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General Characteristics of Solid

1. Definite mass, volume and density

2. High rigidity
3. Minimum Spaces between particles
4. Higher interparticle forces than Liquid and Gas
5. Negligible compressibility and fluidity
Classification of Crystals

Crystalline Solids Amorphous Solids

Regular internal arrangement of Irregular internal arrangement of

particles particles

Regarded as true solids Regarded as supercooled liquids or

pseudo solids

Undergo regular cleavage Undergo irregular cleavage

Classification of Crystals

Crystalline Solids Amorphous Solids

Anisotropic in nature Isotropic in nature

Sharp melting point Melt over a range of temperature

Definite heats of fusion Don’t have definite heats of fusion

Select the correct statements.
P. Crystalline solid are always an isotropic in nature for all physical
properties.
Q. Amorphous solid are isotropic in nature.
R. Amorphous solid may have short range order.
S. Amorphous solid are treated as supercooled liquid.

A. P, Q, R
B. Q, R
C. Q, R, S
D. All correct
 Classification of Crystals

Crystal
Unit Particles Binding forces Properties Examples
Classification

Ionic Positive and Ionic bonds ● Hard and brittle NaCl, PbS
negative ions ● High melting points/
heats of fusion
● Poor thermal and
electrical conductors
in solid state
 Classification of Crystals

Crystal
Unit Particles Binding forces Properties Examples
Classification

Molecular Non - polar Weak Dispersion ● Soft H2, Cl2, I2

molecules Forces or London ● Low melting points
forces ● Poor thermal and
electrical conductors
 Classification of Crystals
Crystal
Unit Particles Binding forces Properties Examples
Classification

Molecular Polar Dipole - dipole forces ● Soft Solid SO2,

molecules ● Moderate melting Solid NH3
points
● Poor thermal and
electrical conductors
 Classification of Crystals
Crystal
Unit Particles Binding forces Properties Examples
Classification

Molecular Hydrogen Hydrogen bonds ● Moderately high Ice, Dry ice

bonded melting points
● Poor thermal and
electrical conductors
Classification of Crystals

Crystal Binding
Unit Particles Properties Examples
Classification forces

Covalent Atoms that are Covalent ● Very hard Diamond,

connected in bonds ● Very high melting Graphite
covalent bond points
network ● Poor thermal and
electrical
conductors
Classification of Crystals

Crystal Binding
Unit Particles Properties Examples
Classification forces

Cations in Metallic ● Soft to very hard All metallic

Metallic electron cloud bonds ● Low to very high elements, for
melting points example, Cu,
● Excellent thermal Fe, Zn.
and electrical
conductors.
 Crystal Lattice

● A regular three dimensional arrangement of points in space is called a Crystal

Lattice.
 Unit Cell
Crystalline solids can be studied based on smaller repeating units which form the
complete crystal.
 Unit Cell
A unit cell is characterised by six parameters:
a, b, c, α, β and γ
 7 Crystal Systems
Crystal System Axial distances Axial angles
or edge lengths

Cubic a=b=c α = β = γ = 900

Tetragonal a=b≠c α = β = γ = 900

Orthorhombic a ≠b≠c α = β = γ = 900

Monoclinic α = γ = 900
a≠b≠c
β ≠ 900

Triclinic a≠b≠c α ≠ β ≠ γ ≠ 900

Hexagonal α = β = 900
a=b≠c
γ = 1200

Rhombohedral or α = β = γ ≠ 900
a=b=c
Trigonal
7 Crystal Systems
Crystal System Axial distances Axial angles
or edge lengths

Cubic

Tetragonal

Orthorhombic

Monoclinic

Triclinic

Hexagonal

Rhombohedral or
Trigonal
Variations within Crystal system
Primitive Unit Cell

When constituent particles are present only on the corner

positions of a unit cell, it is called as primitive unit cell.
Variations within Crystal system
Centered Unit Cell

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 a centred unit cell.
Variations within Crystal system
Centered Unit Cell

Centred unit cells are of three types: End-Centered, Body-Centered and Face-Centered
Variations within Crystal system
Centered Unit Cell

Centred unit cells are of three types: End-Centered, Body-Centered and Face-Centered
Variations within Crystal system
Centered Unit Cell

Centred unit cells are of three types: End-Centered, Body-Centered and Face-Centered
 Bravais Lattices
Variations in Crystal Systems create 14 Bravais Lattices
 Bravais Lattices
Variations in Crystal Systems create 14 Bravais Lattices

