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EXERGY AND THERMODYNAMIC ANALYSIS

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3.19.1

EXERGY AND THERMODYNAMIC ANALYSIS

G. Tsatsaronis, F. Cziesla
Institute for Energy Engineering, Technische Universität Berlin, Germany

Keywords

Energy; Exergy; Thermodynamic Environment; Exergy Destruction; Exergy Loss; Exergetic

Efficiency; Mass, Energy, Entropy and Exergy Balances; Avoidable, Unavoidable,
Endogenous and Exogenous Exergy Destruction.

Contents

1. Introduction
2. Exergy
3. Performance Evaluation with the Aid of Exergetic Variables
3.1 Exergy Destruction
3.2 Exergy Loss
3.3 Exergetic Efficiency
3.4 Exergy Destruction Ratio
4. Comprehensive Thermodynamic Analysis
5. Closure

Glossary

Exergy: Maximum theoretical useful work (shaft work or electric work) obtainable from a
thermal system as this is brought into thermodynamic equilibrium with the exergy-
reference environment while the system interacts only with this environment.

Exergy-reference environment (or thermodynamic environment): Consists of a set of

reference substances at a standard temperature and a standard pressure and with standard
concentrations to be determined by convention. The exergy-reference environment is
used to define reference states for exergy calculations.

Exergy destruction: Exergy destroyed due to irreversibilities within a system.

Exergy loss: Exergy transfer to the system surroundings. This exergy transfer is not further
used in the installation being considered or another one.

Exergy of product: The desired result (expressed in exergy terms) achieved by the system
being considered.

Exergy of fuel: The exergetic resources expended to generate the exergy of product.

Exergetic efficiency: The ratio between exergy of product and exergy of fuel.
Exergy destruction ratio: The ratio between the exergy destruction in a component and the
fuel exergy supplied to the overall system.

Unavoidable exergy destruction: Exergy destruction rate that cannot be reduced due to
technological limitations (e.g., availability and costs of materials and manufacturing
methods) regardless of the amount of investment.

Endogenous exergy destruction: Exergy destruction due to the irreversibilities in a system

component when all remaining system components operate with exergetic efficiencies
of 100 %. The endogenous exergy destruction is that part of the component’s total
exergy destruction that is independent of the changes in the exergy destruction of the
remaining components.

Exogenous exergy destruction: The part of the component’s total exergy destruction that is
caused by the inefficiencies of the remaining system components.

Nomenclature

E exergy
g gravitational acceleration
H enthalpy rate
m mass
nk number of components in a system
p pressure
S entropy
T temperature
U internal energy

v velocity
V volume
y exergy-destruction or exergy-loss ratio
z elevation

Greek Letters

ε exergetic efficiency

Subscripts

0 exergy-reference environment
D exergy destruction
F fuel exergy
k kth system component
L exergy loss
P product exergy
tot overall system

Superscripts

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AD avoidable endogenous exergy destruction
AV avoidable exergy destruction
AX avoidable exogenous exergy destruction
CH chemical exergy
KN kinetic exergy
M mechanical exergy
N nonreactive exergy
PH physical exergy
PT potential exergy
R reactive exergy
T thermal exergy
UD unavoidable endogenous exergy destruction
UN unavoidable exergy destruction
UX unavoidable exogenous exergy destruction

Summary

The only inefficiencies detected by the energy analysis of a system are the energy transfer out
of the system that are not further used in this or another installation. The exergy concept
complements and enhances an energetic analysis by calculating (a) the true thermodynamic
value of an energy carrier, (b) the real thermodynamic inefficiencies in a system, and (c)
variables that unambiguously characterize the performance of a system (or one of its
components) from the thermodynamic viewpoint. Exergy principles can be used in
optimization procedures and may assist in developing new concepts.

