CLASS 12 - CHEMISTRY

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LECTURE NOTES: 01 – A Chapter 01: Solid States

Topics Covered:
1. Solid state and its characteristics
2. Types of solids
3. Differences between crystalline and amorphous solids
4. Classification of crystalline solids
5. Concept of crystal lattice (OR) space lattice (AND) unit cells

Matter may exist in 3 states: Solids, Liquids or Gases



1. Why do some substances exist as solids?

A substance may exist as solid or liquid or a gas depending on the net effect of two opposing
forces:
(i) Intermolecular forces (which tends to keep the constituent particles closer)
(ii) Thermal energy (which tends to keep the constituent particles apart by making them
move faster)
At low temperature, thermal energy is low and intermolecular forces are so strong that the
particles come closer and occupy fixed positions, but can still oscillate about their mean positions.
Hence, the substance exists in solid state.
2. What are fluids? Why are liquids and gases considered as fluids? [EXEMPLAR]
Substances like liquids and gases are called fl uids because of their ability to
fl ow. This fl uidity is because the molecules are free to move about.

3. Why are solids incompressible? [EXEMPLAR]

The constituent particles of a solid are very closely packed. The inter-particle distances are so
small that if we try to bring them closer, repulsions start between their electron clouds. Hence,
they are incompressible.

 SOLID state and its GENERAL CHARACTERISTICS

SOLIDS
Solid are the form of matter which have define shape and volume, rigidity, high density, low
compressibility. The constituent particles ( atoms, molecules or ions) are closely packed and
held together by strong inter-particle forces.

CHARACTERISTICS OF SOLIDS
Solids have:
Definite mass, shape and volume.

Intermolecular forces are strong.


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Constituent particles (atoms, molecules or ions) have fixed positions and can only

oscillate about their mean positions.
They are incompressible and rigid


 TYPES of SOLIDS

Solids can be classified as: (1) Crystalline solids and (2) Amorphous solids on the basis of
the nature of order present in the arrangement of constituent particles.

Characteristics of CRYSTALLINE solids

1. Arrangement of Crystalline solids are the solids which have a regular, ordered and

constituent repetitive arrangement of constituent particles (atoms, molecules or
particles ions) in 3-D space.
2. Shape Crystalline solids consists of a large number of small crystals each

having a definite geometrical shape.
3. Order in Long-range order

arrangement of Crystalline solids have a long-range order which means that there is
constituent a regular pattern of arrangement of particles which repeats itself
particles periodically over the entire crystal.
NOTE: They may have both short-range order and long-range order.
4. Melting point Crystalline solids have a sharp melting point.

At a characteristic temperature they melt abruptly and become liquid.

and therefore they have a definite heat of fusion.
5. Anisotropy Crystalline solids are anisotropic in nature; that means some of their

physical properties like resistance or refractive index show different
values when measured along different directions in the same crystal.
(Reason: Anisotropy is due to different arrangement of constituent
particles along different directions Thus the value of same physical
property is different along each direction.)

Deformations in CD direction displaces row which has two different

types of atoms while in AB direction rows made of only one type of
atoms are displaced.

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6. Cleavage property Crystalline solids on being cut with a knife gives a clean (sharp and

with knife smooth) cleavage.
7. Nature Crystalline solids are called true-solids.


Example: Sodium chloride and Quartz

Characteristics of AMORPHOUS solids

(Amorphous comes from the Greek word ‘amorphos’, meaning ‘no form’.)
1. Arrangement of Amorphous solids are the solids which have an irregular arrangement

constituent of constituent particles (atoms, molecules or ions).
particles
2. Shape Amorphous solid consists of particles of irregular shape.

3. Order in Short-range order

arrangement of Amorphous solids have a short-range order which means that the
constituent regular, ordered and repeating arrangement of constituent particles is
particles observed over short distances only. The arrangement is scattered and
in between it is distorted.
4. Melting point Amorphous solids soften, melt and start flowing over a range of

temperature and can be moulded and blown into various shapes.
Amorphous solids are known as viscous liquids.