Possible
Crystal System Examples
Variations

Cubic Primitive, Body- NaCl, Zinc

Centred, Face- blende, Cu
Centred

Tetragonal Primitive, Body- White tin, SnO2,

centred TiO2, CaSO4

Orthorhombic Primitive, Body- Rhombic

centred, Face- sulphur, KNO3,
centred, End- BaSO4
centred
Variations within Crystal system
Possible
Crystal System Examples
Variations

Primitive, End- Monoclinic sulphur,

Monoclinic
centred Na2SO4.10H2O

K2Cr2O7,
Triclinic Primitive
CuSO4.5H2O, H3BO3

Hexagonal Primitive Graphite, ZnO, CdS

Rhombohedral or Calcite (CaCO3),

Primitive
Trigonal HgS (cinnabar)
Contribution of Lattice Point in Cubic Unit Cell

1. Corner = ⅛
Contribution of Lattice Point in Cubic Unit Cell

2. Face Centre = ½
Contribution of Lattice Point in Cubic Unit Cell

3. Edge Centre = ¼
Contribution of Lattice Point in Cubic Unit Cell

4. Body Centre = 1
A solid has a structure in which W atoms are located at the corners of a
cubic lattice. O atom at the center of the edges and Na atom at center
of the cube. The formula for the compound is
A. NaWO2
B. NaWO3
C. Na2WO3
D. NaWO4
A compound MpXq has FCC arrangement of X. Its unit cell structure is
shown below. The empirical formula of the compound is

A. MX
B. MX2 IIT 2012

C. M2X
D. M5X14
 Edge Length, Coordination Number and
Effective Number of atoms in a Unit Cell, Z
1. Simple Cubic =
8 (corners) x ⅛ (contribution of each corner) = 1
 Edge Length, Coordination Number and
Effective Number of atoms in a Unit Cell, Z
2. Body Centered Cubic =
8 (corners) x ⅛ (contribution of each corner) + 1(Body Centre)x 1(contribution)
 Edge Length, Coordination Number and
Effective Number of atoms in a Unit Cell, Z
 Edge Length, Coordination Number and
Effective Number of atoms in a Unit Cell, Z
3. Face Centered Cubic =
8 (corners) x ⅛ (contribution of each corner) + 6(Face Centre)x ½ (contribution)
 Property SC BCC FCC HCP

Atomic
a/2 a/2
radius(r)

No. of atoms
1 2 4 6
per unit cell (Z)

Coordination
6 8 12 12
Number
 Edge Length, Coordination Number and
Effective Number of atoms in a Unit Cell, Z
Sodium metal crystallizes in a body centred cubic lattice with a unit cell
edge of 4.29Å. The radius of sodium atom is approximately:
A. 1.86 Å
B. 3.22 Å
C. 5.72 Å
D. 0.93 Å
 Packing

Reason due to which variations aries in a crystal system is called “Packing”.

● In one dimension only 1 type of Packing is possible

● Nearest atoms touching each other i.e. Coordination Number = 2

 Packing

● In two dimensions 2 type of Packing is possible:

○ Square Packing ○ Hexagonal Packing
● Coordination Number = 4 ● Coordination number = 6
Packing

Unit Cells formed when each Layer has Square Packing:

1. Simple(Primitive) Cubic
2. Body-Centered Cubic
Square Packing

Simple Cubic Unit Cell

Body Centred Cubic Unit Cell

 Hexagonal Packing

Unit Cells formed when each Layer has Hexagonal Packing

Hexagonal Packing

Unit Cells formed when each Layer has Hexagonal Packing:

1. Face-Centered Cubic ( Cubic Close Packing)
2. Simple(Primitive) Hexagonal
ABCABCvs ABAB

ABAB Packing - ABCABC Packing -

Hexagonal Unit Cell Face Centered Cubic Unit Cell
Closed Packing

Hexagonal Unit Cell

Face Centred Cubic Unit Cell

 Packing Efficiency
The percentage of total space filled by the particles is called packing efficiency.
Different types of packing arrangements have different packing efficiency.
Volume of atoms in a unit cell
Packing efficiency = x 100 %
Total volume of a unit cell

Property SC BCC FCC HCP

Packing
52% 68% 74% 74%
efficiency
 Multiple Option Correct

The correct statement(s) for cubic close packed (ccp) three

dimensional structure is (are)

A. The number of the nearest neighbours of an atom present in the

topmost layer is 12
B. The efficiency of atom packing is 74%
C. The number of octahedral and tetrahedral voids per atom are 1 and
2, respectively
D. The unit cell edge length is 2√2 times the radius of the atom

