Standard :- XII Subject :- Chemistry

CHAPTER NO. 1

SOLID STATE
Marks with option = 5
Marks without option = 3
Introduction
⚫ There are 3 most common states of matter Solid, Liquid and
Gas.
⚫ Solids have definite shape and volume due to strong interparticle
forces.
⚫ The shape and volume of solids slightly change with change in
temperature.
⚫ The smallest constituent particles are atoms,ions or molecules.
Types of solids:- There are two types of solids,
1.Crystalline solids:They have following characteristics
i. Regularity and periodicity in the arrangement of particles.
ii. Sharp melting point.
iii.Anisotropic, except those having cubic structure.
Examples:- Ice, Gold, Copper, Diamond etc.
2.Amorphous solids: They have following characteristics.
i. No regular arrangement of particles.
ii.No sharp melting points.
iii.Isotropic.
Examples:- Glass, Plastic, Rubber etc.
 Isomorphism and Polymorphism
i. Isomorphism :- Existance of two or more substances
having same crystal structure.Examples:-
1. NaF and MgO have same atomic ratio 1:1.
2. NaNO3 and CaCO3 having different atomic ratio 1:1:3.
ii. Polymorphism:- Existance of a single substance in two
or more crystalline forms. Example:-
Calcite and Aragonite are two crystalline forms of CaCO3
In elements Polymorphism is called as allotropy.
Examples:- Diamond, Graphite and Fullerenes are
allotropic forms of carbon.
 Classification of crystalline solids
Types Characteristics Examples Diagrams

Ionic crystals • The constituent particles are ions 1. NaCl

• Interparticle force is electrostatic 2. K2SO4
force of attraction 3. CaF2
• Hard, Brittle and have high Melting
points
• Non conductors of electricity

NaCl

Covalent • The constituent particles are atoms 1. Diamond

network • There is covalent bond between 2. Quartz
solid atoms
• Hard, Incompressible and have high
melting point
• Poor conductors of heat and
electricity
Shri S wami Vivekanand kshan Sanstha, Kolhapur. Diamond
Shi
 Type Characteristic Examples Diagram

Molecular solids • The constituent particles are 1. Phosphorus

molecules. 2. Sulphur
• Intermolecular forces are London
forces, Dipole- Dipole interactions
etc.
• Soft and have low melting points.
• Poor conductors of electricity london force

White Phosphorous

Metallic • Constituent particles are held 1. Sodium

Crystals together by metallic bond. 2. Potassium
• They are malleable 3. Iron
• They are ductile 4. Aluminium
• They are good conductors of heat
and electricity

Shri Swami Vivekanand kshan Sanstha, Kolhapur. Magnesium

Shi
Crystal structure:- It is the ordered three dimensional
arrangement of particles in a crystal.
Lattice :- A geometrical arrangement of points in a three
dimensional periodic array .
Basis: The constituent particles attached to lattice points
form a basis.
 Unit cell:- The smallest repeating structural unit of a
crystalline solid is called as unit cell.
Types of unit cell:- There are four types,
1.Primitive or simple unit cell:- The constituent particles
are present only at a corner of unit cell.
2. Body centred unit cell:- In addition to corner, one particle
is present at centre of body.
3. Face centred unit cell:- In addition to corner,there is one
particle at the centre of each of the faces.
4.Base centred unit cell:- In addition to corner,there is one
particle at the centre of any two of its faces.
Crystal system:- There are only 14 ways in which similar
points can be arranged in a three dimensional order. i.e.
there are only 14 kinds of space lattices, which are known
as Bravais lattices. These 14 Bravais lattices are divided in
to 7 crystal systems.
Cubic system:- There are three types of unit cells in cubic
system, simple cubic unit cell (sc), body centred cubic unit
cell (bcc) and face centred cubic unit cell (fcc).
1.Simple cubic unit cell (sc): It has a particle at each of the
eight corners of a cube.

2. Body centred cubic unit cell(bcc): It has particles at its

eight corners and an additional particle in the centre of the
cube.
3. Face centred cubic unit cell(fcc): It has particle at the
each of six faces in addition to the particles at eight corners
of the cube.
Crystal system and Bravais Lattices
Number of particles in cubic unit cell:-