5. Heat of fusion They have no definite value of heat of fusion.

6. Isotropy Amorphous solids are isotropic in nature, that means the value of any

physical property is same along any direction in the crystal.

(Reason: Amorphous solids are isotropic because there Is no long-

range order in them and arrangement of particles is irregular along all
the directions. Hence, the overall arrangement becomes equal in all
directions. Therefore, any value of physical property would be same
along any direction.)
7. Cleavage property An amorphous solid give an irregular shape on cleavage with knife.

with knife
8. Nature Like liquids, amorphous solids have a tendency to flow, though very

slowly. Therefore, they are also called a pseudo solids or super-
cooled liquids.
Example: Quartz glass, rubber and plastics.
NOTE: Regular patterns are scattered and in between the arrangement in disordered.

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POLY-CRYSTALLINE SOLIDS: Solids which apparently appear amorphous but have micro-
crystalline structure are called poly-crystalline solids. Example: metals occur in poly-crystalline
condition.

USES OF AMORPHOUS SOLIDS:

Amorphous solids are very useful in daily-life.
1. Amorphous silicon is one of the best photo-voltaic material used for conversion of sunlight
into electricity.
2. Glass, rubber and plastics are used in daily lives.

 Differences between Crystalline and Amorphous Solid

CRYSTALLINE SOLID
1 Crystalline solids have a regular and ordered
arrangements of constituent particles.
OR
Crystalline solids have a definite
characteristic geometrical shape.
2 These have long order arrangement of the
particles.
3 Have sharp and characteristic melting point
4 Have high, definite and fixed heat of fusion.
5 They are anisotropic in nature.
6 They give regular, plain and smooth
structure on cleavage.
7 Crystalline solids are anisotropic, in nature
i.e.; their physical properties are different in
different directions due to different
arrangements of particles in different
directions.
8 They are true solids
Examples: Diamond, Graphite, NaCl, Metal
(Fe, Cu, Ag etc) ice.
AMORPHOUS SOLID
Amorphous solids have an irregular
arrangement of constituent particles.
OR
Amorphous solids have an irregular shape.
These have short order arrangement of particle.
They melt over a range of temperature.
They do not have fixed heat of fusion.
They are isotropic in nature.
They give irregular structure on cleavage.
Amorphous solids are isotropic; in nature i.e.
the value of their physical properties is same in
all directions due to irregular arrangement in all
directions.
They are pseudo-solids or super-cooled liquids.
Examples: Glass, rubber, plastics, Quartz glass

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INTEXT QUESTIONS…………..PAGE NO. 04

1.1 Why are solids rigid?

In solids, the constituent particles (atoms, molecules or ions) are very closely packed and have
fixed position. They can only oscillate about their fixed (mean) position. Also, the forces of
attraction are very strong.
Hence solids are rigid.
1.2 Why do solids have a definite volume?
The constituent particles in solids have fixed positions and are not free to move about i.e. they are
rigid. Hence, solids have a definite volume
1.3 Classify the following as amorphous or crystalline solids:
Polyurethane, naphthalene, benzoic acid, teflon, potassium nitrate,
cellophane, polyvinyl chloride, fibre glass, copper.
Amorphous solids: Polyurethane, Teflon, cellophane, polyvinyl chloride and fibre glass
Crystalline solids: Naphthalene, benzoic acid, potassium nitrate and copper.
1.4 Why is glass considered a super-cooled liquid?
Glass is an amorphous solid. Like liquids, it has a tendency to flow, though very slowly.
Example: Glass panes in the windows or doors of old buildings are slightly thicker at the bottom
than at the top. This is because the glass flows down very slowly and makes the bottom portion
slightly thicker.
1.5 Refractive index of a solid is observed to have the same value along all directions. Comment on
the nature of this solid. Would it show cleavage property?
Since the given solid has the same value of refractive index along all directions, it means it is
isotropic in nature and hence it is amorphous. It is because there is no long-range order and the
arrangement is irregular along all the directions.
Being an amorphous solid, it would not show a clean cleavage when cut with a knife. Instead, it
would break into pieces with irregular surfaces.

