JEE Advanced 2024 One Shot

JEE Advanced Exam
No fixed pattern
Often surprises by pattern
Conducting body : IIT
Exam :- In the month of May-

June every Year
Paper 1
9:00 am – 12:00 noon
Paper 2
2:30 pm – 5:30 pm
JEE Advanced Exam
Physical Chemistry: Relative Weightage (2019-23)
Surface
Solid State Chemistry Gaseous State
4.8% 3.6% 2.4% Mole & Redox
Atomic Structure 26.3%
6%
Solutions
8.4%
Equilibrium
10.5% Thermodynamics
13%
Chemical Kinetics
12% Electrochemistry
13%
JEE (Advanced) 2024 : Syllabus
SOLID STATE
Classification of solids, crystalline state,
seven crystal systems (cell parameters a, b, c,
α, β, γ), close packed structure of solids
(cubic and hexagonal), packing in fcc, bcc
and hcp lattices; Nearest neighbours, ionic
radii and radius ratio, point defects.
SOLID STATE
SOLIDS
Definite shape, definite volume and ORDER.
ORDER
Definite pattern of arrangement of atoms or molecules or ions.
SOLIDS
Highest intermolecular attractive forces
Molecules, atoms or ions are closely packed.
Incompressibility
Rigidity
Mechanical Strength
Classification of Solids
On the basis of order of arrangement of their

constituent particles solids are classified as
Crystalline Solids
Amorphous Solids
Crystalline Solids
It has, LONG RANGE ORDER i.e. there is regular pattern of arrangement of

particles which repeat itself periodically over the entire crystal.
Amorphous Solids
It has, SHORT RANGE ORDER i.e. there is regular pattern of arrangement

of particles over short distances only.
Distinction between Crystalline and Amorphous solids
PROPERTY CRYSTALLINE SOLIDS AMORPHOUS SOLIDS
Shape Definite characteristic Irregular shape

geometrical shape
Arrangement of Long range order Only short range order
Particles
Anisotropy Anisotropic in nature Isotropic in nature

Distinction between Crystalline and Amorphous solids
PROPERTY CRYSTALLINE SOLIDS AMORPHOUS SOLIDS
Melt at a sharp and

Gradually soften over a
Melting point characteristic
range of temperature
temperature
They have a definite

They do not have
Heat of fusion and characteristic
definite heat of fusion
heat of fusion
When cut with a sharp

When cut with a sharp
edged tool, they split into
edged tool, they cut
Cleavage two pieces and the newly
into two pieces with
property generated surfaces are
irregular Surfaces
plane and smooth
Lattice (Crystal lattice)
Each point in a lattice is called lattice point.
Lattice points are joined by straight lines to represent the geometry of

lattice.
Lattice should be infinite.
A lattice gives rise to a crystal when points are replaced by particles

such as atoms, molecules or ions.
Unit Cell
Smallest Repeating Unit
Unit Cells must link-up , they cannot have gaps between them
All unit cells must be identical

The Seven Crystal System
To define seven crystal system certain parameter are required, which are
called lattice parameters. These are of two types:
1. Crystallographic axis(a, b, c)
2. Crystallographic angles (interfacial angles α, β, γ )
c
𝜷 𝜶
b
a
𝜸
On the basis of lattice parameters (a, b, c, α, β, γ) these 7 crystal shapes
can be defined.
Edge
Crystal System Angles Examples
Length
NaCl, ZnS,
Cubic a=b=c 𝛼 = 𝛽 = 𝛾 = 90°
Diamond
Tetragonal a=b≠c 𝛼 = 𝛽 = 𝛾 = 90° SnO2, TiO2
Orthorhombic or Rhombic
a≠b≠c 𝛼 = 𝛽 = 𝛾 = 90°
Rhombic Sulphur, KNO3
Rhombohedral
a=b=c 𝛼 = 𝛽 = 𝛾 ≠ 90° CaCO3, MgS
or Trigonal
Edge
Crystal System Angles Examples
Length
𝛼 = 𝛽 = 90°,
Hexagonal a=b≠c Graphite, ZnO
𝛾 = 120°
𝛼 = 𝛾 = 90°, Monoclinic
Monoclinic a≠b≠c
𝛽 ≠ 90° sulphur
CuSO4.5H2O,
Triclinic a≠b≠c 𝛼 ≠ 𝛽 ≠ 𝛾 = 90°
K2Cr2O7
Crystal System Bravais Lattice
Cubic Primitive, Body-centered, Face-centered
Tetragonal Primitive, Body-centered
Orthorhombic or Primitive, Body-centered, Face-centered,

Rhombic End-centered
Rhombohedral
Primitive
or Trigonal
Crystal System Bravais Lattice
Hexagonal Primitive
Monoclinic Primitive, End-centered
Triclinic Primitive
Simple Cubic Close packing (SCC)
In this case one particle lies at each corner.

1
Hence, simple cubic unit cell has a total of × 8 = 1 particle
8
/unit cell.
When a number of two-dimensional square close packed layer are placed,

in such a manner that spheres in each layer comes immediately on top of
below layer, simple cubic packing results.
If a square close pack layer is represented by A then the arrangement in

three dimension is represented by AAA ….. The unit cell of this
arrangement is simple cubic unit cell.
Choice of the
origin of
unit cell is
arbitrary
In this case one particle lies at center of the cube.

Hence, simple cubic unit cell has a total of 1 x 1 = 1 particle /unit
cell.
(1) Packing Fraction

4
Z× πr3
P.F. = 3
V
4 a 3
1×3× π× 2 π a
= = = 0.52 [r = 2 and V = a3, Z = 1]
a3 6
Percentage Packing Efficiency = 0.52×100=52 %
 Void space (100 – 52)= 48 %

Coordination Number (SCC)

Next Nearest neighbours (SCC)

Next to Next Nearest neighbours (SCC)

Nearest neighbour Distance Number
First a 6
Second 2a 12
Third 3a 8
Body Centered Cubic (BCC)
A unit cell having lattice point at the body center and at every corner

3
4 4 3a
Z× πr3 2×3π 4 3π
P.F. = 3
= = = 0.68
V a3 8
3a
[ Z = 2, r = , V = a3]
4
 Void space (100 – 68)= 32 %

Nearest Neighbours (Coordination Number)

Next Nearest Neighbours

Next to Next Nearest Neighbours

Nearest
Distance Number
neighbour
a 3
First 8
2
Second a 6
Third 2a 12
Face Centered Cubic (FCC)
A unit cell having spheres at every face and at every corner lattice point.
4
Z× πr3 a
P.F. = 3
[Z = 4, r = , V = a3]
V 2 2
3
4 a
4×3π× π
2 2
= = = 0.74
a3 3 2
Percentage Packing Efficiency = 0.74×100= 74%
Void space = 100 – 74 = 26 %

Nearest Neighbours (Coordination Number)

Nearest
neighbours in
reference with
face centre
sphere
Next Nearest Neighbours

Next to Next Nearest Neighbours

Nearest neighbour Distance Number
𝑎
First 12
2
Second a 6
3
Third a 24
2
Nearest neighbour Formula Distance
𝑎 𝑎
First 1
2 2
𝑎
Second 2
2
a
𝑎 3
Third 3
2 a
2
nth nearest
Fourth 4
𝑎
2a neighbour
in FCC is at
2
𝑎 5 distance
Fifth 5 a 𝑎
2
2 𝑛 2
𝑎
Sixth 6
2 3a
𝑎 7
Seventh 7
2 a
2
𝑎
Eighth 8
2
2a
Summary of Cubic Unit Cells
Relation Volume
No. of atoms per Coordination
Unit Cell between occupied by
unit cell number
‘r’ & ‘a’ particles (%)
1 a π
Simple Cubic 8× =1 r= 6 × 100 = 52.4
8 2 6
Body
1 a 3 π 3
Centered 8× +1=2 r= 8 × 100 = 68
8 4 8
Cubic (BCC)
Face
1 1 a 2 π
Centered 8× +6× =4 r= 12 × 100 = 74
8 2 4 3 2
Cubic (FCC)
Example
Atoms of metals x, y, and z form face-centred cubic (fcc) unit cell of edge
length Lx, body-centred cubic (bcc) unit cell of edge length Ly, and simple
cubic unit cell of edge length Lz, respectively.
3 8 3
If 𝑟𝑧 = 𝑟 ;𝑟 = 𝑟 ; 𝑀𝑧 = 2 𝑀𝑦 𝑎𝑛𝑑𝑀𝑧 = 3𝑀𝑥 , then the correct statement
2 𝑦 𝑦 3 𝑥
(s) is (are)
[Given : Mx, My, and Mz are molar masses of metals x, y, and z, respectively.
rx, ry, and rz are atomic radii of metals x, y, and z, respectively.]
(A) Packing efficiency of unit cell of x > Packing efficiency of unit cell of
y > Packing efficiency of unit cell of z
(B) Ly > Lz
(C) Lx > Ly
(D) Density of x > Density of y (JEE ADVANCED 2023)
Solution
Solution Atoms of metals x, y, and z form face-centred cubic (fcc) unit cell of edge length
Lx, body-centred cubic (bcc) unit cell of edge length Ly, and simple cubic unit cell
of edge length Lz, respectively.
3 8 3
If 𝑟𝑧 = 𝑟𝑦 ; 𝑟𝑦 = 𝑟𝑥 ; 𝑀𝑧 = 𝑀𝑦 𝑎𝑛𝑑 𝑀𝑧 = 3𝑀𝑥 , then the correct statement (s) is
2 3 2
(are)
[Given : Mx, My, and Mz are molar masses of metals x, y, and z, respectively.
rx, ry, and rz are atomic radii of metals x, y, and z, respectively.]
(A) Packing efficiency of unit cell of x > Packing efficiency of unit cell of
y > Packing efficiency of unit cell of z (JEE ADVANCED 2023)
(B) Ly > Lz
(C) Lx > Ly
(D) Density of x > Density of y
Ans. (A,B,D)
Example
For the given close packed structure of a salt made of cation X and anion
Y shown below (ions of only one face are shown for clarity) , the packing
fraction is approximately
𝑃𝑎𝑐𝑘𝑖𝑛𝑔𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦
(packing fraction = )
100
Y
Y
X
Y
Y
(A) 0.74 (B) 0.63 (C) 0.52 (D) 0.48

Solution (JEE ADVANCED 2021)
Ans. (B)
Density of a Unit Cell
Mass of unit cell

Density of crystal = Density of a unit cell =
Volume of unit cell
Mass of the unit cell = Number of particles per unit cell × Mass of one
particle = Z × m
Molecular mass M
Mass of one particle (m) = =
Avogadro Number NA
M
M Z×N
A
Mass of a unit cell = Z × Density of a unit cell =
NA V
𝑍×𝑀
 Density of Crystal, d = Density of a unit cell =
𝑉×𝑁𝐴
Example
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 × 1024. The value of N is [ JEE Adv-2017 ]
Solution
Ans. (2)
Close Packing of Identical Solid Spheres
Close packing in 3D
ABCABC
1 Cubic Close Packing
(CCP)
Hexagonal
1 planar
arrangement
ABAB
2 Hexagonal Close Packing
(HCP)
Cubic Close Packing (CCP)
A A A A A
A A A A
A A A A A
The hexagonal close packed layer in 2D with center of spheres at A

be given the name layer (A)
A A A A A
C C C C
B B B
A A A A
C C C
B B B B
A A A A A
In hexagonal close packed layer (A), there are two types of voids which are
divided into two sets ‘B' and ‘C' for convenience.
A A A A A
C C C C
B B B
A A A A
C C C
B B B B
A A A A A
It may be noted that it is not possible to place spheres on both

types of voids (i.e. B and C), thus half of the voids remain
unoccupied by the second layer.
A A A A A
C C C C
B B B
A A A A
C C C
B B B B
A A A A A
The spheres of second layer shall be placed either on space denoted

by ‘B' or ‘C’.
A A A A A
C C C C
B B B
A A A A
C C C
B B B B
A A A A A
Let us cover void B in the first layer (A) by placing second hexagonal close
packed layer, also named layer (B).
A A A A A
C C C C
B B B
A A A A
C C C
B B B B
A A A A A
Now cover the voids C by placing the third hexagonal close packed
layer, also named (C) on the second layer (B) in such a way that they
lie over the unoccupied spaces 'C' of the previous layers (A) and (B)
A A A A A
C C C C
B B B
A A A A
C C C
B B B B
A A A A A
If this arrangement is continued in the same order, every fourth

layer becomes identical to the first layer (A) followed by layer (B)
and then (C) .
A A A A A
C C C C
B B B
A A A A
C C C
B B B B
A A A A A
Such arrangement of spheres is called ABCABCABC.... Packing which

is also called CUBIC CLOSE PACKING (CCP).
Cubic close packing (CCP) to Face Centered Cubic (FCC)
A Layer
C Layer
B Layer
A Layer
Side view diagram showing 1+6+6+1=14 selected atoms in FCC

forming CCP (ABCABCABC….. packing)
Example
A compound MpXq has cubic close packing (ccp) arrangement of X. Its unit
cell structure is shown below. The empirical formula of the compound is :
M=
X=
(A) MX (B) MX2 (C) M2X (D) M5X14
Solution (JEE ADVANCED 2012)
Ans. (B)
Hexagonal Close Packing (HCP)
A A A A A
A A A A
A A A A A
The hexagonal close packed layer in 2D with center of spheres at A be given

the name layer (A)
A A A A A
C C C C
B B B
A A A A
C C C
B B B B
A A A A A
In hexagonal close packed layer (A), there are two types of the voids
which are divided into two sets ‘B' and ‘C' for convenience.
A A A A A
C C C C
B B B
A A A A
C C C
B B B B
A A A A A
It may be noted that it is not possible to place spheres on both

types of voids (i.e. B and C), thus half of the voids remain
unoccupied by the second layer.
A A A A A
C C C C
B B B
A A A A
C C C
B B B B
A A A A A
The spheres of second layer shall be placed either on space denoted

by ‘B' or ‘C’.
A A A A A
C C C C
B B B
A A A A
C C C
B B B B
A A A A A
Let us cover void B by placing second hexagonal close packed layer,

also named layer (B) on the first layer (A).
A A A A A
C C C C
B B B
A A A A
C C C
B B B B
A A A A A
If this arrangement is continued in the same order, every third layer

becomes identical to the first layer (A) followed by layer (B) and so on.
A A A A A
C C C C
B B B
A A A A
C C C
B B B B
A A A A A
Such arrangement of spheres is called ABABAB.... Packing which is

also called HEXAGONAL CLOSE PACKING (HCP).
(1) Number of particles per Hexagonal prism
The corner atoms in the layer ‘A’ are shared equally amongst
1
adjacently placed six hexagonal prisms, contributing 6 th volume of
sphere towards each prism
1 Number of particles per Hexagonal prism
𝟏
Contribution = V × 12= 2V
𝟔
The central atoms in the layer ‘A’ are shared equally

amongst adjacently placed two hexagonal prisms,
1
contributing 2 volume of sphere towards each prism
𝟏
Contribution = V × 2= 1V
𝟐
All three spheres of layer 'B' are not exactly inside the Hexagonal
prism. But the contribution of three spheres are taken because the
same volume of other spheres in that layer is also inside the unit cell.
Contribution of Yellow spheres (Layer B) = 3V

𝐙=3 + 3 = 6 particles/hexagonal prism .

