Intermolecular distance increases

Intermolecular forca of attraction

 SOLID
STATE
❑Characteristics of solids
⮚They have fixed mass,
shape, volume and
density.
⮚Solids are hard,
incompressible and rigid.
⮚Intermolecular forces of
attraction is the strongest.
 Classification of
Crystalline Solids Solids

Crystalline Amorphous

Molecula Ionic Covalent Metallic

r Solid Solid Solid Solid

Non-polar
Polar molecular Hydrogen bonded
Molecular
Solid Molecular Solid
Solid
 Arrangement Of Particles in Solids

Closely
packed

Regular arrangement Irregular arrangement

Crystalline Solid Amorphous Solid
 Crystalline Solids
⮚A crystalline solids is a
homogeneous solid in which the
constituent particles, atoms, ions
or molecules are arranged in a
long range definite repeating
pattern.
⮚ They are anisotropic in nature.
⮚Example-: NaCl, KCl, CuSO4 etc.
 Anisotropy
❑ The ability of a
crystalline solid to
change the values
of physical
properties when
measured in
different
directions is called
anisotropy.

Different values when measured in different directions

 Isomorphous
❑ Two or more substance
having same crystal
structure are called
isomorphous.
❑ Examples
⮚ NaF and MgO : atoms are
in the ratio 1:1
⮚ NaNO3 and CaCO3:atoms
are in the ratio 1:1:3
 Polymorphous
❑Poly means many and morphous means forms.
❑A single substance that crystallizes in two or more different forms .They are
also called as allotropes.
❑Ex-: Graphite and diamond are polymophous ,rhombic and monoclinic
sulphurs are also polymorphous solids.

Carbon Sulphur
 Amorphous solids
❑The substances that appear like
solids but do not have well
developed perfectly ordered
crystal structure are called as
amorphous solids.
❑They are isotropic.
❑Examples : Glass, rubber, butter
Difference between crystalline and amorphous solids
Crystalline Solids Amorphous Solids
⮚ Definite shape due to ⮚ Indefinite shape due to
orderly regular orderly regular
arrangement to a long arrangement to a short
range range
⮚ True solids ⮚ Pseudo solids or
supercooled liquids
⮚ They are anisotropic ⮚ They are isotropic
⮚ Heat of fusion is ⮚ Heat of fusion is
definite indefinite
 Crystalline
solids
Molecular solids

Ionic solids

Covalent solids
Metallic solids

Based on the type of constituent particles

 Molecular Solids
• The constituent particles of molecular solids are molecules
( or unbonded single atoms) of the same compound.
• They are classified into three types depending on the type of
molecules involved and the nature of intermolecular forces
of attraction.
• Types of molecular Solids
1. Polar molecular solids
2. Non-polar molecular solids
3. Hydrogen bonded molecular solids
 Polar molecular solids
The force of attraction between the molecules are dipole-
dipole interaction. Ex-: HCl, H2O, SO2 with permanent dipole.

HCl
SO2
 Non-polar molecular solids
• The force of attraction between the molecules are weak London forces
or dispersion forces. Ex-: H2, CH4, Cl2, monoatomic solids like Ar and Ne.

H2 Cl2 CH4
Hydrogen bonded molecular solids
• The force of attraction between the
molecules are strong hydrogen bonds.
• Ex-: NH3, H2O, HF.

NH3 H2O
 Ionic solids
• In ionic solids, the constituent particles are ions of
opposite charges.
• The particles of ionic solids are held by electrostatic force
of attraction between oppositely charged ions.
• They are hard and brittle and have high melting point.
• These are non conductors of electricity in solid state but
are good conductors in molten or aqueous solution.
• Example-: NaCl, K2SO4, CaF2, KCl etc.
 Ionic solids

Each Cl-
is surrounded by
six Na+ and vice
versa

NaCl
 Covalent Network Solids
• The constituent particles in covalent network solids are
atoms.
• The constituent particles are held together by covalent
bonds.
• Covalent solids are also called as network solids.
• They are very hard, incompressible and have high MP and
BP.
• Pure covalent solids are insulators as their valence electrons
are tightly held together except graphite.
Examples of covalent solids
 Metallic solids
• In metallic solids the constituent particles are metal ions.
• Metallic solids consists of positive ions immersed in a sea of
electrons
• The force of attraction between the positively charged metallic ions
and negatively charged sea of delocalised electrons is called as the
metallic bond.
• The presence of mobile electrons make all metallic solids good
conductor of electricity.
Metalic Solid

