SOLID STATE JEE-ADV CHEM-VOL-II

SR-MAIN-CHEM-VOL-II

SOLID STATE
SYNOPSIS
 In solid state atoms, ions or molecules are arranged
orderly in a three dimensional manner due to strong
binding forces.
 Due to this arrangement, solids acquire rigidity and
definite geometric shapes or crystalline structures.
Characteristic properties of the solids
i) They have definite mass, volume and shape.
ii) Intermolecular distances are short
iii) Intermolecular forces are strong
iv) Their constituent particles (atoms, molecules or
ions) have fixed positions and can only oscillate
about their mean positions.
v) They are incompressible and rigid
* The existance of a substance in more than one
solid modification is called polymorphism.
 Annealing: An amorphous substance, on heating
at a certain temperature, may attain crystalline nature
while on cooling regains its amorphous nature. This
phenomenon is called annealing. Ex : Glass on
keeping in semi-solid state for a long time or on
cooling, it melts very slowly, it becomes opaque
due to development of crystals in it.
 Isotropy: Amorphous solids on the other hand
are isotropic in nature. It is because there is no
long range order in them and arrangment is irregular
along all the directions. Therfore, value of any
physical property would same along any direction.
 Anisotropy: Crystalline solids are anisotropic
in nature, that is, some of their physical properties

Distinction between crystalline and amorphous solids

Property Crystalline solids Amorphous solids

Definite characteristic
Shape Irregular shape
geometrical shape

Condition of Slow cooling without Rapid cooling with

formation disturbing the liquid churning of disturbance

Melt at a sharp and Gradually soften over a

Melting point
characteristic temperature range of temperature

When cut a with a sharp edged When cut with a sharp

tool. They split into two pieces edged tool. They cut into
Cleavage property
and the newly generated two pieces with irregular
surfaces are plain and smooth surfaces

They have a definite and They do not have definite

Heat of fusion
characteristic heat of fusion heat of fusion

Anisotropy Anisotropic in nature Isotropic in nature

Order in arrangement
Long range order Only short range order
of constituent particles

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like electrical resistance or refractive index show molecular according to the nature of the building
different values when measured along different units, chemical bonding and the intermolecular
directions in the same crystals. This arises from forces in the crystal.
different arrangement of particles in different The characteristics of various types of solids are
directions. given in the table.
 Classification of Crystalline Solids:
A crystal is classified as ionic, covalent, metallic and

Different types of Solids

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W.E-1.Give the order of the metallic bond strengths
in Mg , Ca and Al
Sol: Bond strength is highest in Al, due to the presence
of three valence electrons. In Mg and Ca, two
valence electrons each are present. But due to large
size, bond is weaker in Ca than in Mg.
Order of metallic bond strength: Ca<Mg<Al

r
Covalent or Network Solids: Crystalline
solids of non-metals result from the formation of
covalent bonds between adjacent atoms throughout
the crystal. They are also called giant molecules.
Covalent bonds are strong and directional in nature,
therefore atoms are held very strongly at their
positions. Such solids are very hard and brittle.
They have extremely high melting points.They are
insulators and do not conduct electricity. Diamond
and silicon carbide are typical examples of such Coordination Number of Crystals: The
solids. Graphite is soft and a conductor of coordination number of an atom or ion in solid is
the number of nearest neighbours for that atom or
electricity. Graphite has layer like structure. It is
ion
good solid lubricant.
Eg :1) In NaCl crystal, coordination number of
Na  ion as well as Cl  ion is 6.
 Applications of amorphous solids:
2) Coordination number of C in diamond is 4
Amorphous solids are used in domest ic
constructions or appliances like photo voltaic cells 3) In SiO2 , coordination of Si is 4 while that of
where the sun light is transformed into electricity. oxygen atom is 2
4) In metal lattices the coordination number of a
metal atom is usually 8 or 12.
Additional Information:
X-Ray study of crystal structure-
Radiusratio :- Bragg’s Equation-X-Ray Difraction
It is the ratio of the smaller ion radius to that of the studies X–Ray study of crystal
 X – ray diffraction studies of crystal clearly reveal
 the internal structure of crystals.
rsmall   The exact pattern of arrangement of crystal
larger ion i.e.
   
 rl arg e 
components, size and shape of the unit cell.
  Electromagnetic radiation propagate in the form of
waves in all directions . In the propagation of waves
In many cases rsmall is the cation radius and rl arg e along a direction, the maximum displacement
perpendicular to motion of the wave is known as
is that of anion. The shape of the crystals depends amplitude of the wave.
on coordination number.  For constructive interference resultant amplitude is
2 E0  E0  Amplitude 
 For destructive interference resultant amplitude is
Zero
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 SOLID STATE
 The waves, if present in the same phase they undergo 
constructive interference on the other hand if the
waves are not in phase, they undergo destructive
interference.
Bragg’s Equation: W.L. Bragg and W.H.
Bragg worked out and gave a mathematical relation
to determine inter atomic distance from X – ray
diffraction pattern. This relation is called the Bragg’s
equation
n  2d sin  ; n = order of reflection;
 Debye - Scherrer Method is used to determine the
  Wave length of x-rays
d  interplanar distance,   angle of reflection
 Space Lattice (or) Crystal Lattice: A space
Order of Bragg’s
n value equation
reflection
 Lattice Point: The point that represents a
Fist order 1 2d sin 
Second order 2 d sin 
Third order 3 2/3 d sin 
th order  2/ d sin 
 (a) Primitive unit cells :When constituent
 As ‘n’ value increases  value increases
 X – rays of definite wave length obtained from
X  ray tube, passes through a slit and falls on a 
known face of the crystal. The position of the crystal
can be read on a scale.
 The intensity of the diffracted X – ray from the crystal
is measured on a photographic plate or an ionization
chamber. The ionization chamber contain CH 3 Br
vapours.
 The extent of ionization in the vapour is shown by
the electrometer reading. As the intensity of the
diffracted X – rays increases, the degree of
ionization also increases
 By changing the angle of incidence the extent of
ionization at different angles is recorded in the
electrometer.
 The Crests of the graph, taken from electrometer
reflect maximum diffraction. The angles
corresponding to the crests are noted from the
graphs.
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The angles are substituted for ' ' in Bragg’ss
equation and the values of ‘d’ are calculated.
Ex : - For NaCl crystal ‘d’ values are in the ratio
1 2
of1: :  1: 0.707 :1.154 . From this it is
2 3
confirmed that the crystal has F.C.C. structure.
Note : - Bragg’s method to be used, large single
crystals are neccessary. The planes of the crystal
must be fully developed and easily identified.
crystal structures.
lattice is an array of points showing how molecules,
atoms or ions are arranged at different sites in three
dimensional space.
molecule, an atom or an ion in a space lattice is
called Lattice point.
Unit Cell: The smallest portion of the crystal lattice
which can be used as repetitive unit in three
dimensional manner to get entire crystal lattice is
called unit cell. Unit cells are broadly divided into
two categories, primitive and centred unit cells.
particles are present only on the corner positions
of a unit cell,it is called as primitive unit cell.
(b) Centred unit cells : When a unit cell
contains one or more constituent particles present
at positions other than corners in addition to those
at corners, it is called Centred unit cell. Centred
unit cells are of three types:
(i) Body-centred unit cells : Such a unit cell
contains one constituent particle (atom, molecule
or ion) at its body-centre besides the ones that are
at its corners.
(ii) Face-centred unit cells : Such a unit
cell contains one constituent particle present at the
centre of each face, besides the ones that are at its
corners.
(iii) End-centred unit cells : In such a unit
cell, one constituent particles is present at the centre
of any two opposite faces besides the ones present
at its corners.
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 From fundamental laws of crystallography there are
14 basic arrangements known as Bravais Lattices.
 The following are characteristics of a crystal lattice
c
a) Each point in a lattice is called lattice point or
b
a
Simple Face-centered Body-centered
lattice site.
Three CUBIC Lattices b) Each point in a crystal lattice represents one
constituent particle which may be an atom, a
c molecule or an ion.
b a c c) Lattice points are joined by straight lines to bring
a b
Simple End face-centered Rhombohedral
out the geometry of the lattice.
Two MONOCLINIC Lattices  These 14 Bravais lattices are grouped into seven
crystal system based on unit cell symmetry .
c
c These seven crystal systems are
c

