Concept of Temperature

The sensation of heat or cold is a matter of daily experience. By touching, we can

say whether a substance is hotter or colder than ourselves. The hot body is said
to possess a higher temperature than a cold body.
When two bodies are brought in contact with each other through a wall, it is found
that, there is a change in their properties, such as volume, pressure etc., due to
exchange of heat. Finally, a state is attained after which there is no further change
as long as external conditions do not change. This is called an equilibrium state
of the combined system. The two bodies are then said to be in thermal equilibrium
with each other.
“Temperature of a system can be defined as the property that determines
whether or not the body is in thermal equilibrium with the neighboring
systems.” If a number of systems are in thermal equilibrium, this common
property of the system can be represented by a single numerical value, called the
temperature. If the two systems are not in thermal equilibrium, they are at
different temperatures.

Zeroth law
“Of three systems, A, B and C, if A and B are separately in thermal
equilibrium with C, then A and B are also in thermal equilibrium with one
another.”

Thermometry
The branch of heat relating to the measurement of temperature of a body is
called thermometry. Thermometer is an instrument to measure the temperature
of a body.
Types of thermometer
The types of thermometers are:
(i) Liquid thermometer
(ii) Gas thermometer
(iii) Resistance thermometer
(iv) Thermoelectric thermometer
(v) Radiation thermometer
(vi) Vapor pressure thermometer
(vii) Bimetallic thermometer
(viii) Magnetic thermometer

Among various types of thermometer, we will discuss about two thermometers.

One is constant volume air thermometer which is a gas thermometer, and
another one is platinum resistance thermometer, which is a resistance
thermometer. Further, a slight discussion will be given on thermocouple.

Jolly’s Constant Volume Air Thermometer

It consists of a glass bulb B, connected to a
Glass tube. The end of the glass tube is connected
to the reservoir of mercury through a rubber tube.
M is a fixed mark on the glass tube. The difference
in the levels of mercury at R an M is observed by a
scale S. The bulb B is filled with 1/7 of its volume
with mercury so that the expansion of the bulb B
is compensated by expansion of mercury in the
bulb. This keeps the volume of air in the bulb up to
the mark M constant.
Working: (a) The bulb B is kept in melting ice.
The reservoir R is suitably adjusted so that the level
of mercury stands at M.
Suppose the difference in level between R and M is ℎ𝑜 . If P is the atmospheric
pressure, then
𝑃𝑜 = 𝑃 + ℎ𝑜 ………………………………………….(1)
Where, 𝑃𝑜 = Pressure of the air in B.

(b) The bulb B is kept in boiling water. The reservoir R is adjusted so that the
level of mercury is at M. Let ℎ1𝑜𝑜 be the difference in levels. Then,
𝑃1𝑜𝑜 = 𝑃 + ℎ1𝑜𝑜 …………………………………….(2)
Where, 𝑃1𝑜𝑜 = Pressure of the air in B.

(c) The bulb B is kept in the bath whose temperature is to be measured. The
reservoir R is adjusted so that the level of mercury is at M. Let ℎ𝑡 be the difference
in levels. Then,
𝑃𝑡 = 𝑃 + ℎ𝑡 ………………………………………….(3)
While volume remaining constant, the pressure increases according to the relation
𝑃𝑡 = 𝑃𝑜 (1 + 𝛾𝑡) ……………………………………..(4)
Also, 𝑃1𝑜𝑜 = 𝑃𝑜 (1 + 100𝛾) …………………………….….(5)
From eq(4),
𝑃𝑡 − 𝑃𝑜 = 𝑃𝑜 𝛾𝑡 ………………………………………. (6)
And 𝑃1𝑜𝑜 − 𝑃𝑜 = 𝑃𝑜 𝛾 × 100 ……………………………. (7)
Dividing eq(6) by (7),
𝑃𝑡 −𝑃𝑜
𝑡=( ) × 100 …………………………………(8)
𝑃1𝑜𝑜 −𝑃𝑜
𝑃+ℎ𝑡 −𝑃−ℎ𝑜
Or, 𝑡=( ) × 100
𝑃+ℎ1𝑜𝑜 −𝑃−ℎ𝑜
ℎ𝑡 −ℎ𝑜
Or, 𝑡=( ) × 100 ………………………………..(9)
ℎ1𝑜𝑜 −ℎ𝑜

Hence t can be calculated.

Platinum Resistance Thermometer
A platinum resistance thermometer
consists of a pure platinum wire wound in
a double spiral to avoid inductive effects.
The wire is wound on a mica plate. The
two ends of the platinum wire are
connected to thick copper leads (for lower
temperature) and connected to the binding
terminals B1, B2. For higher temperature,
the leads are of platinum. C1 and C2 are
the compensating leads exactly similar and
of the same resistance as the leads used
with platinum wire. The platinum wire and the compensating leads are enclosed
in a glazed porcelain tube. The tube is sealed and binding terminals are provided
at the top. The leads pass through mica disc which offer the best insulation and
also prevent convection currents.
The resistance of a wire at 𝑡 ℃ = 𝑅𝑡 and 0 ℃ = 𝑅𝑜 . These resitances are
connected by the relation
𝑅𝑡 = 𝑅𝑜 (1 + 𝛼𝑡 + 𝛽𝑡 2 ) …………………………….….(1)
Here, 𝛼 and 𝛽 are constants and they depend on nature of the material used. The
resistance of the platinum wire is determined at different fixed points: (i) melting
point of ice, (ii) boiling point of water, (iii) boiling point of Sulphur 444.6 ℃ for
high temperature measurement, and (iv) boiling point of oxygen -182.v ℃ for low
temperature measurement.
Putting 100 ℃ and 444.6 ℃ in eq (1), we get
𝑅100 = 𝑅𝑜 (1 + 𝛼 × 100 + 𝛽 × 1002 ) .…………….….(2)
And 𝑅444.6 = 𝑅𝑜 (1 + 𝛼 × 444.6 + 𝛽 × 444.62 ) ……….….(3)
The values of 𝛼 and 𝛽 can be determined by solving the simultaneous equ(2) and
(3). Now, from eq(1), neglecting 𝛽𝑡 2 ( as 𝛽 𝑖𝑠 𝑣𝑒𝑟𝑦 𝑠𝑚𝑎𝑙𝑙), we get

𝑅𝑡 = 𝑅𝑜 (1 + 𝛼𝑡) …………………………………(4)
Or, 𝑅100 = 𝑅𝑜 (1 + 𝛼 × 100)
So, from eq(4), 𝑅𝑡 − 𝑅𝑜 = 𝑅𝑜 𝛼𝑡 ………………………………….(5)
Or, 𝑅100 − 𝑅𝑜 = 𝑅𝑜 𝛼 × 100 …………………………(6)
Dividing equ(5) by (6),
𝑅𝑡 −𝑅𝑜 𝑡
=
𝑅100 −𝑅𝑜 100
𝑅𝑡 −𝑅𝑜
So, 𝑡=( ) × 100 ……………………………..(7)
𝑅100−𝑅𝑜

Knowing the values of 𝑅𝑜 , 𝑅100 , and 𝑅𝑡 , 𝑡 can be calculated. To measure the

resistance of platinum accurately, Callendar and Griffith’s Bridge is used.

Callendar and Griffith’s Bridge

This is modified form of Wheatstone’s bridge.
𝑃 and 𝑄 are two resistances of equal value,
and S is a standard fractional resistance box.
The platinum wire is connected with one of
the arms of Wheatstone’s bridge. The
compensating leads are connected in series
with the resistance 𝑆. XY is the bridge wire of
length 2𝑙 and has the resistance per unit length
𝜌. Let 𝑟 be the resistance of the compensating
leads as well as the leads of the platinum wire.
O the mid-point of the bridge wire. 𝑅 is the
resistance of the platinum wire at the
temperature of the bath. Let D be the
balance point, with some suitable value of 𝑆,
𝑥 cm to the left of O. Then, length
𝑋𝐷 = 𝑙 − 𝑥, and 𝐷𝑌 = 𝑙 + 𝑥
We know from the principle of Wheatstone’s bridge,
𝑃 𝑅 + 𝑟 + (𝑙 − 𝑥)𝜌
=
𝑄 𝑆 + 𝑟 + (𝑙 − 𝑥)𝜌
As 𝑃 = 𝑄, then 𝑅 + 𝑟 + (𝑙 − 𝑥)𝜌 = 𝑆 + 𝑟 + (𝑙 + 𝑥)𝜌
After solving, we get,
𝑅 = 𝑆 + 2𝑥𝜌 ………………………..(8)
(If the balance point is to the right, then 𝑅 = 𝑆 − 2𝑥𝜌). Knowing the values of 𝑆,
𝑥 and 𝜌, we can measure 𝑅𝑡 . (For 𝑅100 = 𝑆100 + 2𝑥100 𝜌. For 𝑅𝑜 = 𝑆𝑜 + 2𝑥𝑜 𝜌)
Correction: The temperature t measured by eq(7) is not accurate, because 𝛽𝑡 2 is
neglected. Therefore, the correct temperature 𝜃 will differ from 𝑡. Here,
𝑅𝑡 −𝑅𝑜
𝜃−𝑡 =𝜃−( ) × 100
𝑅100−𝑅𝑜

Taking, 𝑅𝑡 = 𝑅𝑜 (1 + 𝛼𝜃 + 𝛽𝜃 2 ) and 𝑅100 = 𝑅𝑜 (1 + 𝛼 × 100 + 𝛽 × 1002 ), we

get
𝑅𝑡 −𝑅𝑜 𝛼𝜃+𝛽𝜃2
=
𝑅100 −𝑅𝑜 𝛼×100+𝛽×1002

𝛼𝜃+𝛽𝜃2
𝜃−𝑡 =𝜃− × 100
𝛼×100+𝛽×1002

𝛼𝜃+100𝛽𝜃−𝛼𝜃−𝛽𝜃2
=
𝛼+𝛽×100

100𝛽𝜃−𝛽𝜃2
=
𝛼+𝛽×100

−(100)2 𝛽 𝜃2 𝜃
= [(100)2 − ]
𝛼+𝛽×100 100

𝜃2 𝜃
So, 𝜃 − 𝑡 = 𝛿[(100)2 − ]
100

−(100)2 𝛽
Where, 𝛿=
𝛼+𝛽×100

The value of 𝛿 for pure platinum is nearly 1.5. knowing the value of t from equ(7),
we can measure 𝜃. This thermometer can measure from −200℃ to 1200℃.
Problem 1: (i) The pressure exerted by the air in a constant volume air
thermometer is 100 cm Hg at ice point and 136.6 cm at the steam point. When
the thermometer is inserted in a hot bath, the pressure of air is 131.11 cm Hg.
Calculated the Celsius temperature of the bath.
(ii) The resistance of the platinum wire of a platinum resistance thermometer at
the ice point is 5 ohms and at the steam point 5.93 ohms. When the thermometer
is inserted in a hot bath, the resistance of the platinum wire is 5.795 ohms.
Calculate Celsius temperature of the bath.
Solutions: (i) Here, 𝑃𝑜 = 100 𝑐𝑚 𝐻𝑔, 𝑃1𝑜𝑜 = 136.6 𝑐𝑚 𝐻𝑔, 𝑃𝑡 =
131.11 𝑐𝑚 𝐻𝑔
We know from air thermometer,
𝑃𝑡 − 𝑃𝑜
𝑡=( ) × 100
𝑃1𝑜𝑜 − 𝑃𝑜
131.11−100
=( ) × 100
136.6−100

= 85℃

(ii) ) Here, 𝑅𝑜 = 5 𝑜ℎ𝑚𝑠, 𝑅1𝑜𝑜 = 5.93 𝑜ℎ𝑚𝑠, 𝑅𝑡 = 5.795 𝑜ℎ𝑚𝑠

We know from platinum resistance thermometer,
𝑅𝑡 − 𝑅𝑜
𝑡=( ) × 100
𝑅100 − 𝑅𝑜
5.795−5
=( ) × 100
5.93−5

= 85.48 ℃

Problem 2: If the platinum temperature corresponding to 50 ℃ on the gas (air)

scale is 50.25 ℃, what be the temperature on the platinum scale corresponding to
150 ℃ on the gas scale.
Solution: Here, 𝜃 = 50 ℃ and 𝑡 = 50.25 ℃
 𝜃2 𝜃
𝜃 − 𝑡 = 𝛿[ − ]
(100)2 100
502 50
Or, 50 − 50.25 = 𝛿[(100)2 − ] ………………. (1)
100

Again, 𝜃 = 50 ℃ and 𝑡 =? Then,

1502 150
50 − 𝑡 = 𝛿[(100)2 − ] …………………….(2)
100

Solving equ(1) and (2), 𝑡 = 149.25 ℃

Thermocouple
A thermocouple is a sensor that measures temperature. It consists of two different
types of metals, joined together at one end. When the junction of the two metals
is heated or cooled, a voltage is created that can be correlated back to the
temperature.
Example of a thermocouple thermometer is given below:
Definition of a gas
In case of a gas, the intermolecular distances are much larger than that of a solid
or a liquid and the molecules of a gas are free to move about in the entire space
available to them. Hence a gas has no shape or size.

Assumptions of the kinetic theory

(i) A gas consists of particles called molecules.

(ii) The molecules are in random motion and obey Newton’s laws of
motion.
(iii) The total number of molecules will be large.
(iv) The volume of the molecules is a negligibly small fraction of the
volume occupied by the gas.
(v) No appreciable forces act on the molecules except during a collision.
 (vi) Collisions are elastic and are of negligible duration.

Pressure of a gas
H E

A D y
z

x
G F

B l C

Consider a cubical vessel ABCDEFGH containing a gas. l is the length of each

side of the vessel. So, the volume of the vessel or gas is l3. Consider a molecule
moving in a random direction. c1 is the velocity of the molecule. c1 can be
resolved into three components c1x, c1y and c1z along x, y and z axes, respectively.
Now, the molecule with velocity c1x is striking CDEF face. Let m be the mass of
the molecule. So, mc1x is the momentum of the molecule along x-axes. This
molecule after striking the face CDEF will be reflected back along ‒x-axes. In
this case, the momentum= ‒mc1x.
A molecule starts from face CDEF, moves parallel to -x, strikes ABGH and
moves parallel to +x-axis and finally reflects from the face CDEF. For this
movement of the molecule, the change in its momentum= mc1x‒(‒mc1x) =2mc1x
and the distance traversed by it=2l.
2𝑙
The time-taken by the molecule for this round trip is ∆𝑡 = 𝑠𝑒𝑐.
𝑐1𝑥

2𝑚𝑐1𝑥 𝑐1𝑥 2
𝑚𝑐1𝑥
The change of momentum per sec= = 2𝑚𝑐1𝑥 × =
∆𝑡 2𝑙 𝑙
 2
𝑚𝑐1𝑥
The rate of change of momentum=Force=F. So, 𝐹 = for 1 molecule. If the
𝑙

container has n molecules, then for n molecules, the x component of force:

2
𝑚𝑐1𝑥 2
𝑚𝑐2𝑥 2
𝑚𝑐𝑛𝑥
𝐹𝑥 = + + ⋯……………..+
𝑙 𝑙 𝑙
𝑚 2 2 2
= (𝑐1𝑥 + 𝑐2𝑥 + ⋯ … … … … … … + 𝑐𝑛𝑥 )
𝑙

𝐹𝑜𝑟𝑐𝑒 𝐹
Now, Pressure, 𝑃 = = . The pressure exerted by n molecules on the wall
𝐴𝑟𝑒𝑎 𝐴

DEFC or ABGH is
𝐹𝑥 1 𝑚 2 2 2
𝑃𝑥 = = × (𝑐1𝑥 + 𝑐2𝑥 + ⋯ … … … … … … + 𝑐𝑛𝑥 )
𝐴 𝑙2 𝑙
𝑚 2 2 2
= (𝑐1𝑥 + 𝑐2𝑥 + ⋯ … … … … … … + 𝑐𝑛𝑥 )
𝑙3

𝑚 2 2 2
Similarly, 𝑃𝑦 = (𝑐1𝑦 + 𝑐2𝑦 + ⋯ … … … … … … + 𝑐𝑛𝑦 )
𝑙3
𝑚 2 2 2
and 𝑃𝑧 = (𝑐1𝑧 + 𝑐2𝑧 + ⋯ … … … … … … + 𝑐𝑛𝑧 )
𝑙3
𝑃𝑥 +𝑃𝑦 +𝑃𝑧
The mean pressure, 𝑃=
3
𝑚 2 2 2 2 2 2 2 2
So, 𝑃= {(𝑐1𝑥 + 𝑐1𝑦 + 𝑐1𝑧 ) + (𝑐2𝑥 + 𝑐2𝑦 + 𝑐2𝑧 ) + ⋯ … + (𝑐𝑛𝑥 + 𝑐𝑛𝑦 +
2𝑙 3
2
𝑐𝑛𝑧 )}

𝑚
𝑃= (𝑐12 + 𝑐22 + 𝑐32 + ⋯ … … … … … + 𝑐𝑛2 )
2𝑙 3

Where, 𝑐12 = 𝑐1𝑥

2 2
+ 𝑐1𝑦 2
+ 𝑐1𝑧 , and 𝑙 3 = 𝑉 = 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑣𝑒𝑠𝑠𝑒𝑙
Let, 𝑐𝑟𝑚𝑠 = 𝑟𝑜𝑜𝑡 𝑚𝑒𝑎𝑛 𝑠𝑞𝑢𝑎𝑟𝑒 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠, and
𝑐 +𝑐 +𝑐 +⋯……………+𝑐𝑛 2 2 2 2
Mean square velocity, ̅̅̅
𝑐2 = 1 2 3 , then 𝑐𝑟𝑚𝑠 = √̅̅̅
𝑐2
𝑛
𝑚 𝑚𝑛 ̅̅̅
Thus, 𝑃 = . 𝑛𝑐̅̅̅2 = 𝑐 2 . If M=mass of the gas, then 𝑀 = 𝑚𝑛.
3𝑉 3𝑉
𝑀 1 𝑀
So, 𝑃 = . ̅̅̅
𝑐 2 = 𝜌𝑐̅̅̅2 . Where, 𝜌 = = 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑔𝑎𝑠.
3𝑉 3 𝑉

Relation of pressure and mean square velocity of the gas is

1
𝑃 = 𝜌𝑐̅̅̅2 .
3
Since, 𝑐𝑟𝑚𝑠 = √̅̅̅ 2
𝑐 2 , so, 𝑐𝑟𝑚𝑠 = ̅̅̅
𝑐 2 , So,
1
2 3𝑃
𝑃 = 𝜌𝑐𝑟𝑚𝑠 , and hence 𝑐𝑟𝑚𝑠 = √
3 𝜌

Relation between pressure and mean kinetic energy

1 1 𝑀 ̅̅̅ 2 1 𝑀 ̅̅̅
𝑃 = 𝜌𝑐̅̅̅2 = 𝑐2 = . 𝑐2
3 3𝑉 3 2𝑉
2 1
If 𝑉 = 1𝑚3 , then 𝑃 = . 𝑀𝑐̅̅̅2
3 2
2
= . 𝐸𝑘
3

Where, 𝐸𝑘 = Mean kinetic energy per unit volume of the gas.

The pressure of a gas is, therefore, equal to two-thirds of the mean kinetic energy
of the mass per unit volume. This relation is sometimes called the fundamental
equation of the kinetic theory of gases.

Kinetic interpretation of temperature

According to the kinetic theory,
1 1 𝑀 ̅̅̅
𝑃 = 𝜌𝑐̅̅̅2 = 𝑐2
3 3𝑉
1
Or, 𝑃𝑉 = 𝑀𝑐̅̅̅2
3

Let us consider 1 gm-mol of a gas, which has a temperature T. For 1 gm-mole of

a gas, the equation of state of ideal gas is
𝑃𝑉 = 𝑅𝑇
1
Thus, 𝑀𝑐̅̅̅2 = 𝑅𝑇
3
1 3
Or, 𝑀𝑐̅̅̅2 = 𝑅𝑇
2 2
Therefore, the total translation kinetic energy of M gm of the molecules of an
ideal gas is proportional to the temperature. If we write,
2
𝑐𝑟𝑚𝑠 = ̅̅̅
𝑐2
3 𝑅𝑇
Then, 𝑐𝑟𝑚𝑠 = √̅̅̅
𝑐2 = √
2 𝑀

2
So, 𝑐𝑟𝑚𝑠 ∝𝑇

So, At T=0, the molecular motion ceases according to kinetic theory.

Kinetic energy per molecule

Let, 𝑚=mass of one molecule
𝑁𝐴 =Avogadro’s number=the number of molecules per mole of a gas.
𝑀 = 𝑚𝑁𝐴 = Molecular weight=mass of 1 mole of a gas.
1 3
We know, 𝑀𝑐̅̅̅2 = 𝑅𝑇
2 2
1 3
Or, 𝑚𝑁𝐴 ̅̅̅
𝑐 2 = 𝑅𝑇
2 2
1 3 𝑅
Or, 𝑚𝑐̅̅̅2 = 𝑇
2 2 𝑁𝐴
1 3
Or, 𝑚𝑐̅̅̅2 = 𝑘𝑇
2 2
3
The mean kinetic energy of translation per molecule is = 𝑘𝑇
2

So, mean K. E. ∝ 𝑇, So, corresponding to a temperature there is a K.E, and the

molecular collisions lead to a uniform temperature (thermal equilibrium).

Derivation of the gas law

𝑀′
Let, 𝑀′ = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑔𝑎𝑠, and there are 𝜇 moles of the gas, then 𝜌 = =
𝑉
𝜇𝑀
= 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑔𝑎𝑠. 𝑀= molecular weight.
𝑉
1
𝑃 = 𝜌𝑐̅̅̅2 .
3
1 𝜇𝑀 ̅̅̅
2
= 𝑐
3 𝑉
 1
Or, 𝑃𝑉 = 𝜇𝑀𝑐̅̅̅2
3
2 1
= ( 𝜇𝑀𝑐̅̅̅2 )
3 2
2 1
= 𝜇. 𝑁𝐴 𝑚𝑐̅̅̅2
3 2
2 1
= 𝜇𝑁𝐴 . 𝑚𝑐̅̅̅2
3 2
2 3
= 𝜇𝑁𝐴 . 𝑘𝑇
3 2

= 𝜇𝑁𝐴 𝑘𝑇
So, 𝑃𝑉 = 𝜇𝑅𝑇
When 𝜇 = 1 𝑔𝑚, 𝑃𝑉 = 𝑅𝑇

Derivation of gas laws

(i) Boyle’s law
1 1 𝑀 ̅̅̅
According to the kinetic theory, 𝑃 = 𝜌𝑐̅̅̅2 == 𝑐2.
3 3𝑉
1
Or, 𝑃𝑉 = 𝑀𝑐̅̅̅2
3

When, 𝑇 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡, ̅̅̅

𝑐 2 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡, (𝑐̅̅̅2 ∝ 𝑇)
1
So, 𝑀𝑐̅̅̅2 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
3

Or, 𝑃𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

(ii) Charles’s law

1 1 𝑀 ̅̅̅
According to the kinetic theory, 𝑃 = 𝜌𝑐̅̅̅2 == 𝑐2.
3 3𝑉
1
Or, 𝑃𝑉 = 𝑀𝑐̅̅̅2
3

Consider 1 gm-mole of a gas at absolute temperature.

