AE231 Thermodynamics

Lecture Notes

December 23, 2020

Chapter 8

Exergy

In the previous chapters we presented the general laws — conservation of

mass, conservation of energy and the second law of thermodynamics — for
a control volume and applied them to thermal science problems involving
processes with storage of energy and transfer of energy by flow of mass or as
work and heat transfers.

In this chapter, we will take our attention to the performance of engineering

devices in light of the second law of thermodynamics. Our aim will be the
determination of the general limitations for the operation of systems and
devices so that we can design them for optimal efficiency with a minimal use
of resources to accomplish a certain task.

8.1 Exergy: Work Potential of Energy

When a new energy source is discovered, the first thing done is to estimate
the amount of energy contained in the source. But, this information alone is
not enough to decide whether to build a power plant on that site. What we
really need to know is the work potential of the source—that is, the amount
of energy we can extract as useful work. The rest of the energy is eventually
discarded as waste energy and is not worthy of our consideration. Thus, we
need to have a property to enable us to determine the useful work potential
of a given amount of energy at some specified state. This property is exergy,
which is also called the availability or available energy in some textbooks.

1
The concept of exergy is defined as the possible work we can extract from a
given physical setup when it is allowed to interact with the ambient and the
process end state is at P0 , T0 .

Φ = Wout given an ambient P0 , T0 (8.1)

Exergy is a combination property of a system and its surroundings because

it depends on the state of both the system and surroundings. The exergy of
a system in equilibrium with the surroundings is zero.

8.1.1 Closed Systems

Let’s consider a thermodynamic process:

ˆ State 1 and state 2 are given,

ˆ Ambient conditions P0 and T0 are given.

Then, the question is what is the maximum amount of work this system can
do?

To answer this question, now let’s consider a piston cylinder device the work-
ing fluid in which undergoes an expansion process.

P0, T0

1 2

The 1st law for this system is:

q12 − w12 = e2 − e1 (8.2)

And the 2nd law

Sgen qsurr
= s2 − s1 + (8.3)
m T0
where qsurr = −q12 . Rearranging the terms in the 2nd law, we get

q12 = −T0 (s1 − s2 ) − T0 sgen (8.4)

2
Now, put the equation for q12 into the 1st law and rearrange the terms

w12 = (e1 − e2 ) − T0 (s1 − s2 ) − T0 sgen (8.5)

The only way to maximize w12 is to have a reversible process where sgen = 0.

Then, the maximum amount of work this system can do is

rev
w12 = (e1 − e2 ) − T0 (s1 − s2 ) − T0 sgen (8.6)

Note: During this process (1 → 2), some portion of work is used against the
surroundings’ pressure P0 . That is, when the gas in the piston–cylinder device
expands, part of the work done by the gas is used to push the atmospheric
air outside the device. If the atmospheric pressure P0 is constant, then

wagainst the surroundings pressure = P0 (ν2 − ν1 ) (8.7)

The difference between the actual work w12 and the surroundings work
wsurr (= wagainst the surroundings pressure ) is called the useful work.

w12,useful = w12 − wsurr (8.8)

Combining Eq. 8.8 with Eqs. 8.5 and 8.7, we obtain

w12,useful = (e1 − e2 ) − T0 (s1 − s2 ) + P0 (ν1 − ν2 ) − T0 sgen (8.9)

Then, the reversible useful work can be written as

rev
w12,useful = (e1 − e2 ) − T0 (s1 − s2 ) + P0 (ν1 − ν2 ) (8.10)

For closed systems, per unit mass, exergy φ is expressed as:

φ ≡ (e − e0 ) − T0 (s − s0 ) + P0 (ν − ν0 ) (8.11)

where the 0’s denote the surroundings’ conditions. Then, the maximum
(reversible) useful work is
rev
w12,useful = φ1 − φ2 . (8.12)

At this point let’s redefine the exergy:

3
 Exergy is the maximum useful work that could be obtained from a system
at a given state thinking that it would go through a reversible process and at
the end it would be in equilibrium with the surroundings.