b 120
0
b a b
a a
Simple Body-centered Hexagonal Triclinic
Two TETRAGONAL Lattices

a b
End face-centered Body-centered Face-centered
Simple

Four ORTHORHOMBIC Lattices

 The three cubic lattices : all sides of same

length, angles between faces all 900.
 The two tetragonal : one side different in length
to the other, two angles between faces all 900.
 The four orthorhombic lattices : unequal l
sides, angles between faces all 900.
 The two monoclinic lattices : unequal sides,
two faces have angles different to 900.
 Hexagonal lattice : one side different in length
to the other two, the marked angles on two faces
are 600.
 Rhombohedral lattice : All sides of equal
length, angles on two faces are less than 900.  (c) Crystal systems: A unit cell is characterised
Triclinic lattice : Unequal sides a, b, c are unequal by :
angles with not equal to 900. (i) its dimensions along the three edges, a, b and c.
Bravais Lattices: Bravais showed that there These edges may or may not be mutually
perpendicular.
are 14 different possible kinds of three dimensional
lattices. (ii) angles between the edges,  (between b and
 The geometric shape of the crystal lattice must be c )  (between a and c ) and  (between a
same as that of solid crystal itself. and b ). Thus, a unit cell is characterised by six
Ex : If unit lattice is having cubical structure the
crystal is also a cube. parameters, a, b, c, ,  and  .

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 There are 230 crystal forms possible. These forms  Match box has orthorhombic geometry
may be classified into 32 classes on the basis of  Ice may give hexagonal or trigonal crystals
their symmetry.  Quartz may give hexagonal or trigonal crystals
 On the basis of inter facial angles and axes crystal
systems are 7 types. Calculation of the contribution of lattice
The crystal structures depends on the set of points per unit cell of substance.
crystallographic parameters
Unit cell Contribution of Net no.of
Atom per unit cell constituent
Face Body
particles
Corners center center
(1/8)
(1/2) (1)
Simple 1
c cubic unit 8   1   1
8
cell
  b Face 1 1
centered 8 1 6  3  4
a  8 2
unit cell
Body 1
centered 8 1  1×1=1 2
8
unit cell
End 1 1
centre 8 1 2 1  2
8 2
unit cell

 A lattice point at the corner of a unit cell is shared

by 8 vicinal unit cells.
 A face centered point is shared by two adjacent
unit cells.
 A edge centered point is shared by four adjacent
unit cells
 A body centered lattice point belongs completely
to a specific unit cell.

Close packed structures

Packing of Solids and Voids
 In solids constituent particles are arranged as
spheres in close structure.
 In close packed structure, maximum space is
occupied by constituent particles and leave minimum
vacant space
 When the spheres are closely packed the different
crystal systems are generated.
A) Close packing in one dimension :

Close paking of spheres in one dimension

Co-ordination number is 2.