Fe Fe2+
+ 2e-

Sea of delocalized
e-
 Identify the type of solid

⮚H2O Hydrogen bonded

molecular solid

⮚Fe Metallic solid

⮚ZnS Ionic solid

⮚SiO2 Covalent solid

 Crystal lattice
• A regular arrangement of points in a
crystalline solid is called as crystal
lattice.
• Each point in the crystal lattice is called
as a lattice point.
• Each lattice point represents the
constituent particle ions, atoms or
molecules. Lattice
• The smallest repeating unit in the crystal points
lattice is called as a unit cell.

Unit cell
 Unit cell
•

b
a
Cubic Crystal Systems
Simple cubic cell (SCC)
Atom

⮚ In simple cubic cell, the

constituent particles
are at eight corners of
the cube.
Body centered unit cell (BCC)

⮚ In body centered cubic cell,

the constituent particles are
at eight corners of the cube
as well as in the center of the
cube.
Face centered unit cell (FCC)

⮚ In face centered cubic

cell, the constituent
particles are at eight
corners of the cube as
well as in the center of
each of the six faces of
the cube.
2.Tetragonal Crystals
3.Orthorhombic Crystals
4. Monoclinic Crystals
5. Triclinic Crystals
6.Rhombohedral Crystals
7. Hexagonal Crystals
 Bravais lattice
⮚French mathematician Bravais arranged the lattice points in
14 different ways.
⮚Cubic crystals = 3
⮚Orthorhombic = 4
⮚Trigonal = 2
⮚Monoclinic = 2
⮚Triclinic = 1
⮚Rhombohedral = 1
⮚Hexagonal = 1
Number of particles
in
cubic unit cell
 Simple cubic cell (SCC)

⮚ In SCC each atom at the

corner is shared by 8
neighboring unit cells.

⮚ No of atoms in SCC
= 1/8 x 8
= 1 atom
 Body centered unit cell (BCC)
⮚ In BCC each atom at the corner is shared
by 8 neighboring unit cells.
⮚ One atom at the center which is not
shared by any unit cell
⮚ No of atoms in BCC
= (corners) + (center)
= (1/8 x 8 ) + 1
= 1 + 1
= 2 atoms
8 Atoms at the 8 corners 1 Atom at the center
Face centered unit cell (FCC)
⮚In FCC each atom at the corner is
shared by 8 neighboring unit cells.
⮚One atom at the center of each of
the six faces is shared with one
neighboring unit cell
⮚No of atoms in FCC
= (corners) + (faces)
= (1/8 x 8 ) + (6 x1/2)
= 1 + 3
= 4 atoms 3 Atoms (½ of atom) 1/8th of Atom at 8
at the 6 corners corners
❑ Packing of particles in crystal lattice
• Constituent particles of a crystalline
solids are closed packed.
• Each of the particle is considered as a
hard sphere.
• The number of neighboring spheres that
touch any given sphere is called as the co
ordination number.
• Larger the coordination number, the
closer are the spheres to each other.
 Closed packed structures
1. Closed packing in one
dimension

2. Closed packing in two

dimension

3. Closed packing in three

dimension
 Closed packing in two dimension
Depressions

A A
A B
A A
B
Square closed packing Hexagonal closed
packing
Coordination number
Coordination number = 4
=6
• Video on Packing in crystals
• Video on packing in crystals
• Video on HCP hcp and ccp/fcc
Closed packing in three dimension
Stacking of Square closed
packing

Stacking of Hexagonal closed

packing

Placing third Hexagonal

closed packed layer
 Stacking of Square closed
Closed packing in three dimension packing

A
A
A
A
Simple
Coordination number = 6 cubic cell
Closed packing in three dimension
Polonium is the only metal that
crystallizes in simple cubic closed
packed structure.

