Second Law of Thermodynamics

Second law of thermodynamics is a generalization of certain experiences and

observations. It is mainly concern with two aspects. They are a) efficiency of
engine and b) working of refrigerator. Followings are the statement of second law
of thermodynamics.
Kelvin – Plank Statement: It is impossible for any system to undergo a process in
which it absorbs heat from a reservoir at a single temperature and converts the
heat completely into mechanical work, with the system ending in the same state
in which it began.
This statement is also called engine statement of second law of thermodynamics.
In a heat engine, working substance absorbs some heat from the source i.e.
higher temperature reservoir, converts a part of heat into mechanical work and
rejects the remaining part to the sink i.e. low temperature reservoir. Therefore, it
is essential to have a sink for continuous conversion of heat into work from a
source. In conclusion, we cannot obtain continuous supply of work from a single
body.
Clausius Statement: It is impossible for a self-acting machine unaided by any
external agency to transfer heat from a body at a lower temperature to a body at
a higher temperature.
It is called refrigerator statement of second law of thermodynamics. In nature,
heat energy does not pass spontaneously from cold body to hot body. For
transfer of heat from cold body to the hot body some external agent is required.
For example, in refrigerator, the working substance takes heat from a cold body,
for this, a certain amount of work is done on it by some outside agency and
rejects a large amount of heat to a hotter body. Therefore, for a continuous
supply of heat from a cold body to a hot body the external work done on a system
is essential.
Heat engine
A heat engine is a device that converts heat energy continuously into mechanical
work. It consists of following three parts.

1
(i) Source: A hot body at a constant high temperature from which the heat engine
can draw heat
(ii) Sink: A cold body at a constant low temperature to which any amount of heat
can be rejected.
(iii) Working substance: Matter which can absorb heat from the source and reject
to the sink.
Efficiency of heat engine
The efficiency of heat engine is defined as the ratio of external work done by the
engine to the heat energy absorbed by the working substance from the heat
source at a higher temperature. It is denoted by . Therefore,

Efficiency () =

Let Q1 be the amount of heat absorbed and Q2 be the

amount of heat rejected by a working substance in one
cycle. Then, the net heat absorbed by the engine in one cycle
is,
Q = Q1 - Q2
Since, the system returns to the initial state after one complete
Cycle, dU = 0. Then from first law of thermodynamics,
W = Q1 – Q2
Hence, efficiency of engine is given by,

= =

 = 1 -

In terms of percentage,

 = (1 - )× 100%

2
 Since, Q2˂Q1, efficiency is always less than 100%. For a given value of Q1, smaller
the value of Q2, higher will be the efficiency of the engine.
Why efficiency of heat engine never is 100%?
Answer: The efficiency of heat engine is,

 = (1 - )× 100%

From second law of thermodynamics, heat engine must reject certain amount of
heat to the sink to perform mechanical work. Therefore, Q2 cannot be zero.
Hence, from above relation, efficiency of heat engine never is 100%.

Types of heat engine

Heat engine can be divided into two types
1. External combustion engine: The engine in which fuel is burnt outside the
engine is called external combustion engine. For example, steam engine. In this
engine the working substance (i.e. steam) can be recycled.
2. External combustion engine: The engine in which fuel is burnt inside the engine
is called internal combustion engine. For example, diesel engine, petrol engine
etc. In this engine the working substance (air) can’t be recycled.
Carnot Engine and Carnot Cycle
A hypothetical heat engine that has the maximum possible efficiency and is free
from all the imperfection of an actual engine is called Carnot engine. This engine
can’t be realized in practice.
The essential parts of an ideal engine or Carnot engine are discussed below.
1. Source of heat: A hot body of infinite thermal capacity is a source of heat. It has
higher fixed temperature from which working substance extract heat.

3
2. Cylinder: It is a device containing insulating walls and perfectly conducting
base. It is fitted with movable, frictionless piston and contains ideal gas as a
working substance.