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B)Close packing in two dimensions :
A
A dimensional hexagonal close packed layers. Three
A generated by placing layers one over the other.
A (a) Placing second layer over the first
(AAA Type)
Square close packing - coordination no.4
B This is AB AB type packing.
A
B
A
(ABA) Type
hexagonal close packing coordination no.6
C) Close packing in three dimensions :
(i) Three dimensional close packing from
two dimensional square close-packed
layers: While placing the second square close-
packed layer above the first we follow the same
rule that was followed when one row was placed
adjacent to the other. The second layer is placed
over the first layer such that the spheres of the upper
layer are exactly above those of the first layer. In
this arrangement spheres of both the layers are
perfectly aligned horizontally as well as vertically.
Similarly, we may place more layers one above the
other. If the arrangement of spheres in the first layer
is called ‘A’ type, all the layers have the same
arrangement. Thus this lattice has AAA.... type
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pattern. The lattice thus generated is the simple
cubic lattice, and its unit cell is the primitive cubic
unit cell.
(ii) Three dimensional close packing from two
dimensional close packed structure can be
layer: Let us take a two dimensional hexagonal
close packed layer ‘A’ and place a similar layer
above it such that the spheres of the second layer
are placed in the depressions of the first layer. Since
the spheres of the two layers are alligned differently.
The spheres of the second layer ‘B’ are not covered
all the triangular voids of the first layer ‘A’. This
gives rise to different arrangements. Wherever a
sphere of the second layer is above the void of the
first layer (or vice versa) a tetrahedral void is
formed. These voids are called tetrahedral
voids because a tetrahedron is formed when the
centres of these four spheres are joined.
At other places, the triangular voids in the second
layer are bove the triangular voids in the first layer,
and the triangular shapes of these do not overlap.
One of them has the apex of the triangle pointing
upwards and the other downwards. Such voids
are surrounded by six spheres and are called
octahedral voids.
Let the number of close packed spheres be N,
then :
The number of octahedral voids generated =
N
The number of tetrahedral voids generated =
2N
(b) Placing third layer over the second
layer: When third layer is placed over the second,
there are two possibilities.
(i) Covering Tetrahedral voids : Tetrahedral
voids of the second layer may be covered by the
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 SOLID STATE
spheres of the third layer. In this case, the spheres
of the third layer are exactly aligned with those of
the first layer. Thus, the pattern of spheres is
repeated in alternate layers. This pattern is often
written as ABAB.... pattern. This structure is called
hexagonal close packed (hcp) structure. This sort
of arrangement of atoms is found in many metals
like magnesium and zinc.
(ii) Covering octahedral voids : The third
layer may be placed above the second layer in a
manner such that its spheres cover the octahedral
voids. When placed in this manner, the spheres of
the third layer are not aligned with those of either
the first or the second layer. This arrangement is
called “c” type. Only when fourth layer is placed,
its spheres are alligned with those of the first layer.
This pattern of layers is often written as
ABCABC..... This structure is called cubic close
packed (ccp) or face-centred cubic (fcc) structure.
Metals such as copper and silver crystallise in this
structure.
both these types of close packing are highly efficient
and 74% space in the crystal is filled. In either of
them, each sphere is in contact with twelve
spheres. Thus, the coordination number is 12 in
either of these two structures.
Interstitial Voids : The empty spaces between
the three dimensional layers are known as holes or
voids. The holes are also refered as interstices.
There are three types of holes possible.
Tetrahedral holes : A hole formed by three
spheres in contact with each other of a layer. The
hole is capped by a sphere from an upper
layer.(Planar triangle with vertex down wards)
 A hole formed by three spheres of a layer in contact W.E-3 Atoms of element B from hcp lattice and
with each other and also with a sphere of a next
lower layer (planar triangles with vertex upward)
 Note : In the above types of holes the four spheres
are arranged at the vertices of a regular tetrahedron. Sol: The number of tetrahedral voids formed is equal to
 If ‘X’ spheres form a solid there are a total of ‘2X’
tetrahedral holes.
rvoid
 Radius ratio of tetrahedral void, r  0.225 .
sphere
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Octahedral hole : It is the vacant space between
a group of three spheres in a layer and another set
of three spheres of a next layer. These six spheres
surrounding the hole, lie at the vertices of a regular
octahedron.
 In CCP or FCC lattice, one octahedral void is at
the body centre of the cube and one octahedral
void at the centre of each of the 12 edges. Hence
total number of octahedral voids
1
 1  12   1  3  4.
4
 If there are ‘X’ atoms in a close packed structure,
there are ‘X’ octahedral holes present.
 Thus number of tetrahedral holes is double the
number of octahedral holes. The size of these holes
depends on the size of the spheres producing them.
 Octahedral holes are larger than tetrahedral holes.
r
void
 Radius ratio of octahedral void r  0.414 .
sphere
Formula of a Compound and Number
of Voids Filled
W.E-2 A compound is formed by two elements X
and Y. Atoms of the element Y(as anions) make
ccp and those of the element X(as cations)
occupy all the octahedral voids. What is the
formula of the compound?
Sol: The ccp lattice is formed by the element Y. The
number of octahedral voids generated would be
equal to the number of atoms of Y present in it.
Since all the octahedral voids are occupied by the
atoms of X, their number would also be equal to
that of the element Y. Thus, the atoms of elements
X and Y are present in equal numbers or 1:1 ratio.
Therefore, the formula of the compound is XY.
those of the element A occupy 2/3rd of
tetrahedral voids. What is the formula of the
compound formed by the elements A and B?
twice the number of atoms of element B and only
2/3rd of these are occupied by the atoms of element
A. Hence the ratio of the number of atoms ofA and
B is 2x(2/3):1 or 4:3 and the formula of the
compound is A4 B3 .
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Locating Tetrahedral and Octahedral 1. Efficiency of packing in simple cubic unit
Voids: Generally close packed structures have cell : A simple cube is having 1 sphere per unit
both tetrahedral and octahedral voids. Let us take cell. Let consider the edge of a simple cubic unit as
ccp (or fcc) structure and locate these voids in it. a , then the volume of unit cell is a3 , we known
(a) Locating Tetrahedral Voids: Let us from the earlier discussion that in simple cube
consider a unit cell of ccp or fcc lattice.The unit cell
is divided into eight small cubes. a  2 rs where ' rs ' is the radius of sphere.
Each small cube has atoms at alternate corners. In Percentage efficienty of simple cubic unit cell =
all, each small cube has 4 atoms. When joined to volume of one sphere / volume of unit cell x 100
each other, they make a regular tetrahedron. Thus, (or)
there is one tetrahedral void in each small cube and 4 3 4 3
eight tetrahedral voids in total. Each of the eight    rs     rs 
3  100  3
small cubes have one void in one unit cell of ccp 3 3  100
a  2  rs 
structure. We know that ccp structure has 4 atoms
per unit cell. Thus, the number of tetrahedral voids 4
is twice the number of atoms. 
(b) Locating Octahedral Voids: Let us again (or) 3  100  52.3
consider a unit cell of ccp or fcc lattice. This unit 8
cell has one octahedral void at the body centre of Thus, the volume occupied by sphere in simple cubic
the cube. Besides the body centre, there is one unit cell is 52.3% and void volume is 47.7 per cent.
octahedral void at the centre of each of the 12 2. Efficiency of packing in body-centred unit
edges. Each edge of the cube is shared between cell : Consider a body-centred unit cell with edge
four adjacent unit cells. 1/4th of each void belongs
to a particular unit cell. length ' a ' and with radius of sphere ' rs ' . As body
Thus in cubic close packed structure Octahedral centred unit cell is having two spheres per unit cell
void at the body-centre of the cube=1. and a 3 is the volume of unit cell by taking edge
12 octahedral voids located at each edge and length ' a ' .
1
shared between four unit cells  12   3 G
4 B
 Total number of octahedral voids = 4
We know that in ccp structure, each unit cell has 4 H A
atoms. Thus, the number of octahedral voids is
equal to this number.
C a
Packing Fraction (Density of packing) F C
Efficiency (or packing fraction or density of b
a
packing) of a unit cell is defined in terms of the
percentage volume occupied by spheres in that unit E a D
cell, out of total available volume. It is calculated
by the following formula. From ABC , AC  2a and from ADF ,
No. of spheres / unit cell x
% efficiency = volume occupied by each sphere / AF  3a and we know
total volume of unit cell x 100

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Cubic Lattice Edge Nearest Number of Nearest Second Packing Example

system points length neighbours second nearest neighbor Nearest fraction
(a) neighbours distance neighbor
distance
Simple
1 2r 6 12 a 2a 52.4% Polonium
cube
Al, Cu,
Face 4r a
a Au, Pb,
centred 4 12 6 74%
2 2 Pt, Pd,
cube
Ni & Ca

Body 4r Na, K, Rb,

3 a
centred 2 8 6 a 68% Cs, Ba, Cr,
cube 3 2 Mo & W

 For HCP packing fraction is 74% Ex: Be, Mg, Cd, Co, Zn, Ti and Tl

G B
Body diagonal of cubic unit cell is 3a A
H
4
Thus, AF  4 rs  3a or a  3 rs
b

percentage efficienty of body-centered unit cell = F

C
Volume of two sphere / Volume of cube x 100
4 3
E D
2    rs  From ABC , ,
(or) 3  100
a3 AC  2a  4rs , (or)
4 3 4
2    rs  a rs  2 2 rs
3  100  68.05 2
3
(or)  4  We know that there are four spheres per unit cell in
 rs 
 3  a face-centred unit cell and thus per cent efficiency
of face centred unit cell.
Thus, the volume occupied by spheres in body- = Volume of four spheres / Volume of cube x 100
centred unit cell is 68.05% and void volume is
31.95%. 4 3
4    rs 
 Length of face diagonal - 2a  3  100
a3
 Length of body diagonal - 3a
4 3
3. Efficiency of packing in face-centred unit 4    rs 
3  100  74.06
cell : Consider a face-centred unit cell with edge = 3

3

2 2rs 
length ' a ' and volume a . Radius of sphere is Thus, the volume occupied by spheres in face-
taken as rs . It is clear from the figure that touch centred unit cell (ccp arrangement) is 74.06% and
with the two other atoms diagonally arranged. void volume is 25.94%.