1.Simple cubic unit cell (sc):-

In simple cubic unit cell, each corner of a given unit cell is
shared with seven other neighbouring cubes. i.e. corner
particle contributes its 1/8th part to given unit cell. Hence it
has 1/8 8 = 1 particle per unit cell.
2. Body centred cubic unit cell (bcc):-
In addition to corner, there is one particle at the centre of
cube, which is not shared by any other cube. Hence there
are ( 1/8 8 ) = 1 + 1 =2 particles per unit cell.
3. Face centred cubic unit cell (fcc):-
In addition to corner, there is one particle at the centre of
six faces and each particle is shared with one
neighbouring cube i.e. it contributes 1/2 part to given unit
cell. Hence it has (6 ½ ) = 3 + 1 = 4 particles per unit
cell.
Relationship between molar mass, density of substance
and edge length of unit cell:-
• If m is the mass of one particle, n is the number of
particles per unit cell and ‘a’is the edge length of cubic
unit cell. then,
=m a3
• If M is molar mass and NAis number of particles per
mole
Then, m = M/ NA
Therefore, = n M a3 NA
Packing of particles in crystal lattice :-
Coordination number:-The number of neighbouring
spheres that touch any given sphere is called as
coordination number.
Close packed structures:-
a)Close packing in one dimension:-
It results by arranging the spheres to touch each other in a
row.
b)Close packing in two dimensions:-
It results by stacking the rows together such that they are
in contact with each other.There are two ways to obtain
close packing in two dimensions.
i)Square close packing:-
In this type, one dimensional rows are stacked such that
spheres align vertically and horizontally. If first row is
named as A ,then second row also named as A. This
arrangement is called as A,A,A……type. The coordination
number is 4 and square is obtained by joining centres of
four closest neighbours.
ii)Hexagonal close packing:-
In this type, one dimensional rows are stacked in such a way
that, spheres in one row fit in depression of another row. If
first row is called A type row, then second row is called as B
type.This arrangement is called as ABABAB…….type. The
coordination number in this packing is 6 and hexagon is
obtained by joining centres of 6 closest neighbours.
c)Close packing in three dimensions:-Stacking of two
dimensional layers gives rise to three dimensional crystal
structure.
i)Stacking of square close packed layers:-In this
arrangement, second layer is placed over the first so as to
have its spheres exactly above those of the first layer, it
generates three dimensional cubic structure. In this
arrangement all the layers are perfectly aligned horizontally
as well as vertically.This arrangement is called as AA. type.
The coordination number is 6.Polonium is the only element
that crystalizes in simple cubic close packed structure.
ii)Stacking of two hexagonal close packed layers:-
In this type, spheres of second layer are placed in the
depression of first layer ie AB type. In doing so, all
triangular voids of first layer are not covered by the spheres
of second layer. The voids that are covered generates
tetrahedral void, which is surrounded by four spheres. The
remaining voids have above them the triangular voids of
second layer, which form an octahedral void. It is
surrounded by 6 spheres.
iii)Packing third hexagonal close packed layer:- There are
two ways,
• a)The spheres of third layer are placed over spheres in
first layer ie.ABAB…type, which gives hexagonal close
packed structure (hcp) Ex. Mg, Zn have hcp structure.
• b)The spheres of third layer are placed over octahedral
voids of first layer. In this arrangement spheres of third
layer do not align with spheres of second or first layer,
hence it is called as C layer. This arrangement is called as
ABCABC… It results in cubic close packed (ccp),
which is same as fcc. eg. Cu, Ag have ccp or fcc structure
Coordination number in close packed structure:-
• a)In simple cubic structure, each sphere is surrounded by
6 neighbouring spheres, 4 in its own layer, 1 above and 1
below. Hence coordination number is 6.
• b)In both hcp and ccp / fcc structure, each sphere is
surrounded by 12 neighbouring spheres, 6 in its own
layer, 3 above and 3 below. Hence coordination number
of any sphere is 12.
Number of voids per atom in hcp and ccp:-
There are two tetrahedral and one octahedral void per atom.
Packing efficiency:

Packing efficiency of metal crystal :

1.In simple cubic lattice :
• Step 1: Radius of sphere :
a = 2r
Therefore, r = a / 2
• Step 2 : Volume of sphere :
Volume of one particle = 4/3 r3
= 4/3 (a/2)3
= a3 / 6
• Step 3 : Packing efficiency :

