CHAPTER 3: EXERGY ANALYSIS

Exergy is the tool, which indicates how far the system departs from equilibrium state. The
concept of exergy was put forward by Gibbs in 1878. It was further developed by Rant in
1957.
3.1 QUALITY OF ENERGY
Quantative evaluation of energy in a cycle or in a process can be done using the first law
of thermodynamics. The direction of flow of heat or work is known from the second law of
thermodynamics. However, it is equally important to assign the quality to the energy. As
discussed in Chapter 1, energy can be broadly classified into (1) High grade and (2) Low
grade energy. High grade form of energy are highly organised in nature and conversion of
such energy to some other high grade form

(W W ) is not dictated by the second law

of thermodynamics. Conversion of high grade energy to low grade energy is not

desirable. However, there may be some conversion to low grade energy as work is
converted into other useful form. This is because of dissipation of heat due to friction
(example: mechanical work Electricity, some losses are there due to the friction in
bearing of machineries). Thus both the first and the second law of thermodynamics are to
be considered for analysis.
Low grade energy such as heat due to combustion, fission, fusion reactions as well as
internal energies are highly random in nature. Conversion of such form of energy into high
grade energy

( Q W ) is of interest. This is due to the high quality of organised form of

energy obtained from low quality energy. Second law of thermodynamics dictates that
conversion of 100% heat into work is never possible. That part of low grade energy which
is available for conversion is termed as available energy, availability or exergy. The part,
which according to the second law of thermodynamics, must be rejected is known as
unavailable energy. Exergy analysis helps in finding the following:
It can be used to determine the type, location and magnitude of energy losses in a
system
It can be used to find means to reduce losses to make the energy system more
efficient

At this point, it is worth mentioning that the environment plays an important role in
evaluating the exergy (composite property).

38

3.2 IMPORTANCE OF EXERGY ANALYSIS

Let us take an example. In case of coal fired power plant, the first law indicates that the
condenser greatly effects the power plant efficiency as large amount of heat is transferred
to the cooling water without providing any clue on the real usefulness of this relatively low
temperature fluid. Also, energy balances do not provide information about the internal
losses such as throttling valve and heat exchanger. Second law or exergy balance,
however indicates that there is hardly 1% exergy loss in the condenser with more than
60% in the boiler. The contribution in the boiler exergy loss accounts for irreversibilities
associated with combustion and finite temperature differences. Hence, analysis of exergy
plays a deterministic role in identification of processes and rectifying the components.
3.3 AVAILABLE ENERGY REFERRED TO A CYCLE
Consider a cyclic heat engine as shown in Fig. 3.1. The maximum work output obtainable
from this engine is the available energy

( AE ) . The minimum energy that has to be

rejected to the sink ( as per 2nd law of thermodynamics) is called the unavailable energy

(UE ) .

T1

Q
1
W = AE
max

Q2 = U.E.
T

Fig. 3.1 Available and unavailable energy in a cycle

From energy balance

Again,

Q1 = AE + UE

(3.1)

Wmax = AE = Q1 UE

(3.2)

For the given source and sink temperatures

T1 & T2

39

respectively

(3.3)

T
rev = 1 2
T1
T1

rev

T2 . The lowest practical temperature of

heat rejection is the temperature of the surroundings, T0 .
(3.4)
T
max = 1 0
T1
If

is given,

will increase with decrease of

And,

Wmax

T
= 1 0 Q1
T1

(3.5)

3.4 AVAILABILITY IN A FINITE PROCESS

Let x-y be a finite process in which heat is supplied reversibly to a heat engine. Taking an
elementary cycle (shaded area in Fig. 3.2), let dQ1 be the heat received by the engine

T1 . Then
T T
T
= 1 0 dQ1 = dQ1 0 dQ1 = AE
T1
T1

reversibly at temperature

dWmax

(3.6)

For the whole process x-y,

y
Q

xy
Available energy,
or energy
W max = W

xy

T0
Unavailable energy
=T 0 (S y - S x)
s

Fig. 3.2 Unavailable energy by 2nd law of thermodynamics

40

dW

max

(3.7)

y
y
T0
dQ
= dQ1 dQ1 = dQ1 T0 1
x
x
x T
T1
1
y

Hence, maximum work obtainable is

UE = Qx y Wmax

(3.8)

UE = T0 ( s y sx )

(3.9)

3.5 AVAILABLE ENERGY FROM A FINITE ENERGY SOURCE

.