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 For fcc lattice of an ionic crystal of NaCl type
edgelength, a  2  rc  ra 
 For bcc lattice of an ionic crystal edgelength
3a  2  rc  ra 
Calculation of density of unit cell :
Knowing the unit cell dimensions, the density of a
crystalline substance can be calculated from the 
formula
ZM ZM
 3 or
r 
N0a N0V Where = density
Z = No. of atoms (or) formula units per unit cell
M = Molecular weight of the lattice particle (Atomic
wt / formula wt )
a  unit cell length. v = volume
Defects in Solids: Ø At
Kelvin, a perfectly crystalline substance is said to 
have ideal packing which means that all the lattice
points are occupied by particles of the solid and
the crystal is perfect.
 As the temperature is increased, thermal motions
are induced which create imperfections in the solid. 
 Any deviation from the perfectly crystalline
arrangement in a solid is known as a defect.
 Broadly speaking the defects are of two types,
namely, point defects and line defects.
 Point defects are the irregularities or deviations from
ideal arrangement around a point or an atom in a
crystalline substance, whereas the line defects are 
irregularities or deviations from ideal arrangement
in some rows of lattice points.
Types of defects:
1) Stoichiometric defects
2) Non-stoichiometric defects
1) Stoichiometric defects: These are the
defects in which stoichometry of the ionic
compound remains the same after the defect.
The ratio of cations and anions is maintained even
after the defect.
Types of stoichiometric defects
1) Schottky defect 2) Frenkel defect
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Point defects in Crystals:
 Stoichiometric compounds are called Daltonoides,
non-stoichiometric compounds are called
Berthollides.
 Point defects are the irregularities or deviations from
ideal arrangement around a point or an atom in a
crystalline substance
Properties like density, entropy and heat capacity
are influenced by crystal defects to a lesser extent.
 The defects in the crystal, influence the properties
like mechanical strength, electrical conductivity and
chemical activity of the solids to a greater extent.
 Thermodynamically all solids possess a tendency
to acquire defects because defects result in disorder
and hence increase the entropy of the system
 Electron micro scope is used to know the defects
0 in a solid crystal
The defects in the crystals can be divided in to
different kinds
Types of Crystal defects
Intrinsic defects : These are seen in pure
crystals
 Extrinsic defects : These are due to the
impurities in the solids
 Point defects : These occur at the lattice points
or sites in the crystals
Extended defects: These are present in one or
more dimensions.
In stoichiometric compounds two types of defects
are observed
Stoichiometric defects: They are also called
intrinsic or thermodynamic defects. These are of
two types. ‘Vacancy defect’ and ‘interstitial defect’.
When some of the lattice sites are vacant, the crystal
is having vacancy defect. When some constituent
particles occupy an interstitial site, the crystal is
having interstitial defect. They are shown by non-
ionic solids.
 Ionic solids show.
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 SOLID STATE
a) Schottky defect
(Schottky-Wagner defects)
 This defect arises due to a vacancy at cation sites
and equal number of vacancies at anion sites
 In ionic crystals electrical neutrality is to be
maintained
Conditions for this defect
(a) High co-ordination numbers and
(b) Where the positive and negative ions are of
r
similar size i.e.,   1
r maintain electrical neutrality
Ex : NaCl, CsCl,KCl,AgBr
Consequences of this defect:
 Density of the crystal decreases.
 Stability decreases and the crystal is more prone to
collapsing with increased number of such defects.
 The crystal begins to conduct electricity to some
extent because ions can now move into the
vacancies caused by the defect.
 Schottky defect is found in highly ionic compounds
 Large number of vacancies in the lattice lower the
density
b) Frenkel defect: This type of defect arises due
to a vacancy at a cation site. Actually, The cation
moves to another position between two layers
(intersticial position) and it is surrounded by a greater
number of anions
Conditions Favouring Frenkel Defect:
 Frenkel defect is favoured by a large difference in
sizes between cation and anion
r
 Compounds having ions of different sizes i.e  is
r higher positive charge.
low since positive ions are smaller than negative
ions, generally the positive ions are found in interstitial
positions
 In these compounds the coordination number is
low(usually 4 or 6)
Ex : ZnS, AgBr, AgI, AgCl.
 Some ionic crystals have both the Schottky as well
as Frenkel defects Ex : AgBr
Consequences of Frenkel Defect:
 Density of the crystal is not altered
 Stability decreases
12
JEE-ADV CHEM-VOL-II
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c) Impurity defect : If molten NaCl containing
small quantity of SrCl2 is crystalised, some of the
Na+ ions are replaced by Sr+2. Each Sr+2 replaces
two Na+ ions. It occupies the site of one Na+ ion
and the other site remains vacant. Other example is
the solid solution of CdCl2 and AgCl.
Non Stoichiometric point defects :
They include
Metal excess defect (Due to anion vacancy)
: It is due to absence of anion from lattice site
leaving a hole which is occupied by electron to
A+ B- A+ B-
B- A+ e- A+
F - Centres : Holes occupied by electrons are
called F - Centres (Colour centres). The greater
the number of F - centres the greater is the intensity
of colour of solid and solids are paramagnetic in
nature due to F - centres
Eg : NaCl is yellow, KCl is violet, LiCl is pink
Crystals showing schottky defect also show this
defect.
Metal excess defect due to the presence of
extra cations at interstitial sites :ZnO on
heating loses oxygen and turns yellow. Now there
is excess of Zinc in the crystal. The excess Zn+2
ions move to interstitial sites and the electrons to
neighbouring interstitial sites.
heating 1
ZnO   Zn 2   O2  2e 
2
Metal deficiency defect due to cation
vacancy: It is due to absence of a metal ion from
its lattice site and charge is balanced by ion having
A+ B- O B-
B- A++ B- A+
Transition metals exhibits this defect. A typical
example of this type is FeO which is mostly found
with a composition of Fe0.95O . It may actually
range from Fe0.93O to Fe0.96O . In crystals of FeO
some Fe 2 cations are missing and the loss of
positive charge is made up by the presence of
required number of Fe 3 ions.
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SOLID STATE
Electrical and Magnetic properties
 Properties of solids depending on the nature of
bonding or cohesive forces present in them
 In ionic solids cohesive forces are due to the lattice
 The Magnitude of electrical conductivity strongly
energy and they originated from Coulombic forces
of attractions between the two ions
 In metals electrons are essentially mobile and so 
the properties of metals can be explained in terms
of electron bands formed by molecular orbitals.  when a large number of atoms unite their wave
 Crystals can possess various structures, these
structures can be studied by X-ray diffraction 
methods.
 Pure crystalline solids are also imperfect
arrangements. These defects in solids cause changes 
in the properties of the solids.
 Crystalline solids exhibit a wide range of properties 
namely, Electrical, Mechanical, Magnetic and other
properties.  One half of these resulting orbitals have lowered
 The physical properties of solid, its structure and
its chemical composition are all closely interrelated.
Electrical Properties :Based on electrical 
conductivity, solids can be broadly classified into
three types
 They are Metals, Semi-conductors and Insulators 
or Non-conductors
 Metals are conductors and have conductivity of the
order of 104 to 107 ohm–1m–1
 Insulators have very low conductivity of the order
of 10–20 to 10–10 ohm–1m–1
 At laboratory temperatures the conductivity of the
 The solids whose conductivity lies between those
of Metallic conductors and insulators are called
Semi-conductors. The order of conductivity of semi 
- conductors is 10–6 to 104 ohm–1m–1
 The electrical conductivity that is observed is usually
related to defects in the crystal.
 In such defective crystal the migration of ions or
charge imperfections(in case of Ionic conductivity)
or the motion of electrons and shifting of
holes(increase of electronic conductivity) relate the 
conductivities.
 The mechanism of electrical conductivity may be
NARAYANAGROUP
JEE-ADV CHEM-VOL-II
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given in terms of
a) Vacancy Mechanism
b) Interstitial Mechanism and
c) Interstices Mechanism
depends on the number of electrons available to