= 52.6

Therefore, volume occupied by particles = 52.36

and empty space or void volume = 47.64
Problems from exercise:
1.The density of iridium is 22.4 g /cm3. The unit cell of
iridium is fcc. Calculate the radius of iridium atom. Molar
mass of iridium is 192.2 g / mol.
Solution :
= n M /a3 NA
a3 = n M / NA
= 4 192.2 / 22.4 6.022 1023
= 56.99 10-24
a = 3.84 10-8
Then, r =a/2
= 3.84 10-8 / 2
= 1.36 10-8
r = 136 pm
2.Aluminium crystallizes in cubic close packed structure
with unit cell edge length of 353.6 pm.What is the radius of
Al atom ? How many unit cells are there in 1.00 cm3 of Al ?
Solution : Radius of atom in cubic close packed structure,
r= a/4
r= 353.6 / 4
Shri Swami Vivekanand Shikshan Sanstha, Kolhapur. r = 125 pm
Then,
Number of unit cells = V / a3
= 1 /( 3.536 10-8 )3
= 1 1024 /44.21
= 2.26 1022
Number of unit cells = 2.26 1022
Crystal defects or imperfections:-
The disorders or irregularities in the arrangement of
constituent particles of a solid crystal are called defects or
imperfections.
Point defects:- These defects are irregularities produced in
the arrangement of basis at lattice points in crystalline
solids.
There are three classes:-
a)Stoichiometric point defects:
The stoichiometry i.e. ratio of number of particles remains
the same as shown by its chemical formula.
There are four types,
i)Vacancy defect:- A vacancy created by missing a particle
from its regular site in the crystal lattice, during
crystallization or when substance is heated. Due to vacancy
defect density of substance decreases.
ii)Self interstitial defect in elemental solid :- Some
particles of a crystalline elemental solid occoupy interstitial
sites in the crystal structure.There are two ways,
Firstly, an extra particle occupies an empty interstitial space
in the crystal structure. This defect increases density of
substance.
Secondly, a particle get shifted from its original lattice point
and occoupies an interstitial space. In this defect there is
combination of vacancy defect and self interstitial
defect.This defect preserves density of the substance.
iii)Schottky defect :-It is the vacancy created due to
missing of equal number of cations and anions in an ionic
solid.
Characteristics / conditions for formation of Schottky
defect,
• High degree of ionic character.
• High coordination number of anion.
• Small difference between size of cation and anion.
Consequences of Schottky defect,
• Density of substance decreases.
• The electrical neutrality of compound is preserved.
• This defect is found in ionic crystals such as
NaCl, AgBr,and KCl .
iv)Frenkel defect :- This defect arises when an ion of an
ionic compound is missing from its regular lattice site and
occupies interstitial position. Generally cations occoupy
interstitial sites, as they are small in size.
Conditions for formation of Frenkel defect,
• There should be large difference between sizes of cation
and anion.
• The ions must have low coordination number.
Consequences of Frenkel defect,
• Density of compound remains unchanged.
• Electrical neutrality is preserved.
• This defect is found in ionoic crystals like
ZnS , AgCl , AgI , CaF2 etc
b)Impurity defect :- It arises due to presence of foreign
atom in the crystal.There are two types,
i)Substitutional impurity defect :- In this type, foreign
atoms are at the lattice sites in place of host atoms.
Example :
Solid solution of metals. i.e. alloys: In brass host Cu atoms
are replaced by Zn atoms.
Vacancy through aliovalent impurity:-In this type,
vacancies are created by adding impurities i.e. ions with
oxidation state different from that of host atoms(aliovalent).
Example, If small amount of SrCl2 impurity is added to
NaCl during its crystallization, Sr2+ ions occoupy some of
the regular sites of Na+ ions. To maintain electrical
neutrality. every Sr2+ ion removes two Na+ ions and one of
the vacant lattice is occupied by Sr2+ ion while other remains
vacant.
ii)Interstitial impurity defect :-In this type, impurity atoms
occoupy interstitial spaces.Example, In steel, carbon atoms
occoupy interstitial spaces.