Another important definition of this chapter is irreversibility. It is the dif-

ference between the reversible work and the actual work and denoted by I.
Irreversibility per unit mass is denoted by i. That is,
rev
i12 = w12 − w12 (8.13)

or
rev
i12 = w12,useful − w12,useful (8.14)
Hence,
i12 = T0 sgen (8.15)

For a reversible process i12 = 0, whereas for an irreversible process i12 > 0.
Then, let’s redefine the irreversibility:

Irreversibility is the lost opportunity to do work due to irreversibilities.

And, it is expressed by the following equation

rev
i12 = w12,useful − w12,useful = (φ1 − φ2 ) − (w12 − P0 (ν2 − ν1 )) (8.16)

Now, let’s consider another thermodynamic process:

ˆ State 1 and state 2 are given,

ˆ Surroundings conditions, P0 and T0 , are given,

ˆ Heat transfer from/to the system q12 is given

ˆ Reservoir temperature TR is given

ˆ Heat exchange between the system and the reservoir q12,R is given.

end states of which are given and the surroundings’ conditions are given. Sup-
pose that the system exchanges heat with the surroundings and a reservoir.
In addition to these, reservoir temperature TR and heat transfer between the
system and the reservoir q12,R are given. Then,

q12 = q12,surr + q12,R (8.17)

4
where q12,surr is the heat transfer between the system and the surroundings.

Then, the question is what is the maximum amount of work this system can
do?

To answer this question, let’s start by considering the 1st law for this system,
which is
q12 − w12 = e2 − e1 where q12 = q12,surr + q12,R (8.18)

And the 2nd law

qsurr qR
sgen = s2 − s1 + + (8.19)
Tsurr TR
where qsurr = −q12,surr and qR = −q12,R .

From the 2nd law, we get q12,surr and put it into the 1st law. Then, we have
 
T0
w12 = e1 − e2 − T0 (s1 − s2 ) + q12,R 1 − − T0 sgen (8.20)
TR
and for a reversible process
 
rev T0
w12 = e1 − e2 − T0 (s1 − s2 ) + q12,R 1 − (8.21)
TR

Also, the useful work is

 
T0
w12,useful = e1 − e2 − T0 (s1 − s2 ) + q12,R 1− + P0 (ν1 − ν2 ) − T0 sgen (8.22)
TR
and the useful work in a reversible process
 
rev T0
w12,useful = e1 − e2 − T0 (s1 − s2 ) + q12,R 1 − + P0 (ν1 − ν2 ) (8.23)
TR

Note: When there is a reservoir, the reversible useful work can be expressed
as  
rev T0
w12,useful = φ1 − φ2 + q12,R 1 − (8.24)
TR
And the irreversibility is
rev
i12 = w12 − w12 (8.25)
or
rev
i12 = w12,useful − w12,useful (8.26)

5
Hence,
i12 = T0 sgen (8.27)
Using Eq. 8.26, the irreversibility can be expressed by
 
T0
i12 = φ1 − φ2 − P0 (ν1 − ν2 ) + q12,R 1 − − w12 (8.28)
TR

When there is more than one reservoir, the total irreversibility, I, for a closed
system with boundary work becomes
X  T0

I12 = m(φ1 − φ2 ) − P0 (V1 − V2 ) + Qi 1 − − W12 (8.29)
i
Ti

8.1.2 Open Systems

Open Systems with Steady-State Processes

Consider now a steady-state process

ˆ Inlet and exit conditions are given,

ˆ Surroundings conditions (P0 , T0 ) are given,

ˆ Heat transfer rate of the system Q̇ and the heat exchange rate between
the system and the surroundings Q̇sys,surr are given,

ˆ Reservoir temperature TR is given,

ˆ Heat exchange rate with the reservoir Q̇sys,R is given.

And, the question is what is the maximum amount of work this system can
produce?

To answer this question, let’s begin with the 1st law for a steady-state process:
X  Vi2 Ve2
 X  
Q̇ − Ẇ + ṁi hi + + gzi − ṁe he + + gze = 0 (8.30)
i
2 e
2

where Q̇ = Q̇sys,surr + Q̇sys,R .