participate in the conduction process.
In Metals the conductivity depends on the number
of valence electrons present per atom.
functions interact.
This results in a large number of molecular orbitals
or energy levels, some Bonding and some
antibonding.
These energy levels are closely spaced energy levels
and are known as bands.
The number of energy levels is equal to the number
of Atomic orbitals interacting.
energy levels and are known as bonding orbitals.
They are of similar energies and form a continuous
band of orbitals.
The other half of resultant orbitals have raised energy
levels are known as Antibonding energy levels or
orbitals.
At all real temperatures the band has a large number
of half filled energy levels. Electrons can flow readily
through these bands only when the band is
incompletely filled with electrons or when electronic
band(filled energy levels) is very close to vacant
molecular orbitals.
metals is nearly independent of impurities and the
lattice defects.
At low temperatures the mobility due to vibrations
in the lattice is quite negligible and as a result the
conductivity becomes infinitely large.
 The conductivity of metals generally decrease with
an increase in temperature. This is probably due to
increased vibrations in the lattice points the
resistance to the flow of electrons increases.
The impurities in the metal and the imperfections in
the lattice also contribute to the conductivity.
13
 SOLID STATE
 Measurement of the resistance of the metal as 
resistance ratio 300 K  4.2 K explain the purity of
the metal.
 The conductivity of semi conductors varies
completely in the opposite way to that of the metals.
 Semi conductors conductivities increases with
increase in temperature. This is due to the fact that
the electrons from the valence band jump to the
conduction band.
 Pure semi conductors which exhibit this property
are known as intrinsic semi conductors.
 The temperature zone where the conductivity
depends on the thermal electrons and the holes in
the lattice of the semi conductors is known as intrinsic
region.
 At low temperature the conductivity is mainly
determined by the concentrations of the electron
donors and the acceptors. This region is known as
extrinsic region.
Doping: Addition of B  IIIAGroup   or 
P  or  As VA Group  element to alter the
conductivity of Ge  or  Si is called as doping.
 Pure Si  or  Ge are intrinsic semiconductors
 In doping, group IIIA 13 group element  
element behaves as electron acceptor and group
 Metal sulphides of transition elements also exhibits
VA 15group elements  element behaves as
donor.
Electron - rich impurties: When VA (or)
15th group element is added to Si , the crystal
lattice does not change, but few Si atoms are
replaced by group VA (or) 15th group elements, it
forms covalent bonds with Si the fifth electron is
delocalised, therefore Si becomes electrical
conductor.
 Silicon doped with VA (or) 15th group element is
known as ‘n’ type semi conductor ( n = negatively
charged electrons are responsible for conductivity)
 In doping, VA (or) IIIA group element is called as
dopant
14
JEE-ADV CHEM-VOL-II
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When IIIA (or) 13th group ;element like B (or)
Al or Ga or In is added to Si, the substitution
of few Si atoms by group IIIA takes place
Electron - deficit impurties: IIIA group
element has only 3 valence electrons. One more
electron is required, it is left as a vacant place on
the atom. This is called as electron vacancy or a
hole.
 This electron vacancy in the crystal structure
migrates from one atom to another. This is
responsible for electrical conductivity of Si.
 ‘Si’ doped with IIIA (or) 13th group element is
called p – type semiconductor
Applications: n – type and p – type semi
conductors both are used in electronic devices
Example : Diode, pnp or npn type semiconductors
are used in transistors.
 These transistors are used to detect (or) amplify
radio or audio signals
 In the conversion of radiant energy into electrical
energy solar cell (p – n type ) is used
 Many solid state semiconductors are prepared by
combining IIIA or 13th group elements with VA or
15th group elements and IIB or 12th group elements
with VIA or 16th group
 In this type of conductors bond is not pure covalent.
Nature of the bond depends on electronegativities
of two elements.
Transition metal oxides shows wide variation in this
electrical properties.
wide variation in their electrical properties.
Magnetic Properties: Every substance has
some magnetic properties associated with it. Each
electron in an atom behaves like a tiny magnet. Its
magnetic moment originates from two types of
motions (i) its spin around its own axis. Electron
being a charged particle and undergoing these
motions can be considered as a small loop of curent
which possesses a magnetic moment. Thus, each
electron has a permanent spin and an orbital
magnetic moment associated with it. Magnitude of
this magnetic moment is very small and is measured
in the unit called Bohr magneton  B . It is equal to
9.27  1024 Am 2 .
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(d) Anti Ferromagnetism: It is due to
Magnetic Magnetic compensatory alignment of moments. The net
moment Electron moment
moment is Zero. The alignment of magnetic
moments in these substances is
Electron
Direction
Atomic of spin
nucleus
Ex : MnO2, V2O3, NiO etc.
(a) (b)
(e) Ferrimagnetism :It is due to the unequal
The substances can be classified into five types number of alignment of moments in parallel and
antiparallel directions. It results in the net moment.
depending on their response to an applied magnetic
field.
(a) Diamagnetic Materials : The substances
which are weakly repelled by magnetic field Fe3O4 and Ferrites like MgFe2O4, CuFe2O 4,
examples NaCl, KCl, TiO2 ZnO, H2O Benzene ZnFe2O4, NiFe2O4 , etc.
etc. B <<< H  All the magnetically ordered solids transforms to
Alignment of magnetic moments in diamagnetic the paramagnetic state at elevated temperatures due
substances to the randomization of spins
Ex : V2O3 changes to paramagnetic at 150 K and
NiO at 523 K
The substance also lose ferrimagnetism on heating
and become paramagnetic
(b) Paramagnetic Materials:The substances
which are attracted by magnetic field due to the Bonding in metallic solids : Any theory
presence unpaired electrons on atoms, ions or which is proposed to explain bonding in metals must
molecules. be capable of explaining the following.
They lose their magnetic property when the applied  Bonding between atoms of the same element and
field is removed (i.e identical atoms) between atoms of widely
Ex : O2, Cu++, Fe+2, Fe+3, Cr+3, Na, Ti2O3, differing metals and bonding in. alloys.
VO2 , NO etc B > H  Should not involve directional bonding
 The properties of metals in solutions and in liquid
(c) Ferromagnetic Materials:The substances states etc.
which are strongly attaracted by magnetic field.  The mobility of electrons.
These substances contain domains of magnetization.
(a) Electron Sea model: It was initially
All of them are oriented in the same direction. They
proposed by Drude and refined by Lorentz. It is
retain their magnetism even after withdrawal of
known as Drude – Lorentz theory.
applied field.
 According to this theory, The force that binds a
Ex : Fe, Co, Ni, CrO 2 , Gadalonium
metal ion to the mobile electrons within its sphere
etc. B >>>> H of influence is known as metallic bond.
 Fe, Co, Ni, are the only three elements which show  The formation of metallic bond involves
ferromagnetism at room temperature.  A metal lattice comprises of rigid spheres of metal
The alignment of magnetic moments in these ions
substances is  Each metal atom contributes its valence electrons
to the sea
 These electrons move freely in the lattice free
spaces i.e. interstices
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 Cohesive forces result from electrostatic attractions electron pair bonds.
between the positive metal ions and the electron  Resonance occurs due to the possibility of
cloud. insufficient valence electrons for the formation of
 It explains electrial conductivity and metallic lustre electron pair bonds with each at om of
Defects: Failed to explain quantitative calculations the metal.
for the lattice energies of ionic compounds. Resonance not only involves covalent bonds but
also ionic linkages.
(b) Valence bond theory of metals:It was
Defects:
proposed by Linus Pauling. This theory is also
 does not explain the conduction of heat
referred as Resonance theory. According to this
 Metallic lustre
theory,
 Retention of the metallic properties in either the
 The metallic bond is essentially a polar or a non
liquid state or in the solution.
polar covalent bond.
dimensional hexagonal close packing. .
 The covalent bond involves resonance between a
number of structures having one electron and