EXTRA QUESTIONS
1. Inspite of long-range order in the arrangement of particles why are the crystals usually not
perfect?
This is because when crystallisation occurs at a fast or moderate rate, the constituent particles
may not get sufficient time to arrange themselves in a perfect order.
2. Why amorphous solids are also called as pseudo-solids OR super-cooled liquids?
Amorphous solids have a tendency to fl ow, though very slowly. Therefore, someti mes
these are called pseudo solids or super cooled liquids.
3. ‘Some of the very old glass objects appear slightly milky instead of being transparent’. Give
reason.
Some glass objects from ancient civilizati ons are found to become milky in
appearance because of some crystallizati on.
4. How can a material be made amorphous?
By melting the material and cooling it rapidly.
5. What is a photo-voltaic material?
Material used to convert sunlight into electricity. Ex: Amorphous silicon

 CLASSIFICATION of Crystalline Solids

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Based on the nature of intermolecular forces operating in them, crystalline solids are divided
into 4 categories:
1. Molecular solids
a) Non-Polar molecular solids
b) Polar molecular solids
c) Hydrogen bonded molecular solids
2. Ionic solids
3. Metallic solids
4. Covalent OR network solids

NOTE: The various bonds that hold the constituent particles in a crystalline solid are:
(i) Van-der Waals forces
(ii) Ionic bonds
(iii) Covalent bonds
(iv) Metallic bonds

1. Molecular solids
Solids in which the constituent particles are molecules are called molecular solids.

Depending on nature of molecules, mo lecular solid are further sub-divided into the following
categories:-

Non polar Molecular Solids : The solids in which the constituent particles are atoms,
(i)
(example, argon and helium) or molecules formed by non-polar covalent bonds (example H2,
Cl2 and I2) are known as non-polar molecular solids.
Characteristics:
Soft and non-conductors of electricity.

Atoms or molecules are held by weak dispersion forces or London forces.

Low M.P. and B.P.

Exist in liquid or gaseous state at room temperature and pressure.


Polar Molecular Solids : The crystalline solids in which the constituent particles are polar
(ii)
molecules formed by polar covalent bonds are called polar-molecular solids. Ex: Substances
like HCl, SO2 etc.
Characteristics:
Soft and non-conductors of electricity.

Molecules are held together by strong dipole-dipole interactions .

M.P and B.P. are higher than those of non-polar molecular solids.

Most of these are gases or liquids under room temperature and pressure.

Example – Solid SO2 and solid NH3


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Hydrogen Bonded Molecular Solids : The crystalline solids in which the constituent
(iii)
particles are molecules with polar covalent bonds between hydrogen atom (H) and other
highly electronegative atom small in size such as F, O or N.
Example: H2O, NH3 etc.

Characteristics:
Non-conductors of electricity.

Strong hydrogen bonding exists between molecules of such solids like H2O (ice).

M.P. and B.P. are higher than those of polar and non-polar molecular solids.

Generally, they exist as volatile liquids or soft solids under room temperature and pressure.


2. Ionic solids
The crystalline solids in which the constituent particles are positive and negative ions forming a
three-dimensional arrangement of cations and anions are called ionic solids. Example: NaCl
Characteristics:
The constituent ions are held by strong coulombic (electrostatic) forces of attraction.

Hard and brittle in nature.

High M.P. and B.P.

They are electrical insulators in the solid state because their ions are not free to move about.

But, in the molten (OR) or aqueous state ( i.e. when dissolved in water ), the ions become free to
move about and they conduct electricity.

3. Metallic solids
The solids in which the constituent particles are positively charged metal ions surrounded by
and held together by a sea of free electrons.
These electrons are mobile and are evenly spread out throughout the crystal.

Each metal atom contributes one or more electrons towards this sea of mobile electrons.