IIT 2016
Density of Cubic Unit Cells

Density (d) = Z x M g/cm3

NA . a3
Where ,
Z = effective number of atoms/molecules in unit cell
M = Molar mass of substance
NA = Avogadro Number
a= Edge length of unit cell
 Voids in Unit Cells
● There are always spaces left in the between the spherical atoms in all unit cells
known as voids or Interstitial Voids.
● The maximum size of sphere which can be place in void space is depends on size of
void.
 Location of Voids in cubic unit cell
Tetrahedral Voids at 1/4th
Octahedral Voids at body centre distance from nearest corner
and Edge Centre on body diagonal

C.
A. B. Void at
Void at
Edge Void
Body
Centre
Centre
Location of Voids in cubic unit cell
● The voids in BCC crystals are non-regular or distorted octahedral and tetrahedral voids.
Select the correct statements for fcc arrangements.
A. There are 4 tetrahedral voids per unit cell
B. There are 8 tetrahedral voids per unit cell
C. There are 4 octahedral voids per unit cell
D. Each tetrahedral void is surrounded by 8 spheres.
Select the correct statements.
A. In fcc unit cell all tetrahedral voids completely inside unit cell
B. In fcc unit cell all octahedral voids completely inside unit cell
C. In fcc unit cell each sphere is surrounded by 6-octahedral voids and 8-
tetrahedral voids
D. Octahedral voids present at only edge unit cell.
Structure of compounds containing two different types of atoms.

● The bigger atom or ion will form the lattice & smaller atom / ion will occupy the
voids. Generally, bigger ion is anion and smaller ion is cation.
● The type of void occupies by the cation is decided by radius ratio.
Radius Ratio Rule

● The ratio of radius of smaller ion( generally cation) to the radius of anion larger
ion (generally anion) is known as radius ratio of the ionic solid.
● Radius ratio = (r+ / r- ) , this gives the idea about the type of void occupied.

Limiting r+/r- Co-ord. No. Shape Example

0.225 - 0.414 4 Tetrahedral ZnS

0.414 - 0.732 4 Square Planar PtCl42-

0.414 - 0.732 6 Octahedral NaCl

0.732 - 0.999 8 Cubical Void CsCl

The arrangements of X- ions around A+ ion in solid AX is given in the figure
(not drawn to scale). If the radius of X- is 250 pm, the radius of A+ is

A. 104 pm
B. 125 pm
C. 183 pm
D. 57 pm

IIT 2013
 Diamond Unit Cell

It has carbons on 8 corners, 6 face centre and 4 tetrahedral site

 Representative Ionic Compounds

Sodium Chloride (NaCl)

Positions: Cl- is forming a FCC unit cell in which Na+ is in the octahedral voids. The
coordination number of Na+ is 6 and that of CI- would also be 6.

(b) Ratio of ionic radii =

(c) No. of sodium ions = 12 (At edge centre) x 1/4 + 1 (At body centre) x 1 = 4
No. of chloride ions = 8 (At corners) x 1/8 + 6 (At face centres) x 1/2 = 4 (Thus formula is
Na4CI4 i.e. NaCI)
 Representative Ionic Compounds

Zinc blende or Sphalarite structure (ZnS)

(a) Sulphide ions are face centered and zinc is present in alternate tetrahedral voids.

(b) ∴ No. of ZnS units per unit cell = 4

Representative Ionic Compounds

Caesium chloride structure (CsCl)

Each Cs+ ion is touching eight aCl- ions and each Cl- ions in touching eight Cs+ ions.
No. of Cl- ions = 8 (At corners) x 1/8 = 1
No. of Cs. ions = 1 (At the body centre) x 1 = 1
No. of CsCl unit per unit cell = 1
Representative Ionic Compounds

Fluorite structure (CaF2)

The cations are arranged in cubic close packing (ccp) while the anion occupy all the
tetrahedral voids

No. of F- ions = 8 (T.V.) x 1 = 8

No. of Ca+2 ions = 8 (Corner) x 1/8 + 6 (Face Centres) x ½ = 4
No. of CaF2 unit per unit cell = 4
Representative Ionic Compounds

Antifluorite structure (Na2O)

The anions are arranged in cubic close packing (ccp) while the cations occupy all the
tetrahedral voids.

