SYJC (Sc) THERMODYNAMICS

INTRODUCTION
Thermodynamics is the branch of science which deals with exchange of heat energy between the bodies
and conversion of work (or any form of energy) into heat energy and vice-versa.
According to modern theory, Heat is the form of energy. When the hot object is in contact with the cold
object, The hot object gets cooler and the cold object becomes warmer, and both the objects reach the
same temperature after some time due to exchange of heat.
In this chapter we will try to understand a Thermodynamics system, Thermodynamic variables,
Thermodynamic processes and the Laws that govern these processes. We will also study the most
important and useful application of thermodynamics i.e. the performance and efficiency of Heat engines,
Refrigerators, Air conditioner etc.
THERMODYNAMIC SYSTEM AND SURROUNDING

1. A Thermodynamic system is a group of objects or collection of an extremely large number of atoms or

molecules that can form a unit which may have ability to exchange energy with its surroundings.
2. Anything outside the Thermodynamic system to which energy or matter is exchanged is called its
surroundings or environment.
3. The surface separating the system from surrounding is called boundary.
4. For example: Water kept in vessel is a system the vessel is its boundary and atmosphere around the
vessel is its surrounding.
Classification of Thermodynamic systems

Classification of Thermodynamic systems: A thermodynamic system is of three types as follows

A] OPEN SYSTEM: It is a system that freely allows exchange of both energy and matter with the
Surroundings or environment. Example: Water boiling in kettle is an open system.
Here Heat escapes into the air. This is the exchange of energy with the surroundings.
The steam is also escapes into the air. This is exchange of matter with surroundings.
B] CLOSED SYSTEM: It is a system that does not allow the exchange of matter but allows energy to
be transferred. Example: water boiling in boiler is a closed system.
It allows heat (energy) to be transferred from the source of heat (a burner) to the water (system)
inside. Similarly, Heat is also transferred to the surrounding. But Steam (matter) is not allowed to
escape as long as the valve is kept closed.
C] Isolated system: It is a system that exchanges neither energy nor matter with its environment.
Example: Water kept in thermos flask forms an isolated system.
In this case, neither heat nor the matter (water) is allowed to escape the system.
THERMODYNAMIC EQUILIBRIUM
A System is said to be in Thermodynamic Equilibrium if the following three conditions of
equilibrium are satisfied simultaneously.
1.Mechanical equilibrium:
Chemical for a system to be in mechanical equilibrium, there should not be any unbalanced
forces acting within the system and between the system and its surrounding.
Also, the pressure in the system should be same throughout the system and should not change
with time.
2.Chemical Equilibrium:
For a system to be in Chemical equilibrium, there should not be any chemical reaction going on
within the system
There is no transfer of matter from one part of the system to the other due to diffusion.
A system is in chemical equilibrium when its chemical composition is the same throughout the
system and surrounding and does not change with time.
3.Thermal Equilibrium:
For a system to be in thermal Equilibrium, the temperature of the system should be uniform
throughout and it should not change with time.
When two objects at different temperature are brought in contact and they reaches to same
temperature then they are in thermal Equilibrium. This concept of thermal Equilibrium is used in
the Zeroth Law of Thermodynamics.
Zeroth Law of Thermodynamics

The double arrow represents thermal equilibrium between systems. If system A and C are in
thermal equilibrium, and systems A and B are in thermal equilibrium, then systems B and C
must be in thermal equilibrium. Then systems A, B and C are at the same temperature.

Statement: If two systems are each in thermal Equilibrium with a third system then they are also
in Thermal Equilibrium with each other.
Explanation:
i. The above figure shows a schematic representation of the zeroth law of Thermodynamics
ii.The double arrow represents thermal Equilibrium between the systems.
iii.If system A and C are in thermal Equilibrium, and system A and B are in thermal Equilibrium, Then
System B and C must be in thermal Equilibrium.
 iv.Thus finally the systems A, B and C are at the same Temperature.

Application of Zeroth Law :

The Zeroth law enables us to use a thermometer to compare the temperature of different objects.
When we use a thermometer, the thermometer and objects are in thermal Equilibrium and the thermometer
indicates the temperature of the object.
NOTE: It is called zeroth law as it was proposed long after the first and second law of the thermodynamics had
been formulated and it is so named because it logically precedes the first and second law of the
thermodynamics.
Heat, Internal Energy And Work
Heat (∆Q):
Heat is the form of energy that is transferred between the system and its environment due to Temperature
difference that exist between the two.
Heat is path dependent quantity, i.e. Heat required to change the temperature of a given gas at constant
pressure is different from that required to change the temperature of same gas through same amount at
constant volume.
Explanation of flow of Heat Energy:
• Consider a glass filled with water on a table. Now the glass, along with the water in it forms a system whereas
the table and the other parts of the room will then be its surrounding or environment.
• Let a system with temperature (TS) is kept in an environment of temperature (TE) and heat (Q) energy
transferred between system and the environment.
• If TS and TE are not same then until both the temperature reaches to thermal equilibrium i.e. (TS = TE) there is
flow of heat takes place in following ways:

Case1. When TS < TE

When the temperature of the system is less than that of environment then the energy flows
into the system. As a result, the system gains energy and (Q) is positive.