Characteristics:
High electrical and thermal conductivity (because the electrons are free and mobile. On

applying electric current, these electrons flow through the network of positive ions towards +
charged electrode).
Similarly, when heat is supplied to one part of a metal, the thermal energy is uniformly spread
throughout and carried by these free electrons to all parts of the metal.
They have lustre and colour due to the presence of free electrons.

Metals are highly malleable and ductile.


4. Covalent (OR) Network solids

In these solids the constituent particles are non-metals. These
are formed due to formation of covalent bonds between the
non-metal and adjacent atoms throughout the crystal.
As a result, a network of covalent bonds is formed.
Hence they are also called giant molecules.

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Characteristics:
Very hard and brittle because they have

covalent bonds which are strong and directional in nature
and are held very strongly at their positions.
Have extremely high M.P. and may even decompose before

melting.
They are insulators and do not conduct electricity.

Examples: Diamond and Silicon carbide (SiC)

Exception: Graphite is a covalent solid but it soft and a

conductor of electricity. Its exceptional properties/behaviour
is due to its typical structure in which carbon atoms are
arranged in different layers. In each layer, every carbon
atom is covalently bonded to three neighbouring carbon
atoms in the same layer.
The fourth valence electron of each atom is present between

different layers and is free to move about.
The presence of free electrons makes graphite a good

conductor of electricity.
Different layers can slide one over the other. This makes

graphite a soft solid and a good solid lubricant

Solids are classified on the basis of nature of molecular forces as:

Type of solid Nature of Nature of Physical Electrical M.P. Example

Constituent Bond / Nature conductivity
Particles Attractive
forces
1. Molecular
solids

(i) Non polar Molecules Dispersion Soft Insulator Very Ar, CCl4, H2,
molecules / London low I2, CO2
force

(ii) Polar Molecules Dipole – Soft Insulator Low HCl, SO2

molecules dipole
interaction

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(iii) Hydrogen Molecules Hydrogen Hard Insulator Low H2O (Ice)
bonded bonding
Molecules

2. Ionic Solids Ions Electrostati Hard Insulator in High NaCl, ZnS,

(Positive c (Ionic solid, MgO, CaF2
Brittle
and bonding) conductors in
Negative) molten state
and in
aqueous
solutions

3. Metallic Positive Metallic Hard Conductors in Fairly Fe ,Cu, Ag ,

Solids Ions in a Bonding molten an high Mg
Malleable
sea of solid state
delocalised Ductile

electrons

4. Covalent or Atoms Covalent Hard Insulator Very SiO2(quartz),

network bonding (except high SiC,
Solids graphite C(diamond),
Soft
which is a
C(graphite),
conductor)

INTEXT QUESTIONS…………..PAGE NO. 07

1.6 Classify the following solids in different categories based on the nature of intermolecular forces
operating in them:

potassium sulphate, tin, benzene, urea, ammonia, water, zinc sulphide,

graphite, rubidium, argon, silicon carbide.

 Ionic solids: Potassium sulphate, zinc sulphide

 Covalent solids: Graphite, silicon carbide
 Molecular solids: Benzene, urea, ammonia, water, argon
 Metallic solids: Rubidium, tin

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1.7 Solid A is a very hard electrical insulator in solid as well as in molten state and melts at extremely
high temperature. What type of solid is it?
Covalent or network solid like SiO
2 (quartz) or SiC or C (diamond)

1.8 Ionic solids conduct electricity in molten state but not in solid state. Explain.
Ionic solids conduct electricity in molten state because in the molten state, ionic solids dissociate to
give free ions.
But, in the solid state, since the ions are not free to move about but remain held together by strong
electrostatic forces of attraction, hence they do not conduct electricity.

1.9 What type of solids are electrical conductors, malleable and ductile?
Metallic solids conduct electricity in solid state and are malleable and ductile.

