Chapter 5

Exergy Concept: Introduction

The idea of available energy exists back in last century, when it was first understood
by the French Engineer Sadi Carnot for the specialized case of heat engine. In the next
decades the concept of available work was further developed theoretically, especially
by Herman Helmholtz and J. Willard Gibbs. It has been applied to many kind of
processes, for different purposes, under several different names like availability,
available work, essergy, exergy etc.
Exergy is defined as “the amount of work obtainable when some matter is
brought to a state of thermodynamic equilibrium with the common components of the
natural surroundings, by means of reversible processes, involving interaction only
with the above mentioned components of nature”.

5.1 System with exergy-entropy process

Let us assume a building environmental control system such as lighting, heating, or
cooling systems. Energy and matter are supplied into the system so that it works. The
inputs are exactly the same as the outputs under steady-state conditions. This is due to
the law of energy and mass conservation. If it is so, we do not reuse the energy and
matter as output directly pointed out by Schrodinger, 1945. If we could have used the
wasted energy and matter, most of the so-called energy and environmental problems
would have been already solved. The most general reply to the above statement would
be that the energy and matter as input are different from those as output; or you may
say that the energy and matter as output have something that a system must discard.
To make the idea clearer, we use the concepts of exergy and entropy, which can
express the difference in energy and matter between input and output explicitly.
Exergy and entropy, both of which are thermodynamic concepts, can show us what is
the resource and what is the waste; “exergy” is the concept to articulate “what is
consumed” and “entropy” is “what is disposed of”. Stating in the other way, “exergy”
is the concept, which quantifies the potential of energy and matter to disperse in the
course of their diffusion into their environment and “entropy” is the concept which
quantifies the state of dispersion, to what extent the energy and matter are dispersed.

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Let us take a microscopic view in order to make the concepts easier to understand.
Energy transfer like heat transfer is a transfer of the vibration of particles, which
compose of, for example, a building envelope system as shown in Fig. 5.1.

Fig. 5.1: Energy, exergy and entropy transfer

We assume a steady-state condition that the right-hand side of the system is warmer
than the left-hand side. The particles in the warmer side of the building envelope
vibrate rather strongly; that is; the energy flowing into the building envelope
accompanies a certain amount of exergy. The vibration disperses in the course of
energy transfer; that is, a part of the exergy is consumed as the exergy flows. As a
result, the energy flowing out the building envelope is accompanied with a smaller
amount of exergy. As a result of the dispersion of vibration, the state of dispersion as
a whole within the system increases. This is the generation of entropy, the law of
entropy increase, which is parallel to the law of energy and mass conservation. The
amount of increased entropy is proportional to that of consumed exergy. Since the
steady-state condition is being assumed, the distribution of the temperature inside the
building envelope is unchanged. This implies that the amount of entropy contained by
the whole of the building envelope system is constant. The entropy of a substance,
which is a function of temperature and pressure, remains unchanged unless the
temperature and the pressure of the substance increases or decreases. As described
above, a certain amount of entropy is generated due to exergy consumption within the

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building envelope system. This generated entropy must be discarded into the
surrounding, namely outdoors, from the building envelope system; otherwise it turns
out to be contradictory with our assumption of the steady-state condition and the
characteristics of the entropy as a function of temperature and pressure. It is important
for us to recognize that the energy flowing out the building envelope is accompanied
with not only a decreased amount of exergy but also an increased amount of entropy.

5.2 Theory
Exergy is the quantity of work, which can be extracted by an external energy
consumer during a reversible interaction between a system and surrounding until the
complete equilibrium is reached. The total exergy transfer rate of a material stream
can be calculated with following expression.
• • • • •
E = E k + E p + E phy + EChem --- (5.1)

Where:
⎛C ⎞
E k = m⎜ 0 ⎟ represents the kinetic exergy rate, where C0 is the speed of stream flow
⎝ 2 ⎠
relative to earth surface.
•
E p = m gZ 0 represents the potential exergy rate, where g is the earth gravity and Z0

the stream altitude above the sea level.