Case2. When TS > TE

When the temperature of the system is more than that of environment then the energy
flows from system to the environment. As a result, the system loses energy and (Q) is
negative

Case3. When TS = TE
When the temperature of the system is equal to that of environment then thermal
Equilibrium is reached. As a result there is no transfer of energy and (Q) is zero.
 Internal Energy of a system
i. Internal energy is defined as the energy possessed by motion of molecules of the system and
Molecular configuration in system
ii.The internal energy of system is different than the macroscopic ordered energy of a moving
Object.
For example, a glass of water at rest on ground has no kinetic energy because it is not moving
And its Potential energy can also be taken as zero. But we know, from the kinetic theory, that
The water Molecules in the glass at the given temperature move at a random speed and due to
This, the system has some internal energy.
iii.This internal energy of a system is denoted by (U) .

CHANGE IN INTERNAL ENERGY OF A SYSTEM BY HEATING:

i. Consider a gas filled in cylinder fitted with a movable, massless and frictionless piston
At one end as shown in fig. (a)
ii. Let TS = the temperature of the gas and TE= temperature of Environment
iii. The cylinder can be brought in contact with the source of heat such as burner as
Shown in figure.
iv. When TE > Ts
Then the temperature difference between the source of heat (environment) and the
System will cause of flow of energy (Heat) towards the gas in the cylinder and internal
Energy of system of gas increases.
v. When TE < Ts
Then the energy is transferred from the system of gas to the environment and internal
Energy of gas decreases due to which the gas cools down

CHANGE IN INTERNAL ENERGY OF A SYSTEM BY DOING WORK :

i. Consider a gas filled in cylinder fitted with a movable, massless and frictionless piston at
One end as shown in fig. (b)
ii. Let TS= the temperature of the gas and TE= temperature of Environment
iii. When the piston is pushed inside the cylinder quickly, so that the gas is compressed as
Shown in fig. the piston is doing some work on the gas in moving it through some
Distance and the gas gains some energy due to which its temperature is increased.
 iv. When the gas pushes the piston out, so that the gas is expanded and some work is
Done by the gas due to which the gas loses some of its energy and the gas cools down.

Work done in changing the volume of system

i. Consider an ideal gas enclosed in a cylinder with a movable, massless and frictionless piston at its one
End as shown in diagram (c)
ii. If P = Pressure of the gas(system) in the cylinder(environment) & A = Area of cross-section of piston
Then the force exerted by the gas on the piston of the cylinder is
F = PA
iii. When the piston is pushed outward by an infinitesimal distance (dx) then the work done by the gas is
dW = F dx = P(A dx) = p dV
iv. For a finite change in volume of gas in cylinder from Vi to Vf The total amount of work done is
𝑉𝑓
W = ∫𝑉𝑖 𝑃𝑑𝑉 = P (Vf – Vi )
This is the expression for the amount of work done in changing the volume of the gas (system)

Special case:
1) POSITIVE WORK done by gas (system) as shown in diagram (a)
When the gas is expanding and piston is pushed outward so that the volume of the gas increases (Vf > Vi )
then positive work is done by the gas on piston during its expansion.
2) NEGATIVE WORK done by gas (system) as shown in diagram (b)
When the piston is pushed in so that the volume of the gas decreases (Vf < Vi ) then negative work is done
by the gas on piston during its compression.

First law of thermodynamics :

i. When the amount of heat is added to the system and the system does not do any work during
The process then the amount of heat (Q) supplied is used to increase only its internal energy (△U)
△U = Q ------------------- (1)
ii. When the system does some work to increase its volume and no heat is added to it while
Expanding then the system loses some energy to its surrounding and its internal energy decreases.
 This means that when (W) is positive then (△U) is negative and vice versa. Thus we can write
△U = -W --------------------- (2)
iii. In practice, the internal energy can change by both the ways (i.e. equation 1 & 2).
Therefore we consider the effect of both together and write the change in internal as
△U = Q – W ---------------------- (3)
Statement: According to Equation (3) the change in internal energy of a system is the difference between the
heat supplied to the system and the work done by the system on its surrounding.
This is the mathematical statement of First Law of Thermodynamics.
iv. The Equation (3) can be written as
𝑄 = △U + W ------------------- (4)
𝑇ℎ𝑖𝑠 𝑖𝑠 𝑎𝑛𝑜𝑡ℎ𝑒𝑟 𝑓𝑜𝑟𝑚 𝑜𝑓 First Law of Thermodynamics
Alternate statement: According to Equation(4) When The amount of heat (Q) is added to a system, its internal
energy increased by an amount (△U) and the remaining is lost in the form of work done (W) on its
surrounding.

Thermodynamic state variable

i) A state variable is any measurable or observable characteristics or property of a system when the system
remains in equilibrium.
ii) A thermodynamic system can be described by specifying its pressure, volume, temperature, internal energy
and number of moles. These parameters are called Thermodynamic variables.
iii) The relation between the Thermodynamic variables (P , V , T) of the system is called equation of state
iv) The equation of state for an Ideal gas is PV = nRT

Intensive variable and extensive variable of a system.

i. intensive variable do not depend on the size of the system
ii. Extensive variable depend on the size of the system
iii. Consider a system in equilibrium. Let this system be divided into two equal compartments, each
With half the original volume.
iv. The pressure (P), temperature (T) and density (𝜌) are the same as initial in both compartments.
These are intensive variables.
v. The total mass (M), internal energy (U) of the system however get equally divided in the two
Compartments.
Thus, each compartments now has mass (M/2) and internal energy (U/2). Hence, these are
Extensive variables of the system.