6
And the 2nd law is
Q̇surr Q̇R X X
Ṡgen = + + ṁe se − ṁi si (8.31)
Tsurr TR e i

where Q̇surr = −Q̇sys,surr and Q̇R = −Q̇sys,R .

From the 2nd law we get Q̇sys,surr and put it into the 1st law:
X  Vi2 Ve2
 X    
T0
Ẇ = ṁi hi + +gzi −T0 si − ṁe he + +gze −T0 se +Q̇sys,R 1− −T0 Ṡgen
i
2 e
2 TR
(8.32)
The only way to maximize Ẇ is to have a reversible process where Ṡgen = 0
(recall that all other terms in the equation are fixed, given). Then, the
maximum amount of work this system can do is:
X  Vi2 Ve2
 X    
rev T0
Ẇ = ṁi hi + +gzi −T0 si − ṁe he + +gze −T0 se +Q̇sys,R 1−
i
2 e
2 TR
(8.33)

Note: Unlike in closed systems, in open systems with steady-state processes

these work expressions are already in useful work form, since the boundaries
are fixed in steady-state processes.

Now, let’s mathematically express exergy, ψ, for steady-state processes, per

unit mass flow,
V2
   
ψ ≡ h+ + gz − T0 s − h0 + gz0 − T0 s0 (8.34)
2
where the 0’s denote the surroundings’ conditions. Hence,
 
rev
X X T0
Ẇ = ṁi ψi − ṁe ψe + Q̇sys,R 1 − (8.35)
i e
TR

And the irreversibility rate is

I˙ = Ẇ rev − Ẇ = T0 Ṡgen (8.36)

The irreversibility rate for a steady-state process can also be expressed as

 
˙
X X T0
I= ṁi ψi − ṁe ψe + Q̇sys,R 1 − − Ẇ (8.37)
i e
TR

7
When there is more than one reservoir, the irreversibility rate becomes
 
˙
X X X T0
I= ṁi ψi − ṁe ψe + Q̇sys,Rj 1 − − Ẇ (8.38)
i e j
TRj

Open Systems with Transient Processes

Consider now a transient process

ˆ End states, state 1 and state 2, are given,

ˆ Inlet and exit conditions are given,

ˆ Surroundings conditions (P0 , T0 ) are given,

ˆ Heat transfer to/from the system Q12 and the heat exchange between
the system and the surroundings Q12,sys,surr are given,

ˆ Reservoir temperature TR is given,

ˆ Heat exchange with the reservoir Q12,sys,R is given.

And, the question is what is the maximum amount of work this system can
produce?

To answer this question, let’s begin with the 1st law for a transient process:
X  Vi2 Ve2
 X  
Q12 −W12 + mi hi + +gzi − me he + +gze = U2 −U1 +(KE2 −KE1 )+(PE2 −PE1 )
i
2 e
2
(8.39)
where Q12 = Q12,sys,surr + Q12,sys,R .

And the 2nd law is

Qsurr QR X X
Sgen = (S2 − S1 )cv + + + m e se − m i si (8.40)
T0 TR e i

where Qsurr = −Q12,sys,surr and QR = −Q12,sys,R .

8
From the 2nd law we get Q12,sys,surr and put it into the 1st law:
X  Vi2 Ve2
 X  
W12 = mi hi + + gzi − T0 si − me he + + gze − T0 se
i
2 e
2
+ [U1 − U2 + (KE1 − KE2 ) + (PE1 − PE2 ) − T0 (S1 − S2 )]
 
T0
+ Q12,sys,R 1 − − T0 Sgen
TR
(8.41)

The only way to maximize Ẇ is to have a reversible process where Sgen = 0

(recall that all other terms in the equation are fixed, given). Then, the
maximum amount of work this system can do is:
X  Vi2 Ve2
 X  
rev
W12 = mi hi + + gzi − T0 si − me he + + gze − T0 se
i
2 e
2
+ [U1 − U2 + (KE1 − KE2 ) + (PE1 − PE2 ) − T0 (S1 − S2 )]
 