A
A B
A
B B
A
A B
A
Exploded view Hexagonal close packed

(2) Coordination Number of Hexagonal prism
Each sphere is touched by 12 other spheres in 3D 3

➢ 6 is one layer
➢ 3 in top layer and 6
➢ 3 in bottom layer
and hence the COORDINATION NUMBER IS 12. 3
D
30°
B
O
D
30°
B
O
D
30°
B
O
E
𝑐
2
D
90
30° 𝑎
°
=𝑟
B 2
a = 2r P
OD = 2r = a, AD = r
ADB = 30°
BD = AD sec 30° =
2r
= OB
O
3
E
𝑐
2
D
90
30° 𝑎
°
=𝑟
B 2
P
O
E E
𝑐
𝑐 2
2
D
90
90 30° 𝑎
°
° =𝑟
B r sec 30 D B 2
P
2𝑟 2
EB = ED2 − BD2 = 2𝑟 2 − 3
EB = 2r
2 c
= c = 4r
2
O
3 2 3
Volume of hexagonal prism = area of base × height
Height = 𝑐
a
3 2
Area of base = 6 × Area of Equilateral triangle = a
4
6. 3 2
Volume of hexagonal prism = × a2 × 2 a
4 3
6. 3 2
= × (2r)2 × 2 × (2r) = 24 2r3
4 3
𝑎 2
Z = 6, r = , c = 4r , V = 24 2r3
2 3
4 4
Z× πr3 6× 𝜋 𝑟 3 π
3 3
P.F. = = = = 0.74
V 24 2 𝑟 3 3 2
Percentage Packing Efficiency = 0.74×100 = 74 %
Maximum possible space is occupied by spheres.

Close packing in 3D
For every close packing in 3D
We first form a hexagonal close packed layer in 2D
A A A A A
C C C C
B B B
A A A A
C C C
B B B B
A A A A A
We continue forming such layers considering that the spheres of

next layer occupy and cover the voids formed by previous layer.
Close packing in 3D
As already seen before we can name these differently placed layers as

‘Layer A’ , ‘Layer B’ and ‘Layer C’. The most symmetrical packing formed
by this way was ABCABC……… type(CCP or FCC) and ABABAB……..
Type(HCP or Hexagonal Primitive)
Close packing in 3D
We can form many different types of packing following the

same, where no two consecutive layers should be same or any
layer cannot repeat itself one after the other. For example
ABABCABABACBCBACBCA……..(not symmetrical)
Since any such packing is formed in a similar way ensuring

maximum possible packing efficiency. All these packing are called
as CLOSE PACKING IN 3D.
VOIDS
It has been seen that when the particles are closely packed in the crystals
even then there are some empty spaces left in between the spheres.
These are known as interstices (or interstitial sites or holes or empty

spaces or VOIDS).
VOIDS
Voids in 3D close packing (CCP & HCP)
Tetrahedral voids Octahedral voids

Tetrahedral voids
Tetrahedral voids
Octahedral voids
This vacant space between these six touching spheres is called as

octahedral void.
Position of tetrahedral voids in FCC unit cell
In FCC, one corner sphere and three face centered spheres of

three adjacent faces of the cube form a tetrahedral void.
In FCC, one corner sphere and three face centered spheres of three
adjacent faces of the cube form a tetrahedral void.
In FCC, two tetrahedral voids are therefore found along one body diagonal.
In FCC, there are total eight tetrahedral voids completely lying in the
unit cell.
a
The nearest distance between two tetrahedral voids =
2
1
The center of tetrahedral void is located at 4th of the body
3
diagonal length from the vertex (corner)i.e. 𝑎 .
4
Total number of particles located at
1 1
FCC lattice per unit cell = ×6+8× =4
2 8
(Face centres) (Corners)

Total number of tetrahedral voids = 8
Effective number of tetrahedral voids per particle = 2.
Position of octahedral voids in FCC unit cell
➢ One type of octahedral voids is situated at the body center of the

unit cell which lies completely inside the unit cell.
➢ Another type of octahedral voids is situated at the mid point of all

1
twelve edges giving th contribution each to the unit cell.
4
➢ Total number of particles per unit cell of FCC = 4
➢ Total number of octahedral voids

1
= (1 × 1) + (12 × ) = 1 + 3 = 4
4
(Body centre) (Edge centres)

➢ Effective number of octahedral voids per particle = 1
Voids in FCC
Total number of tetrahedral

voids in FCC = 8
Total number of octahedral

voids in FCC = 4
Example
If the unit cell of a mineral has cubic close packed (ccp) array of oxygen
atoms with m fraction of octahedral holes occupied by aluminium ions
and n fraction of tetrahedral holes occupied by magnesium ions m and
n respectively, are -
1 1 1 1 1 1 1
(A) 2 , 8 (B) 1, 4 (C) 2 , 2 (D) 4 , 8
(JEE ADVANCED 2015)
Solution
Ans. (A)
Example
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
(JEE ADVANCED 2016)
Solution
Ans. (B, C, D)
Position of Tetrahedral voids in HCP
1
Total tetrahedral voids in HCP prism = (8 × 1) + 12 × 3 = 8 + 4 = 12
(Completely inside) (Vertices)

Total number of particles per HCP prism = 6

Effective number of tetrahedral voids per particle = 2.

Position of Octahedral voids in HCP
Total octahedral voids in HCP prism = (6 × 1) = 6
(Completely inside)
Total number of particles per HCP prism = 6

Effective number of octahedral voids per particle = 1.

3D Close packing
In any three dimensional close packing

of maximum efficiency there are
Two Tetrahedral One octahedral

voids per particle void per particle
Packing in Ionic Solids
An ionic crystal contains a large number of cations and anions.

Generally cations are smaller in size than anions.
The cations are surrounded by anions and they touch each other.
To maximize stability we maximize their coordination number.
1. Triangular void
If the size of cation is very small with respect to the size of anion
it will occupy the smallest void.
1. Triangular void
R =Radius of anion
r = Radius of cation
 The smallest void formed by the anions touching each other is the
triangular void.
1. Triangular void
R =Radius of anion
AC = R + r
AB = R
C
BAC = 30°
A 30°
B
C
r
Now, cos 30° AC 
AB 3 R
= R+r A B
2
R
2
r=( – 1)R
3
r= 0.155 R
1. Triangular void
R =Radius of Anion
If r < 0.155 R R
r r
Then R is smaller than the smallest limiting value of R
2. Tetrahedral void
 The cation will always fit exactly in the void formed by anions
in the ideal or limiting case
2. Tetrahedral void
➢ All anions touch each other and the cation touches these four anions
➢ The co-ordination number of cation is 4.
Packing in Ionic Solid
2. Tetrahedral void
R =Radius of Anion
2a
AB = = 2R
2
3a
AO = =R+r
4
R+r 3
Now, =
R 2
3
 r=( – 1)R = 0.225R r
2 Radius Ratio = 0.225
R
3. Octahedral void
The vacant space between six touching spheres is called

octahedral void.
3. Octahedral void
R =Radius of Anion
D C
+
O
A P B
R
3. Octahedral void
R =Radius of Anion
O
AO = R + r
AP = R
45°
OAP = 45° A R P
D C
+
O
AP 1 R
Now, cos 45° =  =
AO 2 R+r
A P B
r= 2−1 R
R
r= 0.414 R 𝑟
Radius Ratio = 0.414
𝑅
4. Cubic void
All the anions touch each other and co-ordination number is 8

4. Cubic void
R =Radius of Anion
– –
AB = a = 2R A – –
AD = 3a = 2 (R + r)
R+r +
Now, = 3
R
–
D
–
 r= 3 − 1 R = 0.732R
B – – C
Radius Ratio (R.R.) = 0.732

r
1. The minimum values for the existence of a cation in a
R
particular void is called limiting radius ratio for that void.
2. With the increase in radius ratio, space between anion will

increase & hence the cation may tend for higher coordination
number.
𝐫 𝐫
Voids CN Limiting Range of
𝐑 𝐑
Triangular 3 0.155 0.155-0.225
Tetrahedral 4 0.225 0.225-0.414
Octahedral 6 0.414 0.414-0.732
Cubic 8 0.732 0.732-1.000
For values lesser than 0.155, crystal will not exist.

r
The limiting radius ratio tells about : R =Radius of Anion
R
(i) Stability of ionic crystal,
(ii) Coordination number,
(iii) Geometry of voids
r r r
> ideal = ideal < ideal
R R R
Stable Stable Unstable

Example
The arrangement 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 -
X-
A+
(A) 104 pm (B) 125 pm (C) 183 pm (D) 57 pm

(JEE ADVANCED 2013)
Solution
Ans. (A)
Example (JEE ADVANCED 2020)
The cubic unit cell structure of a compound containing cation M and
anion X is shown below. When compared to the anion, the cation has
smaller ionic radius. Choose the correct statement(s).
(A) The empirical formula of the compound is MX.
M=
(B) The cation M and anion X have different
X=
coordination geometries.
(C) The ratio of M-X bond length to the cubic unit
cell edge length is 0.866.
(D) The ratio of the ionic radii of cation M to anion X is 0.414.
Solution
Ans. (A, C)
Example
The number of hexagonal faces that present in a truncated octahedron is.

(JEE ADVANCED 2011)
Solution
Ans. (8)
Coordination number Ratio
For BINARY IONIC COMPOUNDS of the general formula AxBy
The ratio of the coordination number of A to the coordination

number of B
Is given by the inverse of the ratio in which A and B is

present.
i.e. y : x
1. Rock Salt (NaCl)
− Cl- occupies FCC lattice points
− Na+ occupies octahedral voids
No. of Cl- per unit cell = 4
No. of Na+ per unit cell = 4
Hence, formula is NaCl
Coordination number of Na+ = 6

(it is present in octahedral voids of Cl-)
Coordination number of Cl– = 6

(by ratio of coordination number)
Consider the unit cell with Cl- asthe
Consider FCC.unit cell with Na+ as FCC.
′ =
𝟐𝒂 = 𝟒𝒓𝑪𝒍− 𝒂 = 𝟐𝒓𝑪𝒍− + 𝟐𝒓𝒂𝑵𝒂 + 𝟐𝒓𝑪𝒍− + 𝟐𝒓𝑵𝒂+ 𝟐𝒂′ = 𝟒𝒓𝑵𝒂+
Choice of the
origin of
unit cell is
arbitrary
1. Rock Salt (NaCl)
Other compounds which have Rock Salt structure are:
❑ Halides of alkali metals except cesium halide
01
02 03 ❑ Oxides of alkaline earth metals

❑ AgCl, AgBr & AgI except beryllium oxide
2. Zinc Blende (ZnS)
− S2- occupies FCC lattice points
− Zn2+ occupies alternate

tetrahedral voids
Number of S2- ions per unit cell = 4
Number of Zn2+ ions per unit cell = 4
Hence, formula is ZnS

C.N 4
EG :- BeO
3. Fluorite (CaF2)
− Ca2+ occupies FCC lattice points
− F- occupies all tetrahedral

voids
Number of Ca2+ ions per unit cell = 4
Number of F- ions per unit cell = 8
Hence, formula is CaF2
Coordination number of F- ions = 4

Coordination number of Ca2+ ions = 8
4. Anti-Fluorite (Li2O)
− O2- occupies FCC lattice points
− Li+ occupies all tetrahedral

voids
Number of O2- ions per unit cell = 4
Number of Li+ ions per unit cell = 8
Hence, formula is Li2O

4. Anti-Fluorite (Li2O)
− Li+ occupies all tetrahedral

voids
Coordination number of Li+ ions = 4

(it is present in tetrahedral voids of Cl-)
(by ratio of coordination number)

5. Cesium Halide
− Cl- occupies corners of the cube
− Cs+ occupies the body centre of

the cube
Number of Cl- ions per unit cell = 1
Number of Cs+ ions per unit cell = 1
Hence, formula is CsCl
Coordination number of Cs+ ions = 8

Coordination number of O2- ions = 8
6. Diamond
− C atom occupies FCC lattice points
− C atom occupies alternate

tetrahedral voids
Number of carbon atoms per unit cell
1 1
Z =( × 8 )+ (6 × )+ (4)= 8
8 2
Coordination number = 4
3𝑎
dC – C = 2r =
4
6. Diamond
Packing fraction
4 4
Z×3πr3 8×3πr3 3π
P.F. = = 3 = ~ 0.34
V 8r 16
3
3a
[ Z = 8, 2r = , V = a3]
4
 Void space (100 – 34)= 66 %