P-V diagram
i. The graphical representation of the change in state of gas by a thermodynamic process is called
P-V Diagram or Indicator diagram.
ii. Indicator diagram is plotted generally in pressure and volume of gas. Each point in P-V diagram
Represents the possible state of the system.
iii. If we draw Indicator diagram, the area bounded by Pressure axis and volume axis represents the
Work done which helps us to calculate work done by the gas or on the gas during expansion and
Compression.
 P-V diagram of positive and negative work.
Diagram :

i. The work done in changing the volume of the gas (system) can be calculated mathematically by
𝑉𝑓
W = ∫𝑉𝑖 𝑃𝑑𝑉 = P (Vf – Vi )
However the work done in changing the volume of the gas (system) can also be calculated
Graphically by finding area under the curve in P-V diagrams.
ii. A gas confined to a cylinder with a movable, frictionless, and massless piston can be
a) Expanded with varying pressure (Fig a)
b) Compressed with varying pressure (Fig b)
C) Compressed at constant pressure (Fig c)
Step1. POSITIVE WORK VARYING PRESSURE (From Fig a)
This figure shows expansion of gas at constant temperature where its volume increases due to
Outward displacement of the piston and the pressure of the gas decreases
𝑉𝑓
Here dV > 0 and Since Area = W = ∫𝑉𝑖 𝑃𝑑𝑉 = P (Vf – Vi )
Therefore the work done is positive

Step2. NEGATIVE WORK WITH VARYING PRESSURE (From Fig b)

This figure shows compression of gas at constant temperature where its volume decreases
Due to inward displacement of the piston and the pressure of the gas increases
𝑉𝑓
Here dV < 0 and since Area = W = ∫𝑉𝑖 𝑃𝑑𝑉 = P(Vf – Vi )
Therefore the work done is negative
Step3. POSITIVE WORK AT CONSTANT PRESSURE (Fig c)
This figure shows volume of gas increases at constant pressure due to outward displacement
Of the piston. Here dV > 0 and
𝑉𝑓
Since Area = W = ∫𝑉𝑖 𝑃𝑑𝑉 = P(Vf – Vi )
Therefore the work done is positive .

Path on P-V diagram:

i. When a thermodynamic system changes from its initial state to its final state, it passes through a series
of intermediate states. This series of intermediate states when plotted on P-V diagram is called a path.
ii. The path tells us the way a system has gone through a change.
 Work done during a Thermodynamic process:
Diagram :

i. Consider a thermodynamic system changes its state from initial state (A) of coordinate (Vi, Pi) to
Final state (B) of coordinate (Vf ,Pf)
ii. The state of system can be changed from its initial state to final in different ways shown by
Path 1, 2, 3 in above diagram (a)
Step1. From Fig (b)
i. The path 1 represents the system which changes itself from A to B where both its pressure and
Volume change. The pressure decreases while volume increases.
ii. The work done by the system is given by the area under the curve. It is positive when the
Volume increases (shown in diagram) or negative when the volume decreases.

Step2. From Fig (c)

i. This path 2 represents the system where volume increases to (Vi ) from the point ( A) up to
The point (C) at the constant pressure (Pi )
ii. After point (C) the pressure of the system decreases to P f at constant volume till point B as
Shown
iii. The system is now in the state B with its coordinate given by (Vf ,Pf) . Work done in this
Process is represented by the shaded area under the curve.
Step3. From Fig (d)
i. The path 3 represents the system where pressure decreases from (Pi) to (Pf) at constant
Volume (Vi) along the path AD
ii. After point D the volume of the system increases to Vf at constant pressure (Pf) as shown.
Work done in this process is represented by the shaded area under the curve.
Conclusion: From Figure (b), (c) and (d) we can conclude that the work done is more when the
System follows path ACB than the work done by the system along the path ADB.
NOTE: It is interesting to note that in all these cases, though work done during the change of state
Different, the initial and the final state of the system is same.

HEAT ADDED DURING THERMODYNAMIC PROCESS

Method I : Expansion of gas at constant temperature
Diagram:

i. Consider a thermodynamic system consisting of an ideal gas confined to a cylinder with movable,
Frictionless and massless piston (shown in fig a).
ii. Suppose we want to change the initial volume (Vi) of the gas to final volume (Vf) at a constant
Temperature Then there are two different ways in which this change in volume can be made
iii. In this case, the gas is heated slowly in a controlled manner so that it expands at a constant
Temperature and reaches the final volume (Vf) isothermally
iv. Here the system absorbs a finite amount of heat energy during this process.

Method II : Uncontrolled free expansion of gas

Diagram:

i. Consider a thermodynamic system consisting of an ideal gas confined to a cylinder with movable,
Frictionless and massless piston.
ii. The gas cylinder is surrounded by an insulating material and it is divided in two Compartments by
a thin breakable partition.
iii. The compartment (X) has volume (Vi) and the compartment (Y) has volume (Vi)’ so that
(Vi)+ (Vi)’=(Vi)
 iv. The compartment (X) of cylinder is filled with the some amount of gas at some temperature
The compartment (Y) is empty, it contains no gas particles or any other form of matter.
The initial state of the system is same in both cases.
v. The partition is now suddenly broken. This causes a sudden, uncontrolled expansion of the
Volume of the gas. The gas occupies the volume that was empty before the partition was
Broken.
vi. There is no exchange of heat between the gas and its environment because the cylinder is now
Surrounded by an insulating material.
vii. The final volume of the system after the partition is broken is (Vf).
viii. In this case, the gas has not done any work during its expansion because it has not pushed any
Piston or any other surface for its expansion. Such expansion is called free expansion.
Example: A common example of free expansion is abrupt puncturing of an inflated balloon or
tyre.

