UNIT-II

SECOND LAW OF THERMODYNAMICS

INTRODUCTION

In this chapter the idea of cycle efficiency in introduced and the Second Law is then
stated and distinguished from the First Law. Formal definition of a reversible process is made
and its implications both for non-flow and steady-flow processes are discussed
A process is said to the reversible, it should trace the same path in the reverse
direction when the process is reversed, and it is possible only when the system passes through
a continuous series of equilibrium state if a system does not pass through continuous
equilibrium state, then the system is said to be irreversible.

The direction of spontaneous change for a ball bouncing on a floor. On each bounce
some of its potential energy is degraded into the thermal motion of the atoms of the floor, and
that energy disperses into the atoms of the floor. The reverse has never been observed to take
place. The reverse, if it occurs, does not violate the1st Law as long as the energy is conserved
Recall also that only a small amount of thermal energy is required to make the ball jump very
high. Hence, the first Law only states that the net work cannot be produced during a cycle
without some supply of heat. However, First Law never says that some proportions of heat
supplied to an engine must be rejected. Hence, as per the First Law, cycle efficiency can be
unity, which is impossible in practice. All that First Law states that net work cannot be
produced during a cycle without some supply of heat, i.e. that a perpetual motion machine of
the first kind is impossible So, the 1st Law is not enough. Something is missing! What is
missing? A law that can tell us about the direction of spontaneous change. The Second Law
of Thermodynamics tells us about the directionality of the process. We need it to ensure that
systems we design will work. As we will see later, ENTROPY is a property that we have
invented (like internal energy) that will allow us to apply the 2nd Law quantitatively.

REVERSIBLE AND IRREVERSIBLE PROCESSES

A process is said to the reversible, it should trace the same path in the reverse
direction when the process is reversed, and it is possible only when the system passes through
a continuous series of equilibrium state if a system does not pass through continuous
equilibrium state, then the system is said to be irreversible

In the course of this development, the idea of a completely reversible process is

central, and we can recall the definition, ``a process is called completely reversible if, after
the process has occurred, both the system and its surroundings can be wholly restored by any
means to their respective initial states’’. Especially, it is to be noted that the definition does
not, in this form, specify that the reverse path must be identical with the forward path. If the
initial states can be restored by any means whatever, the process is by definition completely
reversible. If the paths are identical, then one usually calls the process (of the system)
reversible, or one may say that the state of the system follows a reversible path. In this path
(between two equilibrium states 1 and 2), (i) the system passes through the path followed by
the equilibrium states only, and (ii) the system will take the reversed path 2 to 1 by a simple
reversal of the work done and heat added.
 Reversible processes are idealizations not actually encountered. However, they are
clearly useful idealizations. For a process to be completely reversible, it is necessary that it be
quasi-static and that there be no dissipative influences such as friction and diffusion. The
precise (necessary and sufficient) condition to be satisfied if a process is to be reversible is
the second part of the Second Law.

The criterion as to whether a process is completely reversible must be based on the initial and
final states. In the form presented above, the Second Law furnishes a relation between the
properties defining the two states, and thereby shows whether a natural process connecting
the states is possible.

SECOND LAW OF THERMODYNAMICS

Kelvin –Planck statement: It is impossible to construct an engine working on a

cyclic process which converts all the heat energy supplied to it into equivalent amount of
useful work.
Clausius statement: Heat cannot flow from cold reservoir to hot reservoir without any
external aid. But heat can flow from hot reservoir to cold reservoir without any external aid.

HEAT ENGINE, HEAT PUMP, REFRIGERATOR

ENERGY RESERVOIRS: Thermal energy reservoirs (TER) is defined as a large body of

infinite heat capacity, which is capable of absorbing or rejecting an unlimited quantity of heat
without suffering appreciable changes in its thermodynamic coordinates.

SOURCE: TER from which heat is transferred to the system operating in a heat engine
cycle.

SINK: TER in which heat is rejected from the cycle during a cycle.

HEAT ENGINE
A heat engine is a device which is used to convert the thermal energy into mechanical
energy. Heat supplied is input work done is the output. Hence efficiency of the engine

Work output
Efficiency of the engine = ---------------------------------
Heat supplied

€=(T1-T2)/T1
REFRIGERATOR : A device which operating in a cycle maintains a body at a temperature
lower than the temperature of the surroundings

HEAT PUMP: Heat pump is a device which operating in a cycle process maintains the
temperature of a hot body at a temperature of a hot body at a temperature higher that the
temperature of surrounding. Different between heat pump and refrigeration states that heat
pump is a device which operating in a cycle process maintains the temperature of a hot body
at a temperature of a hot body at a temperature higher that the temperature of surrounding.