Then, molecular weight of the gas, 𝑀 = 𝑚𝑁𝐴
1
So, 𝑃𝑉 = 𝑚𝑁𝐴 ̅̅̅
𝑐2
3
But the mean kinetic energy of a molecule,
1 3
𝑚𝑐̅̅̅2 = 𝑘𝑇, 𝑚𝑐̅̅̅2 = 3𝑘𝑇
2 2
1
So, 𝑃𝑉 = 𝑁𝐴 . 3𝑘𝑇 = 𝑁𝐴 𝑘𝑇
3

𝑉
If P is constant, then 𝑉 ∝ 𝑇, Or, = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇

(iii) Regnault’s law

𝑃𝑉 = 𝑁𝐴 𝑘𝑇 = 𝑅𝑇
If V is constant, then 𝑃∝𝑇

(iv) Avogadro’s law

Let, n1= number of molecules in a gas 1
m1= mass of a molecule
c1= mean square velocity of gas 1
n2= number of molecules in a gas 2
m2= mass of a molecule
c2= mean square velocity of gas 2
Consider same pressure of the two gases, then
𝑃1 = 𝑃2
1 𝑚1 𝑛1 ̅̅̅ 1 𝑚2 𝑛2 ̅̅̅
Or, 𝑐12 = 𝑐22
3 𝑉 3 𝑉
1 1
𝑚1 𝑛1 ̅̅̅
𝑐12 = 𝑚2 𝑛2 ̅̅̅
𝑐22 ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,(1)
3 3

When temperature is same for two gases, we can write,

1 1 1 3
𝑚1 ̅̅̅
𝑐12 = 𝑚2 ̅̅̅
𝑐22 ( 𝑚𝑐̅̅̅2 = 𝑘𝑇)
2 2 2 2

Then from equ(1), 𝑛1 = 𝑛1

Equal volume of all gases at same temperature and pressure contains equal
number of molecules.
Dalton’s law of partial pressure
Let, m1, m2 and m3 are molecular masses of different gases 1, 2 and 3,
respectively.
n1, n2 and n3 are number of molecules per unit volume of gases 1,2 and 3,
respectively.
According to no interaction and a state of thermal equilibrium, the total pressure
will be due to all different types of molecules. So,
1 1 1
𝑃 = 𝑚1 𝑛1 ̅̅̅
𝑐12 + 𝑚2 𝑛2 ̅̅̅
𝑐22 + 𝑚3 𝑛3 ̅̅̅
𝑐32
3 3 3

= 𝑃1 + 𝑃2 + 𝑃3 + ⋯ … … = ∑ 𝑃𝑖
Which is Dalton’s law: The pressure of a mixture of gases equals the sum of
partial pressures of its components [True for ideal gas].

Clapeyron equation
1 1 1 𝑛 1 𝑛
𝑃 = 𝜌𝑐̅̅̅2 = 𝑚𝑛𝑐̅̅̅2 = . 𝑚𝑁𝐴 ̅̅̅
𝑐2 = . 𝑀𝑐̅̅̅2
3 3 3 𝑁𝐴 3 𝑁𝐴
𝑛 𝑛
= . 𝑃𝑉 = 𝑅𝑇 (for 1 gm mole of a gas)
𝑁𝐴 𝑁𝐴
𝑅
=𝑛 𝑇 = 𝑛𝑘𝑇
𝑁𝐴

Calculation of Avogadro’s’ number

Let, 𝑁𝐴 =Avogadro’s number, 𝑚= mass of a molecule, so 𝑚𝑁𝐴 = 𝑀=
𝑀 2
molecular weight. So, 𝑁𝐴 = = , (For H2 gas)
𝑚 3.32×10−22 𝑔

= 6.02 × 1023 /g-mole

= 6.02 × 1026 /kg-mole

Universal gas constant

We know, 𝑃𝑉 = 𝑅𝑇 for 1 g-mole of gas
𝑃𝑉 76×13.6×981×22.4×103 𝑒𝑟𝑔/𝑘−𝑚𝑜𝑙𝑒
𝑅= =
𝑇 273
 = 8.31 × 107 𝑒𝑟𝑔/𝑘 − 𝑚𝑜𝑙𝑒
= 8.31 𝐽/𝑘 − 𝑚𝑜𝑙𝑒
= 1.99 𝐶𝑎𝑙/𝑘 − 𝑚𝑜𝑙𝑒 (Divide by 4.2)

Boltzmann Constant
𝑅 8.31×107
By definition, Boltzmann constant, 𝑘 = =
𝑁𝐴 6.02×1023

= 1.38 × 10−16 𝑒𝑟𝑔/𝑘

= 1.38 × 10−23 𝐽/𝑘

Brownian motion
The British botanist, Robert Brown, discovered in 1827 a peculiar phenomenon
while working with pollen grains. He observed that when pollen grains are
suspended in water and viewed under a high-power microscope, they show a
continuous, random and erratic motion, showing a wild fantastic dance
without stoppage. Subsequently, it was proved that this phenomenon is not
restricted to pollen grains only. Such erratic motion is found in particular of
smoke in still air.
In fact, if any colloidal solution is observed under high power microscope, the
suspended particles in solution exhibit an eternal, irregular, to-and-fro motion.
Each particle is seen to spin, rise, sink and rise again. This in a liquid or gas was
termed as Brownian motion, after the name of its discoverer, who could not
however interpret why the motion is like that.

Salient features of Brownian motion

(i) The motion is continuous, irregular and random
(ii) The motion is independent of the mechanical vibration.
(iii) The smaller the particle size, the greater is the motion
(iv) The higher the temperature, the greater is the motion
 Note 1: Brownian motion provides convincing proof of the existence of
molecular motion
Note 2: Brownian movement is not the result of impact of one molecule; but
rather the result of a number of impacts in one direction prevailing over those
in the opposite direction.
Note 3: Brownian movement is explained by a resultant force in a definite
direction owing to chance difference between the number of molecular
impacts.

Vertical distribution of Brownian particle P+dp

dz
Consider a column of gas bounded by surfaces at P

heights z and z+dz. Pressure st z=zo is Po.

Pressure at height z is P. Pressure at height z

z+dz is P+dp. T is the uniform temperature. ρ is

the density of gas at height z.
The pressure due to gravity on the layer dz of the gas = 𝜌𝑔𝑑𝑧
z=zo Po
The net pressure is such that
𝑃 − (𝑃 + 𝑑𝑝) = 𝜌𝑔𝑑𝑧
Or, 𝑑𝑝 = − 𝜌𝑔𝑑𝑧 ………………………………(1)

𝜌𝑅𝑇 𝑀
Again, 𝑃= ……………….(2) [𝑃𝑉 = 𝑅𝑇, 𝑂𝑟 𝑃. = 𝑅𝑇]
𝑀 𝜌
𝑑𝑝 𝑀𝑔
So, =− 𝑑𝑧
𝑃 𝑅𝑇
𝑃 𝑑𝑝 𝑀𝑔 𝑍
Or, ∫𝑃 =− ∫ 𝑑𝑧
𝑜 𝑃 𝑅𝑇 𝑍 𝑜

𝑃 𝑀𝑔
𝑙𝑛 =− (𝑧 − 𝑧𝑜 )
𝑃𝑜 𝑅𝑇
𝑀𝑔(𝑍−𝑍𝑜 )
Or, 𝑃 = 𝑃𝑜 𝑒 − 𝑅𝑇 …………………………(3)
This is the law of atmosphere or the barometric equation, showing that pressure
decreases exponentially. For perfect gas,
 𝑃 = 𝑛𝑘𝑇, and 𝑃𝑜 = 𝑛𝑜 𝑘𝑇, where n is the number of particles
per unit volume. Substituting these in equ(3),
𝑀𝑔(𝑍−𝑍𝑜 )
𝑛 = 𝑛𝑜 𝑒 − 𝑅𝑇 ……………………….(4)
𝑀
Let, the mass of a molecule=𝑚 = , where 𝑁𝐴 =Avogadro’s number, then
𝑁𝐴
𝑁𝐴 𝑚𝑔(𝑍−𝑍𝑜)
𝑛 = 𝑛𝑜 𝑒 − 𝑅𝑇 …………………….(5)
French Physicist, Jeen Perrin, in 1909, used this relation to evaluate 𝑁𝐴 . Consider
that the particle is spherical in shape. If,
𝑑 = density of the particle and medium
𝑑 ′ = density of inter-particle space
The effective density, 𝑑𝑒 = (𝑑 − 𝑑 ′ )
4
The effective mass, 𝑚 = (𝑑 − 𝑑 ′ ) × 𝜋𝑟 3 , where 𝑟= radius of the spherical
3

particle. From equ(5),

𝑁𝐴 𝑚𝑔(𝑍−𝑍𝑜 ) 𝑛
− = 𝑙𝑛
𝑅𝑇 𝑛𝑜
4
𝑁𝐴 (𝑑−𝑑 ′ )× 𝜋𝑟 3 𝑔(𝑍−𝑍𝑜 ) 𝑛
3
− = 𝑙𝑛
𝑅𝑇 𝑛𝑜
3𝑅𝑇 𝑛𝑜
Then, 𝑁𝐴 = 𝑙𝑛
4𝜋𝑟 3 (𝑑−𝑑 ′ )𝑔(𝑍−𝑍𝑜 ) 𝑛

Mean free path

A molecule, in reality, has a finite size and moves in the space of the vessel
containing it. It collides with other molecules and the walls of the container. The
path covered by a molecule between any consecutive collisions is a straight line
and is called the free path. The direction of the molecules changes after every
collision. After a number of collisions, the total path appears to be zigzag (Figure)
and the free path is not constant. Therefore, a term mean free path is used to
indicate the mean distance travelled by a molecule between two collisions. If
the total distance travelled after N collisions is S, then the mean free path λ
is given by,
𝑆
𝜆= ………………………(1)
𝑁

Derivation of the expression of mean free path

2d B´

A B

A´
Let, d be the diameter of spherical shaped molecules. A collision between two
molecules occurs when the distance between the centers of two molecules is d
(Figure). So, d is the condition of distance for a collision. Now if we consider that
one molecule (A´) has a diameter 2d and the other is single geometrical point
(B´), then a collision may also occur.
So, if we consider that all molecules are point particles and the colliding molecule
(A´) has a diameter 2d, then the molecule A´ has a radius of d. Let v the velocity
of the colliding molecule. Since the radius of molecule A´ is d, then it will sweep
out a cylinder of cross-sectional area 𝜋𝑑 2 during movement.
In time ‘t’, the molecule A´ will travel a distance 𝑆 = 𝑣𝑡
So, the volume of the cylinder= 𝜋𝑑 2 × 𝑣𝑡 = 𝜋𝑑 2 𝑣𝑡
Let the number of B´ molecules per unit volume be n
The cylinder will contain 𝑛 × 𝜋𝑑 2 𝑣𝑡 point particles
Thus, the number of collisions = the number of point particles
Total number of point particles, 𝑁 = 𝑛𝜋𝑑 2 𝑣𝑡
From equ(1), mean free path is,
𝑆 𝑣𝑡 1
𝜆= = =
𝑁 𝑛𝜋𝑑 2 𝑣𝑡 𝑛𝜋𝑑 2
1
𝜆=
𝜋𝑑 2 𝑛
This equation is based on the picture of a molecule hitting stationary targets.
Actually, the molecule hits moving targets. Therefore, we have to measure
particles moving in a certain volume by considering the Maxwell’ statistical
method. This method gives the value of λ as,

1
𝜆=
√2𝜋𝑑 2 𝑛

Maxwell’s speed distribution law

P+dp
dz
P

z=0

Figure shows the distribution of molecules above the earth surface. Let,
m = mass of each molecule of a gas
n = number of molecules in unit volume
g = acceleration due to gravity
dz = thickness of the layer between z and z+dz
Therefore,
Weight of a molecule = mg
Weight of the molecules in unit volume = n.mg
Weight of the molecules in dz in unit area = n.mg.dz
So, the pressure of gas in dz is n.mg.dz
If P = pressure at z
P+dp = pressure at z+dz
The net pressure is such that, 𝑃 − (𝑃 + 𝑑𝑝) = 𝑛. 𝑚𝑔. 𝑑𝑧
Or, 𝑑𝑝 = −𝑛. 𝑚𝑔. 𝑑𝑧 ………………..(1)
At temperature T, the pressure of a gas is,
𝑃 = 𝑛𝑘𝑇 …………………………………(2)
From equ(1) and (2),
𝑑𝑝 𝑚𝑔
=− . 𝑑𝑧 ………………………….(3)
𝑃 𝑘𝑇

If T is constant, then from equ(2),

𝑑𝑝 = 𝑘𝑇𝑑𝑛 ……………………..(4)
From equ(2) and (4),
𝑑𝑝 𝑑𝑛
= ………………………….(5)
𝑃 𝑛

From equ(3) and (5),

𝑑𝑛 𝑚𝑔
=− . 𝑑𝑧 ………………………….(6)
𝑛 𝑘𝑇

After integration, we get,

𝑚𝑔
𝑙𝑛𝑛 = − . 𝑧 + 𝐷1 ………………………….(7)
𝑘𝑇

Where D1 is a constant. As z=0, n=no, then lnno=D1, and we can write,

𝑛 𝑚𝑔
𝑙𝑛 =− .𝑧
𝑛𝑜 𝑘𝑇
𝑚𝑔
Or, 𝑛 = 𝑛𝑜 𝑒 − 𝑘𝑇 .𝑍 …………………….(8)
If we go from z to z+dz, then change in n is (by differentiating 8)
𝑚𝑔
𝑚𝑔 − .𝑍
𝑑𝑛 = − . 𝑛𝑜 𝑒 𝑘𝑇 𝑑𝑧
𝑘𝑇
𝑚𝑔
= 𝐷2 𝑒 − 𝑘𝑇 .𝑍 𝑑𝑧 …………………………(9)
This decrease of n over the interval dz comes from the fact that at z=0, there are
some upward directed molecules, called ‘special molecules’. Let these molecules
have vertical velocity component in the range cz and cz+dcz such that they can
rise above z but not above z+dz.
So, molecules that pass through the layer dz from above or below cannot
contribute to the decrease in dn. Consider,
Probability for 1 unit velocity along z-axis for 1 molecule is f(cz)
Probability for dcz velocity along z-axis for 1 molecule is f(cz).dcz
Probability for dcz velocity along z-axis for n molecule is nf(cz).dcz
Let, 𝑛(𝑐𝑧 ) = 𝑛𝑓(𝑐𝑧 ). Therefore,
𝑛(𝑐𝑧 )𝑑𝑐𝑧 = the number of molecules perunit volume having vertical velocity
components in 𝑐𝑧 and 𝑐𝑧 + 𝑑𝑐𝑧
𝑐𝑧 𝑛(𝑐𝑧 )𝑑𝑐𝑧 = the rate per unit area at which special molecules leave z=0 and
arrive at level z.
Now, 𝑐𝑧 𝑛(𝑐𝑧 )𝑑𝑐𝑧 ∝ 𝑑𝑛
Or, 𝑐𝑧 𝑛(𝑐𝑧 )𝑑𝑐𝑧 = 𝐷3 𝑑𝑛
𝑚𝑔
Or, 𝑐𝑧 𝑛(𝑐𝑧 )𝑑𝑐𝑧 = 𝐷3 × 𝐷2 𝑒 − 𝑘𝑇 .𝑍 𝑑𝑧
𝑚𝑔
= 𝐷4 𝑒 − 𝑘𝑇 .𝑍 𝑑𝑧 ……………………..(10)
From conservation of energy, the molecules have the property,
1 𝑐𝑧2
𝑚𝑐𝑧2 = 𝑚𝑔𝑧, Or, 𝑧=
2 2𝑔
𝑔𝑑𝑧
Or, 𝑚𝑐𝑧 𝑑𝑐𝑧 = 𝑚𝑔𝑑𝑧, or, 𝑐𝑧 =
𝑑𝑐𝑧

Using these two relations in (10)

𝑚𝑔 𝑐2
𝑔𝑑𝑧 − . 𝑧
𝑛(𝑐𝑧 )𝑑𝑐𝑧 = 𝐷4 𝑒 𝑘𝑇 2𝑔 𝑑𝑧
𝑑𝑐𝑧

𝑚𝑐2
𝑧
−
𝑛(𝑐𝑧 )𝑑𝑐𝑧 = 𝐵𝑒 2𝑘𝑇 𝑑𝑐𝑧 …………………(11)
Similarly, we can write:
𝑚𝑐2
𝑥
−
𝑛(𝑐𝑥 )𝑑𝑐𝑥 = 𝐵𝑒 2𝑘𝑇 𝑑𝑐𝑥 …………………(12)
𝑚𝑐2
𝑦
−
𝑛(𝑐𝑦 )𝑑𝑐𝑦 = 𝐵𝑒 2𝑘𝑇 𝑑𝑐𝑦 …………………(13)
 cz

dc
y dc
z
c dc
x

cx
cy

cx

cy

Figure shows a three-dimensional velocity space, where the velocity,

𝑐 2 = 𝑐𝑥2 + 𝑐𝑦2 + 𝑐𝑧2 …………………………..(14)
Consider a volume element whose sides are 𝑑𝑐𝑥 , 𝑑𝑐𝑦 and 𝑑𝑐𝑧 . The volume of the
element in velocity space =𝑑𝑐𝑥 𝑑𝑐𝑦 𝑑𝑐𝑧
A particle in the volume has velocity components in the range, 𝑐𝑥 & 𝑐𝑥 + 𝑑𝑐𝑥 ,
𝑐𝑦 & 𝑐𝑦 + 𝑑𝑐𝑦 and 𝑐𝑧 & 𝑐𝑧 + 𝑑𝑐𝑧 .
Again, let
𝑛(𝑐𝑧 )= the probability that a molecule will have a velocity component in the
range 𝑐𝑧 & 𝑐𝑧 + 𝑑𝑐𝑧 . 𝑛(𝑐𝑥 ) and 𝑛(𝑐𝑦 ) are similarly defined. The probability of
the molecules or the number of molecules that lie at the tip of the velocity c within
the element is:
𝑚𝑐2
𝑥 𝑚𝑐2
𝑦 𝑚𝑐2
𝑧
− − −
𝑛(𝑐𝑥 )𝑑𝑐𝑥 × 𝑛(𝑐𝑦 )𝑑𝑐𝑦 × 𝑛(𝑐𝑧 )𝑑𝑐𝑧 = 𝐷5 𝑒 2𝑘𝑇 ×𝑒 2𝑘𝑇 ×𝑒 2𝑘𝑇 𝑑𝑐𝑥 . 𝑑𝑐𝑦 . 𝑑𝑐𝑧
𝑚𝑐2
−
Or, 𝑛(𝑐)𝑑𝑐 = 𝐷5 𝑒 2𝑘𝑇 𝑑𝑐𝑥 . 𝑑𝑐𝑦 . 𝑑𝑐𝑧
Since we are interested in velocity distribution, we can consider a different
volume element corresponding to all molecules whose speed lie between c and
c+dc.
In this case, we consider, two concentric spheres,
one of radius c and one of radius c+dc.
The volume of the element of dc is 𝑑𝑐𝑥 . 𝑑𝑐𝑦 . 𝑑𝑐𝑧 c+dc

=4πc2dc.
c
So, the number of molecules per unit volume whose
speeds lie between c and c+dc, is
𝑚𝑐2
−
𝑑𝑛𝑐 = 𝑛(𝑐)𝑑𝑐 = 𝐷5 𝑒 2𝑘𝑇 . 4𝜋𝑐 2 . 𝑑𝑐
𝑚𝑐2
So, 𝑛(𝑐) = 𝐷𝑐 2 𝑒 − 2𝑘𝑇 . [Here, D=D5.4π]
∞
But, ∫0 𝑛(𝑐)𝑑𝑐 = 𝑛
𝑚𝑐 2
∞
Or, 𝐷 ∫0 𝑐 2 𝑒 − 2𝑘𝑇 𝑑𝑐 =𝑛
𝑚𝑐 2 𝑚 𝑘𝑇
Let =𝑥 Or, . 2𝑐𝑑𝑐 = 𝑑𝑥 𝑐𝑑𝑐 = dx
2𝑘𝑇 2𝑘𝑇 𝑚
𝑘𝑇
2𝑘𝑇 1 𝑘𝑇 𝑑𝑥
2 𝑚
Again, 𝑐 = 𝑥 and 𝑑𝑐 = 𝑑𝑥 = 1 1
𝑚 𝑐 𝑚 2𝑘𝑇
( )2 𝑥 2
𝑚

2 𝑘𝑇
∞ 2 −𝑚𝑐 ∞ 2𝑘𝑇 𝑑𝑥
So, 𝑛= 𝐷 ∫0 𝑐 𝑒 2𝑘𝑇 𝑑𝑐 = 𝐷 ∫0 𝑥. 𝑒 −𝑥 . 2𝑘𝑇
𝑚
1 1
𝑚
( )2 𝑥 2
𝑚

𝑘𝑇 3 ∞ 3
= 𝐷. ( )2 . √2. ∫0 𝑥 2−1 . 𝑒 −𝑥 𝑑𝑥
𝑚 ∞

𝑘𝑇 3
1
∫ 𝑥 𝑛−1 𝑒 −𝑥 𝑑𝑥 = Γ(𝑛)
= 𝐷. ( ) . √2. √𝜋
2 0
∞ 3−1 −𝑥
𝑚 2 3 1
∫0 𝑥 2 𝑒 𝑑𝑥 = Γ (2) = Γ (2 + 1)
1 1 1
= 2 Γ (2) = 2 √𝜋
2𝑛 𝑚 3 𝑚 3
So, 𝐷= . ( )2 = 4𝜋𝑛. ( )2
√2𝜋 𝑘𝑇 2𝜋𝑘𝑇
3 𝑚𝑐2
𝑚
So, 𝑛(𝑐) = 4𝜋𝑛. ( ) 2 . 𝑐 2 𝑒 − 2𝑘𝑇
2𝜋𝑘𝑇
Let us consider a finite number of molecules N contained in a volume V, Then,
nV=N and n(c)V=N(c).
So, the number of molecules with speeds in the range c and c+dc is
3
𝑚𝑐2
𝑚
. 𝑐 2 𝑒 − 2𝑘𝑇 𝑑𝑐
2
𝑑𝑁𝑐 = 𝑁(𝑐)𝑑𝑐 = 4𝜋𝑁. ( )
2𝜋𝑘𝑇

This is the Maxwell’s velocity distribution law.