Reversible process and Irreversible process

A Thermodynamic process can be reversible process or it can be irreversible process

Reversible process Irreversible process
A Reversible process is a change that can be An Irreversible process is a change that
retraced in reverse(opposite) direction cannot be retraced in reverse(opposite)
shown in P-V diagram (a) direction shown in P-V diagram (b)
Ex. Melting of ice, Freezing of water, Boiling Ex. Puncturing an inflated balloon or a tyre,
of water, Condensation of steam etc. Rubbing our palms together, Burning a
candle etc.
The path of Reversible process is the same in The path of Irreversible process is not same
forward and reverse direction in forward and reverse direction
Reversible changes are very slow and there There is permanent loss of energy from the
is no loss of any energy in the process system due to friction, viscosity or other
dissipative forces and hence some hysteresis
is observed in an irreversible process.
The system comes back to its initial state The change of state depends upon the path
after it is taken along the reverse path taken to change the state during an
irreversible process
Reversible processes are ideal process Irreversible processes are real processes.
 Isothermal process

When a thermodynamic system undergoes a physical change in such a way that its temperature remains
constant, then the change is known as isothermal change.
In this process, P and V changes but T= constant i.e. change in temperature ∆𝑇 = 0
Boyle’s law is obeyed, i.e. PV = constant ⟹ P1V1 =P2V2
Work done in Isothermal process:
Consider the isothermal expansion of an ideal gas where its initial volume (v i) and final volume (Vf)

Step1: The work (dW) done in an infinitesimally isothermal expansion is given by

dW = PdV
The total work done in bringing out the expansion from the initial volume (Vi) to the final
Volume (Vf) is given by
𝑉
W = ∫ 𝑑𝑊 = ∫𝑉 𝑓 𝑃𝑑𝑉 ----------------------- (1a)
𝑖
𝑛𝑅𝑇
But for an ideal gas PV = nRT ⟹ P = Therefore above equation (1a) becomes
𝑉
𝑉𝑓 𝑛𝑅𝑇
W= ∫𝑉 dV
𝑖 𝑉
W = nRT 𝑙𝑜𝑔 𝑉𝑓
𝑒 (𝑉 )
𝑖
W= 2.303nRT 𝑙𝑜𝑔 𝑉𝑓 ----------------------- (1b)
10 ( 𝑉 )
𝑖
Step2: Since for isothermal process PV= constant i.e. P iVi =Pf Vf
Therefore Equation (1b) becomes W = nRT 𝑙𝑜𝑔 𝑃𝑖 = 2.303nRT 𝑙𝑜𝑔 𝑃 ------------(2)
𝑒 (𝑃 ) 10 (𝑃 𝑖 )
𝑓 𝑓

Step3. First Law of Thermodynamics (FLOT) in Isothermal process:

From 𝑄 =△ 𝑈 + 𝑊
Since △ 𝑈 = 0 [𝐴𝑠 △ 𝑇 = 0]
𝑇ℎ𝑒𝑟𝑒𝑓𝑜𝑟𝑒 𝑄 = 𝑊 = nRT 𝑙𝑜𝑔 𝑉𝑓 = nRT 𝑙𝑜𝑔 𝑃 -------------- (3)
𝑒 (𝑉 ) 𝑒 (𝑃 𝑖 )
𝑖 𝑓

Thus, the heat transferred to the gas in isothermal change is completely converted into the
Work done for expansion of gas against the external surrounding.
OR
If the work is on the system then equal amount of heat energy will be liberated from the system
 Isobaric process:

When a Thermodynamic system undergoes a physical change in such a way that its pressure
Remains constant, then the change is known is isobaric process
In this process, P= Constant therefore △ 𝑷 = 𝟎 𝐵𝑢𝑡 𝑜𝑡ℎ𝑒𝑟 quantities are not zero
i.e. therefore 𝑸 ≠ 𝟎 , △ 𝑼 ≠ 𝟎 , 𝑾 ≠ 𝟎 and △ 𝑻 ≠ 𝟎

Work done in isobaric process

When a Thermodynamic system undergoes a physical change in such a way that its pressure
Remains constant, then the change is known is isobaric process
In this process, P= Constant therefore △ 𝑷 = 𝟎 𝐵𝑢𝑡 𝑜𝑡ℎ𝑒𝑟 quantities are not zero
i.e. therefore 𝑸 ≠ 𝟎 , △ 𝑼 ≠ 𝟎 , 𝑾 ≠ 𝟎 and △ 𝑻 ≠ 𝟎