Consider hot gas of mass

mg

at temperature

when the temperature of environment is

T0 . Let the gas be cooled at constant pressure to T0

from state 1 and the heat given up by

.

the gas

Q1

is utilized in heating up reversibly a working fluid of mass

m wf

from state 3 to 1

along the same path so that the temperature difference between the gas and working fluid
at any instant is zero and hence entropy increase of the universe is also zero.
The working fluid expands reversibly and adiabatically in an engine or turbine from state 1
to 2 doing work WE and then rejects heat Q2 reversibly and isothermally to return to the
initial state 3 to complete the heat engine cycle.
Here,

Q1 = mg C pg (T T0 ) = m wf C pwf (T T0 ) =
.

Area 1-4-5-3-1
1

T
mg
W = AE
E
Q

mw f

2
UE

T
0

2
s

Fig. 3.3 Available and unavailable energy in finite processes

41

(3.10)

 m g C pg = mwf C pwf

(3.11)

dT
sgas = mg C pg
T
T

(3.12)

Now
T0

( negative as

swf = mwf C pwf

T0

T0 < T )
(3.13)

dT .
T
= m wf C pwf ln
T
T0

suniv = sgas + swf = 0

.

Q2 = T0 swf = T0 m wf C pwf

T
ln =
T0

(3.14)
(3.15)

Area 2-4-5-3

Available energy

Wmax = Q1 Q2

(3.16)

= m g C pg (T T0 ) T0 m g C pg ln
.

T
T0

= Area 1-2-3-1
.

Hence, exergy of a gas of mass

mg

at temperature

is

T
AE = m g C pg (T T0 ) T0 ln
T0

(3.17)

3. 6 DEMONSTRATION OF QUALITY OF ENERGY BASED ON EXERGY

.

Consider a hot gas of mass m flowing through a pipeline (Fig. 3.4). Due to the heat loss
to the surroundings, the temperature of the gas decreases continuously from the inlet
state ' a ' to the exit state ' b ' . Thus, the process is irreversible. However, for sake of
simplicity, let us consider the process to be reversible and isobaric between the inlet and
outlet. For an infinitesimal reversible process at constant pressure,

42

Fig. 3.4 Energy quality degrades along the flow direction

(3.18)

mC p dT
dS =
T
or,

(3.19)

dT
T
= .
dS mC
p
Thus the slope

dT
dS

depends on temperature

T . With increase in T ,

dT
dS

increases and

vice versa.

Q unit of heat lost to the surroundings as temperature of gas decreases from T1 '
T1 '' , T1 being average of the two temperatures.

Let,

Heat loss at section 1-1

43

to

Q = mC p (T1 ' T1 '' ) = T1S1

.

T1 is
W1 = Q T0 S1 = T1S1 T0 S1 = (T1 T0 ) S1
At section 2-2, let heat loss be same as in section 1-1, Q ( T2 < T1 )

(3.20)

Exergy lost with this heat loss at temperature

Q = mC p (T2' T2'' ) = T2 S 2
Exergy loss due to this heat loss at temperature T2 is
W2 = Q T0 S 2 = (T2 T0 ) S 2
.

T1 and T2
W1 = Q T0 S1 = T1S1 T0 S1 = (T1 T0 ) S1

(3.21)

(3.22)

(3.23)

Considering the exergy loss at temperatures

W2 = Q T0 S 2 = (T2 T0 ) S 2
As

(3.24)
(3.25)

T1 > T2 , S1 < S 2
W1 > W2

(3.26)

Interpretations:
1. For the same heat loss at two different temperatures, exergy loss is more with
higher temperature. For instance, exergy loss is more at 1000 K than that at 300 K
for 1 kJ of heat loss.
2. The more the temperature, the more is the quality of energy. For example, quality
of energy of a gas at 1000 K is superior to that at 400 K, since the gas at 1000 K
has the capacity of doing more work than the gas at 400 K.