No. of Na+ ions = 8 (T.V.) x 1 = 8

No. of O-2 ions = 8 (Corner) x 1/8 + 6 (Face Centres) x ½ = 4
No. of Na2O unit per unit cell = 4
Representative Ionic Compounds

Spinel structure [AB2O4]

● Oxides ion arranged in CCP layers

● 1 tetrahedral holes occupied by one type of metal ion
● 2 of the octahedral holes occupied by another type of metal ion.
○ eg : A spinel is formed by Zn2+, Al3+ and O2- with Zn2+ ion in the tetrahedral holes.
The formula of the spinel is ZnAl2O4.
Representative Ionic Compounds

Perovskite structure [ABO3]

This structure may be described as a cubic lattice, with barium ions occupying the
corners of the unit cell, oxide ions occupying the face centers and titanium ions
occupying the centres of the unit cells. eg : BaTiO3 or MgTiO3.
 Elements of Symmetry in a Cube

Centre of Symmetry
● It is defined as an imaginary point within the crystal such that any line passing
through this point intersects the opposite face of the crystal at equal distances.
● In other words, any line drawn through this point will intersect surface at equal
distance in both the directions.
 Elements of Symmetry in a Cube

Plane of Symmetry

● It is an imaginary plane which divides the crystal into two equal parts such that one is
the mirror image of the other.
● Regular cubic structure can have 9 planes of symmetry.
 Elements of Symmetry in a Cube

Axis of Symmetry

● Axis of Symmetry is a line about which the crystal may be rotated such that it
presents the same appearance more than once during the complete revolution
through 360o.

● If a crystal presents the same appearance 'n' times in complete revolution, the
axis is said to be 'n' fold symmetry.
 Elements of Symmetry in a Cube
● The cube contains three different types of symmetry axes:
○ three 4-fold axes, each of which passes through the centers of two opposite
faces,
○ four 3-fold axes, each of which passes through two opposite vertices, and.
○ six 2-fold axes, each of which passes through the midpoints of two opposite
edges.
For cubic crystal system, select the correct statements.
A. It have 9-plane of symmetry
B. It has three 4-fold axis of symmetry
C. It has one centre of symmetry
D. It have maximum elements of symmetry
A crystalline solid of a pure substance has a face-centred cubic
structure with a cell edge of 400 pm. If the density of the substance in
the crystal is 8g cm-3, then the number of atoms present in 256g of the
crystal is N x 1024. The value of N is

IIT 2017
 Defects in a Crystal

Crystalline solids have short range as well as long range order in the arrangement of
their constituent particles but crystals can have defects

Types of Defects

1. Point Defect: It occurs around a point or an atom in a crystalline substance

2. Line Defect: It occurs on entire rows of lattice points

Types of Point Defects

1. Stoichiometric
2. Impurity
3. Non-stoichiometric
Types of Stoichiometric Defects in Non-ionic Compounds

(i) Vacancy Defect (ii) Interstitial Defect

Some of the lattice sites are vacant When some constituent particles (atoms or
Decrease in density of the substance. molecules) occupy an interstitial site, the
It can also develop when a substance is crystal is said to have interstitial defect.
heated. Increases in density of the substance.
Types of Stoichiometric Defects in Ionic Compounds

(a) Schottky Defects

Equal number of positive and negative ions are missing

More common in ionic compounds with high coordination number and ions of almost
similar sizes

NaCl, KCl, CsCl and AgBr.

Types of Stoichiometric Defects in Ionic Compounds

(b) Frenkel Defect ( Dislocation defect)

An ion leaves its correct lattice site and occupies an interstitial site.
Common in ionic compounds which have low coordination number and in which there
is large difference in size between positive and negative ions.
Example. ZnS. AgCl, AgBr and AgI due to small size of Zn2+ and Ag+ ions.
 Impurity Defects in Ionic Compounds

If molten NaCl containing a little amount of SrCl2 is crystallised, some of the sites of Na+
ions are occupied by Sr2+.

Another similar example is the solid solution of CdCl2 and AgCl.

Non-stoichiometric defects

Metal excess Defects due to Anion Vacancies.

A compound may have excess metal ion if a negative ion is absent from its lattice site,
leaving a 'hole', which is occupied by electron to maintain electrical neutrality.

The anionic sites occupied by unpaired electrons are called F-centres (from the German word
Farbenzenter for colour centre). They impart colour to the crystals.
Non-stoichiometric defects

Metal Deficiency due to cations vacancies

The non-stoichiometric compounds may have metal deficiency due to the absence of a
metal ion from its lattice site. The charge is balanced by an adjacent ion having higher
positive charge.
 Change in Coordination Number
On increasing pressure ⟶Coordination number tends to increase.
On increasing temperature ⟶Coordination number tends to decrease.