Concept of Space Lattice or Crystal Lattice and Unit Cells

(A) Two dimensional Lattices
It is a regular arrangement of points in the plane of the paper. Some unit cells may have an
interior point and are called centered unit cells. The unit cell that does not contain any interior
point is called primitive unit cell.

LATTICE UNIT CELL

(i) Square lattice Square

(ii) Rectangular lattice Rectangle

(iii) Parallelogram lattice Parallelogram

(iv) Rhombic lattice Rectangular with interior point

(v) Hexagonal lattice Rhombus with an angle of 600

(i) Square (ii) Rectangular (iii) Parallelogram (iv) Rectangular with interior point (v) Rhombus

MOTIFS:- In crystal structure, motif (or) basis is the basic structural unit which may be a
molecule, atom or ion. When motifs are placed on points in space lattice, a pattern is generated
i.e. we get the crystal structure.

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obtained by placing motifs in two-

dimesnional space

 Spatial arragement of lattice points gives rise to 2 different types of lattices.

We need only a small part of the space lattice of a crystal to spacify crystal completely. This is the unit
cell.

(B) Three dimensional Lattices

The constituent particles are arranged in a definite fashion in three-dimensional space.

CRYSTAL LATTICE or SPACE LATTICE

A regular repeating three-dimensional arrangement of points ( or constituent particles ) in
space is called a crystal lattice or space lattice.

Characteristics of a crystal lattice:

a) Each point in a lattice is called lattice point or lattice site.

b) Each point in a crystal lattice represents one constituent
particle. ( i.e. an atom, a molecule or an ion ).
c) The lattice points are joined by straight lines to represent
the geometry of the lattice.

BRAVAIS LATTICES
There are only 14 possible three-dimensional crystal lattices
Portion of 3D cubic lattice and its unit cell ( or space lattices) corresponding to 7 crystal
systems. These are called Bravais Lattices.

UNIT CELL

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Unit cell is the smallest portion of a crystal lattice which, when repeated in different
directions, generates the entire lattice.

Parameters / Characteristics of a Unit Cell –

A unit cell is characterized by:

(i) Its dimensions along the three edges, a, b and c,

which may or may not be mutually perpendicular.

(ii) Angles between the edges,

α (between b and c)
β (between a and c) and
γ (between a and b).

Thus, a unit cell is characterized by six parameters, a, b, c, α, β and γ. These parameters

of a typical unit cell are shown in

Selection of a unit cell

Normallly that cell is chosen which has perpendicular sides of shortest lenth and can
construct entire crystal by translational displacement of the unit cell in three dimensions.
Also, unit cells have shapes such that these fill the whole lattice without leaving space
between cells.
The below figure shows movement
of unit cell of a two-dimensional
lattice to construct entire crystal
strucutre.

7 types of CRYSTAL SYSTEM

NOTE: Based on the parameters of the unit cell, there are seven types of unit cells. These
are crystal systems OR crystal habits because any crystalline solid must belong to any one
of these unit cells.
The 7 types of unit cells or crystal systems are: cubic, tetragonal, orthorhombic,
hexagonal, trigonal, monoclinic, triclinic.

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TYPES of UNIT CELLS

There are 2 types of unit cells: Primitive and Centered (non-primitive)

1. Primitive Unit Cell or Simple Cubic: The unit cells in which constituent
Simple cube
particles are present only at the corner positions of the crystal.
2. Centered (or non-primitive) unit cells : The unit cells in which the
constituent particles are present at other positions in addition to the
corner positions of the unit cells.

Centred Unit cells are of three types:

B
a) Body centered unit cells (BCC): Constituent particles are
CC
present at the body centre in addition to the corner positions.
b) Face centered unit cell: Constituent particles are present at
the centre of each face in addition to the corner positions.
c) End centered unit cell : One constituent particle is present at the centre
of any two opposite faces (end faces) in addition to the corner positions.

Calculation of total number of atoms in a unit cell FCC



Primitive Cubic Unit Cell i.e. Simple cubic


In simple cubic unit cell, each corner atom is shared between 8 adjacent unit cells (4 unit cells in
the same layer and 4 unit cells of the upper or lower layer).

