substances change into paramagnetic substances at
higher temperature due to randomization of spins. Fe3O4, is ferrimagnetic at room
temperature and becomes paramagnetic at 850 K.

(iii) Dielectric Properties:

The electrons in insulators are closely bound to the individual atoms or ions and thus they do not
generally migrate under the applied electric field. However, due to shift in charges, dipoles are
createdwhichresultsin polarisation. The alignments of these dipoles in different ways i.e.
compensatory way (zero dipole) or non-compensatory way (net dipole) impart certain characteristic
properties to solids.
If the dipoles align in such a way that there is net dipole moment in the crystals, these crystals are
said to exhibit piezoelectricity or piezoelectric effect i.e. when such crystals are subjected to
pressure or mechanical stress, electricity is produced. Conversely, if an electric field is applied to
such a crystal, the crystal gets deformed due to generation of mechanical strain. This is called
inverse piezoelectric effect.
Some crystals which on heating, acquire electric charges on opposite faces, are said to exhibit
pyroelectric effect.
The solids, in which dipoles are spontaneously aligned in a particular direction, even in the absence of
electric field are called ferroelectric substances and the phenomenon is known as Ferroelectricity.
If the alternate dipoles are in opposite direction, then the net dipole moment will be zero and the
crystal is called anti-ferroelectric.
Ferroelectric solids – Bariumtitanate (BaTiO3), sodium potassium tartrate (Rochelle salt) and
potassium hydrogen phosphate (KH2PO4). Anti-ferroelectric – Lead Zircon ate (PbZrO3).

SuperConducting Materials:The materials which offer no resistance to the passage of

electricity is called superconductor or super conducting material. In this state, the materials
become diamagnetic and are repelled by the magnets. Most of the metals become super
conducting at low temperatures (2 – 5K). Highest temperature at which super conductivity is
known is 23K in alloys of niobium (e.g. Nb3Ge). Many complex metal oxides have been found to
possess super-conductivity at somewhat higher temperatures.]
Material Temperature
Nb3Ge 23 K
Bi2Ca2Sr2Cu3O10 105 K
Ti2Ca2Ba2Cu3O10 125 K
 
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Band theory of solids:
1. According to band Theory, the atomic orbitals of atom in the crystal combine to form
molecular orbital which spreads over the complete crystal structure.
2. As the number of atoms in crystal increases, the number of molecular orbital containing
electrons increased. As the number of molecular orbitals increases the energy difference
between the adjacent orbitals decreases.
3. Until finally the energy gap becomes very small and molecular discrete energy levels
merge into one another to form continuous band of molecular orbitals which extend over
the entire length of crystal.
4. All the molecular orbitals are very close to each other and are collectively called a band.
5. There are two types of bands of molecular orbitals as follows :

 
1. Valence band:The atomic orbitals with filled electrons from the inner shells form
valence bands, where there are no free mobile electrons since they are involved in
bonding.
2. Conduction band: Atomic orbitals which are partially filled or empty on overlapping
form closely placed molecular orbitals giving conduction bands where electrons are
delocalized and can conduct, heat and electricity.
6. In metallic crystals, the valence bands and conduction bands are very close to each other
and a very little energy is required to excite electrons from valence bond in to the
conduction band. In conduction band the electron are delocalized and are free to move
from one end to the other end of the metal piece, this migration of electron makes the
metal good conductor of heat and electricity.
7. In substance which are bad conductor of heat and electricity, the spacing between the
valence band and conduction band is relatively more so that more energy is required to
promote electrons from valence band to conduction bond, hence electrons remains in
valence band and thus cannot move freely thus do not conduct heat and electricity and act
as insulators.
8. If the energy difference between valence band and conduction band is moderate, then the
substance in ordinary condition is non-conductor, but if heated it becomes conductor due to
transition of electrons into conduction band. Such conductors are semiconductors.

 
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Conduction of electricity in Semiconductors: The substance which have poor electrical
conductance at low temperature but increases with increase in temperature is called semiconductor.
A substance containing filled band with electrons and a completely empty band behaves as a
semiconductor.
Example: Si, Ge, etc.
In excitation, empty conduction bands contain electrons to conduct electricity. However electrons
can be added to conduction band by adding impurity (like Arsenic with extra electrons to silicon
conduction band) and hence can become conductor of electricity.
Electron rich impurity:
n-type semiconductor: If the impurity from Group 15 i.e. (Arsenic) is added to group 14 (i.e.
silicon), some of the sites of silicon in the crystal are occupied by arsenic atoms each with one extra
electron in the conduction band and will be available for transport of electricity. Such type of
semiconductor with impurity having extra negative charge due to extra electron of impurity atom is
called n-type semiconductor.

Electron deficient impurity:

p-type semiconductor: If the impurity from Group 13 i.e. (Boron) added to Group 14 (i.e. silicon)
then some atoms of born will occupy some of the sites of silicon atoms. At all sites of boron atoms
one valence electron will be shorter as compared to silicon atoms and there will be a positive hole in
the lattice. Hence an electron from neighbouring silicon atoms jumps into the electron hole and
continues till the electron hole is transferred to the edge of the crystal lattice and movement of
electron takes place. This type of semiconductor is called p-type semiconductor.

Semiconductor  Type 
1  B doped with Si  p‐type 
2  As doped with Si  n‐type 
3  P doped with Si  n‐type 
4  Ge doped with In  p‐type 

 
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