Distinctions between avoidable and unavoidable exergy destruction on one side and
endogenous and exogenous exergy destruction on the other side allow the engineer to focus
on the thermodynamic inefficiencies that can be avoided and to consider the interactions
among system components. The avoidable endogenous and the avoidable exogenous exergy
destruction provide the best guidance for improving the thermodynamic performance of
energy conversion systems.

1. Introduction

Energy can be stored within a system, it can be transformed from one form to another, and it
can be transferred from one system to another. The total amount of energy is conserved in all
storages, transformations and transfers. The energy conservation is expressed by energy
balances that, together with the corresponding mass balances are widely used in the modelling
and analysis of energy conversion systems.

An energy balance can determine energy supply requirements in the form of streams of
matter, heat and work, but fails to provide accurate information on how efficient the supplied
energy is used in a system. This is due to the fact that an energy analysis cannot identify the
real thermodynamic inefficiencies associated with an energy conversion system. The only
inefficiencies detected by the energy analysis of a system are the transfers of energy away
from the system that are not further used in this or another installation. This evaluation is
misleading for two reasons:

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 (1) The heat rejection to the environment may be unavoidable and be dictated by the
second law of thermodynamics (e.g., even in the reversible Carnot Cycle there is
heat rejection to the environment).

(2) The thermodynamic inefficiencies mainly occur within a system (e.g., reducing the
pressure of a fluid in an adiabatic throttle is a dissipative process without energy
transfer to the environment).

An entropy balance determines the entropy generation within a system, which is a measure of
the inefficiencies within it. However, the entropy concept does not allow to develop objective
measures of the efficiency with which energy is being used in a system and in each one of its
components. In addition, costs cannot be assigned to mass, energy or entropy values because
they all fail to account for the quality of energy.

The true thermodynamic value (quality) of an energy carrier is expressed by its potential to
cause a change, or to do something useful. In thermodynamics the quality of an energy carrier
is characterized by its exergy.

2. Exergy

Exergy is the maximum theoretical useful word (shaft work or electrical work) obtainable
from a system as this is brought into thermodynamic equilibrium with the reference
environment while the system interacts only with this environment. Alternatively the exergy
can be defined as the minimum theoretical work required to form a quantity of matter from
substances present in the reference environment and to bring this matter to a specific
thermodynamic state. The exergy is a measure of the departure of the state of a system from
the state of the reference environment.

The reference environment that is necessary for defining exergy is a large equilibrium system
in which the state variables (T0 and p0) and the chemical potential of the chemical components
contained in it remain constant when in a thermodynamic process heat and matter are
exchanged between a system and this environment. This environment is called exergy
reference environment or thermodynamic environment. It is free of irreversibilities and its
exergy value is equal to zero.

The natural environment cannot serve as the exergy-reference environment because it is not in
equilibrium. In fact, industrial processes are possible because the so-called natural resources
are not in equilibrium with the remaining substances in the natural environment. Therefore, a
model is needed for the exergy reference environment. More details about this environment
and its models are given in the article Basic Exergy Concepts. It should be emphasized that
although all known reference models are arbitrary to some extent, the conclusions drawn from
an exergy analysis are independent of the model used to calculate the exergy values.

In the absence of nuclear, magnetic, electrical and surface tension effects, the total exergy of a
system Esys consists of four components: physical exergy Esys PH
, chemical exergy E CH ,
kinetic exergy E KN , and potential exergy E PT :

PH
Esys = Esys + E CH + E KN + E PT (1)

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The subscript sys distinguishes the total exergy and the physical exergy of a system from the
corresponding variables associated with the transfer of material streams. The rate of total
exergy associated with a material stream (subscript ms) is

E ms = E ms
PH
+ E CH + E KN + E PT (2)

The physical exergy of a system and of a material stream are calculated by Equations 3 and 4,
respectively

PH
Esys = (U-U0) + p0 (V-V0) – T0 (S-S0) (3)

E ms
PH
= ( H − H 0 ) − T0 ( S − S 0 ) (4)

The physical exergy of a system or a material stream may be split into thermal exergy, due to
the deviation of the temperature from that of the environment, and mechanical exergy, caused
by the deviation of the pressure from that of the environment.

