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Something
that occupies
space and
has mass

States of Matter
Bulk Properties

Most of the observable characteristics of chemical

systems represent bulk properties of matter

Properties associated
with a collection of a
large number of atoms,
ions or molecules
 Classification of Matter

Matter

States of Matter depends

upon Intermolecular
forces
& thermal energy
Solid Liquid Gas
Intermolecular Forces

Attractive

Intermolecular
Forces

Repulsive
 Intermolecular Attractive Forces
Between polar
Between polar Dipole-dipole molecules
and non-polar attraction
molecules Between non-polar
molecules

Instantaneous
Dipole-induced
dipole-induced
dipole attraction
Attractive dipole attraction
Forces

Between ion
and non-polar
Ion-induced
Ion-dipole molecule
Between ion dipole
attraction
and polar attraction
molecule
 Thermal Energy

Energy of
It is the measure of
a body arising
average K.E.
from motion of
of the particles
its atoms or
of the matter
molecules

Temperature (T)
Thermal Energy ∝ of substance
 Intermolecular Forces vs Thermal Energy

Intermolecular forces tend to Thermal energy tends

keep the molecules together but to keep them apart

The result of balance Three states

between these two forces of matter
Intermolecular Forces vs Thermal Energy

Gas Liquid Solid

Predominance of intermolecular Forces

Gas Liquid Solid

Predominance of thermal Energy

 General Properties of Gaseous State

01 04 Exerts pressure equally in all

No fixed shape & volume
directions

02 Much lower density than the 05 Infinite expansibility & high

solids & liquids compressibility

03 06
Weak forces of attraction Forms homogeneous mixtures
 Pressure
Pressure of the gas is the force exerted by the gas per unit area on
the walls of the container in all directions.

Pressure (P)
1 atm = 1.01325 × 105 Pa

1 bar = 105 Pa = 750 torr = 750 mm of Hg

1 atm = 760 torr = 760 mm of Hg = 76 cm of Hg

1 atm = 1.01325 bar

1 N/m2 = 1 Pa = 10 dyne/cm2
 Volume & Temperature
Volume (V)

The volume of the

1 m3 = 103 L
container is the volume
of the gas sample as
gases occupy the 1L = 103 cm3 or c.c. or mL
entire space available
to them.
1 m3 = 106 cm3

Temperature (T)
Temperature is the
measure of hotness T (K) = t (oC) + 273.15
of the system.
Standard Temperature & Pressure (STP)

T = 273.15 K
STP

P = 1 bar

Molar Volume of an ideal gas = 22.71098 L mol–1

 Gas Laws

Gas Laws Behaviour of gases is governed by some laws

Relationships between measurable properties

pressure, volume, temperature & amount of gases

Interdependent properties,
describes the state of the gas
 Gas Laws

Boyle’s Law Charles’ Law

Gas laws

Gay - Lussac’s
Avogadro’s Law
Law
 Boyle’s Law

1
P ∝ At constant temperature
V

The volume of a fixed amount

(number of moles ‘n’) of gas varies
● T = Constant inversely with its pressure
● Amount of gas = Constant
 Boyle’s Law

1
P ∝ (n, T constant)
V

1
P = k1
V
PV = k1

P1 V2
P1V1 = P2V2 or
P2
= V1

k1 depends on amount &

temperature (T) of gas
 Boyle’s Law

P
P

V 1
V

PV

V
Boyle’s Law at Different Temperatures

P-V Isotherms Constant temperature curves

T2
T3 T3 > T2 > T1
T2
T1
P P
T3
T1
1
V
V
 Charles’ Law

At constant pressure
V ∝ T

The volume of a fixed amount of

● P = Constant gas is directly proportional to its
● Amount of gas = constant absolute temperature.
 Charles’ Law

V ∝ T (P, n constant)

k2 depends on the
amount & P of the gas V = k2T

V
T
= k2

V2 T2
V1
= T1
 Charles’ Law
t
Vt = Vo +
273.15
Vo

For each degree t

rise in temperature, the Vt = Vo 1 +
273.15
volume of a gas
increases by 1 /273.15
of the original volume t + 273.15
of the gas at 0 °C.
Vt = Vo
273.15

