1

3.0 SECOND LAW OF THERMODYNAMICS

3.0 Heat Engine or Power Cycle
For any cycle, the net amount of energy received through heat interactions is
equal to the net energy transferred out in work interaction.
That is, Q
cycle
= W
cycle
(3.0)
A power cycle, or heat engine, is one for which a net amount of energy is
transferred out by work W
cycle
> 0.
In other words, a heat engine is a machine that transforms heat into mechanical
power. Example of this is a steam or gasoline engine.
A power cycle is characterized both by addition of energy by heat transfer, Q
1
,
and the rejection of energy by heat transfer, Q
2
.
Q
cycle
= Q
1
Q
2
(3.1)
Merging the two equations 3.0 & 3.1, we obtain,
W
cycle
= Q
1
Q
2
(3.2)
The thermal efficiency of a heat engine is defined as the ratio of the net work
developed to the total energy added by heat transfer. It is denoted with the symbol h
th
.
h
th
=
1
2
1
2 1
1
1
Q
Q
Q
Q Q
Q
W
cycle
=

= (3.3)
In practice, the thermal efficiency of a heat engine is less than 100%. That is,
some portion of the heat supplied is rejected Q
2
0.
3.1 Heat Engines, Heat Pumps and Refrigerators
A device operating on a cycle is referred to as a heat engine. In other words, a
heat engine is a device operating on a cycle that transforms heat into mechanical power.
In a heat engine, heat flows from a hot cylinder to a cooler exhaust pipe and does
mechanical work as the temperature drops. The net work produced by the engine is given
as:
Q
cycle
= Q
1
Q
2
(3.1) (First law of thermodynamic for heat engines)
A reversed heat engine cycle is a heat pump. Its objective could be to supply
energy to a body or to extract energy from a body. In other words, a heat pump is a
mechanical or chemical device used for heating and air-conditioning. In heating a

2

building, it extracts heat from a low-temperature source and expels it elsewhere at a
higher temperature. The working fluid for a heat pump is a refrigerant.
Energy as heat Q
2
, is extracted from a low temperature body and supplied as heat
Q
1
, to a warmer body. Mechanical work must be done on the refrigerant gas in the
process.
The heat extracted from the cold reservoir is given as:
Q
2
= Q
1
W (3.2)


Fig (1a): Heat engine cycle Fig (1b): Refrigerator
Q
1
= Heat input to engine/cycle Q
2
= Heat rejected from condenser/cycle
Q
2
= Heat rejected from engine/cycle Q
1
= Heat removed from evaporator/cycle
Equation (3.1) describes a mechanical work output accompanied by a drop in
temperature from T
1
to T
2
while equation (3.2) describes a mechanical work input
necessary to raise the temperature of gas from T
2
to T
1
in the system.
3.2 Cycle Efficiency
A Carnot engine is an ideal heat engine that operates between a high temperature
reservoir and a low temperature reservoir. It has the maximum possible efficiency that
cannot be attained by a real engine. The Carnot engine uses reversible processes to form
cycles of operation, hence it is also called a reversible engine.

3



Fig 2: The cycles of a Carnot Engine on a P-V and T-S Diagram respectively
1 2 An Isentropic Compression
2 3 - An Isothermal Heat addition
3 4 An Isentropic expansion
4 1 An Isothermal Cooling
The thermal efficiency of a heat engine is given by:
=
th
Desired energy transfer = Network output =
}
dW 3.4
Requires energy input transfer gross heat input q
1

Recall from the first law of thermodynamics, in a reversible process,

2 1
q q q W = =
} }
3.4a
=
th

1
2
1
2 1
1
q
q
q
q q
=

3.4b
Where, q
2
= heat output
q
1
= heat input
Also,
h
th
= 1 -
23
41
T
T
3.4c
Where the temperatures are in Kelvin K.