•
E phy represents the thermo mechanical exergy based on temperature and pressure of

the stream.
•
EChem represents the chemical exergy based on chemical potential of components in
the stream.
The specific exergy can be written as:

e = ek + ep + ephy + echem --- (5.2)

Where
•
E •
e= •
and m is the mass flow rate of the stream.
m

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Physical exergy
Physical exergy, known also as thermo mechanical exergy, is the work obtainable by
taking the substance through reversible process from its initial state (T, P) to the state
of the environment (T0, P0). The specific physical exergy is written as [Kot 85]
e phy = (h − h 0 ) − T 0 (S − S 0 ) --- (5.3)

For perfect gas with constant Cp

⎡ T P⎤
e phy = C p (T − T0 ) − T0 ⎢C p ln − R ln ⎥ --- (5.4)
⎣ T0 P0 ⎦

For solids and liquids when assuming constant specific heat C,

⎡ ⎛ T ⎞⎤
e phy = C ⎢(T − T0 ) − T0 ⎜⎜ ln ⎟⎟⎥ − v m (P − P0 ) --- (5.5)
⎣ ⎝ T0 ⎠⎦
Where vm is the specific volume determined at temperature T0.
Chemical exergy
Chemical exergy is equal to the maximum amount of work obtainable when the
substance under consideration is brought from the environmental state (T0, P0) to the
dead state (T0, P0, µ0i) by processes involving heat transfer and exchange of
substances only with the environment. The specific chemical exergy (ech) at P0 can be
calculated by bringing the pure component in chemical equilibrium with the
environment. For pure reference components, which also exist in the environment, the
chemical exergy consist of the exergy, which can be obtained by diffusing the
components to their reference concentration P00. The specific molar chemical exergy
of a reference component i present in the environment at partial pressure P00,i is
[Kot 85].
P0
e0 i = RT0 ln --- (5.6)
P00 ,i
When a substance does not exist in the reference environment, it must first react to
reference substances in order to get in equilibrium with the environment. The reaction
exergy at reference conditions equals the standard Gibbs energy change. So the
overall specific chemical exergy term becomes:

echem = ∑ xi [e0i + RT0 ln (xi )] --- (5.7)

i

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Where xi represents the molar fraction of component i, and e0i, standard chemical
exergy.
The chemical exergy of real components can be computed from:

echem = ∑xi ⎡⎣e0i + RT0 ln ( γ i xi ) ⎤⎦ --- (5.8)

i

Where γ I is the activity coefficient of component i,

The chemical exergies of gaseous fuels are computed from the stoichiometric
combustion chemical reactions. The standard chemical exergies of various fuels are
published in the literature (e.g. Kotas (1985), Bejan (1988)).
For many fuels, the chemical exergy can be estimated on the basis of the Net
Combustion Value (NCV). The relation between the NCV and the chemical exergy is:
e chem = φ • NCV --- (5.9)

Where φ can be calculated with formulas based on the atomic composition. For
different fuel oils and petrol φ is between 1.04 and 1.08.

5.3 Exergy analysis

In an energy analysis, based on the first law of thermodynamics, all forms of energy
are considered to be equivalent. Generally, energy balances provide no information
about internal losses like quality loss of energy. For example, the change of the
quality of thermal energy as it is transferred from higher to lower temperature which
is not displayed in an energy analysis. An exergy analysis, based on first and second
law of thermodynamics, shows the thermodynamic perfection of a process, including
all quality losses of materials and energy. The definition of exergy is the maximum
obtainable potential of work of a stream or substance in relation to the environment.
The exergy balance for a control region carried out from which the irreversibility rate
of steady flow process can be calculated. Thus, studying different forms of
irreverssibilities and their effects on the plant performance gives a better and more
useful insight to the process.
5.3.1 Exergy analysis of processes
Plants like power, chemical and process plants are comprises a number of simple
processes. The most common processes related to cryogenic air separation plant are
considered compression, expansion, heat exchange, separation of constituents of
mixture and chemical reactions including combustion or gasification.