3. Sink: It is a body of infinite thermal capacity maintained at lower fixed

temperature T2. Any amount of heat can be rejected in sink by working substance.
4. Insulating stand: An insulating stand is a perfectly non- conducting pad that
serves as a platform during adiabatic processes.
Carnot Cycle
The reversible cycle in which the working substance of Carnot engine undergoes a
four successive operation is known as Carnot cycle.
Let n- moles on an ideal gas are enclosed in a cylinder. The initial pressure P1,
volume V1 and Temperature T1 is represented by a point A in indicator diagram.
One Carnot cycle is completed in following four operations.
1. Operation I (Isothermal expansion)
In this operation, the cylinder is placed on the source at temperature T1. The gas
in the cylinder is allowed to expand isothermally from volume V1 to volume V2. An
ideal gas extract Q1 amount of heat from the source. It is represented by curve AB
in P-V diagram. The amount of work done during the process is,

Q1 = W1 = nRT1ln ( ) ……………… (i)

= Area ABGEA

4
2. Operation II (Adiabatic expansion)
The cylinder is now placed on the insulating stand and piston is allowed to move
out until the temperature of gas falls to T2 and volume becomes V3. The process is
adiabatic expansion which is represented by curve BC in P-V diagram. The work
done in this process is,

W2 = (T1 – T2) ……………………….. (ii)

= Area BCHGB
3. Operation III (Isothermal compression)
In this process, the cylinder is placed on the sink at temperature T2 and an ideal
gas is allowed to compress isothermally from V3 to V4. It is represented by curve
CD in P-V diagram. In this process, the heat Q2 is rejected to the sink. The work
done is,

W3 = Q2 = - nRT2 ln ( )

= nRT2 ln ( ) ………………………. (iii)

= Area CHFDC

5
4. Operation IV (Adiabatic compression)
The cylinder is placed on the insulating stand and the gas is compressed
adiabatically until it attains initial pressure P1, volume V1 and temperature T1. It is
represented by the curve DA in P- V diagram. The work done in this process is,

W4 = - (T2 – T1)

= (T1 – T2) ……………………… (iv)

= Area DFEAD
The net work done by the working substance in one cycle is,
W = W1 + W2 + (-W3) + (-W4)
= W1 – W3 ( because W2 = W4)
= Q1 – Q2 (from equation (i) and (iii))
= area ABCDA
Efficiency of Carnot engine
The efficiency of Carnot engine is define as the ratio of work done to the heat
energy absorbed in one Carnot cycle.i.e,

=

= 1- …………… (v)

From equation (i) and (iii),

= ………………. (vi)

From P- V diagram, B and C lie in the same adiabatic curve, then,

-1 -1
T1V2 = T2V3 ………… (vii)
Similarly, A and D lie in a the same adiabatic curve, then,
6
 -1 -1
T1V1 = T2V4 ………… (viii)
Dividing (vii) by (viii), we get,

Using this value in equation (vi),

From (v),

 = 1- ………………… (ix)

Equation (ix) indicates that the thermal efficiency of Carnot engine is independent
with the nature of working substance but it depends on the temperature of
source (T1) and temperature of sink (T2).
Petrol Engine
The internal combustion engine that uses petrol as a fuel is called petrol engine. It
was designed by Otto Van hence it is also called Otto engine. It consist of a
cylinder fitted with the piston and is provided with inlet valve I, outlet valve O and
sparking plug S. There are four strokes in a complete cycle and hence it is a four
stroke engine.
The working of petrol engine with the help of P-V diagram is discussed below.

7
a) Suction stroke:- In this stroke, the inlet valve I is opened and suitable mixture of
air and petrol vapor (98% air and 2% petrol vapor) is sucked into the cylinder by
the outward motion of piston as shown in the figure. Pressure remains constant
in this stroke. It is represented by a line AB in P-V diagram.
b) Compression stroke:- In this stroke both the inlet valve I and the outlet valve O
are closed. The volume of the mixture reduces to (1/5)th of the original volume
and the temperature rises up to 6000 C due to adiabatic compression. At the end
of this stroke, the mixture is fired by a spark plug. This stroke is represented by
curve BC and CD in the P-V diagram.
c) Working stroke:- During this stroke, both inlet and outlet valves remain closed.
Due to the ignition of mixture, temperature of gas rises about 20000 C. The gas
expands adiabatically and the engine performs mechanical work. It is represented
by the curve DE in indicator diagram.
d) Exhaust stroke:- In this stroke, the outlet valve opens and heat is rejected to
the surrounding at constant volume until its pressure is equal to the atmospheric
pressure. At last, the burnt gas is rejected due to inward motion of piston at
constant pressure. This stroke is represented by the lines EB and BA in the
indicator diagram. Now, the engine is ready to start another fresh cycle.