Coefficient of performance is defined as the ratio of heat of heat extracted of rejected to work
input.
Heat extracted or rejected
COP = ---------------------------------
Work input.

Expression for COP of heat pump and a refrigerator.

COP for heat pump:

Heat rejected T2
COPHP = ----------------------- = ----------
Work Input T2-T1
COP for refrigerator:
Heat Extracted T2
COP Ref = ----------------------- = ----------
Work Input T2-T1

The Second Law states that some heat must be rejected during the cycle and
hence, the cycle efficiency is always less than unity Thus the First Law states that net work
cannot be greater than heat supplied, while the Second Law goes further and states that it
must be less than heat supplied. If energy is to be supplied to a system in the form of heat, the
system must be in contact with a reservoir whose temperature is higher than that of the fluid
at some point in the cycle. Similarly, if heat is to be rejected, the system must be at some time
be in contact with a reservoir of lower temperature than the fluid. Thus Second Law implies
that if a system is to undergo a cycle and produce work, it must operate between two
reservoirs of different temperatures. A machine which will work continuously, while
exchanging heat with only single reservoirs, is known as a perpetual motion machine of the
second kind (PMM II); such a machine contradicts Second Law. It is now possible to see why
a ship could not be driven by an engine using the ocean as a source of heat, or why a power
station could not be run using the atmosphere as a source of heat. They are impossible
because there is no natural sink of heat at a lower temperature than the atmosphere or ocean,
and they would therefore be PMM II.

It should be noted that Second Law does not restrict that work cannot be continuously
and completely converted to heat. In fact, a fluid in a closed vessel may have work done on it
and the heat thus generated is allowed to cross the boundary. The rates of work and heat may
be made equal and the internal energy of the system remaining constant. An important
consequence of Second law is work is a more valuable form of energy transfer than heat as
heat can never be transformed continuously and completely to work, whereas work can
always be transformed continuously and completely to heat.

The following statements summarise the obvious consequences of the Second Law:
a) If a system is taken through a cycle and produces work, it must be exchanging heat with at
least two reservoirs at different temperatures,
b) If a system is taken through a cycle while exchanging heat with one reservoir, the work
done must be zero or negative,
c) Since heat can never be continuously and completely converted into work whereas work
can always be continuously and completely converted into heat, work is more
valuable form of energy transfer than heat.

THE KEIVIN-PLANK’S STATEMENT OF THE SECOND LAW

It is impossible to construct a system, It is impossible to construct a system, which will

operate in a cycle, extract heat from a reservoir and do an equivalent

THE CLAUSIUS STATEMENT OF THE SECOND LAW

It is impossible to construct a system, which will operate in a cycle and transfer heat from a
cooler to a hotter body without work being work done on the system by the surrounding
EQUIVALENCE KELVIN PLANK’S AND CLAUSIUS STATEMENTS.

Proof: Suppose the converse of the Clausius’ proposition is true. The system can be
represented by a heat pump for which W = 0. If it takes Q units of heat from the cold
reservoir, it must deliver Q units to the hot reservoir to satisfy the First Law. A heat engine
could also be operated between the two reservoirs; let it be of such a size that it delivers Q
units of heat to the cold reservoir while performing W units of work. Then the First Law
states that the engine must be supplied with (W + Q) units of heat from the hot reservoir. In
the combined plant, the cold reservoir becomes superfluous because the heat engine could
reject its heat directly to the heat pump. The combined plant represents a heat engine
extracting (W + Q) – Q = W units of heat from a reservoir and delivering an equivalent
amount of work. This is impossible according to Kelvin-Plank’s statement of Second Law.
Hence converse of Clausius’ statement is not true and the original proposition must be true.
CARNOT’S THEOREM.
No heat engine operating in a cycle process between two fixed temperatures can be
more efficient that a reversible engine operating between the same temperature limits.

COROLLARIES OF CORNOT THEOREM

i. All the reversible engines operating between the two given thermal reservoir with
fixed temperature have the same efficient.
ii.The efficient of any reversible heat engine operating between two reservoir is
independent of the nature of the working fluid and depends only on the temperature of the
reservoirs.
CLAUSIUS INEQUALITY
Consider two heat engines operating between two reservoirs kept at temperature T H
and TL as shown in the Figure. Of the two heat engines, one is reversible and the other is
irreversible.