3.6.1 SOME MORE EXAMPLES OF QUALITY DEGRADATION

(A) THROTTLE PROCESS
For frictionless, steady flow process of an ideal gas between sections (1)-(1) and (2)-(2)
in a pipe (Fig. 3.5),

44

p=p - p

P1

P2

Fig. 3.5 Throttled flow through a pipe

Again,

h1 = h2

and

h1 = h2

(3.27)

Tds = dh vdp

(3.28)

pv = RT

ds =

vdp
Rdp
=
T
p

(3.29)

or,
2
dp
= R [ ln p ]1
1 p
2

s2 s1 = R

(3.30)

or,

p
p
s2 s1 = R ln 2 = R ln 1

p1
p

S gen = m R ln

p
p1

p
I = m RT0 ln
p1
.

45

(3.31)

(3.32)

(3.33)

Equation (3.33) is the expression for the irreversibility or lost work in the system
comprising of the sections (1)-(1) and (2)-(2). It is obvious from the expression that quality
degrades logarithmically with pressure drop between the sections as well as with the
mass flow rate for an initial pressure p1 and surrounding temperature T0 .

(B) FLOW WITH FRICTION

Consider a steady and adiabatic flow of an ideal gas through the segment of a pipe.
Applying the first law of thermodynamics between sections (1)-(1) and (2)-(2) (Fig. 3.6)
1

In s u la tio n

p=p - p

P1

P2

Fig. 3.6 Adiabatic steady flow of an ideal gas in a straight pipe

Applying

TdS relationship

h1 = h2

(3.34)

Tds = dh vdp

(3.35)

dh v
ds =
dp
T T

(3.36)

or,

or,
2
vdp
dp
= R
1 T
1
p1

ds =
1

S gen

dp .
p
= mds = m R
= m R ln
1
1 p
p1
1
2

46

(3.37)

(3.38)

where

p
p
ln 1 =
p1
p1

p
<1
p1

since

and higher order terms are neglected.

Hence, lost work or irreversibility is

W lost = m ( h1 T0 s1 ) ( h2 T0 s2 )
.

(3.39)

= mT0 [ s2 s1 ] = T0 S gen = m RT0

.

p
p1

Hence decrease in exergy is proportional to the pressure drop as well as mass flow rate.
(C) MIXING OF TWO FLUID STREAMS
Two fluid streams 1 and 2 of an incompressible fluid or ideal gas mixing adiabatically at
constant pressure as shown in Fig. 3.7.
1
m

3
In s u la t io n

Fig. 3.7 Mixing of two fluid streams

Mass balance:
.

m1 + m2 = m3 = m

(say)

(3.40)

Let,
(3.41)

x=

m1
.

m
+
m
1
2

By first law of thermodynamics,

m1 h1 + m2 h2 = (m1 + m2 )h3

(3.42)

xh1 + (1 x ) h2 = h3

(3.43)

or,

47

Since,
From Eq. (3.43)

h = h(T )

(3.44)

xT1 + (1 x ) T2 = T3

(3.45)

T3
T
= x + (1 x) 2 = x + (1 x )
T1
T1

(3.46)

where,
(3.47)

T
= 2
T1
By second law of thermodynamics,

S gen = m3 s3 m1 s1 m2 s2

(3.48)

S gen = m s3 x m s1 (1 x ) s2

(3.49)

S gen

= ( s3 s2 ) + x ( s2 s1 )

(3.50)

m
.

S gen

T
T
. = C p ln 3 + xC p ln 2
T1
T1
m

(3.51)

or,
.

T T
. = ln 3 2
T1 T1
mC p
S gen

Let,

N S = Entropy generation number=

S gen
.

mC p

48

(3.52)

Now, substituting

T3
= x + (1 x ) from Eq. (3.46) in Eq. (3.52), we get
T1
x + (1 x )
N S = ln
1 x

(3.53)

N S = N S ( x, )

(3.54)

For,

x = 1 , N S = 0 m2 = 0 , the system is with single stream.

For,

= 1, N S = 0 , temperature of both the streams are same.

Rate of exergy loss due to mixing is,

.

Wlost = I = T0 S gen
.