8
Diesel Engine
The internal combustion engine that uses diesel as a fuel is called diesel engine. It
consist of a cylinder provided with three valves namely air inlet valve I, oil sprayed
valve O and the outlet valve E. These valves are opened and closed at proper
moments by suitable mechanism.
The working of diesel engine on the four stroke principle is discussed below with
the help of P-V diagram.

a) Suction stroke:- In this stroke, air inlet valve I is opened and air at atmospheric
pressure enters into the cylinder by the outward motion of the piston. This stroke
is represented by a line EC in the P-V diagram.
b) Compression stroke:- In this stroke, all the valves are closed and air is
compressed adiabatically to about (1/17)th of its original volume by the backward
motion of the piston. In this process, the temperature of air inside cylinder
becomes 10000C. This is represented by the curve CD in the indicator diagram.
c) Working stroke:- The oil valve O is opened and diesel oil burns spontaneously
due to high temperature. The rate of supply of oil is so adjusted that combustion
and expansion of gas takes place at constant pressure. When the temperature
reaches about 2000 K the supply of oil is cut off. The useful work is done in this
stroke. It is represented by the line DA and curve AB in P-V diagram.

9
d) Exhaust stroke:- In this stroke, outlet valve opens and useless gas mixture is
forced out at constant volume. At the end, remaining mixture is rejected at
constant pressure. This is represented by the lines BC and CE in P-V diagram.
Now, the engine is ready for another fresh cycle.
Efficiency of Petrol and Diesel and engine
Let, Q1 be heat energy absorbed by the engine during combustion of oil and Q2 be
heat rejected by the engine during exhaust stroke then the efficiency is given by,

 = (1 - )× 100%

In terms of compression ratio,

 = 1-

Where, is compression ratio and is ratio of two molar heat capacities of air.
Refrigerator
A machine that operates opposite to that of heat engine is called refrigerator. It
absorbs heat from the cold body and rejects to the hot body.

Let Q2 be the amount of heat absorbed by the working substance of refrigerator

from cold body at temperature T2 and W be the external work to be supplied in

10
refrigerator then the total heat rejected by working substance to the hot body at
temperature T1 is,
Q1 = W + Q2
 W = Q1 – Q2 ………….. (i)
Coefficient of performance of refrigerator
It is defined as the ratio of amount of heat energy absorbed from the cold body to
the external work done on running the machine. It is denoted by β.

β=

Or, β =

Or, β = …………….. (ii)

The performance of refrigerator is same as that of ideal heat engine but in

opposite order. Thus, for refrigerator,

Using this relation in equation (ii), we get

β=

β= …………………… (iii)

This is an expression for coefficient of performance of refrigerator. From this

equation it is seen that, for a given temperature of sink, the performance is
greater for lower value of ). Hence, performance of refrigerator is greater
in winter season than in summer season.
Entropy and disorder
Entropy is property of the state of thermodynamic system same as pressure,
volume, temperature and internal energy. It gives the quantitative measure of
disorder of a thermodynamic system.
11
The mathematical expression of entropy is,

dS =

Where, dS is change in entropy and dQ is amount of heat supplied in the system

at constant temperature. Its SI unit is JK-1.
If total heat Q is supplied in the system at constant temperature then the change
in entropy is,

ΔS = S2 – S1 =

The change in entropy is never negative i.e. ΔS≥0.

1. For reversible process, ΔS=0
2. For irreversible process, ΔS˃0

12
13