Each atom is attached to

4 atoms in the same layer

1 atom in the upper layer

1 atom in the lower layer

Coordination number = 6
Staking of Two Hexagonal close packed layers

The first layer with

hexagonal close packing

Octahedral Void

Tetrahedral Void
-- A
The second layer is placed in
-- B the depressions of the first
layer
Tetrahedral and Octahedral Voids
 (Closed packing in three
dimension)
Placing third Hexagonal closed packed layer

C
A
B
B
A
A

Hexagonal Close Packed Cubic Close Packed

Cubic Close Packing/FCC

C
⮚ ABC ABC type of arrangement results in cubic
B
closed packed structure (ccp).
⮚ Cubic closed packing is similar to face centered
cubic cell (FCC)
A
Hexagonal Close Packing

A
⮚ ABAB type of arrangement results in hexagonal
close packing structure (hcp).
B ⮚ Metals like Zn , Mg etc have hcp crystal
structure.
A
 Metals like Magnesium (Mg) and Zinc
(Zn) have hcp crystal structure.

Magnesium(Mg) Zinc (Zn)

 Metals like Silver (Ag) and Copper
(Cu) have ccp or fcc structure.

Silver(Ag) Copper (Cu)

Coordination number of Closed Packed Structures

❑ The number of neighbouring spheres that touch any given

sphere in the crystal structure is its coordinate number.
❑ The magnitude of coordination number is a measure of
compactness of spheres in close packed structures.
❑ The larger the coordination number, closer are the spheres
to each others.
Coordination number of Closed Packed Structures
1 atom in above the
layer

4 atoms in the same

layer

1 atom in below the

layer

Simple cubic Coordination no

cell (SC) =6
Coordination number of Closed Packed Structures

Coordination number = 3 + 6 + 3 = 12

Cubic Close Packing (CCP) / FCC

Coordination number of Closed Packed Structures

Coordination number = 3 + 6 + 3 = 12

Hexagonal Close Packing (HCP)

Tetrahedral Voids VOIDS Octahedral Voids

❑ The empty space present between two spheres in a

crystal lattice is calld as void.
❑ There are two types of voids, tetrahedral voids and
Octahedral voids.
 VOIDS
Tetrahedral Voids
Octahedral Voids

If there are N closed

If there are N closed
spheres then,
spheres then,
⮚No of Tetrahedral
⮚No of octahedral
voids equals to 2N.
voids equals to N.
Tetrahedral and Octahedral Voids
Types Of Voids
 Packing efficiency
⮚Packing efficiency is the fraction or percentage of the
total space occupied by the spheres.

⮚Like coordination number, the magnitude of packing

efficiency gives the measure of how tightly the
particles are packed together.
 Packing efficiency

•
Packing efficiency of Simple cubic cell (SCC)
a = 2r

a a

a
r r

No of particles in Simple cubic unit cell = 1/8th x 8 = 1

 Packing efficiency Of Simple Cubic Unit Cell

•
 Packing efficiency Of Simple Cubic Unit Cell

•
Packing efficiency of Body Centered cubic cell (BCC)

No of particles in BCC = 1/8 th x 8 +

1=2
Packing efficiency of Body Centered cubic cell (BCC)

AC = b
DC = a AC = b AB = BC = a
AD = c = 4r
AC = AB + BC
2 2 2
A
AD2 = AC2 + DC2
b2 = a 2 + a 2
r r a
c2 = b 2 + a 2 b2 = 2a2
= 4
(4r)2 = 2a2 + a2 c r b
16r2 = 3a2 r B
a = 4r r a
Relation between edge
length and radius of atom. D a C
 Packing efficiency Of Body centred Cubic Unit Cell
•
Packing efficiency Of Body Centred Cubic (bcc) Unit Cell

•
Packing efficiency in each cubic unit cell

Type of Coordinat Packing Unoccupi

unit cell ion efficiency ed space
Number
of atoms
SCC 6 52.36 % 47.64 %

BCC 8 68 % 32 %

FCC 12 74 % 26 %
Edge length and particle parameters in cubic
system
Type of unit No of atoms Edge length Radius of
cell per unit cell of cube = a atom