4


Fig 3: Figure of a steam plant operating on a Carnot cycle
Note: Carnot efficiency is dependent only on the high and low absolute temperatures of
the reservoirs and is independent of the working substance used or any particular
design feature of the engine.
Irreversible processes result in degradation of energy and a loss of work transfer;
hence the thermal efficiency of an irreversible cycle is less than that of a reversible
cycle.
The coefficient of performance (COP), b of a refrigerator is given by:
=
REF
heat input from low temperature source 3.5a
Net work input
=
REF

in out
in
q q
q
q q
q
W
q

=
1 2
1 1
3.5b
For heat pump,
=
HP

heat output to high temperature source 3.6a

Net work input
=
in out
out
q q
q
q q
q

1 2
2
3.6b
Thus,
1 + =
REF HP
3.6c

5

Question 1
The work done on a reversed heat engine is 150KJ while the heat transfer to the
engine from the low temperature reservoir is 450KJ. Determine the heat transfer to the
high temperature reservoir and the COP as a refrigerator and as a heat pump.
Solution
Q
out
= Q
in
+ W = 450 + 150 = 600KJ
B
REF
= Q
in
= 450 = 3
W 150
B
HP
= Q
out
= 600 = 4

W 150
B
HP
= B
REF
+ 1 = 3 +1 = 4
3.3 The Statements of the Second Law of Thermodynamics
The second law of thermodynamics is a general principle that places constraints
upon the direction of heat transfer and the attainable efficiencies of heat engines.
Each of the statements of the second law of thermodynamics or corollaries of the
second law are all invalid if one of them is invalid.
The following are some significant statements:
Kelvin-Planck statement of the second law of thermodynamics refers to a Thermal
Reservoir. A Thermal Reservoir is a system that remains at a constant temperature even
though energy is added or removed by heat transfer. Some systems that could be likened
to this are the earths atmosphere, large bodies of water (lake, oceans) etc. the extensive
properties of thermal reservoirs, such as internal energy, can change in interactions with
other systems even though the reservoir temperature remains constant.
1. Kelvin-Planck Statement of the second law states that it is impossible for any
system to operate in a thermodynamic cycle and deliver a net amount of energy
by work to its surroundings while receiving energy by heat transfer from a single
thermal reservoir. Stated in another way, a perpetual-motion machine of the
second kind is impossible.
2. Clausius Statement: says it is impossible for a self-acting machine unaided by an
external agency to move heat from a cooler body to a hotter body. This statement
relates to a refrigerator or a heat pump.

6

3. The entropy of an isolated system never decreases for instance, if all the processes
that occur within a system are reversible, the entropy remains the same, otherwise
the entropy increases.
4. No heat engine (real or ideal) can convert all the heat input into work; since heat
must be rejected.
Note: Kelvin planck and Clausius statements of the second law are expressions
of experimental observations and are equivalent.
3.4 Corollaries of the Second Law
In a heat engine cycle, if no heat is rejected in the cold reservoir, which means all
the heat supplied from the high temperature reservoir is converted to work. This means
that the thermal efficiency h
th
would be100%. This is impossible and violates the second
law; some heat must be rejected to the low temperature reservoir.
The Clausius statement is a corollary of the second law. The others are:
Corollary 2: For an irreversible power cycle and a reversible power cycle operating
between the same two thermal reservoirs, the thermal efficiency of the
irreversible power cycle is always less than that of the reversible power
cycle.

Corollary 3: The thermal efficiency of all reversible power cycles operating between
the same two thermal reservoirs are the same.
Corollary 4: The efficiency of any reversible engine operating between more than two

7

reservoirs cannot be more than that of a reversible engine operating
between two reservoirs having temperatures equal to the highest and
lowest temperatures of the fluids in the original state.
Corollary 4: The Clausius inequality is a corollary as a consequence of an engine
operating between more than two reservoirs. It states that whenever a
system undergoes a cyclic process,

}
s
|
.
|

\
|
b
T
Q
0 3.7
The Clausius inequality provides the basis for introducing two ideas
instrumental for quantitative evaluation of processes of systems from the
second law perspective: Entropy and Entropy generation.
The Clausius inequality states that


}
s
|
.
|

\
|
b
T
Q
0
Where, Q represents the heat transfer at a part of the system boundary during a portion
of the cycle, and T is the absolute temperature at that boundary. The subscript b indicates
that the integrand is evaluated at the boundary of the system executing the cycle. The
symbol
}
indicates that the integral is to be performed over all parts of the boundary and
over the entire cycle.
Note: The equality applies when there are no internal irreversibilities and the inequality
applies when internal irreversibilities are present, as the system executes the
cycle.
Alternatively, the Clausius inequality can be expressed as

}
=
|
.
|

\
|
gen
b
S
T
Q
3.7a
The value of S
gen
is positive when internal irreversibilities are present, and zero
when no internal irreversibilities are present, and can never be negative.
Entropy generation S
gen
, is a measure of the irreversibilities present within the
system executing the cycle. S
gen
is identified as the entropy generated by internal
irreversibilities during the cycle.