Step1. Consider an ideal gas expansion where it’s initial volume (v i), Temperature (Ti) and final volume
(Vf), Temperature (Tf) respectively
Then total work done in bringing out the change under an isobaric process is given by
W = PdV = P(Vf - Vi) = nR (Tf - Ti) ---------------------------------(1a)
Also the change in internal energy of a system is given by
∆𝑈 = 𝑛𝐶𝑣 ∆𝑇 = 𝑛𝐶𝑣 [𝑇𝑓 − 𝑇𝑖 ] --------------------------------- (1b)
Step2. By First Law of Thermodynamics
𝑄 =△ 𝑈 + 𝑊
From Equation (1a) and (1b) we get 𝑄 = 𝑛𝐶𝑣 [𝑇𝑓 − 𝑇𝑖 ] + nR (𝑇𝑓 − 𝑇𝑖 )
𝑄 = (𝑛𝐶𝑣 + nR) (𝑇𝑓 − 𝑇𝑖 )
𝑄 = 𝑛(𝐶𝑣 + R) (𝑇𝑓 − 𝑇𝑖 )
𝑄 = 𝑛𝐶𝑝 (𝑇𝑓 − 𝑇𝑖 ) ------------------------- (2)
Inference: From Equation (2) it is observed that for isobaric process:
i. When temperature changes then its internal energy also changes
ii. The heat exchanged is partly used for increasing the temperature and partly to do
some work
iii. The change in temperature of the system depends on the specific heat at constant
Pressure (Cp)
 Isochoric process:

When a Thermodynamic process undergoes a physical change in such a way that its volume remains
constant then the change is known as isochoric process
In this process, V= Constant therefore △ 𝑽 = 𝟎 𝒂𝒏𝒅 𝒉𝒆𝒏𝒄𝒆 𝑾 = 𝟎
𝐵𝑢𝑡 𝑜𝑡ℎ𝑒𝑟 Quantities are not zero i.e. 𝑸 ≠ 𝟎 , △ 𝑼 ≠ 𝟎 𝒂nd △ 𝑻 ≠ 𝟎
Work done in isochoric process:
When a Thermodynamic process undergoes a physical change in such a way that its volume
Remains constant then the change is known as isochoric process
In this process, V= Constant therefore △ 𝑽 = 𝟎 𝒂𝒏𝒅 𝒉𝒆𝒏𝒄𝒆 𝑾 = 𝟎
𝐵𝑢𝑡 𝑜𝑡ℎ𝑒𝑟 Quantities are not zero i.e. 𝑸 ≠ 𝟎 , △ 𝑼 ≠ 𝟎 𝒂nd △ 𝑻 ≠ 𝟎
Step1. For isochoric process, V= Constant
Therefore △ 𝑉 = 0 and work done is given by W= P△ 𝑉=0 ------------------------------- (1a)
Now the change in internal energy is given by ∆𝑈 = 𝑛𝐶𝑣 ∆𝑇 __________________________(1𝑏)
Syep2. By First Law of Thermodynamics
From 𝑄 =△ 𝑈 + 𝑊
From Equation (1a) and (1b) we get Q = 𝑛𝐶𝑣 ∆𝑇 + 0
Q = 𝑛𝐶𝑣 ∆𝑇 ----------------------------------- (2)
Inference: From Equation (2) it is observed that for isochoric process:
i. The system does not do any work because the volume remains constant
ii. All the energy (Q) supplied is converted into the internal energy (△ 𝑈) of the system.

Adiabatic process:
When a thermodynamic system undergoes a change in such a way that no exchange of heat takes
Place between system and surroundings, the process is known as adiabatic process.
 In this process P, V and T Changes, therefore △ 𝑻 ≠ 𝟎 changes but 𝑸 = 𝟎
When a system undergoes an adiabatic change, its temperature (T) and energy (U) both change.
The change in internal energy of adiabatic process is given by
∆𝑈= nCv (∆𝑇)
Work done in an adiabatic process:
An adiabatic system is thermally isolated from its environment; therefore it can exchange heat
With it.
In this process P, V and T Changes, therefore △ 𝑻 ≠ 𝟎 𝒂𝒏𝒅 △ 𝑼 ≠ 𝟎 changes but 𝑸 = 𝟎
Step1. Consider an adiabatic process of an ideal gas where it’s initial volume (Vi) and final volume (Vf)
The total work done in bringing out the change from the initial volume (Vi) to the final
Volume (Vf) under an adiabatic process is given by
𝑉
W = ∫𝑉 𝑓 𝑃𝑑𝑉 ----------------------- (1a)
𝑖
Step2. But for an adiabatic change 𝑃𝑉 𝛾 = constant = C
𝑉 𝑑𝑉 𝑉 (−𝛾+1)
Therefore above equation (1a) becomes W = 𝐶 ∫𝑉 𝑓 W= C × [ ]
𝑖 𝑉𝛾 1−𝛾
Where volume changes from initial volume (vi) and final volume (Vf)
𝐶 1 1
Therefore W= 1−𝛾 × [𝑉 𝛾−1 − 𝑉 𝛾−1] -------------------------------- (2)
𝑓 𝑖

Step3. Also for adiabatic change, we can write Pi 𝑉𝑖 𝛾 = Pf 𝑉𝑓 𝛾 =C

Therefore above equation (2) becomes
1 Pf 𝑉𝑓 𝛾 Pi 𝑉𝑖 𝛾 1
W= 1−𝛾 × [ 𝑉 𝛾−1 − ] = W= 1−𝛾 × [Pf Vf -Pi Vi]
𝑓 𝑉𝑖 𝛾−1
𝑛𝑅[𝑇𝑓 −𝑇𝑖 ] 𝑛𝑅[𝑇𝑖 −𝑇𝑓 ]
W= --- (3a) OR W= ------ (3b)
1−𝛾 𝛾−1