E PH = E T + E M (5)

Also the chemical exergy may be considered as the sum of reactive and nonreactive exergy:

E CH = E R + E N (6)

The kinetic and potential exergy components are calculated by Equations 7 and 8,
respectively:

1 2
E KN = mv (7)
2

E PT = mgz (8)

More details about the exergy components and their calculation are given in the article Basic
Exergy Concepts.

3. Performance Evaluation with the Aid of Exergetic Variables

The quality of an energy conversion process can be best evaluated from the thermodynamic
viewpoint with the aid of exergy-based variables. These include the following:

3.1 Exergy Destruction

The exergy destruction represents the exergy destroyed E D due to irreversibilities (entropy
generation) within a system. The irreversibilities are caused by chemical reaction, heat
transfer trough a finite temperature difference, mixing of matter, unrestrained expansion and
friction. The exergy destruction is calculated with the aid of either (a) an exergy balance

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formulated for the system being considered, or (b) the entropy generation S gen within the
system (calculated from an entropy balance) and the relationship

E D = T0 S gen (9)

The former way is recommended when a comprehensive exergetic evaluation is conducted.

The exergy destruction in the overall system (subscript tot) is equal to the sum of the exergy
destruction in all systems components:

nk
E D,tot = ∑ E D,k (10)
k =1

The exergy destruction in a component of a system is caused in general, not only by the
inefficiencies of the component being considered but also by the inefficiencies of other
system components. The part of the component’s total exergy destruction that is independent
of the changes in the exergy destruction of the remaining system components represents the
endogenous exergy destruction ( E DEN,k ). The remaining part of the component’s total exergy
destruction depends on the efficiency of the remaining system components and is called
exogenous exergy destruction ( E DEX,k ):

ED,k = EDEN,k + EDEX,k (11)

Another useful splitting of the total exergy destruction within a component is between
avoidable and unavoidable exergy destruction. Unavoidable ( E DUN,k ) is that part of exergy
destruction within one component that cannot be eliminated even if the best available
technology in the near future would be applied. The avoidable exergy destruction ( E DAV,k ) is
the difference between the total and the unavoidable exergy destruction.

ED,k = EDAV,k + EDUN,k (12)

By combining the two concepts we obtain the avoidable endogenous ( E DAD,k ), avoidable
exogenous ( E DAX,k ), unavoidable endogenous ( E DUD,k ) and unavoidable exogenous ( E DUX,k )
components of the exergy destruction within a component of a system:

E D,k = EDAD,k + EDAX,k + E DUD,k + EDUX,k (13)

It is apparent that all efforts to improve the thermodynamic efficiency of a component or

system should focus on avoidable exergy destruction. The best guidance in these efforts is
provided by considering separately the avoidable endogenous and the avoidable exogenous
exergy destruction. Additional discussion of exergy destruction is presented in the article
Exergy Balance and Exergetic Efficiency.

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3.2 Exergy Loss

Exergy loss ( E L ) is the transfer of exergy from the overall system to its surroundings. This
exergy transfer, which is associated with either the transfer of mass or the transfer of energy
(“heat loss”) to the surroundings, is not further used in this or another installation. In most
cases the exergy loss represents a small percentage of the total thermodynamic inefficiencies,
the largest part being formed by the sum of the exergy destructions within the components of
the overall installation. When the boundaries for the component analysis are drawn at the
ambient temperature T0, as it is recommended, the thermodynamic inefficiencies at the
component level consist exclusively of exergy destruction. In this case, exergy losses are
associated only with the overall system but not with any of its components.