7. Corrundum (Al2O3)
− O2– occupies HCP lattice points

2
− Al3+ occupies rd of octahedral
3
voids.
8. Rutile (TiO2)
− O2– occupies HCP lattice points
− Ti4+ occupies half of the

octahedral voids.
9. Pervoskite (CaTiO3)
− Ca2+ occupies corners of the

cube.
− O2– occupies face

centres of the cube.
− Ti4+ occupies body centre

of the cube.
10. Spinel (MgAl2O4)
1
− Mg2+ occupies 8th of tetrahedral
voids
− Al3+ occupies half of octahedral

voids.
11. Inverse Spinel (MgAl2O4)
− Mg2+ occupies 1th of octahedral

4
voids
1
− Al3+ occupies 8th of tetrahedral
1
voids and th of octahedral
4
voids
Example
Consider an ionic solid MX with NaCl structure. Construct a new
structure (Z) whose unit cell is constructed from the unit cell of MX
following the sequential instructions given below. Neglect the charge
balance.
(i) Remove all the anions (X) except the central one
(ii) Replace all the face centered cations (M) by anions (X)
(iii) Remove all the corner cations (M)
(iv) Replace the central anion (X) with cation (M)
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑎𝑛𝑖𝑜𝑛𝑠
The value of in Z is____. (JEE ADVANCED 2018)
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑐𝑎𝑡𝑖𝑜𝑛𝑠
Solution
Ans. (3)
Defects in Solid
Definition
“Any deviation from perfectly ordered arrangement of atoms/ions in a

crystal is called imperfection of crystal defect.”
TYPES OF DEFECTS
1. Point Defects
2. Line Defects
Point Defects
Point defects are the irregularities or deviations from ideal

arrangement around a point or an atom in a crystalline substance.
Point Defects
Stoichiometric Defects
Non – stoichiometric Defects
Impurity Defects
Stoichiometric Defects
These are the point defect that do not disturb the stoichiometry of
the solid. They are also called intrinsic or thermodynamic defects.
These are of two types shown by non-ionic solids.
Vacancy defect (Missing atom from lattice sites become vacant)

density decrease
Interstitial defect (occupy an interstitial site density increase)

Frenkel defect
Frenkel defect is shown by ionic substance in which there is a

large difference in the size of cations and anions, for example,
ZnS, AgCl, AgBr and AgI
❑ The smaller ion (usually cation) is dislocated from its normal

site to an interstitial site.
Frenkel defect
Interstitial defect Vacancy defect

Frenkel defect
Frenkel defect is also called dislocation defect.
It does not change the density of the solid.
Makes solid crystals good conductor.
This defect is shown by ionic solids.

Schottky defect
Schottky defect is shown by ionic substances in which the cation and

anion are of almost similar sizes. For example, NaCl, KCl, CsCl and AgBr
Schottky defect
M+ X– M+ X–
X– M+ X– M+
M+ XX–– M+ XX––
XX–– M+ X– M+
Ideal Crystal Schottky Defect

It is basically a vacancy defect in ionic solids.
It results in significant decrease in density.
It may be noted that AgBr shows both, Frenkel as well as

Schottky defects.
Non-stoichiometric Defects
However, a large number of non-stoichiometric inorganic solids

are known which contain the constituent elements in non-
stoichiometric ratio due to defects in their crystal structures.
Non Stoichiometric Defects
Metal Deficiency Defect Metal Excess Defect

Due to anionic vacancies
Metal Excess Defect
Due to presence of extra

cations at interstitial sites.
(A) Metal excess defect
1. Metal excess defect due to anionic vacancies
Alkali halides like NaCl and KCl show this type of defect.

NaCl F-centers
When crystals of NaCl are heated in an atmosphere of sodium
vapour, the sodium atoms are deposited on the surface of the crystal.

NaCl F-centers
When crystals of NaCl are heated in an atmosphere of sodium
vapour, the sodium atoms are deposited on the surface of the crystal.

NaCl F-centers
As a result the crystal now has an excess of sodium.

NaCl F-centers
The anionic sites occupied by unpaired electrons are called F-centers
(from the German word Farbenzenter for colour center). They impart
yellow colour to the crystals of NaCl.
The colour results by excitation of these electrons when they
absorb energy from the visible light falling on the crystals.
Similarly, excess of lithium makes LiCl crystals pink and

excess of potassium makes KCl crystals violet (or lilac).
2. Metal excess defect due to presence of extra cations at interstitial site
ZnO Metal excess defect
Zinc oxide is white in colour at room temperature. On heating it loses
oxygen and turns yellow.
𝐇𝐞𝐚𝐭 𝟏
ZnO Zn2+ + O2 + 2e–
𝟐
2. Metal excess defect due to presence of extra cations at interstitial site
ZnO Metal excess defect
Now crystal has excess of zinc and its formula becomes Zn1+xO. The
excess Zn2+ ions move to interstitial sites and the electrons to
neighbouring interstitial sites.
(B) Metal deficiency defect
❑ There are many solids which are difficult to prepare in the

stoichiometric composition and contain less amount of the metal
as compared to the stoichiometric proportion.
❑ 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 Fe2+ cations are missing and the loss of
positive charge is made up by the presence of required number of
Fe3+ ions.
(B) Metal deficiency defect
Fe2+ O2– Fe2+ O2–
O2– Fe2+ O2– Fe2+ Fe3+
Fe2+ O2– Fe2+ O2– Fe3+
O2– Fe2+ O2– Fe2+
Ideal crystal Crystal showing metal

deficiency defect
(3) Impurity defect
Na+ Cl– Na+ Cl–
Cl– Na+ Cl– Na+

Cationic vacancy
Na+ Cl– Na+ Cl–

Removed
Sr2+
Cl– Na+ Cl– Na+
If molten NaCl containing a little amount of SrCl2 is crystallized,

some of the sites of Na+ ions are occupied by Sr2+.
(3) Impurity defect
Na+ Cl– Na+ Cl–
Na+
Cl– Sr2+ Cl– Na+
Cationic vacancy
Na+
Na+ Cl– Cl–
Removed
Cl– Na+ Cl– Na+
Each Sr2+ replaces two Na+ Ions. It occupies the site of one ion and a
vacancy is created at other site.
(3) Impurity defect
Na+ Cl– Na+ Cl–
Na+
Cationic vacancy
Na+
Na+ Cl– Cl–
Removed
Cl– Na+ Cl– Na+
The cationic vacancies thus produced are equal in number to that of

Sr2+ ions.
(3) Impurity defect
Na+ Cl– Na+ Cl–
Na+
Cationic vacancy
Na+
Na+ Cl– Cl–
Removed
Cl– Na+ Cl– Na+
Another similar example is the solid solution of CdCl2 and AgCl.

(3) Impurity defect
Ag+ Cl– Ag+ Cl–
Cl– Ag+ Cl– Ag+

Cationic vacancy
Ag+ Cl– Ag+ Cl–

Removed
Cd2+
Cl– Ag+ Cl– Ag+
If molten AgCl containing a little amount of CdCl2 is crystallized,

some of the sites of Ag+ ions are occupied by Cd2+.
(3) Impurity defect
Ag+ Cl– Ag+ Cl–
Ag+
Cl– Cd2+ Cl– Ag+
Cationic vacancy
Ag+
Ag+ Cl– Cl–
Removed
Cl– Ag+ Cl– Ag+
Each Cd2+ replaces two Ag+ Ions. It occupies the site of one ion and a
vacancy is created at other site.
(3) Impurity defect
Ag+ Cl– Ag+ Cl–
Ag+
Cationic vacancy
Ag+
Ag+ Cl– Cl–
Removed
Cl– Ag+ Cl– Ag+
The cationic vacancies thus produced are equal in number to that of

Cd2+ ions.
(3) Impurity defect
Ag+ Cl– Ag+ Cl–
Ag+
Cationic vacancy
Ag+
Ag+ Cl– Cl–
Removed
Cl– Ag+ Cl– Ag+

Note
As temperature increases, number of defects increases exponentially.
During formation of defects : H > 0, S > 0
 Formation of defects is more spontaneous at higher temperatures.
Crystals are always electrically neutral irrespective of number of imperfections

Electrical properties
Solids exhibit an amazing range of electrical conductivities, extending

over 27 orders of magnitude ranging from 10–20 to 107 ohm–1 m–1. Solids
can be classified into three types on the basis of their conductivities.
Conductors
Insulators
Semiconductors
Conductors
❑ The solids with conductivities ranging between 104 to 107ohm–
1m–1 are called conductors. Metals have conductivities in the
order of 107 ohm 1m–1 are good conductors.
Insulators
❑ These are the solids with very low conductivities ranging
between 10–20 to 10–10 ohm–1 m–1.
Semiconductors
❑ These are the solids with conductivities in the intermediate

range from 10–6 to 104 ohm–1 m–1.
Conduction of electricity in metals
➢ The atomic orbitals of metal atoms form molecular orbitals which

are so close in energy to each other as to form a band.
➢ 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.
Conductors
Conduction band
No forbidden gap
Valance band
Insulators
If the gap between filled valence band and the next higher unoccupied
band (conduction band) is large, electron cannot jump to it and such a
substance has very small conductivity and it behaves as an insulator.
Insulators
Conduction band Empty

Impossible to provide
Huge amount of this huge amount of
energy is required to Forbidden gap is large
energy to excite
excite the electrons electrons and hence it
cannot conduct
electricity
Valence band
Full
Conduction of electricity in semiconductor
➢ In case of semiconductors, the gap between the valence band and

conduction band is small.
➢ Therefore, some electrons may jump to conduction band and show some
conductivity.
➢ Electrical conductivity of semiconductors increases with rise in

temperature, since more electrons can jump to the conduction band.
➢ Substances like silicon and germanium show this type of behaviour and
are called intrinsic semiconductors.
Semi-conductor
Result in the
conduction of
electricity to
Conduction band some extent
Room Temperature
If room temperature 25°C
is increased
Narrow
forbidden gap
Valance band
Doping of Semiconductor Nanocrystals
Doping is done with an impurity which is electron rich/deficient as

compared to the intrinsic semiconductor silicon or germanium.
Such impurities introduce electronic defects in them.

Semiconductors
The conductivity of intrinsic semiconductors is too low to be of

practical use.
Their conductivity is increased by adding an appropriate amount

of suitable impurity.
This process is called DOPING.

Magnetic properties
➢ Every substance has some magnetic properties associated with it.
➢ The origin of these properties lies in the moving electrons. Each
moving electron in an atom behaves like a tiny magnet.
➢ Its magnetic moment originates from two types of motions
➢ (i) its orbital motion around the nucleus and an orbital magnetic
moment associated with it
➢ (ii) its spin around its own axis and a spin magnetic moment
associated with it.
➢ Magnitude of this magnetic moment is very small and is measured
in the unit called Bohr magneton, μB. It is equal to 9.27 × 10–24A m2.
Magnetic properties
On the basis of their magnetic properties, substances can be
classified into five categories:
1 Paramagnetic
2 Diamagnetic
3 Ferromagnetic
4 Antiferromagnetic
5 Ferrimagnetic
Magnetic properties
Demonstration of the magnetic moment associated with
(a) an orbiting electron
Magnetic properties
Demonstration of the magnetic moment associated with
(b) a spinning electron
Magnetic properties
The net magnetic moment of all the electron pairs cancel out.
Magnetic properties
The net magnetic moment of all the electron pairs cancel out.
Magnetic properties
Magnetic properties
Magnetic properties
Magnetic properties
Magnetic properties
Magnetic properties
Magnetic properties
Magnetic properties
Magnetic properties
Diamagnetism
➢ Diamagnetic substances are weakly repelled by a magnetic field.

➢ They are weakly magnetized in a magnetic field in opposite direction.
➢ Diamagnetism is shown by those substances in which all the electrons are
paired and there are no unpaired electrons. Pairing of electrons cancels
their magnetic moments and they lose their magnetic character.
➢ H2O, NaCl and C6H6 are some examples of such substances.
Magnetic properties
Magnetic Intensity of the material increases

Magnetic properties
Magnetic properties
Magnetic properties
Paramagnetism
➢ Paramagnetic substances are weakly attracted by an external

magnetic field.
➢ They are magnetized in a magnetic field in the same direction.
➢ They lose their magnetism in the absence of magnetic field.
➢ Paramagnetism is due to the presence of one or more unpaired
electrons which are attracted by the magnetic field.
➢ O2, Cu2+, Fe3+, Cr3+ are some examples of such substances.
Magnetic properties
In ferromagnetic substances more number of electrons are unpaired

Magnetic properties
Magnetic properties
Magnetic properties
Magnetic properties
Magnetic properties
Magnetic properties
Ferromagnetism
➢ A few substances like iron, cobalt, nickel, gadolinium and CrO2 are
attracted very strongly by a magnetic field. Such substances are called
ferromagnetic substances.
➢ Besides strong attractions, these substances can be permanently

magnetized.
➢ In solid state, the metal ions of ferromagnetic substances are grouped

together into small regions called domains. Thus, each domain acts as
a tiny magnet.
➢ In an unmagnetized piece of a ferromagnetic substance the domains

are randomly oriented, and their magnetic moments get cancelled.
Magnetic properties
➢ When the substance is placed in a magnetic field all the domains get
oriented in the direction of the magnetic field and a strong magnetic effect
is produced.
➢ This ordering of domains persist even when the magnetic field is removed
and the ferromagnetic substance becomes a permanent magnet.
Alignment of magnetic moments ferromagnetic substance

Magnetic properties
Anti-ferromagnetism
Substances like MnO showing antiferromagnetism have domain structure

similar to ferromagnetic substance, but their domains are oppositely
oriented and cancel out each other's magnetic moment.
Alignment of magnetic moments anti-ferromagnetic substance

Magnetic properties
Ferrimagnetism
➢ Ferrimagnetism is observed when the magnetic moments of the

domains in the substance are aligned in parallel and anti-parallel
directions in unequal numbers.
➢ They are weakly attracted by magnetic field as compared to

ferromagnetic substances.
➢ Fe3O4 (magnetite) and ferrites like MgFe2O4 and ZnFe2O4 are examples
of such substances.
Magnetic properties
These substances also lose ferrimagnetism on heating and become
paramagnetic.
Alignment of magnetic moments ferrimagnetic substance

SURFACE
CHEMISTRY
SURFACE
CHEMISTRY
SURFACE CHEMISTRY
Elementary concepts of adsorption:
Physisorption and Chemisorption,
Freundlich adsorption isotherm; Colloids:
types, methods of preparation and
general properties; Elementary ideas of
emulsions, surfactants and micelles (only
definitions and examples).
Surface Chemistry
Surface Chemistry is the branch of physical chemistry which deals with

the study of physical and chemical phenomenon that occur at the
interface of two phases.
Adsorption
The accumulation of molecular species at the surface rather than

in the bulk of a solid or liquid due to molecular surface forces is
known as adsorption.
Desorption
The process of removing an adsorbed substance from a surface

on which it is adsorbed is known as desorption.
Adsorbate
Substances like solids, liquids or gases which are adsorbed on the

surface are called as adsorbate.
Adsorbent
The surface of the substances on which adsorption takes place is

called adsorbent.
Absorption
When a substance is uniformly distributed throughout the body of

a solid or a liquid, the phenomenon is called as absorption.
Sorption
The process in which both adsorption and absorption takes

place simultaneously is known as sorption.
Difference between Adsorption & Absorption
Sr. No. Adsorption Absorption

It involves higher concentration It involves uniform
01 of adsorbate at the surface of distribution of the molecular
adsorbent. species throughout the bulk.
02 Rate of adsorption decreases It occurs at a uniform rate.

with time.
It is a surface phenomenon. It occurs throughout the

03
body of the material.
04 It is a fast process. It is a slow process.