T0
+ Q12,sys,R 1 −
TR
(8.42)
The useful work is
X  Vi2 Ve2
 X  
W12,useful = mi hi + + gzi − T0 si − me he + + gze − T0 se
i
2 e
2
+ [U1 − U2 + (KE1 − KE2 ) + (PE1 − PE2 ) + P0 (V1 − V2 ) − T0 (S1 − S2 )]
 
T0
+ Q12,sys,R 1 − − T0 Sgen
TR
(8.43)
And the reversible useful work is
X  Vi2 Ve2
 X  
rev
W12,useful = mi hi + + gzi − T0 si − me he + + gze − T0 se
i
2 e
2
+ [U1 − U2 + (KE1 − KE2 ) + (PE1 − PE2 ) + P0 (V1 − V2 ) − T0 (S1 − S2 )]
 
T0
+ Q12,sys,R 1 −
TR
(8.44)
And the irreversibility is
rev rev
I12 = W12 − W12 = W12,useful − W12,useful (8.45)

9
Or
I12 = T0 Sgen (8.46)

Note: For transient processes, a separate ’exergy (or availability)’ is not

defined. But a combination of φ and ψ can be used.

8.2 Second-Law Efficiency

In Chapter 5, we defined the thermal efficiency and the coefficient of per-

formance for devices as a measure of their performance. They are defined
on the basis of the first law only, and they are sometimes referred to as the
first-law efficiencies. The first law efficiency, however, makes no reference to
the best possible performance, and thus it may be misleading. This is why
the second-law efficiency is introduced.

The second-law efficiency is a measure of the performance of a device relative

to the performance under reversible conditions for the same end states. Let’s
explain this with an example.

Consider two heat engines, both having a thermal efficiency of 0.30, as shown
in the figure below. One of the engines (engine A) is supplied with heat from
a source at 600 K, and the other one (engine B) from a source at 1000 K.
Both engines reject heat to a medium at 300 K.

TH,A = 600 K TH,B = 1000 K

QH,A QH,B

Heat engine A Heat engine B

WA WB

th,A = 0.30
th,B = 0.30

QL,A QL,B

TL = 300 K

10
At first glance, both engines seem to convert to work the same fraction of
heat that they receive; thus they are performing equally well. When we take
a second look at these engines in light of the second law of thermodynam-
ics, however, we see a totally different picture. These engines, at best, can
perform as reversible engines, in which case their efficiencies would be
 
rev TL 300
ηth,A = 1 − =1− = 50%
TH A 600
 
rev TL 300
ηth,B = 1 − =1− = 70%
TH B 1000

Now it is apparent that engine B has a greater work potential available to

it (70% of the heat supplied as compared to 50% for engine A), and thus
should do a lot better than engine A. Therefore, we can say that engine B
is performing poorly relative to engine A even though both have the same
thermal efficiency.

It is obvious from this example that the first-law efficiency alone is not a
realistic measure of performance of engineering devices. To overcome this
deficiency, we define a second-law efficiency ηII as the ratio of the actual
thermal efficiency to the maximum possible (reversible) thermal efficiency
under the same conditions:
ηth
ηII = (8.47)
ηth,rev
Based on this definition, the second-law efficiencies of the two heat engines
discussed above are
0.30 0.30
ηII,A = = 0.60 and ηII,B = = 0.43
0.50 0.70
That is, engine A is converting 60% of the available work potential to useful
work. This ratio is only 43% for engine B.

Remarks:

ˆ For cyclic devices such as refrigerators and heat pumps, the second-law
efficiency is
β
ηII = for refrigerators/air conditioners
βrev
β0
ηII = 0 for heat pumps
βrev

11
 ˆ More generally,
Wuseful
for work-producing devices, such as turbines, ηII = rev
Wuseful
W rev
for work-consuming devices, such as compressors ηII = useful
Wuseful

References:

Fundamentals of Thermodynamics by C. Borgnakke and R.E. Sonntag, 8th

edition, John Wiley & Sons, Inc.

Thermodynamics: An Engineering Approach by M.A. Boles and Y.A. Cengel,

8th edition, McGraw-Hill Education.

12