8

3.5 Entropy and Entropy Generation
3.5.1 Definition of Entropy
i. This is a state variable whose change is defined for a reversible process at T
where Q is the heat absorbed.
ii. Entropy is a measure of the amount of energy which is unavailable to do work.
iii. Entropy is a measure of the disorder of a system.
Consider two cycles executed by a closed system. One cycle consists of an internally
reversible process A from state 1 to state 2, followed by an internally reversible process C
from states 2 to state 1. The other cycle consists of an internally reversible process B
from states 1 to state 2, followed by the same process C from state 2 to state 1 as in the
first cycle. For these cycles, equation 3.5 takes the form,
0
1
2
2
1
= =
|
.
|

\
|
+
|
.
|

\
|
} }
gen
C A
S
T
Q
T
Q
3.8
0
1
2
2
1
= =
|
.
|

\
|
+
|
.
|

\
|
} }
gen
C B
S
T
Q
T
Q
3.9
Where,
S
gen
has been set to zero since the cycles are composed of internally reversible
processes.
Subtracting equation 3.9 from 3.8, we have,
B A
T
Q
T
Q
|
.
|

\
|
=
|
.
|

\
|
} }
2
1
2
1

3.10
Since A and B are arbitrary, it follows that the integral of Q/T has the same value
for any internally reversible process between the two states: the value of the integral
depends on the end states only. It can be concluded, therefore, that the integral defines the
change in some property of the system selecting the symbol S to denote this property, its
changes is given by

rev
T
Q
S S
int
2
1
1 2
|
.
|

\
|
=
}

3.11a
Since entropy is a property, the change in entropy of a system in going from one
state to another is the same for all processes, both internally reversible and irreversible,
between these two states.

9

The definition of entropy change is expressed in differential form below:
rev
T
Q
dS
int
|
.
|

\
|
=

3.11b
From equation 3.11b, it is seen that when heat is transferred to a closed system
undergoing an internally reversible process, the system experiences an increase in
entropy. When heat is removed, it experiences a decrease in entropy.
Note: In an adiabatic internally reversible process of a closed system, the entropy would
remain constant. A constant entropy process is called an ISENTROPIC
PROCESS.
Equation 3.11b becomes,
( ) TdS Q
rev
=
int
3.12
For a internally reversible process of a closed system between states 1 and 2,
Q
int rev
=
}
2
1
TdS m 3.13
Note: When a process is represented by a continuous curve on a plot of temperature
versus specific entropy, the area under the curve is the magnitude of the heat
transfer per unit of the system mass.
3.5.2 Entropy Change for a Perfect Gas Undergoing a Process
From the first law of thermodynamics, Q W = U 1a
and the second law of Thermodynamics; Q = TdS 1b
Recall, that
dw = pdv and u = C
v
dT
Equation (1a) can be rewritten as :-
TdS pdV = C
v
dT 3.14
Dividing both sides by T,
We have,
dS =
V
dV
R
T
dT
C
v
+ 3.15
Integrating both sides,
We have,

10

1
2
1
2
1 2
ln ln
V
V
R
T
T
C S S
v
+ = 3.16
Since,
2
2 2
1
1 1
T
V P
T
V P
= then,
1 2
2 1
1
2
T P
T P
V
V
= 3.17
Therefore,
|
|
.
|

\
|
|
|
.
|

\
|
+ =
1
2
2
1
1
2
1 2
ln ln
T
T
P
P
R
T
T
C S S
v
3.18
|
|
.
|

\
|
+
|
|
.
|

\
|
+ =
1
2
2
1
1
2
ln ln ln
T
T
R
P
P
R
T
T
C
v
3.19
Recall, C
v
+ R = C
p

|
|
.
|

\
|

|
|
.
|

\
|
=
|
|
.
|

\
|
+ =
1
2
1
2
2
1
1
2
1 2
ln ln ln ln
P
P
R
T
T
C
P
P
R
T
T
C S S
p p
3.20
This equation can also be written in terms of volumes and pressures as:-
|
|
.
|