P↑ T↑
4:4 6:6 ; 8:8 6:6

Electrical Properties of Solids

Solids can be classified into three types on the basis of their electrical conductivities.

1. Conductors : Conductivities in the order 107 (Ωm)-1

2. Insulators : Conductivities ranging from 10-20 to 10-10 (Ωm)-1 e.g.; MnO, CoO, NiO, CuO,
Fe2O3, TiO2.
3. Semiconductors : Intermediate conductivities generally from 10-6 to 104 (Ωm)-1
Conductivity of solids is explained theoritically through Band Theory
When a large number of atoms are present in close proximity, the atomic orbitals of
metal atoms form molecular orbitals which are so close in energy to each other as to
form a band.
 Conductors

The conductivity of metals depend upon the number of valence electrons available per atom. If
this band is partially filled or it overlaps with a higher energy unoccupied conduction band, then
electrons can flow easily under an applied electric field and the metal shows conductivity.

Insulators

If the gap between filled valence band and the next higher unoccupied band (conduction band)
is large, electrons cannot jump to it and such a substance has very small conductivity and it
behaves as an insulator
Conductors Insulators Semiconductors
 Doping

The conductivity of these intrinsic semiconductors is too low to be of practical use.

It is increased by adding an appropriate amount of suitable impurity.
This process is called Doping
 Doping

Doping can be done with an impurity which is electron rich or electron deficient as
compared to the intrinsic semiconductor silicon or germanium. Such impurities
introduce electronic defects in them.
a. Electron - rich impurities
b. Electron - deficient impurities
 Super Conductivity

Electrical resistance decreases with decrease in temperature and becomes almost zero
near the absolute zero. Materials in this state are said to possess. superconductivity.

Mercury becomes superconducting at 4.0 K temperature.

Transition Temperature

The temperature at which a substance starts behaving as super-conductor is called

transition temperature.
 Magnetic Properties
Electron’s magnetic moment originates from two types of motions
i. its orbital motion around the nucleus and
ii. its spin around its own axis.
 Classification by Magnetic Properties

On the basis of their magnetic properties, substance can be classified into five
categories:
i. paramagnetic
ii. diamagnetic
iii. ferromagnetic
iv. antiferromagnetic
v. ferrimagnetic
 Magnetic Properties

In solid state, the metal ions of certain substances are

grouped together into small regions called domains.
Thus, each domain acts as a tiny magnet.
 Paramagnetic vs Diamagnetic

Paramagnetic substances are weakly attracted by a magnetic field.

Diamagnetic substances are weakly repelled by a magnetic field.

 Ferromagnetic

Property: Ferromagnetic substances show permanent magnetism even in the absence of

the magnetic field e.g. Fe Ni Co and CrO2.

Domains: This type of magnetism arise due to the spontaneous alignment of magnetic
moments due to unpaired electron in the same direction.
 Anti-ferromagnetic

Property: Possess zero net magnetic moment eg. MnO

Domain: Anti-ferromagnetism is due to the presence equal number of magnetic

moments in the opposite direction.
Magnetic Properties
Property: Substances are expected to possess large magnetism on the basis of
unpaired electrons, but actually have small magnetic momentum are called
ferrimagnetic substances eg. Fe3O4, ferrites of the formula M2+, Fe2O, where M = Mg,
Cu, Zn etc.

Domain: Ferrimagnetism arises due to the unequal moments in opposite direction

resulting in same net magnetic moment. On heating these substance loss their
magnetism and convert in to paramagnetic substance
For cubic crystal system, select the correct statements.
A. fcc arrangement have C.N. = 12
B. For same sized sphere among fcc, bcc and sc arrangement, sc have
minimum volume of unit cell
C. In sc arrangement a sphere touches 4-sphere in same layer, one in
above layer and one in below layer
D. In bcc arrangement distance between nearest neighbours is a√3/2
(a= edge length of unit cell.)
Select the correct statements.
A. For same sized sphere, volume of sc to fcc arrangement is 1: 2√2
B. For same sized sphere, volume of fcc to bcc arrangement is 1 : 2
C. For fcc arrangement Vunit cell =16√2 R3
D. None of the above
TOP RANKER SERIES
Select the correct statement for hcp and ccp arrangement.
A. Both having C.N. = 12
B. Both having P.F. = 0.74
C. In both close packed layer are hexagonal close packed layer in 2-D
D. In both perpendicular distance between close packed layer is same
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