Average speed
Let
N= total number of molecules in a volume
N1= molecules have speed c1
N2= molecules have speed c2
And so on
The average or mean speed is defined as
𝑁1 𝑐1 +𝑁2 𝑐2 +𝑁3 𝑐3 +⋯…….. ∑ 𝑁 𝑖 𝑐𝑖
𝑐̅ = = ∑ 𝑁𝑖
……………………………..(1)
𝑁1 +𝑁2 +𝑁3 +⋯…………

If we have a continuous distribution of molecules, then equ(1) can be written as,

∞ ∞ ∞
∫0 𝑐𝑖 𝑑𝑁𝑖 ∫0 𝑐𝑑𝑁𝑐 ∫0 𝑐.𝑁(𝑐)𝑑𝑐
𝑐̅ = ∞ = ∞ = ∞
∫0 𝑑𝑁𝑖 ∫0 𝑑𝑁𝑐 ∫0 𝑁(𝑐)𝑑𝑐
3
𝑚𝑐2
𝑚
. 𝑐 2 𝑒 − 2𝑘𝑇 𝑑𝑐
2
𝑑𝑁𝑐 = 𝑁(𝑐)𝑑𝑐 = 4𝜋𝑁. ( )
2𝜋𝑘𝑇
1
𝑚 2 𝑚
Let, 𝑎 = ( ); and 𝑏= , Then,
2𝜋𝑘𝑇 2𝑘𝑇
1 ∞ 2 ∞
𝑐̅ = ∫0 𝑐. 4𝜋𝑁. 𝑎3 . 𝑐 2 . 𝑒 −𝑏𝑐 𝑑𝑐 Here, ∫0 𝑁(𝑐)𝑑𝑐 = 𝑁
𝑁
∞ 2
= 4𝜋𝑎3 ∫0 𝑐 3 . 𝑒 −𝑏𝑐 𝑑𝑐
 4𝜋𝑎3 ∞ 2 1 ∞ 𝑑𝑧
= ∫0 𝑐 3 𝑒−𝑏𝑐 𝑑𝑐 = 2 ∫0 𝑧𝑒 −𝑧 𝑑𝑧, 𝑖𝑓 𝑏𝑐 2 = 𝑧, 𝑐𝑑𝑐 = 2𝑏
2𝑏2 2𝑏
3 1 ∞ 2−1 −𝑧 1
𝑚 2
= 2 ∫𝑧 𝑒 𝑑𝑧 = . Γ(2)
2𝜋( ) 2𝑏 0 2𝑏2
2𝜋𝑘𝑇 1 1
= 𝑚 2 = . Γ(1 + 1) = . 1. Γ(1)
( ) 2𝑏2 2𝑏2
2𝑘𝑇
1
𝑎𝑠 [Γ(𝑛 + 1) = 𝑛Γ(𝑛)]
𝜋 𝑚 𝑚 2 1
2 . .(
𝜋√𝜋 2𝑘𝑇 2𝑘𝑇
) = as Γ(1) = 1
= 𝑚 𝑚
2𝑏2
.
2𝑘𝑇 2𝑘𝑇
1
2 2𝑘𝑇 𝑚 2
= . .( )
√𝜋 𝑚 2𝑘𝑇

8𝑘𝑇
=√
𝜋𝑚

Root-mean square speed

N= total number of molecules in a volume, N1= molecules have speed c1
N2= molecules have speed c2
And so on
Root mean square speed is,
𝑁1 𝑐12 +𝑁2 𝑐22 +𝑁3 𝑐32 +⋯…….. ∑ 𝑁𝑖 𝑐𝑖2
𝑐𝑟𝑚𝑠 = √ =√ ∑ 𝑁𝑖
………………………(1)
𝑁1 +𝑁2 +𝑁3 +⋯…………

If we have a continuous distribution of molecules, then equ(1) can be written as,

∞ ∞
∫0 𝑐 2 𝑑𝑁𝑐 ∫0 𝑐 2 𝑁(𝑐)𝑑𝑐 1 ∞
𝑐𝑟𝑚𝑠 = √ ∞ =√ ∞ = √ ∫0 𝑐 2 𝑁(𝑐)𝑑𝑐
∫0 𝑑𝑁𝑐 ∫0 𝑁(𝑐)𝑑𝑐 𝑁

3
𝑚𝑐2
𝑚
. 𝑐 2 𝑒 − 2𝑘𝑇 𝑑𝑐
2
Here, 𝑑𝑁𝑐 = 𝑁(𝑐)𝑑𝑐 = 4𝜋𝑁. ( )
2𝜋𝑘𝑇
 1
𝑚 2
Let, 𝑎 = ( ); and ∞ 2 ∞
∫0 𝑐 4 𝑒−𝑏𝑐 𝑑𝑐 = ∫0 𝑐 3 𝑒−𝑏𝑐 𝑐𝑑𝑐
2
2𝜋𝑘𝑇
3 3
𝑚
𝑏= , Then, =∫
∞ 𝑧2
𝑒−𝑧
𝑑𝑧 2
𝑖𝑓 𝑏𝑐 = 𝑧, 𝑐𝑑𝑐 =
𝑑𝑧 3
,𝑐 =
𝑧
( )2
2𝑘𝑇 0 3 2𝑏 2𝑏 𝑏
𝑏2
1 ∞ ∞ 5−1 −𝑧
∫ 𝑐 2 𝑑𝑁𝑐 =
𝑁 0 =
1
∫
5 0 𝑧
2 𝑒 𝑑𝑧 =
1
5 .Γ( )
5
2
2𝑏2 2𝑏2
1 ∞ −𝑏𝑐 2 5 3
. 4𝜋𝑁𝑎3 ∫0 𝑐 4 𝑒 𝑑𝑐 Now, Γ(𝑛 + 1) = 𝑛Γ(𝑛), 𝑠𝑜, Γ ( ) = Γ ( + 1)
𝑁 2 2
1 5 3 3 3 1 1
= 4𝜋𝑎3 . . Γ( ) = 2 Γ (2) = 2 Γ (2 + 1) 𝑎𝑛𝑑 Γ (2) = √π
5
2
2𝑏2
1 3 1
= 4𝜋𝑎3 . 5 . . . √π
2 2
2𝑏2
3 3
3 𝑚 2
𝜋2 .( )
2 2𝜋𝑘𝑇
= 𝑚
5
( )2
2𝑘𝑇

3 1
3 1 𝑚 𝑚 2
.𝜋2 . 3 . . ( )
2 2𝑘𝑇 2𝑘𝑇
(𝜋) 2
= 1
𝑚 2 𝑚 2
( ) .( )
2𝑘𝑇 2𝑘𝑇

3 2𝑘𝑇
= .
2 𝑚

3𝑘𝑇
So, 𝑐𝑟𝑚𝑠 = √
𝑚

Most probable speed

From Maxwell distribution law of particles
3
𝑚 2 2 −𝑚𝑐 2
𝑁(𝑐) = 4𝜋𝑁. ( ) . 𝑐 𝑒 2𝑘𝑇
2𝜋𝑘𝑇
1
𝑚 2 𝑚
Let, 𝑎 = ( ); and 𝑏= , Then,
2𝜋𝑘𝑇 2𝑘𝑇

2
𝑁(𝑐) = 4𝜋𝑁. 𝑎3 . 𝑐 2 𝑒 −𝑏𝑐 ……………………..(1)
The value of c for which N(c) is maximum is called the most probable velocity
cm.
Differentiating equ(1), we get
 𝑑𝑁(𝑐) 2 2
= 4𝜋𝑁𝑎3 . 2 𝑐. 𝑒 −𝑏𝑐 + 4𝜋𝑁𝑎3 . (−2𝑏𝑐). 𝑐 2 𝑒 −𝑏𝑐
𝑑𝑐
𝑑𝑁(𝑐)
At c=cm, = 0,
𝑑𝑐
2 2
So, 8𝜋𝑁𝑎3 . 𝑐𝑚 𝑒 −𝑏𝑐𝑚 − 8𝜋𝑁𝑎3 . 𝑏. 𝑐𝑚 3 𝑒 −𝑏𝑐𝑚 = 0
2 2
8𝜋𝑁𝑎3 . 𝑐𝑚 𝑒 −𝑏𝑐𝑚 = 8𝜋𝑁𝑎3 . 𝑏. 𝑐𝑚 3 𝑒 −𝑏𝑐𝑚

3 2 1 1
𝑏𝑐𝑚 = 𝑐𝑚 , Or, 𝑐𝑚 = ; Or, 𝑐𝑚 = √
𝑏 𝑏

2𝑘𝑇
𝑐𝑚 = √
𝑚

Energy distribution of molecules (Average Energy)

Let us determine the number dNE of molecules per unit volume whose kinetic
1
energy lies between E and E+dE. We know, 𝐸 = 𝑚𝑐 2
2
2𝐸 𝑑𝐸 2𝐸
𝑐2 = , Or, 𝑑𝑐 = 𝑐2 = , but 2𝑐𝑑𝑐 =
2𝑑𝐸
, 𝑐𝑑𝑐 =
𝑑𝐸
𝑚 √2𝐸𝑚 𝑚 𝑚 𝑚
1 𝑑𝐸 𝑑𝐸 𝑑𝐸
𝑑𝑐 = 𝑐 . 𝑚 = =
2𝐸 √2𝐸𝑚
√ . 𝑚
𝑚

3
𝑚𝑐2
𝑚
. 𝑐 2 𝑒 − 2𝑘𝑇 𝑑𝑐
2
Now, 𝑑𝑁𝑐 = 4𝜋𝑁. ( )
2𝜋𝑘𝑇
3
𝐸
𝑚 2𝐸 𝑑𝐸
) . 𝑚 𝑒 −𝑘𝑇 .
2
So, 𝑑𝑁𝐸 = 4𝜋𝑁. (
2𝜋𝑘𝑇 √2𝐸𝑚
𝐸
1 𝑚.√𝑚 √2𝐸.√2𝐸 − 𝑑𝐸
Or. = 4𝜋𝑁. . 3. 𝑒 .
𝑘𝑇
𝜋.√𝜋 𝑚 √2𝐸𝑚
2.√2.(𝑘𝑇) 2

𝐸
√𝐸 −
So, 𝑑𝑁𝐸 = 2𝑁. 3𝑒
𝑘𝑇 . 𝑑𝐸
√𝜋.(𝑘𝑇)2

Average energy of the molecule is

3 𝐸
∞
̅ = ∫ 𝐸𝑑𝑁𝐸 = ∫ 𝐸𝑑𝑁𝐸 = 1 .
𝑈
2𝑁
3 . ∫0 𝐸 2 . 𝑒 −𝑘𝑇 . 𝑑𝐸
∫ 𝑑𝑁𝐸 𝑁 𝑁
√𝜋.(𝑘𝑇)2
3 3 3
𝐸
Let, = 𝑥, 𝑑𝐸 = 𝑘𝑇𝑑𝑥 and 𝐸 2 = (𝑘𝑇)2 . 𝑥 2
𝑘𝑇
 3 3
2 ∞
So, ̅=
𝑈 3 . (𝑘𝑇)2 . 𝑘𝑇 ∫0 𝑥 2 . 𝑒
−𝑥
. 𝑑𝑥
√𝜋.(𝑘𝑇)2
∞
2𝑘𝑇 ∞ 5−1 −𝑥 ∫0 𝑥 𝑛−1 𝑒 −𝑥 𝑑𝑥 = Γ(𝑛)
= ∫ 𝑥 2 . 𝑒 . 𝑑𝑥
√𝜋. 0 Γ(𝑛 + 1) = 𝑛Γ(𝑛)
1
=
2𝑘𝑇
.Γ( ) =
5 2𝑘𝑇
. Γ ( + 1)
3 Γ ( ) = √𝜋
√ 𝜋. 2 √𝜋. 2 2
2𝑘𝑇 3 3 2𝑘𝑇 3 1
= . .Γ( ) = . . Γ ( + 1)
√ 𝜋. 2 2 √𝜋. 2 2

2𝑘𝑇 3 1 1 3𝑘𝑇
= . . .Γ( ) = . √𝜋
√ 𝜋. 2 2 2 2 √𝜋.

So, ̅ = 3 𝑘𝑇
𝑈
2

Most Probable Energy

The number of molecules between the energy E and (E+dE) out of a total number
N is
3
𝑁𝐸 𝑑𝐸 1 2 1 𝐸

𝑁
= 2𝜋 (
𝜋𝑘𝑇
) . 𝐸 2 . 𝑒 −𝑘𝑇 . 𝑑𝐸
3
𝑁𝐸 1 2 1 𝐸
Or,
𝑁
= 2𝜋 (
𝜋𝑘𝑇
) . 𝐸 2 . 𝑒 −𝑘𝑇

Now for most probable energy, E

𝑑 𝐸 𝑁
(
𝑑𝐸 𝑁
)=0
3
𝑑 1 2 1 𝐸
or {2𝜋 ( ) . 𝐸 2 . 𝑒 −𝑘𝑇 } = 0
𝑑𝐸 𝜋𝑘𝑇

3
1 𝐸 𝐸 1
1 1 1
) {𝐸 2 . (− 𝑘𝑇 𝑒 −𝑘𝑇 ) + 𝑒 −𝑘𝑇 . 2 𝐸 −2 } = 0
2
or 2𝜋 (
𝜋𝑘𝑇
1 𝐸 𝐸 1
1 1
or 𝐸 2 . (− 𝑒 −𝑘𝑇 ) + 𝑒 −𝑘𝑇 . 𝐸 −2 = 0
𝑘𝑇 2
1 1 1 1
or 𝐸 2 . ( ) = 𝐸 −2
𝑘𝑇 2
1
or 𝐸 = 𝑘𝑇 most probable energy
2
Problem 1: Calculate the number of molecules in one cubic centimeter of
oxygen at normal temperature and pressure using the following data:
Density of mercury= 13.6 g/cm3, root mean square velocity of oxygen molecule
at ℃=4.62×104 cm/s, and mass of one molecule of oxygen=52.8× 10‒24 g.

Solution: We know that the formula of pressure,

1
𝑃 = 𝜌𝐶 2
3
1 Here, P=76×13.6×980 dynes/cm2
= 𝑚𝑛𝐶 2
3 C= velocity of each molecule=4.62×104 cm/s
3𝑃 m= mass of a molecule=52.8× 10‒24 g
Or, 𝑛= n= number of molecules per cc
𝑚𝐶 2
3×76×13.6×980
= 2
52.8× 10−24 ×(4.62×104 )

= 2.697 × 1019

Problem 2: At what temperature (in Celsius) will oxygen molecules have the
same root mean square velocity as that of hydrogen molecules at ‒100 ℃.
1 3
Solution: For hydrogen molecules, 𝑚1 𝐶12 = 𝑘𝑇1
2 2
1 3
For oxygen molecules, 𝑚2 𝐶22 = 𝑘𝑇2
2 2

𝑚1 𝐶12 𝑇1
From the above two formula, =
𝑚2 𝐶22 𝑇2
𝑚2
Here, 𝐶1 = 𝐶2 , 𝑇1 = −100℃ = −100 + 273 = 173𝐾, and = 16.
𝑚1
𝑚2
So, 𝑇2 = 𝑇 = 16 × 173 = 2768𝐾 = 2768 − 273 = 2495 ℃
𝑚1 1

Problem 3: Calculate the random kinetic energy and average kinetic energy of a
molecule of gas at a temperature of 27 ℃.

Solution:
3
For random kinetic energy, 𝐸𝑟 = 𝑅𝑇
2

Where 𝑅 = 8.3 × 107 ergs/K, and T=273+27=300K, So, 𝐸𝑟 = 3735 J

 3
For average kinetic energy, 𝐸𝑎 = 𝑘𝑇
2

Where 𝑘 = 1.38 × 10−23 J/K, and T=273+27=300K, So, 𝐸𝑎 = 621 × 10−23 J

Problem 3: Calculate the mean free path of gas molecules in a chamber of 10‒6
mm Hg pressure, assuming the molecular diameter to be 2 Å and the target
molecule on collision is fixed. One g molecule of the gas occupies 22.4 L at
normal temperature and pressure. Take the temperature of the chamber to be 273
K.

Solution: At 760 mm Hg pressure and 273 K temperature, the number of

molecules in 22.4 L of a gas = 6.023×1023

So, the number of molecules per cm3 in the chamber at 10-6 mm pressure and
273 K temperature is

6.023×1023 ×10−6
𝑛= = 3.538 × 1010 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠/𝑐𝑚3
22400×760

And d=2 Å=2×10‒8 cm

1 1
𝜆= = = 2.25 × 104 𝑐𝑚
𝜋𝑑 2 𝑛 3.14×(2×10−8 )2 ×3.538×1010

Degrees of freedom
If a particle moves along a straight line, say along x-axis, its position is
completely specified by one coordinate only. The particle is said to possess one
degree of freedom. If the particle moves in a plane (xy-plane), its motion can be
resolved into two components (cx and cy). Therefore, the particle possesses 2
degrees of freedom. Example- An ant moves in a plane. In order to specify a
particle in space (x, y, z), the particle has 3 degrees of freedom. Example- Motion
of a flying bee. For N particles, the degrees of freedom for translation is 3N.
Molecules can rotate during their motion. If we consider the molecules as point
1
particles, then their rotational kinetic energy is 0 [since 𝐾. 𝐸 = 𝐼𝜔2 ; 𝐼 = 𝑀𝐾 2 ;
2

K=0 for point particle). But molecules are not geometrical point; they have finite
size. They possess mass and moment of inertia (𝐼 = 𝑀𝐾 2 ). So, if the atom is a
rigid sphere and the center of mass is not at the center of the sphere, they have
rotational kinetic energy. If a spherical particle of mass m translates and rotates
1
simultaneously in space, then its translational 𝐾. 𝐸. = 𝑚(𝑐𝑥2 + 𝑐𝑦2 + 𝑐𝑧2 ) and
2
1
rotational 𝐾. 𝐸. = 𝐼(𝜔𝑥2 + 𝜔𝑦2 + 𝜔𝑧2 ) . So, it has 6 degrees of freedom; 3
2

translational and 3 rotational along x, y, and z-axes.

If we consider a molecule that consists of two spherical atoms.
The molecule has a 0 rotational energy along the bond-axis; due to the bond
formation, they cannot rotate about the bond axis or about bond axis K=0. The
molecule can rotate about other two axes; so, it has 2 degrees of freedom for
rotational energy. The molecule can translate in space; so, it has 3 degrees of
freedom for translation. In total, it has 5 degrees of freedom.

Therefore, “the number of degrees of freedom is meant the number of

independent coordinates, necessary for specifying the position and configuration
in space of a dynamical system.”
Let, N = number of particles
rc = number of constraints that restrict the particles to move
f = Degrees of freedom
Thus,
𝑓 = 3𝑁 − 𝑟𝑐
Law of equipartition of energy
Using the laws of statistical mechanics, Maxwell showed that the mean kinetic
energy of a system of molecules in the thermal equilibrium at temperature T is
3
𝑘𝑇.
2

The law of equipartition of energy states that in a dynamical system in thermal

equilibrium, the kinetic energy is equally distributed among the various
𝟏
degrees of freedom and for each degree of freedom it is equal to 𝒌𝑻, where
𝟐

k is the Boltzmann constant.

Proof:
According to the kinetic theory of gases, the mean kinetic energy of a molecule
at temperature T is given by:
1 3
𝑚𝑐̅̅̅2 = 𝑘𝑇 ………………………(1)
2 2

Velocity square components of ̅̅̅

𝑐 2 along x, y and z axes are ̅̅̅
𝑐𝑥2 , ̅̅̅
𝑐𝑦2 and ̅̅̅
𝑐𝑧2 . Then,
̅̅̅
𝑐 2 = ̅̅̅
𝑐𝑥2 + ̅̅̅
𝑐𝑦2 + ̅̅̅
𝑐𝑧2 ……………………………..(2)
A molecule can have equal probability to move along, x or y or z axes. Then, the
velocity components are equal, i.e.,
𝑐𝑥 = 𝑐𝑦 = 𝑐𝑧 …………………………..(3)
Or, ̅̅̅
𝑐𝑥2 = ̅̅̅
𝑐𝑦2 = ̅̅̅
𝑐𝑧2 ………………………….(4)
From equ(2) and (4),
̅̅̅
𝑐 2 = 3𝑐̅̅̅ ̅̅̅2 ̅̅̅2
𝑥 = 3𝑐𝑦 = 3𝑐𝑧 ……………………(5)
2

1 3 3 ̅̅̅ 3 ̅̅̅
Or, 𝑚𝑐̅̅̅2 = 𝑚𝑐̅̅̅
𝑥 = 𝑚𝑐𝑦 = 𝑚𝑐𝑧 ……………..(6)
2 2 2
2 2 2 2

Using equ(1),
3 3 3 ̅̅̅ 3 ̅̅̅
𝑘𝑇 = 𝑚𝑐̅̅̅
𝑥 = 𝑚𝑐𝑦 = 𝑚𝑐𝑧 ……………..(7)
2 2 2
2 2 2 2
1 1 ̅̅̅ 1 ̅̅̅ 1
Or, 𝑚𝑐̅̅̅
2 2 2
𝑥 = 𝑚𝑐𝑦 = 𝑚𝑐𝑧 = 𝑘𝑇
2 2 2 2
 1 1 ̅̅̅ 1 ̅̅̅
But, 𝑚𝑐̅̅̅
2 2 2
𝑥 = 𝑚𝑐𝑦 = 𝑚𝑐𝑧 = Average kinetic energy for each degree of
2 2 2
1
freedom. So, the average kinetic energy for each degree of freedom is 𝑘𝑇.
2

Heat capacity
Heat capacity is the amount of heat added to a body of any mass while its
temperature rise is 1ºC.
Let dH= the amount of heat added to a body of mass m,
dT= Rise of temperature of the body,
𝑑𝐻
Then, 𝑐𝐻 = ; Unit is Cal/ºC
𝑑𝑇

Specific heat
Specific heat of a substance is defined as the amount of heat added to its unit mass
while the temperature rise is 1ºC.
Let m= mass of the substance,
dH= amount of heat added,
dT= rise of temperature of the substance
𝑑𝐻
1 𝑑𝐻 𝑑𝑇 𝑐𝐻 𝐻𝑒𝑎𝑡 𝑐𝑎𝑝𝑎𝑐𝑖𝑡𝑦
Then, 𝑐 = = = = = Heat capacity per unit mass.
𝑚 𝑑𝑇 𝑚 𝑚 𝑚𝑎𝑠𝑠

Specific heat is of two types:

(i) Specific heat at constant pressure
1 𝑑𝐻
𝑐𝑝 = ( )
𝑚 𝑑𝑇 𝑝

(ii) Specific heat at constant volume

1 𝑑𝐻
𝑐𝑣 = ( 𝑑𝑇 )
𝑚 𝑣

Molar heat capacity of a substance

Molar heat capacity of a substance is defined as the amount of heat added in
unit mole of the substance. Its unit is Cal/mole-ºC. Heat capacity of solids varies
from material to material, but molar heat capacity, cm, is nearly 6 Cal/mole-ºC for
all materials except some exception. The amount of heat required per molecule
to raise the temperature of a solid by a given amount (say 1°C) seems to be the
same for all materials.
Consider ideal gas with certain number of moles. Let µ= mass in moles of the
gas. Then by definition of molar heat capacity at constant volume,
1 𝑑𝐻
𝑐𝑣 = ( ) , Or, 𝑑𝐻 = 𝜇𝑐𝑣 𝑑𝑇
𝜇 𝑑𝑇 𝑣

Similarly, 𝑑𝐻 = 𝜇𝑐𝑝 𝑑𝑇

Relation between cp and cv

Sand Sand Sand

Reservoir Reservoir

Constant Constant
pressure volume
gas process gas process gas

T+dT T T+dT
P, V+dV P, V P+dP, V
b a c

P
T T+dT

c
b
a
2
1

V
Figure shows 1 gm-mole of a gas, i.e. mass =1 gm in a container which is placed
in a reservoir. The pressure and temperature of the container is controled by sand
and an external source (Bunsen burner), respectively.
Let P, V and T are its pressure, volume and temperature, respectively. Keeping T
constant, if we increase P, then V decreases. If we draw P versus V graph, we get
curve 1. Restore to Fig a, now, we raise T to T+dT by a source. The gas will
expand and V increases. Keeping T+dT constant, if P changes then V changes.
So, we can also draw P versus V graph as shown curve 2.
Let Fig.a correspond to point ‘a’ of curve 1. Since T tends to T+dT, V tends to
V+dV. Now to keep V constant, we have to put more sand (Fig.c). Then Fig.c
corresponds to point ‘c’ in the curve.
From 1st law of thermodynamics,
𝑑𝐻 = 𝑑𝑈 + 𝑑𝑊, where 𝑑𝐻=amount of heat added, 𝑑𝑈=change in internal energy
= 𝑑𝑈 + 𝑃𝑑𝑉 …………………………….(1)
If V=constant, then PdV=0, So,
𝑑𝐻 = 𝑑𝑈 ……………………………(2)
Specific heat at constant volume is,
1 𝑑𝐻
𝑐𝑣 = ( ) , as m=1 gm and 𝑑𝐻 = 𝑑𝑈, so
𝑚 𝑑𝑇 𝑣
𝑑𝑈
𝑐𝑣 = ( ) Or, 𝑑𝑈 = 𝑐𝑣 𝑑𝑇 ………………………(3)
𝑑𝑇 𝑣

Restore the system to Fig.a and raise T to T+dT by keeping P constant, then V
tends to V+dV (Fig.b). So, Fig.b will correspond to point ‘b’ in curve 2. For this
volume change, we can write
𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 ………………………….(4)
𝑑𝐻
Again for 1 gm-mole, 𝑐𝑝 = ( )
𝑑𝑇 𝑣

Or, 𝑑𝐻 = 𝑐𝑝 𝑑𝑇 ……………………..(5)
From equ(4) and (5),
𝑐𝑝 𝑑𝑇 = 𝑑𝑈 + 𝑃𝑑𝑉
 = 𝑑𝑈 + 𝑅𝑑𝑇 (PV=RT; PdV=RdT)

Or, 𝑑𝑈 = 𝑐𝑝 𝑑𝑇 − 𝑅𝑑𝑇 ……………………………..(6)

For ideal gas, U depends on T. Since, the change from ‘a’ to ‘b’ and ‘a’ to ‘c’
involve the same change of dT, so they involve the same change in dU. That is
dU of equ(3) and (6) is same. Thus,
𝑐𝑣 𝑑𝑇 = 𝑐𝑝 𝑑𝑇 − RdT
Or, 𝑐𝑝 − 𝑐𝑣 = R

𝒄𝒑
Relation between f and ratio of specific heats, 𝜸 =
𝒄𝒗

1 gm-mole of gas contains 𝑁𝐴 (Avogadro’s number) number of molecules.