Crystal No. of formula

S.No Packing Cord.No Example
structure units per unit cell

1. Rock salt (NaCl) Cl in ccp 6 4 Halides of Li,
Na+ in octahedral Na, K, Rb,
voids AgCl, AgBr
NH4Cl
2 
2. Zinc blende(ZnS) S in ccp Zn in 4 4 CuX(Cl, Br, I),
alternate tetrahedral AgI, BeS
voids tetrahedral
voids

3. Wurtzite (Zns) Zn in hcp 4 4 -

S2 in alternate
tetrathedral voids

4. CsCl Cs in Cubic Voids 8 1 CsBr, CsI,


Cl at the corners CsCl,TlCl,
of a cube or TlBr, TlI,
vice versa TlCN
++ ++ 
5. Fluorite (CaF2) Ca in ccp. Ca ,F 4 SrF2, BaF2,
F in tetrahedral (8, 4) BaCl2, CaF2,
voids CdF2, PbF2

6. Antifluorite S2 in ccp, Li+ in Li,S 4 Na2O, Li2O,

(Li2S) tetrahedral voids (4 ,8) K2O, Na2O,
K2 S

16 NARAYANAGROUP
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Dielectric properties: A dielectric is a
substance in which an electric field gives rise to net ADV. MAIN POINTS
flow of electric charge.
 Under the influence of applied field, dipoles are
developed in these susbstances.
 These dipoles align in two different ways
a) in such a way that there is a net dipolemoment
(non - compensatory way)
b) in such a way that there is no net dipolemoment
(compensatory way) (a) (b)
 The crystals in which there is a net dipolemoment
when subjected to a stress, produce electricity. It Fig. Two dimensional strcuture of (a) quartz
is called piezoelectricity or pressure electricity. and (b) quartz glass.
 In some piezoelectric solids, dipoles are
spontaneously aligned in a particular direction, even B
D
in the absence of electric field. They are called
‘ferroelectric substances’.
eg : Barium titanate (BaTiO3), sodium potassium
tartarate, potassium hydrogen phosphate
(KH2PO4) etc.
In some crystals, the dipoles align in opposite
directions, then there is no net dipolement. They
are called ‘antiferroelectric susbstances’
C A
eg : lead zirconate (PbZrO3)
If electricity is produced on heating the crystal then Fig. Anisotropy in cryastals is due to different
it is called pyroelectricity. arrangement of particles along different
 Applications : Piezoelectric crystals are used in directions.
microphones, ultrasonic generators, sonar Poly Crystalline Solids
detectors, transducers etc. In certain crystalline solids the crystals are very fine.
Number of Schottky Defects in a These cannot be seen by the naked eyes. Such
Crystal solids give an impression of being amorphous. Such
fine crystalline solids whi ch appear as amporphones
n  Ne  E / 2 kt as termed as polycrystalline solids.
k = Boltzmann’s constant,
Eg : Metal powders
T = Kelvin temperature
* In a polycrystalline sample, there are small crystals.
E = energy required to create defect
These crystals are randomly oriented . As a result,
N = Number of ions present
a sample of polycrystalline material appears to be
1/ 2
 n   NN i  e E /2 kt isotropic, even when each small crystal is
anisotropic.
N i = number of interstitial spaces
Crystal Lattices and Unit Cell
Spinel Structure:Spinels are oxides with A crystal can be considered to be generated from
two types of metal ions, one is divalent and the other the repetition of some basic unit of pattern such as
is trivalent. atoms, molecules or ions. In other words, a well
For example : MgAl2O4 ordered and regular arrangement of constituents in
 In normal spinel structure, oxide ions from ccp, the three dimensional space is called crystal lattice.
divalent metal ions occupy 1/8th of the tetrahedral A space lattice can be sub-divided into a number
holes and trivalent metal ions occupy 1/2 of the of small cells known as unit cells. It can be defined
octahedral holes. as the smallest block from which entire crystal can

NARAYANAGROUP 17
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be built up by its translational repetition in three
dimensions. Effective Number of Atoms in a Unit Cell
In a crystal atoms located at the corner and face
Lattice Points
center of a unit cell are shared by other cells and
only a portion of such an atom actually lies within a
Y given unit cell.
1. A point that lies at the corner of a unit cell is shared
c
c among eight unit cells and therefore, only one eighth
O b
X b
X of each such point lies within the given unit cell.
a a
Z 2. A point along an edge is shared by four unit cells
Z
and only one-fourth of it lies within any one cell.
Space lattice and Unit cell 3. A face-centred point is shared by two unit cells and
only one half of it is present in a given unit cell.
According to Bravis “three vectors and their angles
study shows morphologically that the unit cells can 4. A body-centred point lies entirely within the unit cell
and contributes one complete point to the cell.
be classified into seven crystal systems based
Type of Contribution to one
on the presence of certain rotation axes.” These
Lattice point unit cell (in Cubic
seven crystal systems are :
Unit Cell)
(i) Cubic (ii) Orthorhombic
Corner 1/8
(iii) Rhombohedral (iv) Monoclinic
Edge 1/4
(v) Triclinic (vi) Tetragonal
Face-center 1/2
(vii) Hexagonal
Body Center 1
Bravis further shows that there would be only four
In IIT-JEE, we only have two crystal systems in
possible ways in which constitutent species of a unit
syllabus, of which only four Bravais lattices exist.
cell can be arranged. They are
Thus we have to study only
(i) Primitive or simple (ii) Body centered
(i) Primitive or simple cubic
(iii) Face centered (iv) End centered
(ii) Body centered cubic
So, the total number of possible unit cells are
(iii) Face centered cubic
7 x 4 = 28. Out of these 28 possible unit ceils, only
(iv) Hexagonal primitive
14 of them exist in nature:
Rank: Rank of a unit cell means the number of
The seven crystal systems and their unit cell
effective atom (or ions) in a unit cell
parameters are shown as

Unit cell parameters

Crystal systems Bravais lattices
Intercepts Crystal angles

1. Cubic Primitive, Face centered, a=b=c  =  =  = 90

Body centered
2. Rhombohedral Primitive a=b=c  =  =   90
Primitive, Face centered,
3. Orthorhombic Body centered, End center a  b  c  =  =   90

4. Triclinic Primitive abc       90

5. Monoclinic Primitive, End centered abc       90
6. Tetragonal Primitive, Body centered a=bc  =  =  = 90
7. Hexagonal Primitive a=bc       120

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Coordination Number: the co-ordination
number is the number of nearest atoms (or ions)
surrounding an atom (or ion) in a crystal lattice.
Simple Cubic Cell : In a lattice of this type,
each corner atom is shared by eight unit cells, four (a) (b) (c)
in one layer and four in the layer above it, as shown HCP Unit Cell :
in figure. Hexagonal Close Packing: Each corner atom
would be common to 6 other unit cells, therefore
their contribution to one unit cell would be 1/6. Total
12
number of atom in 1 hcp unit cell =
(from 12
6
2 3
corners) + (from 2 face centred) + (from
(a) (b) (c) 2 1
body centre) = 6.
Thus, the contribution of each atom placed at the
corner of single cubic unit cell is 1/8. Since, there
are eight corners of a cube, the effective number of
atoms 1 associated with a single primitive unit cell
is 1/8 × 8 = 1.
Thus, the rank of a primitive cubic unit cell is 1.
BCC Unit Cell : In a BCC lattice, each corner
atom is shared by 8 unit cells while the body
centered atom is not shared by any other unit cell.
(a) (b)
So, the number of effective atoms associated with
Hexagonal closest packing of spheres:
1  (a) normal and (b)diagramatic view
a BCC unit cell is   8  + 1 = 2. Thus, the rank Illustration 1: What is the simplest formula of a
8 
solid whose unit cell has the atom A at each
of a BCC unit cell is 2. corner, the atom B at each face centre and a
atom C at the body centre.
(A) A2BC (B) AB2C
(C) AB3C (D) ABC2
Sol: An atom at the corner of a cube is shared among 8
unit cells. As there are 8 corners in a cube, number

(a) (b) (c) 1

of corner atom (A) per unit cell  8    1
8
FCC Unit Cell : In a FCC unit cell, each corner A face-centred atom in a cube is shared by two
atom is shared by 8 unit cells and each face centered unit cells. As ther are 6 faces in a cube, number of
atom is shared by 2 unit cells, so the number of 1
face-centred atoms (B) per unit cell = 6  = 3.
effective atoms in a FCC unit cell would be 2
An atom in the body of the cube is not shared by
1  1  other cells.
 8  8    2  6   4 . Thus the rank of a FCC
     Number of atoms (C) at the body centre per
unit cell is 4, This is shown in Figure. unit cell = 1.
Hence (C), the formula of the solid is AB3C.