Initial volume Final volume

Vo Vt
(at 0 °C ) (at t °C )
 Charles’ Law

t
Vt = Vo +
273.15
Vo

t
Vt = Vo 1 +
273.15

t + 273.15
Vt = Vo
273.15

Initial volume Final volume

Vo Vt
(at 0 °C ) (at t °C )
Absolute Scale of Temperature

= ( Tt
Vt Vo
(
To

Absolute scale or Kelvin scale or

T
thermodynamic scale of temperature

t oC ⇒ Tt = (273.15 + t) K
 Charles’ Law

Volume vs Temperature (K) Volume vs Temperature (oC)

V V
Constant P & n Constant P & n

T (K) -273.15o C t (o C)
 Charles’ Law

T - V Isobars Constant pressure curves

P1

P2 P1 < P 2 < P 3 < P 4

P3
V
P4

t (0C)
(-273.15)
 What Happens at Absolute Zero?

t + 273.15
Vt = Vo
273.15 V

Constant P & n

Let value of t = -273.15

-273.15 oC t (o C)

Vt = Vo - 273.15 + 273.15 = 0
273.15
It means volume of
gas becomes zero at
-273.15 °C
 Volume of Gas is Zero!

Lowest hypothetical or imaginary T at which

Absolute zero
gases supposedly occupy zero volume

Gas will not exist

All the gases get liquified

before this temperature is reached
 Gay-Lussac’s Law

At constant volume
P ∝ T
The pressure of a fixed amount of
a gas is directly proportional
● V = Constant to the temperature.
● Amount of gas = Constant
 Gay-Lussac’s Law

P ∝ T ( V , n constant )

P
P = k3 T
T
= k3

P1 P2
T1
= T2
= k3

k3 depends on amount & V of gas

 Gay-Lussac’s Law
P - T Isochores Constant volume curves

V1

V2

P V3

V4

0 T (K)

V1 < V 2 < V 3 < V 4

 Gay-Lussac’s Law

Constant V & n

P
P
T Constant V & n

P -273.15oC t (oC)
 Avogadro’s Law

V ∝ n Same conditions of P & T

Equal volume of all gases contains

● Same conditions
equal number of molecules
of P & T
 Avogadro's Law

V ∝ n ( P , T constant )

V
V = k4n
n
= k4

V1 V2
n1
= n2

k4 depends on P & T of gas

 Avogadro's Law

V
= Constant
n
V V
V = Constant x n n

n n
 Combining Different Gas Laws

Boyle’s Law Charles’ Law

1
V ∝ V ∝ T
P
At constant n, T At constant n, P

Avogadro’s Law Gay Lussac’s Law

V ∝ n P ∝ T
At constant T, P At constant n, V
 Combining Different Gas Laws
Remember!
nT
V ∝ P Ideal gas is hypothetical.
The real gas follows the gas laws and
nT ideal gas equation only under specific
⇒ V = R
P condition (Low P and high T).

Universal Gas Constant Ideal gas equation (PV = nRT)

is a relation between four
variables and it describes the
Ideal gas state of any ideal gas. Due to
equation
PV = nRT this, it is also known as the
equation of state.
 Values of R

25 8.314 J K-1 mol-1

3

R 2 1.987 cal K-1 mol-1

1
0.0821 L atm K-1 mol-1
12
Ideal Gas Equation in Terms of Density

m
PV = nRT n=
M

m ● m = Mass of gas
PV = RT
M ● M = Molar mass of gas
● V = Volume of the gas
m
PM = RT ● d = Density of gas
V

m
PM = dRT d=
V
 Density of Gases on Compression

Pressure Balloon Volume of Pressure

squeezes gas inside it inside

As the balloon cannot

Gases become denser ( Density )
withstand
the added pressure, it
bursts

Same number of molecules

occupy smaller space
 Gauge Pressure (Pg )

The difference of the actual pressure (P)

& the atmospheric pressure (Pa)

P Pa = Pg
 Measurement of Pressure: Barometer

Measures atmospheric Determining the height of a mercury

pressure by column supported in a sealed glass tube
 Mercury Barometer

Downward pressure of Outside atmospheric

mercury in the column
= pressure

Perfect vacuum Patm A

Mxg P0 = Patm

At equilibrium
Patm A = Mg

P0
P0
Mg
 Mercury Barometer

Mercury column inside the

Net forces are balanced
capillary comes to rest

Applying force balance

M=ρ×V&
Patm × A = M × g
V=A×h

⇒ Patm × A = (ρ × g × h) × A ⇒ Patm = ρgh

 Faulty Barometer
In a faulty barometer, the region above the mercury column is not
completely a vacuum and contains trapped air that creates some
additional pressure.