Mechanism of Adsorption
Thermodynamics of Adsorption
(1) Adsorption is an exothermic process.
H = –ve
(2) Freedom of movement of gases molecules decreases.
Sgas = –ve
(3) Adsorption is a spontaneous process.
G = –ve but Stotal > 0
(4) When G = 0 , state of equilibrium is attained.

Types of Adsorption
Physical Adsorption/ Physisorption
Chemical Adsorption/ Chemisorption
Factors affecting rate of adsorption
For Solids
Adsorption ∝ Surface area of adsorbent.
Nature of Adsorbent
Activated
Charcoal
charcoal
Nature of Adsorbent
For Gases
Adsorption ∝ Critical temperature of gas (TC)
Volume of gases at S.T.P adsorbed by 1 g of Charcoal
Gas H2 N2 CH4 CO2 HCl NH3 SO2

Critical Temperature, Tc(K) 33 126 190 304 324 406 430
Volume adsorbed (mL) 4.7 8 16.2 48 72 181 380
Physical adsorption Chemical adsorption
P = constant
x x
m P = constant m
Temperature (T) Temperature (T)
Where, x = Mass of adsorbate
m = Mass of adsorbent
x
= Extent of adsorption
m
Effect of Pressure : (Adsorption Isotherm)
M(s) + X(g) MX
x
m
Saturation
Pressure
P
Types of Adsorption
Sr. No. Physical Adsorption Chemical Adsorption
It is caused by intermolecular It is caused by chemical bond

01
Vander Waal’s forces. formation.
02 It is not specific. It is highly specific.
03 It is a reversible. It is Irreversible.
Heat of adsorption is low. Heat of adsorption is high.

04
(20 to 40 kJ mol-1) (80 to 240 kJ mol-1)
No appreciable activation High activation energy is

05
energy is involved. involved.
Types of Adsorption
Sr. No. Physical Adsorption Chemical Adsorption
It forms multimolecular
06 It forms unimolecular layer.
layers on adsorbent surface.
It also depends on the nature
It depends on the nature of
of gas. Gases which can react
07 gas. More easily liquefiable
with the adsorbent show
gases are adsorbed readily.
chemisorption.
It decreases with increase of It first increases then
08 temperature. decreases with temperature.
Example
The correct statement(s) pertaining to the adsorption of a gas on a solid
surface is (are) –
(A) Adsorption is always exothermic
(B) Physisorption may transform into chemisorption at high temperature
(C) Physisorption increases with increasing temperature but
chemisorption decreases with increasing temperature
(D) Chemisorption is more exothermic than physisorption, however it is
very slow due to higher energy of activation
[JEE (Advanced) 2011]
Solution
Ans. (A,B,D)
Example
Methylene blue, from its aqueous solution, is adsorbed on activated
charcoal at 25°C. For this process, the correct statement is
(A) The adsorption requires activation at 25°C
(B) The adsorption is accompanied by a decrease in enthalpy
(C) The adsorption increases with increase of temperature
(D) The adsorption is irreversible
Solution
Ans. (B)
Types of adsorption isotherm
Freundlich adsorption isotherm: (Physical adsorption)
Freundlich adsorption isotherm is obeyed by the adsorption where the

adsorbate forms single layer on the surface of the adsorbent.
Freundlich adsorption isotherm equation,

1
x
= KP n ; n1
m
Where,
K and n are constants, and their values are determined graphically.
Value of K and n depends on following three factors :-
(1) Nature of gas (Adsorbate)
(2) Nature of solid (Adsorbent)
(3) Temperature
Freundlich adsorption isotherm: (Physical adsorption)
In Logarithmic form
1
log
x
m
1
= logK + logP
n
; 0≤
n
≤1
x tan = 1/n
log 
m
log K
log P
K and n are constant at a particular temperature and for a

particular adsorbent and adsorbate (gas)
x
(i) At low pressure, ∝ P .....(a)
m
x
(ii) At high pressure, m ∝ P 0 …...(b)
1
x
(iii) At moderate pressure, = KP n ...(c)
m
1
(Where 0 < < 1)
n
Adsorption in solutions (Liquid + Solid)
Examp e
Dye solution + Charcoal
1
x
= KC n [C = concentration of liquid]
m
Drawback of Freundlich adsorption Isotherm :

It explains Physical Adsorption upto moderate pressure but fails to
explain at high pressure.
Example
For physisorption which of the following is correct relationship between
temperatures
(A) T3 > T2 > T1 (B) T1 = T2 = T3
(C) T3 < T2 < T1 (D) T2 > T3 > T1
Solution
T3
T2
x T1
m
Pressure (P)
Ans. (C)
Example
In an adsorption experiment, a graph between log(x/m) versus log P was
found to be linear with a slope of 45°. The intercept on the y-axis was
found to be 0.3. The value of x/m at a pressure of 3 atm for Freundlich
adsorption isotherm if 1/n remains constant is : [Antilog 0.3 = 2]
(A) 2 (B) 4 (C) 6 (D) 5
Solution
Ans. (C)
Langmuir Adsorption Isotherm
He derived the condition of equilibrium theoretically assuming that

adsorption is :
(a) Monolayer
(b) Uniform at solid surface
(c) Adsorbate particles do not interact each other at the surface.
x aP
=
m 1 + bP
Where,
a and b are constants
In low Pressure Region
1 + bP ≅ 1
x x
So, = aP
m m
x
 ∝ P (first order kinetics)
m P
In High Pressure Region
1 + bP ≅ bP
x aP a
So, = = = Constant (zero order kinetics)
m bP b
Example
The Langmuir adsorption isotherm is deduced using the following
assumptions :
(A) The adsorption takes place in multilayers
(B) The adsorption sites are equivalent in their ability to adsorb the
particles
(C) The heat of adsorption varies with coverage
(D) The adsorbed molecules interact with each other
Solution
Ans. (B)
Catalyst and catalysis
Substance which accelerate the rate of chemical reaction and

themselves remain chemically and quantitatively unchanged after the
reaction is known as catalyst and the phenomenon is known as
catalysis.
(a) Homogenous catalysis
When the reactants and the catalyst are in the same phase.
(b) Heterogenous catalysis
When the reactants and the catalyst are in the different phase.
Some other related terms
Inhibitors
Promoters
Catalytic Poison
Auto Catalysis
Important features of Solid catalysis
(a) Activity
The activity of a catalyst depends upon the strength of

chemisorption to a large extent. The reactants must get adsorbed
reasonably strongly on to the catalyst to become active.
(b) Selectivity
The selectivity of a catalyst is its ability to direct a reaction to

yield a particular product.
Substance can act as a catalyst only in a particular reaction and
not for all the reactions.
For Example, starting with H2 and CO, and using different
catalysts, we get different products.
Ni
(i) CO(g) + 3H2(g) CH4(g) + H2O(g)
CuO/ZnO
(ii) CO(g) + 2H2(g) CH3OH(g)
Cu
(iii) CO(g) + H2(g) HCHO(g)
Example
The following information is available for the reaction R → P.
R P: rate = r1
R A P: rate = r2
R B P: rate = r3
R C P: rate = r4
R D P: rate = r5
R A+C P : rate = r6
R A+D P : rate = r7
If r3 < r1 = r4 = r5 < r7 < r2 < r6, then the only incorrect statement is
(A) B is an inhibitor.
(B) C is a catalytic promoter of catalyst A.
(C) D is a catalytic poison of catalyst A.
(D) A is a catalytic promoter of catalyst C.
Solution
Ans. (D)
Catalysts in industry
PROCESS CATALYST
Haber's process for the Finely divided iron, molybdenum as

manufacture of ammonia. promoter.
Now-a-days, a mixture of iron
oxide, potassium oxide and alumina
is used.
Ostwald's process for the Platinized asbestos
manufacture of nitric acid.
Contact process for the Platinized asbestos or vanadium

manufacture of Sulphuric acid. pentoxide (V2O5)
Classification of mixture based on size of solute particles.
Mixture
True Solution Colloids Suspension
<1 nm 1-1000 nm > 1000 nm

True Solution
Homogeneous solution.
Components can not be separated by filtration.
Salt in water
Colloids
Heterogeneous solution looks like homogeneous solution.
Components can not be separated by filtration.
Milk
Suspension
Heterogeneous solution.
Components can be separated by filtration.
Lemonade
Colloid
A colloid is a heterogeneous system in which one substance is dispersed

(dispersed phase) as very fine particles in another substance called
dispersion medium.
Phase of Colloid
A colloidal system is heterogeneous in character. It consists of two phase,

namely a dispersed phase and a dispersion medium.
Classification of Colloids
Dispersed phase (DP)
Present in small proportions.
Just like solute of true solution.
Example : In butter, water is dispersed phase.

Dispersion medium (DM)
Present in excess amount
Just like a solvent of true solution
For Example : In milk, water is dispersion medium.

Depending on the dispersed phase or dispersion medium, colloidal solutions
can be classified by 3 ways -
Physical state of dispersed Phase &

dispersion medium
Classification
of Nature of interaction between
Colloids dispersed Phase & dispersion medium
Type of particles of the dispersed phase

On the basis of physical state of Dispersed Phase and Dispersion Medium
There are 8 types of colloids are possible on the basis of physical

state of Dispersed Phase and Dispersion Medium
Dispersed Dispersion Type of colloidal
Example
phase medium solution
Ruby glass (Gold dispersed in
Solid Solid Solid sol
glass), Gem stones, Minerals
Gemstone
Example
Ink, Colloidal gold, Paints, Cell

Solid Liquid Sol
fluids
Paints
Dispersio
Disperse Type of colloidal
n Example
d phase solution
medium
Solid Gas Aerosol Dust, Soot in air, Smoke
Dust
Example
Liquid Solid Gel Cheese, curd, Jellies, Boot polish
Jellies
Example
Milk, Hair Cream, Butter, Cold

Liquid Liquid Emulsion
Cream
Milk
Example
Fog, Mist, Clouds, Insecticide

Liquid Gas Aerosol
sprays
Clouds
Example
Cork, Pumice stone, Foam

Gas Solid Solid Sol
rubber, Bread, Cake
Pumice stone
Example
Whipped Cream, Shaving

Gas Liquid Foam
Cream, Soda water
Whipped cream
N TE
A colloidal dispersion of one gas in another is not possible since the two
gases would give a homogeneous mixture but colloidal solution is
heterogeneous in nature.
Some special types of sols
Sr. No. Dispersion medium Name of solution
(i) Water Hydrosol or aquasol

(ii) Benzene Benzosol
(iii) Alcohol Alcosol
(iv) Gas Aerosol
Classification based on interaction between Dispersed Phase and
Dispersion Medium.
01 Lyophilic Sol
02 Lyophobic Sol
Lyophilic Sol
Colloidal solutions in which the dispersed phase has considerable affinity

for the dispersion medium, are called lyophilic sols (solvent - loving).
Example : Colloids of gelatine, starch, gum and proteins in water.

Lyophobic Sol
Colloidal solutions in which the dispersed phase has no or less

affinity or attraction for the medium or for the solvent are called
Lyophobic sols (Solvent hating).
Examp e Metals and their sulphides
Gold sol
Comparison of lyophilic sol & lyophobic sol
Sr. No. Property Lyophilic sol Lyophobic sol

1. Preparation Can be easily prepared by Can not be prepared
shaking or warming the easily. Special methods
substance with solvent. are required.
2. Stability More stable. Less stable.
3. Reversibility Reversible. Irreversible.
4. Viscosity Viscosity is much higher Viscosity is nearly same
than that of solvent. as that of the solvent.
5. Hydration or These are highly solvated These are less solvated
solvation as the particle have as the particles have
greater affinity for solvent. less affinity for the
solvent.
Comparison of lyophilic sol & lyophobic sol
Sr. No. Property Lyophilic sol Lyophobic sol

6. Charge The particles have little The particles carry a
charge or no charge at characteristic charge either
all positive or negative
7. Coagulation Precipitated by high Precipitated by low
or concentration of concentration of
precipitation electrolyte electrolyte
8. Migration in May or may not migrate Migrate towards anode
electric field as they may or may not or cathode as these
carry charge particles carry charge
9. General Mostly of organic nature Mostly of Inorganic nature
Example Example: Gelatine, Starch, Example: Metal sols
Gum, Albumin & Cellulose (like Gold, Silver,
Solution Platinum), Metal sulphides
and oxide sols
Example
Choose the correct reason(s) for the stability of the lyophobic colloidal
particle.
(A) Preferential adsorption of ions on their surface from the solution
(B) Preferential adsorption of solvent on their surface from the solution
(C) Attraction between different particles having opposite charges on
their surface
(D) Potential difference between the fixed layer and the diffused layer
of opposite charges around the colloidal particles
Solution
Ans. (A,D)
Classification based on size of dispersed phase particles.
01 Multi - molecular colloids
02 Macro - molecular colloids
03 Associated colloids
Classification based on type of particles of the dispersed phase
1. Multi molecular colloids
Formation by aggregation of a large number of atoms or smaller

molecules in suitable dispersion medium.
Example :-
➢ Gold sol and Sulphur sol
2. Macro molecular colloids
In suitable solvents, macromolecules form solutions in which the size of

particles may be in colloidal range.
Example :-
➢ Naturally occurring macro molecules are starch, cellulose, proteins and

enzymes etc.
➢ Man made macro molecules are Polythene, Nylon, Polystyrene etc.