For the reversible heat engine it has already been proved that

Q H TH

Q L TL
QH QL
 0
TH TL
 dQ 
   0
T  rev

As discussed earlier, the work output from the irreversible engine should be less than
that of the reversible engine for the same heat input Q H. Therefore Q L,Irrev will be greater than
QL,Rev . Let us define

Q L,Irrev =QL,Rev + dQ

then
  dQ  Q QL , Irev
  T  H 
 Irrev TH TL
Q QL ,rev dQ
 H  
TH TL TL
dQ
 0
TL
0

By combining this result with that of a reversible engine we get

 dQ 
  T
 Irrev
0

This is known as Clausius inequality.

The following conditions of clausius inequality

ƒdQ/T ≤ 0 is known as inequality of clausius.
If 1. ƒ dQ/T = 0,the cycle is reversible.
2. ƒ dQ/T < 0,the cycle is irreversible and possible.
3. ƒ dQ/T > 0,the cycle is impossible.

ENTROPY

The measure of irreversibility when the energy transfer takes place within the system
or between system and surrounding is called as change of entropy. It is simply known as
unaccounted heat loss.The change entropy of the system with respect to ambient conditions
or any other standard reference conditions is known as absolute entropy.
Clausius inequality forms the basis for the definition of a ne w property known as
entropy.

Consider a system taken from state 1 to state 2 along a reversible path A as shown in
Figure. Let the system be brought back to the initial state 1 from state 2 along a reversible
path B. Now the system has completed one cycle. Applying Clausius inequality we get
 dQ
 T
0

 dQ   dQ 
2 1

1  T  A  2  T  B  0

Instead of taking the system from state2 to state1 along B, consider another reversible
path C. Then for this cycle 1-A-2-C-1, applying Clausius inequality:

dQ
 T
0

 dQ   dQ 
2 1

1  T  A  2  T  C  0
Comparing, Hence, it can be concluded that the quantity is a point function,
independent of the path followed. Therefore it is a property of the system

Principle of increasing entropy

Applying Clausius inequality,

For any infinitesimal process undergone by a system, change in entropy
dS ≥ dQ/T
For reversible, dQ = 0 hence dS = 0
For irreversible, dS> 0
Consider a system interacting with its surroundings. Let the system and its surroundings are
included in a boundary forming an isolated system. Since all the reactions are taking place
within the combined system, whenever a process occurs entropy of the universe (System plus
surroundings) will increase if it is irreversible and remain constant if it is reversible. Since all
the processes in practice are irreversible, entropy of universe always increases

ie., (∆s)universe>0
 QUESTION
PART -A
1.State the Kelvin –Planck statement of second law of Thermodynamics.
2. State the Clausius statement of second law of Thermodynamics
3. Write the two statement of second law of Thermodynamics
4. State Cornot’s Theorem.
5. What are the corollaries of cornot theorem?
6. Define – PMM of second kind?
7. What is different between heat pump and refrigeration?
8. What is meant by heat engine?
9. Define the term COP?
10. Define change of entropy .How is entropy compared with heat transfer and absolute
temperature?
11. Define the term source, sink and heat reservoir.
12. Why the performance of refrigerator and heat pump are given in terms of C.O.P and not
in terms of efficiency?
13. What is meant by principle of increase of entropy?
14. What do you mean by “clausius inequality”?
PART-B
1.A cyclic heat engine operates between a source temperature of 8000 C and a sink
temperature of 300 C. What is the least rate of heat rejection per kW net output of the engine?

2. A reversible heat engine operates between two reservoirs at temperatures of 600 0 C and
400 C. The engine drives a reversible refrigerator which operates between reservoirs at
temperatures of 400 C and -200 C. The heat transfer to the heat engine is 2000kJ and the net
work output of the combined engine transfer plant is 360kJ.
(a) Evaluate the heat transfer to the refrigerant and the net heat transfer to the
reservoir at 400 C.
(b)Reconsider (a) given that the efficiency of the heat engine and the COP of the
refrigerator are each 40% of their maximum possible values.

3. It is proposed that solar energy be used to warm a large collector plate. This energy would,
in turn, be transferred as heat to a fluid within a heat engine, and engine would reject energy
as heat to the atmosphere. Experiments indicate that about 1880 kJ/m2 h of energy can be
collected when the plate is operating at 900 C. Estimate the minimum collector area that
would be required for a plant producing 1kW of useful shaft power. The atmospheric
temperature may be assumed to be 20 0 C.

4. One kg of ice at -500 C is exposed to the atmosphere which is at 20 0 C. The ice melts and
comes into thermal equilibrium with the atmosphere. (a) Determine the entropy increases of
the universe . (b) what is the minimum amount of work necessary to convert the water back
into ice ar -50 C? Cp of ice is 2.093 kJ/kgK and the latent heat of fusion of ice is 333.3 kJ/kg.