Actual Pressure if some gas is trapped instead of vacuum?

PoA = mg + Pgas A Pgas × A

Pressure due
to trapped air
where, P0 = ρgh + Pgas

Hence, ρgh = P0 – Pgas

P0 × A
Mg
 Manometer

Instrument used for measurement of pressure of gas

 Manometer

| PExternal - PGas | ∝ Δ Height of mercury column

 Partial Pressure of a Gas Component

The pressure that occupies the same volume as the

a component of
mixture at the same temperature
gas would exert if it

Mixture of non reacting gases

 Dalton’s Law of Partial Pressures

For a non reacting gaseous mixture total pressure

of the mixture is the summation of partial pressure
of the different component gases.

PT = P1 + P2 + …..

Partial pressure of a gas is independent

of the other gases present in the mixture
Partial Pressure in Terms of Mole Fraction

● Suppose at temperature T, three gases enclosed in

volume V, exert partial pressures P1, P2 and P3

n1RT
P1 = V

n2RT
P2 = V

n3RT
P3 = V
Partial Pressure in Terms of Mole Fraction
Dalton’s law

PTotal = P1 + P2 + P3

n1RT n2RT n3RT

PTotal = + +
V V V

RT
PTotal = (n1+ n2 + n3)
V

nTotal = n1 + n2 + n3
Partial Pressure in Terms of Mole Fraction

On dividing P1 by PTotal,

P1 n1 RT V
PTotal
= n1 + n2 + n3 × V × RT

P1 n1
PTotal
= nTotal
= 𝛘1

𝛘1 Mole fraction of gas 1

Partial Pressure in Terms of Mole Fraction
Similarly,

P2 P3
PTotal
= 𝛘2 and = 𝛘3
PTotal

Pi = 𝛘 PTotal
i

𝛘i Mole fraction of the ith component

gas in the gaseous mixture
Average Molar Mass of Gaseous Mixture

M1n1 + M2n2
Mavg =
n1 + n 2

● M1 = Molar mass of first gas

● M2 = Molar mass of second gas
● n1 = Moles of first gas
● n2 = Moles of second gas
 Vapour Pressure

Pressure exerted by the

vapour in equilibrium with liquid,
at a given temperature

Vapour pressure doesn’t change if

the temperature remains constant
 Utility of Dalton’s Law
Gases are generally collected over water
and thus, become moist. In such cases,
Dalton’s law is useful in calculating the
pressure of gas. PT = Pg + Pw

Pressure of
water vapour
Pressure of
dry gas

Pressure exerted by saturated water

vapour is called Aqueous tension
 Connecting Vessels

n1 & n2 are moles of two non-reacting gases X & Y

V1 V2
Gas X Gas Y
P1 P2
T T
n1 n2

Container 1 Container 2
 Connecting Vessels

Before opening P1V1 P2V2

valve;
n1 + n 2 = RT
+ RT

After opening
valve;
Pfinal V1 + V2 = n1 + n2 RT

Partial pressure becomes

Gas flows till its
equal in both container
 Connecting Vessels

To calculate moles of gas ‘X’ in each container

PX
1
= PX
2

● Px: Partial pressure of X

Let ‘a’ moles of gas ‘X’ flow from container 1 to 2

RT1 a RT2
n1 - a
V1
= V2
 Remember!!