\
|
+ =
1
2
1
2
1 2
ln ln
V
V
C
P
P
C S S
p v
3.21
3.6 Implications of the Second Law of Thermodynamics
During a reversible adiabatic process, the entropy is a property that remains
constant. The temperature entropy diagram would indicate a process by a straight line
perpendicular to the entropy axis if the process is purely ISENTROPIC. In an
irreversible process, the presence of friction causes the temperature of the fluid to be
higher than it would have been in frictionless (reversible) process. The entropy is
increased during an irreversible process.
3.6.1 Isentropic Efficiency
The entropy change in an irreversible adiabatic process leads to process
efficiency. The ideal constant entropy process is termed isentropic and the ratio of the
specific work transfer in the ideal process to that in the actual process is called the
Isentropic Efficiency.
Majority of adiabatic machines are flow processes, isentropic efficiency is usually
expressed in terms of the useful work W.

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For the compression process, h
ic
=
12
' 12
W
W
3.22
And for the expansion process, h
it
=
' 34
34
W
W
3.23
Where,
For the W
12
and W
34
= isentropic work for compressor and turbine respectively.
and
W
12
and W
34
= actual work for the compressor and turbine respectively.
If changes in kinetic and potential energies are negligible, the SFEE may be used
to rewrite these expressions in terms of specific enthalpy change and for a perfect gas,
enthalpy change may be expressed by temperature change. Thus, for compression
processes, we have:
1 2
1 ' 2
h h
h h
ic

= 3.24
For a perfect gas, it becomes:

1 2
1 ' 2
T T
T T
ic

= 3.25
Question 2
A Carnot heat engine rejects 230 KJ of heat at 25 C. The net cycle work is 375
KJ. Determine the thermal efficiency and the cycle high temperature.
Solution
Source heat Q
1
= ?, Temperature of the heat source T
1
= ?, Heat rejected Q
2
= 230
KJ, Temperature of the sink T
2
= 25 C = 298 K, Net cycle work W = 375 KJ.
Recall,
Thermal efficiency
th
=
1
2 1
1 1
2 1
T
T T
Q
W
Q
Q Q
= =

Q
1
= Q
2
+ W = 230 + 375 = 605 KJ
To calculate the thermal efficiency
th
= W = 375 = 0.62
Q
1
605
To calculate the cycle high temperature T
1
,

12


1
2 1
T
T T
th

= , 0.62 =
1
1
298
T
T


( ) 62 . 0 1
298
1

= T = 784.2 K
The source temperature T
1
= 784.2 K

Question 3
Two reversible heat engines operate in series between a source at 500 C and a
sink at 20 C. If the engines have equal efficiencies and the first rejects 350 KJ to the
second, calculate:
a) The temperature at which heat is supplied to the second engine.
b) The heat taken from the source
c) The work done by each engine, assume each engine operates on the
Carnot cycle.
Solution
From the diagram,
Q1 = ?, T1 = 500 C = 773 K, Q2 = 350 KJ, T2 = ?, Q3 = ?, T3 = 20 C = 293 K.
But, the thermal efficiencies of the engines are equal, that is
th1
=
th2

Therefore,

2
3 2
1
2 1
T
T T
T
T T
=

;

2
2 2
293
773
773
T
T T
=

T
2
= 476 K
The temperature at which heat is supplied to the second engine T
2
= 476 K.
To calculate the thermal efficiency of the first engine,
th1

th1
=
1
2 1
T
T T
= 384 . 0
773
476 773
=

or 38.4 %
(b) To calculate the heat taken from the source, Q1,

1
2 1
1
Q
Q Q
th

= ;

13

Therefore,

( ) 384 . 0 1
350
1

= Q = 568.2 KJ
Heat taken from the source Q
1
= 568.2 KJ.
(c) The work done by each engine assuming each operates on the carnot cycle.
(i) For the first engine, work done is W
1
= Q
1
Q
2
= 568.2 350 = 218.2 KJ.
(ii) For the second engine, work done is W
2
= Q
2
Q
3

To calculate Q
3
,

2
3 2
2
Q
Q Q
th

=
Recall,
th1
=
th2
Therefore,

350
350
384 . 0
3
Q
=
Heat rejected Q
3
= 215.6 KJ
The work done by the second engine W
2
= 350 215.6 = 134.4 KJ.