SCC 1 a = 2r r=a/2
Relationship between
Molar mass
and
Density
 Particle
Molar Mass and Density of cubic unit cells

Edge length of the cube = a

Volume of the cube = a3

a
Mass of the particle = m
a

Molar mass of the particle = M a

Density of the cube =
•

a
⮚Gold crystallizes to from FCC having edge length 408 pm.
Calculate the density of gold.The molar mass of gold is 197
g/mol.
Data: a = 408 pm = 408 x 10-10 cm n=4
Molar mass = 197 g/mol NA = 6.022 x 1023
To find:

Formula:

Solution :
❑ Calculation of number of particles and unit cells in
x g of metallic crystal-:
•
❑ Number of particles in ‘x’ g of Metal-:
•
❑ Number of unit cells in ‘x’ g of metal-:
•
 Defects

⮚ The irregularities in the

arrangements of the constituent
particles is called as defects.
 Line Defect

Types
of
Defects

Point Defect Plain Defect

 Point Defects

❑ Point defects are irregularities

produced in the arrangement of basis
at lattice points in crystalline solids.
 Point
defect

Stoichiometri Non Impurit

c stoichiometric y
Metal Substitution
Vacancy
1 defect 1 deficiency 1 impurity
defect defect
Frenkel
2 defect Interstitial
Metal excess
Schottky 2 2 impurity
3 defect
defect defect
Self interstitial
4 defect
 Stoichiometric defects
⮚Chemical formula of a compound shows the fixed ratio of
number of cations and anions.
⮚This fixed ratio is called as Stoichiometry of a compound.
⮚In stoichiometric defect ,the stoichiometry remains
unchanged i.e the number of cation and anions remains
unchanged.
⮚Types of stoichiometric defects
1. Vacancy defect
2. Self interstitial defect
3. Frenkel defect
4. Schottky defect
 Vacancy defect

• During crystallization if the

particle is missing from its
regular site, it creates a
vacancy in the crystal
lattice.
• Due to the absence of
particles, the density of the
crystal decreases .
 Self interstitial defect
• When some of the particles occupy the interstitial position in the
crystal lattice is called as self interstitial defect.
• This defect occurs in two ways as given below-:
⮚ Extra atom occupies the ⮚ One atom gets shifted from its
interstitial position. original position and occupies
⮚ Density of the substance the interstitial position.
increases. ⮚ It is a combination of vacancy
defect and self interstitial
defect.
⮚ Density remains same.

Extra
atom
❑ Frenkel defect
❑ When an ion from the ionic
solid is missing from its
regular lattice site and
occupies the interstitial
position between the
crystal lattice is called as
Frenkel defect.
❑ It is a combination of both
interstitial and vacancy
defect.
❑ Conditions for the formation of Frenkel
Defect-:
❑ Frenkel defect occurs in ionic
compounds with large difference
between sizes of cation and anion.
❑ The ions of ionic compounds must be
having low coordination number.
❑ Cosequences of Frenkel Defect-:
As no ions are missing from the crystal lattice as a whole,
⮚the density of solid remains unchanged.
⮚its chemical properties remain unchanged.
As equal number of cations and anions are present,
⮚The crystal as a whole remains electrically neutral.
⮚This defect is found in ionic crystals like ZnS, AgCl, AgBr, AgI
etc.
 Schottky defect Paired cation –anion vacancy

⮚ When equal number of cations and

anions are missing from their original
lattice site creating vacancies is called
as Schottky defect.
⮚ There exist two holes per ion pair lost,
one for missing cation and other for
missing anion.
⮚ The density of metal decreases due to
this defect as the ions leave the crystal.
⮚ The number of missing cations and
anions is equal, the electrical neutrality Cation vacancy Anion vacancy
of the compound is preserved.
❑ Conditions for the formation of
Schottky Defect
Schottky defect is found in ionic compounds
with the following characteristics:
⮚ High degree of ionic character.
⮚ High coordination number of anion.
⮚ Small difference between size of cation and
anion.
❑ Consequences of Schottky Defect-:
As equal number of cations and anions are missing.
⮚The density of the substance decreases.
⮚Electrical neutrality is also maintained.
⮚This defect is found in ionic crystals , NaCl, KCl, AgBr etc.
 Non-Stoichiometric defects
• The defect which arises when the ratio of number of cation
to anion becomes different from that indicated by the
chemical formula.
• In other words stoichiometry of the compound is changed.
• However change in stoichiometry does not change the
crystal structure.
• Types of non-stoichiometric defects:
1. Metal deficiency defect
2. Metal excess defect
❑ Metal deficiency defect
• This defect is possible in only
M X M X
those metallic compounds that + - + -
have variable oxidation state.
• In some crystals the positive X M+
M X M
2
metal ions are missing from - + - +

their original lattice site.