Open rigid container: n 1T 1 = n 2T 2 P & V are constant

n1RT1 n2RT2
Closed rigid container:
P1
= P2
V is constant

For Ballon: Pexternal = Pinternal

 Diffusion

Net spontaneous flow of gaseous molecules

from a region of higher concentration (higher
partial pressure) to a region of lower
concentration (lower partial pressure)
 Diffusion
Effusion

Flow of
gaseous
molecules

Gas escapes
Region of through
Region of high a small orifice
higher partial
concentration
pressure to
to lower
lower partial
concentration
pressure
 Graham’s Law of Diffusion

Under similar conditions of pressure

& temperature, the rate of diffusion of
gases are inversely proportional to the
square roots of their densities (d)

1
Rate of diffusion (rgas) ∝ d
Graham’s Law of Diffusion

General form of Graham’s law

PA
rgas ∝
MT

P Partial pressure of gas

A Area of orifice

M Molar mass of gas

T Temperature of gas
 Graham’s Law of Diffusion

Since, PM = dRT

P and T constant

rA dB MB
= = = (V.D.)B
rB dA MA (V.D.)A

V.D. Vapour density

 Importance of Graham’s Law

Separation of gases
Separation of
having different
isotopes
densities

Rate of diffusion is inversely

proportional to square root of
molar mass. So, after doing
diffusion, we get a mixture which
is rich in lighter isotope. If we In determining
repeat process of diffusion densities and
several times, then we get a molecular masses of
mixture which is very rich in lighter Molecular masses of unknown
isotope. Hence, we can separate
unknown gases gases can be determined by
lighter gas and heavier gas comparing its diffusion rate
with that of any known gas.
Kinetic Molecular
Theory of Gases
 Postulates / Assumptions of KTG

A gas consists of tiny spherical particles

called atoms/molecules of the gas which
are identical in shape & size (mass)

The volume occupied by the

particles is negligible in comparison
to the total volume of the gas

Gaseous molecules are always in

random motion and collide with each
other and with the walls of the container
 Postulates / Assumptions of KTG

Pressure is due to the collisions of the Elastic collisions

particles with the walls of the container

Newton’s laws of motion are applicable

on the motion of the gaseous particles

Attractive or repulsive
For an Ideal gas;
forces
= zero
 Postulates / Assumptions of KTG

Effect of gravity is negligible

on the molecular motion

The average K.E. of the Absolute temperature

gaseous molecules
∝ of the gas
Postulates / Assumptions of KTG

Average K.E. ∝ T

3 Depends only on temperature

Average K.E. = k T and not on nature of the gas
2 B

kB Boltzmann constant

T Temperature (K)
 Boltzmann Constant

R
kB = NA

kB = 1.3807 x 10-23 J/K

R Universal gas constant

NA Avogadro number
 Molecular Speed
They collide with Change in their
Gas molecules are
each other and with speed &
always in
the walls of the redistribution of
continuous motion
container energy

Speed & energy of all the molecules

at any instant are not the same

Measuring speed of an individual

molecule is not possible
 Molecular Speeds

Types of molecular speeds

Average Most Probable Root Mean

speed speed Square speed

uavg ump urms

 Average Speed

u1 + u2 + …..+ uN
Arithmetic mean of the speeds uavg =
N
of different molecules of the gas

uavg Average speed of

molecules
1
8RT 2
uavg = 𝛑M Total number of
N
molecules
 Most Probable Speed

Speed possessed by the maximum

number of gas molecules

1
2RT 2
ump = M
 Root Mean Square Speed

1
Square root of the mean of 3RT 2
the squares of the speeds urms = M
possessed by the gas molecules

1
u12 + u22 + …..+ uN2
urms = 2
N

urms Root of mean of square of speeds

N Total number of molecules

 Relationship Between the Different Types of Speeds
For a particular gas at the same temperature (T),

urms : uavg : ump

1 1 1
3RT 2 8RT 2 2RT 2 ● T = Temperature in Kelvin
M
: :
𝛑M M ● M = Molar mass in kg
● R = 8.314 J/mol K
1
: 8 2 :
3 2
𝛑

Conclusion:
1.224 : 1.128 : 1 urms > uavg > ump
Maxwell-Boltzmann Distribution of Speeds

Based on the theory of probability

Gives the statistical average of the speeds

of the whole collection of the gas molecules
 Maxwell's Distribution of Molecular Speeds

Fraction of
molecules 3 - Mu2
1 dN
with speed N du
= 4𝛑 M 2
e 2RT u2
between ‘u’ & 2𝛑RT
‘u + du’