3. Associated colloids (micelles)
Substances which behave as normal electrolytes at low concentration but

get associated at higher concentration and behave as colloidal solutions.
These associated particles are also called micelles.
Example :- Soaps and Detergents

Critical Micelle Concentration (CMC)
The critical micelle concentration (CMC) is the surfactant concentration

at and above which micelles are formed.
CMC of soap lies between 10–4 to 10–3 mol lit–1.
Longer the carbon chain length of hydrophobic

part lesser will be its CMC
Below the CMC, the surface tension decreases with increase in
surfactant concentration.
Above CMC, the surface tension of solution is constant.
Surface
Tension
Surfactant
Concentration
Methods of Preparation
1. Lyophilic sols
The colloidal solution of lyophilic collides like starch, glue, and gelatine
etc can be prepared by dissolving these substances in water (dispersion
medium) either by cooling or warming.
Solutions of colloidal electrolytes such as soaps and dye stuffs can also be
prepared similarly.
2. Lyophobic sols
Lyophobic sols must be prepared by special methods.
(A) Dispersion methods
(B) Condensation methods

In this method larger macro sized particles are broken down to
colloidal size.

In this method colloidal sized particles are built up by aggregating
atoms, ions or molecules.
2. Electro-dispersion
(Bredig’s Arc method)
1. Mechanical 3. Peptization
dispersion
1. Mechanical dispersion
The substance to be dispersed is grinded as finely as possible and then

shaken with the dispersion medium to form a suspension.
This suspension is passed through colloidal mill where the suspended

particles are broken to produce particles of colloidal size.
Examp e
Ink Paints
2. Electro-dispersion (Bredig’s Arc method)
This method is suitable for the preparation of colloidal solutions of

metals like gold (Au), silver (Ag), platinum (Pt) etc.
This process involves dispersion as well as condensation.
An arc is struck between the metal electrodes under the surface of

water containing some stabilizing agent such as a trace of KOH.
The water is cooled by immersing the container in an ice bath.
The intense heat of the arc vaporizes some of the metal which
condenses under cold water.
Preparation of Colloids
3. Peptization
The process of converting a freshly prepared precipitate into colloidal

solution by shaking it with dispersion medium in the presence of small
amount of electrolyte.
This electrolyte is known as peptizing agent.

The process of peptization thus involves the adsorption of suitable ions
(particularly a common ion)
01 FeCl3 + H2O (Hot) → Fe(OH)3 
Fe(OH)3  + FeCl3 → [Fe(OH)3] Fe3+ ⋮ 3Cl–
02 FeCl3 + H2O (Hot) → Fe(OH)3 
Fe(OH)3  + NaOH (Conc.) → [Fe(OH)3] OH– ⋮ Na+

1. Physical Methods
(a) Exchange of solvent

(b) By Excessive Cooling
2. Chemical Methods
(a) Double decomposition

(b) Oxidation
(c) Reduction
(d) Hydrolysis
1. Physical Methods
(a) Exchange of solvent
Colloidal solution of sulphur and phosphorus are soluble in alcohol but

insoluble in water.
Colloidal solution of these substances can be prepared by pouring

their alcoholic solution in excess of water.
(b) By Excessive cooling
A colloidal solution of ice in an organic solvent like ether or chloroform

can be prepared by freezing a solution of water in the solvent.
The molecules of water which can no longer be held in solution,

separately combine to form particles of colloidal size.
2. Chemical Methods
(a) Double decomposition
Double decomposition
As2 O3 + 3H2 S As2 S3 sol + 3H2 O
(b) Oxidation
Oxidation
SO2 + 2H2 S 3S(sol) + 2H2 O
(c) Reduction
Reduction
2AuCl3 + 3HCHO + 3H2 O 2Au sol + 3HCOOH + 6HCl
(d) Hydrolysis
Hydrolysis
FeCl3 + 3H2 O Fe OH 3 sol + 3HCl
Example
Which of the following will form negatively charged colloidal solution ?
(A) 100 ml, 0.1 M AgNO3 + 100 ml, 0.1 M KI
(B) 100 ml, 0.2 M AgNO3 + 100 ml, 0.1 M KI
(C) 100 ml, 0.1 M AgNO3 + 100 ml, 0.2 M KI
(D) 100 ml, 0.2 M AgNO3 + 200 ml, 0.1 M KI
Solution
Ans. (C)
Purification of Colloidal Solution
(A) Dialysis (B) Electro-dialysis (C) Ultrafiltration

(A) Dialysis
It is a process of removing a dissolved substance from a colloidal

solution by means of diffusion through suitable membrane.
Principle
Small particles (impurities) can pass through membranes i.e.

animal membrane, parchment paper and cellophane membrane
etc. but colloidal particles can’t because of their large size.
Concept
Concept of diffusion is used here to separate small particles.
Apparatus
The apparatus used for this purpose is called dialyser.
Process
Colloidal solution is taken in the bag of suitable membrane.
This bag is suspended in the vessel containing fresh water.
Fresh water is continuously flown through the vessel.
Dissolved impurities diffuse from the membrane in outer water leaving

colloidal solution behind.
(A) Dialysis
(B) Electro-dialysis
Process of dialysis can be made faster by applying an electric field if

the dissolved substances in the impure colloidal solution is only an
electrolyte.
(C) Ultrafiltration
Ultrafiltration is the process of separating the colloidal particles from

the solvent and soluble solutes present in the colloidal solution by
especially prepared filters (Ultrafilters).
Principle
Specially prepared filter papers are permeable to all other substances
except colloidal particles.
Concept
Concept of filtration is applied.
Apparatus
Specially prepared ultra-filters are used.
Preparation of Ultrafilters
Soaking a filter paper with collodion solution. (Collodion solution is

a 4% solution of nitrocellulose in a mixture of alcohol and ether).
It is then soaked with formaldehyde to harden the collodion on

pores of filter paper.
The pores are now small enough for ultrafiltration.

Preparation of Colloids
(C) Ultrafiltration
Properties of Colloidal Solutions
1. Brownian movement
2. Colligative Properties
3. Color
4. Tyndall Effect
5. Electrophoresis
Brownian movement
Colloids particles exhibit a ceaseless random and swarming motion. This

kinetic activity of particles suspended in the liquid is called Brownian
movement.
Cause of movement
The Brownian movement has been explained to be due to the unbalanced
bombardment of the particles by the molecules of the dispersion medium.
Importance
The Brownian movement has a stirring effect which does not permit the
particles to settle and thus, is responsible for the stability of sols.
Colligative Properties
Colligative properties depend on the relative number of solute particles

in solution.
Colloidal particles being bigger aggregates, the number of particles in a

colloidal solution is comparatively small as compared to a true solution.
Color
The color of the colloidal solution depends upon the following factors :
(a) Size and shape of colloidal particles.
(b) Wavelength of the light scattered by dispersed particles.
(c) The way an observer receives the light, i.e., whether by reflection or
by transmission.
Examp e
Tyndall Effect
When a strong and converging beam of light is passed through a colloidal

solution, its path becomes visible (bluish light) when viewed at right angles
to the beam of light. This effect is called Tyndall effect.
Tyndall effect is due to scattering of light by the colloidal particles.
Colloidal particles first absorb light and then a part of the absorbed light is
scattered from the surface of the colloidal particles as a light of shorter
wavelength.
Maximum scattering of light takes place at right angles to the place of

incident light, it becomes visible when seen from that direction.
Tyndall Effect
Tyndall effect can be observed only when following two conditions can
be satisfied-
1. Diameter of dispersed particle is not much smaller than

wavelength of light used.
2. The refractive indices of the dispersed phase and dispersion

medium differ greatly in magnitude.
Charge on colloidal particles
Colloidal particles always carry an electric charge.
The nature of charge is same and equal on all the dispersed particles in
a given colloidal solution.
The mutual forces of repulsion between similarly charged particles

prevent them from aggregating and settling under the action of gravity.
This gives stability to the solution.
The charge on the sol particles is due to one or more reasons –
Frictional Electrification
Dissociation of surface molecules
Capture of electron
Dissociation of molecular electrolytes on the surface of particles
Preferential adsorption of ions from solution

Electrical double layer
The combination of the two layers of opposite charges around the sol
particle is called Helmholtz double layer.
The first layer of ions is firmly held and is termed as fixed layer or
compact layer.
The second layer is mobile which is termed as diffused layer.
The diffused layer is only loosely attached to the particle surface and
moves in the opposite direction under an applied electric field.
The potential difference between the fixed layer and the diffused layer of
opposite charge is called electro-kinetic potential or zeta potential.
The addition of more electrolytes to sol supresses the diffused double

layer and reduces the zeta potential.
This decreases the electrostatic repulsion between particles to a large

extent and colloid precipitates. That is why colloid is particularly
sensitive to oppositely charged ions.
Sr. No. Positively charged sols Negatively charged sols
(1) Metallic hydroxides Cr(OH)3, Metallic sulphides like As2S3,
Al(OH)3, Fe(OH)3 & hydrated Sb2S3, CdS and metals like:
metallic oxides Al2O3.xH2O,
Au, Ag, Cu, Pt etc.
CrO3.xH2O
(2) Basic dye stuff like: Acid dye in basic medium stuff
methylene blue sol like: Congo red sols, eosin
(3) Proteins in (acidic medium) Proteins in (basic medium)
(4) Haemoglobin (Hb) Sols of starch, gum, gelatine,

clay&charcoal
N TE Blood is a naturally occuring negatively charged colloid but

Haemoglobin (Hb) is a positively charged colloid.
Electrophoresis
Electrophoresis provides an experimental proof to show that the colloidal

particles are charged particles.
If electric potential is applied across two platinum electrodes dipped in a

colloidal solution, the colloidal particles move towards one or the other
electrode, due to charge on them.
The movement of sol particles under an applied electric potential is

called electrophoresis.
Electro-osmosis
If movement of particles is prevented by some suitable means (like SPM)

then it is observed that dispersion medium begins to move in an electric
field.
The medium will move in opposite direction to the dispersed phase

under the influence of applied electric potential.
Coagulation or flocculation
The process by which dispersed phase particles in a sol are precipitated

is known as coagulation.
If coagulated particles float on the surface of dispersion medium, then

coagulation is called flocculation
This is due to the fact that the colloidal particles take up the ions of
electrolyte whose charges are opposite to that on colloidal particles with
the result that charge on the colloidal particles is neutralized.
The minimum concentration of an electrolyte in millimoles per litre
required to cause precipitation of one litre of a colloidal solution in two
hours is called (coagulation in value or flocculation value) of the
electrolyte for the sol.
The smaller the quantity needed the higher will be the coagulating
power of an ion.
1
(Flocculation power) ∝ (Flocculation value)
By addition of
01
electrolyte
02 By electrophoresis
Coagulation
By mixing two oppositely
of lyophobic 03 charged sols
sol
04 By boiling
05 Chromatography
By repeated dialysis
1. By addition of electrolyte
When an electrolyte is added in solution, it furnishes both the type of

ions in solution.
The oppositely charged ions get adsorbed on the surface of colloidal

particles. This causes neutralization.
Due to greater volume and greater mass these particles settle down and
coagulate.
The ion responsible for neutralization of charge on the particle is called

the flocculating or coagulating ion.
Hardy Schulze Rule
The higher the valency of the coagulating ion, the greater is its
coagulating power.
For the precipitation of As2S3 sol, the coagulating power of Al3+, Ba2+,
and Na+ ions are in the order -
Al3+ > Ba2+ > Na+
For precipitating Fe(OH)3 sol, the coagulating power of [Fe(CN)6]–3,

SO42– and Cl– ions are in the order -
[Fe(CN)6]3– > SO42– > Cl–

2. By electrophoresis
During electrophoresis the charged sol particles migrate towards the

oppositely charged electrode, get discharged and precipitated.
3. By mixing two oppositely charged sols
Oppositely charged sols when mixed in almost equal proportions,

neutralise their charges and get partially or completely precipitated.
This type of coagulation is called mutual coagulation.
Examp e
Fe(OH)3 (positive sol) and Arsenic sulphide (negative sol) when mixed,
they neutralize each other and gets precipitated.
4. By boiling
Sols such as sulphur and silver halides dispersed in water, gets

coagulated when boiled due to increased collisions between sol
particles and water molecules, which removes the adsorbed charged
layer from the sol and therefore the sol particles settle down.
5. By repeated dialysis
When dialysis is repeated again and again then colloidal solution gets
coagulated.
Protective Colloids
Lyophobic sols are more easily coagulated by the addition of suitable

electrolyte.
To avoid the precipitation/ Coagulation of lyophobic sol by the addition

of electrolyte, some lyophilic colloid is added to it.
Protection of lyophobic colloid from the electrolytes is known as

protection and lyophilic colloid is called as protective colloid.
Examples of protective colloids
Gelatine
Albumin
Glue
Starch
Gum Arabic
Coagulation
Protective action of lyophilic colloids
The particles of the protective colloid get adsorbed on the particles of

the lyophobic colloid, thereby forming a protective layer around it.
Protected particles
Protecting particles
The protective layer (lyophilic) prevents the lyophobic sol from coming
in contact with the electrolyte.
Coagulation
Protective action of lyophilic sol is represented in terms of Gold Number

Coagulation
Gold Number
Gold number of a protective colloid is its minimum weight in milligrams

which must be added to 10 ml of a standard red gold sol so that no
coagulation of the gold sol takes place when 1 ml of 10% sodium
chloride solution is added to it.
1 mL
1 mL
Coagulation
The gold number of some colloids are given below.
Protective Colloid Gold Number
Gelatin 0.005-0.01
Haemoglobin 0.03-0.07
Egg Albumin 0.15-0.25
Potato Starch 20-25
Gum Arabic 0.15-0.25
Caseinate 0.01-0.02
N TE Smaller the gold number of a protective colloid, greater is the

protective action.
Example
0.02 gm of lyophilic colloid just prevent coagulation in 100 ml of a red
gold sol on adding 10 ml of 10% NaCl solution. What is the gold number of
lyophilic colloid ?
Solution
Ans. (2)
Emulsions
An emulsion is a colloidal solution of a liquid. It may be defined as

a heterogeneous system consisting of more than one immiscible
liquids dispersed in one another in the form of droplets.
Emulsions
Oil dispersed in water Water dispersed in

(O/W type) oil (W/O type)
Oil dispersed in water (O/W type)
In this type water acts as dispersion medium.
Examples of this type of emulsions are milk and vanishing cream. In milk,
liquid fat is dispersed in water.
Water dispersed in oil (W/O type)
In this oil acts as dispersion medium.
Examples of this type are butter, cold cream, and cod liver oil etc.
Emulsifying agent
This substance which stabilizes the emulsion is called emulsifier or

emulsifying agent.
The commonly used emulsifying agents are soaps, detergents and

lyophilic colloids.
Casein, a lyophilic colloid present in milk, acts as an emulsifier as it

forms a protective layer around fat molecules dispersed in water.
Function of emulsifier
The main function of emulsifier or emulsifying agents is to lower the

interfacial tension between oil and water and thus helps the intermixing
of two liquids.
Uses of colloids
Medicines
The medicines containing gold, silver or calcium etc. in colloidal form are
more effective and easily assimilated by the human systems.
Uses of colloids
Dyes
In dyeing, mordants colloidal substances are used in textile dyeing industry

to fasten dyes.
Uses of colloids
Rubber Industry
Latex is a colloidal solution of negatively charged particles.