1
For 1 molecule and for 1 degree of freedom, the energy is 𝑘𝑇
2
1
For 𝑁𝐴 molecule and for f degree of freedom, the energy is 𝑁𝐴 𝑓𝑘𝑇
2
1 1
Total energy, 𝑈 = 𝑁𝐴 𝑓𝑘𝑇 = 𝑅𝑓𝑇
2 2
𝑑𝑈 1
= 𝑅𝑓
𝑑𝑇 2

For 1 gm-mole of gas, V is constant,

𝑑𝑈 1
𝑐𝑣 = ( ) = 𝑅𝑓
𝑑𝑇 2 𝑣

But from 1st law of thermodynamics:

1
𝑐𝑝 − 𝑐𝑣 = R, Or, 𝑐𝑝 = 𝑐𝑣 + R = 𝑅𝑓 + 𝑅
2
𝑓 2+𝑓
𝑐𝑝 = 𝑅 (1 + ) = 𝑅 ( )
2 2

Ratio of specific heats,

2+𝑓
𝑐𝑝 𝑅( ) 2
2
𝛾= = 1 =1+
𝑐𝑣 𝑅𝑓 𝑓
2

𝛾 increases if f decreases.
Calculations of specific heats ratio
(i) Monoatomic gas: A monoatomic gas has only one type of atom.
Example, inert gas such as He, Ne, Ar etc. The degree of freedom for N
atom is
𝑓 = 3𝑁 − 𝑟𝑐 , where 𝑟𝑐 is number of constraints.
For a free atom, N=1 and 𝑟𝑐 =0 (no constraint). So,
𝑓 =3×1−0=3
A free atom has 3 degrees of freedom solely from translational kinetic energy.
1
For 1 atom and for 1 degree of freedom, 𝑈 = 𝑘𝑇
2
3
For 1 atom and for 3 degrees of freedom, 𝑈 = 𝑘𝑇
2

If we consider 1 gm-mole of gas; it contains 𝑁𝐴 molecules.

3 3
For 𝑁𝐴 atoms, 𝑈 = 𝑘𝑇 × 𝑁𝐴 = 𝑅𝑇
2 2
𝑑𝑈 3
Now, 𝑐𝑣 = ( ) = 𝑅
𝑑𝑇 2 𝑣
3 5
But, 𝑐𝑝 = 𝑐𝑣 + 𝑅 = 𝑅 + 𝑅 = 𝑅
2 2
5
𝑐𝑝 𝑅
2
For monoatomic gas, 𝛾 = = 3 = 1.67
𝑐𝑣 𝑅
2

(ii) Diatomic gas: Diatomic gas contains with molecules, which have two
atoms, joining by chemical bonds. Example, H2, O2, N2 etc.
Each atom of a diatomic molecule has a
constraint of motion along the bond axis.
The degrees of freedom of a molecule is
𝑓 = 3𝑁 − 𝑟𝑐 = 3 × 2 − 1 = 5
The molecule has 3 degrees of translational motion and 2 degrees of rotational
motion. For 5 degrees of freedom, internal energy,
1
𝑈 = 5 × 𝑘𝑇
2
 5 5
For 1 gm-mole of a gas, 𝑈 = 𝑁𝐴 𝑘𝑇 = 𝑅𝑇
2 2
𝑑𝑈 5
Now, 𝑐𝑣 = ( ) = 𝑅
𝑑𝑇 2 𝑣
5 7
But, 𝑐𝑝 = 𝑐𝑣 + 𝑅 = 𝑅 + 𝑅 = 𝑅
2 2
7
𝑐𝑝 𝑅
2
For monoatomic gas, 𝛾 = = 5 = 1.4
𝑐𝑣 𝑅
2

(iii) Triatomic gas: This gas consists of molecules which are made of 3
atoms. Example,
a. Ozone, O3
b. Steam, H2O
a. Degrees of freedom for O3 is
𝑓 = 3𝑁 − 𝑟𝑐 = 3 × 3 − 3 = 6
Triatomic O3 molecule has 6 degrees of freedom. So, internal energy is
1
𝑈 = 6 × 𝑘𝑇 = 3𝑘𝑇
2

For 1 gm-mole of a gas, 𝑈 = 3𝑁𝐴 𝑘𝑇 = 3𝑅𝑇

𝑑𝑈
Now, 𝑐𝑣 = ( ) = 3𝑅
𝑑𝑇 𝑣

But, 𝑐𝑝 = 𝑐𝑣 + 𝑅 = 3𝑅 + 𝑅 = 4𝑅
𝑐𝑝 4𝑅
For monoatomic gas, 𝛾 = = = 1.33
𝑐𝑣 3𝑅

b. For steam, degrees of freedom, number of constraints is 2. So,

𝑓 = 3𝑁 − 𝑟𝑐 = 3 × 3 − 2 = 7

Triatomic H2O molecule has 7 degrees of freedom. So, internal energy is

1 7
𝑈 = 7 × 𝑘𝑇 = 𝑘𝑇
2 2
7 7
For 1 gm-mole of a gas, 𝑈 = 𝑁𝐴 𝑘𝑇 = 𝑅𝑇
2 2
 𝑑𝑈 7
Now, 𝑐𝑣 = ( ) = 𝑅
𝑑𝑇 2 𝑣
7 9
But, 𝑐𝑝 = 𝑐𝑣 + 𝑅 = 𝑅 + 𝑅 = 𝑅
2 2
9
𝑐𝑝 𝑅
2
For monoatomic gas, 𝛾 = = 7 = 1.28
𝑐𝑣 𝑅
2

Note: We know, 𝑓 = 3𝑁 − 𝑟𝑐 , if atoms increase in a molecule, f is expected to

2
increase. And since, 𝛾 = 1 + , so, 𝛾 is expected to decrease. But, for gas, 𝛾 ≯
𝑓

1.67 and 𝛾 ≮ 1. Except monoatomic gases, specific heat of all gases increases
with temperature and decreases with decrease of temperature. The dependence of
specific heats with T cannot be explained by classical physics. Only quantum
mechanics and statistical mechanics are needed to explain it.

Dulong and Petit’s law

Consider 1 gm of solid so that it contains Na number of molecules. The atoms
vibrate around their equilibrium position. The number of degrees of freedom,
𝑓 − 3𝑁𝐴
Total energy of an atom = Kinetic energy + Potential energy = Etot
Let, Average K. E.= Average P. E,
𝐸𝑡𝑜𝑡 = 2𝐾. 𝐸. = 3𝑃, 𝐸
1
The solid has a kinetic energy, 𝐾. 𝐸. = 3𝑁𝐴 × 𝑘𝑇
2
1
So, 𝐸𝑡𝑜𝑡 = 2 × 3𝑁𝐴 × 𝑘𝑇 = 3𝑁𝐴 𝑘𝑇
2

Specific heat at constant volume,

𝑑𝑢
𝐶𝑣 = ( ) = 3𝑁𝐴 𝑘 = 3𝑅
𝑑𝑡 𝑣

𝐶𝑣 == 6 𝐶𝑎𝑙/𝑘. Since 𝑅 ≈ 2 𝐶𝑎𝑙/𝑘

This is Dulong and Petit’s law.
Behavior of real gases
The behavior of a real gas is expressed by equation of state in terms of pressure
P, volume V and temperature T. We have, from kinetic theory of gases, the perfect
gas equation of state:
𝑃𝑉 = 𝑅𝑇 ………………………………(1)
To derive this equation, we have assumed (i) the size of the molecules of the gas
is negligible, (ii) the intermolecular forces are absent. But in actual practice, at
high pressure the size of the molecules and the intermolecular forces cannot be
neglected. Several authors verified the validity of equ(1) [Regnault, Andrew,
Amagat, Kamerling, Onnes etc.] Among them, Andrew’s experiment on CO 2 is
remarkable to develop a very useful equation of state-the Van der Waal’s
equation. Thus, a correction for P and V were necessary.

A B

C C
G

S S′

Andrew’s experiment on CO2

Apparatus: A is a capillary glass tube except lower part. CO2 was passed through
the tube for several hours to remove air. Both ends of the tube were sealed, and
the lower end was subsequently reopened under a mercury surface in a container.
Some of the gas was expelled by heating so that on cooling, a pellet Hg rose into
the tube and trapped CO2 gas.
A similar tube B was mounted, containing air, in a vessel consisting of two strong
Cu cylinders C, C filled with water. The pressure on CO2 was applied by two
screws S, S′. Pressure P=400 atmos could be applied. Due to G, Pressure applied
to each gas will be same. Its value was deduced from the volume of air in the tube
B, assuming Boyle’s law to apply.

Results: A series of values of P and V of CO2 at a fixed T was obtained. The

experiment was repeated to get P and V for other temperatures. The results are
shown in Figure. Consider the isothermal at 13.1ºC. CO2 is in the gaseous form
at A (2nd Figure). As P increases V decreases up to B (50 atmos), where the gas
begins to liquify. When liquefaction continues, P remains constant and V
continually decreases until all the gas is liquified. This shows horizontal line CB,
where liquid and gaseous state coexist. Further increase in P causes small change
in V (in the liquid state). This shows steep part CD and represents that liquids are
highly incompressible. At lower T, liquefaction occurs at lower P and horizontal
portion is larger. At higher T, the isothermals have the same general change but
pressure to produce liquefaction increases; the horizontal portion becomes shorter
i.e. the specific volume (Volume occupied by 1 gm CO2) of vapor at the onset of
condensation is relatively smaller while that of liquid on completion of
condensation is relatively greater.
As T increases, the above changes proceed in the same direction until at
T=31.4ºC, the horizontal portion of the curve just disappears, and the two
volumes become identical. This is called the critical isothermal of CO 2.
Above T=31.4ºC, the horizontal portion is absent. This experiment demonstrates
that it is not possible to produce liquid CO2 at T higher than 31.4ºC. This is called
critical temperature; the pressure just required for liquefaction at critical T is
called critical pressure; the volume occupied by 1g of the substance at critical P
and T is called critical volume. In 2nd Figure, the curve V3CEBV1 correspond to
the existence of both liquid and gaseous phases in the tube. The left of this area
is the liquid region and its right is gaseous region.
Conclusions: (i) The existence of a critical temperature for all gases above which
no gas could be liquefied by pressure alone‒ paramount importance of
liquefaction.
(iii) There exists a continuity of the liquid and gaseous states of a substance in
spite of apparent discontinuous nature of the Andrew’s isothermals below
critical temperature.

Critical constants of a gas

Critical temperature: The critical temperature (Tc) of a gas is the temperature
above which the gas cannot be liquified, no matter how high the pressure is.
Critical Pressure: The critical pressure (Pc) is the pressure just sufficient to liquify
the gas when it is at the critical temperature
Critical volume: The critical volume (Vc) of a gas is the volume occupied by 1
gm of it when subjected to critical pressure at the critical temperature

Van der Waals equation of state

Van der Waals argued to re-correct the two assumptions of kinetic theory
employed to derive equation of state 𝑃𝑉 = 𝑅𝑇 for ideal gas using kinetic theory.
The assumptions of kinetic theory were:
(i) The molecules are simple mass point occupying no or negligible
volume so that volume of the container is volume available to the
molecules.
(ii) The molecules do not exert any force between them so that the gas has
only kinetic energy and no potential energy.
The two corrections are:
 (i) There exist forces among molecules of the gas
(ii) The molecules have finite size

Correction for Pressure

Peff
The molecules attract each other with a
Pideal
force that varies inversely as some Pin
power of the distance between them. It
is effective at short ranges and negligible
at large distance.
A molecule deep within the gas is
Attracted by all surrounding molecules, and the average force for these molecules
is balanced out. The situation is different for surface or boundary molecules.
There will be net force acting perpendicular to the boundary and directed inwards.
This inward pull reduces the momentum with which molecules strike the wall and
hence reduce the effective pressure by an amount P. That is,
𝑃𝑖𝑑𝑒𝑎𝑙 − 𝑃𝑖𝑛 = 𝑃𝑒𝑓𝑓 = 𝑃
So, 𝑃𝑖𝑑𝑒𝑎𝑙 = 𝑃 + 𝑃𝑖𝑛 …………………..(1)

Calculation of Pin
The inward force acting on a molecule will be proportional to the number of
attracting molecules in unit volume in the gas i.e. the molecular density ρ. The
inward force on a molecule,
′
𝐹𝑖𝑛 ∝𝜌
′
𝐹𝑖𝑛 = 𝑘1 𝜌 ………………….………(2)
Again, the number of molecules, n′ heating an area of the surface is also
proportional to ρ. That is,
n′ ∝ 𝜌
n′ = 𝑘2 𝜌 ………………….………(2)
Total force on molecules striking unit area=𝑘1 𝑘2 𝜌2
𝑁
So, the pressure, 𝑃𝑖𝑛 ∝ 𝜌2 ∝ ( )2
𝑉

Where, N is the total number of molecules and V the total volume.

1
So, 𝑃𝑖𝑛 ∝
𝑉2
𝑎
Or, 𝑃𝑖𝑛 =
𝑉2

Correction for volume:

The fact the molecules have finite
size shows that the actual space for
the movement of the molecules is
less than the volume of the vessel.
The molecules have the sphere of
influence around them and due to this there is correction of volume. Let the radius
4
of one molecule be ‘r’. Then the volume of the molecule, 𝑥 = 𝜋𝑟 3 . The center
3

of any two molecules can approach each other only by a minimum distance of 2r.
4
The volume of sphere of influence, 𝑆 = 𝜋(2𝑟)3 = 8𝑥.
3

Consider a container of volume V. If the molecules are allowed to enter one by

one, then,
The volume available for 1st molecule=𝑉
The volume available for 2nd molecule=𝑉 − 𝑆
The volume available for 3rd molecule=𝑉 − 2𝑆
…………………………………………………
The volume available for nth molecule=𝑉 − (𝑛 − 1)𝑆
𝑉+(𝑉−𝑆)+(𝑉−2𝑆)+⋯………+[𝑉−(𝑛−1)𝑆]
Average space available for each molecule=
𝑛
𝑆
= 𝑉 − [1 + 2 + 3 + ⋯ … + (𝑛 − 1)]
𝑛
 𝑆 (𝑛−1).𝑛
=𝑉− .
𝑛 2
𝑛𝑆 𝑆
=𝑉− +
2 2
𝑆
As the number of molecules is very large, then can be neglected. Average space
2
𝑛𝑆 𝑛×8𝑥
available for each molecule = 𝑉 − =𝑉− = 𝑉 − 4(𝑛𝑥) = 𝑉 − 𝑏
2 2

Where b=4nx=Four times the actual volume of the molecules.

For ideal gas, 𝑃𝑉 = 𝑅𝑇
But, after correction by Van der Waals. The equation of a real gas is
𝑎
(𝑃 + )(𝑉 − 𝑏) = 𝑅𝑇
𝑉2

Where a and b are Van der Waals constants.

Short description of Andrew experiment and theory

Using Van der Waals equation, graphs between P and V at various temperatures
are drawn. At lower temperatures below 31.1ºC, the low-pressure region shows a
fluctuation with V. In case of 13.1ºC, a curve AA′BB′C is obtained. This does not
agree with the experimental results for CO2 as obtained by Andrew. The portion
AA′ has been explained on the basis of super heating of the liquid and the portion
B′C is explained by supercooling of the vapors. But the portion B′BA′ cannot be
explained because it shows decrease in volume with decrease in pressure. It
cannot happen in actual practice. The states CB′ and AA′, though unstable, can
be realized in practice by careful experiments. At higher temperatures, the
theoretical and experimental isothermals are similar.

Determination of critical constants

The critical temperature and the corresponding values of pressure and volume at
critical point are called the critical constants. At the critical point, the rate of
change of pressure with volume is 0. This point is called point of inflexion.
According to Van der Waals equation,
𝑎
(𝑃 + )(𝑉 − 𝑏) = 𝑅𝑇
𝑉2
𝑅𝑇 𝑎
Or, 𝑃= −
𝑉−𝑏 𝑉2
𝑑𝑃 𝑅𝑇 2𝑎
Or, = − (𝑉−𝑏)2 + …………………….(1)
𝑑𝑉 𝑉3

At critical point,
𝑑𝑃
= 0, 𝑇 = 𝑇𝑐 , and 𝑉 = 𝑉𝑐
𝑑𝑉
𝑅𝑇𝑐 2𝑎
So, − (𝑉 + =0
𝑐 −𝑏)2 𝑉𝑐3
2𝑎 𝑅𝑇𝑐
Or, = (𝑉 ………………………(2)
𝑉𝑐3 𝑐 −𝑏)
2

Again, from equ(1),

𝑑2𝑃 2𝑅𝑇 6𝑎
= (𝑉−𝑏)3 −
𝑑𝑉 2 𝑉4

At critical point,
𝑑2𝑃
= 0, 𝑇 = 𝑇𝑐 , and 𝑉 = 𝑉𝑐
𝑑𝑉 2
 2𝑅𝑇𝑐 6𝑎
So, − =0
(𝑉𝑐 −𝑏)3 𝑉𝑐4
6𝑎 2𝑅𝑇𝑐
Or, = (𝑉 …………………………(3)
𝑉𝑐4 𝑐 −𝑏)
3

Dividing equ(2) by (3),

𝑉𝑐 𝑉𝑐 −𝑏
=
3 2

Or, 2𝑉𝑐 = 3𝑉𝑐 − 3𝑏

Or, 𝑉𝑐 = 3𝑏
Substituting the value 𝑉𝑐 in equ(2),
2𝑎 𝑅𝑇𝑐
=
27𝑏3 4𝑏2
8𝑎
Or, 𝑇𝑐 =
27𝑅𝑏

Substituting the value of 𝑉𝑐 𝑎𝑛𝑑 𝑇𝑐 in the following equation,

𝑅𝑇𝑐 𝑎 𝑅×8𝑎 𝑎
𝑃𝑐 = − = −
𝑉𝑐 −𝑏 𝑉𝑐2 27𝑅𝑏×2𝑏 9𝑏2
𝑎
Or, 𝑃𝑐 =
27𝑏2

Calculation of ‘a’ and ‘b’ (Van der Waal’s constants)

𝑎 8𝑎
We know, 𝑉𝑐 = 3𝑏, 𝑃𝑐 = , and 𝑇𝑐 =
27𝑏2 27𝑅𝑏
𝑇𝑐2 64𝑎2 27𝑏2 64𝑎
= × =
𝑃𝑐 (27)2 𝑅 2 𝑏2 𝑎 27𝑅 2

27 𝑅 2 𝑇𝑐2
So, 𝑎=
64 𝑃𝑐

𝑇𝑐 8𝑎 27𝑏2 8𝑏
Again, = × =
𝑃𝑐 27𝑅𝑏 𝑎 𝑅
𝑅𝑇𝑐
𝑏=
8𝑃𝑐

Critical coefficient
𝑅𝑇𝑐
The ratio, , is called the critical coefficient, 𝜂𝑐
𝑃𝑐 𝑉𝑐

𝑅𝑇𝑐 8𝑎 27𝑏2 1
So, 𝜂𝑐 = = 𝑅. . .
𝑃𝑐 𝑉𝑐 27𝑅𝑏 𝑎 3𝑏
 8
Or, 𝜂𝑐 = = 2.67
3

Experimental value of 𝜂𝑐 = 3.27 𝑡𝑜 4.99. So, Van der Waals equation is

approximately true.

Expression of Boyle’s temperature from Van der Waals equation

𝑎
We know, (𝑃 + )(𝑉 − 𝑏) = 𝑅𝑇
𝑉2
𝑅𝑇 𝑎
Or, 𝑃= −
𝑉−𝑏 𝑉2
𝑅𝑇𝑉 𝑎
Or, 𝑃𝑉 = −
𝑉−𝑏 𝑉

At Boyle’s Temperature 𝑇𝐵 , 𝑃𝑉 = 𝑅𝑇𝐵

𝑅𝑇𝐵 𝑉 𝑎
So, 𝑅𝑇𝐵 = −
𝑉−𝑏 𝑉
𝑉 𝑎
Or, 𝑅𝑇𝐵 ( − 1) =
𝑉−𝑏 𝑉
𝑏 𝑎
Or, 𝑅𝑇𝐵 =
𝑉−𝑏 𝑉
𝑎 𝑉−𝑏 𝑎
Or, 𝑇𝐵 = . ≈
𝑉 𝑅𝑏 𝑅𝑏
8𝑎 27
Since, 𝑇𝑐 = , So, 𝑇𝐵 = 𝑇𝑐 = 3.375𝑇𝑐
27𝑅𝑏 8

Limitations of Van der Waals equation

(i) The isothermals obtained experimentally do not fit exactly with those
obtained theoretically
(ii) a and b are Van der Waals constants. But they do vary not only with
different substances but also with temperature in the same substance
𝑉
(iii) According to van der Waals, the value of 𝑏 = 𝑐 , but actual value 𝑏 ≈
3
𝑉𝑐
. Further, theoretical value of 𝑏 =4×
2

𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑 𝑏𝑦 𝑎 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒 (𝑥), but actual value 𝑏 = 4 × √2 ×

𝑥.
Thermodynamic process
Suppose a cylinder contains gas whose pressure and volume is P 1 and V1,
respectively. If the pressure increases to P2, its volume changes to V2. We then
say that the system is subjected to a process.
“A system is said to undergo a thermodynamic process, when the values of its
thermodynamic variables change from one equilibrium state to another.”

First law of thermodynamics

Let a system change from one initial equilibrium state ‘i' to a final equilibrium
state ‘f’ in a definite way (path).
H= Heat absorbed by the system
W=Work done by the system.
Compute H minus W. Change the path to go from i to f. Compute H‒W. In each
case, we find that H‒W is same. This means that H‒W does not depend on path
but depends on the initial and final state.
[Recall mechanics: An object of mass m is moved from i to f without friction in
gravitational field, then work done 𝑊 = 𝑚𝑔(ℎ𝑓 − ℎ𝑖 ). So W depends on
(ℎ𝑓 − ℎ𝑖 ), initial and final coordinates, not in path.
In thermodynamics, H‒W also depends on initial and final coordinates. So, we
can conclude that there is a function of thermodynamic coordinates (variables)
whose final value minus initial value gives H‒W. We call this function as internal
energy.
Thus, H‒W = the internal energy change of the system.
Let, Ui= internal energy of the initial system.
Uf = internal energy of the final system.
Then, 𝑈𝑓 − 𝑈𝑖 = 𝐻 − 𝑊
Or, ∆𝑈 = 𝐻 − 𝑊 ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,(1)
Equation (1) is known as the 1st law of thermodynamics.
If our system undergoes only an infinitesimal change in state, only an
infinitesimal amount of heat dH is absorbed and only an infinitesimal amount of
work dW is done, so that the change in internal energy dU is infinitesimal, then
in differential form of first law of thermodynamics is
𝑑𝐻 = 𝑑𝑈 + 𝑑𝑊 ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,(2)
Statement: “ Every thermodynamic system in an equilibrium state possess a state
variable called the internal energy U whose change dU in a differential process is
given by 𝑑𝑈 = 𝑑𝐻 − 𝑑𝑊.”

Some application of 1st law of thermodynamics

(i) Isobaric process P

A process taking place at constant i f

pressure is called an isobaric process.

Example, water is heated in the boiler of
V
a steam engine up to its boiling point and
is vaporized to steam’ then the system is superheated, all processes proceeding
at a constant pressure.

(ii) Adiabatic process

A process that takes place in such a way that no heat flows into or out of the
system is called an adiabatic process. Experimentally such a process is
achieved either by sealing the system off from its surrounding with heat
insulating material or by performing the process quickly as heat flow is slow.
For adiabatic process, dH=0, so
𝑑𝑈 = −𝑑𝑊
Example,
a. Expansion of hot gases in an internal combustion engine
b. Propagation of sound wave in medium
 (iii) Isothermal process
If a system is perfectly conducting to the surroundings and the
temperature remains constant throughout the process, it is called an
isothermal process.

Example,
a. a practical example is a heat engine which works on the basis of Carnot
cycle that works on the basis of isothermal process.
b. Most acid base reactions to form a salt is exothermic. If no thermal
insulation is made between beaker with base solution, and the beaker is put
in a water tub and acid is poured slowly, then the heat of reaction will take
time more from beaker to water. Thus, temperature of solution remains the
same temperature of the water.

(iv) Isochoric process

If the gas is taken in a non-conducting chamber and heat is supplied to the gas,
it will increase the pressure and temperature. The volume of the gas will
remain constant. Such a process is called isochoric process.

Example, The heating or the cooling of the contents of a sealed inelastic

container. Here, the process is the addition or removal of heat; isolation of the
contents of the container establishes the closed system; the inability of the
container to deform imposes the constant volume condition.