Inference: From Equation (3b) it is observed that for adiabatic process:

i. When work is done by the gas i.e. If gas expands, W= positive and [𝑇𝑖 > 𝑇𝑓 ]
i.e. adiabatic expansion produce cooling of system(gas)
ii. When work is done on the gas i.e. If gas is compressed, W= negative and [𝑇𝑖 < 𝑇𝑓 ]
i.e. adiabatic compression produce heating of system(gas)

Cyclic process:

i. A cyclic process consist of a series of changes which return the system back to its initial state.
ii. In case of cyclic process, as Uf = Ui ⟹ ∆𝑈 = Uf − Ui = 0
i.e. change in internal energy for cyclic process is zero
And also 𝑠𝑖𝑛𝑐𝑒 ∆𝑈 ∝ ∆𝑇 ∴ ∆𝑈 = ∆𝑇 = 0 i.e. the temperature of the system remains constant
iii. From First law Of Thermodynamics 𝑄 =△ 𝑈 + 𝑊 ⟹ 𝑄 = 𝑊
i.e. Heat supplied is equal to work done by the system
iv. For Cyclic process P-V graph is a closed curve and area enclosed by the closed path represents the
Work done.
If the cycle is clockwise work done is positive and if the cycle is anticlockwise then work done is
Negative.
v. Working of all heat engines is a cyclic process.

Free Expansion:
These expansions are adiabatic expansions and there is no exchange of heat between a system and its
environment. Also, there is no work done on the system or by the system. Q = W = 0, and according to the
first law of thermodynamics, ∆U = 0.
For example, when a balloon is ruptured suddenly, or a tyre is suddenly punctured, the air inside rushes
out rapidly but there is no displacement of a piston or any other surface.
Free expansion is different than other thermodynamic processes because it is an uncontrolled change. It is
an instantaneous change and the system is not in thermodynamic equilibrium. A free expansion cannot be
plotted on a p-V diagram. Only its initial and the final state can be plotted

Heat Engine :
Heat engines are devices that transform heat partly into work or mechanical energy.
Heat engines work by using cyclic processes and involve thermodynamic changes.
A typical heat engine has the following elements:
(1) A working substance: It is called the system. It can be an ideal gas for an ideal heat engine . For a
practical heat engine, the working substance can be a mixture of fuel vapor and air in a gasoline (petrol) or
diesel engine, or steam in a steam engine. It is the working substance that absorbs heat and does work.

(2) Hot and cold reservoir : The working substance interacts with the reservoirs.
The hot reservoir is the source of heat. It is at a relatively high temperature and is capable of providing
large amount of heat at constant higher temperature, TH. It is also called as the source.
The cold reservoir absorbs large amount of heat from the working substance at constant lower
temperature, TL. It is also called as the sink.
(3) Cylinder: Generally, the working substance is enclosed in a cylinder with a moving, frictionless,
and massless piston. The working substance does some work by displacing the piston in the cylinder.
This displacement is transferred to the environment using some arrangement such as a crank shaft
which transfers mechanical energy to the wheels of a vehicle.

Heat engines are of two basic types. They differ in the way the working substance absorbs heat :
1) External combustion engine : In an external combustion engine , the working substance is heated
externally as in case of a steam engine.
2) Internal combustion engine : In case of the internal combustion engine , the working substance
is heated internally similar to an automobile engine using gasoline or diesel.
Any heat engine works in following three basic steps.
1. The working substance absorbs heat from a hot reservoir at higher temperature.
2. Part of the heat absorbed by the working substance is converted into work.
3. The remaining heat is transferred to a cold reservoir at lower temperature.

Heat engines are diagrammatically represented by an energy flow diagram schematically shown in
Figure :

*Let Q H be the heat absorbed by the working substance at the source, and Q L be the heat rejected by it at
the sink. In a heat engine, Q H is positive and Q L is negative. Also, let W be the work done by the working
substance.
*In the figure, the dotted box represents the engine.
*The ‘heat pipelines’ shown in the diagram represent the heat absorbed, rejected, and converted into
work. The width of the heat ‘pipeline’ indicated by Q H , is proportional to the amount of heat absorbed at
the source.
*Width of the branch indicated by Q L is proportional to the magnitude Q L of the amount of heat rejected
at the sink.
*Width of the branch of the pipeline indicated by W is proportional to the part of the heat converted into
mechanical work.
*One single execution of the steps mentioned above is one operating ‘cycle’ of the engine. Several such
cycles are repeated when a heat engine operates. The quantities Q H and Q L represent the amount of heat
absorbed (positive) and rejected (negative) respectively during one cycle of operation .
*The net heat Q H absorbed per operating cycle is,
QH= W + QL i.e. W = QH - QL
The performance of a heat engine is expressed by means of ‘ Efficiency 𝜂 ’ which is defined as the ratio of
useful work obtained from the engine to the heat supplied to it .
𝜂 = W/Q H
Note : Ideally, we would expect a heat engine to convert all the heat absorbed, Q H , into work. Practically,
this is not possible (According to Second Law of Thermodynamic). There is always some heat lost takes
place i.e. Q L ≠ 0.