5. A fluid undergoes a reversible adiabatic compression from 0.5 MPa, 0.2 m3 to 0.05m3
according to the law, pv1.3 =constant. Determine the change in enthalpy, internal energy and
entropy, and the heat transfer and work transfer during the process.

6. Calculate the available energy in 40kg of water at 75 0 C with respect to the surrounding at
500 C, the pressure of water being 1atm.
7. Air enters a compressor at 1 bar, 30 0 C, which is also the state of environment. It leaves at
3.5 bar, 1410 and 90m/s. Neglecting inlet velocity and P.E. effect, determine (a) whether the
compression is adiabatic or polytropic, (b) If not adiabatic, the polytropic index, (c) the
isothermal efficiency, (d) the minimum work input and irreversibiity and (e) second law
efficiency. Take C p of air =1.0035kJ/kgK

Solutions

1.A cyclic heat engine operates between a source temperature of 800 0 C and a sink
temperature of 300 C. What is the least rate of heat rejection per kW net output of the engine?

Solution: For a reversible engine, the rate of heat rejection will be minimum

2. A reversible heat engine operates between two reservoirs at temperatures of 6000 C and
400 C. The engine drives a reversible refrigerator which operates between reservoirs at
temperatures of 400 C and -200 C. The heat transfer to the heat engine is 2000kJ and the net
work output of the combined engine transfer plant is 360kJ.
(a) Evaluate the heat transfer to the refrigerant and the net heat transfer to the
reservoir at 400 C.
 (b)Reconsider (a) given that the efficiency of the heat engine and the COP of the
refrigerator are each 40% of their maximum possible values.

Solution: (a) Maximum efficiency of the heat engine cycle is given by

3. It is proposed that solar energy be used to warm a large collector plate. This energy would,
in turn, be transferred as heat to a fluid within a heat engine, and engine would reject energy
as heat to the atmosphere. Experiments indicate that about 1880 kJ/m2 h of energy can be
collected when the plate is operating at 90 0 C. Estimate the minimum collector area that
would be required for a plant producing 1kW of useful shaft power. The atmospheric
temperature may be assumed to be 20 0 C.

Solution: The maximum efficiency for the heat engine operating between the collector plate
temperature and the atmospheric temperature is

4. One kg of ice at -500 C is exposed to the atmosphere which is at 200 C. The ice melts and
comes into thermal equilibrium with the atmosphere. (a) Determine the entropy increases of
the universe . (b) what is the minimum amount of work necessary to convert the water back
into ice ar -50 C? Cp of ice is 2.093 kJ/kgK and the latent heat of fusion of ice is 333.3 kJ/kg.
The entropy-temperature diagram for the system at -50 C converts to water at 200 C is shown
in fig.

Fig.7.3.2
 Fig.7.3.3

5. A fluid undergoes a reversible adiabatic compression from 0.5 MPa, 0.2 m3 to 0.05m3
according to the law, pv1.3 =constant. Determine the change in enthalpy, internal energy and
entropy, and the heat transfer and work transfer during the process.

Solution:
TdS = dH - VdP
6. Calculate the available energy in 40kg of water at 75 0 C with respect to the surrounding at
500 C, the pressure of water being 1atm.

Solution:
If the water is cooled at a constant pressure of 1 atm from 750 C to 50 C
(as shown in fig) the heat given up may be used as a source for a series of carnot engines each
using the surrounding as a sink. It is assumed that the amount of energy received by any
engine is small relative to that in the source and the temperature of the source doesnot change
while heat is being exchanged with the engine.
Let us consider that the source has fallen to temperature T, at which level there
operates a carnot engine which takes in heat at this temperature and rejects heat at T0 =278K.
If del S is change in entropy water, the work obtainable is

With a very great number of engines in the series, the total work (maximum) obtainable when
the water is cooled from 348K to 278K would be
7. Air enters a compressor at 1 bar, 300 C, which is also the state of environment. It leaves at
3.5 bar, 1410 and 90m/s. Neglecting inlet velocity and P.E. effect, determine (a) whether the
compression is adiabatic or polytropic, (b) If not adiabatic, the polytropic index, (c) the
isothermal efficiency, (d) the minimum work input and irreversibiity and (e) second law
efficiency. Take C p of air =1.0035kJ/kgK

Solution:
(a) After isentropic compression

Since this temperature is higher than the given temperature of 141 0 C, there is heat loss
to the surroundings. The compression cannot be adiabatic. It must be polytropic.
.