Uses of colloids
Smoke Screen
Smoke screens which consist of titanium dioxide dispersed in air are

used in warfare for the purpose of concealment and camouflage.
Uses of colloids
Delta Formation
The river water carries with it charged clay particles and many other
substances in the form of colloidal solution.
When the sea water meets these particles, the colloidal particles in river
water are coagulated by the electrolytes present in sea water to form deltas.
Uses of colloids
Purification of Water
The turbidity in water is due to the presence of negatively charged clay

particles.
The addition of potash alum, i.e., Al3+ ions neutralizes the negative charge on
the colloidal particles.
Uses of colloids
Artificial Rain
Artificial rain can be caused by throwing electrified sand on clouds

which are colloidal solutions or charged particles of water in air.
Uses of colloids
Smoke Precipitation
In Cottrell precipitator, the smoke is made to pass through

chambers fitted with highly electrically charged plates which
precipitate the charged particles of dust and carbon.
Uses of colloids
Sewage disposal
Sewage water consists of particles of dirt, garbage, mud, etc., which

are of colloidal dimensions and carry an electric charge.
These particles can be removed by cataphoresis.

Uses of colloids
In Photography
In the preparation of photographic plates, the silver bromide in gelatin

is coated on thin glass plates. In developing and fixation, various
colloidal substances are used.
Uses of colloids
Blue color of the sky
In sky there are several dust and water particles. They scatter blue
light and, therefore, sky looks bluish.
Example [JEE (Advanced) 2016]
The qualitative sketches I, II and III given below show the variation of surface
tension with molar concentration of three different aqueous solutions of KCl,
CH3OH and CH3(CH2)11 OSO⊝ 3 Na at room temperature. The correct
⊕
assignment of the sketches is –

I II III
Surface tension
Surface tension
Surface tension concentration concentration concentration
(A) I : KCl II : CH3OH III : CH3 (CH2 )11 OSO⊝

3 Na
⊕
(B) I : CH3 (CH2 )11 OSO⊝

3 Na
⊕
II : CH3OH III : KCl
(C) I : KCl II : CH3 (CH2 )11 OSO⊝
3 Na
⊕
III : CH3OH
(D) I : CH3OH II : KCl III : CH3 (CH2 )11 OSO⊝
3 Na
⊕
Solution Ans. (D)

States of matter
States of matter
STATES OF MATTER: GASES

Gas laws and ideal gas equation, absolute
scale of temperature, van der Waals
equation; Kinetic theory of gases, average,
root mean square and most probable
velocities and their relation with
temperature; Law of partial pressures;
Diffusion of gases. vapour pressure, surface
tension, viscosity
INTRODUCTION
In Periodic table we learn about the property of single atom or
molecules but into chemistry many property of substance depend
on bulk of substance not on single atom, molecules or particle.
Example
An individual molecules of liquid does not boil but bulk boil.
Basically in this chapter we study
(i) Property of substance in bulk
(ii) States of matter

GAS LAWS
The behavior of the gases is governed by some general laws, which were
discovered as a result of their experimental studies. These laws are
relationships between measurable properties of gases.
Gas Laws
1
Boyle’s law Pα (When n and T are constant)
V
Vα T, T(inC)
Charles’ law When n, P = constant Vt = V0 1 +
273.15
Pα𝑇
T(inC)
Gay-lussac’s law (When n, V = constant) Pt = P0 1 +
273.15
𝑉αn
Avogadro’s Law
(Temperature and pressure are constant)
IDEAL OR COMBINED GAS EQUATION
nT nT
On combination, V ∝  V=R⋅
P P
PV = nRT (Combined or ideal gas equation or equation of

state)
where R is universal gas constant
Another form of Ideal gas equation

PM = dRT M = Molar mass
, d = Density of gas in gram per litre
PV
= nR = Constant
T
𝑃1 𝑉1 𝑃2 𝑉2
= or P1V1T2 = P2V2T1
𝑇1 𝑇2
P
Rectangular T3
P hyperbolic T2
n T T1
n↑ T↑
V 1/V
PV
n↑ T↑
T3
T2
T1
V
PRESSURE CALCULATION
(I) Closed container
F
P=
A
F=m×g
h F=V×d×g
Liquid F=A×h×d×g
B A×h×d×g
P= A
A
P = hdg
h = vertical height of liquid column

d = density of liquid
g = gravity
PRESSURE CALCULATION
(II) Open container
h Liquid
Ptotal = Patm + hdg
Note
The value of pressure at same horizontal level is same.

N TE
Sometime certain other liquid can also be used in place of Hg. In

such cases the pressure can be easily calculated by using the
following relation.
PHg = Pliq
hHg × dHg × g = hliquid × dliquid × g
hliquid × dliquid
hHg = dHg
PRESSURE MEASURING INSTRUMENTS
Pressure exerted by gas is measured in terms of height of
mercury column by two instruments.
1. Barometer
2. Manometer
1. Barometer
It is used to measure atmospheric pressure
Perfect vacuum
Hg
1 atm = 76 cm of Hg
2. Manometer
It is used to measure gas or gaseous mixture pressure.

There are two types of manometer.
(i) Open end Manometer (ii) Closed end Manometer
Case I : - Patm
Gas
Pgas = Patm
Hg()
Case II : -
Patm
Gas
Pgas = Patm + hdg
ℎ
= Patm + atm
h cm 76
Hg()
Case III : -
Patm
Gas
Pgas + hdg = Patm
ℎ
Pgas = Patm – 76 𝑎𝑡𝑚
h cm
Hg()
(ii) Closed End Manometer
vacuum
Gas
Pgas = hdg
= h cm
h
h cm = atm
76
Hg()
EXAMPLE
Find the pressure of gas in cm of Hg.
(Assume that atmospheric pressure Patm = 76 cm of Hg)
gas
SOLUTION
h1 d=3.4 40cm
h2 d=27.2 10cm
h3 d=6.8 40cm
Patm
Hg 15cm
h4
Ans. 11 cm of Hg
DALTON'S LAW AND
AMAGAT’S LAW
DALTON'S LAW OF PARTIAL PRESSURE
The total pressure exerted by a non-reacting gaseous mixture is
equal to the sum of partial pressures of the component gases at
constant volume and temperature.
Ptotal = PA + PB + ......
Gas A, nA
Gas B, nB
Partial pressure :
It is the pressure exerted by a gas in non-reacting gaseous
mixture.
RELATION BETWEEN PARTIAL PRESSURE AND TOTAL PRESSURE
nA ⋅RT nB ⋅RT ntotal ⋅RT
PA = , PB = , Ptotal =
V V V
nA RT
PA nA
Now, = V
ntotal RT =n = XA
Ptotal total
V
(i) Pressure fraction = mole fraction

PA nA
=n = XA
Ptotal total
(ii) PA = XA.Ptotal
 partial pressure = mole fraction × total pressure
Amagat’s Law of Partial Volume
The total volume occupied by a non-reacting gaseous

mixture is the sum of partial volumes of the component
gases.
Partial volume of a gas in a non-reacting gaseous mixture

is its volume when the entire pressure of the mixture is
supposed to be exerted only by that gas.
Vtotal = VA + VB
nA .RT RT ntotal .R
VA = VB = nB Vtotal =
Ptotal Ptotal Ptotal
nA .RT
VA 𝑛𝐴
=𝑛
Ptotal
∴ = ntotal .R
Vtotal 𝑡𝑜𝑡𝑎𝑙
Ptotal
(i) volume fraction = mole fraction
(ii) Partial volume = mole fraction × total volume

VA = XA. Vtotal
VAPOUR PRESSURE
RELATIVE HUMIDITY AND
AQUEOUS TENSION
Vapour Pressure
It is the pressure exerted by vapours when the vapours are in
equilibrium with the liquid at that temperature.
Vapour Vaporisation
Liquid Vapour
⇌
Liquid condensation
At equilibrium
rate of vaporisation = rate of condensation
Factors affecting V.P.
(1) Nature of liquid
(2) Temperature
P2 ΔHvap. 1 1
ℓn = −
P1 R T1 T2
Important Points for Vapour Pressure
The vapour pressure of a particular liquid system depends only
on temperature. It is independent from all other factors like
amount of liquid, available space, surface area, etc.
Vapour pressure obeys Dalton's law of partial pressure.
Gas
Ptotal = Pmoist gas
= Pdry gas+ aqueous tension
H2O(ℓ)
In case of water it is also called aqueous tension.

Relative Humidity (RH)
It is the ratio of partial pressure of H2O to maximum vapour
pressure of H2O at that temp.
Partial pressure of water vapour in air

R. H. = × 100 %
vapour pressure of H2 O (ℓቁ
If R.H. decreases, extent of vaporisation of water increases.

EXAMPLE
SOLUTION
Ans. 7
PROBLEMS RELATED WITH
DIFFERENT TYPE OF
CONTAINERS
Problems Related with Different Type of Containers
Types of Container
Closed Open Tyre-tube Connected

Container Container type Container Container
Rigid Closed
container
Non –Rigid
Closed container
1. Closed Container
(i) Rigid Closed Container

Number of moles of gas is always constant because
in this case gas can neither go outside nor it can come
inside.
PV = nRT V, n = Constant always
P ∝ T (Gay-Lussac’s Law) n
𝑃1 𝑇1 V
=
𝑃2 𝑇2
On increasing temperature pressure also increases till

maximum pressure is reached after this explosion occur.
(ii) Non-Rigid Closed Container
In this type of container pressure is always constant
PV = nRT P, n = Constant always
V ∝ T (Charle’s Law)
𝑉1 𝑇1
=
𝑉2 𝑇2
On increasing temperature volume also increases till

maximum volume is attained after this vessel will burst.
2. Open Container
Volume and pressure are always constant and pressure

atmosphere
always equal to atmospheric pressure.
PV = nRT V, P = Constant always
1 air
T∝n
𝑛1 𝑇2
=
𝑛2 𝑇1
On increasing temperature moles of air decreases that means

air escaped out.
moles of air escaped out = ni – nf ni = initial moles of air

moles of air entered = nf – ni nf = final moles of air
EXAMPLE
An open vessel of unknown volume containing air is heated from
27°C to 227°C at constant pressure. If the volume of expelled
air is 200 ml measured at different temperature. Then find the
volume (in ml) of the open vessel.
SOLUTION
Ans. 𝟑00 𝐦𝐥
3. Tyre tube type Container
In this type of container temperature always constant.
(i) Initially on adding gas

volume of tube will increases and pressure of tube will remains
constant until it will gain maximum volume.
𝑉1 𝑛1
PV = nRT P, T = Constant =
𝑉2 𝑛2
V∝n
(ii) After attaining maximum volume
On adding gas pressure reach to maximum possible pressure
PV = nRT V, T = Constant 𝑃1 𝑛2
=
P∝n 𝑃2 𝑛1
I II
4. Connected Container
gas A gas B
After opening the valve nA nB
❑ The gases move from one container to
another container. V1T1 negligible V2T2
❑ Each gas will occupy total volume available. volume
❑ Equilibrium will be attained.
❑ Total pressure and partial pressure of each gas will be same in all
containers.
At equilibrium similarly,
(PA)I = (PA)II (PB)I = (PB)II
nA −x R T1 x R T2 nB −y R T1 y R T2
= =
V1 V2 V1 V2
EXAMPLE
SOLUTION
Ans. 2.22
GRAHAM'S LAW OF
EFFUSION AND
DIFFUSION
Graham's Law of Diffusion and Effusion
Graham's Law
Under identical conditions, the rates of diffusion or

effusion of gases are inversely proportional to the square
root of their densities.
1
rate of effusion or diffusion, r∝
d
1 (I) PM = dRT
r∝
M Md
1
r∝ (II) M = VD × 2
VD M  VD
Where, M = molar mass of gas
d = density of gas
VD = vapour density
N TE
If external pressure is not specified, diffusion or effusion

Is always considered in vacuum.
It is always used to compare the rates of two gases, in

identical conditions.
r1 M2
=
r2 M1
r1 d2
=
r2 d1
Graham’s law of different condition
Condition 1 : If only a mixture of two gases is given.