Wlost = T0 mC p ln

x + (1 x )

(3.55)

(3.56)

1 x

3.7 EXERGY BALANCE FOR CLOSED AND OPEN SYSTEM

Exergy balance for the closed and open systems can be used to determine the locations,
types and magnitude of losses of potential energy resources (fuels) and ways can be
found to reduce such losses for making the energy system more efficient.
3.7.1 CLOSED SYSTEM
For a closed system (Fig. 3.8), exergy or availability transfer occurs through heat and work
interactions. No mass is transferred across the system boundary.

49

Fig. 3.8 A closed system

Ist Law of thermodynamics:
(3.57)

E2 E1 = dQ W12
1

2nd Law of thermodynamics:

2

dQ
S 2 S1
= S gen
1 T

(3.58)

dQ
T0 ( S2 S1 ) T0 = T0 S gen
1 T

(3.59)

or,
2

Subtracting Eq. (3.59) from Eq. (3.57), we get,

dQ
E2 E1 T0 ( S 2 S1 ) = dQ W12 T0 T0 S gen
1
1 T
2

(3.60)

Now, Defining availability function as

A = E + p0V T0 S

(3.61)

A2 A1 = E2 E1 + p0 (V2 V1 ) T0 ( S2 S1 )

(3.62)

50

 T
= 1 0 dQ W12 T0 S gen + p0 (V2 V1 )
1
T
2
T
= 1 0 dQ W12 p0 (V2 V1 ) T0 S gen
1
T
2

(3.63)

T
A2 A1 = 1 0 dQ W12 p0 (V2 V1 ) T0 S gen
1
T
Change in exergy
Exergy destruction
Exergy transfer withwork
2

Exergy transfer with heat

In the form of rate equation,

(3.64)

dA
d

Rate of change of exergy

T0 .
j 1 Q j
Tj
Rate of exergy transfer with heat at boundary

where,

.
dV

I
W p0

d Rate of exergy loss due to irreversibility

Rate of exergy transfer as work

Tj = instantaneous temperature at the boundary

dV
= rate of change of system volume.
d

For an isolated system,

.

A2 A1 = A = I

(3.65)

Since, I > 0 , the only processes allowed by the second law of thermodynamics are those
for which the exergy of the isolated system decreases. In other words,

The exergy of an isolated system can never increase.

(Counterpart of entropy principle, which states that entropy of an isolated system can
never decrease.)

51

3.7.2 OPEN SYSTEM: EXERGY BALANCE FOR A STEADY FLOW SYSTEM

Fig. 3.9 An open system

Consider an open system (Fig. 3.9). Applying the first law of thermodynamics:
(3.66)
mV 2
mV 2

H1 +

+ mgz1 + Q12 = H 2 +

+ mgz2 + W12

Second law of thermodynamics:

dQ
S1 + S2 = S gen
1 T

(3.67)

dQ
T0 ( S1 S 2 ) + T0 = T0 S gen = I
1 T

(3.68)

or,
2

From Eqs. (3.66) and (3.68),

2
T
V22 V1 2
+ mg ( z2 z1 ) = 1 0
H 2 H 1 T0 ( S 2 S1 ) + m
1
2
T

dQ W12 I

or,

T
A2 A1 = 1 0
1
T
2

dQ W12 I

52

(3.70)

(3.69)

In the form of rate equation at steady state,

.
.
.
T0 .
j 1 Q j WCV + m ( a f 1 a f 2 ) I CV = 0
Tj

(3.71)

V1 2 V22
a f 1 a f 2 = ( h1 h2 ) T0 ( s1 s2 ) +
+ g ( z1 z2 )
2

(3.72)

where,

For a single stream entering and leaving, the exergy balance is given by
.

T0 Q
W
I
a
a

=
1
.
.
.
f1
f2
T

m
m
m

(3.73)

3.8 TOOLS FOR EXERGY ANALYSIS

The following are the tools for exergy analysis
1. Value/Grassman/Shankey diagram
2. Pinch point technology
In general, conversion of energy or production of chemical substances in a plant requires
determination of all the exergy flows that are transferred between distinguished
apparatuses or unit operations of the plant. The resulting exergy losses can provide useful
information with regard to the overall performance of the plant. However, it is generally
difficult to judge the thermodynamic losses without any reference. Evaluation of plant
performance will usually require a comparison of the thermodynamic performance of
specific apparatuses or unit operations with available data from previously built plants.
Thus, exergy efficiencies have appeared to be more useful, for large plants or integrated
plants. It bears no significance to components. Exergy efficiencies combined with exergy
flow diagrams can provide the thermodynamic performance of even for a complex system.
3.8.1 VALUE DIAGRAM
Consider the heat transfer between two fluids in a recuperative type of heat exchanger.
Temperature versus heat flow ( T Q ) between the two fluids has been presented in Fig.
3.10.