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Illustration 2: Potassium crystallizes in a body VOIDS IN FCC UNIT CELL
centred cubic lattice. What is the approximate Tetrahedral voids :
number of unit cells in 4.0g of potassium?
Atomic mass of potassium = 39 Tetrahedral
(A) 3.09 × 1022 (B) 2.09 × 1021 Void
21
(C) 4.10 × 10 (D) 3.09 × 1020
Sol: There will be eight atoms at corners of the cube
and one atom at the body centre.
 1
 Number of atoms per unit cell =  8  8 
  Tetrahedron
+1=2
 Number of unit cells in 4.0 g of
4 6.023  1023
potassium =  = 3.09 × 1022
39 2
Hence ‘A’ is the correct Choice.
In CCP unit cell there are 8 tetrahedral voids and 4
octahedral voids.
No. of tetrahedral voids in an unit cell = No. of
octahedral voids `2 (a) (b)
* The HCP and CCP arrangements can also Fig. (a) Eight tetrahedral voids per unit cell of ccp structure
be shown as below : (b) One tetrahedral voids showing the geometry.

Octahedral voids :
Octahedral Void

b b

a
(a)
Octahedron
(b)

A B Fig. Location of octahedral voids per unit cell

Hexagonal closest packing of
Fig : Cubic closest packing of spheres : (a) of ccp or fcc lattice.
generation of unit from closest packed
spheres: (a) normal and (b)
exploded view
layers and (b) rotation to show cubic At the body centre of the cube and at the centre
symmetry.
of each edge.
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Illustration 3: Ferric oxide crystallizes in a BD = r+ + r–
hexagonal close packed array of oxide ions ABC = 60°  BDC = 120° or BDE
with two out of Every three. Octahedral holes = 60°  DBC = 30°
occupied by ferric ions. The formula of the BE
ferric oxide is BD =  r+ + r– =
cos30
(A) FeO (B) Fe3O4 = 1.155r–
(C) Fe2O3 (D) None of these
– – ;
r
Sol: Suppose the number of oxide ions (O ) in the2–  r+ = 1.155r – r+ = 0.155r = 0.155
r
packing = N.
Co-ordination Number 4: (tetrahedron)
No. of octahedral voids = N
As 2/3rd of the octahedral voids are occupied by ferric
ions, therefore, number of ferric ions present B
2 2N
 N 
3 3
D
Therefore, ratio of Fe3+ : O2  2N : N  2 : 3 A C
3
Hence ‘C’, the formula of ferric oxide is Fe2O3.
 Radius Ratio Rules:
The structure of many ionic solids can be accounted
Angle ABC is the tetrahedral angle
by considering the relative sizes of the cation and
  ABC = 109° 28’   ABD =
anion, and their relative numbers. By simple
calculations, we can work out as how many ions of 1
(109° 28) = 54° 44¢
a given size can be in contact with a smaller ion. 2
Thus, we can predict the co-ordination number from AD r
sin (ABD) = 0.8164 =   
the relative size of the ions. AB r  r
Calculation of some limiting radius ratio values
r  r 1 r
 = 1.225 Þ = 0.225
r 0.8164 r
Co-ordination Number 6: (Octahedron):
A A cross section through an octahedral site isshown
in the adjacent figure and the smaller positive ion
touches six larger negative ions. (Only four negative
D ions are shown in the figure but there is one sphere
above and the below the plane of paper).
E
B C In this figure AB = r+ + r– and BD = r–

Co-ordination Number 3: The adjacent figure A

+
shows the smaller positive ion of radius r in contact
with three larger anion of radius r–. B C
D
In this figure, AB = BC = AC = 2r– BE = r–
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ABC = 45°  cos(ABD) = 0.7071 = For cubic crystals of elements:

BD r r
 ; Solving, we get   0.414
AB r   r  r
Limiting Co-ordina- Shape Examples
radius ratio tion number
<0.155 2 Linear BeF2
0.155-0.225 3 Trigonal B2 O3
planar a

0.225-0.414 4 Tetrahedral ZnS , Let the edge of the unit cell = a pm

4
SiO 4 No. of atoms present per unit cell = Z
0.414-0.732 4 Square PtCl42  Atomic mass of the element = M
3 3 3
planar  Volume of the unit cell = (a pm) = a pm
= a3 ´ 10–30 cm3
0.414-0.732 6 Octahedral NaCl
0.732-0.999 8 Body Density of the unit cell,
CsCl
centred  No.of atomsin its unit cell  ×  Massof each atom 
r
cubic 3
a  10
30
Illustration 5: The limiting radius ratio of the
complex [Ni(CN)4]2–is M
= Z
(a) 0.225 – 0.414 (b) 0.414 – 0.732 N
3
A
30
g / cm 3
(c) 0.155 – 0.225 (d) None a  10
Sol: (b) The complex [Ni(CN)4]–2 is square planar. So, Z M
it has limiting radius ratio as octahedral structure (NA – Avogadro’s number) = N  a 3  1030 g/cm3z
A
i.e. 0.414 – 0.732.
For cubic crystals of ionic compounds: Here, Z is
the number of formula units present in one unit cell
Illustration 6: In closest packing of A type of
and M is the formula mass. The formula will remain
atoms (radius, rA), the radius of atom B that
the same viz.
can be fitted Octahedral void is
(a) 0.155 rA (b) 0.125 rA IIllustration 7:Niobium crystallizes in a body
centred cubic structure. If density is 8.55 gcm–
(c) 0.414 r (d) 0.732 rA 3
, The atomic radius of niobium, (given that its
Sol: (c) For octahedral void atomic mass is 93 u) is
rB (A) 49.8 pm (B) 150.1 pm
 0.414 or, rB = 0.414 rA
rA
(C) 143.1 Å (D) 143.1 pm
Calculations Involving Unit Cell Dimensions
Sol:
If we know the type of crystal structure possessed
by the cubic crystal, so that the number of particles M Z 93gmol1  2
a3  
per unit cell are known and the edge length for it is N0 1030 8.55gcm3  6.021023 mol1 1030
known by X-Ray studies, the density of the crystal
can be determined.  3.61 107  36.1 106

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a  (36.1)1/ 3  102 pm  3.304  102 pm  330.4pm and 4 Cl– ions per unit cell. The formula is Na4Cl4
i.e. NaCl. Other examples for this type of structure
 1/ 3 1 1  are all halides of alkali metals except CsCl and all
 x  (36.1) ,logx  3 kg 36.1  3  1.5575  0.519 oxides of alkaline earth metals except BeO.
 

or x = antilog 0.519 = 3.304] Na

For body-centred cubic, Cl 

3
r a  0.433a  0.433  330.4pm  143.1pm .
4

Hence ‘D’ is correct choice.