3.3 Exergetic Efficiency

An appropriately defined exergetic efficiency unambiguously characterizes the performance

of a system or a system component from the thermodynamic viewpoint. The exergetic
efficiency of the kth component ( ε k ) is defined as the ratio between product and fuel. The
product ( E P , k ) and the fuel ( E F , k ) are defined by considering the desired result (expressed in
exergy terms) produced by the component, and the exergetic resources expended to generate
this result, respectively.

E P ,k E D,k + E L,k
εk = = 1− (14)
E F ,k E
F ,k

The definition of exergetic efficiency must be meaningful from both the thermodynamic and
the economic view points. General guidelines for defining exergetic efficiencies have been
proposed by Lazaretto and Tsatsaronis (2006). A distinction between (a) physical and
chemical exergy, or (b) thermal, mechanical and chemical exergy, or (c) thermal mechanical,
reactive and nonreactive exergy may allow the definition of a more rational exergetic
efficiency for some components.

The exergetic efficiency is used to compare the performance of similar components operating
under similar conditions. For the comparison of dissimilar components operating in the same
system, a modified exergetic efficiency can be defined based on the avoidable and
unavoidable exergy destruction concept:

*
E P ,k E DAV,k + E L,k
ε =
k = 1− (15)
E F ,k − E DUN,k E F ,k − E DUN,k

The definition of exergetic efficiencies is further discussed in the articles Exergy Balance and
Exergetic Efficiency and Strengths and Limitations of Exergy Analysis.

3.4 Exergy Destruction Ratio and Exergy Loss Ratio

In addition to the exergy destruction E D ,k and the exergetic efficiencies ε k or ε k* , the exergy
destruction ratio ( y D , k ) is used in the thermodynamic evaluation of a component. This ratio

7
compares the exergy destruction in the kth component with the fuel exergy supplied to the
overall system E F ,tot

E D ,k
y D ,k = (16)
E F ,tot

The difference between the exergy destruction ratio and the exergetic efficiency is that in the
former the exergy destruction within a component is related to the fuel exergy supplied to the
overall system, whereas the latter refers the same exergy destruction to the fuel exergy
supplied to the component. The exergy destruction ratio expresses the percentage of the
decrease of the exergetic efficiency for the overall system caused by the exergy destruction in
the kth system component as the following relation illustrates

E P ,tot E D ,tot + E L ,tot nk

ε tot = = 1− = 1 − ∑ y D ,k − y L ,tot (17)
E F ,tot E F ,tot k =1

The last term in the above equation represents the exergy loss ratio for the overall system,

E L ,tot
y L ,tot = (18)
E F ,tot

which expresses the percentage of the decrease of the overall exergetic efficiency caused by
the exergy loss. Since in almost every case no exergy loss is defined at the component level,
the exergy loss ratio is defined only for the overall system.

4.0 Comprehensive Thermodynamic Analysis

In a thermodynamic analysis first the mass and energy balances need to be chequed. Data
obtained by measurements need to be validated first before engineers proceed with the next
steps of the analysis. Mass and energy balances may be used to determine energy supply
requirements in the form of material streams or heat and work.

An energy balance, however, fails to identify the true thermodynamic inefficiencies because
(a) it considers as a such inefficiency only the rejection of energy to the environment of the
overall system, and (b) it cannot reveal the differences in the thermodynamic quality among
various energy carriers. Therefore, an evaluation based exclusively on the energy concept
might be misleading. An energy-based evaluation variable (for example, the energetic
efficiency of the overall system) should be used only when the exergy to energy ratio is
approximately equal to one for all energy carriers used to define the variable. Otherwise,
energy-based variables lead to wrong conclusions, particularly in the evaluation of system
components.