53

Q,T-diagram
Ts

Sec

a ry
o nd

f lo w

T s,in
T p,out

dTs

T s,out

dTp

Tp

T p,in

P ri

a ry

f lo

T0
dQ

Fig. 3.10 Heat transfer process represented in a Q-T diagram

This diagram may be more informative if modified as follows:

Abscissa: indicates the heat transfer between the two streams
T
Ordinate: temperature T is replaced by the term 1 0 . At T = T0 , the ordinate is zero
T
and at T = , ordinate value is unity (Fig. 3.11).

54

value diagram
[T=~]
1

dQ= area1-3-4-6-1
dEx = area 1-2-5-6-1

1-T0/T

ary flow
second

5'

2'

5 loss of heat
exergy
transfer:
dEx loss =area2-2-5-5-2

2
flow
primary

1
[T=T0]

dQ

Fig. 3.11 Heat transfer process represented in a value diagram

If it is assumed that an infinitesimal small amount of heat dQ is transferred from the
secondary flow, the flow that is cooled down in the heat exchanger, the resulting decrease
in temperature dTs may be neglected. For the energy of this amount of heat can be written
as
(3.74)
T
dExs = 1 0 .dQ
T
In the value diagram (Fig. 3.11) the area 1-3-4-6-1 equals the amount of heat dQ ,
T
whereas the area 1-2-5-6-1 equals the exergy of this amount of heat. The term 1 0
T
indicates which part of the considered heat can be converted into work and can in
principle be converted into work and can be seen as the exergy fraction of this amount of
heat. The total exergy from the secondary flow van be determined by integrating Eq.(3.74)
from the inlet temperature Ts ,i to the outlet temperature Ts ,out
Ts ,out

Exs =

Ts ,in

To
1
Ts

.dQ

55

(3.75)

This amount of exergy equals the whole area below the temperature curve in the value
diagram. Within the heat exchanger the heat dQ is transferred to the primary flow. The
exergy of the heat supplied to this flow is
(3.76)
T
dExs = 1 0 .dQ
Ts
In the value diagram, this exergy is represented by the area 1-2-5-6-1. The area 2-2-5-52 indicates the exergy lost due to temperature difference necessary to transfer heat from
the secondary to the primary flow. The total exergy absorbed by the primary flow is
Tp ,out
(3.77)
T
Ex p = 1 0 .dQ
T
p
T p ,in
where subscript p indicates the primary flow. The absorbed exergy by the primary flow
equals the area below the temperature curve for this flow in the value diagram. The total
exergy loss due to heat transfer, Exs Ex p , is represented by the area between the two
temperature curves.
Thus,the amount of exergy as well as the exergy loss can be easily presented with the
help of value diagram.

3.8.2 PROCESS INTEGRATION: PINCH POINT TECHNOLOGY

A method of using the overall thermal balance of a process
Theoretically predicts minimum energy consumption
Predicts the construction costs of the plant using a heat recovery system.
First put into practical use in 1984, at Linhoff March Co.
Pinch point technology, or process integration, is the name given for a technique
developed by Prof. Linnhof and co-workers (1978) at Leeds university, UK to optimize the
heat recovery in large complex plants with several hot and cold streams of fluids.
To illustrate the basic principle take a case of a plant with two hot and two cold streams,
as shown in Table 3.1.