N Total number of gas molecules

M Molar mass u Speed

 Maxwell-Boltzmann Distribution of Speeds

u2 term dominates

Fraction of molecules
per unit speed interval Exponential term
dominates
1 dN
N du

u
Maxwell-Boltzmann Distribution of Speeds

At a particular temperature,

Individual speed of molecules keeps changing

Distribution of speeds remains the same

 Maxwell-Boltzmann Distribution of Speeds

Maximum fraction of molecules possess a speed

corresponding to the peak of this curve referred to as ump

Actual distribution of molecular

speeds in a gas depends on

1 dN
N du

ump Temperature Molar Mass

u
 Maxwell-Boltzmann Distribution of Speeds
T1
T1 < T 2
T2
Fraction of molecules
(ump)2 > (ump)1
per unit speed interval

1 dN
N du

(ump)1 (ump)2
u

Molecular motion Entire curve shifts

Temperature
becomes rapid towards the right
Distribution of Speeds for Different Molar Masses

M1 > M2

1 dN
N du
M1 M2

(ump)1 (ump)2
u
Maxwell's Distribution of Molecular Speeds
Most probable speed (ump)

Average speed (uavg)

Root mean square speed (urms)

1 dN
N du

u
 Why Average Velocity is Towards the Right?
(ump)
uavg is slightly greater
(uavg)
than the ump

(urms)

1 dN
N du No limit for maximum
velocity

Least possible
velocity = 0 u
Derivation of Kinetic
Gas Equation
Derivation of Kinetic Equation

uy

y u

ux
x
uZ

z
Components of velocity

>
>
>
u = u x i + u y j + u zk
 Abbreviation / Symbol Used

Length of an edge of the cube = l

Number of molecules = N

Mass of a molecule = m
 Consider Collision with Face ABCD
y
uy

>
F C u
pi = mux i

>
D pf = -mux i
G ux
B x

H A uZ
z

|Δp| = >
2mux i
Between Two Successive Collisions with Face ABCD

Distance travelled = 2l

2l
Time taken = ux

ux
Frequency =
2l
 Derivation of Equation

Δp ux mux2
F = 2mux
Δt 2l l

m
Fx, Total = l
{ux 2 + ux 2 + ……………………… ux 2 }
1 2 N
 Derivation of Equation

2 2 2
u x + u x + ………... u x
Average value
of ux2
= ux2 = 1 2 N

Force due to all m

the molecules (Fx)
= l
{Nux2 }
 Derivation of Equation

Average of all three components of velocity are equal

as the motion is totally random in all directions

ux2 = uy2 = u z2

u2 = ux2 + uy2 + u z2 = 3ux2

 Derivation of Equation

m
F = N 1 u2
l 3

F 1 mN 2 Volume of the
P = = 3 l3
u
container ‘V’ = l 3
l2

1
PV = 3
mNu2
 Derivation of Equation

Root mean square speed

urms = u2

u12 + u22 + u32 + …………..+ uN2

u2 =
N
 Deriving urms from Kinetic Gas Equation

1 mNu 2
PV
PV
PV = PV rms
3 PV
Kinetic Gas Equation

3PV 3PV
urms 2
= mN
= mnNA
N = nNA

3nRT For an ideal gas

urms 2
= mnNA
PV = nRT

3RT
urms 2
= mNA
Deriving urms from Kinetic Gas Equation

3RT
urms2 = mNA = M
M

urms = 3RT
M
 Deriving urms from Kinetic Gas Equation
J = Nm
N = kgms-2
R in JK-1mol-1 M in kg mol-1

(Nm)K-1mol-1 × K (kgms-2m)
Unit of urms = =
kg mol-1 kg

= m2s-2 = ms-1
 Collision Frequency (Z)

ū
σ
Collision σ
cross-section is an
area of an imaginary Collision
sphere of radius cross-section
'σ' around the
molecule within which The volume swept by a single
the center of another molecule in unit time is
molecule cannot
penetrate. V = (πσ2)ū

Average speed
 Collision Frequency (Z)

If N* is the number of molecules per

unit volume, then the number of The number of collision made by a
molecules within the volume V is: single molecule in unit time will be

N = VN* Z = N

= (πσ2ū)N* = (πσ2ū)N*
 Collision Frequency (Z)

In order to account
for the movements of
On an average, molecules collide
all molecules, we must while approaching each other
consider the average perpendicularly then the average
velocity along the line of velocity along their centers is 2ū
centers of two colliding
molecules instead of the
average velocity of a
single molecule.
 Collision Frequency (Z)