An exergy analysis should be conducted only after the validity of the mass and energy
balances has been confirmed. Some researchers prefer to use at this point of the
thermodynamic analysis entropy balances instead of exergy balances with the justification
that an exergy balance is obtained by combining the corresponding energy and entropy
balances. It is true that the entropy generation calculated with the aid of an entropy balance
correctly evaluates the thermodynamic inefficiencies within the system being considered
(exergy destruction), but the entropy concept (a) fails to accurately identify the inefficiencies

8
associated with exergy loss, (b) does not allow engineers to develop evaluation variables that
are as objective as the exergetic efficiency, for example, and (c) does not provide a basis for
assigning costs to energy carriers. For these reasons, the exergy concept is superior to the
entropy concept when they both are considered in a mutually exclusive way for the
thermodynamic analysis of an energy conversion system.

It is recommended that a comprehensive exergy analysis of such a system be conducted in the

following order:

• Calculation of the exergy values associated with each material and energy stream. This
includes calculation of the exergy components (e.g., chemical and physical exergy, or
chemical mechanical and thermal exergy) to be used in the analysis

• Calculation of the exergy destruction in each system component (process or

subprocess) with the aid of an exergy balance

• Definition and calculation of the exergetic efficiency for each system component
(process or subprocess) and for the overall system

• Calculation of the exergy destruction ratio for each system component and the exergy
loss ratio for the overall system

• Calculation of the avoidable/unavoidable and endogenous/exogenous exergy

destruction components for the most important system components

• Calculation of the modified exergetic efficiency for the components with the highest
exergy destruction ratios

• Detailed evaluation of each system component (process or subprocess) based on the

variables calculated above

The following guidelines may be used for the evaluation of the thermodynamic
performance:

1. The greater the exergy of a stream, the greater the need to use this exergy effectively.

2. The larger the total exergy destruction in a component, the more attention should be
given to the main causes of this exergy destruction.

3. The higher the endogenous avoidable exergy destruction, the more urgent the need to
improve the efficiency of the component being considered.

4. When the exogenous avoidable exergy destruction in a component is large, the

structure of the overall system and the efficiency of the remaining components must
be improved.

5. The lower the modified exergetic efficiency, the more urgent the need to improve the
efficiency of the component being considered, particularly when the exergy
destruction ratio is relatively large.

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 6. The higher the endogenous unavoidable exergy destruction, the more urgent the need
to replace the component being considered by a different concept.

7. If the exogenous unavoidable exergy destruction in some components is high, efforts

should focus on modifying the overall concept.

The exergy analysis can also be conducted in a graphical way with the aid of an energy-
utilization diagram. Details are given in the article Graphic Exergy Analysis.

Examples of exergy analyses are presented in the articles Exergy Analysis of Simple
Processes and Energetic and Exergy Analysis of Complex Systems. These examples
powerfully demonstrate how an exergy analysis identifies the potential for improving the
thermodynamic efficiency of a system. Particularly promising in that respect are the new
developments reported in the papers by Morosuk, Kelly and Tsatsaronis.

An exergy analysis is a general method that can be applied to any energy-conversion

system. For specific systems, special thermodynamic methods have been developed (e.g.,
“pinch” analysis for a heat-exchanger network) that can lead faster and reliably to
improvements for the specific system being considered. Information about Pinch Analysis
and Process Integration and Improvement are given in the respective articles.

Last but not least, an exergy analysis may assist in developing new concepts that operates
in a more efficient and cost-effective way. When applied correctly, it could enhance the
intuition and creativity of engineers, as demonstrated by an example presented in the
article Strengths and Limitations of Exergy Analysis

5.0 Closure

With the aid of an energy analysis the performance of an energy-conversion system cannot be
evaluated effectively and unambiguously. An exergy analysis complements and enhances an
energy analysis and represents a powerful tool for developing, evaluating, and improving
energy conversion systems.

The lack of a former procedure in using the results from an exergy analysis represents not
only a weakness but also a strength of the method. A strength because an exergy analysis can
be conducted for every thermal system and because the engineers control the evaluation and
optimization process and, thus, they can still use their intuition and creativity as opposed to a
formal optimization procedure in which they do not know how and why specific optimization
results were obtained.