The Heat Engine Cycle and the P - V Diagram :

The P-V diagram of a typical heat engine is shown in Figure

1) The operating cycle begins at the point A in the cycle. The working substance, the gas in this case,
absorbs heat at constant volume and no work is done by the gas or on the gas. The pressure is
increased till the point B is reached.
2) The temperature of the gas also increases and its internal energy increases. The gas starts expanding
by pushing the piston away and its volume changes from the point B to the point C. Because the gas
expands, its pressure is reduced. The gas does work in this part of the cycle.
3) When the point C is reached, the excess heat, the heat that is not utilized in doing work by the gas,
is rejected. The gas cools down and its internal energy decreases. This process is again at constant
volume. The pressure of the gas is reduced and point D on the P-V diagram is reached.

4) The gas is now compressed. Its volume decreases and its pressure increases. The change continues till
the point A is reached.
The cycle is complete and the system is ready for the next cycle.
The operation of a heat engine is a cyclic process therefore, its P-V diagram is a closed loop. The area of
the loop represents the work done during one complete cycle.
Refrigerators and Heat Pumps:
Refrigerators and heat pumps are heat engines that work in backward direction. They convert mechanical
work into heat.
Heat cannot flow from a region of lower temperature to a region of higher temperature on its own. We
can force heat to flow from a region of lower temperature to a region of higher temperature by doing
work on the system (or, on the working substance of a heat engine). Refrigerators or air-conditioners and
heat pumps are examples of heat engines .

Refrigerators :
A refrigerator extracts heat from a cold region (inside the chamber, or the compartments) and delivers it
to the surrounding (the atmosphere) thus, further cooling the cold region.
Figure (a) shows the schematics of the mechanism used in a typical refrigerator. It consists of a
compressor, an expansion valve, and a closed tube which carries the refrigerant. Part of the tube, called
the cooling coil, is in the region which is to be cooed at lower temperature and lower pressure. The other
part which is exposed to the surrounding (generally, the atmosphere) is at a higher temperature and
higher pressure. A fluid such as (fluorinated hydrocarbons) is used as refrigerant. Normally, the cold and
the hot part of the coil contain the refrigerant as a mixture of liquid and vapor phase in equilibrium.

Figure (a) Figure (b)

Schematics of a Refrigerator
The refrigerant goes through the following steps in one complete cycle of refrigeration.
Step 1: The fluid passes through a nozzle and expands into a low-pressure area , the fluid turns into a gas
and cools down. This is essentially an adiabatic expansion.
Step 2: The cool gas is in thermal contact with the inner compartment of the fridge. It heats up as heat is
transferred to it from the contents of the fridge. This takes place at constant pressure, so it's
an isobaric expansion.
Step 3: The gas is transferred to a compressor, which does most of the work in this process.
The gas is compressed adiabatically, heating it and turning it back to a liquid.
Step 4: The hot liquid passes through coils on the outside of the fridge, and heat is transferred to
the atmosphere. This is an isobaric compression process.
The compressor is driven by an external energy source and it does the work W on the working substance
during each cycle.
Heat Pump:
Heat pump is a device which works similar to a refrigerator. It is used to heat a building or a similar larger
structure by cooling the air outside it. A heat pump works like a refrigerator operating inside out. In this
case, the evaporator coils are outside and absorb heat from the cold air from outside. The condenser coils
are inside the building. They release the absorbed heat to the air inside the thus, warming the building.

Performance of Refrigerators and Heat Pumps :

A Refrigerator or Heat Pump is basically a Heat Engine which runs in reverse direction. In it working
substance takes heat Q L from a body at a lower temperature TL , has a net amount of work done W on it
by an external agent (usually compressor) and gives out a large amount of heat Q H to a hot body at
temperature TH .
Thus , it transfers heat from a cold to a hot body resulting cold body cooled more and more. The working
substance is called ‘ Refrigerant ’ .

The performance of a Refrigerator is expressed by means of ‘ Coefficient of Performance K ’ which is

define as :
The ratio of the heat extracted from the cold body to the work needed to transfer it to the hot body .

As , W = Q H - Q L
So ,

Larger is the ratio, better is the refrigerator. That means a refrigerator has the best performance when the
heat extracted by the refrigerant at the cold reservoir is maximum by doing minimum work in one
operating cycle. For a typical household refrigerator, K ≈ 5.

NOTE ; A perfect Refrigerator is one which transfers heat from cold to hot body without doing work ,
i.e. W = 0 so that Q H = Q L and hence , for it K = ∞ (not possible ,according to Second Law of
Thermodynamic )
Air Conditioner :
Working of an air conditioner and a refrigerator is exactly similar . The performance of an air conditioner is
defined by K = Q L /W . It is important to consider the rate of heat removed H and the power P required for
removing the heat.
We define the rate of heat removed as the heat current “ H = Q L /t ” where, t is the time in which heat Q L
is removed. Therefore, the coefficient of performance of an air conditioner can be calculated as ,
𝐇t 𝐇
K = Q L /W = =
𝐏t 𝐏
Typical values of K are 2.5 to 3.0 for room air conditioners.

Second Law of Thermodynamics :

Limitations of the First Law of Thermodynamics :
The First law of thermodynamics tells us that heat can be converted into work and work can also be
converted into heat. It is merely a quantitative statement of the equivalence of heat and work. It has the
following limitations.
(a) It does not tell us whether any particular process can actually occur. According to the first law of
thermodynamics, heat may, on its own, flow from an object at higher temperature to one at lower
temperature and it can also flow from an object at lower temperature to one at higher temperature.
We know that practically, heat cannot flow from an object at lower temperature to another at higher
temperature. The First law of thermodynamics does not predict this practical observation.
(b) According to the First law, we could convert all (100%) of the heat available to us into work.
Similarly, all the work could be converted into heat. Again, we know that practically this is not possible.