M X M X
• An extra negative charge is + - + -
balanced by cations of the
same metal having a higher X M X M
oxidation state than that of - + - +

the missing cation.

❑ Metal Deficiency Defect
Example-: In the compound of
NiO , one Ni+2 ion is missing
creating a vacancy at its lattice
site.The deficiency of +2 charge is
made up by the presence of two
Ni+3 ions at the other lattice
sites of Ni+2 ions .
The composition of NiO then
becomes Ni0.97O1.0 .
Non-stoichiometric Defect
❑ Metal excess defect
• Metal excess defect occurs in
two ways
1. Neutral atom or extra
positive ion occupies the
interstitial position
2. By anion vacancies ( Colour
or F-centres)
In both the cases , non-stoichiometric formula of ZnO is Zn1+xO1.0

In this case, when ZnO is heated-:

Here, in ZnO lattice one
ZnO  Zn+2 + ½ O2 + 2e-
neutral Zn atom is
present in the interstitial The excess Zn+2 ions and the
space. electrons are trapped in the
interstitial space.
 ❑ By anion vacancies ( Colour or F-Centres)

❑ When NaCl crystals are heated, Na atoms are

deposited on the surface of the crystal.
❑ Cl- ions leave their regular sites and combine with Na
on the surface to form NaCl and electrons are
released.
❑ Na + Cl-  NaCl + e- .
❑ The electrons released will go into the crystal and
occupy vacant sites of Cl- forming F-centres or colour-
centres.
 Metal Excess Defect

NaCl shows yellow colour due to the formation of F-

centres.
The crystal of NaCl has excess Na .
The non-stoichiometric formula of NaCl is Na1+xCl1.0
 Impurity defects

• Impurity defect arises when foreign atoms different

from its host atoms are present in the crystal lattice.
• Types of impurity defect:
1. Substitutional impurity defect.
2. Interstitial impurity defect.
❑ Substitutional impurity defect

• The foreign atom are found at the

lattice sites in place of host Cu Cu
Zn Cu
atoms.
• The regular atoms are displaced Cu
Zn Cu Cu
from their lattice sites by impurity
atoms. Cu Cu Zn
Cu
• Example -: Solid solutions of
metals ( alloys) : Brass is an alloy
of Cu and Zn. Zn atoms occupy Brass (Alloy of Cu & Zn)
the regular sites of Cu atoms.
Vacancy through aliovalent impurity
Vacancies are created by the addition
of impurities of aliovalent ions ( ions
with o.s different from that of host
ions) to an ionic solid.
Ex-: suppose a small amount of SrCl2
impurity is added to NaCl during its
crystallization. The added Sr+2 ions (o.s
=2) occupy some regular site of Na+ ions
(o.s = 1) and one site of Na+ will be
vacant .
❑ Interstitial impurity defect
• In this defect the
impurity atoms occupy Fe Fe Fe
the interstitial positions
in the crystal lattice. Fe Fe Fe
Carbon
• Ex-: Steel , Fe atoms atom
Fe Fe Fe
occupy regular sites and
C atoms as impurities
are present in
interstitial spaces. Steel (Alloy of Fe & C)
Sodium crystallises in BCC structure with edge length of
unit cell 4.29 x 10-8cm. Calculate the radius of sodium
atom
•
Niobium is found to crystallize with BCC structure and found to have
density 8.55g cm-3.Determine the radius of niobium if its atomic
mass is 93.

•
Gold crystallises in FCC structure and has a density of 19.3 g cm-
3
Find atomic radius of gold.
(Au = 197g/mol)
•
Thank
you