ū
Number of collision made by a
single molecule with other
molecules per unit time is:
ū
2ū
Z1 = 𝝅σ2 (ūrel)N*

= 2 𝝅σ2ūN*
 Collision Frequency (Z)

ū
The total number of bimolecular
collisions Z11 per unit volume per
unit time is:
ū
2ū 1
Z11 = (Z1N*)
2

1
= 2 ( 2 𝝅σ ūN )N
2 * *

1
= 𝝅σ2ū(N*)2
2
Mean Free Path

Average distance
travelled by a
particle between
two successive
collision

Between two collisions,

particles travel in linear path
 Mean Free Path

Average distance travelled per unit time

λ = Number of collisions made by a single
molecule per unit time

ū
λ = Z1

ū
or λ =
2𝝅σ2ūN*

1
λ =
2𝝅σ2N* 107
 Mean Free Path

At constant V P∝T T = constant λ = constant

P

No effect of T or P variation on λ at constant V

108
 Real Gas

Gases which do not obey Ideal gas

law under all conditions of T & P

Real gas
Ideal gas
Pressure

Volume
 What is Compressibility Factor (Z)?

A measure of the deviation of

real gases from ideal behaviour

Vm is the Molar Vm, real

Volume = Z
Vm, ideal

Measured at the same T & P

 Compressibility Factor

RT Vm, real PVm

Since, Vm, ideal = P
Z = =
Vm, ideal RT

Ideal gas
Z=1 PVm = RT
behaviour

Z
Deviation
Z≠1 PVm ≠ RT from ideal
behaviour
 Compressibility Factor (Z)

At very low pressure Z ≈ 1

Attractive forces ≈ Repulsive forces

At intermediate pressure Z < 1 Negative deviation

Attractive forces > Repulsive forces Gas easy to compress

 Compressibility Factor (Z)

At high pressure

Z > 1 Positive deviation

Attractive forces < Repulsive forces

Gas difficult to compress

 Different T, Same Gas

T Collision Repulsion Z

T4 T
3
T2 T1 > T2 > T3 > T4

T1
Z=1
PVm
Z=
RT

P
 Boyle Temperature (Tb)

Boyle point or temperature

Temperature at which a real gas

behaves like an ideal gas at low
pressure
 Boyle Temperature

Attraction between
Tb ∝ molecules

Tb depends on the
nature of the gas

( Tb )CO, CH
4
> 273 K ( Tb ) H , He
2
< 273 K
 Conclusion

Z = 1

Real gas at
Ideal gas
T = Tb

Low pressure
region
Exceptional Behaviour of H2 and He

Z > 1

T (273 K) > Tb, gas

Repulsive forces dominate

 Conclusion

Z < 1

High P Never

Real gas

Low P If T < Tb, gas

 Real Gases

Volume of gas particles is not

negligible w.r.t the container

On liquefaction, occupy a finite volume

 Real Gases

Interparticle forces of attraction are present

Ideal gas Real gas

 van der Waals Equation of Real Gases
Ideal gas equation
is affected by
Pideal Videal = nRT

Preal Vreal ≠ nRT

Intermolecular Molecular
forces volume

(Preal ± __ ) (Vreal ± __ ) = nRT

 Pressure Correction

Intermolecular Attractive forces are present

Speed during
collisions Momentum Force applied Pressure
will be reduced

Pideal > Preal

 Pressure Correction

Molecules are dragged back

by other molecules
due to intermolecular
attractive forces

Pressure
Pideal = (Pactual + __ ) Pideal = Pactual + correction term
 Pressure Correction

Correction Number of molecules n

term ∝ attracting the colliding molecule ∝ V

Correction Concentration of the n

term ∝ colliding molecules
∝ V
 Pressure Correction

Correction n n Correction n2
term ∝ X ∝
V V term V2

Correction an2
term = V2

a van der Waals constant

‘a’ depends on force of attraction

 Unit of “a”

an2
Pcorrection = V2

Pcorrection [V]2
a =
n2

Unit = atm L2 mol-2

 Significance of ‘a’

Stronger the forces of attraction,

greater will be ‘a’

As a ,
Liquefaction

Value of ‘a’ depends on

the nature of the gas
 Remember!!

a Boiling Point

a (Polar molecules) > a (Non polar molecules)

For non polar molecules

van der
Surface area a
Waals forces
 Volume Correction
Volume available for free
Videal = movement of the gaseous
molecules
V Volume of container

Volume not available

Videal = V - for free movement

Videal = Vcontainer - Vexcluded

Volume that is not available for free

Vexcluded movement is called excluded volume
 Remember!!