Heat Capacities for real gas

𝑎
We know, (𝑃 + 𝑣 2) (𝑉 − 𝑏) = 𝑅𝑇

Differentiating above equation with respect to T,

 𝑎 𝜕𝑉 2𝑎 𝜕𝑉
{(𝑃 +
𝑣2
) (𝜕𝑇 )𝑃 − (𝑉 − 𝑏). 𝑉 3 . (𝜕𝑇 )𝑃 } = 𝑅
𝑎 2𝑎 𝜕𝑉
{(𝑃 +
𝑣2
) − (𝑉 − 𝑏). 𝑉 3 } . (𝜕𝑇 )𝑃 = 𝑅
𝜕𝑉 𝑅 𝑅(𝑉−𝑏)
So, ( )𝑃 = 𝑎 2𝑎 = 𝑎 2𝑎
𝜕𝑇 (𝑃+ 2 )− 3(𝑉−𝑏) (𝑃+ 2 )(𝑉−𝑏)− 3 (𝑉−𝑏)2
𝑣 𝑉 𝑣 𝑉

𝑅(𝑉−𝑏)
= 2𝑎
𝑅𝑇− 3 (𝑉−𝑏)2
𝑉

1 𝜕𝑉 1
Or, ( )𝑃 = 2𝑎
𝑉−𝑏 𝜕𝑇 𝑇{1− (𝑉−𝑏)2 }
𝑅𝑇𝑉3

1 2𝑎
= {1 + (𝑉 − 𝑏)2 } [Binomial expansion and
𝑇 𝑅𝑇𝑉 3 neglecting higher order terms of
a]

Again, let 𝑈 = 𝑈(𝑇, 𝑉)

𝜕𝑈 𝜕𝑈
So, 𝑑𝑈 = ( )𝑣 𝑑𝑇 + ( )𝑇 𝑑𝑉 ……………….(1)
𝜕𝑇 𝜕𝑉
𝜕𝑈
Now, ( )𝑣 = 𝑐𝑉 and 𝑑𝑈 = 𝑑𝐻 − 𝑃𝑑𝑉 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
𝜕𝑇
𝜕𝑈 𝜕𝑆 𝜕𝑃
So, ( ) 𝑇 = 𝑇( ) 𝑇 − 𝑃 = 𝑇( )𝑉 − 𝑃 From thermodynamic relation
𝜕𝑉 𝜕𝑉 𝜕𝑇 𝜕𝑆 𝜕𝑃
From equ(1) and above, ( ) 𝑇 = ( )𝑉
𝜕𝑉 𝜕𝑇
𝜕𝑃
𝑑𝑈 = 𝑐𝑉 𝑑𝑇 + [𝑇 ( ) − 𝑃]𝑑𝑉
𝜕𝑇 𝑉
𝑎 𝑅𝑇
From van der Waals relation, (𝑃 + ) = (𝑉−𝑏)
𝑉2
𝜕𝑃 𝑅
( )𝑉 =
𝜕𝑇 (𝑉−𝑏)
𝜕𝑃 𝑅𝑇 𝜕𝑃 𝑅𝑇 𝑅𝑇 𝑎 𝑎
𝑇( )𝑉 = , so, 𝑇( )𝑉 − 𝑃 = (𝑉−𝑏) − (𝑉−𝑏) + =
𝜕𝑇 (𝑉−𝑏) 𝜕𝑇 𝑉2 𝑉2
𝑎
𝑑𝑈 = 𝑐𝑉 𝑑𝑇 + 𝑑𝑉
𝑉2
𝜕𝑈 𝑎
So, at constant T (from above), ( ) 𝑇 = , ……………………..(2)
𝜕𝑉 𝑉2
𝑎 𝑅𝑇
Now, (𝑃 + 𝑣 2) = (𝑉−𝑏) …………………………(3)
𝜕𝑈 𝑎
Since, ( )𝑇 = ,
𝜕𝑉 𝑉2
 𝜕𝑈 𝑎
So, 𝑃 + ( )𝑇 = 𝑃 + ……………(4)
𝜕𝑉 𝑉2
𝜕𝑈 𝜕𝑈
We know, 𝑑𝐻 = 𝑑𝑈 + 𝑝𝑑𝑉 = ( )𝑣 𝑑𝑇 + ( ) 𝑇 𝑑𝑉 +PdV
𝜕𝑇 𝜕𝑉
𝑑𝐻 𝜕𝑈 𝜕𝑈 𝑑𝑉
Or, = ( )𝑣 + [𝑃 + ( ) ] . ………..(5)
𝑑𝑇 𝜕𝑇 𝜕𝑉 𝑑𝑇 𝑇

If the gas is heated at constant volume, then

𝜕𝐻
𝑑𝑉 = 0 and ( )𝑉 = 𝑐𝑉
𝜕𝑇
𝜕𝐻 𝜕𝑈
From equ(5), ( )𝑉 = ( )𝑣 = 𝑐𝑉
𝜕𝑇 𝜕𝑇

Regain the initial state, If the gas is heated at constant pressure,

𝜕𝐻
( )𝑃 = 𝑐𝑃
𝜕𝑇
𝜕𝑈 𝜕𝑉 𝑎 𝜕𝑉
From (5), 𝑐𝑃 − 𝑐𝑉 = [𝑃 + ( ) ] . ( ) = (𝑃 + 2 ) ( )
𝜕𝑉 𝜕𝑇 𝑉 𝑇 𝜕𝑇 𝑃 𝑃
𝑅𝑇 𝜕𝑉 1 2𝑎
= ( ) = 𝑅𝑇. 𝑇 . {1 + 𝑅𝑇𝑉 3 (𝑉 − 𝑏)2 }
(𝑉−𝑏) 𝜕𝑇 𝑃

2𝑎
𝑐𝑃 − 𝑐𝑉 = 𝑅. {1 + (𝑉 − 𝑏)2 }
𝑅𝑇𝑉 3

Elasticities of a perfect gas

There are two types of elasticities‒ isothermal and adiabatic. By definition,
elasticity or bulk modulus of elasticity, E, is given by
𝑉𝑜𝑙𝑢𝑚𝑒 𝑠𝑡𝑟𝑒𝑠𝑠 Δ𝑃 Δ𝑃
𝐸= = Δ𝑉 = −𝑉
𝑉𝑜𝑙𝑢𝑚𝑒 𝑠𝑡𝑟𝑎𝑖𝑛 − Δ𝑉
𝑉

𝜕𝑝
Adiabatic elasticity is defined by, 𝐸𝑆 = −𝑉 ( ) , where S denotes constant
𝜕𝑉 𝑠

entropy or heat process. On the other hand, isothermal elasticity is defined by,
𝜕𝑝
𝐸𝑇 = −𝑉 ( ) . So,
𝜕𝑉 𝑇
𝜕𝑝
𝐸𝑆 ( )
𝜕𝑉 𝑠
= 𝜕𝑝 ………………………………………..(1)
𝐸𝑇 ( )
𝜕𝑉 𝑇

Taking T as function of V and P, we obtain,

𝑇 = 𝑇(𝑉, 𝑃)
 𝜕𝑇 𝜕𝑇
Or, 𝑑𝑇 = ( )𝑃 𝑑𝑉 + ( ) 𝑑𝑃 ………………………(2)
𝜕𝑉 𝜕𝑃 𝑉

For an isothermal process, dT=0, so that from equ(2),

𝜕𝑇 𝜕𝑇
(𝜕𝑃) 𝑑𝑃 = − (𝜕𝑉)𝑃 𝑑𝑉
𝑉
𝜕𝑇
𝜕𝑝 ( )
𝜕𝑉 𝑃
( )𝑇 = − 𝜕𝑇 ………………………….(3)
𝜕𝑉 ( )
𝜕𝑃 𝑉

Again, let 𝑈 = 𝑈(𝑇, 𝑉)

𝜕𝑈 𝜕𝑈
So, 𝑑𝑈 = ( )𝑣 𝑑𝑇 + ( )𝑇 𝑑𝑉 ……………….(4)
𝜕𝑇 𝜕𝑉

Now, 𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 𝜕𝑈
( ) = 𝑐𝑉
𝜕𝑈 𝜕𝑈
𝑑𝐻 = ( )𝑣 𝑑𝑇 + ( ) 𝑇 𝑑𝑉 + 𝑃𝑑𝑉 𝜕𝑇 𝑣
𝜕𝑇 𝜕𝑉

𝑑𝐻 = 𝑐𝑉 𝑑𝑇 + {𝑃 + ( ) } 𝑑𝑉
𝜕𝑈 𝜕𝑈 𝜕𝑉
𝜕𝑉 𝑇 𝑐𝑃 − 𝑐𝑉 = [𝑃 + ( ) ].( )
𝜕𝑉 𝑇 𝜕𝑇 𝑃
𝑐𝑃 −𝑐𝑉
= 𝑐𝑉 𝑑𝑇 + 𝜕𝑉 . 𝑑𝑉
( )
𝜕𝑇 𝑃

𝜕𝑇
= 𝑐𝑉 𝑑𝑇 + (𝑐𝑃 − 𝑐𝑉 ) ( ) . 𝑑𝑉
𝜕𝑉 𝑃 𝑐𝑃
𝑤ℎ𝑒𝑟𝑒, 𝛾 =
Or,
𝑑𝐻
= 𝑑𝑇 + (𝛾 − 1) ( ) . 𝑑𝑉
𝜕𝑇 𝑐𝑉
𝑐𝑉 𝜕𝑉 𝑃
𝜕𝑇 𝜕𝑇 𝜕𝑇
= ( )𝑃 𝑑𝑉 + ( ) 𝑑𝑃 + (𝛾 − 1) ( ) . 𝑑𝑉 Using equ (2)
𝜕𝑉 𝜕𝑃 𝑉𝜕𝑉 𝑃
𝜕𝑇 𝜕𝑇
= ( ) 𝑑𝑃 + 𝛾 ( ) . 𝑑𝑉
𝜕𝑃 𝑉 𝜕𝑉 𝑃

For adiabatic process, dH=0, the above equation becomes

𝜕𝑇 𝜕𝑇
(𝜕𝑃) 𝑑𝑃 = −𝛾 (𝜕𝑉) . 𝑑𝑉
𝑉 𝑃
𝜕𝑇
𝜕𝑃 −𝛾( )
𝜕𝑉 𝑃
Or, (𝜕𝑉 ) = 𝜕𝑇 ……………………..(5)
𝑆 ( )
𝜕𝑃 𝑉

From equ(1) and using equ(3) and (5),

 𝜕𝑇
−𝛾( )
𝜕𝑉 𝑃
𝜕𝑇
( )
𝐸𝑆 𝜕𝑃 𝑉 𝑐𝑃
= 𝜕𝑇 =𝛾=
𝐸𝑇 ( )𝑃 𝑐𝑉
𝜕𝑉
− 𝜕𝑇
( )
𝜕𝑃 𝑉

The above relation can be obtained by ideal gas equation as follows:

For an isothermal change, we have PV=constant
Or, 𝑃𝑑𝑉 + 𝑉𝑑𝑃 = 0
𝜕𝑃 𝑃
Or, ( ) 𝑇 = − …………………………(1)
𝜕𝑉 𝑉
𝑐𝑃
For an adiabatic process, 𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡, 𝑤ℎ𝑒𝑟𝑒 𝛾 =
𝑐𝑉
𝜕𝑃
So, . 𝑉 𝛾 + 𝑃. 𝛾𝑉 𝛾−1 = 0
𝜕𝑉
𝜕𝑃 𝛾𝑃
Or, ( )𝑆 = − …………………….(2)
𝜕𝑉 𝑉

From equ(1) and (2),

𝜕𝑝
𝐸𝑆 ( )
𝜕𝑉 𝑠
= 𝜕𝑝 =𝛾
𝐸𝑇 ( )
𝜕𝑉 𝑇

Gas equation during adiabatic process

Consider 1 gm ideal gas insulating from its surrounding. Let the external wok
done (i.e. heat applied) on it be 𝑑𝑊 = 𝑃𝑑𝑉. From 1st law of thermodynamics,
𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 ……………………….(1)
From definition of 𝑐𝑉 , 𝑑𝐻 = 𝑐𝑉 𝑑𝑇 , and in this case 𝑑𝑊 = 𝑃𝑑𝑉 = 0, as 𝑑𝑉 =
0, then 𝑑𝑈 = 𝑑𝐻 = 𝑐𝑉 𝑑𝑇 ………………….(2)
We restore the system and change it adiabatically so that T tends to T+dT, and
for this V changes to V+dV.
For adiabatic process, dH=0, since the gas is ideal U depends only on
temperature. Putting dH=0 and 𝑑𝑈 = 𝑐𝑉 𝑑𝑇 in equ(1).
0 = 𝑐𝑉 𝑑𝑇 + 𝑃𝑑𝑉 ……………………..(3)
From ideal gas equation, 𝑃𝑉 = 𝑅𝑇
Or, 𝑃𝑑𝑉 + 𝑉𝑑𝑃 = 𝑅𝑑𝑇
 𝑃𝑑𝑉+𝑉𝑑𝑃
Or, 𝑑𝑇 =
𝑅

Using this relation in equ(3),

𝑃𝑑𝑉+𝑉𝑑𝑃
𝑐𝑉 + 𝑃𝑑𝑉 = 0
𝑅

Or, 𝑐𝑉 (𝑃𝑑𝑉 + 𝑉𝑑𝑃) + 𝑅. 𝑃𝑑𝑉 = 0

But, 𝑐𝑃 − 𝑐𝑉 = 𝑅
So, 𝑐𝑉 (𝑃𝑑𝑉 + 𝑉𝑑𝑃) + (𝑐𝑃 − 𝑐𝑉 )𝑃𝑑𝑉 = 0
𝑐𝑃 . 𝑃𝑑𝑉 + 𝑐𝑉 𝑉𝑑𝑃 = 0
𝑐𝑃 𝑑𝑉 𝑑𝑃
Or, + =0
𝑐𝑉 𝑉 𝑃
𝑐𝑃
Since, =𝛾
𝑐𝑉
𝑑𝑃 𝑑𝑉
So, +𝛾 =0
𝑃 𝑉

After integration,
𝑙𝑛𝑃 + 𝛾𝑙𝑛𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
Or, 𝑙𝑛𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
So, 𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

𝑅𝑇
Taking 𝑃𝑉 = 𝑅𝑇, 𝑃=
𝑉

Since, 𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑅𝑇
Or, 𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡, Since R=constant, So
𝑉

𝑇𝑉 𝛾−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑡

𝑅𝑇
Again, 𝑉=
𝑃

𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑅𝑇
Or, 𝑃( )𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑃
𝑅𝛾𝑇 𝛾
Or, = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑃𝛾−1
𝑃𝛾−1
Or, = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇𝛾
Problem 1: A motor car tyre has a pressure of 2 atmospheres at the room
temperature of 27 ℃. If the tyre suddenly bursts at 1 atmospheric pressure, find
the resulting temperature. Assume 𝛾 = 1.4.

Solution: Here, P1= 2 atmospheres T1= 273+27=300K, P2= 1 atmosphere, T2=?

𝛾−1 𝛾−1
𝑃1 𝑃2
𝛾 = 𝛾
𝑇1 𝑇2
𝛾−1 𝛾
𝑃1 𝑇1
Or, 𝛾−1 = 𝛾
𝑃2 𝑇2

300 1.4
Or, (2)1.4−1 = ( )
𝑇2

Or, 0.4 𝑙𝑜𝑔 (2) = 1.4 (𝑙𝑜𝑔300 − 𝑙𝑜𝑔𝑇2 )

Or, 1.4 𝑙𝑜𝑔𝑇2 = 3.3476
Or, 𝑇2 = 246.1 = −26.9 ℃

Problem: A quantity of air at 27 ℃ and one atmospheric pressure is suddenly

compressed to half its original volume. Find the final pressure and temperature.
Assume 𝛾 = 1.4.

𝑉
Solution: Here, P1= 1 atmospheres, T1= 273+27=300K, 𝑉2 = 1 , P2=?, T2=?
2
𝛾
𝛾 𝛾 𝑃1 𝑉1
(i) 𝑃1 𝑉1 = 𝑃2 𝑉2 , or, 𝑃2 = 𝛾 = 1[2]1.4 = 2.636 𝑎𝑡𝑚𝑜𝑠𝑝ℎ𝑒𝑟𝑒
𝑉2
𝛾−1
𝛾−1 𝛾−1 𝑉1
(ii) 𝑇1 𝑉1 = 𝑇2 𝑉2 ,Or, 𝑇2 = 𝑇1 𝛾−1 = 300[2]0.4 = 395.9 𝐾 =
𝑉2

122.9 ℃
Reversible and irreversible process
Consider a mass M of a gas (real) confined in a cylinder piston arrangement of
volume V; the gas having a pressure P and a temperature T. In equilibrium state,
P, V and T are constant with time. Side walls of the cylinder are ideal heat
insulator.
Base is ideal conductor attached with a
reservoir. Change the state from ‘i’ to
‘f’ by changing P and V; Keeping i
T=constant, change V to ½ V. Consider
f
2nd cases.
(i) We depress the piston very rapidly;
wait for a moment for equilibrium
with R. During this process, the gas
is turbulent and its P and T are not R
well defined. So, we cannot draw P‒V
diagram. We only know Volume=½ V. The system goes from one
equilibrium state ‘i’ to another ‘f’ through non-equilibrium states.

f f
Ti=Tf T=Constant

i i
f

(ii) We depress the piston very slowly; by adding sand on it, so that P, V
and T are well defined. First put a small grain of sand on the piston, V
will decrease and the system departs from equilibrium only slightly. A
small amount of heat H will be transferred to R and the system goes to
equilibrium so that V goes to ½ V.
During this entire process the system is never in a state differing much from
equilibrium state. For a smaller successive increase in P, the intermediate states
will depart from equilibrium. If this increase is very infinitesimal, we arrive at an
ideal process in which the system passes through a continuous succession of
equilibrium states. When a process is carried out extremely slowly such that every
state, through which the system passes, departs only infinitesimally from
equilibrium, the process is said to be quasi static. In this case, we plot a P‒V
diagram.
Process of example (ii) is called reversible process. A reversible process is one
that, by a differential change in the environment, can be made to retrace its path.
Process of example (i) is called irreversible process. A process is said to be
irreversible if it cannot be retraced back exactly in the opposite direction.

Cyclic process
Suppose that we have a system of real gas in an equilibrium state in cylinder
piston arrangement. We can change the state to another equilibrium state by a
variety of processes; we can expand or compress the gas; we can add or subtract
energy in the form of heat; we can do things reversibly or irreversibly.
“If a system goes from one equilibrium state to another and returns to its initial
state by a sequence of process, we call this a cycle.” If the processes involved are
reversible, we call it reversible cycle. In each cycle, there will be a heat flow into
the system or from the system; and there will be work done W by the system or
on the system.
P
Figure shows a reversible cycle on a P‒V b

diagram; abc allows the system to expand: a

c
work done W1=area of abcef. cda allows the
system to return: work done W2= area of d
adcef. The net work done, dW= W1 ‒ W2.
f e V
Heat engine
Let in a cycle, Hot
reservoir
H1= amount of heat absorbed by the
H1
system (Heat engine).
H2= amount of heat given out by the system
H2
dW= net work done by the system
Cold
Let H1 and H2 are positive reservoir
If H1> H2 and if Work is done by the system,
then the mechanical device that causes the system to undergo cyclic change is
called a heat engine.
Figure shows a scheme of a heat engine. Its purpose is to do work continuously
by performing the same cycle repeatedly. Heat engine converts heat into work.
Here,
System=working substance
dW=output of engine=network done
dH= H1‒ H2= input of engine=heat absorbed.

Efficiency of an engine
The thermal efficiency (𝜂) of a heat engine is defined as the ratio of the net work
done to the heat absorbed during the complete cycle.
𝑊𝑜𝑟𝑘 𝑜𝑢𝑡𝑝𝑢𝑡 𝑑𝑊
Thus, 𝜂= =
𝐻𝑒𝑎𝑡 𝑖𝑛𝑝𝑢𝑡 𝐻1

Since, in a cycle, system returns to the initial state, then 𝑑𝑈 = 0. Applying 1st law
of thermodynamics,
𝑑𝑈 = 𝑑𝐻 − 𝑑𝑊
Or, 𝑑𝑊 = 𝑑𝐻 = 𝐻1 − 𝐻2
𝐻1 −𝐻2 𝐻2
So, 𝜂= =1− , since H1> H2, 𝜂 < 1, But why? Is it due to
𝐻1 𝐻1

irreversibility of thermal process? This dictates us to make a heat engine that

would give maximum efficiency.
Examples of heat engines
Common heat engines use steam or a mixture of fuel or air, or fuel and O 2 as
working substance. Heat is obtained from the combustion of a fuel such as
gasoline or coal, or from mass annihilation in nuclear fission in reactors. Heat is
discharged at the exhaust or to a condenser.
Carnot engine
Real heat engines do not operate on a reversible cycle. Then Sadi Carnot, a French
scientist in 1824, conceived an idealized theoretical engine, called Carnot engine
to obtain the maximum attainable thermal efficiency. It is free from all effects of
practical engine. He recognized that 𝜂𝑚𝑎𝑥 corresponds to a thermodynamically
reversible heat engine.

Sand Isothermal process

V2
a b
gas P 2V 2T 1
P 1V 1T 1
V1
Adiabatic process
Adiabatic process
H1 T1

V3

V4 V2

V1 gas gas

V3

P 3V 3T 2
P 4V 4T 2 c
d gas

V4 Isothermal process

H2 T2
Carnot cycle
Carnot cycle is a reversible cycle.
The working substance is ideal gas contained in a cylinder with heat-conducting
bas and non-conducting walls and piston. A part of environment is a heat reservoir
that has large heat capacity at T1 and another reservoir of large heat capacity at
T2 and two non-conducting stands.

P 1V 1
P
1
a
H1, T1

P 2V 2
P2
b

P3

P 4V 4 d
P4
P3V3
H2, T2 c

V1, V4 V2, V3

Working steps of the cycle is shown on PV-diagram.

Step 1: The gas is in equilibrium state with P1,V1,T1 (Fig. at a). We put the
cylinder on reservoir at T1 and allow gas to expand (by taking out sands) slowly
to P2,V2,T1 (Fig. at b). During the process, H1 is absorbed by the gas by
conduction through base. Gas expands isothermally at T1 and does work on piston
and sands.
Step 2: We put cylinder on the non-conducting stand and allow the gas to expand
(by taking out sands) slowly to P3,V3,T2 (Fig. at c). The expansion is adiabatic
because no heat can enter or leave the system. Gas works in raising piston at the
cost of internal energy and its temperature falls to T2.
Step 3: We put the cylinder on reservoir at T2 and compress the gas (by giving
more sands) slowly to P4,V4,T2 (Fig. at d). Heat H2 is transferred from the gas to
the reservoir. Process is isothermal at T2 and work is done on the gas by piston
and load.
Step 4: We put the cylinder on a non-conducting stand and compress the gas (by
giving more sands) slowly to the initial state P1V1T1. Process is adiabatic. Heat
does not enter or go out. Work is done on the gas and its temperature rises to T1
(Fig at a).