Gas A 1 rA MB
r∝ =
M rB MA
Gas B
Condition 2 : If a mixture of two gases with their pressure is given.
Gas A PA P rA 𝑃 MB
r∝ = 𝑃𝐴 ×
Gas B PB M rB 𝐵 MA
Condition 3 : If a mixture of two gases with their moles is given.
Gas A nA
n rA n MB
r∝ = nA ×
M rB MA
Gas B nB B
Rate of diffusion/effusion in terms of effused quantity
number of molecules diffused

=
moles diffused
r= time taken
time taken
𝒅𝒊𝒔𝒕𝒂𝒏𝒄𝒆 𝒕𝒓𝒂𝒗𝒆𝒍𝒍𝒆𝒅 (𝒂𝒓𝒆𝒂 𝒐𝒇𝒄𝒓𝒐𝒔𝒔−𝒔𝒆𝒄𝒕𝒊𝒐𝒏 )
r=
volume diffuse𝑑
=
time taken 𝐭𝐢𝐦𝐞 𝐭𝐚𝐤𝐞𝐧
pressure dropped
r=
time taken
distance travelled in horizontal tube of uniform cross−section

r=
time taken

Gas A Gas B
x (–x)
EXAMPLE
SOLUTION
Ans. B
ADVANCE LEVEL ON GRAHAM'S
LAW
Application of Graham's Law of Diffusion in Enrichment of Isotopes
1 2 3 n
nA nA ’ nA’’ nA n
nB nB’ nB’’ After n Bn

nth step
I step II
step
where, MA > MB [similar condition of T and V] & 𝑛𝐵𝑛 >>>> 𝑛𝐴𝑛

Calculation of number of effusion steps (n)
After I - step :
𝑟𝐴 𝑛𝐴 𝑀𝐵 𝑟𝐴 𝑛𝐴′ Τ𝑡
= =
𝑟𝐵 𝑛𝐵 𝑀𝐴 𝑟𝐵 𝑛𝐵′ Τ𝑡
𝑛𝐴′ 𝑛𝐴 𝑀𝐵
 = ..............(i)
𝑛𝐵′ 𝑛𝐵 𝑀𝐴
After II - step :
𝑛𝐴" 𝑛𝐴′ 𝑀𝐵
"
= ′ ..............(ii)
𝑛𝐵 𝑛𝐵 𝑀𝐴
2
𝑛𝐴" 𝑛𝐴 𝑀𝐵
=
𝑛𝐵" 𝑛𝐵 𝑀𝐴
After III-Step similarly :

3
𝑛𝐴"′ 𝑛𝐴 𝑀𝐵
=
𝑛𝐵"′ 𝑛𝐵 𝑀𝐴
For nth step similarly :

𝒏
𝒏𝒏𝑨 𝒏𝑨 𝑴𝑩
=
𝒏𝒏𝑩 𝒏𝑩 𝑴𝑨
Enrichment factor (f)
It is defined as the ratio of final ratio of moles in the mixture [after

nth step] with initial mole ratio of the mixture.
nnA n
nnB MB final molar ratio
f= = =
nA MA initial molar ratio
nB
X and Y are two volatile liquids with molar weights of 10g mol–1 and
40g mol–1 respectively. Two cotton plugs, one soaked in X and the other
soaked in Y, are simultaneously placed at the ends of a tube of length L
= 24 cm, as shown in the figure. The tube is filled with an inert gas at 1
atmosphere pressure and a temperature of 300K. Vapours of X and Y
react to form a product which is first observed at a distance d cm from
the plug soaked in X. Take X and Y to have equal molecular diameters
and assume ideal behaviour for the inert gas and the two vapours
(JEE ADVANCED 2014)
L = 24 cm
d
Cotton wool Cotton wool
Initial formation Soaked in Y
Soaked in X
of the product
L = 24 cm
(JEE ADVANCED 2014)
d
Soaked in X
of the product
EXAMPLE
The value of d in cm (shown in the figure), as estimated from Graham's
law, is–
(A) 8 (B) 12 (C) 16 (D) 20
SOLUTION
Ans. C
KINETIC THEORY OF GASES (KTG)
The Kinetic Theory of Gases
Postulates / assumptions of KTG :

❑ A gas consists of tiny spherical particles called molecules
of the gas which are identical in shape & size (mass)
❑ The volume of the molecules is negligible in comparison to
the total volume occupied by the gas.
❑ For an ideal gas, volume of the ideal gas molecule ~ 0.
❑ Molecular attraction forces are negligible. In fact, for an
ideal gas attractive or repulsive forces are equal to zero.
1
Average K.E. of molecule = mu2
2
3
Average K.E. = kT
2
(only dependent on temperature not on nature of the gas.)
1 3 3
Average K.E. for one mole =NA mu2 = kNA T = RT
2 2 2
Root mean square speed :
—
3kT 3RT 3RT 3𝑃
urms = u2 = = = = .
m mNA M d
Where m–mass of one molecule
M = molar mass
Dependent on nature of gas i.e. mass of the gas

Average speed
( u1 + u2 + u3 + ............ uN )
uav =
N
8RT 8kT 8𝑃
uav = = =
πM πm π𝑑
k is Boltzmann constant
Most probable speed:
The speed possessed by maximum number of molecules at the

given temperature
2RT 2kT 2𝑃
ump = = =
M m d
Molecular Speed
Most probable Average Root mean

speed speed square
2kT 2RT 8RT 2kT 3RT 3kT

= = =
m M πM m M m
For same gas at certain temperature
urms > uav > ump

8
ump : uav : urms = 2: : 3
π
EXAMPLE
SOLUTION
Ans. C
EXAMPLE
SOLUTION
Ans. D
EXAMPLE
SOLUTION
Ans. 434
EXAMPLE
SOLUTION
Ans. 4
EXAMPLE
SOLUTION
Ans. A,B,C
Maxwell-Boltzmann speed
distribution
Maxwell’s distributions of molecular speeds :
Postulates/Assumptions of speed distributions
It is based upon theory of probability.
It gives the statistical averages of the speed of the whole

collection of gas molecules.
Speed of gaseous molecules may vary from 0 to . The

maxwell distribution of speed can be plotted against fraction
of molecules as follows.
The area under the curve will denote fraction of molecules
having speeds between zero and infinity
Total area under the curve will be constant and will be unity
at all temperatures.
Area under the curve between zero and u1 will give fraction of
molecules having speed between 0 to u1. This fraction is more
at T1 and is less at T2.
The peak corresponds to most probable speed.
At higher temperature, fraction of molecules having speed

less than a particular value decreases.
For Gases with different molar masses will have following

graph at a given temperature.
Maxwell-Boltzmann speed distribution
Maxwell-Boltzmann gave a mathematical equation which provide
the number of gas particle within in particular speed range.
3
M 2 Mu2
− 2RT 2
dN = 4πN e . u du
2πRT
dN = small number of particle having speed between u to (u + du)
N = total gas particles inside the container.
T = Temperature on kelvin scale.
M = Molecular weight of gas.

Speed distribution curve :
3
M 2 Mu2
− 2RT 2
dN = 4π .e . u du
2πRT
3
1 dN M 2 Mu2
− 2RT 2
⇒ . = 4π .e .u
du N 2πRT
2
⇒ y = K1 . e−Kx . x 2
X2 = parabolic
e−Kx = exponentially decreasing
2
1 dN
×
du N
u
2𝑅𝑇
𝑢𝑚𝑝 =
𝑀
Important properties of speed distribution curve:
1. For smaller values of speeds, the curve is parabolic
(u2 dominates), whereas, for larger values of speeds, the
mu2
curve is exponentially decreasing (e −
2RT dominates)
2. 1 dN dN
dA = du × × du =
1 dN N N
× → fraction of particle having
du N
speed between u to (u+du)
u
u (u+du)
du
Total area enclosed by this curve = 1
3. Graph for same gas at different temperature.
[T2 > T1]

1 dN
×
du N
T2
T1
u
2RT1 2RT2
ump1 = ump2 =
M M
On increasing temperature, the peak of the curve shifts

toward higher speed.
Maxwell’s distributions of molecular speeds :
Umps
Uav
Urms Curve will start becoming

flatter with increase in
T1 temperature
fraction of molecule T2 > T1
having particular speed
U1 Umps UavUrms Umps U2

U
4. Different gases at same temperature.
[M2 < M1]

1 dN
×
du N
M2
M1
u
2RT1 2RT2
ump1 = ump2 =
M1 M2
The curve for lighter gases is shifted towards higher speed.

EXAMPLE
If the distribution of molecular speeds of a gas is as per the figure shown
below, then the ratio of the most probable, the average and the roots mean
square speeds, respectively, is
Fraction of
molecules
speed
(A) 1 : 1 : 1 (B) 1 : 1 : 1.224 (C) 1 : 1.128 : 1.224 (D) 1 : 1.128 : 1
[JEE ADVANCED 2020]
SOLUTION
Ans. B
COLLISION THEORY
Collision Theory In Gases
Assumption :
(i) All the gas particles are considered to be uniform spheres
of diameter ''.
The sphere are considered to be hard sphere.
(ii) All the gas particle are assumed to move with equal speed
and this speed is assume to be average speed
8𝑅𝑇
𝑢𝑎𝑣 =
𝜋𝑀
(iii) There are no interactive forces acting between gas particle.
(iv) In a gaseous sample when the gas particle collide, angle of

collision may range from 0° to 180°. However in this theory
an average angle of 90° is selected to be collision angle.
uav
uav
𝑢𝑟𝑒𝑙 = 2𝑢𝑎𝑣
Some important terms related to collision theory
(1) Number Density (N*)
𝑁
𝑁 ∗=
𝑉
N = No. of gas particles in the container.

V = Volume of the container.
PV = nRT
𝑁
PV = ×𝑅×𝑇
𝑁𝐴
𝑅
PV = 𝑁 × kT × 𝑘 =
𝑁𝐴
∗𝑁 𝑃
N = =
𝑉 𝑘𝑇
Note : For closed rigid container :

N* = constant
(2) Collision Diameter ()
It is the minimum distance between the centres of two colliding
gas particles.
  1 2
Collision diameter =  1 +2

Collision diameter =
2
(3) Collision cross sectional Area (2)
 /2
/2
2
(4) Collision Number (Z1) :
It is the number of collision made by a gas particle per unit time.

Z1 = (2)urel × N*
Case-I Case-II
Only one particle moves, If all the particle move
others at rest. urel = 2𝑢𝑎𝑣
 Z1 = 22uavN* 
urel = uav  
 8RT P  → V. imp.
Z1 = (2)uav × N*  Z1 = 2 M  RT 
2
(5) Collision frequency (Z11):
It is the number of bimolecular collisions occuring per unit
volume per unit time.
Z1 × N ∗
Z11 =
2
*
1 2u 2
Z11 = πσ av N∗ → V. imp.
2
2
1 8RT P
Z11 = πσ2
2 πM kT
(6) Mean free path () :
It is the average distance travelled by a gas particle
between two successive collisions.
𝑢𝑎𝑣
λ=
𝑍1
uav
λ=
2πσ2 uav N ∗
1 kT
* λ=
2πσ2 N ∗ * λ=
2πσ2 P
PRESSURE, TEMPERATURE
DEPENDENCE OF , Z1, Z11
Pressure, temperature dependence of 1, Z1, Z11
(1) Mean free path (𝜆)
1 𝑘𝑇
𝜆= ∗ =
2𝜋𝜎 2 𝑁 2𝜋𝜎 2 𝑃
𝑇
𝜆∝
𝑃
Closed rigid container : (N* = constant)

 = constant
(2) Collision Number (Z1)
𝑍1 = 2𝜋𝜎 2 𝑢𝑎𝑣 × 𝑁 ∗
8𝑅𝑇 𝑃
𝑍1 = 2𝜋𝜎 2 ×
𝜋𝑀 𝑘𝑇
𝑃
𝑍1 ∝
𝑇
Closed rigid container :- (N* = constant)
𝑇
𝑍1 ∝
𝑀
(3) Collision frequency : (Z11)
1
𝑍11 = 𝜋𝜎 2 𝑢𝑎𝑣 (𝑁 ∗)2
2
2
1 8𝑅𝑇 𝑃
𝑍11 = 𝜋𝜎 2
2 𝜋𝑀 𝑘𝑇
𝑃2
𝑍11 ∝ 3/2
𝑇
Closed rigid container (N* = constant)
𝑍11 ∝ 𝑇
EXAMPLE
SOLUTION
Ans. TRUE
X and Y are two volatile liquids with molar weights of 10g mol–1 and
40g mol–1 respectively. Two cotton plugs, one soaked in X and the other
soaked in Y, are simultaneously placed at the ends of a tube of length L
= 24 cm, as shown in the figure. The tube is filled with an inert gas at 1
atmosphere pressure and a temperature of 300K. Vapours of X and Y
react to form a product which is first observed at a distance d cm from
the plug soaked in X. Take X and Y to have equal molecular diameters
and assume ideal behaviour for the inert gas and the two vapours
(JEE ADVANCED 2014)
L = 24 cm
d
Soaked in X
of the product
L = 24 cm
(JEE ADVANCED 2014)
d
Soaked in X
of the product
EXAMPLE
The experimental value of d is found to be smaller than the estimate obtained using
Graham's law. This is due to –
(A) Larger mean free path for X as compared to that of Y
(B) Larger mean free path for Y as compared to that of X
(C) Increased collision frequency of Y with the inert gas as compared to that of X with the
inert gas
(D) Increased collision frequency of X with the inert gas as compared to that of Y with the
inert gas
SOLUTION
Ans. D
EXAMPLE
The diffusion coefficient of an ideal gas is proportional to its
mean free path and mean speed. The absolute temperature of
an ideal gas is increased 4 times and its pressure is increased
2 times. As a result, the diffusion coefficient of this gas
increases x times. The value of x is (JEE ADVANCED 2016)
SOLUTION
Ans. 4
Introduction Of Real Gas
Real gas deviates from ideal behaviour because of mainly two

assumptions of "Kinetic theory of gases".
The dimensions of gas particle is negligible as compared to

the volume of container (while the real gas particle may have
some significant dimensions).
There is no interaction between gaseous particles (while

attraction forces exist between real gas particles).
Plot of pressure vs volume for real gas and ideal gas :
Real gas
Ideal gas
Pressure
0
Volume
Ideal Gas Real Gas

(i) Follow Ideal gas equation (i) Do not Follow Ideal gas
PV = nRT equation
PV  nRT
❑ If PV > nRT (Gas is less

compressible than ideal gas).
❑ If PV < nRT(Gas is more
compressible than ideal gas).
Ideal Gas Real Gas
(ii) No liquefaction is possible. (ii) Liquefaction is possible below a
certain temperature.
(iii) No interaction force is present (iii) Interaction force exist between

between gas particles. gas particles which vary
depending upon conditions.
(iv) Dimensions of gas particles is (iv) Volume reserved by gas particles has
negligible with respect to significant value and can not be
volume of container. neglected normally with respect to
volume of container.
Vander Waal Equation Of Real Gases
The ideal gas equation does not consider the effect of

attractive forces and molecular volume.
Vander Waal corrected the ideal gas equation by

taking the effect of
Molecular volume
Molecular attraction
(A) Volume correction
In the ideal gas equation, PV = nRT.