For ideal gas Vi = V

For real gas Vi ≠ V

All volume is not available

for free movement
 Volume Correction
2r For a pair
Excluded of molecules
volume
4
Vexcluded = 3
𝛑 (2r)3

For a
molecule,

1 4 4
Vexcluded = 2 3
𝛑 (2r)3 = 4
3
𝛑 r3
 Volume Correction

b Excluded volume per mole of gas b van der Waals constant

‘b’ depends on size of the gas molecules

b = 4 ✕ Volume of individual molecules ✕ NA

b = 4 ✕ 4 𝛑r3 ✕ NA b ∝
Size of the
3 molecules
 Volume Correction and Unit of “b”

For n moles [V] = [nb]

Vexcluded = nb [V]
b = n

Videal = V - nb
Unit = L mol-1
 Remember!!

If two gases have the same ‘b’ Gas having the larger value of ‘a’
but different ‘a’ then will occupy lesser volume

Distance between
Force of attraction
the molecules
 van der Waals Equation of Real Gases

an2
P+
V 2
[ V - nb ] = nRT

Pressure Volume
correction term correction term

● a & b = van der Waals constants

● n = Number of moles of gas
 Verification of
van der Waals equation
 Compressibility Factor

Real Gas

Z Ideal Gas
Z=1

P
 van der Waals Equation

a
P+ (Vm - b) = RT
Vm 2

V
Vm = n = Volume of 1 mole of gas
 Verification of van der Waals Equation

1 At Low pressure (moderate temperature)

can be neglected in comparison to

Pressure Vm b
Vm

a a
P+ Vm = RT PVm +
Vm
= RT
Vm 2

PVm a
+ = 1
RT VmRT
 Verification of van der Waals Equation

PVm a
Z = 1 -
RT VmRT

Z < 1

Real gas is more compressible

as compared to an Ideal gas
Verification of van der Waals Equation

2 At high pressure (moderate temperature)

Pressure Vm

b can’t be neglected in comparison to Vm

a
Pressure can be neglected
Vm2
 Verification of van der Waals Equation

Pb
P (Vm - b) = RT Z = 1 +
RT

PVm - Pb = RT Z > 1

PVm Pb Real gas is less compressible

= 1+
RT RT as compared to an Ideal gas
Verification of van der Waals Equation

3 Real gas having very large molar volume

a
P+ (Vm - b) = RT
Vm 2

b can be neglected in comparison to Vm

a
Vm is very large can be neglected
Vm2
 Verification of van der Waals Equation

PVm ≈ RT 4 H2 / He

Z ≈ 1 a ≈ 0

Pb
Z = 1 + > 1
Ideal gas condition RT
 Liquefaction of Gases

Phenomenon Occurs when the

of converting a intermolecular forces of
gas into liquid attraction become high

Gas liquification

Pressure Temperature
Andrew’s Isotherm

P - V relationship
(isotherms)
for CO2
 Andrew’s Isotherm

Region CD Compression of liquid at constant T

D

For a small volume change, high pressure is required

C 13.1 ℃ B

A
V
 The ‘Dome’ of Andrew’s Isotherm
Different isotherms for
the same gas

50 ℃

31.1 ℃

P
21.5 ℃
30.98 ℃
13.1 ℃

V
 Critical Isotherm
K

Critical point
J
Pc

P Critical Point
I
A point on the
critical isotherm
where gas & liquid
VC are in equilibrium
V
 Critical Isotherm
Critical Point
H K (Point of inflection)
D
∂P ∂2P
= =0
∂V ∂V 2

P Critical isotherm
G 21.5 ℃ F
I
C 13.1 ℃ B At critical point
E
A
V ΔHvap = 0
 Critical Temperature (T C )

Temperature above which the gas cannot

be liquefied, regardless of the pressure

At Tc
Below Tc

Liquid passes into the

Two phases can gaseous phase continuously
be distinguished and the boundary between
the two phases disappears
Continuity of States

At the critical temperature

(TC), the densities of the
liquid & the vapour phase
becomes identical

No distinction between
vapour & liquid
 Density Variation with Temperature

At T1,

Density of liquid > Density of vapour

At TC,
P
Tc
T1 Density of liquid = Density of vapour

Gas can be
At T1 < TC
liquefied
 Density Variation with Temperature

In liquid-vapour
Temperature
equilibrium region

Density of liquid

Density of vapour
 Did you know?