Calculation of efficiency of a Carnot engine

(i) Consider 1 g mole of a gas. Work done from a to b is (isothermal
process),
𝑉
𝑊1 = ∫𝑉 2 𝑃1 𝑑𝑉 𝑃1 𝑉 = 𝑅𝑇1
1

𝑉 𝑑𝑉
= ∫𝑉 2 𝑅𝑇1
1 𝑉
𝑉2
= 𝑅𝑇1 𝑙𝑛 = 𝐻1 ………………………………..(1)
𝑉1

(ii) Work done from b to c (adiabatic process)

𝑉
𝑊2 = ∫𝑉 3 𝑃2 𝑑𝑉 𝑃2 𝑉𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = 𝐾
2 𝛾 𝛾 1−𝛾
𝑃3 𝑉3 = 𝑃3 𝑉3 = 𝐾 Or 𝐾𝑉3 = 𝑃3 𝑉3
𝑉3 𝑑𝑉 1−𝛾
= ∫𝑉 𝐾 𝑉𝛾 And 𝐾𝑉2 = 𝑃2 𝑉2,
2
𝑃2 𝑉2 = 𝑅𝑇1, and 𝑃3 𝑉3 = 𝑅𝑇2
𝑉−𝛾+1 𝑉3
= 𝐾[ ]
−𝛾+1 𝑉2
1−𝛾 1−𝛾 1−𝛾 1−𝛾
𝑉3 −𝑉2 𝐾𝑉3 −𝐾𝑉2 𝑃3 𝑉3 −𝑃2 𝑉2 𝑅(𝑇2 −𝑇1 )
= 𝐾[ ]= = =
1−𝛾 1−𝛾 1−𝛾 1−𝛾
𝑅(𝑇1 −𝑇2 )
= …………………………(2)
𝛾−1

(iii) Work done from c to d (isothermal process)

𝑉
𝑊3 = ∫𝑉 4 𝑃3 𝑑𝑉
3

𝑉 𝑑𝑉
= ∫𝑉 4 𝑅𝑇2
3 𝑉
𝑉4
= 𝑅𝑇2 𝑙𝑛 = 𝐻2 ………………………………..(3)
𝑉3
 (iv) Work done from d to a (adiabatic process)
𝑉
𝑊4 = ∫𝑉 1 𝑃4 𝑑𝑉
4
𝑅(𝑇1 −𝑇2 )
=− …………………………(4)
𝛾−1

Total work done,

𝑊 = 𝑊1 + 𝑊2 + 𝑊3 + 𝑊4
𝑉2 𝑅(𝑇1 −𝑇2 ) 𝑉3 𝑅(𝑇1 −𝑇2 )
= 𝑅𝑇1 𝑙𝑛 + − 𝑅𝑇2 𝑙𝑛 −
𝑉1 𝛾−1 𝑉4 𝛾−1

𝑉2 𝑉3
= 𝑅𝑇1 𝑙𝑛 − 𝑅𝑇2 𝑙𝑛 ………………………….(5)
𝑉1 𝑉4

The points a and d are on the same adiabatic,

𝑇1 𝑉1𝛾−1 = 𝑇2 𝑉4𝛾−1
𝑇2 𝑉
Or, = ( 1)𝛾−1 …………………………..(6)
𝑇1 𝑉4

The points b and c are on the same adiabatic,

𝑇1 𝑉2𝛾−1 = 𝑇2 𝑉3𝛾−1
𝑇2 𝑉
= ( 2)𝛾−1 …………………………..(7)
𝑇1 𝑉3

From equ(6) and (7),

𝑉 𝑉
( 1)𝛾−1 = ( 2)𝛾−1
𝑉4 𝑉3
𝑉1 𝑉2
=
𝑉4 𝑉3
𝑉2 𝑉3
=
𝑉1 𝑉4

From equ(5),
𝑉2 𝑉2
𝑊 = 𝑅𝑇1 𝑙𝑛 − 𝑅𝑇2 𝑙𝑛
𝑉1 𝑉1
𝑉2
= 𝑅𝑙𝑛 (𝑇1 − 𝑇2 )
𝑉1
𝑈𝑠𝑒𝑓𝑢𝑙 𝑜𝑢𝑡𝑝𝑢𝑡 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 ℎ𝑒𝑎𝑡 𝑐𝑜𝑛𝑣𝑒𝑟𝑡𝑒𝑑 𝑖𝑛𝑡𝑜 𝑤𝑜𝑟𝑘
Efficiency, 𝜂= =
𝑖𝑛𝑝𝑢𝑡 𝑇𝑜𝑡𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 ℎ𝑒𝑎𝑡 𝑖𝑛𝑝𝑢𝑡
𝑉
𝑊 𝑅𝑙𝑛 2 (𝑇1 −𝑇2 )
𝑉 1
𝜂= = 𝑉
𝐻1 𝑅𝑇1 𝑙𝑛 2
𝑉1
 𝑇2
=1− ……………………(8)
𝑇1

This is the expression of efficiency of a Carnot engine.

Equation (8) shows that 𝜂 depends on temperatures of the source and sink and
does not depend on working substance. For, 𝜂 = 1, 𝑇2 = 0 𝐾, which is not
possible. Hence the efficiency of an idealized Carnot engine is less than 1. So, it
is not possible to convert whole heat into work by absorbing the heat from a
source.

𝑊 𝐻1 −𝐻2
Note 1: Again, 𝜂= =
𝐻1 𝐻1
𝐻2
=1− ………………………….(9)
𝐻1

𝐻2 𝑇2
Comparing equ(8) with (9), = …………………….(10)
𝐻1 𝑇1

Note 2:, In Carnot engine, 𝜂 < 1. Every engine operating in cycles has to absorb
heat at higher temperature and reject heat at lower temperature. A complete
conversion of heat into useful work cannot thus be made, although the converse
is possible. This leads to an important law of nature- the second law of
thermodynamics.

Second law of thermodynamics

There are many statements about 2nd law; two of which are discussed below
According to Kelvin:
“It is impossible to get a continuous supply of work from a body by cooling it to
a temperature lower that its surrounding”.
Explanation: Consider a source at T1 and a sink at T2. Let T1>T2. In a heat engine,
steam from the source does work and discharges the remaining heat to the sink,
because T1 of the source must be greater than T2 of the sink; the engine will not
work when T1=T2. The above statement rules out our ambitious heat engines,
because we can have continuous supply of work by returning some heat to the
sink.
According to Clausius:
“It is impossible to make heat flow from a body at a lower temperature to a body
at a higher temperature without doing external work on the working substance”.
Explanation: The above statement rules out our ambitious refrigerator. A
refrigerator is a device that performs a cycle in the direction opposite to that of a
heat engine. In the refrigerator, heat is transferred to the substance from a cooling
body to a hot reservoir. The second law rules out the possibility of heat energy
flowing from a cold to a hot body in such a case and so determines the direction
of heat transfer. The direction can be reversed by expense of work.

Carnot theorem
Carnot developed the concept of a reversible engine and the reversible cycle. He
stated a theorem of great importance.
“The efficiency of all reversible engines operating between the same two
temperatures is the same, and no irreversible engine working between the same
two temperatures can have a greater efficiency than this,”
(i) From first part, we have to prove, 𝜂 = 𝜂´, where 𝜂 and 𝜂´ are
efficiencies of two engines.
(ii) From second part, we have to prove, 𝜂𝑖𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 ≤ 𝜂𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒

From the theorem, nothing is said about the working substance, so that “the
efficiency of reversible engine is independent of the working substance and
depends only on temperatures.”
Proof: 1st part
T1 Heat source
Let Q and Q´ are two reversible
engines. They operate between
H1 𝐻1´ − 𝐻1 𝐻1´
temperatures T1 and T2, where
T1>T2. (The pressure, the length
Q Q´
of stroke or working substance of
W
Q and Q´ may differ. Q runs in the H2 𝐻2´
forward direction, and Q´ runs in 𝐻2´ − 𝐻2

the backward direction.

T2 Cool source

So, Q (heat engine) takes in heat energy H1 at T1 and gives out heat energy H2 at
T2.
Q´ (refrigerator) takes in heat 𝐻2´ at T2 and gives out heat 𝐻1´ at T1.
We connect the engines mechanically and adjust the stroke lengths so that work
done per cycle by Q is just sufficient (equal) to operate Q´.
Suppose efficiency, 𝜂 𝑜𝑓 𝑄 > 𝜂′ 𝑜𝑓 𝑄′
𝐻1 −𝐻2 𝐻1′ −𝐻2′
Since, 𝜂 > 𝜂′ , then > …………………………(1)
𝐻1 𝐻1′

Since work per cycle done by one engine equals the work per cycle done on the
other engine. That is,
𝑊 = 𝑊′
Or, 𝐻1 − 𝐻2 = 𝐻1′ − 𝐻2′ …………………………..(2)
From equ(1) and (2),
1 1
> Or, 𝐻1 < 𝐻1′
𝐻1 𝐻1′

Hence from (2), 𝐻2 < 𝐻2′

Here, both (𝐻1′ − 𝐻1 ) and (𝐻2′ − 𝐻2 ) are positive
So, Hot source gains heat, (𝐻1′ − 𝐻1 ) positive
Cool source loses heat, (𝐻2′ − 𝐻2 ) positive
But no work is done in the process by the combined system, Q+Q′ (as W‒W′=0)
and heat is transferred from a body at lower temperature to a body at higher
temperature without performing any work on the system. This is a direct
contradiction to Clausius statement of 2nd law. Hence,
𝜂 ≯ 𝜂′ (𝜂 cannot be greater than 𝜂′ )
Likewise, by reversing the engine, we can prove
𝜂′ ≯ 𝜂
So, 𝜂 = 𝜂′

2nd Part:
T1 Heat source

H 𝐻

W′ Q R W

𝐻 −W′ 𝐻−𝑊

T2 Cool source

Let, Q= an irreversible engine, R= a reversible engine, T1>T2. Q and R are

coupled. Q drives R backwards. 𝜂𝑖𝑟𝑟 =efficiency of an irreversible engine. 𝜂′ =
efficiency of a reversible engine.
Thus, by above reasoning, 𝜂𝑖𝑟𝑟 ≯ 𝜂′
But Q cannot be reversed because of irreversibility, so we cannot prove that,
𝜂′ ≯ 𝜂𝑖𝑟𝑟
So, 𝜂𝑖𝑟𝑟 is either equal to or less than 𝜂′ . Since, 𝜂′ = 𝜂 = 𝜂𝑟𝑒𝑣 . So,
𝜂𝑖𝑟𝑟 ≤ 𝜂𝑟𝑒𝑣
Problem 1: A Carnot’s engine whose temperature of the source is 400 K takes
200 calories of heat at this temperature and rejects 150 calories of heat to the sink.
What is the temperature of the sink? Also calculate the efficiency of the engine.

Solution: Here, H1= 200 cal, H2=150 Cal, T1= 400 K, T2=?
𝐻1 𝑇1
We know, =
𝐻2 𝑇2

𝐻2 150
Or, 𝑇2 = × 𝑇1 = × 400 = 300 𝐾
𝐻1 200

𝐻2 300
Again, 𝜂 =1− =1− = 0.23 = 23%
𝐻1 400

Problem 2: A Carnot’s refrigerator takes heat from water at 0 ℃ and discards it

to a room temperature of 27 ℃. 1 kg of water at 0 ℃ is to be changed into ice at
0 ℃. Find the amount of heat (in Calories) discarded to the room. What is the
work done by the refrigerator in this process?

Solution: Here, H1=?, H2=mL=1000×80= 80,000 Cal, T1=273+27=300 K,

T2=273 K
𝐻1 𝑇1
We know, =
𝐻2 𝑇2

𝐻2 80000
Or, 𝐻1 = × 𝑇1 = × 300 = 87,900 𝐶𝑎𝑙
𝑇2 273

Work done by the refrigerator, 𝑊 = 𝐽(𝐻1 − 𝐻2 ) = 4.2(87,900 − 80,000)

= 3.183 × 104 𝐽
Entropy
Let, i= initial equilibrium state of a
P
thermodynamic system. R1
i
f= final equilibrium state.
f
The system ‘i' can follow a number of
R2
reversible paths to go from ‘i' to ‘f’.
R1 is a path from ‘i' to ‘f’
V
R2 is a path from ‘f' to ‘i’
The two paths form a reversible cycle, then from Clausius theorem of 2nd law for
reversible cycle,
⬚ 𝑑𝐻
∮𝑅 = 0 ………………….(1)
1 𝑅2 𝑇

𝑓 𝑑𝐻 𝑖 𝑑𝐻
Or, ∫𝑖 (𝑓𝑜𝑟 𝑅1) + ∫𝑓 (𝑓𝑜𝑟 𝑅2) = 0
𝑇 𝑇
𝑓 𝑑𝐻 𝑖 𝑑𝐻
Or, ∫𝑖 (𝑓𝑜𝑟 𝑅1) = − ∫𝑓 (𝑓𝑜𝑟 𝑅2) ………………….(2)
𝑇 𝑇

If the integral of a quantity around any closed path is zero, that quantity is called
a state variable, regardless of how that state was derived at. We call this entropy,
S. As R2 is a reversible path, then,
𝑖 𝑑𝐻 𝑓 𝑑𝐻
− ∫𝑓 (𝑓𝑜𝑟 𝑅2) = ∫𝑖 (𝑓𝑜𝑟 𝑅2 )
𝑇 𝑇
𝑓 𝑑𝐻 𝑓 𝑑𝐻
So, ∫𝑖 (𝑓𝑜𝑟 𝑅1) = ∫𝑖 (𝑓𝑜𝑟 𝑅2) ……………..(3)
𝑇 𝑇

𝑖 𝑑𝐻
So, ∫𝑓 (𝑓𝑜𝑟 𝑅) does not depend on reversible path connecting initial
𝑇

and final states. That is the integral quantity depends on states ‘i' and ‘f’ and does
not depend on R1 and R2.
𝑑𝐻 𝑓 𝑓
Let, 𝑑𝑆 = , then from equ(3) ∫𝑖 𝑑𝑆 (𝑓𝑜𝑟 𝑅1) = ∫𝑖 𝑑𝑆 (𝑓𝑜𝑟 𝑅2) =
𝑇
𝑓
∫𝑖 𝑑𝑆
If the entropy at ‘i' is Si and at ‘f’ is Sf, then
 𝑓 𝑓 𝑑𝐻
𝑆𝑓 − 𝑆𝑖 = ∫𝑖 𝑑𝑆 = ∫𝑖 …………………………(4)
𝑇

Equation(4) indicates that there exists a function of the thermodynamic

coordinates of a system whose value at the final state minus the initial state equals
𝑓 𝑑𝐻
∫𝑖 .This state function was named as “entropy” by Rudolf Clausius.
𝑇

“Entropy depends on initial and final states”.

So, “the thermal property of a body which remains constant between two
adiabatics like the temperature T is constant in isothermal condition, is called the
entropy”

Entropy in a Reversible process

Entropy change of the universe due to reversible process:
When a reservoir absorbs heat H at temperature T from any system during any
𝐻
kind of process, the entropy change of reservoir is .
𝑇

In case of entropy changes of the universe, consider a flow of heat between a

system and a set of reservoirs of temperature ranging from Ti to Tf

T Reservoir

dH
dH

System

For any infinitesimal portion of the process, if dH is absorbed by the system from
one of the reservoirs at temperature T, then
𝑑𝐻
dS of the system=
𝑇
𝑑𝐻
dS of the reservoir=−
𝑇
 𝑑𝐻 𝑑𝐻
Entropy change of the universe= = − =0
𝑇 𝑇

If dH is rejected by the system, then

𝑑𝐻
dS of the system=−
𝑇
𝑑𝐻
dS of the reservoir=
𝑇
𝑑𝐻 𝑑𝐻
Entropy change of the universe= =− + =0
𝑇 𝑇

The change of entropy of the universe is 0 for a reversible process.

Entropy in an Irreversible process

Entropy, like all state variables, depends only on the state of the system and we
must be able to calculate the change in entropy for irreversible processes,
provided only that they begin and end in equilibrium state. Consider the following
example:
Consider the free expansion of a gas. let a gas be double its volume by expanding
into an evacuated enclosure (a gas enclosure and an evacuated enclosure are
connected by pipe with stopcock. For sudden open of stopcock, gas goes to
vacuum and expands freely. Under heat insulation- i.e. the process is adiabatic).
Since no work is done against vacuum, dW=0, since gas is enclosed by non-
conducting walls, dH=0.
From 1st law of thermodynamics, 𝑑𝑈 = 0 𝑜𝑟, 𝑈𝑖 − 𝑈𝑓 = 0 𝑜𝑟 ,
𝑈𝑖 = 𝑈𝑓 …………………..(1)
Here, ‘i’ and ‘f’ are initial and final states respectively. If the gas is ideal gas, U
depends on T, so , 𝑇𝑖 = 𝑇𝑓
Free expansion is an irreversible process. If we turn the stopcock in the opposite
direction, it will not reverse. There is a Sf ‒Si and we cannot calculate it from
equation (1), because this is for reversible path; other difficult is that dH=0.
In free expansion, the convenient reversible path is isothermal expansion from Vi
to Vf=2Vi. Although it is a different set of operation from free expansion, it
connects the same set of ‘i’ and ‘f’. Thus,
𝑓 𝑑𝐻
𝑆𝑓 − 𝑆𝑖 = ∫𝑖 ………………………….(2)
𝑇
𝑅𝑇
For isothermal expansion, 𝑑𝐻 ≠ 0, 𝑏𝑢𝑡 𝑑𝑈 = 0, So, 𝑑𝐻 = 𝑃𝑑𝑉 = 𝑑𝑉
𝑉
𝑓 𝑑𝑉 𝑉𝑓
From equ(2), 𝑆𝑓 − 𝑆𝑖 = ∫𝑖 𝑅 = 𝑅𝑙𝑛 = 𝑅𝑙𝑛2
𝑉 𝑉𝑖

This is positive. So, the entropy of the system increases in irreversible process.

Problem: Calculate the entropy change that an ideal gas undergoes in a reversible
isothermal expansion from a volume Vi to a volume Vf.
From 1st law of thermodynamics, 𝑑𝑈 = 𝑑𝐻 − 𝑃𝑑𝑉
But dU=0, because U depends only on temperature T for an ideal gas and T is a
constant.
𝑑𝐻 = 𝑃𝑑𝑉
𝑑𝐻 𝑃𝑑𝑉
But, 𝑑𝑆 = =
𝑇 𝑇
𝜇𝑅𝑇
Since, 𝑃𝑉 = 𝜇𝑅𝑇 𝑜𝑟 𝑃 =
𝑉
𝑑𝑉
So, 𝑑𝑆 = 𝜇𝑅
𝑉
𝑉 𝑑𝑉 𝑉𝑓
Or, 𝑆𝑓 − 𝑆𝑖 = 𝜇𝑅 ∫𝑉 𝑓 = 𝜇𝑅𝑙𝑛
𝑖 𝑉 𝑉𝑖

If 𝑉𝑓 > 𝑉𝑖 , 𝑡ℎ𝑒𝑛 𝑆𝑓 > 𝑆𝑖 , the entropy of the gas increases

𝑉𝑓
From above, Δ𝑆𝑔𝑎𝑠 = 𝜇𝑅𝑙𝑛 ……..(1)
𝑉𝑖

Again, in a reversible process, the change in entropy

𝑉𝑖
𝑆𝑓 − 𝑆𝑖 = 𝜇𝑅𝑙𝑛
𝑉𝑓

If 𝑉𝑓 > 𝑉𝑖 , then 𝑆𝑓 − 𝑆𝑖 is negative. Let the change in entropy is

=−Δ𝑆𝑔𝑎𝑠 .
So the total change in entropy= Δ𝑆𝑔𝑎𝑠 − Δ𝑆𝑔𝑎𝑠 = 0
Entropy change of an ideal gas
From 1st law of thermodynamics,
𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉
Or, 𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉
1
Or, 𝑑𝑆 = (𝑑𝑈 + 𝑃𝑑𝑉)
𝑇

Let, 𝑈 = 𝑈(𝑇, 𝑉)
𝜕𝑈 𝜕𝑈
So, 𝑑𝑈 = ( )𝑉 𝑑𝑇 + ( ) 𝑇 𝑑𝑉 …………………………(1)
𝜕𝑇 𝜕𝑉
1 𝜕𝑈 1 𝜕𝑈
So, 𝑑𝑆 = ( )𝑉 𝑑𝑇 + [( ) + 𝑃]𝑑𝑉 ………………(2)
𝑇 𝜕𝑇 𝑇 𝜕𝑉 𝑇

If, 𝑆 = 𝑆(𝑇, 𝑉)
𝜕𝑆 𝜕𝑆
Then, 𝑑𝑆 = ( )𝑉 𝑑𝑇 + ( ) 𝑇 𝑑𝑉……………………….(3)
𝜕𝑇 𝜕𝑉

From equations (2) and (3)

𝜕𝑆 1 𝜕𝑈
( )𝑉 = ( )𝑉 ……………………………..(4)
𝜕𝑇 𝑇 𝜕𝑇
𝜕𝑆 1 𝜕𝑈
And ( ) 𝑇 = [( ) + 𝑃]………………………….(5)
𝜕𝑉 𝑇 𝜕𝑉 𝑇

From left hand side of equ (4) and (5), (the 2nd derivatives of S and U with respect
to T and V are independent of the order of differentiation.)
𝜕 𝜕𝑆 𝜕 𝜕𝑆 𝜕2 𝑆 𝜕2 𝑆
[ ( ) ] 𝑇 = [𝜕𝑇 (𝜕𝑉) ]𝑉 = 𝜕𝑉𝜕𝑇 = 𝜕𝑇𝜕𝑉
𝜕𝑉 𝜕𝑇 𝑉 𝑇

From right hand side of equ (4) and (5), (Differentiating the first partially with
respect to V and the second with respect to T)
1 𝜕2 𝑈 1 𝜕2 𝑈 𝜕𝑃 1 𝜕𝑈
= [ + ( ) ] − 2 [( ) + 𝑃]
𝑇 𝜕𝑉𝜕𝑇 𝑇 𝜕𝑇𝜕𝑉 𝜕𝑇 𝑇𝑉 𝜕𝑉 𝑇

Which simplifies to
𝜕𝑈 𝜕𝑃
(𝜕𝑉 ) = 𝑇 (𝜕𝑇 ) − 𝑃 ……………………………….(6)
𝑇 𝑉
𝜕𝑈
But, ( 𝜕𝑇 ) = 𝑐𝑉
𝑉

From equ(1) and (6),

 𝜕𝑃
𝑑𝑈 = 𝑐𝑉 𝑑𝑇 + [𝑇 ( ) − 𝑃]𝑑𝑉 ………………….(7)
𝜕𝑇 𝑉
𝜕𝑆 𝑐𝑉
From equ(4), ( )𝑉 = ………………………(8)
𝜕𝑇 𝑇
𝜕𝑆 𝜕𝑃
From equ(5) and (6), ( ) 𝑇 = ( ) ………………………(9)
𝜕𝑉 𝜕𝑇 𝑉
𝑐𝑉 𝜕𝑃
From equ(3), 𝑑𝑆 = 𝑑𝑇 + ( ) 𝑑𝑉 …………………..(10)
𝑇 𝜕𝑇 𝑉
𝜕𝑃
Or, 𝑇𝑑𝑆 = 𝑐𝑉 𝑑𝑇 + 𝑇 ( ) 𝑑𝑉
𝜕𝑇 𝑉

If T and P are independent variables for enthalpy,

𝜕𝑉
Then we can show, 𝑇𝑑𝑆 = 𝑐𝑃 𝑑𝑇 − 𝑇 ( ) 𝑑𝑃 ………………..(11)
𝜕𝑇 𝑃
𝜕𝑇 𝜕𝑇
We can also show, 𝑇𝑑𝑆 = 𝑐𝑃 ( ) 𝑑𝑉 + 𝑐𝑉 ( ) 𝑑𝑃 …………(12)
𝜕𝑉 𝜕𝑃 𝑃 𝑉

From equ(11), the entropy change between any two states,

2 𝑑𝑇 2 𝜕𝑉
𝑆2 − 𝑆1 = ∫1 𝑐𝑃 − ∫1 ( ) 𝑑𝑃
𝑇 𝜕𝑇 𝑃
𝑅𝑇 𝜕𝑉 𝑅
For an ideal gas, 𝑉= , (𝜕𝑇 ) = 𝑃
𝑃 𝑃
𝑇2 𝑃2
𝑆2 − 𝑆1 = 𝑐𝑃 𝑙𝑛 − 𝑅𝑙𝑛
𝑇1 𝑃1
𝑇2 𝑉2
From equ(10), 𝑆2 − 𝑆1 = 𝑐𝑉 𝑙𝑛 + 𝑅𝑙𝑛
𝑇1 𝑉1
𝑉2 𝑃2
From equ(12) 𝑆2 − 𝑆1 = 𝑐𝑃 𝑙𝑛 − 𝑐𝑉 𝑙𝑛
𝑉1 𝑃1

The entropy change for an isothermal expansion process is

𝑉2
𝑆2 − 𝑆1 = 𝑅𝑙𝑛
𝑉1
𝑃1
= 𝑅𝑙𝑛
𝑃2

Which is greater than 0, in agreement with the principle of increase of energy.

The entropy change for an isobaric process is
𝑇2
𝑆2 − 𝑆1 = 𝑐𝑃 𝑙𝑛
𝑇1
𝑉2
= 𝑐𝑃 𝑙𝑛
𝑉1

The entropy change for an isobaric process is

 𝑇2
𝑆2 − 𝑆1 = 𝑐𝑉 𝑙𝑛
𝑇1
𝑃2
= 𝑐𝑉 𝑙𝑛
𝑃1

Entropy of a Van der Waals gas

Consider the change of a Van der Waals gas from pressure P 1, volume V1 and
temperature T1 to pressure P2, volume V2 and temperature T2. The change in
entropy is given by
𝑇 𝑑𝐻
𝑆2 − 𝑆1 = ∫𝑇 2 ………………..(1)
1 𝑇

From 1st law of thermodynamics,

𝑑𝐻 = 𝑐𝑉 𝑑𝑇 + 𝑃𝑑𝑉 From van der Waals equation,
𝑑𝐻 𝑑𝑇 𝑃 𝑅𝑇
= 𝑐𝑉 + 𝑑𝑉 𝑃= , when a is small
𝑇 𝑇 𝑇 𝑉−𝑏

𝑑𝑇 𝑅
= 𝑐𝑉 + 𝑑𝑉 ……………(2)
𝑇 𝑉−𝑏

From equ (1) and (2),

𝑇 𝑑𝑇 𝑉 𝑑𝑉
𝑆2 − 𝑆1 = 𝑐𝑉 ∫𝑇 2 + 𝑅 ∫𝑉 2
1 𝑇 1 𝑉−𝑏
𝑇2 𝑉2 −𝑏
= 𝑐𝑉 𝑙𝑛 + 𝑅𝑙𝑛
𝑇1 𝑉1 −𝑏

Problem 1: Calculate the increase in entropy when 1 g of ice at ‒10 ℃ is converted

into steam of 100 ℃. Specific heat of ice=0.5, latent heat of ice= 80 cal/g, Latent
heat of steam=540 cal/g.