In the evaluation of an energy-conversion system the analyst must consider the mutual
interdependencies among the system components and focus on the avoidable thermodynamic
inefficiencies. The concepts of endogenous and exogenous exergy destruction as well as
avoidable and unavoidable exergy destruction assist in fulfilling these requirements.

An exergy analysis identifies and evaluates the thermodynamic inefficiencies. The analyst,
however, wants also to know the costs that are associated with these inefficiencies to be able
to compare these costs with the investment expenditures required to reduce the
thermodynamic inefficiencies. This happens in a thermoeconomic (exergoeconomic)
evaluation in which all cost sources are properly identified and compared with each other.

10
 More details about exergoeconomics are providd in the articles Thermoeconomic Analysis
and Application of Thermoeconomics to the Design and Synthesis of Energy Plants.

Bibliography

1. Bejan, A., Tsatsaronis, G., and Moran, M. (1996). Thermal Design and Optimization.
New York: John Wiley & Sons. 542 p. [Contains an introduction to the exergy concept,
applications, and exergy-aided cost minimization of energy conversion systems.]

2. Cziesla F., Tsatsaronis, G., and Gao, Z. (2006). Avoidable thermodynamic inefficiencies
and costs in an externally fired combined cycle power plant. Energy – The International
Journal, 31:1472-1489 [Describes the calculation of avoidable and unavoidable exergy
destruction and of the associated costs.]

3. Kotas, T.J. (1995). The Exergy Method of Thermal Plant Analysis. Malabar, Florida:
Krieger Publishing Company. 328 p. [Provides a detailed discussion of the exergy concept
and its applications.]

4. Lazzaretto, A., and Tsatsaronis, G. (2006). SPECO: A systematic and general

methodology for calculating efficiencies and costs in thermal systems. Energy – The
International Journal, 31:1257-1289. [Discusses the definition and calculation of
exergetic efficiencies using various exergy components.]

5. Morosuk, T.V. and Tsatsaronis, G. (2006). The “cycle method” used in the exergy
analysis of refrigeration machines: From education to research. In: Frangopoulos, Ch.A.,
Rakopoulos, C.D. and Tsatsaronis, G. Proceedings of the 19th International Conference on
Efficiency, Cost, Optimization, Simulation and Environmental Impact of Energy Systems
(ECOS 200t), Agia Pelagia, Crete, Greece, July 12-14-2006, pp. 157-163. [Presents the
combination endogenous/exogenous exergy destruction with avoidable/unavoidable
exergy destruction.]

6. Szargut, J., Morris, D.R., and Steward, F.R. (1988). Exergy Analysis of Thermal,
Chemical and Metallurgical Processes. New York: Hemisphere, New York, 332 p.
[Contains useful information about standard molar chemical exergies and discusses the
exergy concept and its applications.]

7. Tsatsaronis, G. (1999). Design optimization using exergoeconomics. In: Bejan, A., and
Mamut, E. (Eds.) Thermodyamic Optimization of Complex Energy Systems.
Dordrecht/Boston/London: Kluwer Academic Publishers, 101-115. [Gives an overview of
an exergy-aided approach for reducing costs in the design of energy conversion systems.]

8. Tsatsaronis, G., Kelly, S.O., and Morosuk, T.V. (2006). Endogenous and exogenous
exergy destruction in thermal systems. New York: ASME IMECE 2006-13675 [Presents
the definition and calculation of endogenous and exogenous exergy destruction.]

9. Tsatsaronis, G. and Park, M.-H. (1999). On avoidable and unavoidable exergy

destructions and investment costs in thermal systems. In: Ishida, M., Tsatsaronis, G.,
Moran, M., and Katacka, H. (Eds.) Proceedings of the International Conference on
Efficiency, Costs, Optimization, Simulation and Environmental Aspects of Energy Systems
(ECOS ‚99), Tokyo, June 8-10, pp. 116-121. [Presents the concept of avoidable and
unavoidable exergy destruction.]

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