Term vapour is T < Tc

used when

Term gas is T > Tc

used when
 Critical Temperature (T C )

M
At T > TC
50 ℃

Gas can’t be liquefied

Pc for any amount of pressure
P

Vc
V
Significance of Critical Temperature

As intermolecular forces
increase, Tc also increases

Ease of
liquefaction
Critical Pressure (PC ) and Critical Volume(VC)

Minimum pressure which must be applied at

critical temperature to convert a gas into liquid

Volume occupied by one mole of a gas at

critical temperature (TC) & critical pressure (PC)
 Critical Constants

Critical Temperature (TC)

Critical Critical Pressure (PC)

constants

Critical Volume (VC)

Critical Constants in Terms of van der Waals Constants

VC = 3b
Value of VC is not reliable as it
can’t be measured properly

a
PC =
27b2
Determine van der Waals constants
8a (‘a’ & ‘b’) using TC & PC
TC =
27Rb
 Compressibility Factor & Critical Constants
For every gas,

a
× 3b
PCVC 27b2 3
ZC = = = 8
= 0.375
RTC 8a
R×
27Rb
Virial Equation of State

Generalised equation
of gaseous state

Z is expressed in power series

expansion of P or 1
Vm
 Virial Equation of State

PVm B C D
Z = = 1+ + + + …………...
RT Vm V m2 V m3

● 1 ⇒ First virial coefficient

● B ⇒ Second virial coefficient
● C ⇒ Third virial coefficient
● D ⇒ Fourth virial coefficient
 van der Waals Equation in Virial Form

n 2a
P + [V - nb] = nRT
V2

For 1 mol, V = Vm

a
P + [Vm - b] = RT
Vm 2
 van der Waals Equation in Virial Form
RT a Also,
P = -
Vm - b V m2 PVm
Z =
Vm RT
Multiplying both sides by
RT
PVm Vm a Vm a
= - Z = -
RT Vm - b VmRT Vm - b VmRT
van der Waals Equation in Virial Form

1 a
Z = -
1- b VmRT
Vm

Using binomial expansion formula,

1
1-x
= (1 - x)-1 = 1 + x + x2 + x3 + ….

where x << 1
 van der Waals Equation in Virial Form

b b2 b3 a
Z = 1 + + + + ….. -
Vm V m2 V m3 VmRT

1 a b2 b3
Z = 1 + b - + + + …..
Vm RT Vm 2 Vm 3
 van der Waals Equation in Virial Form

1 a b2 b3
Z = 1 + b - + + + …..
Vm RT Vm 2 Vm 3

Comparing van der Waals equation with Virial equation

B C D
Z = 1 + + + + …..
Vm V m2 V m3
 van der Waals Equation in Virial Form
a
B = b-
RT At low pressure, Vm will be very large.

1 1
Hence, , , … and higher terms can be
C = b2
Vm 2 Vm3
neglected.

D = b3 a 1
Z = 1+ b-
RT Vm
Only ‘B’ is temperature dependent,
all other virial coefficients are
independent of temperature
 van der Waals Equation in Virial Form

At low pressure, Vm will be very large.

1 1
Hence, , , … and higher terms can be neglected.
Vm2 Vm3

a 1
Z = 1+ b-
RT Vm
 van der Waals Equation in Virial Form

a
If b- = 0
RT

a
Then, T =
Rb

And Z = 1
van der Waals Equation in Virial Form

a
At T = Rb
At low pressure

Gas will behave as an ideal gas

This temperature is known as the

Boyle temperature (Tb)
 T1
TB

(T1 > TB > T2)

T2

Z
Z = 1 (ideal gas)