The second law of thermodynamics , statement :

(i) The “ Kelvin Planck statement ” or the ‘ First form ’ of the Second law of thermodynamics ;
The “ Engine Law ” or the ‘Engine Statement’ of the Second law of thermodynamics ;

“ It is impossible to extract an amount of heat Q H from a hot reservoir and use it all to do work W.
Some amount of heat Q L must be exhausted to a cold reservoir. ”
This prohibits the possibility of a perfect heat engine .

Practical Heat Engine Perfect Heat Engine

(ii) The or “ Clausius ” statement or the ‘ Second form ’ of the Second law of thermodynamics ;
The “ Refrigerator Law ” or the ‘Refrigerator Statement’ of the Second law of thermodynamics ;
“ It is not possible for heat to flow from a colder body to a warmer body without any work having
been done to accomplish this flow .”

This means that energy will not flow spontaneously from an object at low temperature to an object at a
higher temperature. This rules out the possibility of a perfect refrigerator.

Note : The statements are also applicable to air conditioners and heat pumps, which work on
the same principles.

Carnot Cycle and Carnot Engine

Maximum Efficiency of a Heat Engine and Carnot’s Cycle :
In a Carnot engine, there are basically two processes:

(i) Exchange of heat (steps A to B and C to D in the Figure) : For this to be reversible, the heat exchange
must be isothermal. This is possible if the working substance is at the temperature TH of the source
while absorbing heat. The working substance should be at the temperature of the cold reservoir TL ,
while rejecting the heat.

(ii) Work done (steps B to C and D to A) : For work done to be reversible, the process should be adiabatic .
Thus, the cycle includes two isothermal and two adiabatic processes for maximum efficiency.
 The corresponding P-V diagram will then be as shown in the Figure ;

Carnot Cycle=> AB: Isothermal Expansion, BC: Adiabatic Expansion, CD: Isothermal Expansion, DA: Adiabatic Expansion
we can derive an expression for the efficiency of a Carnot cycle/engine as ;
 Eq. (3) become
(Q L)/(Q H) = (TL )/(TH) ………(5)
So Eq. (2) can be written as

Thus, while designing a heat engine for maximum efficiency, the source temperature T H should be as high
as possible and the sink temperature TL should be as low as possible.

Carnot Refrigerator :
We know that a refrigerator is nothing but a heat engine operated in the reverse direction. Because each
step in the Carnot cycle is reversible, the entire Carnot cycle is reversible. If we operate the Carnot engine
in the reverse direction, we get the Carnot refrigerator. We can write the coefficient of performance of a
Carnot refrigerator as,
K = (Q L)/(Q H - Q L) = [Q L /Q H]/[ 1 – (Q L /Q H) ]
As , (Q L)/(Q H) = (TL )/(TH)

We have ,

This Equation gives the coefficient of performance of an Ideal Refrigerator or, the Carnot Refrigerator.

• It says that the coefficient of performance of a Carnot refrigerator also depends on only the temperature
difference of the hot and the cold reservoir.
• When the temperature difference is very small, the coefficient is very large. In this case, a large quantity
of heat can be removed from the lower temperature to the higher temperature by doing very small
amount of work.
• The coefficient of performance is very small when the temperature difference is large. That means a small
quantity of heat will be removed even when a large amount of work is done.

The Second Law of Thermodynamics and the Carnot Cycle :

" The Carnot engine is the most efficient heat engine as it is ideal. So, all Carnot engines operating
between the same two temperatures have the same efficiency, irrespective of the nature of the working
substance".

Sterling Cycle :
Significance :
i) This is a closed thermodynamic cycle. The Sterling engine is based on this cycle shown in Figure below .
ii) The working substance used in a Sterling engine is air, helium, hydrogen, nitrogen etc.
iii) All the processes in the Sterling cycle are reversible processes.
iv) When the gas is heated, the Sterling engine produces useful work. When work is done on the gas, it
works as a refrigerator. This is reverse working of a Sterling cycle.
v) The reversed Sterling cycle is extensively used in the field of cryogenics to produce extremely low
temperatures or to liquefy air or gases like helium, hydrogen, nitrogen used as working substance.

Processes in Sterling Cycle : The ideal Sterling cycle has two isothermal processes AB and CD. Two isobaric
processes BC and DA . Heat is absorbed at constant temperature TH and rejected at constant temperature
TL . The four processes in a Sterling cycle are described briefly in the following.
• Isothermal expansion (AB): The gas is heated by supplying heat Q H at constant temperature TH.
Useful work is done by the gas in this part of the cycle.
• Isochoric process (BC): Part of the heat absorbed (Q H) by the gas in the previous part of the cycle is
released by the gas to the refrigerator. This heat (Q) is used in the next part of the cycle. The gas cools
down to temperature TL .
• Isothermal compression (CD): The heat generated in this part of the cycle (Q L) is rejected to
the coolant (sink). The temperature of the gas is maintained at T L during this process.

Sterling Cycle

• Isobaric heat absorption (DA): The compressed gas absorbs heat (Q) during this process.
Its temperature is increased to TH .
The cycle repeats when the process reaches the point A.