Solution: Increase in entropy when the temperature of 1 g of ice increases from ‒

10 ℃ (273‒10=263 K) to 0 ℃ (273 K),
𝑇 𝑑𝐻 𝑇 𝑑𝑇 𝑇2
𝑑𝑠 = ∫𝑇 2 = 𝑚𝑠 ∫𝑇 2 = 𝑚𝑠 𝑙𝑛
1 𝑇 1 𝑇 𝑇1

273
= 1 × 0.5 × 𝑙𝑛 = 0.01865 𝐶𝑎𝑙/𝐾
263
Increase in entropy when 1 g of ice at 0 ℃ is converted into water of 0 ℃,
𝑑𝐻 80
𝑑𝑠 = = = 0.293 𝐶𝑎𝑙/𝐾
𝑇 273

Increase in entropy when the temperature of 1 g water is raised from 0 ℃ to 100

℃,
𝑇2 373
𝑑𝑠 = 𝑚𝑠 𝑙𝑛 = 1 × 1 × 𝑙𝑛 =0.312 Cal/K
𝑇1 273

Increase in entropy when 1 g water of 100 ℃ is converted into steam of 100 ℃,

𝑑𝐻 540
𝑑𝑠 = = = 1.447 𝐶𝑎𝑙/𝐾
𝑇 373

Total increase in entropy=0.01865+0.293+0.312+1.447=2.07065 Cal/K

Problem 2: 50 g of water at 0 ℃ is mixed with an equal mass of water at 83 ℃.

Calculate the resultant increase in entropy.

Solution: Here, m1= 50 g, m2= 50 g, T1= 273 K and T2= 353 K. Let the final
temperature of the mixture be T, then 𝑚𝑠(𝑇 − 𝑇1 ) = 𝑚𝑠(𝑇2 − 𝑇)

Or, 50 × 1 × (𝑇 − 273) = 50 × 1 × (353 − 𝑇)

Or, T= 313 K

Increase in entropy by 1 g of water when its temperature rises from 273K to 313K,
𝑇 𝑑𝐻 𝑇 𝑑𝑇 𝑇2
𝑑𝑠 = ∫𝑇 2 = 𝑚𝑠 ∫𝑇 2 = 𝑚𝑠 𝑙𝑛
1 𝑇 1 𝑇 𝑇1

313
= 50 × 1 × 𝑙𝑛 = 6.829 𝐶𝑎𝑙/𝐾
273

Increase in entropy by 1 g of water when its temperature falls from 353K to 313K,
𝑇2 313
𝑑𝑠 = 𝑚𝑠 𝑙𝑛 = 50 × 1 × 𝑙𝑛 = ‒6.023 Cal/K
𝑇1 353

Total increase in entropy is =6.829‒6.023=0.806 Cal/K

Exact differentials and inexact differentials

First law of thermodynamics: 𝑑𝑈 = 𝑑𝐻 + 𝑑𝑊

Here, dW is a differential but we do not know on which variables dW depends

here, and also dH. dW and dH are not differentials of a mathematical functions.
If we write 𝑑𝑊 = 𝐹𝑑𝑥, then it is clear that dW is a function of both F and x.
Here, dW is an exact differentials or perfect differentials. So, in thermodynamics,
dW and dH are called inexact differentials, because they are not the differentials
of functions that depend on state variables; they are only path functions.
However, the sum of two inexact differentials will make an exact differential. If
we write 𝑑𝑊 = −𝑃𝑑𝑉, and 𝑑𝐻 = 𝑇𝑑𝑆, then 𝑑𝑈 = −𝑃𝑑𝑉 + 𝑇𝑑𝑆, is an
exact differential. Suppose,

𝑊 = 𝑊(𝑃, 𝑉), then

𝜕𝑊 𝜕𝑊
𝑑𝑊 = ( ) 𝑑𝑃 + ( 𝜕𝑉 ) 𝑑𝑉 is an exact differential too.
𝜕𝑃 𝑉 𝑃

Characteristic functions and necessity of finding dynamic equilibrium

Often important laws are reformulated to change variables in order to simply the
analysis of a system. For example, Newton’s laws of motion can be rewritten in
equivalent Lagrange’s equations for appropriate coordinate system in classical
mechanics. The variables of Lagrange’s equations are changed to produce
Hamiltonian equations that are fundamentally important in quantum mechanics.
Changes of variables, known as Legendre differential transformations, yield new
functions that are important in thermodynamics. For example, will a process in
which entropy increases necessarily occur? Why all systems have an internal
tendency towards equilibrium? Two laws of thermodynamics cannot equivocally
answer these questions. Then, we need to establish the condition of
thermodynamic equilibrium of physical and chemical system. Thermodynamic
functions can explicitly give a complete information of above questions.

Thermodynamic functions

(i) Helmholtz function or free energy

From first law of thermodynamics, the difference between the change in heat
energy and work done is equal to the change in internal energy:

𝑑𝑈 = 𝑑𝐻 − 𝑃𝑑𝑉 ………………………………(1)

From 2nd law of thermodynamics: 𝑇𝑑𝑆 = 𝑑𝐻 ……………(2)

From (1) and (2): 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 = 𝑇𝑑𝑆 − 𝑑𝑊

Again, 𝑑(𝑇𝑆) = 𝑇𝑑𝑆 + 𝑆𝑑𝑇. If the system is maintained at

constant temperature, dT=0, So,

𝑑(𝑇𝑆) = 𝑇𝑑𝑆 ……………….(3)

So, 𝑑𝑈 = 𝑑(𝑇𝑆) − 𝑑𝑊

Or 𝑑(𝑈 − 𝑇𝑆) = −𝑑𝑊

Or, 𝑑𝐹 = −𝑑𝑊

Where, 𝐹 = 𝑈 − 𝑇𝑆 is known as Helmholtz free energy or work function.

So, 𝐹 = 𝑈 − 𝑇𝑆 ………………………….(4)

Physical conditions relating Free energy and the work done by a system

Consider a thermodynamic system K. It undergoes a transformation from an

initial state ‘i’ to a final state ‘f’. The system is in thermal contact with the
surrounding of temperature T during the process ‘i’ to ‘f’.
Let dH= heat absorbed by the system from the surrounding

dS= Change in entropy of the system

dSO= change in entropy of the surrounding

From the principle of increase of entropy,

𝑑𝐻
𝑑𝑆 + 𝑑𝑆𝑂 ≥ 0, Here, 𝑑𝑆𝑂 = − ; dH= Heat evolved by the surrounding.
𝑇

𝑑𝐻
Or, 𝑑𝑆 − ≥0
𝑇

Or, 𝑇𝑑𝑆 ≥ 𝑑𝐻

So, 𝑑𝐻 ≤ 𝑇𝑑𝑆

Or, (𝑑𝑈 + 𝑑𝑊) ≤ 𝑇𝑑𝑆

Or, 𝑈𝑓 − 𝑈𝑖 + 𝑑𝑊 ≤ 𝑇(𝑆𝑓 − 𝑆𝑖 )

Or, 𝑑𝑊 ≤ (𝑈𝑖 − 𝑈𝑓 ) + 𝑇(𝑆𝑖 − 𝑆𝑓 ) ………………….(6)

Since, 𝐹 = 𝑈 − 𝑇𝑆, So,

𝐹𝑖 − 𝐹𝑓 = (𝑈𝑖 − 𝑇𝑆𝑖 ) − (𝑈𝑓 − 𝑇𝑆𝑓 )

= (𝑈𝑖 − 𝑈𝑓 ) − 𝑇(𝑆𝑖 − 𝑆𝑓 ) ……………………(7)

From equ(5) and (6),

𝑑𝑊 ≤ 𝐹𝑖 − 𝐹𝑓 ………………………………(8)

So, the work done by a system undergoing an isothermal transformation is less

than or equal to the Helmholtz free energy of the system (the process is reversible
or irreversible). From equ(5), as S increases, the available energy (F) decreases.
Significance of free energy

We know, a mechanical system will be equilibrium if the potential energy of the

system is minimum. Let, the system K showing isothermal transformation from
state ‘i' to state ‘f’ be kept inside an enclosure whose walls are rigid but
diathermic. The system exchanges heat with surroundings but no external work
is done. The process is such that V=constant. So, the transformation is isothermal-
isochoric.

So, ∆𝑊 = 0

From equ(8), 𝐹𝑓 ≤ 𝐹𝑖

So, the free energy in the final state can never exceed that of the initial state. Thus,
the state of minimum free energy is the stable state of equilibrium. Since the state
of stable equilibrium in thermodynamics corresponds to the minimum potential
energy of a mechanical system; thus, Helmholtz free energy is called the
thermodynamic potential at constant volume.

Now, 𝐹 = 𝑈 − 𝑇𝑆

Here, U, T and S are functions of states, so F must be a state function.

𝑑𝐹 = 𝑑𝑈 − 𝑇𝑑𝑆 − 𝑠𝑑𝑇 is an exact differential

= −𝑃𝑑𝑉 − 𝑆𝑑𝑇 ……(9) (𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉)

So, F is a function of temperature and volume.

If, 𝐹 = 𝐹(𝑇, 𝑉)

𝜕𝐹 𝜕𝐹
Then. 𝑑𝐹 = ( ) 𝑑𝑇 + ( ) 𝑑𝑉 ……………….(10)
𝜕𝑇 𝑉 𝜕𝑉 𝑇

𝜕𝐹
From equ(9) and (10), 𝑃 = − ( ) ……………(11)
𝜕𝑇 𝑉

𝜕𝐹
And 𝑆 = ( ) …………………(12)
𝜕𝑉 𝑇
So, if F of a system is known, a complete information of its thermal properties is
obtained.

Enthalpy

Let us consider the Clausius inequality for infinitesimal process:

𝑑𝑄 ≤ 𝑇𝑑𝑆

Or, 𝑑𝑈 + 𝑃𝑑𝑉 ≤ 𝑇𝑑𝑆

Or, 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 ≤ 𝑇𝑑𝑆 + 𝑉𝑑𝑃

Or, 𝑑(𝑈 + 𝑃𝑉) ≤ 𝑇𝑑𝑆 + 𝑉𝑑𝑃 …………………..(1)

Let, 𝐸 = 𝑈 + 𝑃𝑉 = 𝐸𝑛𝑡ℎ𝑎𝑙𝑝𝑦=the sum of the internal energy and the product

of pressure and volume.

Fro equ(1), 𝑑𝐸 ≤ 𝑇𝑑𝑆 + 𝑉𝑑𝑃

For isentropic-isobaric process: 𝑑𝐸 ≤ 0

Here, E is also called the total heat function. It is a state variable and an exact
differential.

For infinitesimal reversible process,

𝑑𝐸 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 …………(2)

So, E is a function of entropy and pressure. We may write,

𝐸 = 𝐸(𝑆, 𝑃)

𝜕𝐸 𝜕𝐸
𝑑𝐸 = ( ) 𝑑𝑆 + ( ) 𝑑𝑃 ………………………..(3)
𝜕𝑆 𝑃 𝜕𝑃 𝑆

𝜕𝐸
Equating equ(2) and (3), 𝑇 = ( ) ……………………….(4)
𝜕𝑆 𝑃
 𝜕𝐸
𝑉 = ( ) …………………(5)
𝜕𝑃 𝑆

Equation (4) implies that E is a heat content and (5) shows that in an isentropic
process, increase of P results in an increase of E.

Gibb’s free energy

There exist thermodynamic transformations for which the temperature and the
pressure do not change but are equal to those of the surroundings during the
transformation.

Consider such an isothermal-isobaric process, at temperature T and pressure P.

The system changes for ‘i' to ‘f’. If Vi and Vf are initial and final volumes, then
work done by the system during transformation is

∆𝑊 = 𝑃(𝑉𝑓 − 𝑉𝑖 ) ………………………(1)

We have obtained in previous section.

∆𝑊 ≤ 𝐹𝑖 − 𝐹𝑓 ………………………….(2)

Or, 𝑃(𝑉𝑓 − 𝑉𝑖 ) ≤ (𝑈𝑖 − 𝑇𝑆𝑖 ) − (𝑈𝑓 − 𝑇𝑆𝑓 )

Or, 𝑃𝑉𝑓 − 𝑇𝑆𝑓 + 𝑈𝑓 ≤ 𝑃𝑉𝑖 − 𝑇𝑆𝑖 + 𝑈𝑖 ……………….(3)

Let, 𝐺 = 𝑈 − 𝑇𝑆 + 𝑃𝑉 = 𝐺𝑖𝑏𝑏 ′ 𝑠 𝑓𝑟𝑒𝑒 𝑒𝑛𝑒𝑟𝑔𝑦

So, 𝐺𝑓 ≤ 𝐺𝑖 Or, ∆𝐺 ≤ 0 ………………..(4)

The function G is called the thermodynamic potential at constant pressure. Gibb’s

free energy in the final state cannot exceed that of the initial state. So, the state of
minimum G is the state of equilibrium.

For infinitesimal reversible process,

 𝑑𝐺 = 𝑑𝑈 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇𝑉𝑑𝑃 + 𝑃𝑑𝑉

= −𝑆𝑑𝑇 + 𝑉𝑑𝑃 ……………..(5) (as 𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉)

G is thus a function of two independent variables T and P. So,

𝐺 = 𝐺(𝑇, 𝑃)

𝜕𝐺 𝜕𝐺
𝑑𝐺 = ( ) 𝑑𝑇 + ( ) 𝑑𝑃 ……………..(6)
𝜕𝑇 𝑃𝜕𝑃 𝑇

𝜕𝐺
From equ(5) and (6), 𝑆 = ( ) ……………………….(7)
𝜕𝑇 𝑃

𝜕𝐺
𝑉 = ( ) ……………………..(8)
𝜕𝑃 𝑇

So, we established four thermodynamic potentials as follows:

(i) U(S, V), (ii) F(T, V), (iii) G(T, P) and (iv) E(S, P).

They are called characteristic functions.

Enthalpy in isobaric process and throttling process

Porus wall

Vi Vf
Pi Pf

(ii) Initial state (i) Final state

Imagine a cylinder, thermally insulated and equipped with two adiabatic pistons
on opposite sides of a porous wall that is also adiabatic.

[Porous wall permits mass to flow from one chamber to another while controlling
pressure. It can be a porous plug or a series of holes.]
Let,

Pi is the initial pressure between the porous wall and the left piston

Vi is the initial volume between the porous wall and the left piston

Now, both pistons are moved simultaneously to the right at different speeds.

Pf is the final pressure, Vf is the final volume

A throttling process is a porous plug process and exhibits internal mechanical

irreversibility, due to friction of the gas with the pore walls. Conclusions can be
drawn on dissipative non-equilibrium state.

From 1st law of thermodynamics:

𝑈𝑓 − 𝑈𝑖 = 𝑊 + 𝐻 ……………………………(1)

The throttling process occurs in adiabatic enclosure: So, H=0,

So, 𝑈𝑓 − 𝑈𝑖 = 𝑊 …………………..(2)

The net work done by the pistons on the gas:

0 𝑉
𝑊 = − ∫𝑉 𝑃𝑓 𝑑𝑉 − ∫0 𝑖 𝑃𝑖 𝑑𝑉 = −(𝑃𝑓 𝑉𝑓 − 𝑃𝑖 𝑉𝑖 ) …….(2)
𝑓

So, 𝑈𝑓 − 𝑈𝑖 = −(𝑃𝑓 𝑉𝑓 − 𝑃𝑖 𝑉𝑖 )

Or, 𝑈𝑖 + 𝑃𝑖 𝑉𝑖 = 𝑈𝑓 + 𝑃𝑓 𝑉𝑓

Or, 𝐸𝑖 = 𝐸𝑓

In throttling process, the initial and final enthalpy are equal.

Assume that an arbitrary system undergoes an infinitesimal process from an

initial equilibrium state to a final equilibrium state.

𝑑𝐸 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃

= 𝑑𝐻 + 𝑉𝑑𝑃 ………………………..(3)
 𝑑𝐸 𝑑𝐻 𝑑𝑃
So, = +𝑉
𝑑𝑇 𝑑𝑇 𝑑𝑇

𝑑𝑃 𝑑𝐸 𝑑𝐻
At constant pressure, = 0, So, ( )𝑃 = ( )
𝑑𝑇 𝑑𝑇 𝑑𝑇 𝑃

𝑑𝐻 𝑑𝐸
But, ( )𝑃 = 𝑐𝑃 , So, 𝑐𝑃 = ( )𝑃
𝑑𝑇 𝑑𝑇

From equ(3), if dP=0, 𝑑𝐸 = 𝑑𝐻

Or, 𝐸𝑓 − 𝐸𝑖 = 𝐻𝑓 − 𝐻𝑖 = 𝐻 …………..(4)

The change in enthalpy during an isobaric process is equal to the amount of heat
transferred during the process.

Gibb’s phase rule

Consider a closed system containing a liquid in equilibrium with its saturated

pressure T and P are equal in both phases.

Suppose,

m1 is masses of liquid

m2 is masses of vapour

G1 is Gibb’s potential per unit mass of the liquid

G2 is Gibb’s potential per unit mass of the vapour

So, for the whole system:

𝐺 = 𝑚1 𝐺1 + 𝑚2 𝐺2 …………………….(1)

Consider a small quantity of liquid changes into vapour. Differentiating equ(1),

𝛿𝐺 = 𝛿𝑚1 𝐺1 + 𝛿𝑚2 𝐺2 …………………….(2)

At constant temperature and pressure, the process is isothermal-isobaric. In this

case, dG=0. So,
 𝛿𝑚1 𝐺1 + 𝛿𝑚2 𝐺2 = 0 ………………………(3)

Since, 𝑚1 + 𝑚2 = 0

So, 𝛿𝑚1 + 𝛿𝑚2 = 0 ………………………….(4)

From equ(3) and (4), 𝐺1 = 𝐺2 …………………….(5)

This shows that the thermodynamic potential per unit mass will be equal in two
phases.

Phase Transitions
First order phase transition

Clausius‒Clapeyron equation

Consider an enclosure containing a liquid and its saturated vapour in equilibrium.

If this system undergoes isothermal-isobaric transformation, then Gibb’s
potentials in two phases are equal i.e.

𝐺1 = 𝐺2 …………………….(1)
Let the temperature of the system be increased from T to T+dT, the increase of
Gibb’s potential is dG1 and dG2. For equilibrium,
𝐺1 + 𝑑𝐺1 = 𝐺2 + 𝑑𝐺2
So, 𝑑𝐺1 = 𝑑𝐺2 ……………………..(2)

If the condition of saturation is satisfied, then

𝑑𝐺1 𝑑𝐺2
( )𝑠𝑎𝑡 = ( ) ……………..(3)
𝑑𝑇 𝑑𝑇 𝑠𝑎𝑡

The pressure also changes from P to P+dP. Now

𝐺1 = 𝐺1 (𝑇, 𝑃)

𝜕𝐺1 𝜕𝐺
𝑑𝐺1 = ( ) 𝑑𝑇 + ( 1 ) 𝑑𝑃……………(4)
𝑑𝑇 𝑃 𝑑𝑃 𝑇
 𝑑𝐺1 𝜕𝐺1 𝜕𝐺 𝜕𝑃
=( ) + ( 1) …………………(5)
𝑑𝑇 𝑑𝑇 𝑑𝑃
𝑃 𝑇 𝜕𝑇

Now, 𝐺 = 𝑈 + 𝑃𝑉 − 𝑇𝑆

𝑑𝐺 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇

= 𝑑𝑈 + 𝑃𝑑𝑉 − 𝑑𝑈 − 𝑃𝑑𝑉 + 𝑉𝑑𝑃 − 𝑆𝑑𝑇, (𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉)

𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 ……………………….(6)

𝜕𝐺1 𝜕𝐺1
So, comparing equ(4) and (6), 𝑉 = ( ) and 𝑆=( )
𝑑𝑇 𝑃 𝑑𝑃 𝑇

Substituting these values in equ(5),

𝜕𝐺 𝜕𝑃
( 𝑑𝑇1 ) = −𝑆1 + 𝑉1 ( )𝑠𝑎𝑡
𝜕𝑇
𝑠𝑎𝑡
𝜕𝐺 𝜕𝑃
And ( 𝑑𝑇2 ) = −𝑆2 + 𝑉2 ( )𝑠𝑎𝑡
𝜕𝑇
𝑠𝑎𝑡

Substituting these values in equ(3),

𝜕𝑃 𝜕𝑃
−𝑆1 + 𝑉1 ( ) = −𝑆2 + 𝑉2 ( )𝑠𝑎𝑡
𝜕𝑇 𝑠𝑎𝑡 𝜕𝑇

𝜕𝑃 𝑆2 −𝑆1
(𝜕𝑇 ) =
𝑠𝑎𝑡 𝑉2 −𝑉1

𝜕𝐻 𝐿
But, 𝑆2 − 𝑆1 = = , Where L is latent heat of vapourization.
𝑇 𝑇
𝑑𝑃 𝐿
So, = …………………….(7)
𝑑𝑇 𝑇(𝑉2 −𝑉1 )

This is Clausius-Clapeyron latent heat equation.