56

Table 3.1 Data for 4 (four) fluid streams

Stream
No

Initial
Temp
( 0C )

Final
Temp
( 0C )

Mass
flow rate
( kg / s )

1
2
3
4

205
175
45
105

65
75
180
155

2.00
3.20
3.75
3.00

Sp. Heat Heat

capacity
capacity
(kJ / kgK ) rate
(kW / K )
1.00
2.0
1.25
4.0
0.80
3.0
1.50
4.5

Rate of
enthalpy
increase
(kW )
-280
-400
+405
+225
-50

The hot streams can be combined into an equivalent composite stream as follows: From
Table 3.1, it is clear that both stream 1 and 2 are having common temperature drop
between 175 to 1750 C . For the common processes, we go for process integration by
considering composite thermal capacity. The hot composite curve will consists of (1)
stream1 from 205 to 1750 C with heat capacity 2 kW/K, (2) between temperature 175 to
750 C , a combined stream of thermal capacity rate ( 2+4)=6 kW/K (3) between
temperature 75 to 650 C , stream 1 with heat capacity rate 2 kW/K. Similarly, the cold
streams can be combined. The two composite streams are then plotted on a temperatureheat load graph as shown in Fig. 3.12. The pinch point is defined as the point where
temperature difference between the two composite curves is minimum.

90 kW
Combined
hot streams
1 and 2

Temperature/ ( C)

205
180
175

Stream 1
stream 3

155
125

Combined
cold
streams
3 and 4

20 K

105

Pinch
75
point
65 Stream
1
Stream 3
45
140 kW
0
Rate of change of enthalpy (kW)

Fig. 3.12 Temperature verses rate of enthalpy change for composite hot and cold streams
The temperature difference at the pinch point depends on the design of the heat
exchanger. Smaller the temperature difference, the more expensive is the heat

57

exchanger. A high value of pinch point indicates high thermal losses due to external
irreversibility.
Taking as an example a temperature difference of 20K, say, then the cold stream
(composite) can be moved from left to right on the diagram horizontally on the diagram,
keeping the hot composite curve fixed, until the temperature difference at pinch point is
20K. It is then seen then the external heating load of 90 kW and external cooling load of
140 kW are required for the system, all other energy changes can be achieved by the heat
exchangers between the various streams. Required heating and cooling of each stream
above and below the pinch point is shown in Table. 3.2.
Table 3.2 Cooling and heating above and below pinch point
Stream
1

Above Pinch Point

Cooling:
2 ( 205 125 ) = 160kW

Below Pinch Point

Cooling:
2 (125 65 ) = 120kW

Cooling:
4 (175 125 ) = 200kW

Cooling:
4 (125 75 ) = 200kW

Heating:
3 (180 105 ) = 225kW

Heating:
3 (105 45 ) = 180kW

Heating:
4.5 (155 105 ) = 225kW

Zero

90 kW (Heating)
Net
external
requirement

140 kW (cooling)

From Table 3.2, we can infer that for a pinch point of 20K, we require external heating
load of 90kW and cooling load of 140kW above and below the pinch point respectively.
The process integration above the pinch point is now as follows:
Above pinch point, stream 1 and stream 3 exchange 160 kW heat, stream 2 and stream 4
exchange 200kW. Below pinch point, stream 2 and 3 exchanges 180 kW heat. Stream 2
and 4 are to be externally heated with 65 kW and 25 kW respectively to meet the deficit
/demand of 90kW. Similarly, stream 1 and 3 are to be cooled externally with 120 kW and
20 kW heat exchangers respectively to meet the demand of 140 kW. Possible processes
are shown in Fig. 3.13.

58

205 C

160 kW

External 120 kW
cooling

125 C

65 C

Stream 1
180 C

Stream3

Stream1
105 C

158.3 C

180 kW

45 C

Stream3
External
heating
65 kW

125 C

80 C

200kW

75 C

175 C

Stream2
155 C

Stream2
149. 4 C

105 C

External
cooling
20 kW

Stream4

External
25kW
heating

Fig. 3.13 Possible plant to heat and cool four fluid streams for a minimum 20 K
temperature difference

The following rules should be followed in process integration

1.
2.
3.
4.

Do not transfer heat from one fluid to another across the pinch point
No external heating below pinch point
No external cooling above the pinch point
A heat exchanger should operate on one side of the pinch, either taking a heat
supply from below the pinch, or rejecting heat to a fluid above the pinch
5. A heat pump should operate across the pinch from a cold stream below the pinch
to a hot stream above the pinch.

Summery:
1. Exergy is the maximum work potential of a system
2. Exergy transfer with heat, work and mass
5. For an isolated system exergy always decreases
3. Exergy remains constant in a reversible process
13. Anything that generate entropy is responsible for decrease of exergy

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