Where ‘V’ represents the volume occupied by ideal gas
molecules where the molecules can move freely.
In real gases, a part of the total volume is reserved by the

gas molecules.
Actual volume Volume reserved

Real volume of gas = of — by molecules in
container motion.
Effective molar volume for real gas = Vm – b
Where b is vanderwaal’s constant which is the 'excluded
volume' or 'co-volume' per mole.
Calculation of ‘b’ excluded d

volume
d
Illustration of excluded
volume
➢ b = 4 × volume of one molecule × NA
4
➢ b = 4 × 3 π r 3 × NA
Where r = radius of gaseous particle
After Volume Correction -
RT
P=
Vm −b
Important characteristics of Vander Waal constant ‘b’
Unit of 'b' is lit mole–1 or cm3 mole–1 or m3 mol–1
The value of ‘b’ is unique for each gas and it is temperature

independent, Because it depends only on size of molecule.
The value of ‘b’ gives a measure of size of gas particle.
The value of ‘b’ also gives a measure of repulsive forces acting

between gas particles.
‘b’ increases then repulsive forces increases
‘b’ decreases then repulsive forces decreases

(B) Pressure correction
In order to take account the effect of intermolecular forces

of attraction, let us consider a molecule A in the midst of the
vessel.
A
This molecule is surrounded by other molecules in a symmetrical

manner and is being attracted uniformly on all sides by the
neighbouring molecules with the result that this molecule on the
whole experiences no net force of attraction.
Now, consider a molecule B near the side of the vessel,
which is about to strike one of its sides, thus contributing
towards the total pressure of the gas.
B
There are molecules only in one side of the vessel, i.e.
towards its centre, with the result of that, this molecule
experiences a net force of attraction towards the centre of
the vessel.
This results in decreasing the velocity of the molecule, and

hence its momentum. Thus, the molecule does not contribute
as much force as it would have, had there been no force of
attraction.
Thus, the pressure of a real gas measured would be smaller
than the corresponding pressure of an ideal gas.
RT
P= – (pressure correction term)
Vm −b
Combining both factors :
Pressure Correction Term  N* × Z1
n n
Pressure Correction Term  V V
n2
Pressure Correction Term  V2
an2
Pressure Correction Term = 2
V
a
Pressure Correction Term = 2
V𝑚
Where ‘a’ is Vander Waal’s constant.

RT
So, P = – (pressure correction term)
Vm −b
RT 𝑎
P= —
Vm – b Vm2
+ 𝑃+
𝑎𝑛2
(V – nb) = nRT
V2
Vander Waal’s equation for real gas.

Important properties of Vander Waal’s constant ‘a’
atm×L2 Pa×m6
1. Unit of a : S.I. unit :
mole2 mole2
2. The value of ‘a’ has a unique value for each gas and it is
temperature independent.
3. The value of ‘a’ gives a measure of attractive forces that

are present between gas particle.
(attractive forces)  a
(attractive forces)  a
4. As the size of gas particle increases the value of ‘a’ also

increases.
* As the size of gas particle increases polarization also
increases. This increased polarization results in increase of
attraction forces. Hence the value of ‘a’ also increases.
5. As the Molecular weight increases value of ‘a’ also increases.

EXAMPLE
SOLUTION
Ans. A,C,D
EXAMPLE
SOLUTION
Ans. B
Compressibility Factor
The extent to which a real gas departs from the ideal behaviour
may be expressed in terms of compressibility factor (Z).
Definition : Compressibility factor (Z) is defined as the ratio of

molar volume of a gas at given pressure, temperature to the
molar volume of ideal gas at same pressure, temperature.
Vm(real) (PV)real
Z= =
Vm(ideal) (PV)ideal
PVm
Z =
RT
Z < 1
Z = 1
Z > 1
Graph between compressibility factor (Z) and pressure(P)
Case I : Different gases at same temperature (T = 273 k)
H2
Z
He
N2
CO2
H2O
1 Z=1
(ideal gas)
0 P
Low pressure High pressure
(i) At low pressure and constant temperature :
From Vanderwaal Equation
𝑎
𝑃 + V2 (Vm – b) = RT
m
P → low hence, Vm → high
So, “b” can be neglected in comparison to Vm.

Vm – b  Vm
a
But V2m
can't be neglected as P → low.
Thus equation would be
a
P + V2 Vm = RT
m
a
PVm + = RT
Vm
PVm a
+V =1
RT m RT
PVm a
=1–
RT Vm RT
𝐚
Z = 1 –
𝐕𝐦 𝐑𝐓
a
Z=1–
Vm RT
Here, Z < 1
Vm(real)
Z=V <1
m(ideal)
Vm(real) < Vm(ideal)
Hence, at low pressure, attractive forces dominate between real
gaseous particles.
Real gas is easily compressible as compared to an ideal gas.

(ii) At high pressure and constant temperature :
From Vanderwaal Equation
𝑎
𝑃 + V2 (Vm – b) = RT
m
P → high hence, Vm → low

a
So, can be neglected in comparison to P.
V2m
𝑎
𝑃 + V2  P
m
But "𝑏"can't be neglected as Vm → low.

Then vander Waal's equation will be
P(Vm – b) = RT
PVm – Pb = RT
PVm Pb
= RT + 1
RT
Pb
Z=1+
RT
Pb
Z=1+
RT
Here, Z > 1
V (real)
Z = Vm >1
m(ideal)
Vm(real) > Vm(ideal)
Hence At high pressure, repulsive forces dominate between real
gaseous particles.
Real gas is more difficult to compress as compared to an ideal gas.

(iii) For H2 or He gas :
a  0 because molecules are smaller in size or Vander Waal's
forces will be very weak.
P(Vm – b) = RT
PVm – Pb = RT
PVm Pb
= +1
RT RT
Pb  (Z > 1)
Z=1+
RT
z vs p graph :
Variation of Z with P for real gas at any given constant

temperature is given by following graph.
Vander Waal equation :
a
P+ (Vm – b) = RT
V2m
Z=1
P
Case II : Same gas at Different temperature
Z
T3
T2
T1
Z =1
> >
0 P
Z
T3
T2
T1
Z =1
0 P
a
Z=1– Z=1+
Pb
Vm RT RT
EXAMPLE
SOLUTION
Ans. B
Virial Equation
1. Virial equation for real gas :
1 B C D
P = RT + V2 + V3 + V4 + ⋯ ∞
Vm 𝑚 𝑚 𝑚
Where B = 2nd virial coefficient
C = 3rd virial coefficient
D = 4th virial coefficient
The virial coefficients are temperature dependent.

Virial Equation
The virial equation can also be written as :
1 B C
P = RT + 2 + 3 + ⋯∞
Vm Vm Vm
RT B C
P= 1+ + 2 + ⋯∞
Vm Vm Vm
PVm B C
=1+ + + ⋯∞
RT Vm V2m
B C
Z=1+ + + ⋯∞
Vm V2m
Virial Equation
N TE
In low pressure conditions :

P → Low Vm → High
1 1 1
Z=1+B +C +D + ⋯∞
Vm V2𝑚 V3𝑚
So , … … … Can be neglected
𝐁
𝐙=𝟏+
𝐕𝐦
Virial Equation
N TE
In low pressure region : Z = 1 + 𝐵 .

V𝑚
If B = 0  Z = 1  Real gas behave like an ideal gas.
If B < 0  Z < 1  Attractive forces dominate
If B > 0  Z > 1  Repulsive forces dominate

EXAMPLE
A gas has a compressibility factor of 0.5 and a molar volume of 0.4
dm3 mol−1 at a temperature of 800 K and pressure x atm. If it shows
ideal gas behaviour at the same temperature and pressure, the molar
volume will be y dm3 mol−1. The value of 𝐱/𝐲 is ___.
[Use: Gas constant, R = 8 × 10−2 L atm K−1 mol−1]
(JEE ADVANCED 2023)
SOLUTION
Ans. 100
Boyle Temperature
Boyle’s temperature is that temperature at which real gas
behaves like an ideal gas in low pressure conditions.
In low pressure Range : -
If Temperature < TB  attractive forces dominate (z < 1)
If Temperature = TB  no interaction (z = 1)
If Temperature > TB  repulsive forces dominate (z > 1)
In High pressure Range : Z > 1

Boyle Temperature
Calculation of TB
B C
(i) PVm = RT = 1 + V + V2 +. . . . . at low pressure.
m m
negligible
At T = TB , the second initial coefficient should be 0

B=0
𝑎
or b − RT = 0
B
a
 TB = Rb
Liquefaction of Gas
The phenomenon of converting a gas into liquid is known as liquefaction.
A gas can be liquefied by :
(a) Increasing pressure :
An increase in pressure results increase in inter molecular forces
of attraction
(b) Decreasing temperature :

A decrease in temperature results decrease in kinetic energy of
molecules.
Andrews Isotherms
The essential conditions for liquefaction of gases were discovered by

Andrews (1869) as a result of his study of P–V–T relationship for CO2.
Liquefaction of Gas
At temperature (31.1°C) :
The horizontal portion is reduced to a point.
The isotherm at TC is called critical isotherm.
dP
At point O, dV = 0.
The point O is called the point of inflection and critical point.

Critical Parameters or Critical Constants
Critical Temperature (TC)
The temperature above which a system can never be liquefied by

the application of pressure alone i.e. the temperature above
which a liquid cannot exit is called the critical temperature TC.
Critical pressure (PC)
The minimum pressure required to liquefy the system at the

temperature TC is called the critical pressure PC.
Critical volume (VC)
The volume occupied by one mole of the system at critical

temperature, TC and critical pressure, PC is called the critical
volume (VC) of the gas.
Liquefaction of Gas
By solving,
VC = 3b
The value of critical compressibility
factor in terms of Vander Waal’s
𝑎 constants is given by
PC =
27𝑏 2
a
PC VC ×3b
Z= = 27b2
8b
RTC R×27Rb
8𝑎
TC =
27Rb
3
Z= = 0.375
8
𝑎
TB =
Rb
EXAMPLE
The number of statement's, which are correct with respect to
the compression of carbon dioxide from point (a) in the Andrews
isotherm from the following is _________.
[JEE (Main)-2023]
d
Pressure
c b a
Volume
A. Carbon dioxide remains as a gas upto point (b)

B. Liquid carbon dioxide appears at point (c)
C. Liquid and gaseous carbon dioxide coexist between points (b) and (c)
D. As the volume decreases from (b) to (c), the amount of liquid decreases
SOLUTION
Ans. 2

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JEE Advanced Exam

Often surprises by pattern

Conducting body : IIT

Exam :- In the month of May-

Definite shape, definite volume and ORDER.

Highest intermolecular attractive forces

Molecules, atoms or ions are closely packed.

On the basis of order of arrangement of their

It has, LONG RANGE ORDER i.e. there is regular pattern of arrangement of

It has, SHORT RANGE ORDER i.e. there is regular pattern of arrangement

PROPERTY CRYSTALLINE SOLIDS AMORPHOUS SOLIDS

Shape Definite characteristic Irregular shape

Anisotropy Anisotropic in nature Isotropic in nature

PROPERTY CRYSTALLINE SOLIDS AMORPHOUS SOLIDS

Melt at a sharp and

They have a definite

When cut with a sharp

Each point in a lattice is called lattice point.

Lattice points are joined by straight lines to represent the geometry of

Lattice should be infinite.

A lattice gives rise to a crystal when points are replaced by particles

Smallest Repeating Unit

All unit cells must be identical

Tetragonal a=b≠c 𝛼 = 𝛽 = 𝛾 = 90° SnO2, TiO2

Cubic Primitive, Body-centered, Face-centered

Tetragonal Primitive, Body-centered

Orthorhombic or Primitive, Body-centered, Face-centered,

Monoclinic Primitive, End-centered

In this case one particle lies at each corner.

When a number of two-dimensional square close packed layer are placed,

If a square close pack layer is represented by A then the arrangement in

In this case one particle lies at center of the cube.

(1) Packing Fraction

Percentage Packing Efficiency = 0.52×100=52 %

 Void space (100 – 52)= 48 %

Coordination Number (SCC)

Next Nearest neighbours (SCC)

Next to Next Nearest neighbours (SCC)

Nearest neighbour Distance Number

(2) Packing Fraction

Percentage Packing Efficiency = 0.68×100=68 %

 Void space (100 – 68)= 32 %

Nearest Neighbours (Coordination Number)

Next Nearest Neighbours

Next to Next Nearest Neighbours

(2) Packing Fraction

Percentage Packing Efficiency = 0.74×100= 74%

Void space = 100 – 74 = 26 %

Nearest Neighbours (Coordination Number)

Next Nearest Neighbours

Next to Next Nearest Neighbours

Nearest neighbour Distance Number

(A) 0.74 (B) 0.63 (C) 0.52 (D) 0.48

Mass of unit cell

A crystalline solid of a pure substance has a face-centred cubic

The hexagonal close packed layer in 2D with center of spheres at A

It may be noted that it is not possible to place spheres on both

The spheres of second layer shall be placed either on space denoted

If this arrangement is continued in the same order, every fourth

Such arrangement of spheres is called ABCABCABC.... Packing which

Side view diagram showing 1+6+6+1=14 selected atoms in FCC

(A) MX (B) MX2 (C) M2X (D) M5X14

Solution (JEE ADVANCED 2012)

The hexagonal close packed layer in 2D with center of spheres at A be given