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1. Compression process
In air liquefaction plants compression process usually starts at approximately
environmental temperatures. The exergy balance for a single stage compressor can be
written, with reference to the control region as shown in Fig. 5.2 using specific
quantities.

ε 1 + wc = ε cQ + ε 2 + i --- (5.10)

The negative value of ε cQ corresponds to heat loss by the control region when

temperature T>T0 and to heat gain when T<T0

ε cQ

ε1 ε2

wc

Fig. 5.2: Control region of compression process

During adiabatic compression heat transfer ( ε cQ ) is zero and the exrgy balance can be

put in the form as

ε 1 + wc = ε 2 + i --- (5.11)

wc = ε 2 − ε 1 + i --- (5.12)

In this expression, the increase in the exergy of the stream ε 2 − ε1 can be identified as
the desired output and the shaft work, wc as the necessary input.

The rational exergy efficiency of an adiabatic compressor can be expressed as

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 ε 2 − ε1
ψ= --- (5.13)
wc
i
ψ = 1− --- (5.14)
wc
2. Expansion process
In air liquefaction plants, expansion processes occur mostly at temperatures below
ambient. The primary function of such expansion processes is the production of a
cooling effect. Any shaft power which may be produced during the process can be
regarded as a useful by-product. The exergy balance for a turbine can be written, with
reference to the control region as shown in Fig. 5.3 using specific quantities.

ε 1 + ε exQ = wex + ε 2 + i --- (5.15)

ε exQ

ε1 ε2

wex

Fig. 5.3: Control region of expansion process

With ε exQ =0, the exergy balance for control surface in terms of specific quantities is

ε 1 − ε 2 = wex + i --- (5.16)

The desired output of the expansion device is wex , and the necessary input is the

reduction in the exergy of the stream i.e. ε1 − ε 2 .

The rational exergy efficiency of the expander is given by

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 w ex
ψ = --- (5.17)
ε1 − ε 2
i
ψ = 1− --- (5.18)
ε1 − ε 2
3. Heat exchange process
Heat exchange processes are usually divided into two groups. In group I, during heat
exchange process, the thermal component of exergy of one stream increases at the
expense of a reduction in the thermal component of exergy of another stream. Thus in
this case, a heat exchanger transfers thermal exergy between two streams through
conductive, convective or radiant heat transfer. In the group II, heat transfer processes
are characterized by transfer of thermal energy to or from the environment.
Loss of efficiency of heat exchangers is caused by different forms of irreversibility
due to
i. Heat transfer over a finite temperature difference
ii. Pressure losses
iii. Thermal interaction with environment
iv. Stream wise conduction in the walls of the heat exchanger
The exergy balance of surface heat exchanger consisting of two streams can be
written which applicable to control region as shown in Fig. 5.4.
(E1a − E 2 a ) − (E 2b − E1b ) = i --- (5.19)

Q0

1a 2a

2b 1b

Fig. 5.4: Control region for a simple two stream heat exchanger

The exergy is being transferred from stream ‘a’ to stream ‘b’. Since the function of a
non-dissipative heat exchanger is to transfer exergy between the streams. The heat
exchanger input can be identified as the reduction in the exergy of stream ‘a’ and the
output as the increase in the exergy of stream ‘b’.

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The rational exergy efficiency of a surface heat exchanger with two streams can be
formulated using exergy balance equation is
E 2b − E1b
ψ= --- (5.20)
E1a − E 2 a
i
ψ = 1− --- (5.21)
E1a − E 2 a
4. Separation process
The term separation process will be used here in the most general sense to cover such
applications as sea water desalination, petroleum fractionation or air separation. A
control region of generalised separation plant is shown in Fig. 5.5.