c)Nonstoichiometric defects :-
The ratio of number of cations to anions is different from
that indicated by chemical formula.
There are two types,
i)Metal deficiency defect:- In this type, metal ion having
lower oxidation state is missing, but extra negative charge
is balanced by presence of cation of same metal with higher
oxidation state.Example,in NiO, vacancy is created by
missing of one Ni2+ ion.This deficiency of two positive
charges is made up by presence of two Ni3+ions at the other
lattice sites of Ni2+ions.
.
ii)Metal excess defect :- There are two types,
a)A neutral atom or an extra positive ion occoupies
interstitial position :-
In ZnO lattice, either one Zn atom is present in the
interstitial space or Zn2+ ions produced by heating of ZnO
are trapped in the interstitial spaces also electrons diffuse in
the crystal. In both cases nonstoichiometric formula of ZnO
is Zn1+xO1.
b)By anion vacancies (Colour or F- centres):-
It imparts colour to colourless crystal.Example,when NaCl
crystal is heated in the atmosphere of sodium, sodium atoms
are deposited on the surface of crystal, with which Cl- ions
combine to form NaCl and electrons released from Na atoms
occoupy vacant spaces of Cl- ions. These electrons are F-
centres or colour centres.
Classification of solids on basis of electrical conductivity
i)Conductors :-
Electrical conductivity is in the range 104 to 107 ohm-1 m-
Conduct electricity by movement of electrons.
ii)Insulators :-
Electrical conductivity is in the range of 10-20 to 10-10
ohm-1 m-1.
Most of the non-metals and molecular solids are insulators.
iii)Semiconductors :-
Electrical conductivity is in range 10-6 to 104 ohm-1 m-1.
Metaloids like silicon , germanium etc. are semiconductors.
Band Theory :-
Interaction of energy levels of electrons in the closely
spaced constituent atoms in solid results in the formation of
bands.
i)Conduction band:
• It is the highest energy band containing electrons.
• It is formed by interaction of the outermost energy levels
of closely spaced atoms in solids.
• Electrons in conduction band are mobile and delocalised
over entire solid.
 ii)Valence band :
• The energy of valence band is lower than conduction band.
• The electrons in valence band are not free to move.
iii)Band gap:
• It is the energy difference between valence band and
conduction band.
• When band gap is small, electrons in valence band can be
promoted to conduction band.
• If band gap is too large, electrons in valence band can not
be promoted to conduction band.It is called forbidden zone.
 Electrical Properties of solids:
Metals :
• They are good conductors of
electricity.
• The number of electrons in
conduction band is large.
• The conduction can be labelled
as ‘s’band, overlapping s and p
bands.
• Conductivity of metals decreases
with increase in temperature.
Insulators :
• Conduction band is empty, while
valence band is filled with
electrons.
• There is forbidden zone i.e.
energy gap is large.
• Thermal energy is insufficient to
promote electrons from valence
band to conduction band.
Semiconductors :
• Electric conduction is intermediate between that
of metals and insulators.
• Energy gap between valence band and
conduction band is small.
• Thermal energy is sufficient to promote
electrons from valence band to conduction band.
Hence it conducts small amount of electricity
and called as intrinsic semiconductor.
• The electrical conductivity increases with
increase in temperature.
Extrinsic semiconductor :
A doped semiconductor having higher conductivity than
intrinsic semiconductor is called as extrinsic semiconductor.
There are two types ,
i)n - type semiconductor :
• It is obtained by adding group 15 element to intrinsic
semiconductor which belongs to group 14.
• Added atoms occoupy some vacant sites in lattice.
• Due to presence of extra electron, conduction band
contain more number of electrons.
• Hence, conductivity of doped element is higher than that
of pure element.
Example, Si or Ge doped with P, Sb, As, or Bi
ii)p-type semiconductor :
• It is obtained by adding group 13 element to element
which belongs to group 14.
• Added atom occoupy some normal positions of some of
the atoms in lattice.
• Added atom forms bond with three atoms of original
element, while missing electron creates a hole.
• Under influence of potential, electrons in valence band
and holes move in opposite directions.
Example, Si or Ge doped with B, Ga or In.
Magnetic properties of solids : Classification of solids,
i)Diamagnetic solids :
The substances with all electrons paired and are weakly
repelled by magnetic fields are called as diamagnetic solids.
Examples, N2, F2, NaCl, H2O and benzene.
ii)Paramagnetic solids :
The substances with unpaired electrons, which are weakly
attracted by magnetic fields are called as paramagnetic
substances.
Examples, Oxygen, Cu2+, Fe3+, Cr3+.
iii)Ferromagnetic substances : The substances containing
large number of unpaired electrons, which are attracted
strongly by magnetic fields are called as ferromagnetic
substances.
Examples, Fe, Co, Ni, Gd, CrO2.
Questions asked in previous H. S. C. Board
Examinations.
March 2019
1.Define Anisotropy. Distinguish between crystalline
solids and amorphous solids. (3 Marks)
2. What is the ratio of octahedral holes to the number of
anions inhexagonal close packed structure ? (1 Mark)
July 2019
1.Give the relation between radius of atom and edge length
in body centred cubic crystal. (1 Mark)
2. Classify the following solids,
1) Diamond 2.) NaCl 3.) P4 molecule 4.) Brass
What is Schottky defect ? (3 Marks)
March 2020
1.The number of atoms per unit cell of bcc is,
a) 1 b) 2 c) 4 d) 6 (1 Mark)
2. Classify the following solids into different types
a) Silver b) P4 c) Diamond d) NaCl (2 Marks)
3.Unit cell of a metal has edge length of 288 pm and density
of 7.86 g cm-3 . Determine the type of crystal lattice.
(Atomic mass of metal = 56 g mol-1 ) (3 Marks)