Illustration 8: Copper crystallizes into a fcc Iattice
with edge length 3.61 x 10–8 cm. The calculated Zinc Blende Structure (ZnS): Sulphide ions are
density is face centred and zinc is present in alternate
(A) 8.97 gm/cc (B) 10.9 gm/cc tetrahedral voids. Formula is Zn4S4, i.e. ZnS.
Coordination number of Zn is 4 and that of sulphide
(C) 5.45 gm/cc (D) 6.02 gm/cc
is 4. Other substance that exists in this kind of a
Z M structure is BeO.
Sol: 
a3  V0
for fcc lattice of copper, Z = 4 ; Zn2

atomic mass of copper, M  63.5 gmol1 S2

4  63.5 gmol1

(3.61 108 cm)3  (6.022  10 23 mol1 )
S2ion surrounded
 8.97 gcm3 tetrahedrally
Hence ‘A’ is the correct choice. by four Zn2+ ions

Classification of Ionic Structures

Simple ionic compounds are of the type ABAB2 Cesium Chloride (CsCl) type structure: CsCl
where A and B represent the positively and has body-centred cubic (bcc) arrangement. Each
negatively charged ions respectively. (In any solid Cs+ ion is surrounded by 8 Cl– ions and each Cl–
of the type AxBy, the ratio of co-ordination number ion is surrounded by 8 Cs+ ions i.e. this structure
of A to B would be y : x. has 8:8 co-ordination. A unit cell of CsCl consists
of only one unit of CsCl i.e. One Cs+ ion and one
Structures of Type AB:
Cl– ion. Few examples of compounds having CsCl
Ionic compounds of the type AB means compounds structure are CsBr, CsI, CsCN, TlCl, TlBr, TlI and
having the positively and negativelycharged ions TlCN.
in the ratio 1:1. These compounds can have
following three type of structures.
1. Rock salt (NaCl) type
2. Cesium chloride (CsCl) type
3. Zinc blende (ZnS) type
Rock Salt (NaCl) type Structure: Cl– is forming a
FCC unit cell in which Na+ is in the octahedral voids.
The co-ordination number of Na+ is 6 and that of +
Cs ion surrounded

–
Cl would also be 6. Moreover, there are 4Na ions+ by 8 Cl ions

NARAYANAGROUP 23
 SOLID STATE
Structure of Ionic Compounds of the Type AB2:
These are the ionic compounds having cations/
anions or anions/cations in the ratio 1:2. Most of
these compounds have calcium-fluorite (CaF2) type
structure. These compounds have cubic close
packing (CCP) arrangement in which Ca2+ ions are
present at the corners and the centre of each face
of the cube.
Each Ca2+ ion is surrounded by 8F– ions i.e. it has
a co-ordination number of 8 whereas each F– ion
is surrounded by 4 Ca2+ ions i.e. has a co-ordination
number of 4. Thus this structure has 8:4 co-
Defects in Solids:
ordination. Few examples of such compounds
having CaF2 structure are BaF2, BaCl2, SrF-2,
SrCl2, CdF2, PbF2 and ThO2.
Ca
2

F
Metal excess and metal deficiency defects
+
In Na2O each oxide ion is co-ordinated to 8 Na
ions and each Na+ ion to 4 oxide ions. Hence it has
4:8 co-ordination. This is called anti-fluorite
structure. Others examples being Cl2O, K2O,
Li2O, K2S, Na2S etc.
Structure of truncated octahedron
The truncated octahedron is the 14-faced
Archimedean solid, with 14 total faces : 6 squares
and 8 regular hexagons.
Truncated octahedron
The truncated octahedron is formed by removing
the six right square pyramids one from each point
of a regular octahedron as
24
JEE-ADV CHEM-VOL-II
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Truncated octahedron unfolded in two dimensions.
Schottky defects: In this type of defect, a
vacancy is created in a metal by the migration of
metal atom (or ion) to the surface. If a Schottky
defect occurs in an ionic crystal, both anion and
cation migrate.
Frenkel defects: These defects arise when an
atom or an ion becomes displaced from its proper
position in the crystal lattice and takes up an
interstitial position along side. This is possible when
the lattice contains large enough interstices.
i) Metal excess defects: When a crystal of
NaCl is heated in sodium vapours, it acquires a
yellow color. This yellow color results from the
formation of a non stoichiometric compound of
NaCl in which there is a slight excess of Na+ ions
which are formed as a result of their ionization.
ii) Metal deficiency defects: This deficiency
arises when one of the metallic cations (ie positive
ion) is missing from its lattice site. The extra negative
charge there by created is balanced by another metal
ion near it acquiring an additional +ve charge. A
deficiency of metal ions thus occurs.
Properties of Solids
Electrical Properties: Solids can be broadly
classified into three types, on the basis of electrical
conductivity.
(a) Metals (conductors)
(b) Insulators
(c) Semi-conductors
Electrical conductivity of metals is very high and
is of the order of 106 – 108 ohm–1 cm–1 whereas
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for insulators, it is of the order of 10–12 ohm–1 cm–1. * The conductivity of semi conductor increases with
Semi-conductors have intermediate conductivity in a rise in temperature and also called as intrinsic
the range of 10 2 – 10 –9 ohm–1 semiconductors.
cm–1. Electrical conductivity of solids may arise
Magnetic Properties
through the motion of electrons and holes (positive)
or through the motion of ions. The conduction Diamagnetic Materials: Those materials
through electrons is called n-type conduction and which are weakly repelled by the magnetic field are
through (positive) holes is called p-type conduction. called diamagnetic materials. e.g. Cu+, TiO2, NaCl
Pure ionic solids where conduction can take place and benzene. They do not have unpaired electrons.
only through movement of ions are insulators. The Paramagnetic Materials: The materials which
presence of defects in the crystal structure increases are weakly attracted by magnetic field are called
their conductivity.
paramagnetic materials. These materials have
The conductivity of semi-conductors and insulators permanent magnetic dipoles due to presence of
is mainly due to the presence of interstitial electrons atoms, ions or molecules with unpaired electron.
and positive holes in the solids due to imperfections. e.g. O2, Cu2+, Fe2+ etc. But these materials lose
The conductivity of semi-conductors and insulators
their magnetism in the absence of magnetic field.
increases with increase in temperature while that of
metals decrease. Ferromagnetic Materials: The materials
which show permanent magnetism even in t he
Conduction of Electricity in semi conductors:
absence of magnetic field are called ferromagnetic
materials. These materials are strongly attracted by
Energy Energy
the magnetic field. e.g. Fe, Co, Ni and CrO2.
Vacant Vacant Ferromagnetism arises due to spontaneous
conduction conduction
band band alignment of magnetic moments of ions or atoms in
Small the same direction.
energy gap
Eg (Large)
Filled
Alignment of magnetic moments in opposite
Valance directions in a compensatory manner and resulting
Filled band
Valance in zero magnetic moment gives rise to anti-
band ferromagnetism

Insulator Intrinsic  ;  ; 

Semiconductor ferromagnetism Anti  ferromagnetism Ferrimagnetism

for example, MnO, Mn2O3 and MnO2.

Energy Alignment of magnetic moments in opposite

Vacant directions resulting in a net magnetic moment due
conduction
band to unequal number of parallel and anti-parallel
magnetic dipoles give rise to ferri- magnetism
Impurity e.g. Fe3O4.
band
Ferromangetic and ferrimagnetic substances change
into paramagnetic substances at higher temperature
Filled
Valance due to randomisation of spins. Fe 3O 4 , is
band
ferrimagnetic at room temperature and becomes
Impurity paramagnetic at 850 K.
Semiconductor

NARAYANAGROUP 25