Win EH

Em Ep

Ee Q0
Fig. 5.5: Control region of the generalized separation plant

The mixture stream is shown separated into two product streams, although in
particular plants the number of useful product streams may be one or several. There is
also a stream of waste material which is dumped into the environment as example
nitrogen rejected to atmosphere from air separation plant. In general input to the plant
is in two forms, shaft work and heating, provided at temperature TH.
The exergy balance of a generalized separation plant can be expressed as

∑E
p
p − E m = E H + Win − i --- (5.22)

In this plant, the exergy input and output are

Input = E H + Win --- (5.23)

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 Output = ∑ E p − E m --- (5.24)
p

The rational exergy efficiency is given by

∑E
p
p − Em
ψ= --- (5.25)
E H + Win
i
ψ = 1− --- (5.26)
E H + Win
Irreversibilities in the condenser and the reboiler
The heat transfer in both condenser and reboiler take place over a temperature
difference exists. Let the temperature difference in condenser and reboiler is 3 K. The
heating medium will have to be supplied at a correspondingly higher temperature and
the cooling medium at a lower temperature.
The irreversibility due to heat transfer over a constant finite temperature difference in
the condenser is given by
⎡1 1 ⎤
I T∆T = QT T0 ⎢ − x ⎥ --- (5.27)
⎣ TT TT ⎦
Similarly, the irreversibility due to heat transfer over a constant finite temperature
difference in the reboiler is given by
⎡1 1 ⎤
I B∆T = QB T0 ⎢ − x ⎥ --- (5.28)
⎣ TB TB ⎦
Where TT is the distillation top temperature
TB is the distillation bottom temperature
TTx is the new required temperature by considering temperature difference in
condenser.
TBx is the new required temperature by considering temperature difference in reboiler.
5. Chemical processes including combustion
Combustion is chemical reaction in which oxidation take place. The open system
undergoing a steady-flow process involving one or more chemical reaction is shown
in Fig. 5.6.

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 .
EQ

. .

∑E IN
J ∑E
OUT
k

.
wx

Fig. 5.6: Control region of the chemical processes including combustion

The exergy balance for such system in its basic form is essentially the same as for an
open system undergoing purely physical processes and can be written conveniently in
the form
. . . .
∑ E j − ∑ E k = − E Q + wx + i
IN OUT
--- (5.29)

Where subscripts j and k refer to streams entering and leaving the control volume.
5.3.2 Performance analysis
As per first law of thermodynamics, overall thermal efficiency and coefficient of
performance are the main tools to evaluate the performance of thermal power plants
and refrigeration systems respectively. In this performance analysis, reverence is not
made to the second law of thermodynamics. The fundamentals and methods of exergy
analysis are presented in the book of Kotas and Szargut. Cornelissen has given three
forms of exergy efficiency namely, simple exergy efficiency, rational exergy
efficiency and transiting exergy efficiency. The definition of rational exergy
efficiency has been used for the exergy analysis of air separation integrated with
gasifier plant and plant components in this work.
5.3.2.1 Simple exergy efficiency
The Simple exergy efficiency is the ratio of the total exergy leaving to the total exergy
entering into the control volume.
E out
η= --- (5.30)
Ein

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5.3.2.2 Rational exergy efficiency of different component
The ratio of desired exergy output to the exergy used for that purpose is called as
rational exergy efficiency.
E desired output
Ψ= --- (5.31)
Eused
1. Adiabatic compressor
The rational exergy efficiency for an adiabatic compressor is given by
E out − Ein
Ψ= --- (5.32)
Win
Where Win is the work input of the compressor.
2. Turbine
The rational exergy efficiency of turbine is defined as the ratio of the work output to
the exergy decrease of the incoming and outgoing flows.
Wout
Ψ= --- (5.33)
E out − Ein
3. Counter flow heat exchanger
The rational exergy efficiency of counter flow heat exchanger is given by

∑ ∆E T
J
Ψ= J
--- (5.34)
∑ ∆EK
T
K

Where ∆E JT is thermal component of exergy gained by Jth stream and ∆E kT is thermal

component of exergy lost by Kth stream.

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