Maxwell’s thermodynamic relations
From 1st and 2nd law of thermodynamics, Maxwell derived fundamental
thermodynamic relations. The state of a system can be specified by any pair of
quantities, such as, pressure (P), volume (V), temperature (T) and entropy S.
From the 1st law,
𝑑𝐻 = 𝑑𝑈 + 𝑑𝑊 = 𝑑𝑈 + 𝑃𝑑𝑉
Or 𝑑𝑈 = 𝑑𝐻 − 𝑃𝑑𝑉 ………………………..(1)
From the 2nd law,
𝑑𝐻
𝑑𝑆 = Or, 𝑇𝑑𝑆 = 𝑑𝐻 ……………..(2)
𝑇

From equ(1) and (2),

𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 ……………………….(3)
Let us consider that U, S and V are functions of two independent variables x and
y (where x and y may be two variables out of P, V, T and S). Then,
𝜕𝑈 𝜕𝑈
𝑑𝑈 = ( )𝑦 𝑑𝑥 + ( )𝑥 𝑑𝑦
𝜕𝑥 𝜕𝑦
𝜕𝑆 𝜕𝑆
𝑑𝑆 = ( )𝑦 𝑑𝑥 + ( )𝑥 𝑑𝑦
𝜕𝑥 𝜕𝑦
𝜕𝑉 𝜕𝑉
𝑑𝑉 = ( )𝑦 𝑑𝑥 + ( )𝑥 𝑑𝑦
𝜕𝑥 𝜕𝑦

Substituting these values in equ(3),

𝜕𝑈 𝜕𝑈 𝜕𝑆 𝜕𝑆 𝜕𝑉 𝜕𝑉
( )𝑦 𝑑𝑥 + ( )𝑥 𝑑𝑦 =T[( )𝑦 𝑑𝑥 + ( )𝑥 𝑑𝑦] − 𝑃[( )𝑦 𝑑𝑥 + ( )𝑥 𝑑𝑦]
𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑦
𝜕𝑆 𝜕𝑉 𝜕𝑆 𝜕𝑉
= [𝑇( )𝑦 − 𝑃 ( ) ]𝑑𝑥 + [𝑇( )𝑥 − 𝑃 ( ) ]𝑑𝑦
𝜕𝑥 𝜕𝑥 𝜕𝑦 𝑦 𝜕𝑦 𝑥

Comparing the coefficients of dx and dy from both sides, we get,

𝜕𝑈 𝜕𝑆 𝜕𝑉
( )𝑦 = [𝑇( )𝑦 − 𝑃 ( ) ] ……………………..(4)
𝜕𝑥 𝜕𝑥 𝜕𝑥 𝑦
𝜕𝑈 𝜕𝑆 𝜕𝑉
( )𝑥 = [𝑇( )𝑥 − 𝑃 ( ) ] ……………………….(5)
𝜕𝑦 𝜕𝑦 𝜕𝑦 𝑥

Differentiating equ(4) with respect to y and equ(5) w.r.t x:

𝜕2 𝑈 𝜕𝑇 𝜕𝑆 𝜕2 𝑆 𝜕𝑃 𝜕𝑉 𝜕2 𝑉
= ( )𝑥 ( ) + 𝑇 − ( )𝑥 ( ) − 𝑃
𝜕𝑦𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑦𝜕𝑥 𝑦 𝜕𝑦 𝜕𝑥 𝜕𝑦𝜕𝑥 𝑦
 𝜕2 𝑈 𝜕𝑇 𝜕𝑆 𝜕2 𝑆 𝜕𝑃 𝜕𝑉 𝜕2 𝑉
And = ( )𝑦 ( ) + 𝑇 − ( )𝑦 ( ) − 𝑃
𝜕𝑥𝜕𝑦 𝜕𝑥 𝜕𝑦 𝜕𝑥𝜕𝑦 𝜕𝑥 𝜕𝑦
𝑥 𝜕𝑥𝜕𝑦 𝑥

The change in internal energy due to changing V and T, where V is changed to

by dV first and T by dT later or vice versa.
It means dU is a perfect differential, So
𝜕2 𝑈 𝜕2 𝑈
=
𝜕𝑦𝜕𝑥 𝜕𝑥𝜕𝑦

𝜕𝑇 𝜕𝑆 𝜕2 𝑆 𝜕𝑃 𝜕𝑉 𝜕2 𝑉 𝜕𝑇 𝜕𝑆
Or ( )𝑥 ( ) + 𝑇 − ( )𝑥 ( ) − 𝑃 = ( )𝑦 ( ) +
𝜕𝑦 𝜕𝑥 𝜕𝑦𝜕𝑥𝑦 𝜕𝑦 𝜕𝑥 𝜕𝑦𝜕𝑥 𝜕𝑥 𝜕𝑦 𝑦 𝑥

𝜕2 𝑆 𝜕𝑃 𝜕𝑉 𝜕2 𝑉
𝑇 − ( )𝑦 ( ) − 𝑃
𝜕𝑥𝜕𝑦 𝜕𝑥 𝜕𝑦 𝜕𝑥𝜕𝑦 𝑥

Simplifying,
𝜕𝑇 𝜕𝑆 𝜕𝑃 𝜕𝑉 𝜕𝑇 𝜕𝑆 𝜕𝑃 𝜕𝑉
( )𝑥 ( ) − ( )𝑥 ( ) = ( )𝑦 ( ) − ( )𝑦 ( ) ……(6)
𝜕𝑦 𝜕𝑥 𝜕𝑦 𝜕𝑥
𝑦 𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑦 𝑦 𝑥 𝑥

(i) Taking T and V as independent variables, i.e. x=T and y=V, So

𝜕𝑇 𝜕𝑉
= 1, and =1
𝜕𝑥 𝜕𝑦
𝜕𝑇 𝜕𝑉
= 0, and =0
𝜕𝑦 𝜕𝑥
𝜕𝑆 𝜕𝑃
From equ(6), (𝜕𝑉) = (𝜕𝑇 )𝑉 , (1st relation)……………..(7)
𝑇
𝑑𝐻
But, 𝑑𝑆 =
𝑇
𝜕𝐻 𝜕𝑃
So, ( 𝜕𝑉 ) = 𝑇(𝜕𝑇 )𝑉 ……………………..(8)
𝑇

(ii) Taking T and P as independent variables, i.e. x=T and y=P, So

𝜕𝑇 𝜕𝑃
= 1, and =1
𝜕𝑥 𝜕𝑦
𝜕𝑇 𝜕𝑃
= 0, and =0
𝜕𝑦 𝜕𝑥

Then from equ(6),

𝜕𝑆 𝜕𝑉
(𝜕𝑃) = −(𝜕𝑇 )𝑃 , (2nd relation)………………..(9)
𝑇
 𝑑𝐻
But, 𝑑𝑆 =
𝑇
𝜕𝐻 𝜕𝑉
So, ( 𝜕𝑃 ) = −𝑇(𝜕𝑇 )𝑃 ……………………..(10)
𝑇

(iii) Taking S and V as independent variables, i.e. x=S and y=V, So

𝜕𝑆 𝜕𝑉
= 1, and =1
𝜕𝑥 𝜕𝑦
𝜕𝑆 𝜕𝑉
= 0, and =0
𝜕𝑦 𝜕𝑥

Then from equ(6),

𝜕𝑇 𝜕𝑃
(𝜕𝑉) = −( 𝜕𝑆 )𝑉 , (3rd relation)…………..(11)
𝑆
𝜕𝑇 𝜕𝑃
So, (𝜕𝑉) = −𝑇(𝜕𝐻)𝑉 ……………………..(12)
𝑆

(iv) Taking S and P as independent variables, i.e. x=S and y=P, So

𝜕𝑆 𝜕𝑃
= 1, and =1
𝜕𝑥 𝜕𝑦
𝜕𝑆 𝜕𝑃
= 0, and =0
𝜕𝑦 𝜕𝑥

Then from equ(6),

𝜕𝑇 𝜕𝑉
(𝜕𝑃) = ( 𝜕𝑆 )𝑃 , (4th relation)…………..(13)
𝑆
𝜕𝑇 𝜕𝑉
So, (𝜕𝑃) = 𝑇(𝜕𝐻)𝑃 ……………………..(14)
𝑆

(v) Taking P and V as independent variables, i.e. x=P and y=V, So

𝜕𝑃 𝜕𝑉
= 1, and =1
𝜕𝑥 𝜕𝑦
𝜕𝑃 𝜕𝑉
= 0, and =0
𝜕𝑦 𝜕𝑥

Then from equ(6),

𝜕𝑇 𝜕𝑆 𝜕𝑇 𝜕𝑆
(𝜕𝑃) (𝜕𝑉)𝑃 − (𝜕𝑉)𝑃 (𝜕𝑃)𝑉 = 1, (5th relation)…………..(15)
𝑉

(i) Taking T and S as independent variables, i.e. x=T and y=S, So

𝜕𝑇 𝜕𝑆
= 1, and =1
𝜕𝑥 𝜕𝑦
 𝜕𝑇 𝜕𝑆
= 0, and =0
𝜕𝑦 𝜕𝑥

Then from equ(6),

𝜕𝑃 𝜕𝑉 𝜕𝑃 𝜕𝑉
(𝜕𝑇 ) ( 𝜕𝑆 ) 𝑇 − ( 𝜕𝑆 ) 𝑇 (𝜕𝑇 )𝑆 = 1, (6th relation)…………..(16)
𝑆

All these are important thermodynamic relation. Solving a particular problem,

suitable equation is used.

Thermodynamic relations with heat capacities

Let T and V as independent variables, then
𝜕𝑆 𝜕𝑆
𝑆 = 𝑆(𝑇, 𝑉), 𝑑𝑆 = ( )𝑉 𝑑𝑇 + ( ) 𝑇 𝑑𝑉
𝜕𝑇 𝜕𝑉
𝜕𝑆 𝜕𝑆 𝜕𝑆 𝜕𝑉
So, ( )𝑃 = ( )𝑉 + ( ) 𝑇 ( )𝑃
𝜕𝑇 𝜕𝑇 𝜕𝑉 𝜕𝑇
𝜕𝑆 𝜕𝑆 𝜕𝑆 𝜕𝑉
Or, 𝑇( )𝑃 − 𝑇 ( ) = 𝑇( ) 𝑇 ( )𝑃
𝜕𝑇 𝜕𝑇 𝜕𝑉 𝜕𝑇 𝑉

𝜕𝑆 𝜕𝑉
Or, 𝑐𝑃 −𝑐𝑉 = 𝑇( ) 𝑇 ( )𝑃 ……………………………(1)
𝜕𝑉 𝜕𝑇
𝜕𝑃 𝜕𝑉 𝜕𝑇
We know, (𝜕𝑉 ) (𝜕𝑇 ) (𝜕𝑃) = −1
𝑇 𝑃 𝑉
𝜕𝑃 𝜕𝑃 𝜕𝑉
Or, (𝜕𝑇 ) = − (𝜕𝑉 ) (𝜕𝑇 ) …………………….(2)
𝑉 𝑇 𝑃
𝜕𝑉 𝜕𝑃 𝜕𝑉
And, (𝜕𝑇 ) = − (𝜕𝑇 ) (𝜕𝑃 ) ……………………(3)
𝑃 𝑉 𝑇

Using successively equ(2) and (3) in equ(1),

𝜕𝑃 𝜕𝑉
𝑐𝑃 −𝑐𝑉 = −𝑇 ( ) ( )2𝑃 ……………………………(4)
𝜕𝑉 𝜕𝑇 𝑇
𝜕𝑉 𝜕𝑃
And 𝑐𝑃 −𝑐𝑉 = −𝑇 ( ) ( )2𝑉 ……………………………(5)
𝜕𝑃 𝜕𝑇 𝑇

𝜕𝑃 𝜕𝑉
(i) For all known substances, ( ) is positive and ( )2𝑃 is positive. So,
𝜕𝑉 𝜕𝑇 𝑇

𝑐𝑃 −𝑐𝑉 is positive, 𝑐𝑃 > 𝑐𝑉 .

𝜕𝑉
(ii) When ( )𝑃 = 0, as with water at 4ºC, 𝑐𝑃 −𝑐𝑉 = 0, Or, 𝑐𝑃 = 𝑐𝑉 .
𝜕𝑇
 (iii) As T tends to 0, 𝑐𝑃 𝑡𝑒𝑛𝑑𝑠 𝑡𝑜 𝑐𝑉 , when absolute zero is approached,
𝑐𝑃 = 𝑐𝑉
𝜕𝑆 𝜕𝑃
From 1st law: ( )𝑇 = ( )
𝜕𝑉 𝜕𝑇 𝑉
𝜕 𝜕𝑆 𝜕2 𝑃 S is a state function, the order
Or, { ( ) } = (𝜕𝑇 2 ) of differential is immaterial
𝜕𝑇 𝜕𝑉 𝑇 𝑉 𝑉

𝜕 𝜕𝑆 𝜕2 𝑃
Or, { ( ) } = (𝜕𝑇 2 ) ……………….(6)
𝜕𝑉 𝜕𝑇 𝑉 𝑇 𝑉
𝜕𝑆
But, 𝑇 ( ) = 𝑐𝑉 , So
𝜕𝑇 𝑉
𝜕𝑐 𝜕2 𝑃
( 𝜕𝑉𝑉) = 𝑇 (𝜕𝑇 2 ) ………………………..(7)
𝑉
𝜕𝑆 𝜕𝑉
From 2nd law, ( ) 𝑇 = −( )𝑃
𝜕𝑃 𝜕𝑇
𝜕 𝜕𝑆 𝜕2 𝑉
{ ( ) } = −(𝜕𝑇 2 )𝑃
𝜕𝑇 𝜕𝑃 𝑇 𝑃

𝜕 𝜕𝑆 𝜕2 𝑉
{ ( ) } = −(𝜕𝑇 2 )𝑃 …………………(8)
𝜕𝑃 𝜕𝑇 𝑃 𝑃

𝜕𝑐𝑃 𝜕2 𝑉
{ } = −𝑇( ) ……………………….(9)
𝜕𝑃 𝑇 𝜕𝑇 2 𝑃

Problem: Using Maxwell’s relation show that 𝑐𝑃 − 𝑐𝑉 = 𝑅 for a perfect gas.

𝜕𝐻 𝜕𝑆 𝜕𝐻 𝜕𝑆
Ans: Here, 𝑐𝑃 = ( )𝑃 = 𝑇( )𝑃 and 𝑐𝑉 = ( )𝑉 = 𝑇( )𝑉
𝜕𝑇 𝜕𝑇 𝜕𝑇 𝜕𝑇

Considering S is a function of temperature and volume,

𝜕𝑆 𝜕𝑆
𝑑𝑆 = ( )𝑉 𝑑𝑇 + ( ) 𝑇 𝑑𝑉
𝜕𝑇 𝜕𝑉
𝜕𝑆 𝜕𝑆 𝜕𝑇 𝜕𝑆 𝜕𝑉
Or, ( )𝑃 = ( ) ( ) + ( ) ( )𝑃
𝜕𝑇 𝜕𝑇 𝜕𝑇 𝜕𝑉 𝜕𝑇 𝑉 𝑇
𝜕𝑆 𝜕𝑃
Again, (𝜕𝑉 ) = (𝜕𝑇 )
𝑇 𝑉
𝜕𝑆 𝜕𝑆 𝜕𝑃 𝜕𝑉
So, 𝑇( )𝑃 = 𝑇 ( ) + 𝑇 ( ) ( )𝑃
𝜕𝑇 𝜕𝑇 𝜕𝑇 𝜕𝑇 𝑉 𝑉
𝜕𝑃 𝜕𝑉
Or, 𝑐𝑃 = 𝑐𝑉 + 𝑇 ( ) ( )𝑃
𝜕𝑇 𝜕𝑇 𝑉
For a perfect gas, 𝑃𝑉 = 𝑅𝑇
𝜕𝑃 𝑅 𝜕𝑉 𝑅
Or, (𝜕𝑇 ) = 𝑉 and (𝜕𝑇 ) = 𝑃
𝑉 𝑃
𝜕𝑃 𝜕𝑉
So, 𝑐𝑃 − 𝑐𝑉 = 𝑇 ( ) ( )𝑃
𝜕𝑇 𝜕𝑇 𝑉
𝑅 𝑅 𝑅2𝑇 𝑅2𝑇
= 𝑇. . = =
𝑉 𝑃 𝑃𝑉 𝑅𝑇

=𝑅

𝑎
𝑅(𝑃+ 2 )
Problem: Using Maxwell’s relation, show that 𝑐𝑃 − 𝑐𝑉 = 𝑎
𝑉
2𝑎𝑏 for a Van der
𝑃− 2 + 3
𝑉 𝑉

Waals gas.
Ans: For 1 mole of Van der Waal’s gas,
𝑅𝑇 𝑎
𝑃= − …………………………..(1)
𝑉−𝑏 𝑉2
𝜕𝑃 𝑅
So, ( )𝑉 =
𝜕𝑇 𝑉−𝑏

From equ(1),
𝑎 𝑅𝑇 𝑎
𝑃+ = Or, (𝑃 + )(𝑉 − 𝑏) = 𝑅𝑇
𝑉2 𝑉−𝑏 𝑉2
𝑎 𝑎𝑏
Or, 𝑃𝑉 + − 𝑃𝑏 − = 𝑅𝑇
𝑉 𝑉2

Differentiating with respect to T,

𝜕𝑉 𝑎 𝜕𝑉 2𝑎𝑏 𝜕𝑉
𝑃( )𝑃 − (𝜕𝑇 ) + (𝜕𝑇 ) = 𝑅
𝜕𝑇 𝑉2 𝑃 𝑉3 𝑃

𝜕𝑉 𝑅
( )𝑃 = 𝑎 2𝑎𝑏
𝜕𝑇 𝑃− 2 + 3
𝑉 𝑉

𝜕𝑃 𝜕𝑉
But, 𝑐𝑃 − 𝑐𝑉 = 𝑇 ( ) ( )𝑃
𝜕𝑇 𝜕𝑇 𝑉
𝑅 𝑅
=𝑇 . 𝑎 2𝑎𝑏
𝑉−𝑏 𝑃− 2+ 3
𝑉 𝑉
𝑎
𝑅(𝑃+ 2 ) 𝑎 𝑅𝑇
𝑉
= 𝑎 2𝑎𝑏 (𝑃 + ) =
𝑃− 2 + 3
𝑉 𝑉 𝑉2 𝑉−𝑏
Problem: Show that 𝑐𝑃 − 𝑐𝑉 can be expressed for a pure substance in terms of the
coefficient of volume expansion 𝛼 and isothermal compressibility (𝐾𝑇 ) or
isothermal elasticity (𝐸𝑇 )

𝜕𝑃 𝜕𝑉
Ans: We know, 𝑐𝑃 − 𝑐𝑉 = 𝑇 ( ) ( )𝑃 ………………………(1)
𝜕𝑇 𝜕𝑇 𝑉
𝜕𝑃 𝜕𝑉
= −𝑇 ( ) ( )2𝑃 [Confusion]
𝜕𝑉 𝜕𝑇 𝑇

Another form is also obtainable from equ(1), using the

important property of partial differentials, that if f(P, V, T)=0.
𝜕𝑃 𝜕𝑉 𝜕𝑇
( ) ( ) ( ) = −1
𝜕𝑉 𝑇 𝜕𝑇 𝑃 𝜕𝑃 𝑉
𝜕𝑃 𝜕𝑃 𝜕𝑉
(𝜕𝑇 )𝑉 = −(𝜕𝑉) 𝑇 (𝜕𝑇 )𝑃

Now, the coefficient of volume expansion,

1 𝜕𝑉
𝛼 = ( )𝑃 ………………………..(2)
𝑉 𝜕𝑇
𝜕𝑉
Or, ( )2𝑃 = 𝛼 2 𝑉 2
𝜕𝑇
1 𝜕𝑉 𝜕𝑃 1
Again, 𝐾𝑇 = − ( ) 𝑇 Or ( )𝑇 = −
𝑉 𝜕𝑃 𝜕𝑉 𝐾𝑇 𝑉

From equ(1), (2) and (3),

1
𝑐𝑃 − 𝑐𝑉 = 𝑇. 𝛼 2 𝑉 2 .
𝐾𝑇 𝑉

𝑇.𝛼 2 𝑉 2
=
𝐾𝑇 𝑉
1
= 𝑇𝐸𝑇 𝛼 2 𝑉 Here, 𝐸𝑇 =
𝐾

Problem: For 1 mole of Van der Waals gas undergoing a reversible isothermal
expansion from a volume V1 to V2, show that the heat transferred Q is given by
𝑉2 −𝑏
𝑄 = 𝑅𝑇𝑙𝑛
𝑉1 −𝑏
Ans: If, 𝑆 = 𝑆(𝑇, 𝑉), then
𝜕𝑆 𝜕𝑆
𝑑𝑆 = ( )𝑉 𝑑𝑇 + ( ) 𝑇 𝑑𝑉
𝜕𝑇 𝜕𝑉
𝜕𝑆 𝜕𝑆
Or, 𝑇𝑑𝑆 = 𝑇( )𝑉 𝑑𝑇 + 𝑇( ) 𝑇 𝑑𝑉
𝜕𝑇 𝜕𝑉
𝜕𝑆
= 𝑐𝑉 𝑑𝑇 + 𝑇( ) 𝑇 𝑑𝑉
𝜕𝑉
𝜕𝑃
= 𝑐𝑉 𝑑𝑇 + 𝑇( )𝑉 𝑑𝑉
𝜕𝑇
𝜕𝑃
For isothermal expansion, 𝑇𝑑𝑆 = 𝑇( )𝑉 𝑑𝑉
𝜕𝑇
𝑅𝑇 𝑎 𝜕𝑃 𝑅
Now, 𝑃 = − Or, ( )𝑉 =
𝑉−𝑏 𝑉2 𝜕𝑇 𝑉−𝑏
𝜕𝑃
Amount of heat transfer, 𝑄 = ∫ 𝑇𝑑𝑆 = ∫ 𝑇( )𝑉 𝑑𝑉
𝜕𝑇
𝑉 𝑅
= ∫𝑉 2 𝑇 𝑑𝑉
1 𝑉−𝑏
𝑉2 −𝑏
= 𝑅𝑇𝑙𝑛
𝑉1 −𝑏

2𝑎
Problem: Show that for a Van der Waals gas, 𝑐𝑃 − 𝑐𝑉 = 𝑅(1 + )
𝑅𝑇𝑉

𝑅𝑇 𝑎
Ans: We know, 𝑃 = −
𝑉−𝑏 𝑉2
𝜕𝑃 𝑅
So, ( )𝑉 =
𝜕𝑇 𝑉−𝑏

𝑎
Now, (𝑃 + )(𝑉 − 𝑏) = 𝑅𝑇
𝑉2

Differentiating with respect to T with P=constant,

2𝑎 𝑎 𝜕𝑉
[−(𝑉 − 𝑏) + (𝑃 + )] (𝜕𝑇 ) = 𝑅
𝑉3 𝑉2 𝑃
2𝑎 𝑅𝑇 𝜕𝑉
Or, [− (𝑉 − 𝑏) + ]( ) = 𝑅
𝑉3 𝑉−𝑏 𝜕𝑇 𝑃
2𝑎 𝑅𝑇 𝜕𝑉 𝑅
Or, [− + ]( ) = , Dividing both sides by (V-b)
𝑉3 (𝑉−𝑏)2 𝜕𝑇 𝑉−𝑏
𝑃
 𝜕𝑃 𝜕𝑉
𝑐𝑃 − 𝑐𝑉 = 𝑇 ( ) ( )𝑃
𝜕𝑇 𝜕𝑇 𝑉
𝑅 𝑅 1
=𝑇 . . 𝑅𝑇 2𝑎
𝑉−𝑏 𝑉−𝑏 −
(𝑉−𝑏)2 𝑉3

𝑅
= 2𝑎 (𝑉−𝑏)2
1− 3
𝑉 𝑅𝑇

𝑅
≈ 2𝑎 Since, b is very small
1−
𝑉𝑅𝑇

2𝑎 −1
𝑐𝑃 − 𝑐𝑉 = 𝑅(1 − )
𝑉𝑅𝑇
2𝑎
=1+
𝑅𝑇𝑉

Problem: Prove that for an adiabatic expansion of a Van der Waal’s gas (𝑃 +
𝑎 𝑐𝑃
)(𝑉 − 𝑏)𝛾 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡, where 𝛾 = .
𝑉2 𝑐𝑉

𝜕𝑆 𝜕𝑆
Ans: From TdS relation, 𝑇𝑑𝑆 = 𝑇( )𝑉 𝑑𝑇 + 𝑇( ) 𝑇 𝑑𝑉
𝜕𝑇 𝜕𝑉
𝜕𝑆
= 𝑐𝑉 𝑑𝑇 + 𝑇( ) 𝑇 𝑑𝑉
𝜕𝑉
𝜕𝑃
= 𝑐𝑉 𝑑𝑇 + 𝑇( )𝑉 𝑑𝑉
𝜕𝑇

For adiabatic process, dQ=0, i.e. dS=0. So,

𝜕𝑃
𝑐𝑉 𝑑𝑇 = −𝑇( )𝑉 𝑑𝑉
𝜕𝑇

For 1 gm mole of Van der Waal’s gas,

𝑅𝑇 𝑎
𝑃= −
𝑉−𝑏 𝑉2
𝜕𝑃 𝑅
So, ( )𝑉 =
𝜕𝑇 𝑉−𝑏
𝑅𝑇
Or, 𝑐𝑉 𝑑𝑇 = − 𝑑𝑉
𝑉−𝑏
𝑑𝑇 𝑅
Or, 𝑐𝑉 + 𝑑𝑉 = 0
𝑇 𝑉−𝑏

Integrating, 𝑐𝑉 𝑙𝑛𝑇 + 𝑅𝑙𝑛(𝑉 − 𝑏) = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡

𝑅
𝑙𝑛𝑇 + 𝑙𝑛(𝑉 − 𝑏) = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑐𝑉
𝑅
𝑇(𝑉 − 𝑏) 𝑐𝑉
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ……………………..(1)
 𝑎
But, (𝑃 + )(𝑉 − 𝑏) = 𝑅𝑇 …………………………..(2)
𝑉2

From equ(1) and (2), [by multiplication],

𝑅
𝑎
𝑇(𝑉 − 𝑏) . (𝑃 +
𝑐𝑉
)(𝑉 − 𝑏) = 𝑅𝑇
𝑉2
𝑅
𝑎 +1
So, (𝑃 + 𝑉 2 ) (𝑉 − 𝑏) 𝑐𝑉
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

But, 𝑐𝑃 − 𝑐𝑉 = 𝑅 Or, 𝑐𝑃 = 𝑅 + 𝑐𝑉
𝑅
Or, 𝛾= +1
𝑐𝑉
𝑎
So, (𝑃 + 𝑉 2 ) (𝑉 − 𝑏)𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