Hence, contribution of each atom present at the corner = 1

(i.e. only 1/8th of atom actually belongs to unit cell)
8
1
∴ Total number of atoms present in one unit cell is 8 × 8 =1 atom

Open structure Space filling structure Actual portion of atoms belonging to one unit- cell

Body-Centred Cubic Unit Cell (BCC)


BCC unit cell has 8 atoms on corners and 1 atom at its body centre (which wholly belongs to unit cell)

in which it is present). Thus, an atom at the body centre is shared by no other unit cell.
1
8 × = 1 atom
∴ Contribution by 8 atoms present on the corners =
8
Contribution by the atom at the body centre = 1 x 1 = 1 atoms
Therefore, total number of atoms per unit cell= 1 + 1 = 2 atoms

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Open structure Space filling structure Actual portion of atoms belonging to one unit- cell

Face-Centred Cubic Unit Cell (FCC)


FCC unit cell has 8 atoms on the corners and 6 atoms on the faces (one on each face)

Each atom at the face-centre is shared between two adjacent unit cells and only 1
2 of each atom belongs to a
unit cell.
1
8 × = 1 atom
∴ Contribution by 8 atoms present on the corners =
8
Contribution by atoms on the faces = 6 × 1 = 3 atoms
2
Therefore, total number of atoms per unit cell= 1 + 3 = 4 atoms

Types of cubic unit cells and no of atoms per unit cell

TYPE OF CALCULATION OF No. ATOMS No. of atoms

UNIT CELL per unit cell

(Z)

Primitive or 8 (corner atoms) × 1 (atom per unit cell) 1

simple cubic 8

Body centred 8 (corner atoms) × 1 (atom per unit cell) + 1 2

(BCC) 8

Face centred 8 (corner atoms) × 1 (atom per unit cell) + 6 (face centred atoms) × 4
(FCC) 8
1 (atom per unit cell)
2
End centred 8 (corner atoms) × 1 (atom per unit cell) + 2 (face centred atoms) × 1 2
(ECC) 8 2

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(atom per unit cell)

INTEXT QUESTIONS…………..PAGE NO. 14

1.10 Give the signifi cance of ‘latti ce point’.
Each point in a crystal lattice of a solid is called
lattice point or lattice site.
Each point in a crystal lattice represents one constituent particle of the solid. It may be an atom, a
molecule (group of atoms) or an ion.
1.11 Name the parameters that characterize a unit cell.
A unit cell is characterized by 6 parameters, a, b, c, α, β and γ. These are:
Its dimensions along the three edges,
(i) a, b and c, which may or may not be
mutually perpendicular.
Angles between the edges,
(ii)
α (between b and c)
β (between a and c) and
γ (between a and b).
1.12 Distinguish between: (i) Hexagonal and monoclinic unit cells
(ii)
Face-centered and end-centered unit cells.
(i)
Hexagonal unit cell Monoclinic unit cell
For hexagonal unit cell: For Monoclinic unit cell :
a=b≠c a≠b≠c
α = β = 90°, γ = 120° α = γ = 90°, β ≠ 90°

Examples are graphite, ZnO Examples: Na2SO4.10H2O, monoclinic S.

(ii)
Face-centred unit cell End-centred unit cell
Constituent particles are present at all Constituent particles are present at all the
the corners and centre of each face. corners and at the centres of any two opposite.
No. of atoms per unit cell = No. of atoms per unit cell =
8 ×   + 6 ×   = 4 8 ×   + 2 ×   = 2
1.13 Explain how much portion of an atom located at (
i) corner and (ii) body-centre of a cubic unit
cell is part of its neighbouring unit cell.
(i) ‘n’ atom at the corner is shared equally by 8 adjacent unit cells. Hence, only one-
eighth (1/8) of each such point belongs to the given unit cell.
(ii) A body-centered point belongs entirely to one unit cell since it is not shared by any
other unit cell.

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